TW202600565A - Fused heterocyclic compounds and its uses thereof - Google Patents

Abstract

The present invention provides a fused heterocyclic compound of formula (I), or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof, wherein, Q, R1, Y, R2 and R<SP>2x</SP> are as defined in the detailed description. The present invention also provides methods for their preparation and use of the compounds of formula (I) as a pest control agent.

Description

Dysfused heterocyclic compounds and their uses

This invention relates to compounds of formula (I). In particular, this invention relates to fused heterocyclic compounds of formula (I) and methods for their preparation. This invention further relates to compositions comprising such compounds and their use as pest control agents.

Currently available modern pesticides and miteicides must meet many requirements, such as their activity level, persistence, breadth of insecticidal effect, and other beneficial effects and potential uses. Over the past few decades, efforts have been made to develop selective pesticides that act specifically on the biochemical mechanisms of insects or mites, but exhibit their properties in advantageous ways different from known pesticides.

Heterocyclic compounds with insecticidal properties are known and described, for example, in PCT patent publication WO2020250183. However, there is a continuous need for new compounds that are more effective, less toxic, and safer for the environment. Furthermore, some existing pesticides are highly toxic or persist in the environment for extended periods due to their residual properties, which can become an increasingly serious problem due to ecosystem destruction.

Therefore, there is a continuous need for new pest control agents with improved insecticidal activity, a wider range of efficacy, longer-lasting activity, stronger plant compatibility, higher environmental safety, better formulation performance, and lower risk of resistance development.

Therefore, the present invention aims to provide a compound that can meet or overcome the shortcomings of the prior art.

Surprisingly, we found that some of the novel insecticidal fused heterocyclic compounds with sulfur-containing substituents involved in this invention have good performance as insecticides and, as expected, are safer for the environment.

Therefore, the present invention provides a fused heterocyclic compound of formula (I), or a salt thereof, a stereoisomer, a metal complex, a polymorph, or an N-oxide. (I) Wherein, ^R1 , Y, Q, ^R2 and ^R2x are as defined in the manual.

This invention also relates to a method for preparing a compound of formula (I) or a salt thereof.

This invention provides a composition for controlling or preventing invertebrate pests. The composition comprises a bioavailable amount of a compound of formula (I) or a salt thereof, a stereoisomer, a metal complex, a polymorph or an N-oxide, and at least one additional component selected from surfactants and adjuvants.

The composition additionally includes at least one biocompatible compound selected from fungicides, insecticides, nematicides, mite killers, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients.

This invention provides the use of a compound of formula (I) or its salt, stereoisomer, polymorph, metal complex, N-oxide, or a combination thereof for the control of invertebrate pests in agricultural and horticultural crops, or parasites on animals or wooden residential and commercial buildings.

This invention provides a method for controlling invertebrate pests, comprising: bringing an invertebrate pest, its habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the invertebrate pest is growing or may grow, or material, plant, seed, soil, surface or space protected from pest infestation or contamination into contact with a bioavailable amount of a compound of formula (I) or its salt, stereoisomer, metal complex, polymorph, N-oxide, composition thereof or combination thereof.

Definition:

The definitions provided herein for the purposes of illustration only and do not in any way limit the scope of the invention disclosed herein.

As used herein, the terms "comprises," "comprising," "includes," "has," "having," "contains," "characterized by," or any other variation thereof are used to cover non-exclusive inclusion, subject to any expressly indicated limitations. For example, a composition, mixture, process, or method that includes a list of elements is not necessarily limited to those elements, but may also include other elements not expressly listed or inherent in such composition, mixture, process, or method.

The conjunction "consisting of" excludes any unspecified elements, steps, or components. If it appears in a request, it prevents the request from containing any material other than the stated material, unless it is an impurity typically associated with it. When the phrase "consisting of" appears in a sentence within the body of a request, rather than immediately following the preamble, it only restricts the elements specified in that sentence; other elements are not excluded from the entire request.

The conjunction "consisting essentially of" is used to define a composition or method in which the materials, steps, features, components, or elements included, other than those disclosed in the text, do not substantially affect the essential and novel features of the claimed invention. The phrase "consisting essentially of" occupies a middle position between "including" and "consisting of".

Furthermore, unless there is an explicit statement to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, a condition A "or" B is satisfied by any of the following: A is true (or exists), B is false (or does not exist), A is false (or does not exist), B is true (or exists), and both A and B are true (or exist).

Similarly, the indefinite article "a" (and an) preceding an element or component of the invention is to not limit the instances (i.e., the number of times) of that element or component. Therefore, "a" (a or an) should be understood to include one or at least one, and the singular form of an element or component also includes the plural, unless the number clearly refers to the singular.

As stated in this manual, the term "invertebrate pest" includes economically important arthropods, gastropods, and nematodes. The term "arthropod" includes, but is not limited to, insects, mites, spiders, scorpions, centipedes, millipedes, islet beetles, and myriapods. The term "gastropod" includes, but is not limited to, snails, slugs, and other stylomatophores. The term "nematode" refers to living organisms of the phylum Phylum Nematoda. The term "helminths" includes, but is not limited to, roundworms, heartworms, phytotoxic nematodes, trematodes, acanthocephala, and cetoda.

The term "agronomic" refers to the production of crops (such as food and fiber) and includes corn, soybeans and other legumes, rice, grains (such as wheat, oats, barley, rye, rice, and corn), leafy vegetables (such as lettuce, cabbage, and other cruciferous vegetables), fruit vegetables (such as tomatoes, peppers, eggplants, cruciferous vegetables, and gourds), potatoes, sweet potatoes, grapes, cotton, tree fruits (such as pome fruits, stone fruits, and citrus fruits), small fruits (berries, cherries), and other specialty crops (such as rapeseed, sunflowers, and olives).

The term "nonagronomic" refers to crops other than agricultural crops, such as horticultural crops (e.g., greenhouses, nurseries, or ornamental plants not grown in fields), residential, agricultural, commercial and industrial structures, turf (e.g., turf farms, ranches, golf courses, lawns, sports fields), wood products, stored products, agricultural and forestry and vegetation management, and applications in public health (i.e., human) and animal health (e.g., domesticated animals (such as pets, livestock and poultry) and undomesticated animals (such as wild animals)).

Non-agronomic applications include protecting animals from invertebrate parasitic pests by applying to them parasiticly effective (i.e., biologically effective) amounts of the compound of the invention, typically in the form of formulations for veterinary use. As used in this disclosure and claim, the terms "parasiticidal" and "parasitically" refer to the observable effect of providing protection against invertebrate parasitic pests, typically involving a reduction in the occurrence or activity of the target invertebrate parasitic pest. Such effects on pests include necrosis, death, stunted growth, or reduced growth capacity in or within the host animal. These effects on invertebrate parasitic pests provide control (including prevention, reduction, or elimination) of animal infestation or infection.

The compounds disclosed herein may exist as pure substances or as various possible isomers or as optical isomers, such as stereoisomers, for example, racemic mixtures, individual stereoisomers, or mixtures of structural isomers. Various stereoisomers include mirror isomers, non-mirror isomers, palmar isomers, rotation-resistant isomers, configurational isomers, tautomers, optical isomers, polymorphs, and geometric isomers. Any desired mixtures of these isomers fall within the scope of the claims herein. Those skilled in the art will understand that a stereoisomer, when enriched relative to other isomers or when separated from other isomers, may be more active and/or may exhibit beneficial effects. Furthermore, those skilled in the art know processes, methods, or techniques for separating, concentrating, and/or selectively preparing said isomers.

The definitions of the various terms used in this manual will now be explained.

The terms "aliphatic compound" or "aliphatic group" used here refer to organic compounds in which carbon atoms are linked in straight chains, branched chains, or non-aromatic rings.

The term "alkyl" (alykl) is used, whether alone or in compound forms (e.g., "alkylthio" or "haloalkyl" or -N(alkyl) or alkylcarbonylalkyl or alkylsulfonamide), including straight-chain or branched _C1 to _C24 alkyl, preferably _C1 to _C15 alkyl, more preferably _C1 to _C10 alkyl, and especially preferably _C1 to _C6 alkyl. Representative examples of alkyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2 -Dimethylpropyl, 1-Ethylpropyl, Hexyl, 1,1-Dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1 2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl, and 1-Ethyl-2-methylpropyl, or different isomers. If the alkyl group is at the end of the complex substituent, for example in an alkylcycloalkyl group, then the starting portion of the complex substituent, such as the cycloalkyl group, can be mono- or poly-substituted, either the same as or different from the alkyl group, independently. This also applies to complex substituents in which other groups, such as alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy, etc., are at the end.

The term "alkenyl," whether used alone or in a compound form, refers to _C2 to _C24 alkenes, whether linear or branched, preferably _C2 to _C15 alkenes, more preferably _C2 to _C10 alkenes, and most preferably _C2 to _C6 alkenes. Representative examples of alkenes include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, and 2-methyl-3-butenyl. 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-1-propenyl, 1,2-Dimethyl-2-propenyl, 1-Ethyl-1-propenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-1-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1-pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2-pentenyl, 1-Methyl-3-pentenyl 2-Methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2 3-Dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and 1-ethyl-2-methyl-2-propenyl, and various isomers. "Alkenyl" also includes polyenes, such as 1,2-propadienyl and 2,4-hexadienyl. Unless specifically defined elsewhere, this definition also applies to alkenyl groups, such as halogenated groups, which are part of a complex substituent.

The term "alkynyl" is used, whether alone or in compound form, and includes straight-chain or branched _C2 to _C24 alkynyls, preferably _C2 to _C15 alkynyls, more preferably _C2 to _C10 alkynyls, and most preferably _C2 to _C6 alkynyls. Non-limiting examples of yne hydrocarbons include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1- Methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1-ethyl-1-methyl-2-propynyl, as well as various isomers. Unless otherwise defined, this definition also applies to alkynyl groups that are part of a complex substituent, such as halogenyl groups. The term "alkynyl" can also include a part consisting of multiple triple bonds, such as 2,5-hexadiynyl.

The term "cycloalkyl" refers to an alkyl group that is closed to form a ring. Non-limiting examples include, but are not limited to, cyclopropyl, cyclopentyl, and cyclohexyl. Unless otherwise defined, this definition also applies to cycloalkyl groups that are part of a complex substituent, such as cycloalkylalkyl groups.

The term "cycloalkylalkyl" refers to cycloalkyl substitution on an alkyl group. It means that the cycloalkyl group is attached to the rest of the molecule through an alkyl linker group.

For example, when used here, the term " _C3 - _C6 -cycloalkyl- _{C1 - Cn} -alkyl-" refers to a _C1 - _{Cn-alkyl group substituted with one or more C3-C6 - cycloalkyl} groups as defined above. _{C3 - C6 - cycloalkyl} - _C1 - _C3 -alkyl is interpreted accordingly. Examples include, but are not limited to, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopentylethyl, and cyclohexylmethyl.

The term "cycloalkenyl" refers to an alkenyl group that is closed to form a ring, including monocyclic and partially unsaturated hydrocarbon groups. Non-limiting examples include, but are not limited to, cyclopropenyl, cyclopentenyl, and cyclohexenyl. Unless otherwise defined, this definition also applies to cycloalkenyl groups that are part of a complex substituent, such as cycloalkenylalkyl groups.

The term "cycloalkynyl" refers to an alkynyl group that is closed to form a ring, including monocyclic and partially unsaturated hydrocarbons. Non-limiting examples include, but are not limited to, cyclopropynyl, cyclopentynyl, and cyclohexynyl. Unless otherwise defined, this definition also applies to cycloalkynyl groups that are part of a complex substituent, such as cycloalkynylalkyl groups.

The terms "cycloalkoxy" and "cycloalkenyloxy" have similar definitions. Non-limiting examples of cycloalkoxy groups include cyclopropoxy, cyclopentoxy, and cyclohexoxy. Unless otherwise defined, this definition also applies to cycloalkoxy groups that are part of a complex substituent, such as cycloalkoxyalkyl groups.

The term "halogen," whether used alone or in compound forms (e.g., "haloalkyl"), includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound forms such as "haloalkyl," the alkyl group may be partially or wholly replaced by one or more halogen atoms, which may be the same or different. Non-limiting examples of "halogenated" include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 1,1-dichloro-2,2,2-trifluoroethyl, and 1,1,1-trifluoropropyl-2-yl. Unless specifically defined elsewhere, this definition also applies to halogenated groups that are part of a complex substituent, such as halogenated aminoalkyl groups.

The terms "haloalkenyl" and "haloalkynyl" have similar definitions, the difference being that the alkenyl and alkynyl groups exist as substituents rather than alkyl groups.

The term "haloalkoxy" refers to a straight-chain or branched alkoxy group in which some or all of the hydrogen atoms in these groups can be replaced by the aforementioned halogen atoms. Non-limiting examples of haloalkoxy groups include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoroprop-2-oxy. Unless specifically defined elsewhere, this definition also applies to halogenated compounds, such as halogenated alkyl compounds, which are part of a complex substituent.

The term "haloalkylthio" refers to straight-chain or branched alkylthio groups in which some or all of the hydrogen atoms in these groups can be replaced by the aforementioned halogen atoms. Non-limiting examples of halogenated thiols include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2-difluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio, and 1,1,1-trifluoroprop-2-thio. Unless specifically defined elsewhere, this definition also applies to halogenated thio groups, such as halogenated thioalkyl groups, which are part of a complex substituent.

Non-limiting examples of "haloalkylsulfinyl" include _CF3S (O), _CCl3S (O), _CF3CH2S (O), and _CF3CF2S (O). Examples of "haloalkylsulfonyl" include _{CF3S ( O} ) ₂ , _CCl3S (O) _{2 , CF3CH2S} (O) ₂ , and _CF3CF2S (O) _{2 .}

The term "hydroxy" refers to -OH, and "amino" refers to -NRR, where R can be H or any possible substituent, such as alkyl. The term "carbonyl" refers to -C(O)-, "carbonyloxy" refers to -OC(O)-, "oxo" refers to =O, "sulfinyl" refers to SO, and "sulfonyl" refers to S(O) ₂ .

The term "alkoxy" is used, whether alone or in a compound form, including _C1 to _C24 alkoxy, preferably _C1 to _C15 alkoxy, more preferably _C1 to _C10 alkoxy, and most preferably _C1 to _C6 alkoxy. Examples of alkoxy groups include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, and 1-ethyl-2-methylpropoxy, as well as various isomers. Unless specifically defined elsewhere, this definition also applies to alkoxy groups that are part of a complex substituent, such as halogenated alkoxy, alkynyl alkoxy, etc.

_The term "alkoxyalkyl" refers to alkoxy substitution on _an alkyl _{group .} Non-limiting examples _{of "} alkoxyalkyl _" include _{CH3OCH2 , CH3OCH2CH2 , CH3CH2OCH2 , CH3CH2CH2CH2OCH2} , _{and CH3CH2OCH2CH2 .}

The term "alkoxyalkoxy" refers to the substitution of an alkoxy group on an alkoxy group.

The term "alkylthio" includes branched or linear alkylthio groups, such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylethylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2- Different isomers including methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutyrothio, 1,2-dimethylbutyrothio, 1,3-dimethylbutyrothio, 2,2-dimethylbutyrothio, 2,3-dimethylbutyrothio, 3,3-dimethylbutyrothio, 1-ethylbutyrothio, 2-ethylbutyrothio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio, and 1-ethyl-2-methylpropylthio.

The definitions of halogenated alkyl, halogenated alkenyl, alkyl cycloalkyl, cycloalkylalkyl, cycloalkoxyalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, halogenated carbonyl, cycloalkyl carbonyl, halogenated carbonyl, halogenated carbonyl, etc., are similar to the examples above.

The term "alkylthioalkyl" indicates alkylthioalkyl substitution on _an alkyl group. _{Representative} examples of _" alkylthioalkyl" include _-CH₂SCH₂ , _{-CH₂SCH₂CH₂ , CH₃CH₂SCH₂ , CH₃CH₂CH₂CH₂SCH₂ , and CH₃CH₂SCH₂CH₂ .} The term " _{alkylthioalkoxy} " indicates alkylthioalkyl substitution on an alkoxy group. The term " _{cycloalkylalkylamino} " indicates cycloalkyl substitution _{of an} alkylamino group.

The definitions of terms such as alkoxyalkoxyalkyl, alkylaminoalkyl, dialkylaminoalkyl, cycloalkylaminoalkyl, and cycloalkylaminocarbonyl are similar to those of "alkylthioalkyl" and cycloalkylalkylamino.

The term "alkoxycarbonyl" refers to an alkoxy group that is attached to the skeleton via a carbonyl group (-CO-). Unless otherwise defined, this definition also applies to alkoxycarbonyl groups that are part of a complex substituent, such as cycloalkylalkoxycarbonyl groups.

The term "alkoxycarbonylalkylamino" indicates alkoxycarbonyl substitution on an alkylamino group. "Alkylcarbonylalkylamino" indicates alkylcarbonyl substitution on an alkylamino group. The definitions of terms such as alkylthioalkoxycarbonyl, cycloalkylalkylamino, and alkyl are similar.

Non-limiting examples of "alkylsulfinyl" include, but are not limited to, methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, hexylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, and 1-methylpentyl. Sulphinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl, and 1-ethyl-2-methylpropylsulfinyl, as well as various isomers. The term "arylsulfinyl" includes Ar-S(O), where Ar can be any carbocyclic or heterocyclic ring. Unless specifically defined elsewhere, this definition also applies to alkylsulfinyl groups that are part of a complex substituent, such as halogenated alkylsulfinyl groups.

The term _C1 - _C6 alkylsulfonyl refers to a group of the formula –S(O) _2R , where R is a _C1 - _C6 alkyl group as generally defined above.

Non-limiting examples of "alkylsulfonyl" include, but are not limited to, methanesulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, and 1-methylpentyl. Sulfoyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl, and 1-ethyl-2-methylpropylsulfonyl, as well as various isomers. The term "arylsulfonyl" includes Ar-S(O) _₂ , where Ar can be any carbocyclic or heterocyclic ring. Unless specifically defined elsewhere, this definition also applies to alkylsulfonyl groups that are part of a complex substituent, such as alkylsulfonylalkyl groups, etc.

The definitions of "alkylamino" and "dialkylamino" are similar to those in the examples above.

The term _C1 - _C6 -hydroxyalkyl represents a group in which the _C1 - _C6 alkyl group is substituted with a hydroxyl group. Non-limiting examples include _-CH2OH , -CH( _CH3 )-OH, and _{CH2CH2 -} OH.

The term "optionally substituted" as used here means that the referenced group is either unsubstituted or substituted with a specified substituent. For example, " _C3 - _C4 -cycloalkyl is optionally substituted with one or two halogen atoms" means _C3 - _C4 -cycloalkyl, _C3 - _C4 -cycloalkyl substituted with one halogen atom, and _C3 - _C4 -cycloalkyl substituted with two halogen atoms. The term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted".

The term "carbocycle" includes "aromatic carbocyclic ring systems" and "nonaromatic carbocyclic ring systems," or polycyclic or bicyclic (spiro, fused, bridged, non-fused) cyclic compounds, where the rings can be aromatic or non-aromatic (aromatic indicates that the Huckel rule is satisfied, and non-aromatic indicates that the Huckel rule is not satisfied).

The term "hetero" in relation to rings refers to a ring in which at least one ring atom is not carbon and may contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, assuming that each ring contains no more than 4 nitrogen atoms, no more than 2 oxygen atoms and no more than 2 sulfur atoms.

The term "aromatic" indicates compliance with the Handel rules, while "non-aromatic" indicates non-compliance with the Handel rules.

The term "heterocycle" includes "aromatic heterocycles" or "heteroaromatic ring systems" and "non-aromatic heterocyclic ring systems," or polycyclic or bicyclic (spiro, fused, bridging, non-fused) cyclic compounds, wherein the rings can be aromatic or non-aromatic, wherein the heterocycle contains at least one heteroatom selected from N, O, S(O) _0-2 , and/or the carbon ring members of the heterocycle can be replaced by C(=O), C(=S), C(=CR*R*), and C=NR*, where * represents an integer.

The term "non-aromatic heterocycle" or "non-aromatic heterocycle" is used. Heterocyclic refers to a saturated or partially unsaturated heterocycle with three to fifteen members, preferably three to twelve members, containing one to four heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur. The heterocycle is monocyclic, bicyclic, or tricyclic, and in addition to the carbon ring member, it contains one to three nitrogen atoms and/or one oxygen atom or sulfur atom, or one or two oxygen atoms and/or sulfur atoms. If it also contains more than one oxygen atom, they are not directly adjacent. Examples include: oxiranyl, aziridinyl, thietanyl, oxetanyl, and azetidinyl. ), 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolinyl, 4-isothiazolinyl, 5-isothiazolinyl, 1-pyrazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl Oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 1-imidazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-1-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidinyl -1-yl, 1,3,4-triazolidine-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,4-dihydrofuran-2-yl, 2,4-dihydrofuran-3-yl, 2,3-dihydrothiophen-2-yl, 2,3-dihydrothiophen-3-yl, 2,4-dihydrothiophen-2-yl, 2,4-dihydro Thiophene-3-yl, pyrrolinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isooxazoline-3-yl, 3-isooxazoline-3-yl, 4-isooxazoline-3-yl, 2-isooxazoline-4-yl, 3-isooxazoline-4-yl 4-Isooxazoline-4-yl, 2-Isooxazoline-5-yl, 3-Isooxazoline-5-yl, 4-Isooxazoline-5-yl, 2-Isothiazoline-3-yl, 3-Isothiazoline-3-yl, 4-Isothiazoline-3-yl, 2-Isothiazoline-4-yl, 3-Isothiazoline-4-yl, 4-Isothiazoline-4-yl, 2-Isothiazoline Azoline-5-yl, 3-isothiazoline-5-yl, 4-isothiazoline-5-yl, 2,3-dihydropyrazole-1-yl, 2,3-dihydropyrazole-2-yl, 2,3-dihydropyrazole-3-yl, 2,3-dihydropyrazole-4-yl, 2,3-dihydropyrazole-5-yl, 3,4-dihydropyrazole-1-yl, 3,4-dihydropyrazole- 3-yl, 3,4-dihydropyrazole-4-yl, 3,4-dihydropyrazole-5-yl, 4,5-dihydropyrazole-1-yl, 4,5-dihydropyrazole-3-yl, 4,5-dihydropyrazole-4-yl, 4,5-dihydropyrazole-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol -4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, piperidinyl (pipe ridinyl), 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, pyrazynyl, morpholinyl, thiomorphlinyl, 1,3-diox-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiophenyl, 3-hexahedrazine, 4-hexahedrazine, 2-hexahedrimyrimidyl, 4-hexahedrimyrimidyl, 5-hexahedrimyrimidyl, 2-piperidinyl, 3,5-hexahedrimitrazine-2-yl, 1,2,4-hexahedrimitrazine-3-yl, cycloserine, 2,3,4,5-tetrahydro[1H]azine epin)-1- or-2- or-3- or-4- or-5- or-6- or-7-yl, 3,4,5,6-tetrahydro[2H]azinon-2- or-3- or-4- or-5- or-6- or-7-yl, 2,3,4,7-tetrahydro[1H]azinon-1- or-2- or-3- or-4- or-5- or-6- or-7-yl, 2,3,6,7-tetrahydro[1H]azinon-1- or-2- or-3- or-4- or-5- or-6- or-7-yl, hexahydroazinon-1- or-2- or-3- or-4-yl, tetrahydro- and hexahydrooxepinyl, for example 2,3,4,5 ... [H]oxadiazon-2- or -3- or -4- or -5- or -6- or -7-yl, 2,3,4,7-tetrahydrogen[1H]oxadiazon-2- or -3- or -4- or -5- or -6- or -7-yl, 2,3,6,7-tetrahydro[1H]oxo-2- or -3- or -4- or -5- or -6- or -7-yl, hexahydrooxo-1- or -2- or -3- or -4-yl, tetrahydro- and hexahydro-1,3-diazepinyl, tetrahydro- and hexahydro-1,4-diazepinyl, tetrahydro- and hexahydro-1,3-oxazepinyl, tetrahydro- and hexahydro-1,4-oxazepinyl, tetrahydro- and hexahydro-1,3-dioxepinyl, tetrahydro- and hexahydro-1,4-dioxepinyl. Unless specifically defined elsewhere, this definition also applies to heterocyclic groups, such as heterocyclic alkyl groups, which are part of a complex substituent.

The term "heteroaryl" or "aromatic heterocyclic" refers to a five- or six-membered, fully unsaturated monocyclic system containing one to four heteroatoms selected from oxygen, nitrogen, and sulfur; if it also contains more than one oxygen atom, they are not directly adjacent; a five-membered heteroaryl contains one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom; a five-membered heteroaryl may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members in addition to carbon atoms. For example (but not limited to): furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3,4-triazolyl, tetrazolyl Tetrazolyl; a nitrogen-bonded five-membered heteroaryl containing 1 to 4 nitrogen atoms, or a benzo-fused nitrogen-bonded five-membered heteroaryl containing 1 to 3 nitrogen atoms: a five-membered heteroaryl, in addition to carbon atoms, may contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, wherein two adjacent carbon ring members or one nitrogen atom and one adjacent carbon ring member can be bonded by butylene oxide. -1,3-diene-1,4-diyl group bridging, wherein one or two carbon atoms may be replaced by nitrogen atoms, wherein these rings are linked to the main chain through one of the nitrogen ring members, non-limiting examples: 1-pyrrole, 1-pyrazolyl, 1,2,4-triazol-1-yl, 1-imidazolyl, 1,2,3-triazol-1-yl, and 1,3,4-triazol-1-yl.

Six-membered heteroaryl groups containing 1 to 4 nitrogen atoms: These include six-membered heteroaryl groups containing 1 to 3 nitrogen atoms and 1 to 4 nitrogen atoms as ring members, in addition to carbon atoms, such as (but not limited to) 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-darazinyl, 4-darazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, and 1,2,4,5-tetraazin-3-yl; benzofused five-membered heteroaryl groups containing 1 to 3 nitrogen atoms or 1 nitrogen atom and 1 oxygen or sulfur atom, such as (but not limited to) indole. Indole-1-yl, indole-2-yl, indole-3-yl, indole-4-yl, indole-5-yl, indole-6-yl, indole-7-yl, benzimidazol-1-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-1-yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl, 1-benzofuran Furan-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl, 1,3-benzothiazol-2-yl, 1,3-benzothiazol-4-yl, 1,3-benzothiazol-5-yl, 1,3-benzothiazol-6-yl, 1,3-benzothiazol-7-yl, 1,3-benzooxazole 1,3-benzoxazol-2-yl, 1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl and 1,3-benzoxazol-7-yl; benzo-fused six-membered heteroaryl groups containing 1 to 3 nitrogen atoms, such as (but not limited to) quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl.

Unless specifically defined elsewhere, this definition also applies to heteroaryl groups, such as heteroarylalkyl groups, which are part of a complex substituent.

The term "heteroarylalkyl" refers to heteroaryl substitution on an alkyl group. It means that the heteroaryl group is attached to the rest of the molecule through an alkyl linker group.

As used herein, the term "5 or 6-membered heteroaryl- _C1 - _C3 -alkyl" refers to a _C1 - _C3 -alkyl group as generally defined above, substituted by a 5 or 6-membered heteroaryl ring. Examples include, but are not limited to, imidazolemethyl, oxadiazolemethyl, thiadiazolemethyl, pyridinylethyl, pyrazineethyl, pyridinylmethyl, pyrazinemethyl, pyrimidinemethyl, and pyrimidineethyl.

As used herein, the term "3 to 4-membered heteroaryl- _C1 - _C3 -alkyl" refers to a _C1 - _C3 -alkyl group as generally defined above, substituted by a 3 to 4-membered heteroaryl ring. Examples include, but are not limited to, azetidinylmethyl, oxetanylmethyl, azetidinylethyl, and oxetanylethyl.

The term "trialkylsilyl" includes three branched and/or straight-chain alkyl groups linked to and through silicon atoms, such as trimethylsilyl, triethylsilyl, and tributyl-dimethylsilyl. "Halotrialkylsilyl" indicates that at least one of the three alkyl groups is partially or completely substituted with the same or different halogen atoms. The term "alkoxytrialkylsilyl" indicates that at least one of the three alkyl groups is substituted with one or more alkoxy groups, which may be the same or different. The term "trialkylsilyloxy" indicates a trialkylsilyl functional group linked through oxygen.

Non-limiting examples of "alkylcarbonyl" include C(O) _CH3 , C(O) _{CH2CH2CH3 ,} and C(O)CH( _CH3 ) ₂ . Non-limiting examples of "alkoxycarbonyl" include _CH3OC (=O), _CH3CH2OC (=O _{) , CH3CH2CH2OC (} =O), ( _CH3 ) _2CHOC (=O), and various _{butoxy or} pentoxy carbonyl isomers. Non-limiting examples of "alkylaminocarbonyl" include _CH3NHC (=O), _CH3CH2NHC (=O ₎ , _CH3CH2CH2NHC (=O), ( _CH3 ) _2CHNHC (=O) _, and various butamino or _pentamino carbonyl isomers. Non-limiting examples of "dialkylaminocarbonyl" include ( _CH3 ) _2NC (=O), ( _CH3CH2 ) _2NC (=O), _{CH3CH2 ( CH3} )NC(=O), _{CH3CH2CH2 ( CH3} )NC(= _O ), and ( _{CH3 )2CHN(CH3 ) C} (=O). Non _- limiting examples of _" alkoxyalkylcarbonyl" include _CH3OCH2C ( _{= O} ) _{, CH3OCH2CH2C} (=O), _{CH3CH2OCH2C ( =} O), _{CH3CH2CH2CH2OCH2C} ( _{= O )} , _{and CH3CH2OCH2CH2C} (= _O ). Non-limiting examples of "alkylthioalkylcarbonyl" include _CH3SCH2C (=O ₎ , _CH3SCH2CH2C (= _O ), _CH3CH2SCH2C ( _{= O )} , _{CH3CH2CH2CH2SCH2C} (=O), and _{CH3CH2SCH2CH2C} (=O). The definitions of _{halogenated sulfonylaminocarbonyl} , _{alkylsulfonylaminocarbonyl} , _{alkylthioalkoxycarbonyl} , _{alkoxycarbonylalkylamino ,} etc., are _similar .

Non-limiting _examples of "alkylaminoalkylcarbonyl" include _CH3NHCH2C ( _{= O} ), _CH3NHCH2CH2C (= _O ), _CH3CH2NHCH2C ( _{= O ) , CH3CH2CH2CH2NHCH2C} (=O ₎ , _{and CH3CH2NHCH2CH2C} (= _{O )} .

The term "amide" refers to A-R'C=ONR''-B, where R' and R'' represent substituents, and A and B represent any group.

The term "thioamide" refers to A-R'C=SNR''-B, where R' and R'' represent substituents, and A and B represent any group.

The total number of carbon atoms in the substituents is indicated by the prefix "C_{_i}-C_{_j}", where i and j are numbers from 1 to 21. For example, C _₁-C_₃alkylsulfonyl represents methanesulfonyl to propanesulfonyl; C _₂alkoxyalkyl represents CH _₃OCH_₂; C _₃alkoxyalkyl represents, for example, CH _₃CH(OCH_₃), CH _₃OCH_₂CH_₂, or CH_₃CH_₂OCH_₂; C _₄alkoxyalkyl refers to various isomers of alkyl groups substituted with alkoxy groups containing a total of 4 carbon atoms, examples of which include CH _₃ CH ₂CH₂OCH_₂ and CH_₃CH_₂OCH_₂CH ₂. In the above description, when the compound of formula (I) consists of one or more heterocycles, all substituents are linked to these rings by substituting hydrogen on any available carbon or nitrogen.

When a compound is substituted by a substituent with a subscript, and the substituent indicates that the number of substituents can exceed 1, then the substituents (when they exceed 1) are independently selected from the defined set of substituents. Furthermore, when the subscript m in (R) _m represents an integer ranging from, for example, 0 to 4, then the number of substituents can be selected from integers between 0 and 4, including 0 and 4.

When a group contains a substituent that can be hydrogen, then the group is considered unsubstituted when the substituent is considered to be hydrogen.

The embodiments described herein, along with their various features and advantageous details, are explained by referring to the non-limiting embodiments in the specification. Descriptions of well-known components and processing techniques are omitted to avoid unnecessarily obscuring the embodiments herein. The examples used herein are intended only to facilitate an understanding of how the embodiments herein can be practiced and to enable those skilled in the art to practice the embodiments herein. Therefore, these examples should not be construed as limiting the scope of the embodiments herein.

The description of specific embodiments will fully reveal the general nature of the embodiments herein, which can be easily modified and/or adapted by others using existing knowledge without departing from the general conception, and thus such modifications and adaptations should and are intended to be understood within the semantics and equivalent scope of the disclosed embodiments. It should be understood that the wording or terminology used herein is descriptive rather than limiting. Therefore, although the embodiments herein are described as preferred embodiments, those skilled in the art will recognize that the embodiments herein can be implemented after modifications within the spirit and scope of the embodiments described.

Any discussion in this specification of documents, acts, materials, devices, articles, etc., is merely to provide background for this case. It should not be construed as an admission that any or all of these matters constitute part of the prior art or general knowledge in the relevant field that existed anywhere prior to the date of the priority of this case.

While the values mentioned in the specification and the specification/request may constitute a key part of the invention, any deviation from these values shall still fall within the scope of the invention if such deviation follows the same scientific principles disclosed herein. Where appropriate, the compounds of the invention may exist in mixtures of different possible isomeric forms, especially stereoisomers such as E and Z, threo and erythro, and optical isomers. However, tautomers may also exist where appropriate. Any desired mixtures of E and Z isomers, threo and erythro isomers, optical isomers, and possible tautomers are disclosed and protected.

For the purposes of this article, the term "pest" includes, but is not limited to, fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects, and rodents.

The term "plant" is understood here to refer to all plants and plant communities, including both desirable and unwanted wild plants and crops (including naturally occurring crops). Crops can be plants that can be obtained through conventional breeding and optimization methods or through biotechnology and genetic engineering methods or combinations thereof, including genetically modified plants and cultivated varieties that are protected or unprotected by the rights of plant breeders.

For the purposes of this disclosure, the term "plant" includes living organisms such as trees, shrubs, herbs, grasses, ferns and mosses, which typically grow in one place, absorb water and necessary substances through their roots, and synthesize nutrients in their leaves through photosynthesis.

Examples of "plants" used for the purposes of this invention include, but are not limited to, agricultural crops (such as wheat, rye, barley, black wheat, oats, or rice); beets (such as sugar beets or feed beets); fruits and fruit trees (such as pome, drupes, or soft fruits (such as apples, pears, plums, peaches, apricots, cherries, strawberries, raspberries, blackberries, or currants)); legumes (such as lentils, peas, alfalfa, or soybeans); oilseed plants (such as rapeseed, mustard, olives, sunflowers, coconuts, cocoa beans, castor oil plants, oil palms, peanuts, or soybeans); cucurbits (such as pumpkins, cucumbers, or melons); fiber plants (such as cotton, flax, hemp, or jute); citrus fruits and citrus trees (such as oranges, lemons, grapefruits, or...). Oranges); any horticultural plants, vegetables (such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, cucurbitaceae or peppers); Lauraceae plants (such as avocados, cinnamon or camphor); Cucurbitaceae plants; oil plants; energy and raw material plants (such as grains, corn, soybeans, other legumes, rapeseed, sugarcane or oil palm); tobacco; nuts; coffee; tea; cocoa; bananas; pepper; grapevines (table grapes and wine grapes); hops; turf; stevia (also known as stevia); natural rubber plants or ornamental and forestry plants (such as flowers, shrubs, broad-leaved trees or evergreens (such as conifers)); and plant propagation materials (such as seeds) and crop materials of these plants.

Preferably, the plants used for the purposes of this invention include, but are not limited to, grains, corn, rice, soybeans and other legumes, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oil-producing plants, tobacco, coffee, tea, cocoa, sugar beets, sugarcane, cotton, potatoes, tomatoes, onions, peppers and vegetables, ornamental plants, any flowering plants and other plants for human and animal use.

The term "plant parts" should be understood to refer to all parts and organs of a plant, both above and below ground. For the purposes of this disclosure, the term "plant parts" includes, but is not limited to, cuttings, leaves, branches, tubers, flowers, seeds, branches, roots (including taproot, lateral roots, root hairs, root tips, root caps, and rhizomes), shoots, fruits, fruiting bodies, bark, stems, buds, auxiliary buds, meristematic tissues, nodes, and internodes.

The term "locus thereof" includes the soil, the surroundings of plants or plant parts, and the equipment or tools used before, during, or after sowing/planting plants or plant parts.

Applying the compound of this invention, or a composition of the compound of this invention that may optionally include other compatible compounds, to a plant or plant material or its location, including by means of techniques known to a person skilled in the art to which this invention pertains, including but not limited to spraying, coating, dipping, fumigating, impregnating, injection, and dusting.

The term "applied" refers to attaching something to a plant or part of a plant by physical or chemical means (including soaking).

The embodiments of the present invention are as follows:

Implementation Example 01:

Therefore, the present invention provides a fused heterocyclic compound of formula (I), (I) Wherein, ^R1 is a _C1 - _C6 alkyl; Y is selected from O or ^NRY ; ^RY is selected from the group consisting of: hydrogen, nitrile, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogenyl, _C2 -C6-halogenyl, _C3 - _{C5 -} cycloalkyl, _C3 - _C5 -cycloalkyl- _C1 - _C3 -alkyl and -C(O) ^R1a ; ^R1a is selected from the group consisting of: _C1 - _C6 -alkyl, _C1 - _C6 -halogenyl, _C3 - _C5 -cycloalkyl and _C3 - _C5 -cycloalkyl- _C1 - _C3 -alkyl; R ^R2a is selected from the group consisting of: cyclopropyl, pyrimidinyl, ^CR2b , ^R2c , ^R2d , and ^NR11 , ^R12 ; the cyclopropyl and pyrimidinyl groups may optionally be substituted with one or more groups of ^R2a ; ^R2a is independently selected from the group consisting of: halogen, nitrile, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogenyl, _C3 - _C8 -cycloalkyl, ^OR4 , and ^NR5 , ^R6 ; ^R2b is selected from the group consisting of: halogen, hydroxyl, _C1 - _C6 -halogenyl, _C3 - _C4 -cycloalkyl, and ^OR4 ; R ^R2c is selected from the group consisting of: hydrogen, halogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, and _C2 - _C6 -ynyl; ^R2d is selected from the group consisting of: hydrogen and _C1 - _C6 -alkyl; ^R2x is selected independently from the group consisting of: halogen, nitrile, _C1 - _C6 -alkyl, _C3 - _C6 -cycloalkyl, _C1 - _C6 -alkoxy, _C1 - _C6 -alkoxy- _C3 - _C6 -cycloalkyl, _C1 - _C6 -halogenyl, and _C1 - _C6 -halogenalkoxy; Q is selected from the group consisting of: Q1a, Q1b, Q1c, Q1d, Q1e, Q1f, and Q1g; # indicates the linkage point of the pyrazolopyrimidine ring. ^R3 is independently selected from the following groups: halogen, _C1 - _C3 -halogen, _C1 - _C3 -halogenalkoxy, -S(O) _0-2C1 - _C3 -halogen, and -S(O) _{0-1 .} ^R9 = ^NR10 ; ^R4 is selected from the following groups: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogen, _C2 - _C6 -halogenalenyl, and _C3 - _C8 -cycloalkyl; ^R5 is selected from the following groups: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, ^OR5a R5a is selected from the following groups: _C1 - _C6 -halogenated, _C2 - _C6 -halogenated, _C3 - _C8 -cycloalkyl, _C3 - _C8 -cycloalkyl- _C1 - _C6 -alkyl, 3- to 6-membered non-aromatic heterocyclic compounds, phenyl, and phenyl- _C1 - _C6 -alkyl; wherein each group may optionally be substituted by one or more groups of ^R5b ; ^R5a is selected from the following groups: _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, benzyl, and 3- to 6-membered non-aromatic heterocyclic compounds; ^R5b is selected independently from the following groups: halogen, nitrile, _C1 - _C6 -alkyl, and _C1 - _C6 -alkoxy; ^R6 is selected from the following groups: hydrogen, _C1 - _C6... -alkyl, _C2 - _C6 -alkenyl, C2-C6-ynyl, _C1 - _C6 -halogenyl, _C2 - _C6 -halogenenyl, and _C3 - _C6 -cycloalkyl; R7 is selected from the group consisting of: _C1 - _C6 -alkyl, _C3 - _C8 -cycloalkyl, C2- _C6 -alkenyl, C2- _C6 -ynyl, C1-C6-halogenyl, C2- _C6 -halogenenyl, -C(O) _OC1 -C3alkyl, and _C1 - _C6 -alkoxy; ^R8 is selected from the group consisting of: _C1 - _{C6 -} alkyl, _C3 - _C8 -cycloalkyl, C2- _C6 -alkenyl, C2-C6-ynyl, _{C1 - C6} -cycloalkyl, _C2 -C6-alkoxy, C2-C6-cycloalkyl, C2- _C6 -alkenyl, C2- _C6 -ynyl, _C1 - _C6 -cycloalkyl, _C2 - _C6 -cycloalkyl ^, C2-C6-alkeneyl, _{C2 ...} -Halalkyl, _C2 - _C6 -halogen, _C1 - _C6 -alkoxy, _C1 - _C6 -alkylamino, and _C1 - _C6 -dialkylamino; ^R9 is selected from the group consisting of: _C1 - _C6 -alkyl, _C2 - _{C6-alkenyl, C2-C6} -ynyl, _C1 - _C6 -halogen, _C2 - _C6 -halogenenyl, and _{C3 - C8} -cycloalkyl; ^R10 is selected from the group consisting of: hydrogen, nitrile, _C1 - _C6 -alkyl, C2- _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogen, _C2 - _C6 -halogenenyl, _{C3 - C8 -} cycloalkyl, and C(=O) ^R1 ; R ¹¹ is selected from the group consisting of: _C2 - _C6 -alkyl, nitrile, _C2 - _C6 -alkenyl, C2-C6-ynyl, _C1 - _C6 -nitrilealkyl, _C1 - _C6 -halogenalkyl, _C2 - _C6 -halogenenyl, _C1 - _C6 -alkoxy, _C3 - _C8 -cycloalkyl, _C3 - _C8 -cycloalkyl- _{C1 - C6 -} alkyl, 3 to 8 members of non-aromatic heterocyclic, 3 to 4 members of non-aromatic heterocyclic- _C1 - _C3 -alkyl, 5 to 6 members of heteroaryl- _C1 - _C3 -alkyl, ^NR5R6 , ^C1 _{- C6} -alkylsulfonyl, -C(O) ^R7 , and _C1 - _C3 -alkyl-C(O) ^R8. Each group may be optionally substituted by one or more groups of R ^11a ; R ^11a is independently selected from the group consisting of: halogen, nitrile, _C1 - _C6 -alkyl, _C1 - _C6 -alkoxy, _C1 - _C6 -alkylthio, _C3 - _C6 -cycloalkyl, -C(O) _OC1 - _C3alkyl , lateraloxy, hydroxyl, and _C1 - _C6 -hydroxyl; R ¹² is selected from the group consisting of: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogenyl, _C2 - _C6 -halogenalenyl, and _C3 - _C6 -cycloalkyl; or R ¹¹ and R ¹² together with the nitrogen atom to which it is attached forms a 3- to 6-member non-aromatic heterocycle; wherein the heterocycle may optionally contain one or two heteroatoms independently selected from N, O, or S(O) _O-2 ; the heterocycle may optionally be substituted by one or more substituents selected from: halogen, nitrile, lateral oxygen, _C1 - _C6 -alkyl, _C1 - _C6 -alkoxy, or _C1 - _C6 -halogen; or NR ¹¹ R ¹² represents -N=S(O) ^{RX RXa} , wherein ^RX and ^RXa are independently selected from the group consisting of: nitrile, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -Alkyne, phenyl, benzyl, and 3 to 6 non-aromatic heterocycles; wherein the phenyl, benzyl, and 3 to 6 non-aromatic heterocycles may be optionally substituted by one or more groups selected from halogens or _C1 - _C6 -alkyl groups; or ^R1X and ^R1Xa together with the sulfur atom attached thereto form a 5 to 6 non-aromatic heterocycle; wherein the heterocycle may optionally contain one or two independent heteroatoms selected from N, O, or S(O) _0-2 ; the heterocycle may optionally be substituted by one or more substituents selected from: halogens, nitrile groups, lateral groups, _C1 - _C6 -alkyl groups, _C1 - _C6 -alkoxy groups, or _C1 - _C6 -halogen groups; ^R13 is selected from the group consisting of: hydrogen and _C1 - _C6... -alkyl; "n" is an integer from 1 to 2; or its salts, stereoisomers, polymorphs, metal complexes or N-oxides.

Example-02: In one embodiment of the present invention, the compound formula (I) is represented by formula (I-1), (I-2) or (I-3); Wherein, m is 1 or 2; R ^2x is selected from the group consisting of: hydrogen, halogen, nitrile, _C1 - _C6 -alkyl, _C3 - _C6 -cycloalkyl, _C1 - _C6 -alkoxy, C1- _C6 -alkoxy- _{C3 -C6 -} cycloalkyl, _C1 - _C6 -halogen or _C1 - _C6 -halogenalkoxy; R ¹ , Q, R ² and R ^Y are defined as compounds of formula (I).

Example-03: According to Example 01, the compound of formula (I) is represented by the compound of formula (IA); (IA) where ^R1 , Q, ^R2 and Y are defined as in compounds of formula (I).

Example-04: According to Example 01 or 03, the compound of formula (I) or (IA) is preferably represented by formula (IA-1), (IA-2), (IA-3), (IA-1 ^x ), (IA-2 ^x ) or (IA-3 ^x ); ^R1 , Q, ^R2 and ^RY are defined as compounds of formula (I).

The following list provides definitions of substituents Q, Y, RY, R1, R2, R2x, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R1a, ^R2a , ^R2b , ^R2c , ^R2d , ^R5a , ^R5b , and ^R11a in compounds of formula (I ⁾ or (IA to IE) or (IA- ¹ to IA ^{- 3} ) or (IA ^{-1x to} IA ^{- 3x )} or (I ^{-1 to I - 3 ) or} ( ^{Z )} of the present invention, including preferred definitions.

Example-05: According to any of the above embodiments, Q is selected from the following groups: Q is selected from the following groups: Q1a, Q1b, Q1c, Q1d, Q1e, Q1f and Q1g; Here, # represents the connection point of the pyrazolopyrimidine ring.

Example 06: According to Example 05, Q is preferably selected from the following groups: Q1a-1, Q1b-1, Q1c-1, Q1d-1, Q1e-1, Q1e-2, Q1f-1, Q1f-2, and Q1g-1: Here, # represents the connection point of the pyrazolopyrimidine ring.

Example-07: According to Example 05 or 06, ^R3 is selected from the group consisting of: halogen, _C1 - _C3 -halogen, -S(O) _{0-2C1 - C3} -halogen and _C1 - _C3 -halogenoxy.

Example-08: According to Example 05, 06 or 07, for Q1a to Q1f and Q1a-1 to Q1f-2, ^R3 is preferably _C1 - _C3 -halogenated, and for Q1g and Q1g-1, ^R3 is preferably -S(O) _0-2C1 - _halogenated .

Example-09: According to Example 05, 06, 07, or 08, for Q1a to Q1f and Q1a-1 to Q1f-2, ^R3 is preferably selected from a fluoromethyl group, a difluoromethyl group, a chlorofluoromethyl group, a chlorodifluoromethyl group, or a trifluoromethyl group; more preferably, ^R3 is a trifluoromethyl group. For Q1g and Q1g-1, ^R3 is more preferably -S(O) _{0-2CF3 .}

Example 10: According to Example 05, R ¹³ is selected from hydrogen or _C1 - _C6 -alkyl.

Example 11: According to Example 05 or 10, R ¹³ is preferably selected from hydrogen or _C1 - _C3 -alkyl, and more preferably R ¹³ is methyl.

Example 12: According to any of the above embodiments, ^R1 is a _C1 - _C3 -alkyl group.

Example 13: According to Example 12, ^R1 is preferably ethyl.

Example 14: According to any of the above embodiments, Y is preferably oxygen (O).

Example 15: According to any of the above embodiments, Y is preferably NR ^Y.

Example 16: According to Example 15, R ^Y is selected from the group consisting of: hydrogen, nitrile, _C1 - _C4 -alkyl, _C2 - _C4 -alkenyl, C2- _C4 -ynyl, _C1 - _C4 -halogenyl, _C2 - _C4 -halogenyl, _C3 - _C5 -cycloalkyl, _C3 - _{C5 -} cycloalkyl- _C1 - _C3 -alkyl and -C(O)R ^1a .

Example 17: According to Example 16, R ^1a is selected from the group consisting of: _C1 - _C4 -alkyl, _C1 - _C4 -halogen, _C3 - _C5 -cycloalkyl and _C3 - _C5 -cycloalkyl- _C1 - _C3 -alkyl.

Example 18: According to any of the above embodiments, ^R2 is preferably cyclopropyl, wherein the cyclopropyl ring may optionally be replaced by one or more ^R2a groups.

Example 19: According to any of the above embodiments, ^R2 is preferably a pyrimidine group, wherein the pyrimidine ring may optionally be substituted with one or more ^R2a groups.

Example 20: According to any of the above embodiments, R ² is preferably CR ^2b R ^2c R ^2d .

Example 21: According to any of the above embodiments, R ² is preferably NR ¹¹ R ¹² .

Example 22: According to Example 18 or 19, R ^2a is selected from the group consisting of: halogen, nitrile, _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C3 -halogenyl, _C3 - _C6 -cycloalkyl, OR ⁴ and NR ⁵ R ⁶ .

Example 23: According to Example 18, 19 or 22, R ^2a is selected from the group consisting of: halogen, nitrile, _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, OR ⁴ , _C1 - _C3 -halogenyl and _C3 - _C6 -cycloalkyl.

Example 24: According to Example 20, R ^2b is selected from the group consisting of: halogen, hydroxyl and _C1 - _C3 -halogen.

Example 25: According to Example 20, R ^2c is selected from the group consisting of: hydrogen, hydrogen and _C1 - _C3 -alkyl.

Example 26: According to Example 20, R ^2d is selected from the group consisting of: hydrogen and _C1 - _C3 -alkyl.

Example 27: According to Example 26, R ^2d is selected from the group consisting of: hydrogen and _C1 - _C2 -alkyl.

Example 28: According to Example 21, R ¹¹ is selected from the group consisting of: _C2 - _C6 -alkyl, nitrile, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, C1-C6-nitrilealkyl, _C1 - _C6 -halogenalkyl, _C2 - _C6 -halogenenyl, _C1 - _C6 -alkoxy, _C3 - _C8 -cycloalkyl, _{C3 - C8} -cycloalkyl- _C1 - _C6 -alkyl, 3 to ₈ members of non-aromatic heterocyclic, 3 to 4 members of non-aromatic heterocyclic- _C1 - _C3 -alkyl, 5 to 6 members of heteroaryl- _C1 - _C3 -alkyl, ^NR5R6 , ^C1 _{- C6} -alkylsulfonyl, -C(O) ^R7 , and _C1 -C ₃ -alkyl-C(O) ^R8 ; wherein each group may be optionally substituted by one or more ^R11a groups.

Example 29: According to Example 21 or 28, R ¹¹ is selected from the group consisting of: _C2 - _C6 -alkyl, nitrile, _C2 - _C6 -alkenyl, _C2 -C6-ynyl, _C1 - _{C4 -} nitrilealkyl, _C1 - _C4 -halogenalkyl, _C2 - _C6 -halogenenyl, _C1 - _C4 -alkoxy, _C3 - _C6 -cycloalkyl, _C3 - _C6 -cycloalkyl- _C1 - _C3 -alkyl, 3 to 6 members of non-aromatic heterocyclic, 3 to 4 members of non-aromatic heterocyclic- _C1 - _C3 -alkyl, 5 to 6 members of heteroaryl- _C1 - _C3 -alkyl, ^NR5R6 , ^C1 _{-C3 -} alkylsulfonyl, -C(O) ^R7 , and _{C1 -C3} -alkyl-C(O) ^R8 ; wherein each group may be optionally substituted by one or more ^R11a groups.

Example 30: According to Examples 21, 28, or 29, R ¹¹ is preferably selected from the group consisting of: _C2 - _C4 -alkyl, nitrile, _C2 - _C4 -alkenyl, C2- _C4 -alkynyl, _C1 - _C4 -nitrilealkyl, _C1 - _C4 -halogenalkyl, _C1 - _C4 -alkoxy, _C3 - _C6 -cycloalkyl, _C3 - _{C6 -} cycloalkyl- _C1 - _C3 -alkyl, 3 to 6 members of non-aromatic heterocyclic, 3 to 4 members of non-aromatic heterocyclic- _C1 - _C3 -alkyl, 5 to 6 members of heteroaryl- _C1 - _C3 -alkyl, ^NR5R6 , _C1 - _C3 -alkylsulfonyl, -C(O) ^{R7 ,} and _C1 - _C3 -alkyl-C(O) ^R8 ; wherein each group may be optionally substituted by one or more ^R11a groups.

Example 31: According to any one of Examples 28 to 30, R ^11a is independently selected from the group consisting of: halogen, nitrile, _C1 - _C4 -alkyl, _C1 - _C4 -alkoxy, _C1 -C4-alkylthio, _C3 - _{C6 -} cycloalkyl, -C(O) _OC1 - _C3alkyl , lateraloxy, hydroxyl, and _C1 - _C4 -hydroxyalkyl.

Example 32: According to any one of Examples 28 to 31, R ^11a is independently selected from the group consisting of: halogen, nitrile, _C1 - _C3 -alkyl, _C1 - _C3 -alkoxy, _C1 -C3-alkylthio, _C3 - _{C5 -} cycloalkyl, -C(O) _OC1 - _C3alkyl , lateraloxy, hydroxyl, and _C1 - _C3 -hydroxyalkyl.

Example 33: According to Example 21, R ¹² is selected from the group consisting of: hydrogen, _C1 - _C4 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _{C4-halogenyl, C2-C4 - halogenalkenyl} and _C3 - _C6 -cycloalkyl.

Example 34: According to Example 21 or 33, R ¹² is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C2 - _C3 -alkenyl, _C2 - _C3 -ynyl, _C1 -C3-halogenyl, _C2 - _{C3 -} halogenalkenyl and _C3 - _C5 -cycloalkyl.

Example 35: According to Example 21, R ¹¹ and R ¹² together form a 3- to 6-member non-aromatic heterocycle with the nitrogen atom to which they are attached; wherein the heterocycle may optionally contain one or two heteroatoms independently selected from N, O or S(O) _0-2 ; wherein the heterocycle may optionally be substituted by one or more substituents independently selected from: halogen, nitrile, lateral oxy, _C1 - _C4 -alkyl, _C1 - _C4 -alkoxy or _C1 - _C4 -halogen.

Example 36: According to Example 21, NR ¹¹ R ¹² represents -N=S(O)R ^X R ^Xa , wherein R ^X and R ^Xa are independently selected from the group consisting of: nitrile, _C1 - _C3 -alkyl, _C2 - _C3 -alkenyl, _C2 - _C3 -ynyl, phenyl, benzyl and 3 to 6 non-aromatic heterocycles; wherein the phenyl, benzyl and 3 to 6 non-aromatic heterocycles may be optionally substituted by one or more groups selected from halogen or _C1 - _C3 -alkyl.

Example 36A: According to Example 36, ^RX and ^RXa together form a 6-membered non-aromatic heterocycle with the sulfur atom attached thereto; wherein the heterocycle may optionally contain one or two heteroatoms independently selected from N, O or S(O) _O-2 ; wherein the heterocycle may optionally be substituted by one or more substituents independently selected from: halogen, nitrile, lateral oxy, _C1 - _C3 -alkyl, _C1 - _C3 -alkoxy or _C1 - _C3 -halogen.

Example 37: According to any of the above embodiments, R ^2x is independently selected from the group consisting of: halogen, nitrile, _C1 - _C4 -alkyl, _C3 - _C5 -cycloalkyl, _C1 - _C4 -alkoxy, _C1 - _C4 -alkoxy- _C3 - _C5 -cycloalkyl, _C1 - _C4 -halogen, and _C1 - _C4 -halogenalkoxy.

Example 38: According to Example 37, R ^2x is independently selected from the group consisting of: halogen, nitrile, _C1 - _C3 -alkyl, _C3 - _C5 -cycloalkyl, _C1 - _C3 -alkoxy, _C1 - _C3 -alkoxy- _C3 - _C5 -cycloalkyl, _C1 - _C3 -halogen and _C1 - _C3 -halogenalkoxy.

Implementation Example 39: According to Implementation Example 37 or 38, R ^2x preferably does not exist.

Example 40: According to any of the above embodiments, R ⁴ is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C3 -halogenyl, _C2 - _C4 -halogenalkenyl and _C3 - _C6 -cycloalkyl.

Example 41: According to Example 40, R ⁴ is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C1 - _C3 -halogen and _C3 - _C6 -cycloalkyl.

Example 42: According to any of the above embodiments, ^R5 is selected from the group consisting of: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, ^OR5a , _C1 - _C6 -halogenyl, _C2 - _C6 -halogenyl, C3- _C8 -cycloalkyl, _C3 - _C8 -cycloalkyl- _C1 - _C6 -alkyl, ₃ to 6 non-aromatic heterocyclic, phenyl, and phenyl- _C1 - _C6 -alkyl; wherein each group may be optionally substituted by one or more groups of ^R5b .

Example 43: According to Example 42, R ⁵ is selected from the group consisting of: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, C1-C6-halogenyl, _C2 - _C6 -halogenyl, _C3 - _C8 -cycloalkyl, _C3 - _C8 -cycloalkyl- _C1 - _{C6 -} alkyl, ₃ to 6 non-aromatic heterocyclic, phenyl, and phenyl- _C1 - _C6 -alkyl; wherein each group may be optionally substituted by one or more groups of R ^5b .

Example 44: According to Example 42 or 43, R ⁵ is selected from the group consisting of: hydrogen, _C1 - _C4 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C3 -halogenyl and _C3 - _C6 -cycloalkyl;

Example 45: According to any one of Examples 42 to 43 above, R ^5a is selected from the group consisting of: _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, benzyl and 3 to 6 non-aromatic heterocycles.

Example 46: According to any one of Examples 42 to 43 above, R ^5b is selected from the group consisting of: halogen, nitrile, _C1 - _C3 -alkyl and _C1 - _C3 -alkoxy.

Example 47: According to any of the above embodiments, R ⁶ is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C3 -halogenyl, _C2 - _C4 -halogenalkenyl and _C3 - _C6 -cycloalkyl.

Example 48: According to Example 47, R ⁶ is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C1 - _C3 -halogen and _C3 - _C6 -cycloalkyl.

Example 49: According to any of the above embodiments, R ⁷ is selected from the group consisting of: _C1 - _C3 -alkyl, C(O) _OC1 - _C3- alkyl, _C1 - _C3 -alkoxy and _C3 - _C6 -cycloalkyl.

Example 50: According to any of the above embodiments, R ⁸ is selected from the group consisting of: _C1 - _C3 -alkyl, _C1 - _C3 -alkoxy, _C1 - _C3 -alkylamino and _C1 - _C3 -dialkylamino.

Example 51: According to any of the above embodiments, R ⁹ is selected from the group consisting of: _C1 - _C3 -alkyl, _C2 - _C3 -alkenyl, _C2 - _C3 -alkynyl, C1- _{C3-halogenyl, C2 -C3 - halogenalkenyl} and _C3 - _C6 -cycloalkyl.

Example 52: According to any of the above embodiments, R ¹⁰ is selected from the group consisting of: hydrogen, nitrile, C1- _C3 -alkyl, _C2 - _C3 -alkenyl, _C2 - _C3 -ynyl, _C1 - _C3 -halogenyl, _C2 - _C3 -halogenyl, _C3 - _C6 -cycloalkyl and C(=O) ^{R 1} _.

Implementation Example-53: According to any of the above embodiments, n is 1.

Example 54: According to this example, for compounds of formula (I) or (IA) or their salts, stereoisomers, polymorphs, metal complexes, or N-oxides, the values of the groups are as follows: ^R1 is _C1 - _C3 -alkyl; Y is selected from O or ^NRY ; ^RY is selected from the group consisting of: hydrogen, nitrile, _C1 - _C4 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C4 -halogenyl, _C2 -C4-halogenenyl, _C3 - _C5 -cycloalkyl, _{C3-C5 - cycloalkyl} - _C1 - _C3 -alkyl, and -C(O) ^R1a ; ^R1a is selected from the group consisting of: _C1 - _C4 -alkyl, C1- _C4 -alkyl, _{C2 ...} -Haloxy, _C3 - _C5 -cycloalkyl and _C3 - _C5 -cycloalkyl- _C1 - _C3 -alkyl; ^R2 is selected from the group consisting of: cyclopropyl, pyrimidinyl, ^{CR2b R2c R2d} and ^{NR11 R12} ; the cyclopropyl and pyrimidinyl groups may optionally be substituted with one or more groups of ^R2a ; ^R2a is selected from the group consisting of: halogen, nitrile, _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, ^OR4 , _C1 - _C3 -haloxyalkyl and _C3 - _C6 -cycloalkyl; ^R2b is selected from the group consisting of: halogen, hydroxyl and _C1 - _C3 -haloxyalkyl; R ^2c is selected from the following groups: hydrogen, halogens, and _C1 - _C3 -alkyl; R ^2d is selected from the following groups: hydrogen and _C1 - _C3 -alkyl; Q is selected from the following groups: Q1a, Q1b, Q1c, Q1d, Q1e, Q1f, and Q1g; Here, # represents the connection point of the pyrazolopyrimidine ring. ^R3 is selected from the group consisting of: halogens, _C1 - _C3 -halogenated, -S(O) _{0-2C1 -C3 -} halogenated, and _C1 - _C3 -halogenated; ^R4 is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C3 -halogenated, _C2 - _C4 -halogenated, and _C3 - _C6 -cycloalkyl; ^R5 is selected from the group consisting of: hydrogen, _C1 - _C4 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C3 -halogenated, and _C3 - _C6 -cycloalkyl; R ^R6 is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C1 - _C3 -halogen, and _C3 - _C6 -cycloalkyl; ^R7 is selected from the group consisting of: _C1 - _C3 -alkyl, -C(O) _OC1 - _C3- alkyl, _C1 - _C3 -alkoxy, and _C3 - _C6 -cycloalkyl; ^R8 is selected from the group consisting of: _C1 - _C3 -alkyl and _C3 - _C8 -cycloalkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogen, _C2 - _C6 -halogenenyl, _C1 - _C3 -alkoxy, _C1 - _C3 -alkylamino, and _C1 - _C3 -dialkylamino; R ¹¹ is selected from the group consisting of: _C2 - _C4 -alkyl, nitrile, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, C1-C4-nitrilealkyl, _C1 - _C4 -halogenalkyl, _C1 - _C4 -alkoxy, _C3 - _C6 -cycloalkyl, _C3 - _C6 -cycloalkyl- _C1 - _C6 - _alkyl , 3 to ₆ members of non-aromatic heterocyclic, 3 to 4 members of non-aromatic heterocyclic- _C1 - _C3 -alkyl, 5 to 6 members of heteroaryl- _C1 - _C3 -alkyl, ^NR5R6 , _C1 - _C6 -alkylsulfonyl, ^-C (O) ^R7 and _C1 - _C3 -alkyl-C(O) ^R8 ; wherein each group may optionally consist of one or more R Group substitution of ^11a ; R ^11a is independently selected from the group consisting of: halogen, nitrile, _C1 -C3 _- alkyl, _C1 - _C3 -alkoxy, _C1 - _C3 -alkylthio, _C3 - _C5 -cycloalkyl, -C(O) _OC1 - _C3alkyl , lateraloxy, hydroxyl, and _C1 - _C3 -hydroxyalkyl; R ¹² is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C2 - _C3 -alkenyl, _C2 - _C3 -ynyl, _C1 - _C3 -halogenyl, _C2 - _C3 -halogenalenyl, and _C3 - _C5 -cycloalkyl; or R ¹¹ and R ¹² together with the nitrogen atom to which it is attached forms a 3- to 6-member non-aromatic heterocycle; wherein the heterocycle may optionally contain one or two heteroatoms independently selected from N, O, or S(O) _O-2 ; the heterocycle may optionally be substituted by one or more substituents independently selected from: halogen, nitrile, lateral oxygen, _C1 - _C4 -alkyl, _C1 - _C4 -alkoxy, or _C1 - _C4 -halogen; or NR ¹¹ R ¹² represents -N=S(O) ^{RX RXa} , wherein ^RX and ^RXa are independently selected from the group consisting of: nitrile, _C1 - _C3 -alkyl, _C2 - _C3 -alkenyl, _C2 - _C3 - alkynyl, phenyl, benzyl and 3 to 6 non-aromatic heterocycles; wherein the phenyl, benzyl and 3 to 6 non-aromatic heterocycles may optionally be substituted by one or more groups selected from halogens or _C1 - _C3 -alkyl; ^R13 is selected from the group consisting of hydrogen and _C1 - _C3 -alkyl; "n" is an integer from 1 to 2.

Example 55: According to this embodiment, the compound of formula (I) or (IA) or (IA-1) is preferably represented by the compound of formula (IB); (IB) wherein the cyclopropyl ring may be optionally substituted with one or more ^R2a groups; and ^R1 , ^R2a , Q and Y are as defined in the compound of formula (I) or any of the above embodiments.

Example 56: According to this embodiment, the compound of formula (I) or (IA) or (IA-1) is preferably represented by the compound of formula (IC); (IC) wherein the pyrimidine ring may be optionally substituted with one or more ^R2a groups; and ^R1 , ^R2a , Q and Y are as defined in the compound of formula (I) or any of the above embodiments.

Example 57: According to this embodiment, the compound of formula (I) or (IA) is preferably represented by the compound of formula (ID); (ID) wherein ^R1 , ^R2b , ^R2c , ^R2c , ^R2d , Q and Y are as defined in compound (I) or any of the above embodiments.

Example 58: According to this embodiment, the compound of formula (I) or (IA) is preferably represented by the compound of formula (ID); (IE) wherein ^R1 , ^R11 , ^R12 , Q and Y are as defined in compound (I) or any of the above embodiments.

Example 59: According to this embodiment, for compounds of formula (I) or (IA) or (IA-1) to (IA-3), (IA-1 ^x to IA-3 ^x ) or (IB) to (IE), Q is preferably selected from Example 08.

Example 60: According to this embodiment, the present invention provides a compound of formula (Z); (Z) wherein ^R1 , Q, ^R2 and ^R2x are defined as compounds of formula (I) or any of the above embodiments, provided that 2-(ethylthio)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine is excluded from the definition of compounds of formula (Z).

Example 61: According to this embodiment, the compound of formula (Z) is an intermediate product for the preparation of the compound of formula (I).

Example-62: According to a preferred embodiment of the present invention, the compound of formula (I) of the present invention disclosed in Table-A is selected from the following: N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-methylhydroxylamine (N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-methylhydroxylamine); N-cyclopropyl-2-(ethyl N-cyclopropyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-cyclopropyl-2-(ethylsulfonyl)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine ... [4,5-b]pyridine (N-cyclopropyl-2-(ethylsulfonyl)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amineimidazo[4,5-b]pyridine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3- (3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl) (luoromethyl)-3H-imidazo[4,5-b]pyridine); N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetamide (N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetamide); 1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)) -3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropane-1-carbonitrile (1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropane-1-carbonitrile); 2-(7-cyclopropyl-2-(ethylsulfonylurea)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2- (7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine); 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[ 1,2,4]triazolo[1,5-a]pyridine); N-cyclopropyl-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine 2-(7-(3,3-difluoroazetidin-1-yl)-2-(eth)pyridin-2-yl)pyrazolo-3-H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)methanesulfonamide; 2-(7-(3,3-difluoroazetidin-1-yl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(7-(3,3-difluoroazetidin-1-yl)-2-(eth) 2-(7-(azetidin-1-yl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine); 2-(7-(azetidin-1-yl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(7-(azetidin-1-yl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl) l)-3H-imidazo[4,5-b]pyridine); N-(2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropanecarboxamide (N-(2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropanecarboxamide); 2-(6-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropanecarboxamide 2-(6-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 7-cyclopropyl-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine pyridin-2-yl)pyrazolo[1,5-a]pyrimidine); N-(2,2-difluoroethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(2,2-difluoroethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-( 3-Methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1-methylcyclopropyl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1-methylcyclopropyl)pyrazolo[1,5-a]pyrimidin-7-amine); N,N-diethyl-2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a] Pyrimidin-7-amine (N,N-diethyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine)acetonitrile (2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine)acetonitrile (2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine) idazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)acetonitrile); 2-(ethylsulfonyl)-N-isopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-isopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-am ine); 7-cyclopropyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine (7-cyclopropyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine); 1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimin-7-yl)cyclopropane-1-carboxylonitrile (1-(2-(ethylsulfonyl) )-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile；(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-thionone（(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]p yridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone；N-(cyclopropylmethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-propylpyrazolo[1,5-a]pyrimidin-7-amine（N-(cyclopropylmethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-propylpyrazol[1,5-a]pyrimidin-7-yl)-N-propylpyrazol[4,5-b]pyridin-2-yl)-N-propylpyrazol[1,5-a]pyrimidin-2 ...)(ethyl)(imino)-3H-imidazo[4,5-b]pyridin-2-yl)-N-propylpyrazol[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-3H-imidazo[4,5-b]pyridin-2-yl)-N-propylpyrazol[1,5-a olo[1,5-a]pyrimidin-7-amine); N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyanamide (N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyanamide); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin -2-yl)-N-(1,1,1-trifluoropropan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1,1,1-trifluoropropan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-allyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-allyl-2-( 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(prop-2-yn-1-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(prop-2-yn-1-yl)pyrazolo[1,5-a]pyrimidin-7-amine) yl)-N-(prop-2-yn-1-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-N-isobutyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-isobutyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(1-cyclopropylethyl)-2-( (N-(1-cyclopropylethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-cyclobutyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7- Amine (N-cyclobutyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(tert-butyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine) )-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(but-3-yn-2-yl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(but-3-yn-2-yl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin -7-amine); (7-cyclopropyl-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone ((7-cyclopropyl-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone); (7-cyclopropyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[ 1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone (7-cyclopropyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(thiobutyron-3-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl) -6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(thietan-3-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl) cyanamide (N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl) cyanamide l)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)cyanamide); 2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridinium( ... (7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(methylimino)-λ6-sulfanone (7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(methylimino)-λ6-sulfanone); (7-(tert-butylamino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(methylimino)-λ6-sulfanone [-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-thiodanone ((7-(tert-butylamino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone); (2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-L-methyl propionate (methyl (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-L-alaninate); N-((7-(tert-butylamino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl) cyanamide (N- ((7-(tert-butylamino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)cyanamide); 2-(ethylsulfonylurea)-N-(2-methoxyethyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[ 1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(2-methoxyethyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonylurea)-N-(2-methoxypropyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin- 7-amine (2-(ethylsulfonyl)-N-(2-methoxypropyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(tetrahydro-2H-pyran-4-yl)pyrazolo[1,5-a]pyrimidin-7-amine) 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(tetrahydro-2H-pyran-4-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine) ethyl-1-ol (2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-) yl)amino)ethan-1-ol); 1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)prop-2-ol (1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)prop-2-ol (1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)prop-2-ol) -b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)propan-2-ol); N-(tert-butyl)-2-(ethylsulfonylurea)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethyl 6-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 6-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (6-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine); (7-cyclopropyl-3-(7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine) 2-(7-cyclopropyl-3-(7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone; 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine(2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(t (7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone ((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)- λ6-sulfaneylidene)cyanamide (N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)cyanamide); N-(cyclopropylmethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(cyclopropylmethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine) (in-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(3-methylbut-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl) yl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(3-methylbutan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonylurea)-N-(2-fluoroethyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2 -(ethylsulfonyl)-N-(2-fluoroethyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); (7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(ethylimine)-λ6-thionone ((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(ethylimine)-λ6-thionone (ino)-λ6-sulfanone); 2-(ethylsulfonyl)-N-(1-methoxypropan-2-yl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(1-methoxypropan-2-yl)-3-(3-methyl-6-(trifluoro) methyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(7-(2-(tert-butyl)hydrazinyl)-2-(ethylsulfonylurea)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(2-(7-(2-(tert-buty l)hydrazineyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine); 2-(2-(ethylsulfonyl)-7-(1-methylhydrazineyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(2-(ethylsulfonyl)-7-(1-methylhydrazineyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine); N-(2,2-difluoropropane) N-(2,2-difluoropropyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; ethyl(imino)(3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; -imidazo[4,5-b]pyridin-2-yl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)-λ6-sulfanone); N-(sec-butyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(sec-butyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5- [b]pyridin-2-yl)-N-(1-(pyridin-3-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1-(pyridin-3-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1-(pyridin-4-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1-(pyridin-4-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1-(pyridin-4-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine pyridin-2-yl)-N-(1-(pyridin-4-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine); ethyl(3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(methylimino)-λ6-sulfanone (ethyl(3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(methylimino)-λ6-sulfanone); N-(ethyl(3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(methylimino)-λ6-sulfanone); N-(ethyl(3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(methylimino)-λ6-sulfanone); [1,5-b]pyridin-2-yl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(sidekoxy)-λ6-thionyl)nitrylamine (N-(ethyl(3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyr imidin-2-yl)(oxo)-λ6-sulfaneylidene)cyanamide); N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropanemethylamine (-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluorom ethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropanecarboxamide); N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-N-methylacetamide (N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-N-methylacetamide); 3-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)- 3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)butan-2-ol (3-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)butan-2-ol); 2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1-(pyridin-2-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)N-(1-(pyridin-2-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine) (in-2-yl)-N-(1-(pyridin-2-yl)ethyl)pyrazolo[1,5-a]pyrimidin-7-amine); (7-cyclopropyl-3-(7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(methylimino)-λ6-sulfanone ((7-cyclopropyl-3-(7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(methylimino)-λ6-sulfanone); N-((7-cyclopropyl-3-(7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(methylimino)-λ6-sulfanone); N-((7-cyclopropyl-3-(7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)cyanamide; N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-N-methylcyclopropanemethylamide 3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-N-methylcyclopropanecarboxamide; (7-(tert-butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone ((7-(tert-butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone); 2 -(2-(ethylsulfonyl)-7-(1-isopropylhydrazineyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(2-(2-(ethylsulfonyl)-7-(1-isopropylhydrazineyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(tri) 2-(2-(ethylsulfonyl)-7-(2-isopropylhydrazineyl)pyrazol[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine olo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(5-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; (5-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl 2-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone; 2-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)prop-2-ol (2-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin- 7-yl)propan-2-ol); (5-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(methylimino)-λ6-thionone ((5-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyri) din-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(methylimino)-λ6-sulfanone；2-(2-(ethylsulfonyl)-7-(4-methoxypyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine(2-(2-(ethylsulfo) (nyl)-7-(4-methoxypyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine); N-((5-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-thionyl) nitridine sulfaneylidene)cyanamide); 4-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)morpholine (4-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]) pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)morpholine); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl)acetamide (N-((7-cyclopropyl-3-(3-me thyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)acetamide); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-thionyl)-2,2,2-trifluoroacetamide (ethyl)(oxo)-λ6-sulfaneylidene)-2,2,2-trifluoroacetamide); 1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)pyrrolidine-2-one (1-(2-(ethylsulfonyl)-3-(3-methyl- 6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)pyrrolidin-2-one); 2-(2-(ethylsulfonylurea)-7-(3-methoxy-3-(trifluoromethyl)azabutyron-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl ...pyrazolo[1,5-a]pyrimidin-3-yl)-pyrazolo[1,5-a]pyrimidin-3-yl)-pyrazolo[1,5-a]pyrimidin-2-one)-pyrazolo[1,5-a]pyrimidin-3-yl)-pyrazolo[1,5-a]pyrimidin-2-one)-pyrazolo[1,5-a]pyrimidin-3-yl)pyrazolo[1,5-a]pyrimidin-2-one)-pyrazolo[1,5-a]pyrimidin-3-yl)pyrazolo[1,5-a]pyrimidin-7-yl)pyrazolo[1,5-a]pyrimidin-2-one)-pyrazolo[1,5-a]pyrimidin-7-yl)pyrazolo[1,5-a]pyrimidin-2-one)-pyrazolo[ N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl)-2,2-difluoroacetamide ]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)-2,2-difluoroacetamide；(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(cyclopropylimino)(ethyl)-λ6-sulfanone（(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(cyclopropylimino)(ethyl)-λ6-sulfanone；1-(2- (ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)pyridin-2(1H)-one (1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1 ,5-a]pyrimidin-7-yl)pyridin-2(1H)-one；(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)((cyclopropylmethyl)imino)(ethyl)-λ6-thionone（(7-cyclopropyl-3-(3-methyl-6-(trifluoromet (7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)((cyclopropylmethyl)imino)(ethyl)-λ6-sulfanone e); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)acetamide); 2-(ethylsulfonylurea)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)acetamide); (trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1,1,1-trifluoropropan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-N-(1,1,1-trifluoropropan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo [1,5-a]pyrimidin-2-yl)(ethyl)(sidekyl)-λ6-thionyl)neopramylamine (N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)pivalamide); (7-cyclopropyl-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-thionone ((7-cycl opropyl-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone); N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(6-(trifluoromethyl)imidazo[1,2-a]pyri din-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(7-(difluoromethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(7-(difluoromethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine); 2-(ethylsulfonyl)-7-(pyrimidin-2-yl)-3-(6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(ethylsulfonyl)-7-(pyrimidin-2-yl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine; N-(tert-butyl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)i midazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl)isobutylamine (N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(o xo)-λ6-sulfaneylidene)isobutyramide); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)propionamide (N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)pro pionamide); 2-(2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine); N-ethyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3 ... N-(tert-butyl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-(tert-butyl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine zolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine); 2-(7-(1,1-difluoroethyl)- 2-(ethylsulfonylurea)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine); 2-(ethylsulfonylurea)-N-(1-methylcyclopropyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(eth N-(1-methylcyclopropyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(tert-butyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)- 3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(tert-butyl)-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl) 2-(ethylsulfonyl)-N-isopropyl-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-isopropyl-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(1-cyclopropylethyl)-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(1-c 2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine); 2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl) -yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine); O-(tert-butyl)-N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)hydroxyamine (O-(tert-butyl)-N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)h ydroxylamine); N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-N-(terpentyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[ 2-(ethylsulfonyl)-N-(tert-pentyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)-N-(1,1,1-trifluoropropyl-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine 2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)-N-(1,1,1-trifluoropropan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine(2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl) hyl)-[1,2,4]triazolo[1,5-a]pyridine); N-cyclopropyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-cyclopropyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)-N-(1,1,1-trifluoropropan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-ethyl-2-(ethylsulfonylurea)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine -amine (N-ethyl-2-(ethylsulfonyl)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(cyclopropylmethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(cyclopropylmethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine) 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)-N-(1-methylcyclopropyl)pyrazolo[1,5-a]pyrimidin-7-amine 1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl -3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(3,3-difluorocyclobutyl)-2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin- 7-amine (N-(3,3-difluorocyclobutyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 3-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine)propionitrile (3-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine) ethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)propanenitrile); 2-(ethylsulfonyl)-N-(2-methoxyethyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(2-methoxyethyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyr azolo[1,5-a]pyrimidin-7-amine); N-ethyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-ethyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N,N-diethyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N,N-diethyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine [5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N,N-diethyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-isopropylhydroxyamine (N-(2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-isopropylhydroxyamine ethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-isopropylhydroxylamine); 2-cyclopropyl-N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl)acetamide (2-cyclopropyl-N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[ 4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)acetamide); 2-chloro-N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl)-2,2-difluoroacetamide (2-chloro-N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyr 2,2,2-trichloro-N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)acetamide [4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)acetamide); N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)isobutylamide (N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin idin-7-yl)isobutyramide); N-ethyl-2-(ethylsulfonyl)-N-methyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-ethyl-2-(ethylsulfonyl)-N-methyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-N-isopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4 [2-(ethylsulfonyl)-N-isopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-isopropylhydroxyamine (trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-isopropylhydroxylamine); 2-(ethylsulfonyl)-N-(2-methoxypropyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(2-methoxypropyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-]pyridin-2-yl)pyrazolo[1,5-]pyrimidin-7-yl) [c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-N,O-dimethylhydroxylamine (N-(2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-N,O-dimethylhydroxylamine); N,N -diethyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N,N-diethyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-N-(2,2,3,3,3-pentafluoropropyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine Pyridine-7-amine (2-(ethylsulfonyl)-N-(2,2,3,3,3-pentafluoropropyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); O-ethyl-N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)hydroxyamine (O-ethyl-N-(2-(ethylsulfonyl)-3-(3-methyl-6-) (trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)hydroxylamine); N-(3,3-dimethylbutan-2-yl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(3,3-dimethylbutan-2-yl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyr (R)-(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone (R)-(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone); S)-(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone ((S)-(7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone 2-(ethyl(oxo)-λ6-sulfaneylidene)-2,2-difluoroacetamide (N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)-2,2-difluoroacetamide); 2-(ethylsulfonylurea)-N-(terpentyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl) )pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(tert-pentyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(1-cyclopropylethyl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(1-cyclopropylethyl)-2-(ethylsulfonyl)-3-(7-( trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl)-2,2,2-trifluoroacetylamine (N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazo lo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)-2,2,2-trifluoroacetamide); N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazol[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazol o[1,5-a]pyrimidin-7-amine); N-cyclopropyl-2-(ethylsulfonyl)-N-methyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylsulfonyl)-N-(3-methoxypropyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; -[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(3-methoxypropyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(sideoxy)-λ6-thionyl)neopentylamine (N-((7-c) yclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)pivalamide); 2-(ethylsulfonyl)-N-(2-methylbut-3-yn-2-yl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(2-methylbut-3-yn-2-) yl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 3-((2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine)propionitrile (3-((2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]py rimidin-7-yl)amino)propanenitrile); 2-(ethylsulfonyl)-N-(oxetan-3-ylmethyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(oxetan-3-ylmethyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 4-(2-(ethylsulfonyl)-3-(7-(trifluoromethyl) )-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)morpholine(4-(2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)morpholine); 2-(7-(azacyclobutanol-1-yl)-2-(ethylsulfonylurea)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine(2-(7-(azetidin-1-yl)-2-(eth 2-(2-(ethylsulfonyl)-7-(pyrrolidin-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine); 2-(2-(ethylsulfonyl)-7-(pyrrolidin-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(2-(ethylsulfonyl)-7-(pyrrolidin-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine zolo[1,5-a]pyridine); 2-(2-(ethylsulfonyl)-7-(4-methylpyrazin-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(2-(ethylsulfonyl)-7-(4-methylpiperazin-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine); 2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine -2-yl)-N-(1,1,1-trifluoropropan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)-N-(1,1,1-trifluoropropan-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(1-ethylcyclopropyl)-2-(ethylsulfonylurea)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(1-ethylc N-(cyclopropylmethyl)-N-ethyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-(cyclopropylmethyl)-N-ethyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine hyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-((2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)(methyl)amino)acetonitrile(2-((2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)(methy l)amino)acetonitrile); N-(2,2-difluoropropyl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(2,2-difluoropropyl)-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); N-cyclobutyl-N-ethyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1) [2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-cyclobutyl-N-ethyl-2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); 1-((2-(ethylsulfonylurea)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine)cyclopropane-1-carboxylonitrile (1-((2-(ethylsulfonyl ...3-(7-(trifluoromethyl)-3-(7-(trifluoromethyl)-3-(7-(trifluoromethyl)-3 yl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropane-1-carbonitrile; ethyl(imino)(3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)-7-((1-methylcyclopropyl)amino)pyrazolo[1,5-a]pyrimidin-2-yl)-λ6-thioketone (ethyl(imino)(3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)-7-((1-methylcyclopropyl)amino)pyrazolo[1,5-a]pyrimidin-2-yl)-λ6-thioketone zo[4,5-c]pyridin-2-yl)-7-((1-methylcyclopropyl)amino)pyrazolo[1,5-a]pyrimidin-2-yl)-λ6-sulfanone); 2-(ethylsulfonyl)-N-(2-methylcyclopropyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(2-methylcyclopropyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin -2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); (1-((2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropyl)methanol ((1-((2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropyl)methanol); 2-(7-(1,1 -difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine); ethyl(7-((1-ethylcyclopropyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(imino)- λ6-sulfanone (ethyl(7-((1-ethylcyclopropyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(imino)-λ6-sulfanone; N-(1-cyclopropylethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(1-cyclopropylethyl)-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl) -yl)pyrazolo[1,5-a]pyrimidin-7-amine); 2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)-N-(2-methylcyclopropyl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2) -yl)-N-(2-methylcyclopropyl)pyrazolo[1,5-a]pyrimidin-7-amine); (R)-2-ethyl-4-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amine)isooxazolidine-3-one ((R)-2-ethyl-4-((2-(ethylsulfonyl)-3-(3- methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)isoxazolidin-3-one); (2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)methyl glycine (methyl (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)glycinate); (7-(tert-butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-thionone ((7-(tert-) -butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone；(2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)ethyl glycine (ethyl (2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)glycinate); 1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)methyl cyclopropane-1-carboxylate (methyl 1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropane-1-carboxylate); 2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)-N,N-dimethylacetamide (2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)-N,N-dimethylacetamide); 2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)-2-oxadiazine ethyl acetate) 2-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)-2-oxoacetate；(7-(tert-butyl(methyl)amino)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-thioketone（(7-(tert-butyl(methyl)amino)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)- λ6-sulfanone); 2-((2-(ethylsulfonylurea)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)-2-ethyl oxalicumene (ethyl 2-((2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)-2-oxoacetate); 1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropane-1-carboxylonitrile (1-((2-( ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropane-1-carbonitrile); (2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)methyl carbamate (methyl (2-(ethylsulfonyl)-3-(6-(trifluoromethyl) l)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)carbamate); 2-(ethylsulfonyl)-N-(2-(methylthio)ethyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (2-(ethylsulfonyl)-N-(2-(methylthio)ethyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)p yrazolo[1,5-a]pyrimidin-7-amine); O-(cyclopropylmethyl)-N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)hydroxyamine (O-(cyclopropylmethyl)-N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)hydroxylam ine); N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-isobutylhydroxylamine (N-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O-isobutylhydroxylamine); 2-(7-(2-cyclopropylhydrazine)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin -3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (2-(7-(2-cyclopropylhydrazineyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine); 1-((2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropane-1-carboxylic acid ethyl ester (ethyl 1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropane-1-carboxylate); (1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropyl)methanol) (1-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)amino)cyclopropyl)methanol); ((S)-7-(tert-butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)- λ6-sulfanone (((S)-7-(tert-butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone; ((R)-7-(tert-butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)- λ6-Sulfanone (((R)-7-(tert-butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)- λ6-sulfanone); N-((7-(tert-butyl(methyl)amino)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylide 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole (2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole); 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole (2-(7-cyclopropyl-2-(eth 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole); 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole); 2-(2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfinyl)benzo[d]oxazole 2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole); N-(tert-butyl)-2-(ethylsulfonyl)-3-(5-((trifluoromethyl)sulfonyl)benzo[d]oxazole-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)pyrimidin ...rimidin-3-yl)pyrazolo[1,5-a]pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)pyrimidin-2-yl)pyrimidin-3-yl)pyrimidin-3-yl)pyrimidin-2-yl)pyrimidin-3-(trifluoromethyl)sulfonyl)pyrimidin-2-yl)pyrimidin-7-amine (N-(tert-butyl)-2-(ethylsulfonyl)pyrimidin-2-yl)pyrimidin-3-yl)pyrimidin-3-yl)pyrimidin-3-yl)pyrimidin-3-yl)pyrimidin-3-yl)pyrimidin-3-yl)pyrimidin-3-yl)pyrimidin-3-yl)pyrimidin-3-yl)py ((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine); ((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-λ6-thionone (((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazol) o[1,5-a]pyrimidin-7-yl)imino)dimethyl-λ6-sulfanone；((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone（((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ 6-sulfanone); ((2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-λ6-sulfanone (((2-(ethylsulfonyl)-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-λ6-sulfanone); ((2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-λ6-sulfanone); ((2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]pyrimidin-7-yl)imino)dimethyl-λ6-sulfanone); Triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-λ6-sulfanone (((2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-λ6-sulfanone); 4-((2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)-1,4 λ6-oxathiane 4-oxide (4-((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)-1,4λ6-oxathiane 4-oxide); ethyl ((2-(ethylsulfonyluyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)(methyl)- λ6-sulfanone (ethyl((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)(methyl)-λ6-sulfanone or tributyl((2-(ethylsulfonylurea)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)(methyl)- λ6-sulfanone (tert-butyl((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)(methyl)- λ6-sulfanone).

The compounds of this invention may exist as one or more stereoisomers. Different stereoisomers include mirror isomers, non-mirror isomers, resistive isomers, and geometric isomers. Those skilled in the art will understand that a stereoisomer may be more active and/or exhibit more beneficial effects when enriched relative to or separated from other stereoisomers. Furthermore, those skilled in the art know how to isolate, enrich, and/or selectively prepare said stereoisomers. The compounds of this invention may exist as mixtures of stereoisomers, individual stereoisomers, or as optically active forms.

When the compound of formula (I) is a cation or capable of forming a cation, the anionic moiety of the salt may be inorganic or organic. Alternatively, when the compound of formula (I) is an anion or capable of forming anion, the cation moiety of the salt may be inorganic or organic. Examples of inorganic anionic moieties of salts include, but are not limited to: chlorides, bromides, iodides, fluorides, sulfates, phosphates, nitrates, nitrites, bicarbonates, and bisulfates. Examples of the organic anionic moiety of salts include, but are not limited to: formates, alkylates, carbonates, acetates, trifluoroacetates, trichloroacetates, propionates, glycolates, thiocyanates, lactates, succinates, malicates, citrates, benzoates, cinnamates, oxalates, alkyl sulfates, alkyl sulfonates, aryl sulfonates, aryl disulfonates, alkyl phosphonates, aryl phosphonates, aryl diphosphonates, p-toluenesulfonates, and salicates. Examples of the inorganic cation moiety of salts include, but are not limited to: alkali metals and alkaline earth metals. Examples of organic cations of salts include, but are not limited to: pyridine, methylamine, imidazole, benzimidazole, histidine, phosphazene, tetramethylammonium, tetrabutylammonium, choline, and trimethylamine.

The metal ions in the metal complexes of formula (I) are particularly ions of Group II elements (especially calcium and magnesium), ions of Group III and IV elements (especially aluminum, tin, and lead), and ions of Group I to VIII transition elements (especially chromium, manganese, iron, cobalt, nickel, copper, zinc, and others). There is a particular preference for metal ions of Group IV and Group I to VIII transition elements. Here, metals can exist at various valence levels they can afford.

In one embodiment, the present invention provides a compound of formula (I), its salt, metal complex, stereoisomer or N-oxide, and an assembly having an adductor, an inert carrier or other necessary components (e.g., a surfactant, an additive, a solid diluent and a liquid diluent).

The salts of the compounds of formula (I) are preferably veterinary or agriculturally acceptable salts, more preferably agriculturally acceptable salts. They can be used conventionally, for example, if the compounds of formula (I) have a basic function, they can be formed by reacting the compound with an acid of the relevant anion.

The term "N-oxide" includes compounds of formula (I) that have at least one tertiary nitrogen atom and are oxidized to an N-oxide moiety.

Compounds of formula (I) include all their stereoisomers, N-oxides, and salts, and generally exist in more than one form; therefore, formula (I) includes all crystalline and amorphous forms represented by compounds of formula (I). Amorphous forms include embodiments of solids (e.g., waxes and resins) and embodiments of liquids (e.g., solutions and melts). Crystalline forms include embodiments that substantially represent single crystal types and embodiments that represent mixtures of homomorphic polymorphs (i.e., different crystal types). The term "polymorph" refers to a specific crystal form of a compound that can crystallize through different crystal forms, which have different molecular arrangements and/or conformations in the crystal lattice. Although polymorphs may have the same chemical composition, their compositions may differ due to the presence or absence of co-crystallized water or other molecules, which may be weakly or strongly bonded in the crystal lattice. Polymorphs may have different chemical, physical, and biological properties, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate, and bioavailability. Those skilled in the art to which this application pertains will understand that a polymorph of a compound represented by formula (I) may exhibit beneficial effects relative to another polymorph or a mixture of polymorphs of the same compound represented by formula (I) (e.g., suitability for the preparation of useful formulations, improved biological properties). The preparation and separation of a particular polymorph of a compound represented by formula (I) can be achieved by methods known to those skilled in the art to which this application pertains, including, for example, crystallization using a selected solvent and temperature.

In one embodiment, the present invention discloses a method for preparing a compound of formula (I) or an agriculturally acceptable salt thereof.

The compounds of the present invention can be prepared by the process shown below, wherein, unless otherwise stated, each variable is defined as above for the compound of formula (I).

Compounds of formula (I) can be prepared according to procedures 1-10 and the chemical examples described herein.

A method for preparing compounds of formula (Z), particularly compounds of formula (Za), comprises reacting a compound of formula (2a) with a compound of formula (3) wherein M is NR ¹³ to obtain a compound of formula (Za). A summary of this method is shown in flowchart 1: Flowchart 1 ^R1 , ^R2 , ^R3 and n have the meanings described above, and ^A1 = M, _A4 and _A5 = N or C.

The compound of formula (3) is commercially available or can be prepared by known methods or similar methods described in PCT patent publications WO200665703, WO2009131237, WO2010125985, WO2011043404, WO2011040629, WO2012086848, WO2013018928 and WO2015000715.

In process 1, the carboxylic acid group in the compound of formula (2a) can be converted into a more reactive functional group, such as an acetyl halogen, mixed anhydride, acetyl azidide, N-acetylbenzotriazole, active ester, or by using a peptide conjugate such as bis(2-oxo-3-oxazolidinyl)phosphinic acid. Initiated with chloride (BOP-Cl); in situ conversion of dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), followed by amide bond formation of compound (3) in a solvent such as dichloromethane, dichloroethane, N,N-dimethylacetamide, tetrahydrofuran, acetonitrile, or mixtures thereof to obtain compound (5). Organic nonnucleophilic bases such as triethylamine, ethyldiisopropylamine, pyridine, N-methylpyrrolidine, and 1,8-diazabicyclo[5.4.0]undec-7-ene can be used. The reaction can be carried out at temperatures ranging from about 0°C to about 150°C.

Compound (4) can be converted to compound (Za) by dehydration at approximately 25°C to approximately 185°C, under normal conditions or microwave conditions, in the presence of an acidic catalyst (such as methanesulfonic acid or p-toluenesulfonic acid) and an inert solvent (such as N-methylpyrrolidine). Such a method has been described in PCT patent publications WO2009131237, WO2010125985, WO2011043404, WO2011040629, WO2012086848, WO2013018928, WO2015000715 and WO2015121136.

Alternatively, diisopropyl azodicarboxylate or triphenylphosphine can be used in an inert solvent (such as diethyl ether or tetrahydrofuran) at a temperature range of about 25°C to about 50°C under Mitsunobu reaction conditions well known to those skilled in the art. The compound of formula (4) is converted into a compound of formula (Za) (where M is oxygen). This method has been described in PCT patent publication number WO2009131237.

Compounds of formula (I) (where Y = O or Y = NR ^Y ) can be obtained by using similar methods described in Org. Lett., 1999, 1, 189-191; J. Am. Chem. Soc., 2006, 128, 6012-6013; Tetrahedron Lett. 2005, 46, 8007-8008 and PCT patent publication WO2015071180A1 by sulfoxidation/sulfoximination of the corresponding sulfides.

Process 2 provides a method for preparing (Zb) compounds: Among them, ^R1 , ^R2 and ^R3 have the meanings described above, and _A1 = N or C.

Weinreb amide of formula (5) can be converted by reacting N,O-dimethylhydroxylamine with the carboxylic acid of formula (2a) using a similar method as described in PCT patent publication number WO201175643 and European patent number EP2671582. Then, following the method described in Tetrahedron Letters 1981, 22, 3815, Weinreb amide of formula (5) is treated with a granizal reagent of formula (R'CH ₂ MgHal) to obtain compound (6).

The amine cyclization of compound (6) with formula (7) to obtain compound (Zb) can be carried out in the presence of Lewis acid (e.g., indium (III) triflate) or zinc (II) iodide, in a solvent (e.g., 1,2-dichlorobenzene or chlorobenzene), in the presence of a catalytic divalent copper salt (e.g., copper acetate), under an oxygen or air atmosphere. The reaction can be carried out in the temperature range of 100°C to 180°C, as precedents have been found in the literature; see, for example (Adv. Synth. Catalysis, 2013, 355, 1741; J. Org. Chem, 2013, 78, 12494).

Alternatively, the compound of formula (6) can be converted into the compound of formula (8) (where X is a halogen (preferably chlorine or bromine) using a halogenating agent (e.g., N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, iodine, copper(II) bromide, bromine in acetic acid, or _PhNMe3 ⁺ _Br3- ⁾ , typically in a solvent (e.g., methanol, acetonitrile, tetrahydrofuran, ethyl acetate, chloroform, or dichloromethane, or mixtures thereof) at a temperature in the range of 0°C to 150°C, preferably between 25°C and 120°C, and optionally under microwave heating conditions. Such a process has been described before, for example in PCT patent publication WO2016/071214. Compound (Zb) is obtained by condensing compound (7) with compound (8) in an inert solvent (e.g., ethanol or acetonitrile), optionally in the presence of a suitable alkali (e.g., sodium carbonate, potassium carbonate, or cesium carbonate), at a temperature between 80°C and 150°C, optionally under microwave heating conditions. Such a process has been described before, for example in PCT patent publication WO2003/031587. Compound (32) is commercially available or can be prepared by methods known to those skilled in the art.

Compounds of formula (I) (where Y = O or Y = NR ^Y ) can be obtained by using similar methods described in Org. Lett., 1999, 1, 189-191; J. Am. Chem. Soc., 2006, 128, 6012-6013; Tetrahedron Lett. 2005, 46, 8007-8008 and PCT patent publication WO2015071180A1 by sulfoxidation/sulfoximination of the corresponding sulfide (Zb) compounds.

Procedure 3 provides a method for preparing compounds of formula (Zc) and formula (Zd): Procedure: 3 Where A1 = N or C, ^R1 , ^R2 , ^R3 and n have the meanings described above.

Compound (Zc) can be prepared by reacting compound (9) (where Y ^- is a halogen ion or mesitylenesulfonate) with compound (11), optionally in the presence of a suitable alkali and an inert solvent. Compound (Zd) can be prepared by reacting compound (10) (where Y ^- is a halogen ion or mesitylenesulfonate) with compound (11), optionally in the presence of a suitable alkali and an inert solvent.

Compounds of formula (9) or (10) can be modified by using O-mesitylenesulfonylhydroxylamine (MSH) as an amination agent or an equivalent thereof to compound (7). Prepared by N-amineation, as described in PCT patent publication WO201334506 and US patent US201359833.

Compounds of formula (I) (where Y = O or Y = NR ^Y ) can be obtained by using similar methods described in Org. Lett., 1999, 1, 189-191; J. Am. Chem. Soc., 2006, 128, 6012-6013; Tetrahedron Lett. 2005, 46, 8007-8008 and PCT patent publication WO2015071180A1 by sulfoxidation/sulfoximination of the corresponding sulfide compounds of formula (Zc) or formula (Zd).

Procedures 4 through 10 provide methods for preparing pyrazolopyrimidine.

Synthetic methods for compounds with description formulas (2aa-2ac) in process 4a-c: Process: 4a Where X is a halogen, and ^R1 and ^R2 have the meanings described above.

When treated with an amphiphilic compound of formula (13) or its protected/masked form (e.g., an aldehyde masked to an acetal), the pyrazole derivative of formula (12) can undergo a cyclization condensation reaction to provide a compound of formula (14). The condensation can be carried out in the presence of a solvent and an acid. Examples of acids include, but are not limited to, acetic acid, sulfonic acid (e.g., PTSA), sulfuric acid, or hydrochloric acid, which release reactive functional groups. Examples of solvents include, but are not limited to, methanol, ethanol, isopropanol, or ethylene glycol. The reaction can be carried out in a temperature range from 0°C to 150°C.

Compound (15) can be obtained by treating compound (14) with a halogenating agent in the presence or absence of an alkali. Examples of solvents include, but are not limited to, acetonitrile, chloroform, tetrahydrofuran, 1,4-dioxane, toluene, or N,N-dimethylformamide. Examples of halogenating agents include, but are not limited to, phosphorus oxychloride, thionyl chloride, phosphorus pentachloride, or glyphosate. Examples of alkalis include, but are not limited to, N,N-dimethylaniline, diisopropylethylamine, or N-methylmorpholine. The reaction can be carried out in a temperature range of 50-200°C.

The halogen compound of formula (15) can be conveniently coupled with boric acid or borate ester of formula (16) under Suzuki cross-coupling conditions to obtain the compound of formula (18). Suzuki cross-coupling reactions can be catalyzed by palladium-based catalysts, including but not limited to 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) or tetrakis(triphenylphosphine)palladium(O), in suitable solvents (e.g., tetrahydrofuran (THF), N,N-dimethylformamide (DMF), 1,2-dimethoxyethane or 1,4-dioxane) or solvent systems (e.g., mixtures of tetrahydrofuran (THF)/water, 1,2-dimethoxyethane/water or 1,4-dioxane/water). The reaction is typically carried out in the presence of a suitable alkali, such as potassium carbonate, cesium carbonate, or potassium phosphate. The reaction temperature is preferably in the range of room temperature (20°C) to the boiling point of the reaction mixture, as illustrated in precedents in the literature, such as Chem. Soc. Rev. 2014, 43, 412-443 or PCT patent publication number WO2014070978.

Alternatively, the compound of formula (15) can also be coupled with the tin-containing compound of formula (17) in a catalyst (e.g., bis(triphenylphosphine)palladium(II)dichloride, tetrakis(triphenylphosphine)palladium(O), [1,1'-bis(diphenylphosphine)ferrocene]palladium(II)dichloride, tris(diphenylmethylacetone)dipalladium(O)). The catalysts used are: nzylideneacetone)dipalladium(0) and palladium acetate(II); nickel catalysts (e.g., bis(cyclooctadiene)nickel(0) and nickel chloride(II)); and copper catalysts (e.g., copper iodide(I) and copper chloride(I)), in the presence of alkalis (e.g., alkali metal hydroxides, alkali metal carbonates or organic alkalis), and in the presence of suitable solvents (e.g., acetonitrile, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), 1,2-dimethoxyethane or The reaction is carried out in 1,4-dioxane at a temperature ranging from 25°C to the solvent reflux temperature, or under microwave radiation at a temperature ranging from 70°C to 150°C. A ligand and/or inorganic halogen may be added to the reaction if necessary. Examples of usable ligands include triphenylphosphine, Xantphos, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and 1,1'-bis(diphenylphosphino)-1,1'-binaphthyl. Examples of inorganic halides include ferrocene, 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl, 2-aminoethanol, 8-hydroxyquinoline, or 1,10-phenanthroline.

The hydrolysis of compound (18) can be carried out using an alkali (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or bis(tributyltin) oxide) in a solvent (such as tetrahydrofuran, water, methanol, ethanol, or toluene or mixtures thereof) to give compound (2aa). The reaction can be carried out in a temperature range of 50°C to 150°C.

The method for synthesizing compound (2ab) is described in procedure 4b: Procedure: 4b ^R1 and ^R2 have the meanings described above.

Compound (20) can be obtained by cyclizing a pyrazole derivative of formula (12) with commercially available 2-halo-malonaldehydes of formula (19) under acidic catalytic conditions. Examples of acids include, but are not limited to, acetic acid, sulfonic acid (e.g., PTSA), sulfuric acid, or hydrochloric acid. Examples of solvents include, but are not limited to, methanol, ethanol, isopropanol, or ethylene glycol. The reaction can be carried out in a temperature range of 0°C to 150°C. Compound (20) can be coupled with a reagent of formula (21) under standard Suzuki cross-coupling conditions or Stille cross-coupling conditions to obtain compound (22) as in step 3 or step 4 of process 4a. Subsequent alkaline hydrolysis of compound (22) as described in step 5 of process 4a can provide compound (2ab).

Formula (2ac) can be prepared according to the following process 4c: Process: 4c ^R1 and ^R2 have the meanings described above.

The pyrazole derivative of formula (12) can be cyclized in the presence of a suitable alkali using 1,3-dimethyluracil of formula (23) or an alkoxyacrylate derivative of formula (24) to provide a pyrimidin-5-one derivative of formula (25). Examples of suitable alkalis include sodium ethoxide, sodium methoxide, potassium tert-butyl, potassium carbonate, sodium carbonate, cesium carbonate, or potassium phosphate. Solvents include methanol, ethanol, isopropanol, ethylene glycol, N,N-dimethylacetamide, or N,N-dimethylformamide. The reaction can be carried out in a temperature range of 50-150°C. Such reactions are known in the literature, and alternative reactions are also described in the literature, for example, J. Org. Chem 2007, 72, 1046; PCT patent publication number WO2018081417. Compound (25) can be halogenated using phosphorus oxychloride or phosphorus oxybromide to obtain compound (26). Compound (26) can be coupled under standard Suzuki cross-coupling conditions or Stieler cross-coupling conditions to obtain compound (27) as in step 3 or 4 of process 4a. Subsequent alkaline hydrolysis of compound (27) as described in step 5 of process 4a can provide compound (2ac). Process: 5 Among them, ^R1 , ^R11 and ^R12 have the meanings described above.

Compounds of formula (29a-c) can be prepared by reacting compounds of formula (15/20/26) with reagents of formula (28) in the presence of an alkali and a solvent. Examples of alkalis include sodium carbonate, potassium, or cesium, or sodium or potassium terbutoxide, or diisopropylethylamine, or triethylamine, or DBU, or pyridine. Examples of solvents include tetrahydrofuran, N,N-dimethylformamide, acetonitrile, or dimethyl sulfoxide. The reaction can be carried out in a temperature range of 25°C to 130°C.

Alternatively, compounds of formula (29a-c) can be prepared under transition metal catalysis by reacting compounds of formula (15/20/26). The reaction can be catalyzed by palladium-based catalysts, such as bis(dibenzylideneacetone)palladium(0), Pd(dba) ₂ or tris(dibenzylideneacetone)dipalladium(0), _Pd2 (dba) _3. ); (optionally in the form of a chloroform adduct), or palladium(II)acetic acid) and ligands (e.g., XantPhos ((5-di-phenylphosphanyl-9,9-dimethyl-xanthen-4-yl)diphenylphosphane), XPhos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl), RuPh The reaction is catalyzed by os (2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl) or BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene) in the presence of an alkali (e.g., sodium carbonate, potassium, or cesium; sodium or potassium terbutoxide; or potassium phosphate), in a solvent or solvent mixture (e.g., dioxane, 1,2-dimethoxyethane, or toluene), preferably under an inert atmosphere. The reaction temperature can preferably be from 25°C to the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. The above-mentioned reactions and alternative conditions, such as iron or copper catalysis, have been described in, for example, PCT patent publication number WO2018/099812.

Alternatively, compounds of formula (29a-c) can be prepared by copper or nickel catalysis. Such catalysts include, but are not limited to, cuprous iodide, cuprous bromide, cuprous chloride, cuprous oxide, trifluoromethanesulfonic acid, cuprous salts and benzene complexes, cuprous salts of 2-thiophenecarboxylic acid; and nickel catalysts (e.g., bis(cyclooctadiene)nickel(0) and nickel(II) chloride) and ligands (e.g., 1,10-phenanthroline, 8-hydroxyquinoline, trans-1,2-cyclohexanediamine, 2,2'-bipyridine, 2-aminoethanol, triphenylphosphine, 1,2-bis(diphenylphosphine) Ethane, 1,3-bis(diphenylphosphine)propane, XantPhos ((5-di-phenylphosphanyl-9,9-dimethyl-xanthen-4-yl)diphenylphosphine), XPhos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) l), RuPhos (2-Dicyclohexylphosphino-2',6'-diisopropoxybiphenyl), BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene), 1,1'-bis(diphenylphosphino)ferrocene Examples of alkalis include, but are not limited to, alkaline earth metal carbonates or diisopropylethylamine or pyridine or 1,8-diazabicyclo[5.4.0]undec-7-ene or 4-(dimethylamino)pyridine, in a suitable solvent (e.g. acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidine), in a temperature range of 25°C to 120°C.

As described in step 5 of process 4a, subsequent alkaline hydrolysis of compound (29a-c) yields compound (2a-c). Process: 6 Among them, Q, ^R1 , ^R2 , ^R11 and ^R12 have the meanings described above.

Compound (Z-1) can be prepared by reacting compound (30a-c) according to process-6, using the conditions described in step-3 or step-4 of process-4a. Similarly, compound (Z-2) can be prepared by reacting compound (28) using the conditions described in step-1 of process-5.

The method for synthesizing compound (30a-c) is described in procedure 7: Procedure: 7 ^R1 and Q have the meanings described above.

The organothioalkylene of formula (32) can be formed by reacting the compound of formula (31) with CS₂ in the presence of an alkali (such as an alkaline metal carbonate, an alkaline metal hydroxide, lithium, sodium or potassium hexamethyldisilamide, sodium hydroxide or potassium hydroxide) in a suitable solvent (such as tetrahydrofuran, acetonitrile or N,N-dimethylformamide) within a temperature range of 0°C to 50°C. The compound of formula (32) can be cyclized with hydrazine to form an aminopyrazole derivative of formula (33). These methods are described in the literature, for example, Russian Journal of Organic Chemistry, 2014, 50(3), 412-421. This aminopyrazole derivative can be converted to compound (30a-c) using the methods described in process 4a (steps 1 and 2), process 4b (step 5), or process 4c (steps 1 and 2). Process: 8 Among them, ^R1 , ^R2 and Q have the meanings described above.

In another process, compound (Z-1A) can be prepared by reacting a pyrazole derivative of formula (33) with a compound of formula (34) under cyclization condensation conditions in the presence of a solvent and an acid. Examples of acids include acetic acid, sulfonic acid (e.g., PTSA), sulfuric acid, or hydrochloric acid, which release reactive functional groups. Examples of solvents include, but are not limited to, methanol, ethanol, isopropanol, or ethylene glycol. The reaction can be carried out in a temperature range of 50°C to 150°C.

The synthesis method of the reagent of preparative formula (34) is known in the literature, for example, Organic Chemistry Frontiers (2022), 9(16), 4416-4420. Procedure: 9 Q, ^R1 , ^R2 , ^R2x , and ^R2a have the meanings described above. ^R2x also includes hydrogen.

Compounds of formula (I-1) (where m=1 (sulfene) and/or m=2 (sulfene)) can be obtained by oxidation of the corresponding sulfides of formula (Z) when appropriate oxidants and conditions are known to those skilled in the art. Oxidants such as m-chloroperoxybenozic acid (mCPBA), hydrogen peroxide/glacial acetic acid, hydrogen peroxide/trifluoroacetic acid, hydrogen peroxide/potassium permanganate, hydrogen peroxide/p-toluenesuflonylimidazole, urea hydrogen peroxide/trifluoroacetic acid, potassium hydrogen sulfate, sodium periodate, sodium hypochlorite, or other organic high acids can be used here in the temperature range of 0°C to 100°C. Examples of solvents used in this reaction include aliphatic halogenated hydrocarbons (such as dichloromethane or chloroform) and alcohols (such as methanol or ethanol) or mixtures thereof. Process: 10 Q, ^R1 , ^R2 , ^R2x , and ^RY have the meanings described above. ^R2x also includes hydrogen.

The compound of formula (I-2) (where R ^Y = H) can be obtained by reacting the compound of formula (Z) with a suitable nitrogen source (e.g., ammonia, ammonium carbamate or ammonium acetate) in the presence of a hypervalent iodine reagent (e.g., diacetoxyiodobenzene, PhI(OAc) ₂ ) in a solvent (e.g., toluene, acetonitrile or an alcohol (preferably methanol, 2,2,2-trifluoromethanol or 2,2,3,3,4,4,5,5-octafluoropent-1-ol)) in a temperature range of 0 to 100 °C (preferably around 25 °C).

Compounds of formula (I-3) (where R ^_Y is a group other than "hydrogen") can be prepared by the reagent R_{^Y -X} (where X is a leaving group, such as a halogen (e.g., chlorine, bromine, or iodine), an aromatic group, or an alkyl sulfonate (e.g., trifluoromethanesulfonate)). The alkylation reaction can be carried out in the presence of an alkali (e.g., sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, or triethylamine) and a solvent (e.g., dichloromethane, dichloroethane, DMF, DMSO, ethanol, or methanol) in a temperature range of 0°C to 150°C. Metal-catalytic coupling for the preparation of compounds of formula (I-3) (where R ^{and Y} are groups other than "hydrogen") can be carried out in the presence of an alkali (e.g., sodium carbonate, potassium carbonate, cesium carbonate, or sodium hydroxide), in an inert solvent (e.g., toluene, DMF, N-methylpyrrolidine (NMP), DMSO, dioxane, or THF), and optionally in the presence of a catalyst (e.g., palladium(II) acetate, tris(dibenzylideneacetone)dipalladium(O), Pd(dba) ₂ ), or tris(dibenzylideneacetone)dipalladium(O), _Pd2 (dba) _3). (optionally in its chloroform adduct form) or a precatalyst for palladium (e.g., tert-BuBrettPhos Pd G3 (methanesulfonic acid-2-(di-tert-butylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)palladium(II)), [(2-Di-tert-butylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate) or BrettPhos Pd In the presence of G3 ((2-dicyclohexylphosphino)-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl-2-(2'-amino-1,1'-biphenyl)palladium(II) or [(2-di-cyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate), and optionally in the presence of a ligand (e.g., SPhos, t-BuBrettPhos, or XantPhos), in a temperature range of 50°C to 120°C, optionally under microwave heating conditions.

Chemical examples:

The following examples illustrate, but are not limited to, the ways and methods of preparing the compounds of the present invention, and include the best mode of implementation conceived by the inventors.

Example-1: Synthesis of 2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound-39) (2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine)

Step-1: 2-Cyano-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide

In a stirred solution of 2-acrylonitrile-acetic acid (33.4 g, 392 mmol) in dichloromethane (300 mL), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (48.1 g, 251 mmol) and N,N-diisopropylethylamine (82 mL, 471 mmol) were added and stirred at 0 °C for 0.5 h. Then, N-2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (30.0 g, 157 mmol) was added at 0 °C. The resulting reaction mixture was stirred at 25 °C for 24 h under a nitrogen atmosphere. After the reaction was complete, the reaction mixture was evaporated and diluted with water (500 mL). The aqueous layer was extracted with ethyl acetate (4 x 250 mL). The combined organic layer was washed with water (250 mL) and an aqueous salt solution (250 mL), dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain the residue, which was washed with hexane to give 2-cyano-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide (39 g, 151 mmol; yield 96%). ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ 9.63 (s, 1H), 8.26 (d, J = 1.0 Hz, 1H), 7.64 (d, J = 2.2 Hz, 1H), 6.96 (d, J = 4.6 Hz, 1H), 3.85 (s, 2H), 2.87 (d, J = 4.6 Hz, 3H);ESI MS (m/z) 258.95 (MH) ⁺ .

Step-2: 2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acetonitrile

A solution of 2-cyano-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide (39 g, 151 mmol) in acetic acid (230 mL) was heated at 110 °C for 2 hours. After the reaction was complete, the reaction mixture was evaporated under reduced pressure and diluted with ethyl acetate (250 mL) and water (250 mL). The organic layer was dried with anhydrous sodium sulfate and evaporated under reduced pressure to obtain a crude product, which was further washed with hexane to obtain: 2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acetonitrile (31 g, 129 mmol; yield 85%). ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ 8.74 (d, J = 1.2 Hz, 1H), 8.54 (d, J = 1.7 Hz, 1H), 4.67 (s, 2H), 3.80 (s, 3H); ESI MS (m/z) 241.10 (MH) ⁺ .

Step-3: 3,3-bis(ethylthio)-2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acrylonitrile

In a mixture of potassium hydroxide (KOH) (17.0 g, 258 mmol) and acetonitrile (300 mL), 2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acetonitrile (31 g, 129 mmol) was added at 0 °C. The resulting reaction mixture was stirred at 25 °C for 1 hour and then cooled again to 0 °C, followed by the dropwise addition of carbon disulfide (8.60 mL, 142 mmol) over 10 minutes. The resulting reaction mixture was stirred at 0 °C for 1 hour, followed by the dropwise addition of ethyl iodine (20.80 mL, 258 mmol) over 15 minutes at the same temperature. The resulting reaction mixture was stirred at 0°C for 2 hours, then cooled to 25°C and stirred at the same temperature for 12-15 hours. After the reaction was complete, the reaction mixture was evaporated under reduced pressure to obtain a crude product, which was then purified by rapid column chromatography to obtain 3,3-bis(ethylthio)-2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acrylonitrile (41 g, 110 mmol; yield 85%). ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ 8.84 (d, J = 1.5 Hz, 1H), 8.62 (d, J = 1.7 Hz, 1H), 3.87 (s, 3H), 3.25 (q, J = 7.3 Hz, 2H), 2.84 (q, J = 7.3 Hz, 2H), 1.36 (t, J = 7.3 Hz, 3H), 1.14 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 473.00 (MH) ⁺ .

Step-4: 3-(Ethylthio)-4-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-1H-pyrazol-5-amine

In a stirred solution of 3,3-bis(ethylthio)-2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acrylonitrile (34.0 g, 91 mmol) in acetonitrile (150 mL) and ethanol (300 mL), hydrazine monohydrate (5.40 mL, 110 mmol) was added dropwise at 0 °C. The resulting reaction mixture was stirred at 0 °C for 1 hour, followed by the addition of ice-cold water. The resulting solid was filtered and purified by rapid column chromatography to give 3-(ethylthio)-4-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-1H-pyrazol-5-amine (16 g, 46.7 mmol; yield 51.2%). ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ 12.00 (s, 1H), 8.68 (s, 1H), 8.39 (s, 1H), 5.73 (s, 2H), 3.76 (s, 3H), 2.88 (q, J = 7.1 Hz, 2H), 1.21-1.14 (m, 3H);ESI MS (m/z) 343.40 (MH) ⁺ .

Step-5: 2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one)

In a stirred solution of 5-(ethylthio)-4-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-1H-pyrazol-5-amine (17 g, 49.7 mmol) in acetic acid (160 mL), methyl 3,3-dimethylpropionate (8.45 mL, 59.6 mmol) was added. The resulting reaction mixture was stirred at 120 °C for 10 hours. After the reaction was complete, the acetic acid was evaporated under reduced pressure. The residue was diluted with water (200 mL) and extracted with ethyl acetate (4 x 75 mL). The combined organic layer was dried with anhydrous sodium sulfate and evaporated under reduced pressure to obtain a crude product, which was then purified by rapid column chromatography to give 2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one) (12 g, 30.4 mmol; yield 61.3%). ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ 12.41 (s, 1H), 8.80 (d, J = 1.5 Hz, 1H), 8.57 (d, J = 1.5 Hz, 1H), 7.84 (d, J = 7.6 Hz, 1H), 5.87 (d, J = 7.3 Hz, 1H), 3.77 (s, 3H), 3.15 (q, J = 7.3 Hz, 2H), 1.32 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 395.00 (MH) ⁺ .

Step-6: 2-(7-Bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(7-Bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine)

In a stirred suspension of 2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one) (7 g, 17.7 mmol) in acetonitrile (200 _mL ), _K₂CO₃ (8.59 g, 62.1 mmol) and phosphorus oxybromide (15.27 g, 53.2 mmol) were successively added at 25 °C. The reaction mixture was heated at 95 °C for 6 hours. The reaction mixture was cooled to 25°C and then quenched with ice water (200 mL), the pH was adjusted to 7-8 using a saturated _NaHCO3 aqueous solution, and extracted with ethyl acetate (4 x 100 mL). The combined organic layers were washed with a saline aqueous solution (200 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain a crude product, which was purified by rapid column chromatography to give 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (6.25 g, 13.6 mmol; yield 77%). ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ 8.77 (d, J = 1.1 Hz, 1H), 8.55 (d, J = 1.5 Hz, 1H), 8.48 (d, J = 4.6 Hz, 1H), 7.65 (d, J = 4.6 Hz, 1H), 3.92 (s, 3H), 3.25 (q, J = 7.3 Hz, 2H), 1.40 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 458.80 (MH) ⁺ .

Step-7: 2-(7-Bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(7-Bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine)

In a stirred solution of 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (3.0 g, 6.6 mmol) in dichloromethane (40 mL), 3-chloroperoxybenzoic acid (4.15 g, 14.4 mmol) was added at 0 °C. The resulting reaction mixture was stirred at 25 °C for 6 hours. After the reaction was complete, the reaction mixture was diluted with dichloromethane (200 mL), saturated sodium bicarbonate solution (100 mL), and sodium thiosulfate solution (100 mL). The organic layer was dried with anhydrous sodium sulfate and evaporated under reduced pressure to obtain the residue, which was purified by rapid column chromatography to give 2-(7-bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2.3 g, 4.70 mmol; yield 71.7%). ¹ H-NMR (400 MHz, DMSO- d ₆ ) δ 8.85 (d, J = 1.2 Hz, 1H), 8.65 (d, J = 4.4 Hz, 1H), 8.63 (d, J = 1.5 Hz, 1H), 7.97 (d, J = 4.6 Hz, 1H), 3.80-3.73 (m, 5H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 490.90 (MH) ⁺ .

Step-8: 2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(2-(Ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine)

In a stirred solution of 2-(7-bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2.7 g, 5.5 mmol) and 2-(tributylstannyl)pyrimidine (2.63 mL, 8.3 mmol) in tetrahydrofuran (THF) (50 mL), tetrakis(triphenylphosphine)palladium(0) (0.64 g, 0.5 mmol) and copper bromide (0.16 g, 1.1 mmol) were added under a nitrogen atmosphere. The resulting reaction mixture was stirred at 60 °C for 10 hours. After the reaction was complete, the reaction mixture was diluted with water (50 mL) and extracted with dichloromethane (4 x 50 mL). The combined organic layers were washed with a saline aqueous solution (200 mL), dried in anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain a crude product, which was purified by rapid column chromatography to give: 2-(2-(ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(2-(Ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine) (1.55 g, 3.2 mmol; yield 57.5%). ^¹H -NMR (400 MHz, DMSO- d ₆ ) δ 9.19 (d, J = 4.9 Hz, 2H), 9.03 (d, J = 4.2 Hz, 1H), 8.86 (q, J = 0.9 Hz, 1H), 8.64 (d, J = 1.2 Hz, 1H), 7.87 (d, J = 4.2 Hz, 1H), 7.83 (t, J = 4.9 Hz, 1H), 3.82 (s, 3H), 3.68 (q, J = 7.3 Hz, 2H), 1.23 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 489.20 (MH) ⁺ .

Example-2: Synthesis of N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)cyanamide (compound-38)

Step-1: 2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine)

In a stirred solution of 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2.0 g, 4.4 mmol) in 1,4-dioxane (20 mL), cyclopropylboronic acid (0.75 g, 8.7 mmol) and potassium phosphate (2.79 g, 13.1 mmol) were added; water (2.0 mL) was added at 25 °C. The resulting reaction mixture was purged with nitrogen and stirred at the same temperature for 10 minutes, followed by the addition of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.32 g, 0.4 mmol). The resulting reaction mixture was stirred at 90 °C for 2 hours. After the reaction was complete, the mixture was diluted with water (10 mL) and extracted with ethyl acetate (2 x 25 mL). The combined organic layers were dried with anhydrous sodium sulfate and evaporated under reduced pressure to give a crude product, which was purified by rapid column chromatography to give 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine) (1.02 g, 2.4 mmol, yield 55.7%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.74 (q, J = 0.9 Hz, 1H), 8.52 (d, J = 4.6 Hz, 2H), 6.84 (d, J = 4.6 Hz, 1H), 3.93 (s, 3H), 3.25 (q, J = 7.3 Hz, 2H), 2.93-2.86 (m, 1H), 1.41-1.33 (m, 5H), 1.30-1.26 (m, 2H); ESI MS (m/z) 418.55 (MH) ⁺ .

Step-2: (7-Cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone ((7-Cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone)

In a stirred solution of 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (3.4 g, 8.1 mmol) in methanol (80 mL) and acetonitrile (40 mL), iodophenyldiacetic acid (6.54 g, 20.3 mmol) was added. The reaction mixture was cooled to 0°C and then, at the same temperature, amine carbamate (1.90 g, 24.4 mmol) was added in portions over 0.5 hours. The resulting reaction mixture was stirred at 25°C for 15 hours. After the reaction was complete, the reaction mixture was evaporated under reduced pressure to give a crude product, which was purified by rapid column chromatography to give (7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone ((7-Cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone) (1.8 g, 4.0 mmol, yield 49.3%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (t, J = 1.1 Hz, 1H), 8.65 (d, J = 4.4 Hz, 1H), 8.60 (d, J = 1.5 Hz, 1H), 7.07 (d, J = 4.6 Hz, 1H), 4.77 (s, 1H), 3.78 (s, 3H), 3.59 (ddd, J = 24.2, 14.5, 7.1 Hz, 2H), 2.95-2.89 (m, 1H), 1.46-1.41 (m, 2H), 1.31-1.24 (m, 5H);ESI MS (m/z) 450.20 (MH) ⁺ Mirror isomers were separated using a palmar-HPLC column: YMC Cellulose-SB (4.6*250mm) 5μm. Mobile phase: A: n-hexane; B: isostrong ethanol (EtOH Isocratic); (A: B; 60:40); Flow rate: 1.0 ml/min; Detection: 237 nm; Injection flow rate: 1.2 μL. Mirror isomer 1 was extracted at 5.33 min of residence time, while mirror isomer 2 was extracted at 6.90 min.

Step-3: N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)cyanamide)

In a stirred solution of (7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone (200 mg, 0.4 mmol) in dichloromethane (5 mL), DMAP (109 mg, 0.9 mmol) and hydrogen bromide (141 mg, 1.3 mmol) were added at 0 °C. The resulting reaction mixture was stirred at 25 °C for 15 hours. After the reaction was complete, the reaction mixture was diluted with dichloromethane (25 mL). The organic layer was washed with ice-cold water (20 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain the crude product, which was purified by rapid column chromatography to give N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-λ6-sulfaneylidene)cyanamide (94 mg, 0.2 mmol, Yield 44.5% ). ^¹H -NMR (400 MHz, DMSO- d⁶ ) δ 8.87 (t, J = 1.0 Hz, 1H), 8.78 (d, J = 4.6 Hz, 1H), 8.65–8.64 (m, 1H), 7.23 (d, J = 4.6 Hz, 1H), 4.42–4.26 (m, 2H), 3.88 (s, 3H), 2.95–2.89 (m, 1H), 1.50–1.45 (m, 2H), 1.41–1.34 (m, 5H); ESI MS (m/z) 474.60 (MH) ⁺ .

Example-3: Synthesis of 1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile) (compound-23)

Step-1: Tert-Butyl 2-cyano-2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetate

The mixture of 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (1.0 g, 2.2 mmol), N,N-dimethylformamide (20 mL), tert-butyl cyanoacetate (0.38 mL, 2.6 mmol), and sodium hydroxide (0.21 g, 5.25 mmol) was added at 0 °C. The resulting reaction mixture was heated to 25 °C and stirred for 16 hours. After the reaction was complete, the reaction mixture was quenched with ice water (100 mL) and extracted with ethyl acetate (4 x 50 mL). The combined organic layers were evaporated under reduced pressure to obtain a crude product, which was purified by rapid column chromatography to give tert-Butyl 2-cyano-2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetate (700 mg, 1.3 mmol, yield 61.8%). ¹ H-NMR (400 MHz, METHANOL-d4) δ 8.76 (t, J = 1.0 Hz, 1H), 8.38 (d, J = 1.5 Hz, 1H), 7.89 (d, J = 7.6 Hz, 1H), 7.55 (d, J = 7.6 Hz, 1H), 3.94 (s, 3H), 3.39 (q, J = 7.3 Hz, 2H), 1.57 (s, 9H), 1.47 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 516.15 (MH) ⁺ .

Step-2: (2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetonitrile ((2-(2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetonitrile)

Sodium chloride (0.34 ml, 5.8 mmol) was added at 25 °C to a stirred solution of tert-Butyl 2-cyano-2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetate (600 mg, 1.1 mmol) in DMSO (15 mL). The resulting reaction mixture was stirred at 130 °C for 3 hours. After the reaction was complete, the reaction mixture was cooled to 25°C, diluted with water (50 mL), and extracted with ethyl acetate (4 x 25 mL). The combined organic layers were evaporated under reduced pressure to give a crude product, which was purified by rapid column chromatography to give (2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetonitrile (2-(2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetonitrile) (250 mg, 0.6 mmol, yield 51.7%). ^¹H -NMR (400 MHz, CHLOROFORM-d) δ 8.71–8.69 (m, 1H), 8.63 (d, J = 4.3 Hz, 1H), 8.38 (d, J = 1.5 Hz, 1H), 7.18 (d, J = 4.3 Hz, 1H), 4.39 (d, J = 0.9 Hz, 2H), 4.04 (d, J = 4.3 Hz, 3H), 3.34-3.28 (m, 2H), 1.48 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 417.65 (MH) ⁺ .

Step-3: 1-(2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (1-(2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile)

In a stirred solution of (2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetonitrile (500 mg, 1.2 mmol) in acetonitrile (10 mL), cesium carbonate (1.17 g, 3.6 mmol) and 1,2-dibromoethane (0.31 mL, 3.6 mmol) were added. (mmol) was added at 25°C. The resulting reaction mixture was stirred at 80°C for 16 hours. After the reaction was complete, the reaction mixture was cooled to 25°C, diluted with water (100 mL), and diluted with ethyl acetate (4 x 25 mmol). Extracted by extraction (mL). The combined organic layers were evaporated under reduced pressure to give the crude product, which was purified by rapid column chromatography to give 1-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (1-(2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile) (60 mg, 0.2 mmol, yield 11.30%). ^¹H -NMR (400 MHz, DMSO- d6 ) δ 8.76 (s, 1H), 8.70 (d, J = 4.6 Hz, 1H), 8.55 (s, 1H), 7.32 (d, J = 4.6 Hz, 1H), 3.95 (s, 3H), 3.30-3.27 (m, 1H), 2.00-1.90 (m, 4H), 1.45 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 444.00 (MH) ⁺ .

Step-4: 1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (1-(2-(Ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile)

The target compound, 1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (1-(2-(Ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile) (90 mg, 0.2 mmol, (Yield 52.5%) was prepared from 1-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (1-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (160 mg, 0.3 mmol) following the reaction conditions of step 7 of Example 1. ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.87-8.85 (m, 2H), 8.63 (d, J = 1.5 Hz, 1H), 7.63 (d, J = 4.4 Hz, 1H), 3.80 (d, J = 4.6 Hz, 3H), 3.74 (q, J = 7.3 Hz, 2H), 2.07-2.03 (m, 2H), 1.96-1.92 (m, 2H), 1.30 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 476.35 (MH) ⁺ .

Example-4: Synthesis of N-cyclopropyl-2-(ethylsulfonyl)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (Compound-3)

In a stirred solution of 2-(7-bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (200 mg, 0.4 mmol) in N,N-dimethylformamide (3 mL), N-methylcyclopropylamine (0.09 mL, 1 mmol) was added. The resulting reaction mixture was stirred at 25 °C for 2 hours. After the reaction was complete, the reaction mixture was diluted with ethyl acetate (20 mL) and the organic layer was washed with water (3 x 20 mL). The combined organic layers were dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain a crude product, which was purified by rapid column chromatography to give N-cyclopropyl-2-(ethylsulfonyl)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (140 mg, 0.3 mmol, yield 71.4%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (t, J = 1.0 Hz, 1H), 8.58 (d, J = 2.2 Hz, 1H), 8.45 (d, J = 5.4 Hz, 1H), 6.87 (d, J = 5.6 Hz, 1H), ESI MS (m/z) 480.45 (MH) ⁺ .

Example-5: Synthesis of 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (compound-52)

Step-1: 7-Cyclopropyl-2-(ethylthio)-N-(5-(methylamino)-2-(trifluoromethyl)pyridin-4-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide

HATU (646 mg, 1.70 mmol) was added to a stirred solution of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (379 mg, 1.44 mmol) in pyridine (3 mL). The reaction mixture was stirred at 25 °C for 30 min, followed by the addition of N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (250 mg, 1.31 mmol). The resulting reaction mixture was stirred at 110 °C for 16 h. After the reaction was complete, the pyridine was evaporated. The crude product (300 mg) was used in the next step without purification. ESI MS (m/z) 437.05 (MH) ⁺¹ .

Step-2: 2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine)

A stirred solution of 7-cyclopropyl-2-(ethylthio)-N-(5-(methylamino)-2-(trifluoromethyl)pyridin-4-yl)pyrazolo[1,5-a]pyrimidine-3-methamide (300 mg, 0.69 mmol) in acetic acid (20 mL) was heated at 110 °C for 15 hours. After the reaction was complete, the solvent was evaporated under reduced pressure, and the residue was diluted with ethyl acetate (50 mL) and water (50 mL). The organic layer was washed with 10% hydrochloric acid aqueous solution (50 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain the crude product, which was purified by rapid column chromatography to give 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (150 mg, 0.36 mmol, 52.2% yield) as a white solid. ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.13 (s, 1H), 8.53 (d, J = 4.6 Hz, 1H), 8.19 (s, 1H), 6.85 (d, J = 4.6 Hz, 1H), 4.00 (s, 3H), 3.24 (q, J = 7.3 Hz, 2H), 2.93-2.86 (m, 1H), 1.42-1.36 (m, 5H), 1.30-1.26 (m, 2H); ESI MS (m/z) 419.05 (MH) ⁺ .

Step-3: 2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine)

The target compound, 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (62 mg, 0.14 mmol, (Yield 52.4%) was prepared from 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (110 mg, 0.26 mmol) following the reaction conditions of step 7 of Example 1. ¹ H-NMR (400 MHz, CHLOROFORM-d) δ 8.95 (s, 1H), 8.59 (d, J = 4.4 Hz, 1H), 8.13 (d, J = 1.0 Hz, 1H), 6.65 (d, J = 4.4 Hz, 1H), 3.93 (s, 3H), 3.68 (q, J = 7.5 Hz, 2H), 3.12 (s, 1H), 1.54-1.52 (m, 2H), 1.43 (t, J = 7.5 Hz, 3H), 1.25-1.22 (m, 2H);ESI MS (m/z) 451.00 (MH) ⁺ .

Example-6: Synthesis of 6-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (Compound-50)

Step-1: 7-Cyclopropyl-2-(ethylthio)-N-(3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide

In a stirred solution of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (1.64 g, 6.25 mmol) in N,N-dimethylformamide (10 mL), HATU (2.57 g, 6.77 mmol) and N,N-diethylpropylethylamine (1.82 mL, 10.41 mmol) were successively added, and the resulting mixture was stirred at 25°C for 0.5 hours.

In a stirred solution of N3-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (1.0 g, 5.20 mmol) in N,N-dimethylformamide (10 mL), sodium hydroxide (0.63 g, 15.61 mmol) was slowly added at 25 °C, and the resulting mixture was stirred for 0.5 hours. The aforementioned reaction mixture (active ester) was then added to this solution at 25 °C, and the mixture was stirred for another 6 hours at 25 °C. After the reaction was complete, the reaction mixture was poured into water (100 mL) and extracted with ethyl acetate (4 x 25 mL). The combined organic layers were washed with saturated saline solution (100 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid column chromatography to give solid 7-cyclopropyl-2-(ethylthio)-N-(3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide (0.7 g, 1.60 mmol, yield 30.7%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 10.04 (s, 1H), 8.69 (d, J = 4.9 Hz, 1H), 8.26 (s, 1H), 6.94 (dd, J = 7.8, 4.6 Hz, 2H), 3.24 (q, J = 7.3 Hz, 2H), 3.03 (d, J = 4.6 Hz, 3H), 2.93-2.84 (m, 1H), 1.46-1.36 (m, 5H), 1.34-1.30 (m, 2H);ESI MS (m/z) 438.35 (MH) ⁺ .

Step-2: 6-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine

A stirred solution of 7-cyclopropyl-2-(ethylthio)-N-(3-(methylamino)-6-(trifluoromethyl)darazin-4-yl)pyrazolo[1,5-a]pyrimidine-3-carbamate (0.7 g, 1.60 mmol) in acetic acid (10 mL) was heated at 110 °C for 16 hours. After the reaction was complete, the reaction mixture was evaporated under reduced pressure to give the residue. Water (100 mL) was added to the residue, and the mixture was extracted with ethyl acetate (2 x 100 mL). The combined organic layers were washed with saturated sodium bicarbonate aqueous solution (50 mL) and saturated salt aqueous solution (50 mL), dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to give the crude product. The crude product was purified by rapid column chromatography to give 6-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (0.5 g, 1.192 mmol, yield 74.5%) as a solid. ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.59 (d, J = 4.9 Hz, 1H), 8.53 (s, 1H), 6.91 (d, J = 4.9 Hz, 1H), 4.14 (s, 3H), 3.27 (q, J = 7.3 Hz, 2H), 2.93-2.88 (m, 1H), 1.43-1.38 (m, 5H), 1.32-1.27 (m, 2H);ESI MS (m/z) 420.40 (MH) ⁺ .

Step-3: 6-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine

The target compound, 6-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (145 mg, 0.321 mmol, yield 67.4%), was obtained. %) was prepared from 6-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (200 mg, 0.48 mmol) following the reaction conditions of step 7 of Example 1. ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.73 (d, J = 4.6 Hz, 1H), 8.69 (s, 1H), 7.17 (d, J = 4.6 Hz, 1H), 4.00 (s, 3H), 3.78 (q, J = 7.3 Hz, 2H), 2.95-2.89 (m, 1H), 1.49-1.44 (m, 2H), 1.32-1.22 (m, 5H);ESI MS (m/z) 452.20 (MH) ⁺ .

Example-7: Synthesis of 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (compound-8)

Step-1: 1,2-Diamino-4-(trifluoromethyl)pyridin-1-ium diphenylphosphinate

O-(aminooxyphosphine oxide) (4.03 g, 17.3 mmol) was added at 25 °C to a stirred solution of 4-(trifluoromethyl)pyridin-2-amine (2.0 g, 12.3 mmol) in dichloromethane (40 mL). The resulting reaction mixture was stirred at 25 °C for 16 hours. After the reaction was complete, the reaction mixture was diluted with diethyl ether (40 mL). The resulting solid was filtered, washed with ether (20 mL), and dried under reduced pressure to give a white solid of 1,2-diamino-4-(trifluoromethyl)pyridin-1-ium diphenylphosphinate (3.8 g, 9.6 mmol, yield 78%). ESI MS (m/z) 178.00 (MH) ⁺ .

Step-2: 2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine)

In a stirred solution of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (600 mg, 2.3 mmol) in dichloromethane (20 mL), triethylamine (0.95 mL, 6.8 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (481 mg, 2.5 mmol), and 1-hydroxybenzotriazole (339 mg, 2.5 mmol) were added. The resulting mixture was stirred at 25°C for 1 hour and then evaporated under reduced pressure to obtain the residue. The residue was dissolved in pyridine (10 mL), followed by the addition of 1,2-diamino-4-(trifluoromethyl)pyridin-1-ium diphenylphosphinate (1.17 g, 2.7 mmol). The resulting reaction mixture was stirred at 85°C for 16 hours. After the reaction was complete, the reaction mixture was cooled to 25°C and poured into ice water. The resulting solid was filtered, washed with water, and evaporated under reduced pressure to obtain a crude product, which was purified by rapid column chromatography to give 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (280 mg, 0.69 mmol; yield 30.4%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.23 (d, J = 7.1 Hz, 1H), 8.54-8.51 (m, 1H), 8.39 (q, J = 1.0 Hz, 1H), 7.46 (dd, J = 7.1, 2.0 Hz, 1H), 6.80 (d, J = 4.6 Hz, 1H), 3.28 (t, J = 7.3 Hz, 2H), 2.90-2.83 (m, 1H), 1.43 (t, J = 7.3 Hz, 3H), 1.38-1.29 (m, 2H), 1.27-1.23 (m, 2H);ESI MS (m/z) 405 (MH) ⁺ .

Step-3: 2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine)

In a stirred solution of 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (200 mg, 0.49 mmol) in dichloromethane (20 mL), chloroperoxybenzoic acid (276 mg, 1.04 mmol) was added at 0 °C. The resulting reaction mixture was stirred at 25 °C for 6 hours. After the reaction was complete, the reaction mixture was quenched with an aqueous sodium thiosulfate solution (100 mL) and extracted with dichloromethane (2 x 50 mL). The combined organic layers were washed with saturated sodium bicarbonate aqueous solution (2 x 50 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to give a crude product, which was purified by rapid column chromatography to give solid 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (70 mg, 0.160 mmol, yield 32.4%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.31 (d, J = 7.1 Hz, 1H), 8.69 (d, J = 4.4 Hz, 1H), 8.50 (t, J = 1.0 Hz, 1H), 7.57 (dd, J = 7.1, 2.0 Hz, 1H), 7.09 (d, J = 4.6 Hz, 1H), 3.93 (q, J = 7.4 Hz, 2H), 2.92-2.86 (m, 1H), 1.44-1.39 (m, 2H), 1.30-1.16 (m, 5H);ESI MS (m/z) 437.30 (MH) ⁺ .

Example-8: Synthesis of (7-cyclopropyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone ((7-cyclopropyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone (compound-36)

In a stirred solution of 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (500 mg, 1.24 mmol) in methanol (10 mL) and acetonitrile (10 mL), iodophenyl diacetic acid (1.19 g, 3.71 mmol) was added at 25 °C, followed by the addition of carbamic acid ammonium salt (290 mg, 3.71 mmol). The resulting reaction mixture was stirred at 25°C for 16 hours. After the reaction was complete, the reaction mixture was concentrated and the residue was purified by rapid tube chromatography to give solid (7-cyclopropyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ6-sulfanone (100 mg, 0.230 mmol, yield 18.58%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.31 (d, J = 7.3 Hz, 1H), 8.69 (d, J = 4.4 Hz, 1H), 8.51 (t, J = 1.0 Hz, 1H), 7.56 (dd, J = 7.1, 2.0 Hz, 1H), 7.05 (d, J = 4.4 Hz, 1H), 5.16 (s, 1H), 3.80-3.67 (m, 2H), 2.92-2.85 (m, 1H), 1.42-1.40 (m, 2H), 1.38-1.32 (m, 3H), 1.29-1.26 (m, 2H);ESI MS (m/z) 435.50 (MH) ⁺ .

Example 9: Synthesis of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid

Step-1: Ethyl 2-(ethylthio)-7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylate

In a stirred solution of ethyl 5-amino-3-(ethylthio)-1H-pyrazole-4-carboxylate (10 g, 46.5 mmol) in acetic acid (250 mL), methyl 3,3-dimethoxypropanoate (9.9 mL, 69.7 mmol) was added at 25 °C. The resulting reaction mixture was stirred at 120 °C for 18 hours. After the reaction was complete, the acetic acid was evaporated under reduced pressure, and the residue was diluted with ice-cold water (500 mL). The resulting solid was filtered and washed with water (500 mL) and hexane (500 mL), and dried under reduced pressure to give ethyl 2-(ethylthio)-7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylate (10 g, 37.4 mmol; yield 81%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 11.87 (s, 1H), 7.76 (d, J = 7.6 Hz, 1H), 5.91 (d, J = 7.6 Hz, 1H), 4.29 (q, J = 7.1 Hz, 2H), 3.10-3.17 (m, 2H), 1.32-1.37 (m, 3H), 1.26-1.32 (m, 3H);ESI MS (m/z) 268 (MH) ⁺ .

Step-2: Ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate

The target compound, ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (5 g, 15.1 mmol, 81% yield), was prepared from ethyl 2-(ethylthio)-7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylate (5 g, 18.7 mmol) under the reaction conditions of step 6 of Example 1. ¹ H-NMR (400 MHz, CHLOROFORM-d) δ 8.43 (d, J = 4.6 Hz, 1H), 7.20 (d, J = 4.6 Hz, 1H), 4.47 (q, J = 7.1 Hz, 2H), 3.30 (q, J = 7.4 Hz, 2H), 1.47-1.51 (m, 3H), 1.42-1.60 (m, 3H);ESI MS (m/z) 331.75 (MH) ⁺ .

Step-3: Ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate

In a stirred solution of ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (7 g, 21.2 mmol), cyclopropylboronic acid (7.28 g, 85 mmol), and tripotassium phosphate (13.45 g, 63.6 mmol) in 1,4-dioxane (70 ml), [1,1'-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane adduct (1.73 g, 2.1 mmol) was added under nitrogen purging. The resulting reaction mixture was stirred at 90°C for 3 hours. After the reaction was complete, the mixture was cooled to 25°C and filtered with diatomaceous earth ( ^celite® ). The filtrate was diluted with water (50 mL) and extracted with ethyl acetate (4 x 50 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to give a crude product, which was purified by rapid column chromatography to give ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (3 g, 10.3 mmol; yield 48.6%). ¹ H-NMR (400 MHz, CHLOROFORM-d) δ 8.55 (d, J = 4.8 Hz, 1H), 6.39 (d, J = 4.8 Hz, 1H), 4.53-4.44 (m, 2H), 3.35-3.24 (m, 2H), 1.50-1.37 (m, 8H), 1.22-1.12 (m, 2H);ESI MS (m/z) 291.95 (MH) ⁺ .

Step-4: 7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid

In a stirred solution of 3 g (10.3 mmol) of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate in ethanol (30 mL), lithium hydroxide monohydrate (4.32 g, 103 mmol) dissolved in water (30 mL) was added at 25 °C. The resulting reaction mixture was stirred at 60 °C for 4 hours. After the reaction was complete, the mixture was cooled to 25 °C and evaporated under reduced pressure to obtain a residue, which was acidified with concentrated hydrochloric acid. The resulting solid was filtered and dried under reduced pressure to give 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (2.2 g, 8.4 mmol; yield 81%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.51 (d, J = 4.9 Hz, 1H), 6.81 (d, J = 4.8 Hz, 1H), 3.20-3.14 (m, 2H), 2.85-2.73 (m, 1H), 1.38 (t, J = 7.3 Hz, 3H), 1.35-1.31 (m, 2H), 1.24-1.20 (m, 2H);ESI MS (m/z) 264.00 (MH) ⁺ .

Example-10: Synthesis of N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (Compound-99)

Step-1: 2-(Chloromethyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridine

In a mixture of 13.0 g (80.0 mmol) of 5-(trifluoromethyl)pyridin-2-amine (ethanol) in 150 mL of stirred solution, 1,3-dichloroprop-2-one (20.36 g (160.0 mmol)) was added, and the resulting reaction mixture was stirred at 90 °C for 24 hours. After the reaction was complete, the mixture was poured into a saturated sodium bicarbonate aqueous solution (400 mL). The aqueous layer was extracted with ethyl acetate (2 x 200 mL). The combined organic layers were washed with a saline aqueous solution (200 mL), dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to give the crude product. The crude product was purified by rapid column chromatography to give 2-(chloromethyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridine (10.54 g, 44.9 mmol, yield 56%) in liquid form. ¹ H-NMR (400 MHz, CHLOROFORM-d) δ 8.46 (td, J = 2.1, 1.1 Hz, 1H), 7.72 (d, J = 0.5 Hz, 1H), 7.67 (dd, J = 9.5, 0.7 Hz, 1H), 7.34 (dd, J = 9.5, 1.7 Hz, 1H), 4.76 (d, J = 0.5 Hz, 2H); ESI MS (m/z) 235.80 (MH) ⁺ .

Step-2: 2-(6-(Trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)acetonitrile

Trimethylsilyl cyanide (15.43 mL, 115.0 mmol) and tetrabutyl ammonium fluoride (115 mL, 115.0 mmol) were added to a stirred solution of 2-(chloromethyl)-6-(trifluoromethyl)imidazo[1,2-a]pyridine (18.0 g, 77.0 mmol) in acetonitrile (180 mL). The resulting reaction mixture was stirred at 25 °C for 48 hours. After the reaction was complete, the reaction mixture was poured into water (300 mL). The aqueous layer was extracted with ethyl acetate (3 x 100 mL); the combined organic layer was washed with saturated sodium brine (50 mL), dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to give the crude product. The crude product was purified by rapid column chromatography to give the desired solid 2-(6-(Trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)acetonitrile (14.2 g, 63.1 mmol, yield 82%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.50-8.49 (m, 1H), 7.76 (d, J = 0.7 Hz, 1H), 7.67 (d, J = 9.5 Hz, 1H), 7.38 (dd, J = 9.4, 1.8 Hz, 1H), 3.96 (d, J = 0.7 Hz, 2H);ESI MS (m/z) 226.0 (MH) ⁺ .

Step-3: 3,3-bis(Ethylthio)-2-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)acrylonitrile

To a stirred solution of potassium hydroxide (7.47 g, 133 mmol) in acetonitrile (300 mL) at 25 °C, 2-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)acetonitrile (15.0 g, 66.6 mmol) was added. The resulting reaction mixture was stirred at 25 °C for 1 hour and cooled to -5 °C, followed by dropwise addition of carbon disulfide (4.0 mL, 66.6 mmol) over 10 minutes. The resulting reaction mixture was stirred at -5 °C for 1 hour, followed by dropwise addition of ethyl iodine (10.8 mL, 133.0 mmol) over 15 minutes. The mixture was stirred at 0°C for 2 hours, followed by stirring at 25°C for 16 hours. The volatile solvent was evaporated under reduced pressure to give a crude product, which was purified by rapid column chromatography to give solid 3,3-bis(Ethylthio)-2-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)acrylonitrile (17.14 g, 48.0 mmol, yield 72%). ESI MS (m/z) 358.2 (MH) ⁺ .

Step-4: 3-(Ethylthio)-4-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)-1H-pyrazol-5-amine

In a stirred solution of 19.0 g (53.2 mmol) of 3,3-bis(Ethylthio)-2-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)acrylonitrile ( ...200 mL) and ethanol (200 mL) at 0 °C, hydrazine hydrate (3.9 mL, 80.0 mmol) was added dropwise. The reaction mixture was stirred at 25 °C for The combined organic layers were washed with a saturated brine solution (100 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain solid 3-(ethylthio)-4-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)-1H-pyrazol-5-amine (13 g, 39.7 mmol, yield 74.7%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 11.88 (s, 1H), 9.26 (s, 1H), 8.25 (s, 1H), 7.68 (d, J = 9.3 Hz, 1H), 7.42 (dd, J = 9.5, 1.7 Hz, 1H), 6.05 (s, 2H), 2.95 (d, J = 6.1 Hz, 2H), 1.27 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 328.0 (MH) ⁺ .

Step-5: 2-(Ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (2-(Ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one)

In a stirred solution of 3-(ethylthio)-4-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)-1H-pyrazol-5-amine (9.0 g, 27.5 mmol) and methyl 3,3-dimethoxypropionate (4.7 mL, 33.0 mmol) in toluene (150 mL), p-toluenesulfonic acid monohydrate (15.7 g, 82.0 mmol) was added. The resulting reaction mixture was heated at 130 °C for 6 hours. After the reaction was complete, the reaction mixture was cooled to 25 °C, and the solvent was removed under reduced pressure. Water (200 mL) was added to the residue and extracted with DCM (2 x 100 mL). The combined organic layers were washed with a saturated sodium bicarbonate aqueous solution (100 mL), dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product, which was washed with n-hexane (2 x 250 mL) to give the desired solid 2-(ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (7 g, 18.45 mmol, yield 67.1%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 11.81 (s, 1H), 9.34 (s, 1H), 8.36 (d, J = 5.9 Hz, 1H), 7.76-7.72 (m, 1H), 7.54 (ddd, J = 9.4, 5.6, 1.8 Hz, 1H), 6.99 (dd, J = 15.9, 7.3 Hz, 1H), 5.82 (d, J = 7.6 Hz, 1H), 3.70 (s, 2H), 1.40 (td, J = 7.3, 3.4 Hz, 3H); ESI MS (m/z) 379.7 (MH) ⁺ .

Step-6: 7-Bromo-2-(ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine

In a stirred solution of 2-(ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (9.8 g, 25.8 mmol) in acetonitrile (500 mL), phosphorus oxybromide (29.6 g, 103 mmol) and potassium carbonate (14.28 g, 103.0 mmol) were slowly added. The resulting reaction mixture was stirred at 95 °C for 16 hours. After the reaction was complete, the reaction mixture was cooled to 25°C and poured into a saturated sodium bicarbonate aqueous solution (400 mL). The aqueous layer was washed with ethyl acetate (2 x 500 mL), while the combined organic layer was washed with a salt solution (100 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain a crude solid. The crude product was purified by rapid column chromatography to give 7-bromo-2-(ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine (5 g, 11.31 mmol, yield 43.8%), presenting as the desired solid. ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.33 (d, J = 1.33 Hz, 1H), 8.66 (d, J = 0.5 Hz, 1H), 8.44 (d, J = 4.4 Hz, 1H), 7.77 (dd, J = 9.5, 0.7 Hz, 1H), 7.51 (d, J = 4.6 Hz, 1H), 7.46-7.43 (m, 1H), 3.30-3.24 (m, 2H), 1.47-1.40 (m, 3H);ESI MS (m/z) 443.3 (MH) ⁺ .

Step-7: 7-Bromo-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine

In an ice-cold solution of 7-bromo-2-(ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine (2.84 g, 6.42 mmol) in dichloromethane (120 mL), 3-chloroperoxybenzoic acid (4.43 g, 15.41 mmol) was added, and the resulting reaction mixture was stirred at 25 °C for 6 hours. After the reaction was complete, the reaction mixture was diluted with dichloromethane (200 mL). The organic layer was washed with saturated sodium bicarbonate aqueous solution (2 x 50 mL), sodium thiosulfate (2 x 30 mL), and saturated salt aqueous solution (2 x 50 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid column chromatography to give solid 7-bromo-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine (1.4 g, 2.95 mmol, yield 46.0%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.39 (s, 1H), 8.66-8.64 (m, 2H), 7.88 (d, J = 4.4 Hz, 1H), 7.82 (d, J = 9.8 Hz, 1H), 7.52 (dd, J = 9.5, 2.0 Hz, 1H), 4.09 (q, J = 7.4 Hz, 2H), 1.25 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 475.9 (MH) ⁺ .

Step-8: N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine

In a stirred solution of 7-bromo-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine (250 mg, 0.53 mmol) in N,N-dimethylformamide (3 mL), triethylamine (0.22 mL, 1.58 mmol) and N-methyl-tert-butylamine (115 mg; 1.32 mmol) were added. The resulting reaction mixture was stirred at 25 °C for 4 hours. After the reaction was complete, the reaction mixture was poured into water (25 mL). The aqueous layer was extracted with ethyl acetate (3 x 10 mL), the combined organic layer was washed with a saline solution (10 mL), dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid column chromatography to give N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (85 mg, 0.177 mmol, yield 33.6%), which was a yellow solid. ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.36 (s, 1H), 8.65 (d, J = 7.6 Hz, 1H), 8.49 (d, J = 4.9 Hz, 1H), 7.78 (d, J = 7.5 Hz, 1H), 7.48 (d, J = 7.7 Hz, 1H), 6.95 (d, J = 5.1 Hz, 1H), 4.04 (q, J = 7.4 Hz, 2H), 3.09 (s, 3H), 1.45 (s, 9H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 481.10 (MH) ⁺ .

Example-11: Synthesis of 2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (compound-115)

Step-1: 1,2-Diamino-5-(trifluoromethyl)pyridin-1-ium diphenylphosphinate

In a mixture of 5-(trifluoromethyl)pyridin-2-amine (30 g, 185 mmol) and dichloromethane (500 mL), O-(aminooxyphosphine oxide) (43.2 g, 185 mmol) was added at 25 °C. The resulting reaction mixture was stirred for 18 hours. After the reaction was complete, the mixture was diluted with hexane (250 mL). The resulting precipitate was filtered, washed with ether (200 mL), and dried under reduced pressure to obtain a white solid, 1,2-diamino-5-(trifluoromethyl)pyridin-1-ium diphenylphosphinate (44 g, 111 mmol, yield 60.1%); ESI MS (m/z) 178.10 (MH) ⁺ .

Step-2: 2-(ethylthio)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (2-(ethylthio)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one)

In a stirred solution of 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylic acid (15.13 g, 63.2 mmol) and 1,2-diamino-5-(trifluoromethyl)pyridin-1-ium diphenylphosphinate (25 g, 63.2 mmol) in pyridine (250 mL), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide) Hydrochloride (18.18 g, 95 mmol) and 1-hydroxybenzotriazole hydrate (1H-1,2,3-benzotriazol-1-ol hydrate) (10.82 g, 63.2 mmol) were added at 25 °C. The resulting reaction mixture was stirred at 85 °C for 16 hours. After the reaction was complete, the reaction mixture was cooled to 25 °C, and the volatiles were removed under reduced pressure. The residue was diluted with water (1000 mL), and the aqueous layer was extracted with ethyl acetate (3 x 500 mL). The combined organic layers were washed with 1N HCl solution (500 mL), dried over anhydrous sodium sulfate, filtered, and concentrated to give a crude product, which was purified by rapid column chromatography to give 2-(ethylthio)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (9 g, 23.66 mmol, yield 37.4%). ^¹H -NMR (400 MHz, DMSO- d6 ) δ 11.93 (brs, 1H), 9.60 (d, J = 1.2 Hz, 1H), 7.98 (d, J = 1.2 Hz, 2H), 7.85 (d, J = 6.0 Hz, 1H), 5.89 (d, J = 3.2 Hz, 1H), 3.24 (q, J = 7.6 Hz, 2H), 1.39 (t, J = 7.6Hz, 3H);ESI MS (m/z) 380.9 (MH) ⁺ .

Step-3: 2-(7-chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine

POCl₃ (22.05 mL, 237 mmol) was added to a stirred solution of 2-(ethylthio)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (9 g, 23.66 mmol) in toluene (100 mL) and acetonitrile (100 mL). The resulting reaction mixture was stirred at ₁₀₀ °C for 10 hours. After the reaction was complete, the reaction mixture was cooled to 25°C and poured into ice water (1000 mL). The aqueous layer was extracted with ethyl acetate (2 x 500 mL), and the combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated to give a crude product, which was purified by rapid column chromatography to give 2-(7-chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (6.1 g, 15.30 mmol, yield 64.6%). ESI MS (m/z) 399.0 (MH) ⁺ .

Step-4: 2-(7-chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine)

In a stirred solution of 2-(7-chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (6 g, 15.05 mmol) in 120 mL of dichloromethane, m-CPBA (8.79 g, 33.1 mmol) was added at 0 °C, and the resulting reaction mixture was stirred at 25 °C for 3 hours. After the reaction was complete, the reaction mixture was quenched with 10% sodium thiosulfate aqueous solution (100 mL). The aqueous layer was extracted with dichloromethane (2 x 250 mL), the combined organic layer was washed with saturated sodium bicarbonate solution (2 x 250 mL), dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the crude product, which was purified by rapid column chromatography to give 2-(7-chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (6.1 g, 14.16 mmol, (Yield 94%). ^¹H -NMR (400 MHz, DMSO- d⁶ ) δ 9.83 (s, ¹H), 8.80 (d, J = 4.8 Hz, ¹H), 8.14 (d, J = 9.6 Hz, ¹H), 8.04–8.01 (m, ¹H), 8.82 (d, J = 4.4 Hz, ¹H), 3.95 (q, J = 7.2 Hz, 2H), 1.28 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 430.9 (MH) ^⁺ .

Step-5: 1-(2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)ethan-1-one (1-(2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)ethan-1-one)

In a stirred solution of 2-(7-chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (800 mg, 1.86 mmol) in 1,4-dioxane (20 mL), tributyl(1-ethoxyvinyl)stannane (805 mg, 2.228 mmol) was added. The resulting mixture was purged with nitrogen for five minutes and treated with tetrakis(triphenylphosphine)palladium(0) (129 mg, 0.111 mmol), followed by stirring at 90 °C for 2 hours. After the reaction was complete, the reaction mixture was filtered and concentrated under reduced pressure to obtain the residue, which was dissolved in a 4.0 M dioxane hydrochloride solution (112 mL). The resulting reaction mixture was stirred at 25 °C for 2 hours, extracted with ethyl acetate (100 mL), and washed with saturated saline aqueous solution (2 x 100 mL). The organic layer was dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which was purified by rapid column chromatography to give 1-(2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)ethan-1-one (450 mg, 1.03 mmol, yield 56.3%). ESI MS (m/z) 439.1 (MH) ⁺ .

Step-6: 2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine)

DAST (0.24 ml, 1.83 mmol) was added at 0 °C to a stirred solution of 200 mg (0.46 mmol) of 1-(2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)ethan-1-one in dichloromethane (10 mL). The resulting reaction mixture was stirred at 25 °C for 2 hours. After the reaction was complete, the reaction mixture was quenched with ice-cold water (100 mL). The aqueous layer was extracted with dichloromethane (2 x 50 mL), and the combined organic layer was dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the crude product, which was purified by rapid column chromatography to give 2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine) (175 mg, 0.380 mmol, yield 83%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.83 (s, 1H), 8.99 (d, J = 4.4 Hz, 1H), 8.15 (d, J = 9.3 Hz, 1H), 8.03 (dd, J = 9.5, 1.7 Hz, 1H), 7.69 (d, J = 4.4 Hz, 1H), 3.91 (q, J = 7.4 Hz, 2H), 2.39-2.29 (m, 3H), 1.28 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 461.2 (MH) ⁺ .

Example 12: Synthesis of 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylic acid

Step-1: ethyl 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylate

A mixture of ethyl 5-amino-3-(ethylthio)-1H-pyrazole-4-carboxylate (25 g, 116 mmol) and methyl 3,3-dimethoxypropionate (19.76 mL, 139 mmol) in acetic acid (250 mL) was stirred at 110 °C for 18 hours. After the reaction was complete, the reaction mixture was cooled to 25 °C, and the acetic acid was removed under reduced pressure. The residue was diluted with cold water (1 L) to give a precipitate, which was filtered and washed with water (1 L) and hexane (500 mL), and dried to give ethyl 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylate (30 g, 112 mmol, yield 97%). ESI MS (m/z) 268.0 (MH) ⁺ .

Step-2: 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylic acid

In a stirred ethanol (250 mL) solution of ethyl 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylate, sodium hydroxide (29.9 g, 748 mmol) dissolved in water (250 mL) was added at 25 °C. The resulting reaction mixture was stirred at 70 °C for 16 hours. After the reaction was complete, the reaction mixture was cooled to 25 °C and the solvent was evaporated. The residue was acidified with concentrated hydrochloric acid (pH=1). The resulting precipitate was filtered and dried to give 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylic acid (15.5 g, 64.8 mmol, yield 87%). ESI MS (m/z) 239.85 (MH) ⁺ .

Example-13: Synthesis of 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole (2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole) (compound-198)

Step 1: 2-nitro-4-((trifluoromethyl)thio)phenol

In a stirred solution of 4-((trifluoromethyl)thio)phenol (40 g, 206 mmol) in acetic acid (177 mL, 0.309 mol), a mixture of nitric acid (17.5 mL, 247 mmol) and acetic acid (11.8 mL, 206 mmol) was added dropwise, followed by sulfuric acid (12.3 mL, 227 mmol), while maintaining the internal temperature at 10°C. The reaction mixture was stirred at 25°C for 3 hours. After the reaction was complete, the mixture was poured into ice water (1.5 L), and the yellow solid precipitate was filtered and washed with water (4 x 1 L). The product was dried under vacuum to give the desired 2-nitro-4-((trifluoromethyl)thio)phenol (46 g, 192 mmol, yield 93%). ^¹H -NMR (400 MHz, CHLOROFORM-d) δ 10.78 (s, 1H), 8.45 (d, J = 2.4 Hz, 1H), 7.84 (dd, J = 8.8 Hz, 2.0 Hz, 1H), 7.24 (d, J = 8.8 Hz, 1H); ESI MS (m/z) 237.8 (MH) ^- .

Step-2: 2-amino-4-((trifluoromethyl)thio)phenol

Iron powder (28.0 g, 502 mmol) and ammonium chloride (89 g, 1.67 mol) in water (400 mL) were added to a stirred ethanol (400 mL) solution of 2-nitro-4-((trifluoromethyl)thio)phenol (40 g, 167 mmol) at 25 °C. The reaction mixture was stirred at 70 °C for 18 hours. After the reaction was complete, the reaction mixture was filtered through a diatomaceous earth mat and washed with ethyl acetate (2 L). The filtrate was washed with brine (1 L), dried over anhydrous sodium sulfate, filtered, and concentrated to obtain a crude product, which was purified by rapid column chromatography to give 2-amino-4-((trifluoromethyl)thio)phenol (30 g, 143 mmol, yield 86%). ESI MS (m/z) 208.4 (MH) ^- .

Step-3: 2-cyano-N-(2-hydroxy-5-((trifluoromethyl)thio)phenyl)acetamide

In a stirred solution of 2-cyanoacetic acid (30.5 g, 359 mmol) in dichloromethane (500 mL), N,N-diisopropylethylamine (75 mL, 430 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (41.2 g, 215 mmol), and 2-amino-4-((trifluoromethyl)thio)phenol (30 g, 143 mmol) were added sequentially at 25 °C. The reaction mixture was stirred at 25 °C for 18 hours. After the reaction was complete, the reaction mixture was diluted with water (1 L) and extracted with dichloromethane (2 x 500 mL). The combined organic layers were washed with water (500 mL) and saturated salt solution (500 mL), dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which was purified by rapid column chromatography to give 2-cyano-N-(2-hydroxy-5-((trifluoromethyl)thio)phenyl)acetamide (13 g, 47.1 mmol, yield 32.8%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 10.92 (s, 1H), 9.73 (s, 1H), 8.27 (d, J = 2.0 Hz, 1H), 7.31 (dd, J = 8.8 Hz, 2.0 Hz, 1H), 6.99 (d, J = 8.8 Hz, 1H), 4.01 (s, 2H);ESI MS (m/z) 274.9 (MH) ^- .

Step-4: 2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acetonitrile

POCl₃ (37.1 mL, 398 mmol) was added to a stirred solution of 2-cyano-N-(2-hydroxy-5-((trifluoromethyl)thio)phenyl)acetamide (11 g, 39.8 mmol) in toluene (200 mL), and the reaction mixture was stirred at ₁₀₀ °C for 8 hours. After the reaction was complete, the mixture was cooled to 25 °C and concentrated under reduced pressure. The residue was diluted with water (500 mL) and extracted with ethyl acetate (2 x 500 mL). The combined organic layers were dried with anhydrous sodium sulfate, filtered and concentrated to obtain a crude product, which was purified by rapid column chromatography to obtain the desired 2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acetonitrile (5 g, 19.36 mmol, yield 48.6%). ¹ H-NMR (400 MHz, CHLOROFORM-d) δ 8.08 (d, J = 2.0 Hz, 1H), 7.72 (dd, J = 8.8 Hz, 1.6 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 4.14 (s, 2H); ESI MS (m/z) 256.9 (MH) ^- .

Step-5: 3,3-bis(ethylthio)-2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acrylonitrile

Potassium hydroxide (3.19 g, 56.9 mmol) was added at 0 °C to a stirred solution of 200 mL of acetonitrile containing 7 g (27.1 mmol) of 2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acetonitrile. The resulting reaction mixture was stirred at 25 °C for 1 hour. After 1 hour, the reaction mixture was cooled to 0 °C and carbon disulfide (1.96 mL, 32.5 mmol) was added dropwise over 10 minutes. The reaction mixture was stirred at 25°C for 1 hour, followed by the dropwise addition of ethyl iodine (8.75 mL, 108 mmol) over 10 minutes at 0°C. The reaction mixture was then stirred at 25°C for 16 hours. After the reaction was complete, the reaction mixture was diluted with water (500 mL). The resulting precipitate was filtered, washed with water (200 mL), and dried under reduced pressure to give crude product 3,3-bis(ethylthio)-2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acrylonitrile (10 g, 25.6 mmol, yield 94%), which was used in the next step without any further purification. ¹ H-NMR (400 MHz, CHLOROFORM-d) δ 8.13 (d, J = 2.0 Hz, 1H), 7.68 (dd, J = 8.8 Hz, 1.6 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 3.31-3.19 (m, 4H), 1.45-1.34 (m, 6H);ESI MS (m/z) 390.8 (MH) ⁺ .

Step-6: 3-(ethylthio)-4-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)-1H-pyrazol-5-amine

In a stirred solution of 3,3-bis(ethylthio)-2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acrylonitrile (8 g, 20.49 mmol) in acetonitrile (100 mL) and ethanol (100 mL), hydrazine hydrate (5.1 mL, 102 mmol) was added at 25 °C. The resulting reaction mixture was stirred at 75 °C for 16 hours. After the reaction was complete, the reaction mixture was cooled to 25 °C and concentrated under reduced pressure. The resulting residue was diluted with cold water (500 mL) and extracted with ethyl acetate (3 x 250 mL). The combined organic layers were dried with anhydrous sodium sulfate, filtered, and concentrated to obtain a crude product, which was purified by rapid column chromatography to give the desired 3-(ethylthio)-4-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)-1H-pyrazol-5-amine (3.6 g, 9.99 mmol, yield 48.8%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 12.10 (s, 1H), 7.93 (d, J = 1.6 Hz, 1H), 7.78 (d, J = 8.4 Hz, 1H), 7.57 (dd, J = 8.8 Hz, 2.0 Hz, 1H), 6.52 (s, 2H), 3.06 (q, J = 7.2 Hz, 2H), 1.32 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 360.9 (MH) ⁺ .

Step-7: 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole

In a stirred solution of 3-(ethylthio)-4-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)-1H-pyrazol-5-amine (800 mg, 2.22 mmol) in acetic acid (20 mL), (E)-1-cyclopropyl-3-(dimethylamino)prop-2-en-1-one (618 mg, 4.44 mmol) was added at 25 °C, and the resulting reaction mixture was stirred at 110 °C for 3 hours. After the reaction was complete, the reaction mixture was cooled to 25°C and concentrated under reduced pressure to obtain the residue. The residue was diluted with water (200 mL), and the precipitated solid was filtered, washed with water (200 mL) and ether (50 mL), and dried under reduced pressure to give 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole (800 mg, 1.833 mmol, yield 83%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.64 (d, J = 4.8 Hz, 1H), 8.12 (d, J = 1.6 Hz, 1H), 7.94 (d, J = 4.8 Hz, 1H), 7.68 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 6.92 (d, J = 4.4 Hz, 1H), 3.33 (q, J = 7.2 Hz, 2H), 2.91-2.84 (m, 1H), 1.44 (t, J = 7.2 Hz, 3H), 1.42-1.36 (m, 2H), 1.31-1.26 (m, 2H);ESI MS (m/z) 437.3 (MH) ⁺ .

Step-8: 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole (2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole)

The target compound, 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole (150 mg, 0.300 mmol, yield 32.7%), was obtained. %) was prepared by 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole (400 mg, 0.916 mmol) following the reaction conditions of step 7 of Example 1. ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.86 (d, J = 4.8 Hz, 1H), 8.65 (d, J = 1.2 Hz, 1H), 8.30 (d, J = 8.0 Hz, 1H), 8.19 (dd, J = 8.4 Hz, 1.6 Hz, 1H), 7.21 (d, J = 4.4 Hz, 1H), 3.97 (q, J = 7.6 Hz, 2H), 2.94-2.87 (m, 1H), 1.48-1.43 (m, 2H), 1.34-1.28 (m, 5H);ESI MS (m/z) 500.9 (MH) ⁺ .

Example-14: Synthesis of ((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone (((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone) (compound-204)

Step-1: 2-(6-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2-(6-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine)

In a stirred solution of 2-(ethylthio)-4-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-1H-pyrazol-5-amine (2.3 g, 6.72 mmol) in ethanol (23 mL) and acetic acid (0.38 mL, 6.72 mmol), 2-bromomalondialdehyde (1.217 g, 8.06 mmol) was added, and the resulting reaction mixture was stirred at 85 °C for 5 hours. After the reaction was complete, the reaction mixture was cooled to 25 °C. The resulting solid was filtered, washed with hexane, and dried under reduced pressure to give 2-(6-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (1.4 g, 3.06 mmol, yield 45.6%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 9.75 (d, J = 2.4 HZ, 1H), 8.78 (d, J = 2.4 HZ, 1H), 8.76-8.75 (m, 1H), 8.54-8.51 (m, 1H), 3.91 (s, 3H), 3.21 (q, J = 7.2 Hz, 2H), 1.36 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 456.90 (MH) ⁺ .

Step-2: ((2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone (((2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone)

In a stirred solution of 2-(6-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (0.20 g, 0.44 mmol) in toluene (6 mL), iminodimethyl-λ6-sulfanone (0.06 g, 0.66 mmol) and tripotassium phosphate (0.186 g, 0.87 mmol) were added sequentially, and the reaction mixture was degassed under a nitrogen atmosphere for 5 minutes. Next, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (42 mg, 0.09 mmol) and tris(dibenzylideneacetone)dipalladium(0) (40 mg, 0.044 mmol) were added, and the resulting reaction mixture was stirred at 110°C for 5 hours. After the reaction was complete, the reaction mixture was cooled to 25°C, filtered and concentrated to obtain a crude product, which was purified by rapid column chromatography to give ((2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone (((2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone) (106 mg, 0.226 mmol, yield 51.7%). ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.74-8.73 (m, 1H), 8.63 (d, J = 2.4 Hz, 1H), 8.50-8.49 (m, 1H), 8.40 (d, J = 2.4 Hz, 1H), 3.93 (s, 3H), 3.36 (s, 6H), 3.18 (q, J = 7.2 Hz, 2H), 1.35 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 469.90 (MH) ⁺ .

Step-3: ((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone (((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone)

The target compound ((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone (((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone) (64 mg, 0.128 mmol, yield 37.4%) It is prepared by ((2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone (((2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-λ6-sulfanone) (160 mg, 0.341 mmol) following the reaction conditions of step 7 of Example 1. ¹ H-NMR (400 MHz, DMSO- d6 ) δ 8.84.8.83 (m, 1H), 8.78 (d, J = 2.4 Hz, 1H), 8.60 (d, J = 1.2 Hz, 1H), 8.53 (d, J = 2.4 Hz, 1H), 3.78 (s, 3H), 3.69 (q, J = 7.6 Hz, 2H), 3.41 (s, 6H), 1.24 (t, J = 7.6 Hz, 3H); ESI MS (m/z) 502.0 (MH) ⁺ .

Table A: Representative compounds disclosed herein were prepared according to the appropriate methods described in the corresponding procedures and examples. Compound number Structure Analyze data 1 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.62 (s, 1H), 8.83 (d, J = 1.5 Hz, 1H), 8.60 (d, J = 1.5 Hz, 1H), 7.31 (d, J = 8.1 Hz, 1H), 6.18 (d, J = 7.8 Hz, 1H), 3.87 (s, 3H), 3.71 (s, 3H), 3.50 (q, J = 7.3 Hz, 2H), 1.20 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 455.95 (MH)+.} 2 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.99 (s, 1H), 8.81 (q, J = 0.9 Hz, 1H), 8.58-8.57 (m, 1H), 8.42 (d, J = 5.4 Hz, 1H), 6.71 (d, J = 5.6 Hz, 1H), 3.78-3.72 (m, 5H), 2.77-2.72 (m, 1H), 1.24 (t, J = 7.4 Hz, 3H), 0.94-0.87 (m, 2H), 0.83-0.79 (m, 2H);ESI MS (m/z) 466.05 (MH)+.} 3 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (t, J = 1.0 Hz, 1H), 8.58 (d, J = 2.2 Hz, 1H), 8.45 (d, J = 5.4 Hz, 1H), 6.87 (d, J = 5.6 Hz, 1H), ESI MS (m/z) 480.45 (MH)+.} 4 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.09 (s, 1H), 8.82 (t, J = 1.0 Hz, 1H), 8.59 (d, J = 1.5 Hz, 1H), 8.48 (d, J = 5.4 Hz, 1H), 6.90 (d, J = 5.6 Hz, 1H), 4.44 (d, J = 8.1 Hz, 2H), 3.81-3.76 (m, 5H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 508.00 (MH)+.} 5 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84 (t, J = 1.0 Hz, 1H), 8.69 (d, J = 4.4 Hz, 1H), 8.61 (d, J = 2.0 Hz, 1H), 7.13 (d, J = 4.6 Hz, 1H), 3.78-3.73 (m, 5H), 2.97-2.88 (m, 1H), 1.47-1.42 (m, 2H), 1.31-1.21 (m, 5H); ESI MS (m/z) 451.00 (MH)+.} 6 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.36 (s, 1H), 8.84 (q, J = 0.9 Hz, 1H), 8.71 (d, J = 5.1 Hz, 1H), 8.61 (q, J = 0.9 Hz, 1H), 8.00 (d, J = 5.1 Hz, 1H), 3.81-3.73 (m, 5H), 2.44 (s, 3H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 468.35 (MH)+.} 7 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.75 (s, 1H), 8.83 (d, J = 1.5 Hz, 1H), 8.59 (d, J = 1.5 Hz, 1H), 8.57 (d, J = 5.4 Hz, 1H), 6.87 (d, J = 5.4 Hz, 1H), 3.78-3.72 (m, 5H), 1.82 (dd, J = 8.4, 5.5 Hz, 2H), 1.58 (dd, J = 8.6, 5.6 Hz, 2H), 1.25 (t, J = 7.4 Hz, 3H);ESI MS (m/z) 491.00 (MH)+.} 8 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.31 (d, J = 7.1 Hz, 1H), 8.69 (d, J = 4.4 Hz, 1H), 8.50 (t, J = 1.0 Hz, 1H), 7.57 (dd, J = 7.1, 2.0 Hz, 1H), 7.09 (d, J = 4.6 Hz, 1H), 3.93 (q, J = 7.4 Hz, 2H), 2.92-2.86 (m, 1H), 1.44-1.39 (m, 2H), 1.30-1.16 (m, 5H); ESI MS (m/z) 437.30 (MH)+.} 9 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.80 (t, J = 0.8 Hz, 1H), 8.69 (d, J = 4.6 Hz, 1H), 8.12 (d, J = 9.2 Hz, 1H), 8.01 (dd, J = 9.5, 1.8 Hz, 1H), 7.08 (d, J = 4.6 Hz, 1H), 3.93 (q, J = 7.4 Hz, 2H), 2.92-2.86 (m, 1H), 1.44-1.39 (m, 2H), 1.30-1.22 (m, 5H); ESI MS (m/z) 436.90 (MH)+.} 10 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.36 (s, 1H), 8.68-8.67 (m, 2H), 8.45 (d, J = 5.4 Hz, 1H), 7.77 (d, J = 8.8 Hz, 1H), 7.47 (dd, J = 9.5, 2.0 Hz, 1H), 6.64 (d, J = 5.1 Hz, 1H), 4.10 (q, J = 7.3 Hz, 2H), 2.77-2.72 (m, 1H), 1.22 (t, J = 7.3 Hz, 3H), 0.92-0.87 (m, 2H), 0.81-0.77 (m, 2H);ESI MS (m/z) 451.05 (MH)+.} 11 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84 (d, J = 1.5 Hz, 1H), 8.61 (d, J = 1.5 Hz, 1H), 8.15 (d, J = 6.8 Hz, 1H), 6.84 (d, J = 6.8 Hz, 1H), 3.74 (s, 3H), 3.60 (q, J = 7.4 Hz, 2H), 3.19-3.53 (1H), 3.11-3.07 (m, 3H), 1.22 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 503.95(MH)+.} 12 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.2 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.41 (d, J = 5.4 Hz, 1H), 6.44 (d, J = 5.4 Hz, 1H), 5.05 (t, J = 11.7 Hz, 4H), 3.73-3.75 (m, 5H), 1.25 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 501.75(MH)+.} 13 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.80 (t, J = 1.1 Hz, 1H), 8.56 (d, J = 1.5 Hz, 1H), 8.25 (d, J = 5.2 Hz, 1H), 6.17 (d, J = 5.5 Hz, 1H), 4.78-4.45 (m, 4H), 3.77 (s, 3H), 3.71 (q, J = 7.3 Hz, 2H), 2.46-2.44 (m, 2H), 1.25 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 465.80(MH)+.} 14 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.44 (s, 1H), 9.38 (s, 1H), 8.72 (d, J = 4.9 Hz, 1H), 8.67 (d, J = 0.7 Hz, 1H), 7.88 (d, J = 5.1 Hz, 1H), 7.81 (d, J = 9.3 Hz, 1H), 7.50 (dd, J = 9.5, 2.0 Hz, 1H), 4.13 (q, J = 7.4 Hz, 2H), 2.64-2.57 (m, 1H), 1.26 (t, J = 7.3 Hz, 3H), 1.03-0.98 (m, 4H);ESI MS (m/z) 500.80 (MNa)+} 15 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28-9.27 (m, 1H), 8.84 (q, J = 0.9 Hz, 1H), 8.77 (d, J = 2.0 Hz, 1H), 8.61 (d, J = 1.5 Hz, 1H), 3.78 (s, 3H), 3.72 (q, J = 7.3 Hz, 2H), 2.17-2.12 (m, 1H), 1.23 (t, J = 7.3 Hz, 3H), 1.11-1.06 (m, 2H), 0.99-0.95 (m, 2H);ESI MS (m/z) 450.95 (MH)+.} 16 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.38 (s, 1H), 8.69-8.66 (m, 2H), 7.80 (d, J = 9.5 Hz, 1H), 7.50 (dd, J = 9.5, 1.7 Hz, 1H), 7.03 (d, J = 4.6 Hz, 1H), 4.10 (q, J = 7.4 Hz, 2H), 2.91-2.84 (m, 1H), 1.43-1.38 (m, 2H), 1.30-1.22 (m, 5H);ESI MS (m/z) 435.50 (MH)+} 17 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (s, 2H), 8.58 (s, 1H), 8.43 (d, J = 5.4 Hz, 1H), 6.80 (d, J = 5.6 Hz, 1H), 6.45-6.16 (m, 1H), 4.00 (t, J = 14.8 Hz, 2H), 3.81-3.76 (m, 5H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 490.10(MH)+.} 18 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.09 (s, 1H), 8.81 (s, 1H), 8.57 (s, 1H), 8.40 (d, J = 3.9 Hz, 1H), 6.67 (s, 1H), 3.77 (s, 5H), 1.44 (s, 3H), 1.25 (t, J = 7.4 Hz, 3H), 0.91 (d, J = 43.8 Hz, 4H); ESI MS (m/z) 479.50(MH)+.} 19 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (d, J = 1.5 Hz, 1H), 8.57 (d, J = 1.5 Hz, 1H), 8.28 (d, J = 5.6 Hz, 1H), 6.57 (d, J = 5.6 Hz, 1H), 3.90 (q, J = 6.9 Hz, 4H), 3.78 (s, 3H), 3.73 (q, J = 7.3 Hz, 2H), 1.33 (t, J = 7.0 Hz, 6H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 482.05(MH)+.} 20 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.18 (s, 1H), 8.83 (d, J = 1.2 Hz, 1H), 8.59 (d, J = 1.5 Hz, 1H), 8.54 (d, J = 5.4 Hz, 1H), 6.80 (d, J = 5.6 Hz, 1H), 4.73 (s, 2H), 3.80-3.75 (m, 5H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 465.00(MH)+.} twenty one _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (s, 1H), 8.57 (s, 1H), 8.35-8.30 (m, 2H), 6.62 (d, J = 5.6 Hz, 1H), 4.09 (t, J = 6.0 Hz, 1H), 3.80-3.75 (m, 5H), 1.36 (d, J = 6.4 Hz, 6H), 1.25 (d, J = 7.3 Hz, 3H); ESI MS (m/z) 468.05(MH)+.} twenty two _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.90 (d, J = 7.3 Hz, 1H), 8.71 (s, 1H), 8.68 (d, J = 4.4 Hz, 1H), 8.11 (s, 1H), 7.23 (dd, J = 7.2, 1.8 Hz, 1H), 7.03 (d, J = 4.6 Hz, 1H), 4.11 (q, J = 7.4 Hz, 2H), 2.91-2.85 (m, 1H), 1.43-1.39 (m, 2H), 1.28-1.22 (m, 5H);ESI MS (m/z) 436.0 (MH)+.} twenty three _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.87-8.85 (m, 2H), 8.63 (d, J = 1.5 Hz, 1H), 7.63 (d, J = 4.4 Hz, 1H), 3.80 (d, J = 4.6 Hz, 3H), 3.74 (q, J = 7.3 Hz, 2H), 2.07-2.03 (m, 2H), 1.96-1.92 (m, 2H), 1.30 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 476.35 (MH)+.} twenty four _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (t, J = 1.1 Hz, 1H), 8.65 (d, J = 4.4 Hz, 1H), 8.60 (d, J = 1.5 Hz, 1H), 7.07 (d, J = 4.6 Hz, 1H), 4.77 (s, 1H), 3.78 (s, 3H), 3.59 (ddd, J = 24.2, 14.5, 7.1 Hz, 2H), 2.95-2.89 (m, 1H), 1.46-1.41 (m, 2H), 1.31-1.24 (m, 5H);ESI MS (m/z) 450.20(MH)+.} 25 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (d, J = 1.5 Hz, 1H), 8.57 (d, J = 1.5 Hz, 1H), 8.31 (d, J = 5.6 Hz, 1H), 6.67 (d, J = 5.9 Hz, 1H), 3.90 (t, J = 7.7 Hz, 2H), 3.82 (d, J = 6.8 Hz, 2H), 3.78 (s, 3H), 3.74 (q, J = 7.4 Hz, 2H), 1.76 (q, J = 7.7 Hz, 2H), 1.26 (t, J = 7.3 Hz, 4H), 0.94 (t, J = 7.3 Hz, 3H), 0.56-0.51 (m, 2H), 0.41-0.37 (m, 2H);ESI MS (m/z) 522.30 (MH)+} 26 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.78 (d, J = 1.5 Hz, 1H), 8.53 (d, J = 1.5 Hz, 1H), 8.09 (d, J = 5.4 Hz, 1H), 6.44 (d, J = 5.4 Hz, 1H), 3.75 (s, 3H), 3.70 (q, J = 7.3 Hz, 2H), 1.22 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 451.00(MH)+.} 27 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.92 (d, J = 9.0 Hz, 1H), 8.82 (d, J = 1.5 Hz, 1H), 8.59 (d, J = 1.5 Hz, 1H), 8.46 (d, J = 5.4 Hz, 1H), 6.94 (d, J = 5.6 Hz, 1H), 5.07-5.03 (m, 1H), 3.80-3.75 (m, 5H), 1.59 (d, J = 6.8 Hz, 3H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 522.00(MH)+.} 28 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.89 (t, J = 6.2 Hz, 1H), 8.81 (d, J = 1.2 Hz, 1H), 8.57 (d, J = 1.5 Hz, 1H), 8.35 (d, J = 5.6 Hz, 1H), 6.49 (d, J = 5.6 Hz, 1H), 5.96-5.88 (m, 1H), 5.32 (dd, J = 17.4, 1.5 Hz, 1H), 5.21 (dd, J = 10.3, 1.5 Hz, 1H), 4.13 (t, J = 5.6 Hz, 2H), 3.80-3.75 (m, 5H), 1.26 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 466.00(MH)+.} 29 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.06 (d, J = 5.9 Hz, 1H), 8.82 (s, 1H), 8.58 (d, J = 1.7 Hz, 1H), 8.46 (d, J = 5.4 Hz, 1H), 6.63 (d, J = 5.4 Hz, 1H), 4.34 (d, J = 2.4 Hz, 2H), 3.80-3.74 (m, 5H), 3.35 (t, J = 2.3 Hz, 1H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 464.15(MH)+.} 30 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (dd, J = 2.1, 0.6 Hz, 1H), 8.71 (t, J = 6.4 Hz, 1H), 8.57-8.57 (m, 1H), 8.33 (d, J = 5.6 Hz, 1H), 6.61 (d, J = 5.6 Hz, 1H), 3.78 (q, J = 7.4 Hz, 5H), 3.32-3.29 (m, 2H), 2.09-2.02 (m, 1H), 1.26 (t, J = 7.3 Hz, 3H), 0.96 (d, J = 6.6 Hz, 6H);ESI MS (m/z) 482.00 (MH)+.} 31 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (d, J = 1.5 Hz, 1H), 8.57 (d, J = 1.5 Hz, 1H), 8.49 (d, J = 8.8 Hz, 1H), 8.30 (d, J = 5.4 Hz, 1H), 6.61 (d, J = 5.9 Hz, 1H), 3.81-3.76 (m, 5H), 3.39-3.33 (m, 1H), 1.41-1.31 (m, 4H), 1.27 (t, J = 7.5 Hz, 3H), 0.58-0.52 (m, 1H), 0.50-0.44 (m, 1H), 0.40-0.30 (m, 2H);ESI MS (m/z) 494.00 (MH)+.} 32 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84-8.81 (m, 2H), 8.57 (t, J = 1.1 Hz, 1H), 8.34 (d, J = 5.2 Hz, 1H), 6.51 (d, J = 5.5 Hz, 1H), 4.35-4.26 (m, 1H), 3.80-3.74 (m, 5H), 2.43-2.29 (m, 4H), 1.80-1.70 (m, 2H), 1.25 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 480.00(MH)+} 33 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.2 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.36 (d, J = 5.4 Hz, 1H), 7.11 (s, 1H), 6.82 (d, J = 5.6 Hz, 1H), 3.81-3.75 (m, 5H), 1.57 (s, 9H), 1.25 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 482.00 (MH)+.} 34 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.91 (s, 1H), 8.82 (t, J = 1.0 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.43 (d, J = 5.4 Hz, 1H), 6.71 (d, J = 5.6 Hz, 1H), 4.86-4.83 (m, 1H), 3.80-3.74 (m, 5H), 3.43 (d, J = 2.4 Hz, 1H), 1.64 (d, J = 6.8 Hz, 3H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 478.00(MH)+} 35 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.82 (s, 1H), 8.69 (d, J = 4.6 Hz, 1H), 8.13 (d, J = 9.5 Hz, 1H), 8.01 (dd, J = 9.3, 1.7 Hz, 1H), 7.05 (d, J = 4.6 Hz, 1H), 5.19 (d, J = 8.9 Hz, 1H), 3.82-3.67 (m, 2H), 2.92-2.85 (m, 1H), 1.42-1.40 (m, 2H), 1.36 (q, J = 7.1 Hz, 3H), 1.32-1.22 (m, 2H);ESI MS (m/z) 435.60 (MH)+.} 36 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.31 (d, J = 7.3 Hz, 1H), 8.69 (d, J = 4.4 Hz, 1H), 8.51 (t, J = 1.0 Hz, 1H), 7.56 (dd, J = 7.1, 2.0 Hz, 1H), 7.05 (d, J = 4.4 Hz, 1H), 5.16 (s, 1H), 3.80-3.67 (m, 2H), 2.92-2.85 (m, 1H), 1.42-1.40 (m, 2H), 1.38-1.32 (m, 3H), 1.29-1.26 (m, 2H);ESI MS (m/z) 435.50 (MH)+.} 37 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.15 (d, J = 8.3 Hz, 1H), 8.79 (d, J = 1.2 Hz, 1H), 8.55 (d, J = 1.5 Hz, 1H), 8.35 (d, J = 5.5 Hz, 1H), 6.74 (d, J = 5.5 Hz, 1H), 5.25-5.16 (m, 1H), 3.82-3.72 (m, 7H), 3.37-3.32 (m, 2H), 1.23 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 497.55(MH)+.} 38 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.87 (t, J = 1.0 Hz, 1H), 8.78 (d, J = 4.6 Hz, 1H), 8.65-8.64 (m, 1H), 7.23 (d, J = 4.6 Hz, 1H), 4.42-4.26 (m, 2H), 3.88 (s, 3H), 2.95-2.89 (m, 1H), 1.50-1.45 (m, 2H), 1.41-1.34 (m, 5H); ESI MS (m/z) 474.60(MH)+.} 39 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (d, J = 4.9 Hz, 2H), 9.03 (d, J = 4.2 Hz, 1H), 8.86 (t, J = 1.0 Hz, 1H), 8.64 (d, J = 1.5 Hz, 1H), 7.87 (d, J = 4.2 Hz, 1H), 7.83 (t, J = 4.9 Hz, 1H), 3.82 (s, 3H), 3.68 (q, J = 7.3 Hz, 2H), 1.23 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 488.55(MH)+.} 40 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (dd, J = 2.1, 0.6 Hz, 1H), 8.63 (d, J = 4.4 Hz, 1H), 8.58-8.58 (m, 1H), 7.06 (d, J = 4.6 Hz, 1H), 3.77-3.57 (m, 5H), 2.96-2.89 (m, 1H), 2.57 (d, J = 5.9 Hz, 3H), 1.47-1.42 (m, 2H), 1.32-1.28 (m, 2H), 1.25 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 463.60(MH)+.} 41 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.80 (d, J = 1.2 Hz, 1H), 8.57 (d, J = 1.5 Hz, 1H), 8.33 (d, J = 5.6 Hz, 1H), 7.06 (s, 1H), 6.77 (d, J = 5.6 Hz, 1H), 4.73 (s, 1H), 3.79 (s, 3H), 3.63 (qd, J = 7.3, 2.4 Hz, 2H), 1.56 (s, 9H), 1.25 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 481.10 (MH)+.} 42 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.2 Hz, 1H), 8.77 (d, J = 8.8 Hz, 1H), 8.59 (d, J = 1.5 Hz, 1H), 8.39 (d, J = 5.6 Hz, 1H), 6.64 ESI MS (m/z) 512.15(MH)+.} 43 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.85 (t, J = 1.0 Hz, 1H), 8.62 (d, J = 1.5 Hz, 1H), 8.44 (d, J = 5.4 Hz, 1H), 7.20 (s, 1H), 6.92 (d, J = 5.6 Hz, 1H), 4.44-4.37 (m, 1H), 4.35-4.28 (m, 1H), 3.87 (s, 3H), 1.58 (s, 9H), 1.39 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 506.10 (MH)+.} 44 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.5 Hz, 1H), 8.58 (d, J = 1.5 Hz, 2H), 8.35 (d, J = 5.4 Hz, 1H), 6.65 (d, J = 5.6 Hz, 1H), 3.81-3.75 (m, 5H), 3.67-3.64 (m, 2H), 3.61 (t, J = 4.8 Hz, 2H), 3.29 (s, 3H), 1.26 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 484.40 (MH)+} 45 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.5 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.54-8.50 (m, 1H), 8.35 (d, J = 5.6 Hz, 1H), 6.65 (d, J = 5.9 Hz, 1H), 3.81-3.76 (m, 5H), 3.68 (t, J = 5.7 Hz, 1H), 3.52 (s, 2H), 3.28 (s, 3H), 1.26 (t, J = 7.3 Hz, 3H), 1.17 (d, J = 6.1 Hz, 3H);ESI MS (m/z) 498.25 (MH)+} 46 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (q, J = 0.9 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.47 (d, J = 8.8 Hz, 1H), 8.35 (d, J = 5.6 Hz, 1H), 6.76 (d, J = 5.9 Hz, 1H), 4.01-3.92 (m, 3H), 3.80-3.75 (m, 5H), 3.49-3.43 (m, 2H), 1.96-1.87 (m, 4H), 1.27-1.21 (m, 3H);ESI MS (m/z) 510.50(MH)+.} 47 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.2 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.52 (t, J = 6.1 Hz, 1H), 8.35 (d, J = 5.6 Hz, 1H), 6.63 (d, J = 5.6 Hz, 1H), 4.94 (d, J = 5.1 Hz, 1H), 3.81-3.75 (m, 5H), 3.68 (dd, J = 9.9, 5.3 Hz, 2H), 3.56 (q, J = 5.7 Hz, 2H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 470.35 (MH)+} 48 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.2 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.45 (t, J = 6.0 Hz, 1H), 8.34 (d, J = 5.6 Hz, 1H), 6.65 (d, J = 5.6 Hz, 1H), 5.00 (d, J = 4.9 Hz, 1H), 3.99-3.94 (m, 1H), 3.81-3.76 (m, 5H), 3.48-3.38 (m, 2H), 1.26 (t, J = 7.3 Hz, 3H), 1.15 (d, J = 6.4 Hz, 3H);ESI MS (m/z) 484.10 (MH)+} 49 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (t, J = 1.1 Hz, 1H), 8.59 (d, J = 1.5 Hz, 1H), 8.46 (d, J = 5.1 Hz, 1H), 7.03 (d, J = 5.4 Hz, 1H), 3.78-3.71 (m, 5H), 3.15 (s, 3H), 1.48 (s, 9H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 496.05(MH)+.} 50 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.73 (d, J = 4.6 Hz, 1H), 8.69 (s, 1H), 7.17 (d, J = 4.6 Hz, 1H), 4.00 (s, 3H), 3.78 (q, J = 7.3 Hz, 2H), 2.95-2.89 (m, 1H), 1.49-1.44 (m, 2H), 1.32-1.22 (m, 5H);ESI MS (m/z) 452.20 (MH)+} 51 _{1H-NMR (400 MHz, DMSO- D6 ) δ 8.68 (t, J = 4.3 Hz, 2H), 7.11 (d, J = 4.6 Hz, 1H), 4.82 (s, 1H), 3.98 (s, 3H), 3.64-3.57 (m, 2H), 2.95-2.91 (m, 1H), 1.48-1.43 (m, 2H), 1.32-1.21 (m, 5H);ESI MS (m/z) 451.05 (MH)+} 52 _{1H-NMR (400 MHz, CHLOROFORM-d) δ 8.95 (s, 1H), 8.59 (d, J = 4.4 Hz, 1H), 8.13 (d, J = 1.0 Hz, 1H), 6.65 (d, J = 4.4 Hz, 1H), 3.93 (s, 3H), 3.68 (q, J = 7.5 Hz, 2H), 3.12 (s, 1H), 1.54-1.52 (m, 2H), 1.43 (t, J = 7.5 Hz, 3H), 1.25-1.22 (m, 2H);ESI MS (m/z) 451.00 (MH)+} 53 _{1H-NMR (400 MHz, CHLOROFORM-d) δ 8.93 (s, 1H), 8.56 (d, J = 4.4 Hz, 1H), 8.13 (d, J = 0.7 Hz, 1H), 6.62 (d, J = 4.6 Hz, 1H), 4.28 (s, 1H), 3.97 (s, 3H), 3.79-3.73 (m, 2H), 3.08-3.01 (m, 1H), 1.55-1.50 (m, 5H), 1.26-1.22 (m, 2H);ESI MS (m/z) 450.15 (MH)+} 54 _{1H-NMR (400 MHz, CHLOROFORM-d) δ 8.99 (s, 1H), 8.64 (d, J = 4.4 Hz, 1H), 8.11 (d, J = 0.7 Hz, 1H), 7.26 (s, 2H), 6.74 (d, J = 4.6 Hz, 1H), 4.28 (td, J = 14.5, 7.3 Hz, 1H), 4.12 (td, J = 14.5, 7.3 Hz, 1H), 4.03 (s, 3H), 3.15-3.08 (m, 1H), 1.62-1.55 (m, 3H), 1.36-1.28 (m, 2H);ESI MS (m/z) 475.05 (MH)+} 55 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (t, J = 1.0 Hz, 1H), 8.76 (t, J = 6.1 Hz, 1H), 8.58 (d, J = 2.0 Hz, 1H), 8.34 (d, J = 5.6 Hz, 1H), 6.66 (d, J = 5.6 Hz, 1H), 3.81-3.76 (m, 5H), 3.38 (t, J = 6.6 Hz, 2H), 1.28-1.21 (m, 4H), 0.53-0.49 (m, 2H), 0.40-0.36 (m, 2H);ESI MS (m/z) 479.85(MH)+.} 56 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (t, J = 1.1 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.32 (d, J = 5.4 Hz, 1H), 8.24 (d, J = 9.3 Hz, 1H), 6.65 (d, J = 5.9 Hz, 1H), 3.81-3.75 (m, 5H), 3.70 (dd, J = 15.5, 7.2 Hz, 1H), 2.04 (q, J = 7.0 Hz, 1H), 1.30 (d, J = 6.6 Hz, 3H), 1.26 (t, J = 7.5 Hz, 3H), 0.96 (dd, J = 7.8, 6.8 Hz, 6H); ESI MS (m/z) 496.25(MH)+.} 57 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.5 Hz, 1H), 8.78 (t, J = 6.1 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.38 (d, J = 5.6 Hz, 1H), 6.69 (d, J = 5.4 Hz, 1H), 4.78-4.63 (m, 2H), 3.88 (t, J = 5.4 Hz, 1H), 3.83-3.75 (m, 6H), 1.26 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 472.15 (MH)+} 58 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (s, 1H), 8.63 (d, J = 4.6 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 7.06 (d, J = 4.6 Hz, 1H), 3.77-3.72 (m, 4H), 3.62-3.56 (m, 1H), 3.01-2.83 (m, 3H), 1.46-1.42 (m, 2H), 1.31-1.28 (m, 2H), 1.24 (t, J = 7.3 Hz, 3H), 0.86 (t, J = 7.0 Hz, 3H);ESI MS (m/z) 478.05(MH)+.} 59 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (s, 1H), 8.58 (s, 1H), 8.34 (d, J = 5.6 Hz, 1H), 8.26 (d, J = 9.3 Hz, 1H), 6.69 (d, J = 5.9 Hz, 1H), 4.20 (t, J=6.5 Hz, 1H), 3.81-3.75 (m, 5H), 3.66-3.62 (m, 1H), 3.50 (q, J=4.9 Hz, 1H), 3.30 (s, 3H), 1.31-1.21 (m, 6H);ESI MS (m/z) 498.50 (MH)+} 60 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.44 (s, 1H), 8.82 (d, J = 1.5 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.37 (d, J = 5.4 Hz, 1H), 6.88 (d, J = 5.6 Hz, 1H), 4.96 (d, J = 2.0 Hz, 1H), 3.82-3.77 (m, 5H), 1.25 (t, J = 7.3 Hz, 3H), 1.14 (s, 9H); ESI MS (m/z) 497.55(MH)+.} 61 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (t, J = 1.0 Hz, 1H), 8.57 (d, J = 1.5 Hz, 1H), 8.33 (d, J = 5.6 Hz, 1H), 6.97 (d, J = 5.6 Hz, 1H), 5.47 (s, 2H), 3.90 (s, 3H), 3.79-3.73 (m, 5H), 1.25 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 455.05(MH)+.} 62 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.88 (t, J = 6.8 Hz, 1H), 8.82 (d, J = 1.5 Hz, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.42 (d, J = 5.4 Hz, 1H), 6.78 (d, J = 5.6 Hz, 1H), 4.01 (td, J = 13.9, 6.8 Hz, 2H), 3.82-3.76 (m, 5H), 1.74 (t, J = 19.1 Hz, 3H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 504.10 (MH)+} 63 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.18 (d, J = 4.9 Hz, 2H), 8.98 (d, J = 4.2 Hz, 1H), 8.84 (s, 1H), 8.63 (d, J = 2.0 Hz, 1H), 7.83 (t, J = 4.9 Hz, 1H), 7.79 (d, J = 4.2 Hz, 1H), 4.77 (s, 1H), 3.82 (s, 3H), 3.49 (qd, J = 14.3, 7.0 Hz, 2H), 1.22 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 488.15(MH)+.} 64 _{1H-NMR (400 MHz, CHLOROFORM-d) δ 8.70 (d, J = 1.5 Hz, 1H), 8.38 (d, J = 5.4 Hz, 1H), 8.29 (d, J = 2.0 Hz, 1H), 6.57 (d, J = 8.8 Hz, 1H), 6.25 (d, J = 5.6 Hz, 1H), 3.91 (s, 3H), 3.79-3.73 (m, 3H), 1.83-1.75 (m, 2H), 1.45-1.41 (m, 6H), 1.06 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 482.60 (MH)+} 65 _{1H-NMR (400 MHz, CHLOROFORM-d) δ 8.72-8.70 (m, 2H), 8.63 (dd, J = 4.6, 1.5 Hz, 1H), 8.31-8.28 (m, 2H), 7.73 (dt, J = 7.9, 1.9 Hz, 1H), 7.36 (dd, J = 7.7, 4.5 Hz, 1H), 7.09 (d, J = 6.1 Hz, 1H), 6.04 (d, J = 5.4 Hz, 1H), 4.95-4.89 (m, 1H), 3.90 (s, 3H), 3.85-3.75 (m, 2H), 1.86 (d, J = 6.8 Hz, 3H), 1.45 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 531.05 (MH)+} 66 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.09 (d, J = 8.1 Hz, 1H), 8.81 (d, J = 1.2 Hz, 1H), 8.58-8.55 (m, 3H), 8.30 (d, J = 5.6 Hz, 1H), 7.55 (dd, J = 4.5, 1.6 Hz, 2H), 6.44 (d, J = 5.6 Hz, 1H), 5.13 (t, J = 7.2 Hz, 1H), 3.83-3.75 (m, 5H), 1.72 (d, J = 6.8 Hz, 3H), 1.28 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 531.00 (MH)+.} 67 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.18 (d, J = 4.9 Hz, 2H), 8.97 (d, J = 4.2 Hz, 1H), 8.84 (s, 1H), 8.62 (s, 1H), 7.84-7.79 (m, 2H), 3.80 (s, 3H), 3.68-3.58 (m, 2H), 2.55 (s, 3H), 1.23-1.19 (m, 3H); ESI MS (m/z) 502.40(MH)+.} 68 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (d, J = 5.1 Hz, 2H), 9.11 (d, J = 4.4 Hz, 1H), 8.89 (d, J = 1.2 Hz, 1H), 8.67 (d, J = 1.7 Hz, 1H), 7.97 (d, J = 4.2 Hz, 1H), 7.84 (t, J = 4.9 Hz, 1H), 4.37-4.23 (m, 2H), 3.92 (s, 3H), 1.36 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 513.30 (MH)+.} 69 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.62 (s, 1H), 8.84 (d, J = 1.5 Hz, 1H), 8.70 (d, J = 5.1 Hz, 1H), 8.61 (d, J = 1.5 Hz, 1H), 7.97 (d, J = 5.1 Hz, 1H), 3.82-3.77 (m, 5H), 2.67-2.65 (m, 1H), 1.27 (t, J = 7.5 Hz, 3H), 1.04-1.00 (m, 4H);ESI MS (m/z) 494.30 (MH)+} 70 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.91 (d, J = 4.6 Hz, 1H), 8.85 (d, J = 1.2 Hz, 1H), 8.63 (d, J = 1.5 Hz, 1H), 7.66 (d, J = 4.6 Hz, 1H), 3.82 (s, 3H), 3.75 (q, J = 7.3 Hz, 2H), 3.36 (s, 3H), 2.11 (s, 3H), 1.25 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 481.95 (MH)+} 71 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (d, J = 1.5 Hz, 1H), 8.58 (d, J = 2.0 Hz, 1H), 8.35 (d, J = 5.6 Hz, 1H), 7.85-7.74 (m, 1H), 6.67 (dd, J = 7.9, 5.7 Hz, 1H), 5.11 (dd, J = 13.3, 5.0 Hz, 1H), 3.94-3.75 (m, 8H), 1.30-1.24 (m, 6H), 1.21-1.14 (m, 3H);ESI MS (m/z) 498.30 (MH)+} 72 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82-8.78 (m, 2H), 8.62-8.60 (m, 1H), 8.58-8.58 (m, 1H), 8.34 (d, J = 5.6 Hz, 1H), 7.84 (td, J = 7.7, 1.8 Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.37-7.33 (m, 1H), 6.54 (d, J = 5.9 Hz, 1H), 5.19 (t, J = 7.2 Hz, 1H), 3.83-3.77 (m, 5H), 1.71 (d, J = 6.8 Hz, 3H), 1.28 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 531.00 (MH)+} 73 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.67 (d, J = 5.9 Hz, 2H), 7.10 (d, J = 4.6 Hz, 1H), 3.96 (s, 3H), 3.75-3.61 (m, 2H), 2.95-2.91 (m, 1H), 2.59 (s, 3H), 1.49-1.44 (m, 2H), 1.33-1.30 (m, 2H), 1.26 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 465.00 (MH)+} 74 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 4.6 Hz, 1H), 8.71 (s, 1H), 7.27 (d, J = 4.9 Hz, 1H), 4.38-4.28 (m, 2H), 4.08 (s, 3H), 2.95-2.89 (m, 1H), 1.52-1.48 (m, 2H), 1.42-1.34 (m, 5H);ESI MS (m/z) 476.00 (MH)+} 75 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.91 (d, J = 4.4 Hz, 1H), 8.85 (q, J = 0.9 Hz, 1H), 8.63 (t, J = 1.1 Hz, 1H), 7.66 (d, J = 4.6 Hz, 1H), 3.84 (d, J = 13.2 Hz, 3H), 3.74 (q, J = 7.4 Hz, 2H), 3.40 (s, 3H), 1.77-1.72 (m, 1H), 1.27-1.22 (m, 3H), 0.96-0.92 (m, 2H), 0.77-0.72 (m, 2H);ESI MS (m/z) 508.00 (MH)+} 76 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.80 (d, J = 1.2 Hz, 1H), 8.57 (d, J = 1.7 Hz, 1H), 8.43 (d, J = 5.4 Hz, 1H), 6.97 (d, J = 5.1 Hz, 1H), 4.73 (s, 1H), 3.80 (s, 3H), 3.64-3.53 (m, 2H), 3.15 (s, 3H), 1.48 (s, 9H), 1.28 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 495.60 (MH)+} 77 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (q, J = 0.9 Hz, 1H), 8.57 (dd, J = 2.1, 0.6 Hz, 1H), 8.37 (d, J = 5.6 Hz, 1H), 6.96 (d, J = 5.6 Hz, 1H), ESI MS (m/z) 483.40 (MH)+.} 78 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.90 (s, 1H), 8.81 (d, J = 1.2 Hz, 1H), 8.57 (d, J = 1.7 Hz, 1H), 8.35 (d, J = 5.4 Hz, 1H), 6.80 (d, J = 5.4 Hz, 1H), 5.29 (s, 1H), 3.78 (dd, J = 14.4, 7.6 Hz, 5H), 3.36-3.34 (m, 1H), 1.26 (t, J = 7.5 Hz, 3H), 1.03 (d, J = 6.4 Hz, 6H); ESI MS (m/z) 483.05 (MH)+.} 79 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.3 Hz, 1H), 8.83 (q, J = 0.9 Hz, 1H), 8.59 (t, J = 1.1 Hz, 1H), 7.44 (d, J = 7.3 Hz, 1H), 3.82-3.76 (m, 5H), 2.35-2.31 (m, 1H), 1.24 (t, J = 7.3 Hz, 3H), 1.19-1.14 (m, 2H), 1.07-1.03 (m, 2H);ESI MS (m/z) 450.95+} 80 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.23 (d, J = 7.0 Hz, 1H), 8.81 (d, J = 1.5 Hz, 1H), 8.58 (d, J = 1.8 Hz, 1H), 7.37 (d, J = 7.3 Hz, 1H), 4.71 (s, 1H), 3.82-3.75 (m, 3H), 3.66-3.53 (m, 2H), 2.34-2.28 (m, 1H), 1.25 (q, J = 7.4 Hz, 3H), 1.18-1.10 (m, 2H), 1.08-1.03 (m, 2H);ESI MS (m/z) 450.00 (MH)+} 81 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.87 (d, J = 4.4 Hz, 1H), 8.84 (s, 1H), 8.61 (d, J = 1.5 Hz, 1H), 7.57 (d, J = 4.6 Hz, 1H), 6.12 (s, 1H), 3.81 (s, 3H), 3.74 (d, J = 7.3 Hz, 2H), 1.82 (s, 6H), 1.25 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 469.05 (MH)+.} 82 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.25 (d, J = 7.3 Hz, 1H), 8.81 (d, J = 1.5 Hz, 1H), 8.56 (d, J = 1.7 Hz, 1H), 7.36 (d, J = 7.3 Hz, 1H), 3.78-3.69 (m, 4H), 3.67-3.59 (m, 1H), 2.54 (d, J = 8.3 Hz, 3H), 2.33-2.27 (m, 1H), 1.22 (t, J = 7.5 Hz, 3H), 1.16-1.12 (m, 2H), 1.04-1.00 (m, 2H);ESI MS (m/z) 485.65 (MNa)+} 83 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.02 (d, J = 4.4 Hz, 1H), 8.88-8.86 (m, 2H), 8.64 (t, J = 1.1 Hz, 1H), 7.95 (d, J = 4.2 Hz, 1H), 7.25 (d, J = 5.9 Hz, 1H), 4.07 (s, 3H), 3.83 (s, 3H), 3.72 (q, J = 7.4 Hz, 2H), 1.24 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 518.60 (MH)+} 84 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.40 (d, J = 7.3 Hz, 1H), 8.86 (d, J = 1.5 Hz, 1H), 8.62 (d, J = 1.8 Hz, 1H), 7.55 (d, J = 7.3 Hz, 1H), 4.41-4.29 (m, 2H), 3.87 (s, 3H), 2.42-2.35 (m, 1H), 1.35 (q, J = 7.0 Hz, 3H), 1.24-1.17 (m, 3H), 1.14-1.08 (m, 2H);ESI MS (m/z) 475.45 (MH)+} 85 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.5 Hz, 1H), 8.59 (d, J = 1.5 Hz, 1H), 8.49 (d, J = 5.4 Hz, 1H), 6.81 (d, J = 5.4 Hz, 1H), 3.90 (d, J = 5.4 Hz, 4H), 3.86-3.82 (m, 4H), 3.74 (q, J = 7.2 Hz, 5H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 496.25 (MH)+.} 86 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84 (d, J = 1.2 Hz, 1H), 8.69 (d, J = 4.4 Hz, 1H), 8.64-8.63 (m, 1H), 7.13 (d, J = 4.6 Hz, 1H), 3.97-3.85 (m, 2H), 3.71 (s, 3H), 2.94-2.89 (m, 1H), 1.46 (t, J = 6.1 Hz, 5H), 1.35-1.26 (m, 5H);ESI MS (m/z) 492.70 (MH)+} 87 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.85 (d, J = 1.5 Hz, 1H), 8.76 (d, J = 4.6 Hz, 1H), 8.62-8.61 (m, 1H), 7.21 (d, J = 4.6 Hz, 1H), 4.38-4.30 (m, 2H), 3.74 (s, 3H), 2.91-2.87 (m, 1H), 1.49-1.44 (m, 2H), 1.41-1.36 (m, 3H), 1.35-1.32 (m, 2H);ESI MS (m/z) 546.50 (MH)+} 88 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84 (d, J = 1.2 Hz, 1H), 8.82 (d, J = 4.6 Hz, 1H), 8.62 (d, J = 1.5 Hz, 1H), 7.58 (d, J = 4.9 Hz, 1H), 4.36 (t, J = 7.0 Hz, 2H), 3.79 (s, 3H), 3.74 (q, J = 7.4 Hz, 2H), 2.67 (t, J = 7.9 Hz, 2H), 2.27-2.19 (m, 2H), 1.28-1.23 (m, 3H);ESI MS (m/z) 494.20(MH)} 89 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (d, J = 1.2 Hz, 1H), 8.57 (d, J = 1.2 Hz, 1H), 8.39 (d, J = 5.4 Hz, 1H), 6.41 (d, J = 5.4 Hz, 1H), 4.94-4.77 (m, 4H), 3.78-3.72 (m, 5H), 3.57 (s, 3H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 564.15 (MH)+.} 90 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.83 (s, 1H), 8.73 (d, J = 4.2 Hz, 1H), 8.61 (s, 1H), 7.17 (d, J = 4.2 Hz, 1H), 5.84 (t, J = 54.0 Hz, 1H), 4.25-4.15 (m, 2H), 3.72 (s, 3H), 2.91 (t, J = 4.4 Hz, 1H), 1.47 (d, J = 6.4 Hz, 2H), 1.37-1.31 (m, 5H);ESI MS (m/z) 528.50 (MH)+} 91 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (s, 1H), 8.64 (d, J = 4.6 Hz, 1H), 8.58 (s, 1H), 7.07 (d, J = 4.6 Hz, 1H), 3.76 (s, 3H), 3.70-3.52 (m, 3H), 2.97-2.90 (m, 2H), 1.46-1.43 (m, 2H), 1.31-1.29 (m, 2H), 1.22 (t, J = 7.2 Hz, 3H), 0.37-0.32 (m, 1H), 0.22 (d, J = 6.1 Hz, 2H), 0.00-0.05 (m, 1H);ESI MS (m/z) 490.65 (MH)+} 92 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.06 (d, J = 4.4 Hz, 1H), 8.87 (s, 1H), 8.65 (s, 1H), 7.88 (d, J = 4.4 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.68-7.75 (1H), 6.68 (d, J = 9.5 Hz, 1H), 6.56 (s, 1H), 3.83 (s, 3H), 3.67 (d, J = 7.6 Hz, 2H), 1.20 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 504.25 (MH)+.} 93 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.5 Hz, 1H), 8.64 (d, J = 4.4 Hz, 1H), 8.58-8.57 (m, 1H), 7.06 (d, J = 4.6 Hz, 1H), 5.63-5.52 (m, 1H), 4.87-4.82 (m, 1H), 4.74 (dt, J = 10.3, 1.2 Hz, 1H), 3.83-3.74 (m, 4H), 3.67-3.60 (m, 1H), 3.03-2.97 (m, 1H), 2.95-2.89 (m, 1H), 2.87-2.81 (m, 1H), 2.00-1.92 (m, 2H), 1.44 (dt, J = 11.8, 3.4 Hz, 2H), 1.32-1.28 (m, 2H), 1.25 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 503.95 (MH)+} 94 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.63 (d, J = 4.6 Hz, 1H), 8.22 (d, J = 0.7 Hz, 1H), 7.06 (d, J = 4.6 Hz, 1H), 3.85 (s, 3H), 3.76-3.67 (m, 1H), 3.65-3.56 (m, 1H), 2.95-2.89 (m, 1H), 2.57 (s, 3H), 1.47-1.43 (m, 2H), 1.32-1.28 (m, 2H), 1.24 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 463.55 (MH)+} 95 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.24 (s, 1H), 8.68 (d, J = 4.6 Hz, 1H), 8.26 (d, J = 1.0 Hz, 1H), 7.13 (d, J = 4.6 Hz, 1H), 3.95-3.84 (m, 2H), 3.82 (s, 3H), 2.92-2.89 (m, 1H), 1.48-1.44 (s, 5H), 1.32-1.27 (m, 5H);ESI MS (m/z) 491.55 (MH)+} 96 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.86 (d, J = 1.5 Hz, 1H), 8.63 (s, 1H), 7.56 (d, J = 8.1 Hz, 1H), 6.34 (d, J = 8.3 Hz, 1H), 4.48 (q, J = 7.3 Hz, 1H), 3.77 (d, J = 3.4 Hz, 3H), 3.40-3.34 (m, 2H), 3.08 (s, 3H), 1.30-1.13 (m, 6H);ESI MS (m/z) 536.15 (MH)+} 97 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.83 (d, J = 1.5 Hz, 1H), 8.70 (d, J = 4.4 Hz, 1H), 8.62 (d, J = 1.5 Hz, 1H), 7.14 (d, J = 4.6 Hz, 1H), 4.18-3.98 (m, 2H), 3.74 (s, 3H), 2.93-2.87 (m, 1H), 1.50-1.43 (m, 2H), 1.31 (t, J = 7.3 Hz, 5H), 0.65 (s, 9H);ESI MS (m/z) 534.35 (MH)+} 98 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.40 (s, 1H), 8.83 (d, J = 0.5 Hz, 1H), 8.69 (d, J = 4.6 Hz, 1H), 7.85 (d, J = 8.8 Hz, 1H), 7.53 (d, J = 7.8 Hz, 1H), 7.01 (d, J = 4.6 Hz, 1H), 6.19 (s, 1H), 3.81-3.74 (m, 1H), 3.70-3.61 (m, 1H), 2.89-2.83 (m, 1H), 1.38 (t, J = 7.3 Hz, 5H), 1.33-1.22 (m, 2H);ESI MS (m/z) 434.70 (MH)+} 99 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.36 (s, 1H), 8.65 (d, J = 7.6 Hz, 1H), 8.49 (d, J = 4.9 Hz, 1H), 7.78 (d, J = 7.5 Hz, 1H), 7.48 (d, J = 7.7 Hz, 1H), 6.95 (d, J = 5.1 Hz, 1H), 4.04 (q, J = 7.4 Hz, 2H), 3.09 (s, 3H), 1.45 (s, 9H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 481.10 (MH)+} 100 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.01 (d, J = 4.0 Hz, 1H), 8.86 (d, J = 1.5 Hz, 1H), 8.64 (d, J = 1.5 Hz, 1H), 7.87-7.81 (m, 1H), 7.77-7.74 (m, 1H), 3.80 (d, J = 3.4 Hz, 3H), 3.75 (q, J = 7.3 Hz, 2H), 1.28-1.23 (m, 3H); ESI MS (m/z) 461.10 (MH)+.} 101 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.41 (s, 1H), 9.17 (d, J = 4.9 Hz, 2H), 9.02 (d, J = 4.0 Hz, 1H), 8.71 (s, 1H), 7.84-7.80 (m, 2H), 7.75 (d, J = 4.0 Hz, 1H), 7.52 (dd, J = 9.5, 1.8 Hz, 1H), 4.02 (q, J = 7.3 Hz, 2H), 1.22 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 474.15 (MH)+} 102 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.89 (d, J = 7.1 Hz, 1H), 8.72 (s, 1H), 8.40 (d, J = 5.4 Hz, 1H), 8.07 (s, 1H), 7.22 (dd, J = 7.1, 1.7 Hz, 1H), 6.89 (s, 1H), 6.74 (d, J = 5.4 Hz, 1H), 4.15 (q, J = 7.3 Hz, 2H), 1.55 (s, 9H), 1.25 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 466.50 (MH)+} 103 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.83 (d, J = 1.2 Hz, 1H), 8.70 (d, J = 4.6 Hz, 1H), 8.62 (t, J = 1.1 Hz, 1H), 7.13 (d, J = 4.6 Hz, 1H), 4.11-4.04 (m, 1H), 4.02-3.95 (m, 1H), 3.74 (d, J = 5.5 Hz, 3H), 2.94-2.87 (m, 1H), 1.97-1.90 (m, 1H), 1.49-1.42 (m, 2H), 1.35-1.25 (m, 5H), 0.63-0.59 (m, 3H), 0.58-0.53 (m, 3H);ESI MS (m/z) 520.5 (MH)+.} 104 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84 (t, J = 1.0 Hz, 1H), 8.69 (d, J = 4.6 Hz, 1H), 8.63 (d, J = 1.5 Hz, 1H), 7.13 (d, J = 4.6 Hz, 1H), 3.96 (tt, J = 21.4, 7.1 Hz, 2H), 3.72 (d, J = 5.4 Hz, 3H), 2.95-2.88 (m, 1H), 1.79 (dt, J = 23.9, 7.5 Hz, 1H), 1.60 (dt, J = 23.7, 7.6 Hz, 1H), 1.50-1.42 (m, 2H), 1.36-1.28 (m, 5H), 0.54 (t, J = 7.6 Hz, 3H); ESI MS (m/z) 506.5 (MH)+.} 105 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.24 (s, 1H), 9.19 (d, J = 4.9 Hz, 2H), 9.03 (d, J = 4.4 Hz, 1H), 8.27 (d, J = 0.7 Hz, 1H), 7.87 (d, J = 4.4 Hz, 1H), 7.83 (t, J = 4.9 Hz, 1H), 3.93 (s, 3H), 3.68 (q, J = 7.3 Hz, 2H), 1.22 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 489.2 (MH)+.} 106 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.1 Hz, 1H), 8.50-8.46 (m, 2H), 8.35 (d, J = 5.6 Hz, 1H), 7.54 (dd, J = 7.2, 1.8 Hz, 1H), 6.54 (d, J = 5.4 Hz, 1H), 3.91 (q, J = 7.3 Hz, 2H), 3.55-3.48 (m, 2H), 1.28-1.22 (m, 6H); ESI MS (m/z) 439.9(MH)+.} 107 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.1 Hz, 1H), 8.47 (d, J = 1.0 Hz, 1H), 8.37 (d, J = 5.6 Hz, 1H), 7.55 (dd, J = 7.3, 2.0 Hz, 1H), 6.97 (s, 1H), 6.78 (d, J = 5.4 Hz, 1H), 3.93 (q, J = 7.4 Hz, 2H), 1.54 (d, J = 15.4 Hz, 9H), 1.27 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 467.9 (MH)+.} 108 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.34 (d, J = 7.0 Hz, 1H), 9.18 (d, J = 5.2 Hz, 2H), 9.04 (d, J = 4.3 Hz, 1H), 8.54 (s, 1H), 7.82 (t, J = 4.9 Hz, 2H), 7.60 (dd, J = 7.0, 1.8 Hz, 1H), 3.87 (q, J = 7.3 Hz, 2H), 1.25 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 475.0 (MH)+.} 109 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.23 (s, 1H), 8.99 (d, J = 4.4 Hz, 1H), 8.27 (d, J = 0.7 Hz, 1H), 7.73 (d, J = 4.2 Hz, 1H), 3.91 (t, J = 7.2 Hz, 3H), 3.74 (q, J = 7.3 Hz, 2H), 2.40-2.30 (m, 3H), 1.28-1.22 (m, 3H); ESI MS (m/z) 475.2 (MH)+.} 110 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.3 Hz, 1H), 8.89 (s, 1H), 8.47 (s, 1H), 8.41 (d, J = 5.2 Hz, 1H), 7.55 (dd, J = 7.3, 1.8 Hz, 1H), 6.64 (d, J = 5.2 Hz, 1H), 3.90 (q, J = 7.3 Hz, 2H), 1.44 (s, 3H), 1.26 (t, J = 7.3 Hz, 3H), 0.98-0.95 (m, 2H), 0.84 (dd, J = 6.9, 5.0 Hz, 2H);ESI MS (m/z) 466.2 (MH)+} 111 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.36 (d, J = 5.5 Hz, 1H), 8.23 (s, 1H), 7.12 (s, 1H), 6.82 (d, J = 5.5 Hz, 1H), 3.87 (s, 3H), 3.78 (q, J = 7.3 Hz, 2H), 1.55 (d, J = 14.1 Hz, 9H), 1.25 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 482.0 (MH)+.} 112 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.78 (s, 1H), 8.37 (d, J = 5.6 Hz, 1H), 8.10 (d, J = 9.3 Hz, 1H), 7.99 (d, J = 9.3 Hz, 1H), 6.95 (s, 1H), 6.78 (d, J = 5.6 Hz, 1H), 3.93 (q, J = 7.3 Hz, 2H), 1.56 (s, 9H), 1.27 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 468.0(MH)+.} 113 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.77 (s, 1H), 8.35 (d, J = 5.6 Hz, 1H), 8.10-8.07 (m, 2H), 7.98 (dd, J = 9.4, 1.8 Hz, 1H), 6.58 (d, J = 5.6 Hz, 1H), 4.07 (dd, J = 13.7, 6.4 Hz, 1H), 3.92 (q, J = 7.4 Hz, 2H), 1.35 (d, J = 6.4 Hz, 6H), 1.27 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 454.4 (MH)+.} 114 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.79 (s, 1H), 8.33 (d, J = 5.6 Hz, 1H), 8.25 (s, 1H), 8.11 (d, J = 9.5 Hz, 1H), 8.01-7.99 (m, 1H), 6.59 (d, J = 5.6 Hz, 1H), 3.95 (q, J = 7.4 Hz, 2H), 3.36 (d, J = 7.8 Hz, 1H), 1.41 (d, J = 6.6 Hz, 3H), 1.39-1.35 (m, 1H), 1.30 (t, J = 7.3 Hz, 3H), 0.57-0.53 (m, 1H), 0.51-0.45 (m, 1H), 0.41-0.33 (m, 2H); ESI MS (m/z) 480.2 (MH)+.} 115 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.83 (s, 1H), 8.99 (d, J = 4.4 Hz, 1H), 8.15 (d, J = 9.3 Hz, 1H), 8.03 (dd, J = 9.5, 1.7 Hz, 1H), 7.69 (d, J = 4.4 Hz, 1H), 3.91 (q, J = 7.4 Hz, 2H), 2.39-2.29 (m, 3H), 1.28 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 461.2 (MH)+.} 116 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.09 (s, 1H), 8.11 (s, 1H), 7.24 (d, J = 6.4 Hz, 1H), 5.86 (d, J = 6.1 Hz, 1H), 3.88 (s, 3H), 3.74 (q, J = 7.4 Hz, 2H), 1.26-1.21 (m, 12H); ESI MS (m/z) 498.0 (MH)+.} 117 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.78 (s, 1H), 8.48 (d, J = 5.2 Hz, 1H), 8.10 (d, J = 9.5 Hz, 1H), 8.02-7.98 (m, 1H), 6.99 (d, J = 5.2 Hz, 1H), 3.93-3.84 (m, 2H), 3.09 (d, J = 14.4 Hz, 3H), 1.46 (t, J = 14.8 Hz, 9H), 1.34-1.24 (m, 3H); ESI MS (m/z) 482.0 (MH)+.} 118 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.78 (s, 1H), 8.36 (d, J = 5.5 Hz, 1H), 8.10 (d, J = 9.5 Hz, 1H), 7.99 (dd, J = 9.5, 1.5 Hz, 1H), 6.81 (s, 1H), 6.77 (d, J = 5.5 Hz, 1H), 3.93 (q, J = 7.3 Hz, 2H), 1.90 (q, J = 7.4 Hz, 2H), 1.49 (d, J = 14.4 Hz, 6H), 1.28 (t, J = 7.3 Hz, 3H), 0.89 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 482.0 (MH)+.} 119 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.79 (s, 1H), 8.74 (d, J = 9.0 Hz, 1H), 8.47 (d, J = 5.4 Hz, 1H), 8.10 (d, J = 9.5 Hz, 1H), 8.00 (dd, J = 9.5, 1.7 Hz, 1H), 6.91 (d, J = 5.6 Hz, 1H), 5.06-4.97 (m, 1H), 3.93 (q, J = 7.4 Hz, 2H), 1.59 (d, J = 6.8 Hz, 3H), 1.28 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 507.9 (MH)+} 120 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.85 (s, 1H), 9.18 (d, J = 5.1 Hz, 2H), 9.04 (d, J = 4.4 Hz, 1H), 8.15 (d, J = 9.3 Hz, 1H), 8.03 (dd, J = 9.4, 1.8 Hz, 1H), 7.82 (dd, J = 6.0, 4.5 Hz, 2H), 3.88 (q, J = 7.3 Hz, 2H), 1.24 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 474.9 (MH)+.} 121 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.97 (s, 1H), 8.41 (d, J = 5.4 Hz, 1H), 8.22 (s, 1H), 6.71 (d, J = 5.6 Hz, 1H), 3.87 (s, 3H), 3.74 (q, J = 7.3 Hz, 2H), 2.79-2.74 (m, 1H), 1.24 (t, J = 7.3 Hz, 3H), 0.94-0.86 (m, 2H), 0.85-0.79 (m, 2H);ESI MS (m/z) 465.9 (MH)+.} 122 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.93 (d, J = 8.3 Hz, 1H), 8.45 (d, J = 5.6 Hz, 1H), 8.23 (s, 1H), 6.94 (d, J = 5.6 Hz, 1H), 5.04 (d, J = 7.3 Hz, 1H), 3.88 (s, 3H), 3.77 (q, J = 7.3 Hz, 2H), 1.59 (d, J = 6.8 Hz, 3H), 1.25 (q, J = 7.1 Hz, 3H); ESI MS (m/z) 521.9 (MH)+.} 123 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.33 (d, J = 5.4 Hz, 1H), 8.21 (d, J = 0.7 Hz, 1H), 6.56 (d, J = 5.6 Hz, 1H), 4.01 (q, J = 7.0 Hz, 2H), 3.87 (s, 3H), 3.73 (q, J = 7.3 Hz, 2H), 3.33 (s, 3H), 1.32 (t, J = 7.0 Hz, 3H), 1.27-1.22 (m, 3H);ESI MS (m/z) 468.1 (MH)+.} 124 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.73 (s, 1H), 8.34 (d, J = 5.4 Hz, 1H), 8.22 (s, 1H), 6.66 (d, J = 5.6 Hz, 1H), 3.87 (d, J = ESI MS (m/z) 479.9 (MH)+.} 125 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 9.00 (s, 1H), 8.42-8.39 (m, 1H), 8.21 (s, 1H), 6.67 (d, J = 5.4 Hz, 1H), 3.87 (s, 3H), 3.75 (q, J = 7.3 Hz, 2H), 1.44 (s, 3H), 1.25 (t, J = 7.3 Hz, 3H), 0.98-0.91 (m, 2H), 0.87-0.84 (m, 2H);ESI MS (m/z) 480.1 (MH)+.} 126 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.05 (s, 1H), 8.53 (d, J = 3.9 Hz, 1H), 8.27 (s, 1H), 7.18 (s, 1H), 6.50 (s, 1H), 4.13 (t, J = 7.2 Hz, 2H), 3.99 (d, J = 13.4 Hz, 3H), 3.89 (d, J = 5.9 Hz, 2H), 1.47 (d, J = 13.7 Hz, 3H); ESI MS (m/z) 507.8 (MH)+.} 127 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.46 (d, J = 5.1 Hz, 1H), 8.22 (s, 1H), 7.02 (d, J = 5.1 Hz, 1H), 3.89 (d, J = 8.3 Hz, 3H), 3.73 (q, J = 7.3 Hz, 2H), 3.14 (s, 3H), 1.57-1.42 (m, 9H), 1.33-1.22 (m, 3H); ESI MS (m/z) 496.0 (MH)+.} 128 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 9.04 (s, 1H), 8.38 (d, J = 5.4 Hz, 1H), 8.22 (s, 1H), 6.62 (d, J = 5.6 Hz, 1H), 4.29 (dd, J = 13.6, 6.2 Hz, 1H), 3.88 (d, J = 9.5 Hz, 3H), 3.76 (q, J = 7.4 Hz, 2H), 3.20-3.01 (m, 4H), 1.27-1.22 (m, 3H); ESI MS (m/z) 515.9 (MH)+.} 129 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.69-8.94 (1H), 8.41 (d, J = 5.4 Hz, 1H), 8.22 (s, 1H), 6.79 (d, J = 5.6 Hz, 1H), 3.89 (s, 3H), 3.83-3.75 (m, 4H), 2.95 (t, J = 6.5 Hz, 2H), 1.27-1.22 (m, 3H); ESI MS (m/z) 478.9 (MH)+.} 130 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.57 (s, 1H), 8.35 (d, J = 5.5 Hz, 1H), 8.21 (d, J = 0.6 Hz, 1H), 6.65 (d, J = 5.5 Hz, 1H), 3.88 (d, J = 5.2 Hz, 3H), 3.77 (q, J = 7.3 Hz, 2H), 3.65 (dt, J = 21.9, 4.9 Hz, 4H), 3.29 (s, 3H), 1.27-1.22 (m, 3H);ESI MS (m/z) 483.9 (MH)+.} 131 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.65 (s, 1H), 8.34 (d, J = 5.5 Hz, 1H), 8.21 (d, J = 0.6 Hz, 1H), 6.59 (d, J = 5.5 Hz, 1H), 3.88 (s, 3H), 3.76 (q, J = 7.3 Hz, 2H), 3.53 (q, J = 7.1 Hz, 2H), 1.28-1.22 (m, 6H); ESI MS (m/z) 453.9 (MH)+.} 132 _{1H-NMR (400 MHz, CHLOROFORM- d) δ 9 8.93 (d, J = 6.8 Hz, 1H), 8.26 (d, J = 5.4 Hz, 1H), 8.13 (s, 1H), 6.21 (d, J = 5.4 Hz, 1H), 3.94 (q, J = 6.9 Hz, 7H), 3.71-3.63 (m, 2H), 1.46-1.40 (m, 9H); ESI MS (m/z) 482.1 (MH)+.} 133 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.07 (s, 1H), 9.20 (d, J = 7.1 Hz, 1H), 8.36 (s, 1H), 7.57 (dd, J = 7.2, 1.8 Hz, 1H), 7.31 (d, J = 8.1 Hz, 1H), 6.21 (d, J = 7.8 Hz, 1H), 4.34-4.28 (m, 1H), 3.94 (q, J = 7.4 Hz, 2H), 1.26-1.15 (m, 9H);ESI MS (m/z) 470.0 (MH)+} 134 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84 (t, J = 1.1 Hz, 1H), 8.69 (d, J = 4.6 Hz, 1H), 8.62-8.62 (m, 1H), 7.13 (d, J = 4.6 Hz, 1H), 3.99 (tt, J = 21.4, 7.1 Hz, 2H), 3.73 (s, 3H), 2.94-2.90 (m, 1H), 1.61 (ddd, J = 25.4, 15.7, 7.0 Hz, 2H), 1.48-1.44 (m, 2H), 1.35-1.28 (m, 5H), 0.48-0.44 (m, 1H), 0.13-0.11 (m, 2H), -0.29--0.32 (m, 2H);ESI MS (m/z) 532.25 (MH)+.} 135 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84 (d, J = 1.5 Hz, 1H), 8.76 (d, J = 4.6 Hz, 1H), 8.62 (d, J = 1.7 Hz, 1H), 7.20 (d, J = 4.6 Hz, 1H), 4.44-4.30 (m, 2H), 3.76 (d, J = 6.8 Hz, 3H), 2.93-2.89 (m, 1H), 1.49-1.45 (m, 2H), 1.39 (t, J = 7.2 Hz, 3H), 1.36-1.32 (m, 2H);ESI MS (m/z) 561.90 (MH)+.} 136 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.83 (d, J = 1.5 Hz, 1H), 8.75 (d, J = 4.6 Hz, 1H), 8.60 (d, J = 1.5 Hz, 1H), 7.20 (d, J = 4.6 Hz, 1H), 4.47 1.41 (t, J = 7.3 Hz, 3H), 1.37-1.33 (m, 2H);ESI MS (m/z) 595.90 (MH)+.} 137 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.21 (s, 1H), 9.21 (s, 1H), 8.72 (d, J = 5.1 Hz, 1H), 8.24 (d, J = 0.7 Hz, 1H), 8.01 (d, J = 5.1 Hz, 1H), 3.87 (s, 3H), 3.78 (q, J = 7.3 Hz, 2H), 3.33-3.26 (m, 1H), 1.27 (t, J = 7.5 Hz, 3H), 1.19 (d, J = 6.8 Hz, 6H); ESI MS (m/z) 495.9 (MH)+.} 138 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.3 Hz, 1H), 8.47 (s, 1H), 8.35 (d, J = 5.4 Hz, 1H), 7.54 (dd, J = 7.2, 1.8 Hz, 1H), 6.53 (d, J = 5.6 Hz, 1H), 4.00 (q, J = 6.9 Hz, 2H), 3.86 (q, J = 7.4 Hz, 2H), 3.29 (s, 3H), 1.31-1.22 (m, 6H); ESI MS (m/z) 454.2 (MH)+.} 139 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.34-8.31 (m, 2H), 8.21 (d, J = 0.7 Hz, 1H), 6.62 (d, J = 5.9 Hz, 1H), 4.13-3.99 (m, 1H), 3.89 (d, J = 12.2 Hz, 3H), 3.79-3.69 (m, 2H), 1.36-1.31 (m, 6H), 1.29-1.20 (m, 3H); ESI MS (m/z) 467.9 (MH)+.} 140 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.53 (s, 1H), 8.83 (t, J = 1.0 Hz, 1H), 8.60-8.57 (m, 1H), 7.26 (d, J = 7.3 Hz, 1H), 6.17 (d, J = 7.6 Hz, 1H), 4.35-4.28 (m, 1H), 3.72 (s, 3H), 3.50 (d, J = 7.6 Hz, 2H), 1.26 (d, J = 6.4 Hz, 6H), 1.20 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 484.1 (MH)+.} 141 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.48 (s, 1H), 8.35 (d, J = 5.6 Hz, 1H), 8.22 (d, J = 0.7 Hz, 1H), 6.65 (d, J = 5.6 Hz, 1H), 3.91 (d, J = 20.5 Hz, 3H), 3.78 (q, J = 7.3 Hz, 2H), 3.68 (td, J = 12.0, 6.0 Hz, 1H), 3.57-3.49 (m, 2H), 3.27 (d, J = 12.0 Hz, 3H), 1.33-1.22 (m, 3H), 1.17 (d, J = 6.1 Hz, 3H);ESI MS (m/z) 498.1 (MH)+.} 142 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.31 (d, J = 7.3 Hz, 1H), 8.65 (d, J = 4.9 Hz, 1H), 8.50 (t, J = 0.9 Hz, 1H), 7.57 (dd, J = 7.2, 2.0 Hz, 1H), 7.03 (d, J = 4.9 Hz, 1H), 3.91 (q, J = 7.4 Hz, 2H), 3.81 (s, 3H), 3.65 (s, 3H), 1.29-1.26 (m, 3H); ESI MS (m/z) 456.1 (MH)+.} 143 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.3 Hz, 1H), 8.47 (d, J = 0.9 Hz, 1H), 8.30 (d, J = 5.8 Hz, 1H), 7.54 (dd, J = 7.2, 2.0 Hz, 1H), 6.55 (d, J = 5.8 Hz, 1H), 3.86 (dt, J = 15.9, 7.2 Hz, 6H), 1.28 (dt, J = 16.2, 7.2 Hz, 9H); ESI MS (m/z) 468.4 (MH)+.} 144 _{1H-NMR (400 MHz, DMSO- d6 ) δ 89.30 (d, J = 7.0 Hz, 1H), 8.87 (s, 1H), 8.50-8.48 (m, 2H), 7.56 (dd, J = 7.2, 2.0 Hz, 1H), 6.82 (d, J = 5.2 Hz, 1H), 4.46 (t, J = 15.1 Hz, 2H), 3.94 (q, J = 7.4 Hz, 2H), 1.29-1.25 (m, 3H); ESI MS (m/z) 544.0 (MH)+.} 145 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.57 (s, 1H), 8.83 (d, J = 1.5 Hz, 1H), 8.60 (d, J = 1.5 Hz, 1H), 7.29 (d, J = 7.8 Hz, 1H), 6.18 (d, J = 7.6 Hz, 1H), 4.12 (q, J = 7.0 Hz, 2H), 3.71 (s, 3H), 3.50 (q, J = 7.2 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H), 1.22-1.17 (m, 3H);ESI MS (m/z) 470.0 (MH)+.} 146 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.1 Hz, 1H), 8.47 (s, 1H), 8.36 (d, J = 5.4 Hz, 1H), 7.55 (dd, J = 7.1, 2.0 Hz, 1H), 7.34 (d, J = 10.3 Hz, 1H), 6.77 (d, J = 5.9 Hz, 1H), 3.93 (tt, J = 21.6, 7.3 Hz, 3H), 1.32-1.22 (m, 6H), 0.98 (s, 9H); ESI MS (m/z) 496.2 (MH)+.} 147 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (t, J = 0.9 Hz, 1H), 8.65 (d, J = 4.6 Hz, 1H), 8.60 (t, J = 1.1 Hz, 1H), 7.07 (d, J = 4.6 Hz, 1H), 4.77 (s, 1H), 3.78 (s, 3H), 3.64-3.49 (m, 2H), 2.95-2.89 (m, 1H), 1.46-1.41 (m, 2H), 1.31-1.22 (m, 5H);ESI MS (m/z) 450.20 (MH)+.} 148 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (dd, J = 2.1, 0.6 Hz, 1H), 8.65 (d, J = 4.6 Hz, 1H), 8.60 (d, J = 1.5 Hz, 1H), 7.07 (d, J = 4.6 Hz, 1H), 4.77 (s, 1H), 3.78 (s, 3H), 3.64-3.53 (m, 2H), 2.95-2.89 (m, 1H), 1.46-1.41 (m, 2H), 1.31-1.24 (m, 5H); ESI MS (m/z) 450.20 (MH)+.} 149 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.22 (s, 1H), 8.73 (d, J = 4.6 Hz, 1H), 8.25 (d, J = 1.0 Hz, 1H), 7.18 (d, J = 4.6 Hz, 1H), 5.86 (t, J = 53.9 Hz, 1H), 4.26-4.10 (m, 2H), 3.82 (s, 3H), 2.94-2.88 (m, 1H), 1.51-1.43 (m, 2H), 1.40-1.28 (m, 5H); ESI MS (m/z) 574.0 (MH)+.} 150 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.1 Hz, 1H), 8.48 (s, 1H), 8.36 (t, J = 5.5 Hz, 1H), 7.55 (dd, J = 7.3, 2.0 Hz, 1H), 6.81 (s, 1H), 6.77 (d, J = 5.4 Hz, 1H), 3.93 (q, J = 7.3 Hz, 2H), 1.90 (q, J = 7.4 Hz, 2H), 1.50 (s, 6H), 1.30-1.22 (m, 3H), 0.89 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 482.1 (MH)+.} 151 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.1 Hz, 1H), 8.47 (s, 1H), 8.32 (d, J = 5.6 Hz, 1H), 8.25 (s, 1H), 7.55 (dd, J = 7.2, 1.8 Hz, 1H), 6.57 (d, J = 5.9 Hz, 1H), 3.93 (q, J = 7.4 Hz, 2H), 1.39 (t, J = 6.5 Hz, 3H), 1.36-1.32 (m, 1H), 1.30-1.24 (m, 3H), 0.92 (t, J = 7.1 Hz, 1H), 0.58-0.43 (m, 2H), 0.39-0.29 (m, 2H);ESI MS (m/z) 480.1 (MH)+.} 152 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.24 (s, 1H), 8.75 (d, J = 4.4 Hz, 1H), 8.24 (d, J = 0.7 Hz, 1H), 7.21 (d, J = 4.6 Hz, 1H), 4.39-4.24 (m, 2H), 3.85 (s, 3H), 2.92-2.85 (m, 1H), 1.51-1.43 (m, 2H), 1.40-1.28 (m, 5H); ESI MS (m/z) 546.2 (MH)+.} 153 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.3 Hz, 1H), 8.48 (d, J = 5.1 Hz, 2H), 7.55 (dd, J = 7.3, 2.0 Hz, 1H), 7.00 (d, J = 5.1 Hz, 1H), 3.86 (q, J = 7.3 Hz, 2H), 3.11 (s, 3H), 1.50-1.42 (m, 9H), 1.32-1.26 (m, 3H); ESI MS (m/z) 481.9 (MH)+.} 154 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.3 Hz, 1H), 8.48-8.46 (m, 2H), 7.55 (dd, J = 7.1, 2.0 Hz, 1H), 6.84 (d, J = 5.4 Hz, 1H), 3.87 ESI MS (m/z) 466.2 (MH)+.} 155 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.1 Hz, 1H), 8.50-8.47 (m, 2H), 8.36 (d, J = 5.4 Hz, 1H), 7.55 (dd, J = 7.1, 2.0 Hz, 1H), 6.52 (d, J = 5.6 Hz, 1H), 3.91 (q, J = 7.4 Hz, 2H), 3.52 (d, J = 3.7 Hz, 2H), 3.43 (t, J = 6.0 Hz, 2H), 3.24 (d, J = 12.2 Hz, 3H), 1.94-1.87 (m, 2H), 1.28-1.22 (m, 3H); ESI MS (m/z) 483.9(MH)+.} 156 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.23 (s, 1H), 8.70 (d, J = 4.4 Hz, 1H), 8.25 (d, J = 0.7 Hz, 1H), 7.14 (d, J = 4.6 Hz, 1H), 4.14-4.07 (m, 1H), 4.05-3.98 (m, 1H), 3.83 (d, J = 11.5 Hz, 3H), 2.91-2.86 (m, 1H), 1.48-1.41 (m, 2H), 1.35-1.28 (m, 5H), 0.69 (s, 9H);ESI MS (m/z) 534.4 (MH)+.} 157 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.30 (d, J = 7.1 Hz, 1H), 8.49-8.48 (m, 2H), 7.70 (s, 1H), 7.56 (dd, J = 7.1, 2.0 Hz, 1H), 6.91 (d, J = 5.6 Hz, 1H), 3.92 (q, J = 7.4 Hz, 2H), 3.69 (s, 1H), 1.79 (s, 6H), 1.27 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 477.9 (MH)+.} 158 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.1 Hz, 1H), 8.69 (s, 1H), 8.48 (t, J = 0.9 Hz, 1H), 8.42 (d, J = 5.4 Hz, 1H), 7.55 (dd, J = 7.3, 2.0 Hz, 1H), 6.75 (d, J = 5.4 Hz, 1H), 3.94 (q, J = 7.4 Hz, 2H), 3.80 (t, J = 5.9 Hz, 2H), 2.95 (t, J = 6.6 Hz, 2H), 1.27 (t, J = 7.3 Hz, 3H);ESI MS (m/z) 464.9 (MH)+.} 159 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.1 Hz, 1H), 8.47 (t, J = 0.9 Hz, 1H), 8.37-8.34 (m, 1H), 7.55 (dd, J = 7.3, 2.0 Hz, 1H), 6.62 (q, J = 5.5 Hz, 1H), 4.66 (dd, J = 7.8, 6.1 Hz, 2H), 4.41 (t, J = 6.0 Hz, 2H), 3.92 (q, J = 7.4 Hz, 2H), 3.79 (d, J = 7.3 Hz, 2H), 3.42-3.35 (m, 1H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 481.9 (MH)+.} 160 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.30 (d, J = 7.1 Hz, 1H), 8.52-8.49 (m, 2H), 7.56 (dd, J = 7.2, 1.8 Hz, 1H), 6.78 (d, J = 5.1 Hz, 1H), 3.88 (q, J = 7.7 Hz, 10H), 1.27 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 481.9 (MH)+.} 161 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.27 (d, J = 7.3 Hz, 1H), 8.45 (s, 1H), 8.26 (d, J = 5.4 Hz, 1H), 7.53 (dd, J = 7.1, 2.0 Hz, 1H), 6.13 (d, J = 5.4 Hz, 1H), 4.61 (s, 4H), 3.83 (q, J = 7.3 Hz, 2H), 2.44 (t, J = 7.7 Hz, 2H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 452.0 (MH)+.} 162 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.27 (d, J = 7.3 Hz, 1H), 8.46 (t, J = 0.9 Hz, 1H), 8.24 (d, J = 5.6 Hz, 1H), 7.54 (dd, J = 7.2, 1.8 Hz, 1H), 6.30 (d, J=5.4 Hz, 1H), 4.03 (d, J=27.9 Hz, 4H), 3.85 (q, J=7.4 Hz, 2H), 2.00 (t, J=6.7 Hz, 4H), 1.26 (t, J=7.3 Hz, 3H);ESI MS (m/z) 466.1 (MH)+.} 163 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.1 Hz, 1H), 8.49-8.48 (m, 2H), 7.55 (dd, J = 7.1, 2.0 Hz, 1H), 6.77 (d, J = 5.4 Hz, 1H), 3.88 (q, J = 7.4 Hz, 6H), 2.55 (t, J = 4.8 Hz, 4H), 2.26 (s, 3H), 1.28 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 494.5 (MH)+.} 164 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.30 (d, J = 7.3 Hz, 1H), 8.74 (d, J = 9.0 Hz, 1H), 8.49-8.46 (m, 2H), 7.56 (dd, J = 7.1, 2.0 Hz, 1H), 6.91 (d, J = 5.6 Hz, 1H), 5.01 (t, J = 7.6 Hz, 1H), 3.93 (q, J = 7.4 Hz, 2H), 1.59 (d, J = 6.8 Hz, 3H), 1.28 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 507.9 (MH)+.} 165 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.1 Hz, 1H), 8.86 (s, 1H), 8.47 (s, 1H), 8.39 (d, J = 5.4 Hz, 1H), 7.55 (dd, J = 7.3, 2.0 Hz, 1H), 6.62 (d, J = 5.4 Hz, 1H), 3.90 (q, J = 7.4 Hz, 2H), 1.68 (q, J = 7.3 Hz, 2H), 1.26 (t, J = 7.5 Hz, 3H), 0.98-0.94 (m, 5H), 0.87-0.84 (m, 2H);ESI MS (m/z) 480.2 (MH)+.} 166 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.1 Hz, 1H), 8.47 (s, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.55 (dd, J = 7.1, 2.0 Hz, 1H), 6.65 (d, J = 5.4 Hz, 1H), 3.94 (q, J = 7.0 Hz, 2H), 3.89-3.82 (m, 4H), 1.31-1.22 (m, 7H), 0.54-0.49 (m, 2H), 0.37-0.34 (m, 2H);ESI MS (m/z) 494.0 MH)+.} 167 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.30 (d, J = 7.1 Hz, 1H), 8.58 (d, J = 5.1 Hz, 1H), 8.50 (s, 1H), 7.56 (dd, J = 7.1, 2.0 Hz, 1H), 6.83 (d, J = 5.4 Hz, 1H), 5.16 (s, 2H), 3.90 (q, J = 7.3 Hz, 2H), 1.28 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 464.9 MH)+.} 168 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.3 Hz, 1H), 8.69 (s, 1H), 8.48 (t, J = 0.9 Hz, 1H), 8.43 (d, J = 5.6 Hz, 1H), 7.55 (dd, J = 7.1, 2.0 Hz, 1H), 6.74 (d, J = 5.4 Hz, 1H), 4.03-3.91 (m, 4H), 1.73 (t, J = 19.2 Hz, 3H), 1.29-1.26 (m, 3H); ESI MS (m/z) 490.1 MH)+.} 169 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.3 Hz, 1H), 8.48 (s, 1H), 8.42 (d, J = 5.1 Hz, 1H), 7.55 (dd, J = 7.1, 2.0 Hz, 1H), 6.54 (d, J = 5.4 Hz, 1H), 4.44 (t, J = 7.2 Hz, 1H), 4.03 (q, J = 7.0 Hz, 2H), 3.88 (q, J = 7.3 Hz, 2H), 2.41 (dd, J = 15.3, 7.0 Hz, 2H), 2.12 (q, J = 9.6 Hz, 2H), 1.74-1.67 (m, 2H), 1.27 (t, J = 7.3 Hz, 3H), 1.07 (t, J = 7.0 Hz, 3H); ESI MS (m/z) 493.9 MH)+.} 170 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.59 (s, 1H), 9.30 (d, J = 7.3 Hz, 1H), 8.58 (d, J = 5.1 Hz, 1H), 8.48 (s, 1H), 7.56 (dd, J = 7.2, 1.8 Hz, 1H), 6.83 (d, J = 5.1 Hz, 1H), 3.91 (q, J = 7.4 Hz, 2H), 1.79 (dd, J = 8.4, 5.5 Hz, 2H), 1.57 (dd, J = 8.6, 5.6 Hz, 2H), 1.27 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 477.1 MH)+.} 171 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.18 (s, 1H), 8.98 (s, 1H), 8.37 (d, J = 5.4 Hz, 1H), 8.20 (d, J = 0.7 Hz, 1H), 6.63 (d, J = 5.4 Hz, 1H), 4.65 (s, 1H), 3.88 (s, 3H), 3.67-3.54 (m, 2H), 1.45 (s, 3H), 1.25 (t, J = 7.3 Hz, 3H), 0.98-0.95 (m, 2H), 0.92-0.85 (m, 2H);ESI MS (m/z) 478.9 MH)+.} 172 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.1 Hz, 1H), 8.76 (s, 1H), 8.46 (s, 1H), 8.42 (t, J = 5.0 Hz, 1H), 7.54 (dd, J = 7.3, 1.7 Hz, 1H), 6.55 (d, J = 5.4 Hz, 1H), 3.88 (q, J = 7.3 Hz, 2H), 2.45 (t, J = 3.5 Hz, 1H), 1.25 (t, J = 7.3 Hz, 3H), 1.18-1.11 (m, 4H), 1.01-0.96 (m, 1H), 0.73-0.69 (m, 1H);ESI MS (m/z) 465.9 MH)+.} 173 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.3 Hz, 1H), 8.71 (s, 1H), 8.46 (s, 1H), 8.38 (d, J = 5.4 Hz, 1H), 7.54 (dd, J = 7.2, 1.8 Hz, 1H), 6.70 (d, J = 5.6 Hz, 1H), 4.97 (t, J = 6.0 Hz, 1H), 3.90 (q, J = 7.4 Hz, 2H), 3.58 (d, J = 5.9 Hz, 2H), 1.27 (t, J = 7.3 Hz, 3H), 0.97 (dd, J = 15.5, 10.1 Hz, 4H); ESI MS (m/z) 481.9 MH)+.} 174 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.34 (d, J = 7.1 Hz, 1H), 8.99 (d, J = 4.2 Hz, 1H), 8.54 (s, 1H), 7.69 (d, J = 4.2 Hz, 1H), 7.60 (dd, J = 7.2, 1.8 Hz, 1H), 3.91 (q, J = 7.3 Hz, 2H), 2.39-2.29 (m, 3H), 1.28 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 460.9 MH)+.} 175 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.18 (s, 1H), 8.96 (s, 1H), 8.35 (d, J = 5.4 Hz, 1H), 8.21 (s, 1H), 6.61 (d, J = 5.4 Hz, 1H), 4.67 (s, 1H), 3.89 (s, 3H), 3.62 (dt, J = 24.9, 7.2 Hz, 2H), 1.72-1.66 (m, 2H), 1.25 (t, J = 7.3 Hz, 3H), 0.99-0.93 (m, 5H), 0.89-0.86 (m, 2H);ESI MS (m/z) 492.9 MH)+.} 176 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.50 (d, J = 9.0 Hz, 1H), 8.30 (d, J = 5.6 Hz, 1H), 8.22 (s, 1H), 6.61 (d, J = 5.6 Hz, 1H), 3.89 (d, J = 8.1 Hz, 3H), 3.78 (q, J = 7.4 Hz, 2H), 3.37 (q, J = 7.0 Hz, 1H), 1.41-1.37 (m, 3H), 1.36-1.32 (m, 1H), 1.28-1.22 (m, 3H), 0.57-0.52 (m, 1H), 0.50-0.45 (m, 1H), 0.38-0.31 (m, 2H);ESI MS (m/z) 494.0 MH)+.} 177 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.96 (s, 1H), 8.42-8.40 (m, 1H), 8.21 (s, 1H), 6.59 (d, J = 5.4 Hz, 1H), 3.87 (s, 3H), 3.79-3.71 (m, 2H), 2.43-2.47 (1H), 1.24 (t, J = 7.3 Hz, 3H), 1.18-1.11 (m, 4H), 1.03-0.98 (m, 1H), 0.73 (dd, J = 12.3, 5.5 Hz, 1H);ESI MS (m/z) 479.9 MH)+.} 178 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 9.12 (d, J = 9.3 Hz, 1H), 8.43 (d, J = 5.6 Hz, 1H), 8.22 (s, 1H), 6.85 (d, J = 5.6 Hz, 1H), 5.39 (q, J = 9.3 Hz, 1H), 4.74 (t, J = 8.4 Hz, 1H), 4.39 (dd, J = 10.3, 8.3 Hz, 1H), 3.89 (s, 3H), 3.80-3.75 (m, 2H), 3.65-3.54 (m, 2H), 1.26 (t, J = 7.3 Hz, 3H), 1.19 (t, J = 7.1 Hz, 3H); ESI MS (m/z) 538.9 MH)+.} 179 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.21 (s, 1H), 8.84 (t, J = 6.5 Hz, 1H), 8.39 (d, J = 5.6 Hz, 1H), 8.23 (s, 1H), 6.62 (d, J = 5.4 Hz, 1H), 4.41 (d, J = 6.4 Hz, 2H), 3.90 (s, 3H), 3.78 (q, J = 7.3 Hz, 2H), 3.72 (s, 3H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 497.9 MH)+.} 180 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.18 (s, 1H), 8.43 (d, J = 5.4 Hz, 1H), 8.22 (s, 1H), 6.97 (d, J = 5.1 Hz, 1H), 4.72 (s, 1H), 3.90 (s, 3H), 3.61-3.54 (m, 2H), 3.15 (s, 3H), 1.48 (s, 9H), 1.28 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 495.0 MH)+.} 181 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.82 (s, 1H), 8.39 (d, J = 5.4 Hz, 1H), 8.22 (s, 1H), 6.61 (d, J = 5.6 Hz, 1H), 4.39 (d, J = 4.2 Hz, 2H), 4.18 (q, J = 7.1 Hz, 2H), 3.90 (s, 3H), 3.78 (q, J = 7.3 Hz, 2H), 1.28-1.22 (m, 6H); ESI MS (m/z) 512.0 MH)+.} 182 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.45 (s, 1H), 9.21 (s, 1H), 8.41 (d, J = 5.5 Hz, 1H), 8.23 (s, 1H), 6.57 (d, J = 5.5 Hz, 1H), 3.89 (s, 3H), 3.76 (q, J = 7.3 Hz, 2H), 3.65 (s, 3H), 1.69 (d, J = 3.4 Hz, 2H), 1.47 (d, J = 3.1 Hz, 2H), 1.26 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 524.0 MH)+.} 183 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.39 (d, J = 5.4 Hz, 1H), 8.31 (s, 1H), 8.23 (d, J = 0.7 Hz, 1H), 6.56 (d, J = 5.6 Hz, 1H), 4.41 (s, 2H), 3.90 (s, 3H), 3.78 (q, J = 7.4 Hz, 2H), 3.06 (s, 3H), 2.91 (s, 3H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 510.9 MH)+.} 184 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.29 (s, 1H), 9.23 (s, 1H), 8.81 (d, J = 4.9 Hz, 1H), 8.26 (d, J = 0.9 Hz, 1H), 7.94 (d, J = 4.9 Hz, 1H), 4.39 (q, J = 7.1 Hz, 2H), 3.90 (s, 3H), 3.78 (q, J = 7.4 Hz, 2H), 1.36 (t, J = 7.2 Hz, 3H), 1.27 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 525.9 MH)+.} 185 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.81 (s, 1H), 8.48 (d, J = 5.1 Hz, 1H), 8.11 (d, J = 9.3 Hz, 1H), 7.99 (dd, J = 9.3, 1.7 Hz, 1H), 6.95 (d, J = 5.1 Hz, 1H), 5.21 (s, 1H), 3.77-3.65 (m, 2H), 3.11 (s, 3H), 1.46 (s, 9H), 1.37 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 481.1 MH)+.} 186 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.13 (d, J = 9.3 Hz, 1H), 9.83 (s, 1H), 8.83 (d, J = 4.9 Hz, 1H), 8.14 (d, J = 9.3 Hz, 1H), 8.04-8.01 (m, 1H), 7.90 (d, J = 4.9 Hz, 1H), 4.39 (q, J = 7.1 Hz, 2H), 3.98 (q, J = 7.3 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H), 1.29 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 511.9 MH)+.} 187 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.74 (s, 1H), 9.20 (s, 1H), 8.57 (d, J = 5.5 Hz, 1H), 8.24 (d, J = 8.3 Hz, 1H), 6.87 (d, J = 5.2 Hz, 1H), 3.87 (s, 3H), 3.75 (q, J = 7.3 Hz, 2H), 1.90-1.76 (m, 2H), 1.57 (dd, J = 8.1, 5.7 Hz, 2H), 1.27-1.22 (m, 3H); ESI MS (m/z) 490.8 MH)+.} 188 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.07 (s, 1H), 9.79 (s, 1H), 8.67 (d, J = 5.2 Hz, 1H), 8.11 (d, J = 9.5 Hz, 1H), 8.00 (dd, J = 9.5, 1.5 Hz, 1H), 7.67 (d, J = 5.2 Hz, 1H), 3.92 (q, J = 7.3 Hz, 2H), 3.84 (s, 3H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 469.9 MH)+.} 189 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.28 (d, J = 7.1 Hz, 1H), 8.48 (d, J = 13.9 Hz, 2H), 8.37 (d, J = 5.1 Hz, 1H), 7.55 (d, J = 6.1 Hz, 1H), 6.63 (d, J = 5.4 Hz, 1H), 3.92 (q, J = 7.3 Hz, 2H), 3.68 (t, J = 6.5 Hz, 2H), 2.81 (t, J = 7.0 Hz, 2H), 2.15 (s, 3H), 1.26 (t, J = 7.5 Hz, 3H);ESI MS (m/z) 486.0 MH)+.} 190 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.61 (s, 1H), 9.22 (s, 1H), 8.24 (s, 1H), 7.34 (s, 1H), 6.24 (s, 1H), 3.89 (d, J = 7.1 Hz, 2H), 3.83 (s, 3H), 3.52 (d, J = 6.8 Hz, 2H), 1.22-1.15 (m, 4H), 0.53 (d, J = 7.6 Hz, 2H), 0.30 (d, J = 4.6 Hz, 2H);ESI MS (m/z) 496.6 MH)+.} 191 _{1H-NMR (400 MHz, DMSO- d6 ) δ 11.60 (s, 1H), 9.22 (s, 1H), 8.24 (s, 1H), 7.34 (s, 1H), 6.22 (d, J = 7.3 Hz, 1H), 3.84 (d, J = 6.4 Hz, 5H), 3.52 (q, J = 7.2 Hz, 2H), 2.05-1.98 (m, 1H), 1.22-1.16 (m, 3H), 0.93 (d, J = 6.8 Hz, 6H); ESI MS (m/z) 498.6 MH)+.} 192 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.20 (s, 1H), 8.41 (d, J = 5.4 Hz, 1H), 8.22 (s, 1H), 6.92 (d, J = 5.4 Hz, 1H), 5.54 (s, 2H), 3.87 (s, 3H), 3.75 (q, J = 7.4 Hz, 2H), 3.39-3.36 (m, 1H), 1.24 (t, J = 7.3 Hz, 3H), 0.92-0.88 (m, 4H); ESI MS (m/z) 481.0 MH)+.} 193 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.43 (s, 1H), 9.21 (s, 1H), 8.41 (d, J = 5.4 Hz, 1H), 8.23 (s, 1H), 6.55 (d, J = 5.4 Hz, 1H), 4.12 (q, J = 7.1 Hz, 2H), 3.88 (s, 3H), 3.76 (d, J = 7.3 Hz, 2H), 1.69 (d, J = 3.2 Hz, 2H), 1.46 (d, J = 2.9 Hz, 2H), 1.26 (t, J = 7.3 Hz, 3H), 1.14 (t, J = 7.1 Hz, 3H);ESI MS (m/z) 538.2 MH)+.} 194 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.19 (s, 1H), 8.96 (s, 1H), 8.37 (d, J = 5.4 Hz, 1H), 8.22 (d, J = 0.7 Hz, 1H), 6.75 (d, J = 5.4 Hz, 1H), 4.99 (t, J = 6.0 Hz, 1H), 3.87 (s, 3H), 3.76 (q, J = 7.3 Hz, 2H), 3.59 (d, J = 5.9 Hz, 2H), 1.25 (t, J = 7.3 Hz, 3H), 0.97 (d, J = 12.5 Hz, 4H); ESI MS (m/z) 496.1 MH)+.} 195 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.18 (s, 1H), 8.43 (d, J = 5.4 Hz, 1H), 8.21 (d, J = 0.7 Hz, 1H), 6.97 (d, J = 5.4 Hz, 1H), 4.72 (s, 1H), 3.90 (s, 3H), 3.63-3.52 (m, 2H), 3.15 (s, 3H), 1.47 (s, 9H), 1.28 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 495.4 MH)+.} 196 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.18 (s, 1H), 8.43 (d, J = 5.1 Hz, 1H), 8.22 (s, 1H), 6.97 (d, J = 5.4 Hz, 1H), 4.72 (s, 1H), 3.90 (s, 3H), 3.63-3.52 (m, 2H), 3.15 (s, 3H), 1.47 (s, 9H), 1.28 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 495.3 MH)+.} 197 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.24 (s, 1H), 8.53 (d, J = 4.4 Hz, 1H), 8.25 (s, 1H), 7.09 (d, J = 4.4 Hz, 1H), 4.38-4.27 (m, 2H), 3.99 (s, 3H), 3.19 (s, 3H), 1.47 (s, 9H), 1.38 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 520.2 MH)+.} 198 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.86 (d, J = 4.8 Hz, 1H), 8.65 (d, J = 1.2 Hz, 1H), 8.30 (d, J = 8.0 Hz, 1H), 8.19 (dd, J = 8.4 Hz, 1.6 Hz, 1H), 7.21 (d, J = 4.4 Hz, 1H), 3.97 (q, J = 7.6 Hz, 2H), 2.94-2.87 (m, 1H), 1.48-1.43 (m, 2H), 1.34-1.28 (m, 5H);ESI MS (m/z) 500.9 (MH)+} 199 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 4.4 Hz, 1H), 8.26 (d, J = 1.2 Hz, 1H), 8.02 (d, J = 8.8 Hz, 1H), 7.79 (dd, J = 8.4 Hz, 1.6 Hz, 1H), 7.18 (d, J = 4.4 Hz, 1H), 3.94 (q, J = 7.2 Hz, 1H), 2.93-2.86 (m, 1H), 1.46-1.41 (m, 2H), 1.33-1.22 (m, 5H); ESI MS (m/z) 469.10 (MH)+.} 200 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84 (d, J = 4.8 Hz, 1H), 8.41 (d, J = 1.2 Hz, 1H), 8.21 (d, J = 8.4 Hz, 1H), 7.97 (dd, J = 8.4 Hz, 0.8 Hz, 1H), 7.19 (d, J = 4.4 Hz, 1H), 3.96 (q, J = 7.6 Hz, 1H), 2.93-2.88 (m, 1H), 1.46-1.42 (m, 2H), 1.34-12.7 (m, 5H); ESI MS (m/z) 485.15 (MH)+.} 201 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.22-9.18 (m, 3H), 8.69 (d, J =1.6 Hz, 1H), 8.34 (d, J = 8.0 Hz, 1H), 8.22 (dd, J = 8.4 Hz, 1.6 Hz, 1H), 7.95 (d, J = 4.4 Hz, 1H), 7.83 (t, J = 4.8 Hz, 1H), 3.89 (q, J = 7.6 Hz, 2H), 1.30 (t, J = 7.6 Hz, 3H); ESI MS (m/z) 538.80 (MH)+.} 202 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.59 (d, J = 1.6 Hz, 1H), 8.49 (d, J = 4.8 Hz, 1H), 8.27 (d, J = 7.6 Hz, 1H), 8.16 (dd, J = 8.8 Hz, 2.0 Hz, 1H), 7.18 (s, 1H), 6.90 (d, J = 6.0 Hz, 1H), 3.97 (q, J = 7.2 Hz, 2H), 1.56 (s, 9H), 1.31 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 532.00 (MH)+.} 203 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.6 Hz, 1H), 8.57 (d, J = 1.6 Hz, 1H), 8.42 (d, J = 5.2 Hz, 1H), 6.88 (d, J = 5.2 Hz, 1H), 3.80-3.69 (m, 11H), 1.25 (t, J = 7.6 Hz, 3H); ESI MS (m/z) 502.05 (MH)+.} 204 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.84.8.83 (m, 1H), 8.78 (d, J = 2.4 Hz, 1H), 8.60 (d, J = 1.2 Hz, 1H), 8.53 (d, J = 2.4 Hz, 1H), 3.78 (s, 3H), 3.69 (q, J = 7.6 Hz, 2H), 3.41 (s, 6H), 1.24 (t, J = 7.6 Hz, 3H); ESI MS (m/z) 502.0 (MH)+.} 205 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.29 (d, J = 7.2 Hz, 1H), 8.47-8.46 (m, 1H), 8.43 (d, J = 5.2 Hz, 1H), 7.55 (dd, J = 7.2 Hz, 1.6 Hz, 1H), 6.84 (d, J = 5.2 Hz, 1H), 3.89 (q, J = 7.6 Hz, 2H), 3.31 (s, 6H), 1.30 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 488.3 (MH)+.} 206 _{1H-NMR (400 MHz, DMSO- d6 ) δ 9.78 (s, 1H), 8.42 (d, J = 5.2 Hz, 1H), 8.09 (d, J = 9.6 Hz, 1H), 7.98 (dd, J = 1.6 Hz, 8.8 Hz, 1H), 6.84 (d, J = 5.2 Hz, 1H), 3.89 (q, J = 7.6 Hz, 2H), 3.70 (s, 6H), 1.25 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 487.95 (MH)+.} 207 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.82 (d, J = 1.6 Hz, 1H), 8.58 (d, J = 1.6 Hz, 1H), 8.46 (d, J = 5.2 Hz, 1H), 6.89 (d, J = 5.2 Hz, 1H), 4.24-4.19 (m, 2H), 4.09-3.98 (m, 4H), 3.90-3.86 (m, 2H), 3.78 (s, 3H), 3.73 (q, J = 7.2 Hz, 2H), 3.70 (s, 6H), 1.25 (t, J = 7.6 Hz, 3H);ESI MS (m/z) 544.0 (MH)+.} 208 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (d, J = 1.6 Hz, 1H), 8.57 (d, J = 2.0 Hz, 1H), 8.41 (d, J = 5.2 Hz, 1H), 6.89 (d, J = 5.2 Hz, 1H), 3.89-3.79 (m, 2H), 3.77 (s, 3H), 3.72 (q, J = 7.2 Hz, 2H), 3.66 (s, 3H), 1.43 (t, J = 7.2 Hz, 3H), 1.24 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 516.0 (MH)+.} 209 _{1H-NMR (400 MHz, DMSO- d6 ) δ 8.81 (d, J = 1.2 Hz, 1H), 8.57 (d, J = 1.2 Hz, 1H), 8.40 (d, J = 5.2 Hz, 1H), 6.91 (d, J = 5.2 Hz, 1H), 3.86 (s, 3H), 3.71 (q, J = 7.2 Hz, 2H), 3.59 (s, 3H), 1.57 (s, 9H), 1.26 (t, J = 7.2 Hz, 3H); ESI MS (m/z) 544.2 (MH)+.} * The compound name was generated using Chemdraw Professional 23.1.

In one embodiment, the present invention provides a composition for controlling or preventing invertebrate pests. The composition comprises a bioavailable amount of a compound of formula (I) and at least one additional component selected from surfactants and adjuvants.

In another embodiment, the invention provides a conventional type of agricultural chemical composition of a compound of formula (I) or its N-oxide or salt, such as: solution, emulsion, suspension, powder, granule, paste, granule, compressor, capsule, and mixture thereof. Examples of component types include suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, tablets, wettable powders or powders (e.g., WP, SP, WS, DP, DS), compression formulations (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations for treating plant propagation materials such as seeds (e.g., GF). These and other component types are defined in "Catalogue of pesticide Formulation types and international coding system, Technical Monograph No. 2, ^6th Ed. May 2008, CropLife International".

In another embodiment, the invention provides an agricultural chemical composition containing a compound of formula (I), comprising 0.01% to 95%, more preferably 0.1% to 90%, more preferably 1% to 70%, particularly 10% to 60% by weight of an active substance. The active substance is used with a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectroscopy).

Water-soluble concentrates (LS), suspensions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gel formulations (GF) are commonly used for the treatment of plant propagation material (particularly seeds). After dilution two to ten times, the active ingredient concentration in ready-to-use formulations is 0.01% to 60% by weight, preferably 0.1% to 40%. Application can be made before or during sowing.

Methods of applying compounds of formula (I) and their components to plant propagation material, particularly seeds, include dressing, coating, granulation, powdering, soaking, and in-furrow application. Preferably, compounds of formula (I) or their components are applied to the plant propagation material by methods that do not induce germination (e.g., through dressing, granulation, coating, and powdering).

When used for plant protection, the amount of active substance applied, depending on the type of effect expected, is 0.001 to 2 kg per hectare, preferably 0.005 to 2 kg per hectare, more preferably 0.05 to 0.9 kg per hectare, and particularly 0.1 to 0.75 kg per hectare.

When processing plant propagation material (such as seeds), for example by dusting, coating or soaking the seeds, 0.1 to 1000 grams, preferably 1 to 500 grams, more preferably 1 to 100 grams, and even more preferably 5 to 100 grams of active ingredient per 100 kilograms of plant propagation material (preferably seeds) is usually necessary.

When used to protect materials or store products, the amount of active substance depends on the type of application and the desired effect. The amount typically used for material protection ranges from 0.001 g to 2 kg, with a preferred range of 0.005 g to 1 kg of active substance per cubic meter of treated material.

Different types of oils, humectants, adjuvants, fertilizers or micronutrients, and additional pesticides (e.g., herbicides, insecticides, fungicides, growth regulators, and safetyners) can be added as premixes to the active substance or a composition containing the active substance, or, if appropriate, added until just before use (canning). These reagents can be mixed with the composition according to the invention at a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

Users typically apply the composition of this invention from pre-application devices, backpack sprayers, spray cans, aircraft sprays, or irrigation systems. Generally, the agricultural composition is prepared from water, buffers, and/or other adjuvants to the desired application concentration, thereby obtaining the ready-to-use spray or agricultural composition of this invention. Typically, 20 to 6000 liters, preferably 35 to 1000 liters, and more preferably 50 to 500 liters of ready-to-use spray are applied per hectare of usable agricultural area.

According to one embodiment, the various components of the composition of the invention, such as the reagent kit portion or the binary or ternary mixture portion, can be mixed by the user in the spray can, and additional additives can be added, if appropriate.

The compounds and compositions of this invention are therefore useful in agronomy for protecting crops from phytophagous invertebrate pests, and also in agronomy for protecting other horticultural crops and plants from phytophagous invertebrate pests. This application includes protecting crops and other plants (i.e., agronomic and agronomic) that contain genetic material introduced through genetic engineering (i.e., gene transfer) or modified through mutagenesis to provide advantageous traits.

The compounds of this invention are characterized by a favorable metabolic and/or soil residual pattern and exhibit activity in controlling a range of agronomic and non-agronomic invertebrate pests. The compounds of this invention are active ingredients with preventative and/or curative value in the field of pest control, effective even at low application rates for controlling pesticide-resistant pests (e.g., insects) and/or possessing a very favorable biocidal spectrum, with good tolerance to warm-blooded animals, fish, and plants.

In the context of this specification, "invertebrate pest control" refers to suppressing the development (including mortality) of invertebrate pests, thereby significantly reducing predation or other injury or damage caused by pests; (related terms are defined similarly). As described in this invention, the term "invertebrate pest" includes economically important pests such as arthropods, gastropods, and nematodes. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, isochoria, and myriapods.

The term "gastropod" includes snails, slugs, and other stalked-eye animals. The term "nematode" encompasses all helminths, such as roundworms, heartworms, phytophagous nematodes, trematodes, acanthocephala, and cetoda. Those skilled in the art will understand that not all compounds are equally effective against all pests.

The compounds of this invention exhibit activity against economically important pests in agronomy, forestry, greenhouses, nurseries, ornamental plants, turf, food and fiber, public and animal health, household and commercial structures, and home and storage products. These pests include larvae of Lepidoptera, such as armyworms, cutworms, loopers, and heliothine species (e.g., fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exigua Hubner), black cutworm (Agrotis ipsilon Hufnagel), cabbage looper (Trichoplusia ni Hubner), and tobacco budworm (Heliothis virescens)). Fabricius); derived from the family Pyralidae: borers, casebearers, webworms, coneworms, cabbage worms, and skeletonizers (e.g., European corn borer, Ostrinia nubilalis Hubner, navel orange worm, Amyelois transitella Walker, corn root webworm, Crambus caliginosellus Clemens, sod worm, Herpetogramma licarsisalis Walker); and from the family Tortricidae: leafrollers, budworms, seed worms, and fruit worms (e.g., codling moth). The following species are listed: *Cydia pomonella Linnaeus*, *Grape berry moth*, *Endopiza viteana Clemens*, and *Oriental fruit moth* (*Grapholita molesta Busck*); and many other economically important Lepidoptera (e.g., diamondback moth, *Plutella xylostella Linnaeus*, pink bollworm, *Pectinophora gossypiella Saunders*, and gypsy moth, *Lymantria dispar Linnaeus*); nymphs and adults of Blattodea, including cockroaches from the families Blattellidae and Blattidae (e.g., *Oriental cockroach*, *Blatta orientalis*). The following are examples of cockroaches: *Linnaeus*, *Asian cockroach* (Blatella asahinai Mizukubo), *German cockroach* (Blattella germanica Linnaeus), *Brown-banded cockroach* (Supella longipalpa Fabricius), *American cockroach* (Periplaneta Americana Linnaeus), *Brown cockroach* (Periplaneta brunnea Burmeister), and *Madeira cockroach* (Leucophaea maderae Fabricius). Leaf-eating larvae and adults of the order Coleoptera include weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., the boll weevil (Anthonomus grandis Boheman) and the rice weevil). Water weevil, *Lissorhoptrus oryzophilus* Kuschel, grain weevil (*Sitophilus granaries* Linnaeus), rice weevil (*Sitophilus oryzae* Linnaeus); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers (e.g., Colorado potato beetle (*Leptinotarsa decemlineata Say*) and western corn rootworm (*Diabrotica virgifera virgifera LeConte*)); chafers and other beetles from the family Scaribaeidae (e.g., Japanese scarab beetle). Beetle, Popillia japonica Newman and European chafer (Rhizotrogus majalis Razoumowsky); carpet beetle from the family Dermestidae; wireworm from the family Elateridae; bark beetle from the family Scolytidae and flour beetle from the family Tenebrionidae. In addition, it also includes: adults and larvae of the order Dermaptera, including earthworms (e.g., European earwig, Forficula auricularia Linnaeus, black earwig, Chelisoches morio Fabricius) from the family Forficulidae; adults and nymphs of the orders Hemiptera and Homoptera, such as plant bugs from the family Miridae, cicadas from the family Cicadidae, and leafhoppers (e.g., Empoasca) from the family Cicadellidae. (spp.), planthoppers from the families Fulgoroidae and Delphacidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scale insects from the families Coccidae, Diaspididae, and Margarodidae, lace bugs from the family Tingidae, and chinchillas from the family Lygaeidae. Bugs (e.g., Blissus spp.) and other seed bugs, the spittlebug from the Cercopidae family, the red bug from the Pyrrhocoridae family, and the cotton stainer. This also includes adult and larval mites of the order Acari (mite), such as spider mites and red mites of the family Tetranychidae (e.g., European red mite, Panonychus ulmi Koch, two-spotted spider mite, Tetranychus urticae Koch, McDaniel mite, Tetranychus mcdanieli McGregor), flat mites of the family Tenuipalpidae (e.g., citrus flat mites, Brevipalpus lewisi McGregor), and rust mites and bud mites of the family Eriophyidae. Dust mites (Epidermoptidae), leaf-eating mites, and mites important to human and animal health, including dust mites (Epidermoptidae), ticks (Ixodidae, such as deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus), and scab mites (Psoroptidae, Pyemotidae, and Sarcoptidae). mite; adults and larvae of the order Orthoptera, including grasshoppers, locusts, and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas)), American grasshoppers (e.g., Schistocerca Americana Drury)), desert locusts (Schistocerca gregaria Forskal), migratory locusts (Locusta migratoria Linnaeus), house crickets (Acheta domesticus Linnaeus), mole crickets (Gryllotalpa). (spp.)); Adults and larvae of the order Diptera, including leafminers, midges, fruit flies (Tephritidae), wheat stalk flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, and horn flies. fly), green-headed flies (e.g., *Chiysomya* spp., *Phormia* spp.), and other fly pests, horse flies (e.g., *Tabanus* spp.), bot flies (e.g., *Gastrophilus* spp., *Oestrus* spp.), cattle grubs (e.g., *Hypoderma* spp.), deer flies (e.g., *Chrysops* spp.), sheep ticks (e.g., *Melophagus ovinus* Linnaeus) and other Brachycera, mosquitoes (e.g., *Aedes* spp.) The following are included in the list of insect species: *Anopheles* spp., *Culex* spp., black flies (e.g., *Prosimulium* spp., *Simulium* spp.), biting midges, sandflies, sciarids, and other Nematocera species; adults and larvae of Thysanoptera, including onion thrips (*Thrips tabaci* Lindeman) and other leaf-eating thrips; and hymenoptera pests, including ants of the family Formicidae, such as the red carpenter ant (*Camponotus ferrugineus*). Fabricius, black carpenter ant (Camponotus pennsylvanicus De Geer), Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Fδrster), and odorous house ant (Tapinoma sessile). Say). Other Hymenoptera include bees (including carpenter bees), hornets, yellow jackets, and wasps; Isoptera pests, including the eastern subterranean termite (Reticulitermes flavipes Kollar), the western subterranean termite (Reticulitermes hesperus Banks), the Formosan subterranean termite (Coptotermes formosanus Shiraki), the West Indian drywood termite (Incisitermes immigrans Snyder), and other economically important termites; and Thysanura pests, such as silverfish (Lepisma saccharina). Linnaeus and the domestic silverfish (Thermobia domestica Packard); pests of the order Mallophaga, including head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurysternus Nitzsch), and long-nosed cattle louse (Linognathus vituli). Linnaeus and other parasitic lice that attack humans and animals by sucking and chewing; pests of the order Siphonoptera, including the Oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus), and other fleas that torment mammals and birds. Other arthropod pests included are spiders of the order Araneae, such as the brown recluse spider (Loxosceles reclusa). Gertsch and Mulaik, as well as black widow spiders (Latrodectus mactans Fabricius) and centipedes of the order Scutigeromorpha, such as the common house centipede (Scutigera coleoptrata). Linnaeus). The disclosed compound is also effective against members of the classes Nematoda, Polyspinosa, Trematoda, and Acanthocephala, including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida, such as (but not limited to) economically important agricultural pests (i.e., root knot nematode of the genus Meloidogyne, lesion nematode of the genus Pratylenchus, and stubby root nematode of the genus Trichodorus). nematode, etc.) and animals harmful to the health of animals and humans (i.e. all economically important flukes, tapeworms and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis in dogs) Leidy), Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).

The compounds of this invention exhibit particularly high activity against lepidopteran pests, such as the cotton leaf worm (Alabama argillacea Hubner), the fruit tree leaf roller (Archips argyrospila Walker), the European leaf roller (A. rosana Linnaeus), other Archipelago species, the rice stem borer (Chilo suppressalis Walker), the rice leaf roller (Cnaphalocrosis medinalis Guenee), the corn root webworm (Crambus caliginosellus Clemens), the bluegrass webworm (Crambus teterrellus Zincken), and the codling moth (Cydia pomonella Linnaeus). The following are listed as common bollworm species: * *Earias insulana Boisduval* (spiny bollworm), * *Earias vittella Fabricius* (spotted bollworm), * *Helicoveipa armigera Hύbner* (American bollworm), * *Helicoverpa zea Boddie* (corn earworm), * *Heliothis virescens Fabricius* (tobacco budworm), * *Herpetogramma licarsisalis Walker* (sod webworm), * *Lobesia botrana Denis and Schiffeπnύller* (grape berry moth), * *Pectinophora gossypiella Saunders* (pink bollworm), and * *Phyllocnistis citrella* (citrus leaf miner). Stainton (citrus leafminer), large white butterfly (Pieris brassicae Linnaeus), small white butterfly (Pieris rapae Linnaeus), diamondback moth (Plutella xylostella Linnaeus), beet armyworm (Spodoptera exigua Hubner), tobacco cutworm (Spodoptera litura Fabricius), fall armyworm (Spodoptera frugiperda J.E. Smith), cabbage looper (Trichoplusia ni Hύbner), and tomato leafminer (Tuta absoluta Meyrick).

The invented compounds exhibit particularly high activity against Homoptera pests, including: pea aphid (Acyrthosiphon pisum Harris, pea aphid), cowpea aphid (Aphis craccivora Koch, cowpea aphid), black bean aphid (Aphis fabae Scopoli, black bean aphid), cotton aphid (Aphis gossypii Glover, cotton aphid, melon aphid), apple aphid (Aphis pomi De Geer, apple aphid), spirea aphid (Aphis spiraecola Patch, spirea aphid), potato aphid (Aulacorthum solani Kaltenbach, foxglove aphid), strawberry aphid (Chaetosiphon fragaefolii Cockerell, strawberry aphid), and Russian wheat aphid (Diuraphis noxia Kurdjumov/Mordvilko, Russian). Wheat aphid, rose apple aphid (Dysaphis plantaginea Paaserini, rosy apple aphid), apple wool aphid (Eriosoma lanigerum Hausmann, woolly apple aphid), peach plum aphid (Hyalopterus pruni Geoffroy, mealy plum aphid), radish aphid (Lipaphis erysimi Kaltenbach, turnip aphid), wheat web-less long-tubed aphid (Metopolophium dirrhodum Walker, cereal aphid), euphorbiae Thomas, potato aphid (Macrosiphum euphorbiae Thomas, potato aphid), peach aphid (Myzus persicae Sulzer, peach-potato aphid, green peach aphid), lettuce aphid (Nasonovia ribisnigri Mosley, lettuce aphid), gall aphid (Pemphigus spp.) (root aphid) *Rhopalosiphum maidis Fitch*, *Rhopalosiphum padi Linnaeus*, *Schizaphis graminum Rondani*, *Sitobion avenae Fabricius*, *Therioaphis maculate Buckton*, *Toxoptera aurantii Boyer de Fonscolombe*, *Toxoptera citricida Kirkaldy*, *Adelges spp.* (adelgid); *Phylloxera devastatrix*. Pergande, pecan phylloxera; tobacco whitefly (Bemisia tabaci Gennadius, tobacco whitefly, sweetpotato whitefly), silver leaf whitefly (Bemisia argentifolii Bellows and Perring, silverleaf whitefly), citrus whitefly (Dialeurodes citri Ashmead, citrus whitefly), and greenhouse whitefly (Trialeurodes vaporariorum Westwood, greenhouse whitefly); potato leafhopper (Empoasca fabae Harris, potato leafhopper), small brown planthopper (Laodelphax striatellus Fallen, smaller brown planthopper), aster leafhopper (Macrolestes quadrilineatus Forbes, aster leafhopper), green leafhopper (Nephotettix cinticeps Uhler, green leafhopper), rice leafhopper (Nephotettix nigropictus Stal, rice leafhopper). The following planthoppers are commonly known as leafhoppers: * *Nilaparvata lugens Stal* (brown planthopper), * *Peregrinus maidis Ashmead* (corn planthopper), * *Sogatella furcifera Horvath* (white-backed planthopper), * *Sogatodes orizicola Muir* (rice delphacid), * *Typhlocyba pomaria McAfee* (white apple leafhopper), * *Erythroneoura spp.* (grape leafhopper), * *Magicidada septendecim Linnaeus* (periodical cicada), * *Icerya purchasi Maskell* (cottony cushion scale), * *Quadraspidiotus perniciosus Comstock* (San Jose scale), and * *Planococcus citri* (citrus mealybug). Risso, citrus mealybug; Pseudococcus spp. (other mealybug complexes); Cacopsylla pyricola Foerster, pear psylla; Trioza diospyri Ashmead, persimmon psylla.

These compounds are also active against members of the order Hemiptera, including: green stink bug (Acrosternum hilare Say), squash bug (Anasa tristis De Geer), chinch bug (Blissus leucopterus leucopterus Say), cotton lace bug (Corythuca gossypii Fabricius), tomato bug (Cyrtopeltis modesta Distant), cotton stainer bug (Dysdercus suturellus Herrich-S chaffer), brown stink bug (Euchistus servus Say), and one-spotted stink bug (Euchistus variolarius Palisot deBeauvois). Bugs, a complex genus of bugs (Graptόsthetus spp.) (a complex of broad-skinned bugs), pine-leaved bugs (Leptoglossus corculus Say, leaf-footed pine seed bug), pasture bugs (Lygus lineolaris Palisot de Beauvois, tarnished plant bug), rice green bugs (Nezara viridula Linnaeus, southern green stink bug), rice bugs (Oebalus pugnax Fabricius, rice stink bug), large milkweed bugs (Oncopeltus fasciatus DaEas, large milkweed bug), and cotton fleahopper bugs (Pseudatomoscelis seriatus Reuter, cotton fleahopper).

Other insect orders controlled by the compound of formula (I) of this invention include: Thysanoptera (e.g., western flower thrips (Frankliniella occidentalis Pergande, citrus thrips), citrus thrips (Scirthothrips citri Moulton, citrus thrips), soybean thrips (Sericothrips variabilis Beach, soybean thrips), and onion thrips (Thrips tabaci Lindeman, onion thrips)); and Coleoptera (e.g., Colorado potato beetle (Leptinotarsa decemLineata Say, Mexican beetle), Mexican bean beetle (Epilachna varivestis Mulsant). Nematodes of the genera *Agriotes*, *Athous*, or *Limonius*.

In particular, compounds of formula (I), their N-oxides, their isomers, their polymorphs, and their salts are especially suitable for effective control of the following pests: insects of the order Lepidoptera, such as: small cutworm (Agrotis ypsilon), yellow cutworm (Agrotis segetum), cotton leafroller (Alabama argillacea), bean moth (Anticarsia gemmatalis), apple seed moth (Argyresthia conjugella), owl moth (Autographa gamma), pine looper (Bupalus piniarius), yellow leafroller (Cacoecia murinana), cotton brown-banded leafroller (Capua reticulana), looper moth (Cheimatobia brumata), and spruce leafroller (Choristoneura). fumiferana, western spruce aphid (Choristoneura ℃cidentalis), American armyworm (Cirphis unipuncta), apple codling moth (Cydia pomonella), European pine caterpillar (Dendrolimus pini), melon borer (Diaphania nitidalis), giant corn borer (Diatraea grandiosella), cotton bollworm (Earias insulana), square bollworm (Earias vittella), small corn borer (Elasmopalpus lignosellus), grape borer (Eupoecilia ambiguella), European pine branch moth (Evetria bouliana), grain cutworm (Feltia subterranea), large wax moth (Galleria mellonella), plum fruit moth (Grapholita funebrana), pear fruit moth (Grapholita Tomato moth (Helicoverpa armigera), American tobacco moth (Helicoverpa virescens), cotton bollworm (Helicoverpa zea), cabbage moth (Hellula undalis), gray skirt looper (Hibernia defoliaria), American white moth (Hyphantria cunea), apple leafminer (Hyponomeuta malinellus), tomato codling moth (Keiferia lycopersicella), hemlock looper (Lambdina fiscellaria), beet armyworm (Laphygma exigua), coffee leafminer (Leucoptera coffeella), spiral leafminer (Leucoptera scitella), spotted leafminer (Lithocolletis blancardella), grape berry leafroller (Lobesia botrana), yellow-green leafminer (Loxostege) The following are listed: *Sticticalis*, *Leucinodes orbonalis*, *Lymantria dispar*, *Lymantria monacha*, *Lyonetia clerkella*, *Malacosoma neustria*, *Mamestra brassicae*, *Orgyia pseudotsugata*, *Ostrinia nubilalis*, *Panolis flammea*, *Pectinophora gossypiella*, *Peridroma saucia*, *Phalera bucephala*, *Phthorimaea operculella*, *Phyllocnistis citrella*, and *Pieris*. brassicae, alfalfa green armyworm (Plathypena scabra), diamondback moth (Plutella xylostella), soybean armyworm (Pseudoplusia includens), pine leafroller (Rhyacionia frustrana), rice stem borer (Scirpophaga incertulas), tomato leafminer (Scrobipalpula absoluta), wheat moth (Sitotroga cerealella), grape long-bearded leafroller (Sparganothis pilleriana), armyworm (Spodoptera frugiperda), gray-winged armyworm (Spodoptera littoralis), striped armyworm (Spodoptera litura), grass armyworm (Spodoptera exigua), pine banded moth (Thaumatopoea pityocampa), oak green leafroller (Tortrix viridana), powdery armyworm (Trichoplusia) ni) and the spruce leafroller (Zeiraphera canadensis); and

Beetles (Coleoptera), such as the pear beetle (Agrilus sinuatus), striped click beetle (Agriotes lineatus), dark wire beetle (Agriotes obscurus), June beetle (Amphimallus solstitialis), hole-boring borer (Anisandrus dispar), cotton bell weevil (Anthonomus grandis), apple flower weevil (Anthonomus pomorum), euphorite flea beetle (Aphthona euphoridae), red-tailed click beetle (Athous haemorrhoidalis), linear cryptid beetle (Atomaria linearis), large pine bark beetle (Blastophagus piniperda), tent leaf moth (Blitophaga undata), bean weevil (Bruchus rufimanus), pea weevil (Bruchus pisorum), lentil weevil (Bruchus lentis), apple leaf weevil (Byctiscus betulae), beet beetle (Cassida nebulosa), bean leaf beetle (Cerotoma trifurcata), golden flower beetle (Cetonia aurata), cabbage pod weevil (Ceuthorrhynchus assimilis), stem weevil (Ceuthorrhynchus napi), beet twig beetle (Chaetocnema tibialis), tobacco wireworm (Conoderus vespertinus), asparagus beetle (Crioceris asparagi), click beetle subspecies (Ctenicera ssp.), longhorn leaf beetle (Diabrotica longicornis), cucumber half-star leaf beetle (Diabrotica semipunctata), twelve-spotted cucumber leaf beetle (Diabrotica undecimpunctata), Brazilian leaf beetle (Diabrotica speciosa), corn root leaf beetle (Diabrotica The following species are listed: virgifera, Mexican bean ladybug (Epilachna varivestis), tobacco flea beetle (Epitrix hirtipennis), cotton borer (Eutinobothrus brasiliensis), pine weevil (Hylobius abietis), Egyptian alfalfa weevil (Hypera brunneipennis), alfalfa leaf weevil (Hypera postica), spruce bark beetle (Ips typographus), striped mud beetle (Lema bilineata), black horned mud beetle (Lema melanopus), potato beetle (Leptinotarsa decemLineata), beet wireworm (Limonius californicus), rice weevil (Lissorhoptrus oryzophilus), cotton nematode (Melanotus communis), rapeseed slug beetle (Meligethes). aeneus, Melolontha hippocastani, Melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta pyri, Phyllotreta chrysocephala, Phyllotophaga sp., Phyllotopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona Lineatus and grain weevil (Sitophilus granaria); flies and mosquitoes (Diptera), such as Aedes aegypti, Aedes albopictus, Aedes vexans, Anatrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, and Ceratitis. Culex captiveata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta *Inornata*, *Culiseta melanura*, *Dacus cucurbitae*, *Dacus oleae*, *Dasineura brassicae*, *Delia antique*, *Delia coarctata*, *Delia platura*, *Delia radicum*, *Dermatobia hominis*, *Fannia canicularis*, *Geomyza tripunctata*, *Gasterophilus intestinalis*, *Glossina morsitans*, *Glossina palpalis*, *Glossina fuscipes*, *Glossina* Tachinoides), harassing hornfly (Haematobia irritans), saddle-shaped goat (Haplodiplosis equestris), gnaw flies (Hippelates spp.), species fly (Hylemyia platura), patterned fly (Hypoderma lineata), bridle midge (Leptoconops torrens), American spotted leaf fly (Liriomyza sativae), African daisy leaf fly (Liriomyza trifolii), goat green fly (Lucilia caprina), copper green fly (Lucilia cuprina), silky green fly (Lucilia sericata), white poplar fly (Lycoria pectoralis), Mansonia titillanus, Black forest wheat straw fly (Mayetiola destructor), autumn fly (Musca) autumnalis, house fly (Musca domestica), stag fly (Muscina stabulans), sheep-nose fly (Oestrus ovis), grain fly (Opomyza florum), Swedish wheat stalk fly (Oscinella frit), beet leaf miner (Pegomya hysocyami), onion fly (Phorbia antiqua), cabbage fly (Phorbia brassicae), meal fly (Phorbia coarctata), silver-legged sandfly (Phlebotomus argentipes), Colombian scale fly (Psorophora columbiae), carrot stem fly (Psila rosae), discolor scale fly (Psorophora discolor), mixed black fly (Prosimulium mixtum), cherry fruit fly (Rhagoletis) cerasi), apple fruit fly (Rhagoletis pomonella), red-tailed flesh fly (Sarcophaga haemorrhoidalis), flesh fly (Sarcophaga spp.), daphnia (Simulium vittatum), stink fly (Stomoxys calcitrans), horsefly (Tabanus bovinus), black horsefly (Tabanus atratus), banded horsefly (Tabanus lineola), pseudobronchi (Tabanus similis), common mosquito (Tipula oleracea), and European mosquito (Tipula paludosa); termites (Isoptera), such as European wood termite (Calotermes flavicollis), common termite (Leucotermes flavipes), and golden heterotermite (Heterotermes). *Reticulitermes aureus*, *Reticulitermes flavipes*, *Reticulitermes virginicus*, *Reticulitermes lucifugus*, *Reticulitermes santonensis*, *Reticulitermes grassei*, *Termes natalensis*, and *Coptotermes formosanus*; cockroaches (Blattaria Blattodea), such as the German cockroach (Blattella germanica), Asian cockroach (Blattella asahinae), American cockroach (Periplaneta americana), Japanese cockroach (Periplaneta japonica), brown cockroach (Periplaneta brunnea), and smoke cockroach (Periplaneta...). *Periplaneta australasiae* and *Blatta orientalis*; ants, bees, wasps, and sawflies (Hymenoptera), such as *Athalia rosae*, *Atta cephalotes*, *Atta capiguara*, *Atta cephalotes*, *Atta laevigata*, *Atta robusta*, *Atta sexdens*, *Atta texana*, *Crematogaster*, *Hoplocampa minuta*, and *Hoplocampa*. Testudinea, caterpillar ant (Lasius niger), kitchen ant (Monomorium pharaonis), tropical fire ant (Solenopsis geminata), red fire ant (Solenopsis invicta), black fire ant (Solenopsis richteri), California fire ant (Solenopsis xyloni), red harvester ant (Pogonomyrmex barbatus), California harvester ant (Pogonomyrmex californicus), big-headed ant (Pheidole megacephala), western ant wasp (Dasymutilla cidentalis), bumblebee (Bombus spp.), yellow wasp (Vespula squamosa), common yellow wasp (Paravespula vulgaris), tree yellow wasp (Paravespula pennsylvanica), German yellow wasp (Paravespula germanica), white-faced yellow wasp (Dolichovespula) * *Pterygium maculata*, *Vespa crabro*, *Polistes rubiginosa*, *Camponotus floridanus*, and *Linepithema humile*; crickets, grasshoppers, and locusts (Orthoptera), such as the house cricket (*Acheta domestica*), the European mole cricket (*Gryllotalpa*), the migratory locust (*Locusta migratoria*), the bivittatus grasshopper (*Melanoplus bivittatus*), the femurrubrum grasshopper (*Melanoplus femurrubrum*), the mexican grasshopper (*Melanoplus mexicanus*), the migratory grasshopper (*Melanoplus sanguinipes*), the spretus grasshopper (*Melanoplus spretus*), the red-winged locust (*Nomadacris septemfasciata*), and the Schistocerca grasshopper (*Schistocerca*). Americana, desert locust (Schistocerca gregaria), Moroccan locust (Dociostaurus maroccanus), greenhouse cricket (Tachycines asynamorus), Senegalese car locust (Oedaleus senegalensis), stink gland locust (Zonozerus variegatus), horned cane locust (Hieroglyphus daganensis), Indian rosewood locust (Kraussaria angulifera), Italian locust (Calliptamus italicus), Australian plague locust (Chortoicetes terminifera), and South African locust (Locustana pardalina); Araneida, such as black widow spider (Latrodectus mactans) and brown hider spider (Loxosceles reclusa); fleas (Siphonaptera), such as cat flea (Ctenocephalides felis) and dog flea (Ctenocephalides Canis, Indian mouse flea (Xenopsylla cheopis), human flea (Pulex irritans), leaf miner (Tunga penetrans), and striped mouse flea (Nosopsyllus fasciatus); silverfish (Lepisma saccharina) and firebrat (Thermobia domestica); centipedes (Chilopoda), such as Mediterranean centipede (Scutigera oleoptrata); millipedes (Diplopoda), such as millipedes (Narceus spp.); earthworms (Dermaptera), such as European earthworm (forficula auricularia); lice (Phthiraptera), such as human head lice (Pediculus humanus capitis) and human body lice (Pediculus humanus). corporis, pubic lice (Pthirus pubis), cattle lice (Haematopinus eurysternus), pig lice (Haematopinus suis), cattle jaw lice (Linognathus vituli), cattle bird lice (Bovicola bovis), chicken lice (Menopon allinae), large chicken lice (Menacanthus stramineus), and small short-nosed cattle lice (Solenopotes capillatus); Collembola (springtails), such as the subspecies Onychiurus ssp.

Compound of formula (I) of this invention is also suitable for controlling nematodes: plant-parasitic nematodes, such as root knot nematodes, northern root knot nematode (Meloidogyne hapla), southern root knot nematode (Meloidogyne incognita), Javan root knot nematode (Meloidogyne javanica) and other root knot nematode species; cyst-forming nematodes, golden nematode (Globodera rostochiensis) and other globodera species; wheat cyst nematode (Heterodera avenae), soybean cyst nematode (Heterodera glycines), beet cyst nematode (Heterodera schachtii), clover cyst nematode (Heterodera... Trifolii and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species species, including *Criconemoides* species, *Mesocriconema* species; stem and bulb nematodes, *Ditylenchus destructor*, *Ditylenchus dipsaci* and other stem and bulb nematode species; awl nematodes, *Dolichodorus* species; spiral nematodes, *Helicotylenchus multicinctus* and other spiral nematode species; sheath and sheathoid nematodes. *Hemicycliophora* and *Hemicriconemoides*; *Hirshmanniella* species; *Lance nematodes*, *Hoploaimus* species; *False rootknot nematodes*, *Nacobbus* species; *Needle nematodes*, *Longidorus elongatus* and other *Longidorus* species; *Lesion nematodes*, *Pratylenchus neglectus*, *Pratylenchus penetrans*, *Pratylenchus* * *curvitatus*, *Pratylenchus goodeyi*, and other *Pratylenchus* species; *Burrowing nematodes*, *Radopholus similis*, and other *Radopholus* species; *Reniform nematodes*, *Rotylenchus robustus*, and other *Rotylenchus* species; *Scutellonema* species; *Stubby root nematodes*, *Trichodorus primitivus*, and other *Trichodorus* species, and *Paratrichodorus* species. species); Stunt nematodes, tobacco dwarf nematode (Tylenchorhynchus claytoni), adventitious dwarf nematode (Tylenchorhynchus dubius) and other dwarf nematode species (Tylenchorhynchus); Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant-parasitic nematode species.

Compounds of formula (I) and their salts are also effective in controlling arachnids (Arachnoidea), such as those in the order Acarina, including families Argasidae, Ixodidae, and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, and Ornithodorus. * *Moubata*, *Otobius megnini*, *Dermanyssus gallinae*, *Psoroptes ovis*, *Rhipicephalus appendiculatus*, *Rhipicephalus evertsi*, *Sarcoptes scabiei*; and *Eriophyidae* spp., such as *Aculus schlechtendali*, *Phyllocoptrata oleivora*, and *Eriophyes sheldoni*; and *Tarsonemidae* spp., such as *Phytonemus*. The genera *Tenuipalpidae* include *Brevipalpus phoenicis*, *Tetranychidae* includes *Tetranychus cinnabarinus*, *Tetranychus kanzawai*, *Tetranychus pacificus*, *Tetranychus telarius*, *Tetranychus urticae*, *Panonychus ulmi*, *Panonychus citri*, and *oligonychus pratensis*.

In one embodiment of the present invention, the present invention provides a compound of formula (I) which is useful for controlling insects selected from sucking or piercing insects, such as insects of the orders Thysanoptera, Diptera and Hemiptera, especially the following species:

Thysanoptera: Tobacco Brown Thrips (Frankliniella fusca), Western Flower Thrips (Frankliniella occidentalis), Flower Thrips (Frankliniella tritici), Orange Thrips (Scirtothrips citri), Rice Thrips (Thrips oryzae), Southern Yellow Thrips (Thrips palmi), and Tobacco Thrips (Thrips tabaci);

Diptera: Aedes aegypti, Aedes albopictus, Aedes vexans, Anatrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya bezziana The following mosquitoes are listed: hominivorax, rice golden fly (Chrysomya macellaria), deer fly (Chrysops discalis), yellow-ochre tussock fly (Chrysops silacea), Atlantic tussock fly (Chrysops atlanticus), sheep spirochete fly (Cochliomyia hominivorax), tall barbel goat fly (Contarinia sorghicola), shield fly (Cordylobia anthropophaga), hairy fly (Culicoides furens), five-banded pale Culex (Culex pipiens), black-bearded Culex (Culex nigripalpus), quinquefasciatus (Culex quinquefasciatus), vector Culex (Culex tarsalis), pure-colored veined caterpillar (Culiseta inornata), black-tailed veined caterpillar (Culiseta melanura), melon fly (Dacus). cucurbitae), olive fruit fly (Dacus oleae), brass pod fly (Dasineura brassicae), onion seed fly (Delia antique), wheat seed fly (Delia coarctata), grey seed fly (Delia platura), cabbage seed fly (Delia radicum), human skin fly (Dermatobia hominis), yellow-bellied barn fly (Fannia canicularis), three-spotted rice fly (Geomyza tripunctata), Malaysian stomach fly (Gasterophilus intestinalis), stinging tongue fly (Glossina morsitans), barn tongue fly (Glossina palpalis), licking tongue fly (Glossina fuscipes), glossy tongue fly (Glossina tachinoides), harassing horn fly (Haematobia) *Irritans*, *Haplodiplosis equestris*, *Hippelates* spp., *Hylemyia platura*, *Hypoderma lineata*, *Leptoconops torrens*, *Liriomyza sativae*, *Liriomyza trifolii*, *Lucilia caprina*, *Lucilia cuprina*, *Lucilia sericata*, *Lycoria pectoralis*, *Mansonia titillanus*, *Mayetiola destructor*, *Musca autumnalis*, *Musca domestica*, *Muscina* stabulans), sheep-nosed fly (Oestrus ovis), grain fly (Opomyza florum), Swedish wheat stalk fly (Oscinella frit), beet leaf miner (Pegomya hysocyami), onion fly (Phorbia antiqua), cabbage fly (Phorbia brassicae), wheat fly (Phorbia coarctata), silver-footed sandfly (Phlebotomus argentipes), Colombian scale fly (Psorophora columbiae), carrot stem fly (Psila rosae), discolor scale fly (Psorophora discolor), mixed black fly (Prosimulium mixtum), cherry fruit fly (Rhagoletis cerasi), apple fruit fly (Rhagoletis) The species include: pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, Tabanus similis, Tipula oleracea, and Tipula paludosa.

Hemiptera, especially aphids: *Acyrthosiphon onobrychis*, *Adelges laricis*, *Aphidula nasturtii*, *Aphis fabae*, *Aphis forbesi*, *Aphis pomi*, *Aphis gossypii*, *Aphis grossulariae*, *Aphis schneideri*, *Aphis spiraecola*, *Aphis sambuci*, *Acyrthosiphon pisum*, *Aulacorthum solani*, *Brachycaudus cardui*, *Brachycaudus* helichrysi, peach black short-tailed aphid (Brachycaudus persicae), plum aphid (Brachycaudus prunicola), cabbage aphid (Brevicoryne brassicae), hornhorn aphid (Capitophorus horni), square-winged lace bug (Cerosipha gossypii), strawberry frigaefolia (Chaetosiphon fragaefolii), tea creeping aphid (Cryptomyzus ribis), Normandy ball aphid (Dreyfusia nordmannianae), spruce ball aphid (Dreyfusia piceae), root phylloxera (Dysaphis radicola), green potato aphid (Dysaulacorthum pseudosolani), apple pink inferior aphid (Dysaphis plantaginea), pear aphid (Dysaphis pyri), potato leafhopper (Empoasca fabae), plum big-tailed aphid (Hyalopterus) pruni), *Hyperomyzus lactucae*, *Macrosiphum avenae*, *Macrosiphum euphorbiae*, *Macrosiphon rosae*, *Megoura viciae*, *Melanaphis pyrarius*, *Metopolophium dirhodum*, *Myzodes persicae*, *Myzus ascalonicus*, *Myzus cerasi*, *Myzus varians*, *Nasonovia ribis-nigri*, *Nilaparvata lugens*, *Pemphigus bursarius*, *Perkinsiella* The species include *Saccharicida*, *Phorodon humuli*, *Psylla mali*, *Psylla piri*, *Rhopalomyzus ascalonicus*, *Rhopalosiphum maidis*, *Rhopalosiphum padi*, *Rhopalosiphum insertum*, *Sappaphis mala*, *Sappaphis mali*, *Schizaphis graminum*, *Schizoneura lanuginosa*, *Sitobion avenae*, *Trialeurodes vaporariorum*, *Toxoptera aurantiiand*, and *Viteus vitifolii*.

In one embodiment, the invention provides a composition comprising a bioavailable amount of a compound of formula (I) and at least one additional biocompatible compound selected from: fungicides, insecticides, nematicides, miteicides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients.

In one embodiment, the invention provides a composition comprising a bioavailable amount of a compound of formula (I) according to claim 1 and at least one additional biocompatible compound selected from: fungicides, insecticides, nematicides, miteicides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients.

Compounds used in this composition and compounds combined with compounds of formula (I) are also called active compatible compounds.

Known and reported fungicides, insecticides, nematicides, miteicides, biopesticides, herbicides, plant growth regulators, antibiotics, and nutrients may be combined with at least one compound of formula (I) of the present invention. For example, fungicides, insecticides, nematicides, miteicides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, and nutrients disclosed and reported in PCT Patent Publication No. WO2016156129 and/or PCT Patent Publication No. WO2017153200 may be combined with at least one compound of formula (I) of the present invention.

The fungicides, insecticides, nematicides, miteicides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers and nutrients reported in PCT Patent Publication No. WO2016156129 and/or PCT Patent Publication No. WO2017153200 are incorporated herein by reference as non-limiting examples and may be used in conjunction with at least one compound of formula (I) of the present invention.

In particular, the compounds of the present invention can be mixed with at least one additional biocompatible compound (mixture pair), including but not limited to insecticides, fungicides, nematicides, bactericides, miticides, growth regulators (e.g., rooting stimulants, chemical fungicides, semiochemicals, insect repellents, attractants, pheromones, feeding stimulants, other bioactive compounds) or insect pathogens, viruses, or fungi to form a multi-component pesticide that provides a wider range of agricultural uses.

PCT patent publication number WO2019072906A1 (pages 27 to 37) discloses examples of such bioactive compounds or reagents/mixtures that can be combined/formulated with the compound of formula (I) of the present invention.

In one embodiment, the biological agents used to mix with the compounds of the present invention include Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, and naturally occurring and genetically modified viral insecticides, including members of the Baculoviridae family and entomophagous fungi.

In some cases, combinations with other invertebrate pest control compounds or agents (having similar control spectra but different modes of action) will be particularly beneficial for resistance management. Therefore, the formulations of the present invention may further include a bioavailable amount of at least one additional invertebrate pest control compound or agent having a similar control spectrum but a different mode of action. Contacting genetically modified plants or the plant sites that express plant protective compounds (e.g., proteins) with a bioavailable amount of the compound of the present invention can also provide broader plant protection and facilitate resistance management.

In one embodiment of the present invention, the biologically effective amount of the compound of formula (I) in the composition is, on a weight basis, 0.1% to 99% of the total weight of the composition, preferably, 5% to 50% of the total weight of the composition.

The present invention also provides a method for controlling invertebrate pests, the method comprising: bringing an invertebrate pest, its habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the invertebrate pest is growing or may grow, or material, plant, seed, soil, surface or space protected from pest infestation or contamination, into contact with a biologically effective amount of a compound or composition of the present invention.

Control of invertebrate pests and protection of agronomic, horticultural and specialty crops, animal and human health are achieved by applying effective amounts of one or more compounds of the invention to the environment of the pest (including agronomic and/or non-agronomic crop-infected areas), to the area to be protected, or directly to the pest to be controlled. Therefore, the invention further includes methods for controlling invertebrates inhabiting leaves and soil and for protecting agronomic and/or non-agronomic crops, comprising contacting the invertebrate or its environment with bioavailable amounts of one or more compounds of the invention, or with a composition comprising at least one of these compounds, or comprising at least one of these compounds and an effective amount of at least one additional bioactive compound or reagent. A preferred method of contact is by spraying. Alternatively, granular compositions containing the compounds of the present invention can be applied to plant leaves or soil. The compounds of the present invention can also be effectively transferred to plants through contact with soil infusions containing the compounds of the present invention applied by means of liquid formulations, granular formulations applied to soil, seedling tray treatments, or transplant soaking. Other contact methods include application of the compounds or compositions of the present invention by direct and residual spraying, air spraying, gels, seed coatings, microencapsulations, systemic absorption, baits, ear tags, boluses, sprays, fumigants, aerosols, powders, and many others.

The compounds of this invention can be incorporated into baits consumed by invertebrate pests or used in devices such as traps, bait platforms, and similar objects. Granules or baits containing 0.01%-5% active ingredient, 0.05%-10% humectant, and 40%-99% vegetable powder are effective in controlling soil insects at extremely low application rates, especially at doses of active ingredient that are lethal through ingestion rather than direct contact. The compounds of this invention can be used in their pure form, but the most common application is in formulations containing one or more compounds with suitable carriers, diluents, and surfactants, and may be combined with food products according to the intended end use. Preferred application methods include spraying aqueous dispersions or refined oil solutions of the compound. Combining with spray oils, spray oil concentrates, spreading agents, adhesives, adjuvants, other solvents, and synergists such as piperonyl butoxide typically enhances the compound's efficacy.

The application rate (i.e., the "biologically effective amount") required for effective control should be determined based on factors such as the type of invertebrate to be controlled, the life cycle and stage of the pest, its size, location, season, host crop or animal, feeding behavior, mating behavior, ambient humidity, temperature, and similar factors. Under normal conditions, an application rate of approximately 0.01 kg to 2 kg of active ingredient per hectare is sufficient to control pests in an agro-ecological ecosystem, but as little as 0.0001 kg per hectare may be sufficient or as much as 8 kg per hectare may be necessary. For non-agricultural applications, the effective application rate should be in the range of approximately 1.0 mg/m² to 50 mg/m², but as little as 0.1 mg/m² may be sufficient or as much as 150 mg/m² may be necessary. Those skilled in the art to which this application pertains can easily determine the bioeffective amount required for the desired level of invertebrate pest control.

Animal pests (i.e., arthropods, gastropods, and nematodes), plants, the soil or water in which the plants grow may come into contact with a compound of formula (I), its N-oxide and salt, or a composition containing a compound of formula (I), its N-oxide and salt, in any manner of application well known in the art to which this application pertains. As used herein, “contacting” includes direct contact (the direct application of the compound/composition to an animal pest or plant, typically to the leaves, stems, or roots of a plant) and indirect contact (the application of the compound/composition to the location of the animal pest or plant).

The compounds of this invention, or insecticidal compositions comprising the above compounds, can protect growing plants/crops from attack or infection by animal pests (especially insects, mites, or arachnids) by bringing them into contact with at least an insecticidally effective amount of the compounds of this invention. The term "crop" refers to both growing and harvested crops.

In one embodiment, the present invention provides a method for protecting crops from attack or infestation by invertebrate pests, the method comprising: bringing the crop into contact with a bioavailable amount of a compound or composition thereof, isomer, polymorph, N-oxide or salt thereof of the present invention.

The compound of the present invention, either alone or as a composition, is applied, by means of an insecticidally effective amount, to insects or plants, plant propagation materials (e.g., seeds, soil, surfaces, materials, or spaces protected from insecticidal attack). This application can be performed before and after the plant, plant propagation material (e.g., seeds, soil, surfaces, materials, or spaces) is infected by insects.

In one embodiment, the present invention also provides a method for protecting seeds from soil insects and for protecting seedling roots and buds from soil and leaf insects, the method comprising: contacting the seeds with a compound or composition of the present invention, its N-oxide or salt, prior to sowing and/or germination.

Furthermore, the present invention provides a method for treating or protecting an animal from parasite infestation or infection, the method comprising: orally, locally or non-enterally administering or applying to the animal a biologically effective amount of a compound or its components, isomers, polymorphs, N-oxides or veterinary acceptable salt of the present invention.

For use in treating crops, the application rate (effective dosage) of the compound of the present invention can be in the range of 1 gram of active ingredient (gai) per hectare to 5000 grams of active ingredient (gai) per hectare in agricultural or horticultural crops, preferably 25 grams to 600 grams per hectare, and more preferably 50 grams to 500 grams per hectare.

The compounds and compositions of this invention are particularly suitable for controlling large numbers of insects on various cultivated plants, such as grains, root crops, oil crops, vegetables, spices, ornamental plants, such as durum wheat seeds and other wheat, barley, oats, rye, corn (feed corn and sugar corn/sweet corn and common corn), soybeans, oil crops, cruciferous plants, cotton, sunflowers, bananas, rice, rapeseed, turnip rapeseed, sugar beets, feed beets, eggplants, potatoes, grass, lawns, turf, feed grass, tomatoes, leeks, pumpkins/squash, cabbage, lettuce, pepper, cucumbers, melons, and Brassica. Plants such as melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugarcane, tobacco, grapes, morning glories, geraniums/pelargoniums, pansies, and impatiens.

In particular, the compounds or components of this invention can be used to protect crops such as grains, corn, rice, soybeans and other legumes, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oil plants, tobacco, coffee, tea, cocoa, sugar beets, sugar cane, cotton, potatoes, tomatoes, onions, peppers and other vegetables, as well as ornamental plants.

The compound of this invention is effective through contact (through soil, glass, walls, mosquito nets, carpets, plant parts or animal parts) and ingestion (bait or plant parts).

The compounds of this invention can also be used to combat non-crop invertebrate pests, such as ants, termites, wasps, flies, mosquitoes, crickets, or cockroaches. For use against these non-crop pests, the compounds of this invention are preferably used in bait compositions.

The lure can be a liquid, solid, or semi-solid formulation (e.g., a gel). Solid lures can be formed into various shapes and forms suitable for individual application, such as granules, blocks, rods, and discs. Liquid lures can be filled into various devices such as open containers, spray devices, droplet sources, or evaporation sources to ensure proper application. Gels can be based on aqueous or oil-based bases and can be formulated to meet specific needs in terms of viscosity, water retention, or aging characteristics.

The bait used in the composition is a product that is sufficiently attractive to entice insects such as ants, termites, wasps, flies, mosquitoes, crickets, or cockroaches to eat it. This attraction can be manipulated using feeding stimulants or sex pheromones. Feeding stimulants are derived from, for example (but not limited to), animal and/or plant proteins (meat meal, fish meal or blood meal, insect parts, egg yolks), animal and/or plant-derived fats and oils, or single, oligosaccharides, or polysaccharides, especially sucrose, lactose, fructose, dextrose, glucose, starch, pectin, or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects, or specific parts thereof can also be used as feeding stimulants. Sexual pheromones are known to be more insect-specific. Specific pheromones are described in the literature and are known to those skilled in the art.

For bait compositions, the typical content of the active ingredient is 0.001% to 15% by weight, ideally 0.001% to 5% by weight of the active compound.

The compound of this invention, in the form of an aerosol (e.g., in a spray can), oil spray, or pump spray, is highly suitable for non-professional users to control pests such as flies, fleas, ticks, mosquitoes, or cockroaches. The aerosol formulation preferably comprises: an active compound; a solvent, such as a low alcohol (e.g., methanol, ethanol, propanol, butanol), or a ketone (e.g., acetone, methyl ethyl ketone), having a temperature of approximately 50 °C to 250 °C. Paraffinic hydrocarbons (e.g., kerosene) with boiling points in the range of °C, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons (e.g., toluene, xylene), and water; in addition, auxiliaries such as emulsifiers, such as sorbitol monooleate, oleyl ethoxylates of ethylene oxide having 3 to 7 moles, fatty alcohol ethoxylates, fragrance oils (e.g., essential oils), esters formed from medium-carbon fatty acids and low-carbon alcohols, and aromatic carbonyl compounds; where appropriate, stabilizers (e.g., sodium benzoate), amphoteric surfactants, low-carbon epoxides, and triethyl orthoformate; and, if necessary, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of such gases.

The difference between oil spray formulations and aerosol formulations is that no propellant is used. When used in spray formulations, the active ingredient content is 0.001% to 80% by weight, preferably 0.01% to 50% by weight, and most preferably 0.01% to 15% by weight of the active compound.

The compounds of this invention and their respective components can also be used in mosquito coils and fumigating coils, chimneys, evaporator plates or long-term evaporators, as well as mothproof paper, mothproof mats or other heat-independent evaporator systems.

Methods of controlling insect-borne infectious diseases (such as malaria, dengue fever and yellow fever, lymphatic filariasis and leishmaniasis) using compounds of formula (I) and their respective components also include treating the surfaces of sheds and houses, air spraying and impregnating curtains, tents, clothing, mosquito nets, fly traps or similar objects. Insecticidal compositions applied to fibers, fabrics, knitwear, nonwovens, mesh materials or foils and waterproof fabrics preferably comprise a mixture of an insecticide, an optional repellent, and at least one adhesive. Suitable repellents include, for example, N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperine, and (2-hydroxymethylcyclohexyl)acetic acid. lactone, 2-ethyl-1,3-hexandiol, indalone, methylneodecanamide (MNDA), and pyrethroids not used for insect control (such as {(+/-)-3-allyl-2-methyl-4-sideoxycyclopentan-2-(+)-enyl-(+)-trans-chrysanthemate ester {(+/-)-3-allyl-2-meth yl4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), antagonists derived from plant extracts or similar sources (such as limonene, eugenol, (+)-eucamalol (1), (-)-1-epi-eucamalol (-)-l-epi-eucamalol), or antagonists derived from crude plant extracts (such as limonene (Eucalyptus maculate), Vitex rotundifolia, Cymbopogan martini, Cymbopogan citratus, and Cymopogan nartdus). Suitable adhesives are selected from polymers and copolymers such as: aliphatic acid vinyl esters (such as vinyl acetate and vinyl versatate), alcohol acrylates and methacrylates (such as butyl acrylate, 2-ethylhexyl acrylate and methyl acrylate), mono- and diene unsaturated hydrocarbons (such as styrene) and aliphatic dienes (such as butadiene).

Drip curtains and mosquito nets are generally applied by immersing the fabric material in an emulsion or dispersion, or by spraying the emulsion or dispersion onto the net.

The compounds and mixtures thereof of the present invention can be used to protect wood materials, such as trees, wooden fences, railway sleepers, frames, works of art, and buildings, and also to protect building materials, furniture, leather, fibers, vinyl products, wires and cables from ants and/or termites, and to control the damage caused by ants and termites to crops or humans (e.g., when pests invade houses and public facilities). The compound of this invention can be applied not only to the surface of the surrounding soil or the soil under the floor to protect wood materials, but also to wood products (such as the surface of concrete under the floor, niche columns, beams, plywood, furniture, etc.), wood products (such as particleboard, half-board, etc.) and vinyl products (such as coated wires, vinyl sheets, insulation materials (such as polystyrene foam), etc.).

In cases where the compound is applied to ants that harm crops or humans, the compound of this invention is applied to crops or surrounding soil, or directly to ant nests, etc.

In one embodiment, the present invention provides a method for controlling insect and mite pests, the method comprising: bringing the insect and mite pests, their habitats, breeding grounds, food sources, plants, seeds, soil, areas, materials, or environments in which the insect and mite pests are growing or may grow, or materials, plants, seeds, soil, surfaces, or spaces protected from pest infestation or contamination, into contact with a bioavailable amount of a compound of formula (I) of the present invention or its salts, stereoisomers, polymorphs, metal complexes, N-oxides, or compositions thereof.

In another embodiment, the present invention provides a method for protecting crops from insect and mite pests, comprising: bringing the crop into contact with a compound of formula (I) as claimed in claim 1, or a salt thereof, a stereoisomer, a polymorph, a metal complex or an N-oxide thereof, or with a composition or combination thereof containing a compound of formula (I).

In another embodiment, the invention provides a method comprising: applying an effective amount of the compound of formula (I) to an agricultural or horticultural crop, the effective amount being from 1 gram of active ingredient to 5,000 grams of active ingredient per hectare.

In another embodiment, the invention provides a method for protecting seeds, plants and plant parts from soil insects and for protecting seedling roots and buds from soil and leaf insects, comprising: contacting the seeds with a compound of formula (I) or a salt thereof, a stereoisomer, a polymorph, a metal complex, an N-oxide, or a composition or combination thereof containing a compound of formula (I) before sowing and/or after pre-germination.

In another embodiment, the invention provides the use of a compound of formula (I) or a salt thereof, a stereoisomer, a polymorph, a metal complex, an N-oxide, or a composition or combination thereof containing a compound of formula (I) for the control of insects and mites in crops and horticultural crops, for the control of household and vector-borne pests and animal parasites.

Seed treatment

The present invention further provides a treated seed containing the compounds of the present invention, wherein the amount of the seed before treatment is about 0.0001% to about 1% by weight.

The compounds of this invention are also suitable for treating seeds to protect them from pests (especially soil-dwelling insects and mites), and to protect the roots and shoots of the resulting plants from soil pests and leaf pests.

The compounds of this invention are particularly useful for protecting seeds from soil pests and for protecting the roots (termites, nematodes, and slugs) and buds of the resulting plants from soil pests and leaf insects. Protection of the roots and buds of the resulting plants is preferred. Protection of the buds of the resulting plants is even more preferred, especially protection against piercing-sucking insects, and most importantly, protection against aphids, jassids, thrips, and whiteflies.

Therefore, the present invention includes a method for protecting seeds from insects (especially soil insects) and protecting the seedling roots and buds from insects (especially soil and leaf insects), the method comprising: contacting the seeds with the compounds of the present invention before sowing and/or after pre-germination of the seeds. Particularly preferred is a method for protecting the roots and buds of the plant; more preferably, a method for protecting the buds of the plant from piercing-sucking and sucking insects; and most preferably, a method for protecting the buds of the plant from aphids.

The term "seed" encompasses all categories of seeds and plant propagules, including but not limited to true seeds, seed tubers, haustoria, bulbs, scales, fruits, tubers, grains, cuttings, branches and the like, and in a preferred embodiment refers to true seeds.

The term "seed treatment" encompasses all suitable seed treatment techniques known in this field, such as seed dressing, seed coating, seed powdering, seed soaking, and seed pelleting.

This invention also includes seeds coated with or containing an active compound. These seeds can be coated using seed coating compositions containing compounds of this invention. For example, seed coating compositions are reported in European Patent Nos. EP3165092, EP3158864, PCT Patent Publication Nos. WO2016198644, WO2016039623, WO2015192923, Canadian Patent No. CA2940002, US Patent Publication Nos. US2006150489, and US Patent Publication No. US200423. 7395, PCT Patent Publication No. WO2011028115, European Patent No. EP2229808, PCT Patent Publication No. WO2007067042, European Patent No. EP1795071, European Patent No. EP1273219, PCT Patent Publication No. WO200178507, European Patent No. EP1247436, Dutch Patent No. NL1012918 and Canadian Patent No. CA2083415.

The term "coated with and/or containing" generally indicates that the active ingredient is mostly on the surface of the propagation product when applied, although a greater or lesser portion of the ingredient may penetrate into the propagation product, depending on the application method. When the propagation product is (re)planted, it can absorb the active ingredient and moisture.

Suitable seeds include grains, root crops, oil crops, vegetables, spices, and ornamental plants, such as durum wheat seeds and other wheat, barley, oats, rye, corn (feed corn and sugar corn/sweet corn and common corn), soybeans, oil crops, cruciferous plants, cotton, sunflowers, bananas, rice, rapeseed, turnip rapeseed, and sugar beets. Seeds of beets, eggplants, potatoes, grass, lawns, turf, forage grass, tomatoes, leeks, pumpkins/cucumbers, cabbage, lettuce, peppers, cucumbers, melons, sages, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugarcane, tobacco, grapes, petunias, geraniums/sanctuaries, pansies, and impatiens.

In addition, the compounds of this invention can also be used to treat seeds from plants that have become resistant to herbicides, fungicides, or insecticides through breeding (including genetic engineering).

For example, the compounds of this invention can be used to treat seeds from plants that are resistant to herbicides selected from the group consisting of sulfonylureas, imidazolinones, glufosinate-ammonium, or glyphosate-isopropylammonium and similar active substances (see, for example, Europe). Patent No. EP242236, European Patent No. EP242246 (PCT Patent Publication No. WO92/00377) (US Patent No. EP257993, US Patent No. US5013659), or in genetically modified crop plants (e.g., cotton), the ability to produce Bacillus thuringiensis toxin (Bt toxin) and to make such plants resistant to certain pests (European Patent No. EP142924, European Patent No. EP193259).

Furthermore, the compounds of this invention can be used to treat seeds derived from plants that possess modified properties compared to existing plants, which can be produced through, for example, conventional breeding methods and/or the generation of mutants, or through recombination procedures. For example, numerous cases have described recombination modifications of crop plants aimed at modifying the starch synthesized in plants (e.g., PCT Patent Publication No. WO92/11376, PCT Patent Publication No. WO92/14827, PCT Patent Publication No. WO91/19806) or for the purpose of genetically modified crop plants with modified lipids (PCT Patent Publication No. WO91/13972).

The seed treatment of the compound of this invention is carried out by spraying or sowing before the plants are sown and before they emerge.

Compositions particularly suitable for seed treatment include, for example: A. Water-soluble concentrates (SL, LS) B. Emulsions (EW, EO, ES) C. Suspensions (SC, OD, FS) D. Water-dispersible and water-soluble granules (WG, SG) E. Water-dispersible and water-soluble powders (WP, SP, WS) F. Gel preparations (GF) G. Powderable powders (DP, DS)

Commonly known seed treatment formulations include, for example, flowable concentrates (FS), solutions (LS), powders (DS) for drying treatment, water-dispersible powders (WS), water-soluble powders (SS), emulsions (ES and EC), and gel formulations (GF) for slurry treatment. These formulations can be applied to diluted or undiluted seeds. They can be applied directly to the seeds before sowing or after germination.

In one embodiment, seed treatment is performed using an FS formulation. Typically, an FS formulation may contain 1-800 g/l of active ingredient, 1-200 g/l of surfactant, 0 to 200 g/l of antifreeze, 0 to 400 g/l of binder, 0 to 200 g/l of pigment, and up to 1 liter of solvent, preferably water.

Other preferred FS formulations of the compounds of the present invention for seed treatment contain 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, 0.1 to 20% by weight (1 to 200 g/l) of the active ingredient, and 0.1 to 20% by weight (1 to 200 g/l) of the active ingredient. The composition includes at least one surfactant (e.g., 0.05 to 5% by weight of a wetting agent) and 0.5 to 15% by weight of a dispersant, up to 20% by weight (e.g., 5 to 20% by weight of an antifreeze agent), 0 to 15% by weight (e.g., 1 to 15% by weight of a pigment and/or dye), 0 to 40% by weight (e.g., 1 to 40% by weight of a binder (adhesive/adhesive), selectively up to 5% by weight (e.g., 0.1 to 5% by weight of a thickener), selectively 0.1 to 2% by weight of a defoamer and selectively a preservative (e.g., a biocide, antioxidant, etc., for example, in an amount of 0.01 to 1% by weight) and up to 100% by weight of a filler/carrier.

Seed treatment formulations may additionally include adhesives and selective colorants.

Adhesives can be added to improve the adhesion of the treated active material to the seeds. Suitable adhesives include homopolymers and copolymers of epoxides (such as ethylene oxide or propylene oxide), polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone and its copolymers, ethylene-vinyl acetate copolymers, homopolymers and copolymers of acrylic acid, polyvinylamine, polyvinylpyridine and polyvinylpyrimidine, polysaccharides (such as cellulose, cellulose and starch), homopolymers and copolymers of polyolefins (such as olefin/maleic anhydride copolymers, polyurethanes, polyesters, homopolymers and copolymers of polystyrene).

Alternatively, the colorant may also be included in the formulation. The colorants or dyes suitable for seed treatment preparations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1, Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 80, Pigment Yellow 1, Pigment Yellow 13, Pigment Red 112, Pigment Red 48:2, Pigment Red 48:1, Pigment Red 57:1, Pigment Red 53:1, Pigment Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Violet 10, Basic Violet 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Basic Red 10, and Basic Red 108.

An example of a gelling agent is carrageenan (Satiagel®).

In seed treatment, the application rate of the compound of the invention is generally from 0.1 g to 10 kg per 100 kg of seeds, preferably from 1 g to 5 kg per 100 kg of seeds, more preferably from 1 g to 1000 g per 100 kg of seeds, and especially from 1 g to 200 g per 100 kg of seeds. Therefore, the invention also provides seeds containing a compound of formula (I) as defined herein or an agriculturally useful salt of formula (I). The amount of the compound of formula (I) or its agriculturally useful salt is generally from 0.1 g to 10 kg per 100 kg of seeds, preferably from 1 g to 5 kg per 100 kg of seeds, and especially from 1 g to 1000 g per 100 kg of seeds. For certain crops, such as lettuce, the application rate can be higher.

In one embodiment, the invention provides a seed comprising a compound of formula (I) or a salt thereof, a stereoisomer, a polymorph, a metal complex, an N-oxide, or a composition or composition comprising a compound of formula (I), wherein the amount of the compound of formula (I) in the seed is from 0.0001% to 1% by weight.

Animal health

The invention also provides an agricultural and/or veterinary composition comprising at least one compound of the invention.

The invention also relates to the use of the compounds, N-oxides or veterinary acceptable salts of the invention, or compositions thereof, for the preparation of medicines for the treatment or protection of animals from invertebrate pests or parasites.

Compounds of formula (I), their N-oxides and/or their veterinary acceptable salts are also particularly suitable for the prevention and control of parasites inside and outside the body of animals.

Therefore, one objective of this invention is to provide a new method for controlling parasites inside and on the bodies of animals. Another objective of this invention is to provide a safer pesticide for animals. Another objective of this invention is to provide a pesticide for animals that can be used at lower dosages than existing pesticides. A further objective of this invention is to provide an pesticide for animals that provides long-residual control of parasites.

The invention also relates to a composition comprising at least one compound of formula (I), an N-oxide, or a veterinary acceptable salt thereof and an acceptable carrier, containing an effective amount of the antiparasitic compound, for the prevention and control of parasites inside and on the surface of animals.

The present invention also provides a method for treating, controlling, preventing and protecting animals from parasitic infestation and infection, the method comprising orally, topically or parenterally administering or applying to the animal an effective amount of the parasite-killing compound of the present invention or a composition comprising the compound.

The present invention also provides a method for preparing a composition for treating, controlling, preventing or protecting animals from parasitic infection or infestation, the composition comprising an effective amount of the compound of the present invention or a composition comprising the compound for killing parasites.

The activity of a compound against agricultural pests does not imply its suitability for controlling endoparasites and ectoparasites inside and outside animals. This requires, for example, low non-emetic doses (in the case of oral administration), metabolic compatibility with animals, low toxicity, and safe handling.

It has been surprisingly discovered that the compounds of this invention are effective against internal and external parasites in animals.

The compounds of this invention and compositions comprising such compounds are preferably used for the control and prevention of infection and contamination of animals, including warm-blooded animals (including humans) and fish. For example, they are suitable for the control and prevention of infection and contamination of the following: mammals, such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs, cats, buffalo, donkeys, yellow deer, and reindeer; and fur-bearing animals, such as mink, chinchillas, and raccoons; birds, such as chickens, geese, turkeys, and ducks; and fish, such as freshwater and saltwater fish, such as trout, carp, and eels.

The compounds of this invention and compositions comprising such compounds are preferably used for the control and prevention of infection and contamination in domestic animals such as dogs or cats.

Infections to warm-blooded animals and fish include, but are not limited to, lice, ticks, ticks, midges, mud flies, fly larvae, chiggers, midges, mosquitoes, and fleas.

The compounds of this invention and compositions comprising such compounds are suitable for systemic and/or non-systemic control of ectoparasites and/or endoparasites. They have activity against all or part of the developmental stages.

The compounds of this invention and compositions comprising such compounds are particularly suitable for the control of ectoparasites.

The compounds of this invention are particularly effective against parasites of the following orders and species: fleas (Siphonaptera), such as the cat flea (Ctenocephalides felis), dog flea (Ctenocephalides canis), Indian rat flea (Xenopsylla cheopis), human flea (Pulex irritans), leaf miner (Tunga penetrans), and striped rat flea (Nosopsyllus fasciatus); cockroaches (Blattaria-Blattodea), such as the German cockroach (Blattella germanica), Asian cockroach (Blattella asahinae), American cockroach (Periplaneta americana), Japanese cockroach (Periplaneta japonica), brown cockroach (Periplaneta brunnea), black-breasted cockroach (Peroplaneta fuligginosa), and Australian cockroach (Periplaneta... The order Diptera includes *Aedes aegypti*, *Blatta orientalis*, flies, and mosquitoes (Diptera), such as *Aedes aegypti*, *Aedes albopictus*, *Aedes vexans*, *Anastrepha ludens*, *Anopheles maculipennis*, *Anopheles crucians*, *Anopheles albimanus*, *Anopheles gambiae*, *Anopheles freeborni*, *Anopheles leucosphyrus*, *Anopheles minimus*, *Anopheles quadrimaculatus*, *Calliphora vicina*, and *Chrysomya*. bezziana, American golden fly (Chrysomya hominivorax), rice golden fly (Chrysomya macellaria), deer fly (Chrysops discalis), deer fly (Chrysops silacea), Atlantic fly (Chrysops atlanticus), spiral fly (Cochliomyia hominivorax), shield fly (Cordylobia anthropophaga), fluke midge (Culicoides furens), five-banded pale mosquito (Culex pipens), Aedes mosquito (Culex nigripalpus), tropical house mosquito (Culex quinquefasciatus), Aedes mosquito (Culex tarsalis), white-spotted velvet mosquito (Culiseta inornata), black-tailed velvet mosquito (Culiseta melanura), horse fly (Dermatobia hominis), yellow-bellied stag fly (Fannia) Canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp.), housefly (Musca domestica), carrion fly (Muscina stabulans), sheep-nosed fly (Oestrus ovis), silver-footed sandfly (Phlebotomus argentipes), black rice paddy scale fly (Psorophora columbiae), discoloring scale fly (Psorophora discolor), mixed fly (Prosimulium mixtum), red-tailed flesh fly (Sarcophaga haemorrhoidalis), flesh fly (Sarcophaga sp.), spider fly (Simulium vittatum), stinging fly (Stomoxys calcitrans), horsefly (Tabanus bovinus), black horsefly (Tabanus atratus), thin-striped horsefly (Tabanus lineola), and zebra fly (Tabanus Similis, lice (order Phthiraptera), such as the human head lice (Pediculus humanus capitis), human body lice (Pediculus humanus corporis), pubic lice (Pthirus pubis), cattle lice (Haematopinus eurysternus), pig lice (Haematopinus suis), cattle jaw lice (Linognathus vituli), cattle bird lice (Bovicola bovis), chicken lice (Menopon gallinae), large chicken lice (Menacanthus stramineus), and small short-nosed cattle lice (Solenopotes capillatus); ticks and parasitic mites (order Parasitiformes): ticks (suborder Ixodida), such as the scapular tick (Ixodes scapularis), holocyclus tick (Ixodes holocyclus), and Pacific hard tick (Ixodes holocyclus). The parasites include *Pseudomonas pacificus*, brown dog ticks (*Rhiphicephalus sanguineus*), *Dermacentor andersoni*, *Dermacentor variabilis*, American flower ticks (*Amblyomma americanum*), Gulf of Mexico ear ticks (*Ambryommama culatum*), rodent ticks (*Ornithodorus hermsi*), relapsing heat ticks (*Ornithodorus turicata*), and parasitic mites (Mesostigmata), such as *Ornithonyssus bacoti* and *Dermanyssus*. Gallinae, suborders Actinedida (Prostigmata) and Acaridida (Astigmata), including genera such as *Acarapis* spp., *Cheyletiella* spp., *Ornithocheyletia* spp., *Myobia* spp., *Psorergates* spp., *Demodex* spp., *Trombicula* spp., *Listrophorus* spp., *Acarus* spp., *Tyrophagus* spp., and *Caloglyphus*. spp.), Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp., stink bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, and Reduvius (senile insectivorous stink bug). The following genera are included: *Senilis*, *Triatoma* spp., *Rhodnius* ssp., *Panstrongylus* ssp., and *Arilus critatus*; *Anoplurida*, including genera such as *Haematopinus* spp., *Linognathus* spp., *Pediculus* spp., *Phtirus* spp., and *Solenopotes* spp.; *Mallophagida* (including suborders Arnblycerina and Ischnocerina), including genera such as *Trimenopon* spp., *Menopon* spp., and *Trinoton*. The genera include *Bovicola* spp., *Werneckiella* spp., *Lepikentron* spp., *Trichodectes* spp., and *Felicola* spp.

Roundworms Nematoda:

Wipeworms and trichinosis (order Trichosyringida), such as Trichinellidae (genus Trichinella spp.), Trichuridae (genus Trichuris spp.), and Capillaria spp.); Rhabditida, such as Rhabditis spp., Strongyloides spp., and Helicphalobus spp.; Strongylidae, such as Strongylus spp., Ancylostoma spp., and Necator. americanus), Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp.), Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus The following nematodes are listed: *Dentatus*, *Syngamus trachea*, *Ancylostoma* spp., *Uncinaria* spp., *Globocephalus* spp., *Necator* spp., *Metastrongylus* spp., *Muellerius capillaris*, *Protostrongylus* spp., *Angiostrongylus* spp., *Parelaphostrongylus* spp., *Aleurostrongylus abstrusus*, and *Dioctophyma*. *Ascaridida*, a class of intestinal roundworms, including species such as *Ascaris lumbricoides* (human roundworm), *Ascaris suum* (swine roundworm), *Ascaridia galli* (chicken roundworm), *Parascaris equorum* (horse roundworm), *Enterobius vermicularis* (threadworm), *Toxocara canis* (canine roundworm), *Toxascaris leonine* (lion roundworm), *Skrjabinema spp.* (species of *Skrjabinema*), and *Oxyuris equi* (horse worm). *Camallanida*, a class of worms, includes species such as *Dracunculus medinensis* (Guinea worm). Worms, specifically the order Spirurida, including genera such as *Thelazia* spp., *Wuchereria* spp., *Brugia* spp., *Onchocerca* spp., *Dirofilaria* spp., *Dipetalonema* spp., *Setaria* spp., *Elaeophora* spp., *Spirocerca lupi*, and *Habronema* spp.; hookworms (order Acanthocephala), including genera such as *Acanthocephalus*. The following genera are listed: *Macracanthorhynchus hirudinaceus* and *Oncicola* spp.; vortices (flatworms); trematodes (Trematoda), such as *Faciola* spp., *Fascioloides magna*, *Paragonimus* spp., *Dicrocoelium* spp., *Fasciolopsis buski*, *Clonorchis sinensis*, *Schistosoma* spp., *Trichobilharzia* spp., and *Alaria*. The genera *Alata*, *Paragonimus* spp., and *Nanocyetes* spp., as well as monogenean trematodes (*Cercomeromorpha*), especially tapeworms (*Cestoda*, *Tapeworms*), such as *Diphyllobothrium* spp., *Tenia* spp., *Echinococcus* spp., *Dipylidium caninum*, *Multiceps* spp., *Hymenolepis* spp., *Mesocestoides* spp., *Vampirolepis* spp., *Moniezia* spp., and *Anoplocephala*. The genera *Sirometra*, *Anoplocephala*, and *Hymenolepis* are mentioned.

Compounds of formula (I) and compositions containing such compounds are particularly suitable for controlling pests of the order Diptera, Siphonaptera and Ixodida.

In one embodiment, the present invention provides a compound of formula (I) and compositions comprising thereof for use in the control of mosquitoes.

In one embodiment, the present invention provides a compound of formula (I) and compositions comprising thereof for use in the control of flies.

In one embodiment, the present invention provides a compound of formula (I) and compositions comprising thereof for use in the prevention and control of fleas.

The use of the compounds and compositions thereof in the control of ticks is another embodiment of the invention.

The compounds of this invention are also particularly suitable for combating endoparasites (roundworms nematoda, thorny headed worms, and planarians).

In one embodiment, the administration of the compound according to the invention can be carried out both preventively and therapeutically.

In another embodiment, the compound of the invention is administered directly or in a suitable formulation, orally, locally/percutaneously, orally.

For oral administration to warm-blooded animals, the compound of this invention can be formulated into animal feed, animal feed premix, animal feed concentrate, pills, solutions, pastes, suspensions, drenches, gels, tablets, pellets, and capsules. Additionally, the compound of this invention can be administered to animals in their drinking water. For oral administration, the selected dosage form should provide the animal with 0.01 mg to 100 mg of the compound of this invention per kilogram of body weight per day, preferably 0.5 mg to 100 mg per kilogram of body weight per day.

Alternatively, the compounds of the present invention can be administered to animals non-enterovenously, for example, via rumen, intramuscular, intravenous, or subcutaneous injection. The compounds of the present invention can be dispersed or dissolved in physiologically acceptable carriers for subcutaneous injection. Alternatively, the compounds of the present invention can be formulated into implants for subcutaneous administration. Additionally, the compounds of the present invention can be administered to animals transdermally. For non-enterovenous administration, the selected dosage form should provide the animal with 0.01 mg to 100 mg of the compounds of the present invention per kilogram of animal body weight per day.

The compounds of this invention can also be applied topically to animals in the form of extracts, powders, granules, rings, tablets, sprays, shampoos, drops, and pourable formulations, as well as in the form of ointments, oil-in-water emulsions, or water-in-oil emulsions. For top application, extracts and sprays typically contain 0.5 ppm to 5000 ppm, and preferably 1 ppm to 3000 ppm, of the compounds of this invention. Furthermore, the compounds of this invention can be formulated into ear tags for animals, particularly quadrupeds such as cattle and sheep.

Suitable formulations include: solutions, such as oral solutions, diluted concentrates for oral administration, solutions for use on the skin or in body cavities, pourable formulations, gels; emulsions and suspensions for oral or transdermal administration; semi-solid formulations; formulations in which the active compound is incorporated into an ointment base or an oil-in-water emulsion or water-in-oil emulsion base; solid formulations, such as powders, premixes or concentrates, granules, pellets, tablets, large pills, capsules; aerosols and inhalers; and molded articles containing active compounds.

Injectable formulations are prepared by dissolving the active ingredient in a suitable solvent and selectively adding other components such as acids, alkalis, buffer salts, preservatives, and solubilizers.

The solution was filtered and sterilely filled.

Suitable solvents are physiologically tolerable solvents, such as water; alkanols, such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycol; N-methylpyrrolidone; 2-pyrrolidone and mixtures thereof.

The active compound can be selectively dissolved in physiologically tolerable vegetable or synthetic oils suitable for injection.

Suitable solubilizers are solvents that promote the dissolution of active compounds in the main solvent or prevent their precipitation. Examples include polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.

Suitable preservatives include benzyl alcohol, chlorobutanol, p-hydroxybenzoate, and n-butanol.

Oral solutions are administered directly. Concentrates are administered orally after being pre-diluted to the intended concentration. Oral solutions and concentrates are prepared using existing technology and as described above regarding injectable solutions; aseptic procedures are not required.

Solutions used on the skin are applied by dripping, spreading, wiping, spraying, or sprinkling.

The solution for use on the skin is prepared using existing technology and according to the description of injectable solutions above; aseptic procedures are not required.

Other suitable solvents include polypropylene glycol; phenethyl alcohol; phenoxyethanol; esters, such as ethyl acetate or butyl acetate, methyl benzoate; ethers, such as alkyl glycol ethers (e.g., dipropylene glycol monomethyl ether); ketones, such as acetone, methyl ethyl ketone; aromatic hydrocarbons; vegetable oils and synthetic oils; N,N-dimethylformamide; dimethylacetamide; diethylene glycol monoethyl ether (transcutol); glycerol acetone (solketal); propylene carbonate and mixtures thereof.

Adding a thickener during the preparation process can be advantageous. Suitable thickeners include inorganic thickeners (such as bentonite, colloidal silica, aluminum monostearate), organic thickeners (such as cellulose derivatives, polyvinyl alcohol and its copolymers), acrylates, and methacrylates.

The gel is applied to or spread on the skin or introduced into a body cavity. The gel is prepared by treating a solution as described in the injectable solution with sufficient thickener, which is a transparent substance having a consistency similar to an ointment. The thickener used is one listed above.

Pour-on formulations are applied by pouring or spraying onto a defined area of the skin. The active compound penetrates the skin and acts throughout the body. Pour-on formulations are prepared by dissolving, suspending, or emulsifying the active compound in a suitable skin-compatible solvent or solvent mixture. Where appropriate, other adjuvants (such as colorants, bioavailability enhancers, antioxidants, light stabilizers, and adhesives) are added.

Suitable solvents include, for example: water; alkanols; glycols; polyethylene glycol; polypropylene glycol; glycerol; aromatic alcohols, such as benzyl alcohol, phenethyl alcohol, phenoxyethanol; esters, such as ethyl acetate, butyl acetate, benzoate; ethers, such as alkyl glycol alkyl ethers (such as dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether); ketones, such as acetone, methyl ethyl ketone; cyclic carbonates, such as propylene carbonate, ethylene carbonate. Aromatic and/or aliphatic hydrocarbons; vegetable or synthetic oils; DMF; dimethylacetamide; N-alkylpyrrolidone, such as methylpyrrolidone, N-butylpyrrolidone or N-octylpyrrolidone; N-methylpyrrolidone; 2-pyrrolidone; 2,2-dimethyl-4-oxy-methylene-1,3-dioxolane or glycerol formaldehyde.

Suitable colorants are, for example, all colorants that are permitted for use on animals and are soluble or suspendable.

Suitable absorption enhancers include, for example, dimethyl monoxide; spreading oils such as isopropyl tetradecanoate, dipropylene glycol nonanoate, polysiloxane and its copolymers with polyethers, fatty acid esters, triglycerides, and fatty alcohols.

Suitable antioxidants include sulfites or metabisulfites (such as potassium metabisulfite), ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, or tocopherol.

Suitable light stabilizers include, for example, novantisolic acid (2-phenylbenzimidazole-5-sulfonic acid). Suitable adhesives include, for example, cellulose derivatives, starch derivatives, polyacrylates, or natural polymers such as alginate and gelatin. The emulsion can be administered orally, transdermally, or by injection. The emulsion is either water-in-oil or oil-in-water.

It is prepared by dissolving the active compound in a hydrophobic phase or a hydrophilic phase and homogenizing it with other phase solvents by means of a suitable emulsifier and, where appropriate, other auxiliaries (such as colorants, absorption promoters, preservatives, antioxidants, light stabilizers, viscosity enhancers).

A suitable hydrophobic phase (oil) is:

Liquid paraffin; polysiloxane oil; natural vegetable oils, such as sesame oil, almond oil, castor oil; synthetic triglycerides, such as caprylic/capric diglycerides and triglyceride mixtures formed with vegetable fatty acids of _C1 - _C12 chain length or other specially selected natural fatty acids; mixtures of metaglycerides of saturated or unsaturated fatty acids that may also contain hydroxyl groups; monoglycerides and diglycerides of Cs-do fatty acids; fatty acid esters, such as ethyl stearate, di-n-butyl adipate, hexyl laurate, dipropylene glycol nonanoate; esters formed from branched fatty acids of medium chain length and saturated fatty alcohols of _C16 - _C18 chain length; isopropyl myristate; isopropyl palmitate; chain length _C12 -C ₁₈ saturated fatty alcohols, including caprylate/decanoate esters; isopropyl stearate; oleyl alcohol ester; decyl oleate; ethyl oleate; ethyl lactate; waxy fatty acid esters, such as synthetic ducktail fat, dibutyl phthalate, diisopropyl adipate and mixtures of esters related to the latter; fatty alcohols, such as isotriadecanool, 2-octyldodecanool, hexadecylstearyl, oleyl alcohol; and fatty acids, such as oleic acid; and mixtures thereof.

Suitable emulsifiers include, for example: nonionic surfactants such as polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, and alkylphenol polyglycol ether; amphoteric surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin.

Suitable anionic surfactants include, for example, sodium lauryl sulfate, fatty alcohol ether sulfates, and mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; suitable cationic surfactants include, for example, hexadecyltrimethylammonium chloride.

Other suitable additives include, for example, substances that enhance viscosity and stabilize emulsions, such as carboxymethyl cellulose, methyl cellulose and other celluloses and starch derivatives, polyacrylates, alginate, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycol, wax, gelatinous silica, or mixtures of the aforementioned substances.

The suspension can be administered orally or topically/dermally. It is prepared by suspending the active compound in a suspending agent, and, where appropriate, by adding other additives such as humectants, colorants, bioavailability enhancers, preservatives, antioxidants, light stabilizers, etc.

Liquid suspensions are all homogeneous solvents and solvent mixtures.

The appropriate wetting agent (dispersant) is the emulsifier listed above.

Other adjuvants that may be mentioned are those listed above.

Semi-solid formulations can be administered orally or via surface/dermal dosing. They differ from the suspensions and emulsions mentioned above only in their higher viscosity.

When preparing solid formulations, the active compound is mixed with a suitable excipient (and, where appropriate, by adding an adjuvant) and brought into the desired form.

Suitable excipients are any physiologically tolerable solid inert substances. Excipients used can be inorganic or organic. Inorganic substances include, for example, sodium chloride, carbonates (such as calcium carbonate), bicarbonates, alumina, titanium oxide, silicic acid, clay, precipitated silica or colloidal silica, or phosphates. Organic substances include, for example, sugars, fiber, food and feed (such as milk powder, animal meal, grain meal and cereal crumbs), and starch.

Suitable adjuvants include the preservatives, antioxidants and/or colorants mentioned above.

Other suitable additives include lubricants and flow aids, such as magnesium stearate, stearic acid, talc, and bentonite; disintegration promoters, such as starch or cross-linked polyvinylpyrrolidone; adhesives, such as starch, gelatin, or linear polyvinylpyrrolidone; and anhydrous adhesives, such as microcrystalline cellulose.

Generally, the term "parasiticly effective amount" refers to the amount of active ingredient required to achieve an observable effect on growth, including necrosis, death, delay, prevention, removal, and destruction or otherwise reducing the presence and activity of target organisms. The parasiticly effective amount of the various compounds/compositions used in this invention can vary. The composition of the parasiticly effective amount will also vary depending on key conditions such as the desired parasitic effect and duration, target species, application mode, and similar conditions. Compositions used in this invention generally comprise from about 0.001% to 95% of the compounds of this invention.

Generally, the compound of the present invention should be applied at a total dose of 0.5 mg/kg to 100 mg/kg daily, preferably 1 mg/kg to 50 mg/kg daily. The formulation contains a concentration of 10 ppm to 80% by weight, preferably 0.1% by weight to 65% by weight, more preferably 1% by weight to 50% by weight, most preferably 5% by weight to 40% by weight of the compound acting on parasites, and more preferably on ectoparasites. The formulation diluted before use contains a concentration of 0.5% by weight to 90% by weight, preferably 1% by weight to 50% by weight of the compound acting on ectoparasites. In addition, the formulation contains the compound of the invention that combats endoparasites at a concentration of 10 ppm to 2% by weight, preferably 0.05% by weight to 0.9% by weight, and particularly preferably 0.005% by weight to 0.25% by weight.

In one embodiment, the composition of the compound comprising the invention is applied transdermally/surface.

In another embodiment, surface application is performed in the form of shaped articles containing compounds (such as collars, discs, earrings, strips and adhesive strips and foils attached to body parts).

Solid formulations of the compound of the invention are generally preferred to be applied over a three-week period, releasing a total amount of 10 mg to 300 mg per kilogram of the treated animal's body weight, preferably 20 mg to 200 mg, and most preferably 25 mg to 160 mg.

Thermoplastic and flexible plastics, as well as elastomers and thermoplastic elastomers, are used in the preparation of molded articles. Suitable plastics and elastomers are polyethylene resins, polyurethanes, polyacrylates, epoxy resins, cellulose, cellulose derivatives, polyamides, and polyesters that are fully compatible with the compounds of the present invention. A detailed list of plastics and elastomers and the preparation procedures for molded articles are provided, for example, in PCT patent publication number WO 2003/086075.

Positive crop response:

The compounds of this invention not only effectively control insects and mites, but also exhibit positive crop responses, such as promoting plant growth (e.g., enhancing root growth and tolerance to drought, high salinity, high temperature, cold, frost, or light radiation), increasing flowering, improving nutrient utilization (e.g., enhancing nitrogen assimilation), improving the quality of plant products, increasing the number of productive tillers, and enhancing resistance to fungi, insects, and pests, thereby increasing yield.

As described herein, the compounds of formula (I) exhibit insecticidal activity against a variety of insects that attack important crops. The activity of the compounds of this invention is evaluated as described in the following tests:

Biological examples:

Example A: Tomato armyworm (Helicoverpa armigera)

The diet incorporation method is used, in which the required amount of the test compound is weighed and dissolved in a test tube containing a solvent solution. The test tube is placed in a vortex at 2000 rpm for 90 minutes to allow proper mixing. When the temperature in the bioassay container is approximately 60°C, the semi-synthesized feed is added to the solution. The compound and feed are thoroughly stirred to ensure proper mixing, and then allowed to cool for 30 minutes. The solidified feed is cut into equal portions, and each portion is transferred to one cell of the bioassay tray. A single, hungry third-instar larva is released into each cell of the bioassay tray, and the tray is then covered. The bioassay trays were then maintained under laboratory conditions of 25°C and 65% relative humidity. Dead, dying, and surviving larvae were recorded 96 hours after larval release. Dying larvae were considered dead when calculating the mortality rate. The following compounds had a mortality rate of ≥70% at 300 ppm: 5, 8, 9, 22, 32, 33, 39, 41, 49, 50, 51, 52, 103, 108, 109, 112, and 127.

Example B: Spodoptera litura

The diet incorporation method is used, in which the required amount of the test compound is weighed and dissolved in a test tube containing a solvent solution. The test tube is placed in a vortex at 2000 rpm for 90 minutes to allow proper mixing. When the temperature in the bioassay container is approximately 60°C, the semi-synthesized feed is added to the solution. The compound and feed are thoroughly stirred to ensure proper mixing, and then allowed to cool for 30 minutes. The solidified feed is cut into equal portions, and each portion is transferred to one cell of the bioassay tray. A single, hungry third-instar larva is released into each cell of the bioassay tray, and the tray is then covered. The bioassay trays were then maintained under laboratory conditions of 25°C and 65% relative humidity. Dead, dying, and surviving larvae were recorded 96 hours after larval release. Dying larvae were considered dead when calculating the mortality rate. The following compounds had a mortality rate of ≥70% at 300 ppm: 5, 8, 22, 24, 25, 33, 34, 39, 41, 49, 52, 104, and 108.

Example C: Diamondback moth (Plutella xylostella)

The test was conducted using the leaf dip method, in which the required amount of the compound was weighed and dissolved in a test tube containing the solvent solution. The test tube was placed in a vortex at 2000 rpm for 90 minutes to allow proper mixing, and then diluted to the required test concentration with 0.01% Triton-X solution. Cabbage leaves were immersed in the compound solution for 10 seconds, air-dried for 20 minutes, and then transferred to the cells of a bioassay tray. Single, hungry second-instar larvae were released into each cell of the bioassay tray, and the tray was covered. The bioassay tray was then maintained under laboratory conditions of 25°C and 65% relative humidity. Dead, dying, and surviving larvae were recorded 72 hours after larval release. Dying larvae are considered dead when calculating mortality rates. The following compounds have a mortality rate of ≥70% at 300 ppm: 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 15, 16, 17, 18, 19, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 42, 43, 44, 45, 46, 48, 49, 50, 51, 52, 53, 54, 55, 56, 5 7, 58, 59, 60, 61, 62, 63, 64, 66, 67, 68, 69, 70, 71, 75, 76, 77, 78, 79, 81, 83, 86, 87, 89, 90, 91, 93, 94, 95, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 112, 113, 114, and 127.

Example D: Tobacco whitefly (Bemisia tabaci)

The leaf-immersion method was used for testing, in which the required amount of the compound was weighed and dissolved in a test tube containing the solvent solution. The test tube was placed in a vortex at 2000 rpm for 90 minutes to allow proper mixing, and then diluted to the required test concentration with 0.01% Triton-X solution. Brinjal leaves were immersed in the compound solution for 10 seconds, air-dried for 20 minutes, and then placed abaxially upwards on the lids of perforated containers each containing 4 ml of 1% agar-agar solution. A known number of newly hatched whitefly adults were collected using a modified aspirator and released into a perforated container with the lid of the treated leaf. Containers were stored in plant growth chambers at 25°C and 65% relative humidity. Dead, dying, and surviving adults were recorded 72 hours after release. Dying larvae were considered dead when calculating the mortality rate. The following compounds had a mortality rate of ≥70% at 300 ppm: 5, 6, 9, 24, 27, 33, 34, 38, 40, 41, 49, 50, 51, 52, 53, 58, 66, 70, 73, 76, 81, 86, 94, 95, 104, 109, 125, 127, 135, 156, 160, 165, 171, 175, 180, 195, and 196.

Example E: Peach aphid (Myzus persicae)

The leaf-immersion method was used for testing, in which the required amount of the compound was weighed and dissolved in a test tube containing the solvent solution. The test tube was placed in a vortex at 2000 rpm for 90 minutes to mix appropriately, and then diluted to the required test concentration with 0.01% Triton-X solution. Capsicum leaves were immersed in the compound solution for 10 seconds, air-dried for 20 minutes, and then placed with the dorsal side of the leaves facing up on bioassay plates containing 4 ml of 1% agar-agar solution. A known number of third-instar nymphs were collected from the petri dishes and released into cells containing the treated leaves, which were covered with perforated lids for better aeration. The test trays were stored in plant growth chambers at 25°C and 65% relative humidity. Dead, dying, and surviving nymphs were recorded 72 hours after nymph release. Dying larvae were considered dead when calculating the mortality rate. The compounds recorded below were measured at 300... The following concentrations of mercury have a mortality rate greater than or equal to 70% at ppm: 1, 2, 3, 4, 5, 6, 7, 8, 9, 13, 15, 16, 17, 18, 19, 20, 21, 24, 27, 28, 29, 33, 34, 36, 38, 39, 40, 41, 42, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 68, 67, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 81, 85, 86, 87, 90, 91, 93, 94, 95, 97, 100, 101, 10 2, 103, 104, 105, 106, 107, 108, 109, 110, 112, 113, 114, 115, 116, 118, 119, 120, 124, 125, 127, 128, 134, 135, 136, 138, 139, 140, 141, 142, 143, 144, 145, 147, 148, 150, 151, 152, 153, 154, 156, 160, 161, 164, 165, 166, 167, 168, 169, 170, 171, 174, 176, 177, 178, 180, 187, 193, 194, 195, and 196.

Example F: Brown rice fly (Nilaparvata lugens)

The seedling dip method was used for testing, in which the required amount of compound was weighed and dissolved in a test tube containing the solvent solution. The test tube was placed in a vortex at 2000 rpm for 90 minutes to allow proper mixing, and then diluted to the required test concentration with 0.01% Triton-X solution. Rice paddy seedlings were immersed in the compound solution for 10 seconds, air-dried for 20 minutes, and then placed in glass test tubes with the roots submerged. Fifteen third-instar nymphs were released into each test tube, and the test tubes were stored in a plant growth chamber at 25°C and 65% relative humidity. Seventy-two hours after nymph release, the number of dead, dying, and surviving nymphs were recorded. Dying larvae were considered dead when calculating the mortality rate. The following compounds, at 300 ppm, exhibit a mortality rate greater than or equal to 70%: 2, 4, 5, 6, 7, 8, 9, 15, 16, 17, 18, 21, 24, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 44, 45, 46, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 61, 63, 67, 70, 73, 75, 76, 86, 87, 90, 93, 94, 99, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 117, 120 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 141, 142, 145, 147, 148, 149, 152, 153, 154, 155, 156, 159, 160, 163, 164, 165, 167, 168, 169, 171, 173, 174, 175, 176, 177, 178, 180, 182, 183, 184, 187, 188, 191, 192, 193, 194, 195, and 196.

Since the invention has been described with reference to certain preferred embodiments, other embodiments will be readily apparent to those skilled in the art to which this invention pertains, taking into account this specification. It will be apparent to those skilled in the art to which this invention pertains that various modifications to the materials and methods can be made without departing from the scope of the invention.

Claims (20)

A compound of formula (I), Formula (I) wherein ^R1 is a _C1 - _C6 alkyl; Y is selected from O or ^NRY ; ^RY is selected from the group consisting of: hydrogen, nitrile, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogenyl, _C2 -C6-halogenyl, _C3 - _{C5 -} cycloalkyl, _C3 - _C5 -cycloalkyl- _C1 - _C3 -alkyl and -C(O) ^R1a ; ^R1a is selected from the group consisting of: _C1 - _C6 -alkyl, _C1 - _C6 -halogenyl, _C3 - _C5 -cycloalkyl and _C3 - _C5 -cycloalkyl- _C1 - _C3 -alkyl; R ^R2a is selected from the group consisting of: cyclopropyl, pyrimidinyl, ^CR2b , ^R2c , ^R2d , and ^NR11 , ^R12 ; the cyclopropyl and pyrimidinyl groups may optionally be substituted with one or more groups of ^R2a ; ^R2a is independently selected from the group consisting of: halogen, nitrile, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogenyl, _C3 - _C8 -cycloalkyl, ^OR4 , and ^NR5 , ^R6 ; ^R2b is selected from the group consisting of: halogen, hydroxyl, _C1 - _C6 -halogenyl, _C3 - _C4 -cycloalkyl, and ^OR4 ; R ^R2c is selected from the group consisting of: hydrogen, halogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, and _C2 - _C6 -ynyl; ^R2d is selected from the group consisting of: hydrogen and _C1 - _C6 -alkyl; ^R2x is selected independently from the group consisting of: halogen, nitrile, _C1 - _C6 -alkyl, _C3 - _C6 -cycloalkyl, _C1 - _C6 -alkoxy, _C1 - _C6 -alkoxy- _C3 - _C6 -cycloalkyl, _C1 - _C6 -halogenyl, and _C1 - _C6 -halogenalkoxy; Q is selected from the group consisting of: Q1a, Q1b, Q1c, Q1d, Q1e, Q1f, and Q1g; Wherein, # represents the linkage site of the pyrazolopyrimidine ring; ^R3 is independently selected from the following groups: halogen, _C1 - _C3 -halogen, _C1 - _C3 -halogenalkoxy, -S(O) _{0-2C1 -C3 -} halogen, and -S(O) _0-1 ; ^R9 = ^NR10 ; ^R4 is selected from the following groups: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogen, _C2 - _C6 -halogenalenyl, and _C3 - _C8 -cycloalkyl; ^R5 is selected from the following groups: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, OR ^5a , _C1 - _C6 -halogenated, _C2 - _C6 -halogenated, C3-C8-cycloalkyl, _C3 - _C8 -cycloalkyl- _C1 - _C6 -alkyl, 3- to 6-membered non-aromatic heterocyclic, phenyl, and phenyl- _C1 - _C6 -alkyl; wherein each group may optionally be substituted by one or more groups of ^R5b ; ^R5a is selected from the group consisting of: _{C1 - C6} -alkyl, C2- _C6 -alkenyl, _C2 - _C6 -ynyl, benzyl, and 3- to 6-membered non-aromatic heterocyclic; ^R5b is independently selected from the group consisting of: halogen, nitrile, _C1 - _C6 -alkyl, and C1-C6-alkoxy; ^R6 is selected from the group consisting of: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkyl, C1-C6-alkyl, and C1- _C6 -alkoxy. ₆ -alkyl, _C2 - _C6 -alkenyl, _C2 -C6-ynyl, _C1 - _C6 -halogenyl, _{C2- C6-halogenenyl, and C3-C6-cycloalkyl; R7 is selected from the group consisting of: C1-C6-alkyl, C3-C8} ^- _cycloalkyl , _C2 - _C6 -alkenyl, C2-C6-ynyl, C1-C6-halogenyl, _C2 -C6-halogenenyl, -C(O) _OC1 -C3alkyl, and C1- _{C6-alkoxy; R8 is selected from the group consisting of: C1-C6-alkyl, C3-C8 - cycloalkyl ,} C2-C6-alkenyl, _C2 -C6-ynyl, _C1 - _C6 -cycloalkyl, C2-C6-alkenyl, C2- _C6 -ynyl, C3-C6-cycloalkyl, _C2 -C6-alkenyl, C2- _C6 -cycloalkyl ...cycloalkyl, C2-C6-cycloalkyl, C3- ^C6 -cycloalkyl, _C2 - _C6 -cycloalkyl, C2- _C6 -cycloalkyl, _C3 - _{C6-cycloalkyl, C2-C6-cycloalkyl, C2-C6-cycloalkyl, C2-C6-cycloalkyl, C2-C6-cycloalkyl, C2-C6-cycloalkyl, C2 - C6 - cycloalkyl} , C2-C6-cycloalkyl, C2-C6-cycloalkyl, C2-C6-cycloalkyl, _C2 -C6-cycloalkyl, _C2 -C6-cycloalkyl, _C2 -C6-cycloalkyl, _C2 -C6-cycloalkyl, _C -Halalkyl, _C2 - _C6 -halogen, _C1 - _C6 -alkoxy, _C1 - _C6 -alkylamino, and _C1 - _C6 -dialkylamino; ^R9 is selected from the group consisting of: _C1 - _C6 -alkyl, _C2 - _{C6-alkenyl, C2-C6} -ynyl, _C1 - _C6 -halogen, _C2 - _C6 -halogenenyl, and _{C3 - C8} -cycloalkyl; ^R10 is selected from the group consisting of: hydrogen, nitrile, _C1 - _C6 -alkyl, C2- _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogen, _C2 - _C6 -halogenenyl, _{C3 - C8 -} cycloalkyl, and C(=O) ^R1 ; R ¹¹ is selected from the group consisting of: _C2 - _C6 -alkyl, nitrile, _C2 - _C6 -alkenyl, C2- _C6 -ynyl, _C1 -C6-nitrilealkyl, _C1 - _C6 -halogenalkyl, _C2 - _C6 -halogenenyl, _C1 - _C6 -alkoxy, _C3 - _C8 -cycloalkyl, _C3 - _C8 -cycloalkyl- _{C1 - C6 -} alkyl, 3 to 8 members of non-aromatic heterocyclic, 3 to 4 members of non-aromatic heterocyclic- _C1 - _C3 -alkyl, 5 to 6 members of heteroaryl- _C1 - _C3 -alkyl, ^NR5R6 , ^C1 _{- C6} -alkylsulfonyl, -C(O) ^R7 , and _C1 - _C3 -alkyl-C(O) ^R8. Each group may be optionally substituted by one or more groups of R ^11a ; R ^11a is independently selected from the group consisting of: halogen, nitrile, _C1 - _C6 -alkyl, _C1 - _C6 -alkoxy, _C1 - _C6 -alkylthio, _C3 - _C6 -cycloalkyl, -C(O) _OC1 - _C3alkyl , lateraloxy, hydroxyl, and _C1 - _C6 -hydroxyl; R ¹² is selected from the group consisting of: hydrogen, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -ynyl, _C1 - _C6 -halogenyl, _C2 - _C6 -halogenalenyl, and _C3 - _C6 -cycloalkyl; or R ¹¹ and R ¹² together with the nitrogen atom to which it is attached forms a 3- to 6-member non-aromatic heterocycle; wherein the heterocycle may optionally contain one or two independent heteroatoms selected from N, O, or S(O) _O-2 ; the heterocycle may optionally be substituted by one or more substituents selected from: halogen, nitrile, lateral oxygen, _C1 - _C6 -alkyl, _C1 - _C6 -alkoxy, or _C1 - _C6 -halogen; or NR ¹¹ R ¹² represents -N=S(O) ^{RX RXa} , wherein ^RX and ^RXa are selected from the group consisting of: nitrile, _C1 - _C6 -alkyl, _C2 - _C6 -alkenyl, _C2 - _C6 -Alkyne, phenyl, benzyl, and 3 to 6 non-aromatic heterocycles; wherein the phenyl, benzyl, and 3 to 6 non-aromatic heterocycles may be optionally substituted by one or more groups selected from halogens or _C1 - _C6 -alkyl groups; or ^R1X and ^R1Xa together with the sulfur atom attached thereto form a 5 to 6 non-aromatic heterocycle; wherein the heterocycle may optionally contain one or two independent heteroatoms selected from N, O, or S(O) _0-2 ; the heterocycle may optionally be substituted by one or more substituents selected from: halogens, nitrile groups, lateral groups, _C1 - _C6 -alkyl groups, _C1 - _C6 -alkoxy groups, or _C1 - _C6 -halogen groups; ^R13 is selected from the group consisting of: hydrogen and _C1 - _C6... -alkyl; "n" is an integer from 1 to 2, or a salt, stereoisomer, polymorph, metal complex or N-oxide thereof. The compound of formula (I) as described in claim 1 is represented by a compound of formula (IA). (IA) where ^R1 , Q, ^R2 and Y are as defined in Request 1. The compound of formula (I) as described in claim 1 or 2, wherein ^R1 is a _C1 - _C3 -alkyl group. Compound of formula (I) as described in claim 1 or 2, wherein Y is O. Compound of formula (I) as described in claim 1 or 2, wherein Y is NR ^Y. The compound of formula (I) as described in claim 1 or 2, wherein R ² is cyclopropyl; wherein the cyclopropyl group may optionally be substituted by one or more groups of R ^2a ; said R ^2a as defined in claim 1. The compound of formula (I) as described in claim 1 or 2, wherein ^R2 is a pyrimidine group; wherein the pyrimidine group may optionally be substituted by one or more groups of ^R2a , as defined in ^claim 1. The compound of formula (I) as described in claim 1 or 2, wherein ^R2 is ^{CR2b R2c R2d} ; wherein ^R2b , ^R2c and ^R2d are as defined in claim 1. The compound of formula ⁽ I) as described in claim 1 or 2, wherein ^R2 is ^NR11R12 ; wherein ^R11 and ^R12 are as defined in claim 1. The compound of formula (I) as described in claim 1 or 2, wherein ^R1 is _C1 - _C3 -alkyl; Y is selected from O or ^NRY ; ^RY is selected from the group consisting of: hydrogen, nitrile, _C1 - _C4 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C4 -halogenyl, _C2 - _C4 -halogenyl, _C3 - _C5 -cycloalkyl, _C3 - _C5 -cycloalkyl- _C1 - _C3 -alkyl and -C(O) ^R1a ; ^R1a is selected from the group consisting of: _C1 - _C4 -alkyl, _C1 - _C4 -halogenyl, _C3 - _C5 -cycloalkyl and _C3 - _C5 -cycloalkyl- _C1 - _C3 -alkyl; R ² is selected from the group consisting of: cyclopropyl, pyrimidinyl, CR ^2b R ^2c R ^2d , and NR ¹¹ R ¹² ; the cyclopropyl and pyrimidinyl groups may optionally be substituted with one or more groups of R ^2a ; R ^2a is selected from the group consisting of: halogen, nitrile, _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, OR ⁴ , _C1 - _C3 -halogenyl, and _C3 - _C6 -cycloalkyl; R ^2b is selected from the group consisting of: halogen, hydroxyl, and _C1 - _C3 -halogenyl; R ^2c is selected from the group consisting of: hydrogen, halogen, and _C1 - _C3 -alkyl; R ^2d is selected from the following groups: hydrogen and _C1 - _C3 -alkyl; Q is selected from the following groups: Q1a, Q1b, Q1c, Q1d, Q1e, Q1f and Q1g; # indicates the linkage site of the pyrazolopyrimidine ring ^{. R3} is selected from the following groups: halogen, _C1 - _C3 -halogen, -S(O) _{0-2C1 -C3 -} halogen, and _C1 - _C3 -halogenalkoxy; ^R4 is selected from the following groups: hydrogen, _C1 - _C3 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C3 -halogen, _C2 - _C4 -halogenalenyl, and _C3 - _C6 -cycloalkyl; ^R5 is selected from the following groups: hydrogen, _C1 - _C4 -alkyl, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, _C1 - _C3 -halogen, and _C3 - _C6 -cycloalkyl. -cycloalkyl; ^R6 is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C1 - _C3 -halogen, and _C3 - _C6 -cycloalkyl; ^R7 is selected from the group consisting of: _C1 - _C3 -alkyl, C(O) _OC1 - _C3- alkyl, _C1 - _C3 -alkoxy, and _C3 - _C6 -cycloalkyl; ^R8 is selected from the group consisting of: _C1 - _C3 -alkyl and _C3 - _C8 -cycloalkyl, _C2 - _C6 -alkenyl, _C2 -C6-ynyl, _C1 - _C6 -halogen, _C2 - _C6 -halogenenyl, _C1 - _C3 -alkoxy, _{C1 -C3 -} alkylamino, and _C1 - _C3 -dialkylamino; R ¹¹ is selected from the group consisting of: _C2 - _C4 -alkyl, nitrile, _C2 - _C4 -alkenyl, _C2 - _C4 -ynyl, C1-C4-nitrilealkyl, _C1 - _C4 -halogenalkyl, _C1 - _C4 -alkoxy, _C3 - _C6 -cycloalkyl, _C3 - _C6 -cycloalkyl- _C1 - _{C3 -} alkyl, ₃ to 6 members of non-aromatic heterocyclic, 3 to 4 members of non-aromatic heterocyclic- _C1 - _C3 -alkyl, 5 to 6 members of heteroaryl- _C1 - _C3 -alkyl, ^NR5R6 , _C1 - _C3 -alkylsulfonyl, ^-C (O) ^R7 and _C1 - _C3 -alkyl-C(O) ^R8 ; wherein each group may optionally consist of one or more R Group substitution of ^11a ; R ^11a is independently selected from the group consisting of: halogen, nitrile, _C1 -C3 _- alkyl, _C1 - _C3 -alkoxy, _C1 - _C3 -alkylthio, _C3 - _C5 -cycloalkyl, -C(O) _OC1 - _C3alkyl , lateraloxy, hydroxyl, and _C1 - _C3 -hydroxyalkyl; R ¹² is selected from the group consisting of: hydrogen, _C1 - _C3 -alkyl, _C2 - _C3 -alkenyl, _C2 - _C3 -ynyl, _C1 - _C3 -halogenyl, _C2 - _C3 -halogenalenyl, and _C3 - _C5 -cycloalkyl; or R ¹¹ and R ¹² together with the nitrogen atom to which it is attached forms a 3- to 6-member non-aromatic heterocycle; wherein the heterocycle may optionally contain one or two independent heteroatoms selected from N, O, or S(O) _O-2 ; the heterocycle may optionally be substituted by one or more substituents selected from: halogen, nitrile, lateral oxygen, _C1 - _C4 -alkyl, _C1 - _C4 -alkoxy, or _C1 - _C4 -halogen; or NR ¹¹ R ¹² represents -N=S(O) ^{RX RXa} , wherein ^RX and ^RXa are selected from the group consisting of: nitrile, _C1 - _C3 -alkyl, _C2 - _C3 -alkenyl, _C2 - _C3 - alkynyl, phenyl, benzyl and 3 to 6 non-aromatic heterocycles; wherein the phenyl, benzyl and 3 to 6 non-aromatic heterocycles may optionally be substituted by one or more groups selected from halogens or _C1 - _C3 -alkyl; ^R13 is selected from the group consisting of: hydrogen and _C1 - _C3 -alkyl; "n" is an integer from 1 to 2; or a salt, stereoisomer, polymorph, metal complex or N-oxide thereof. An ingredient comprising a compound of formula (I) as claimed in claim 1, or a salt thereof, a stereoisomer, a polymorph, a metal complex, or an N-oxide, and at least one additional component selected from the group consisting of surfactants and adjuvants. The composition as claimed in claim 11, wherein the composition additionally includes at least one biocompatible compound selected from fungicides, insecticides, nematicides, mite killers, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients. The composition as described in claim 11, wherein the amount of the compound of formula (I) is from 0.1% to 99% by weight of the total weight of the composition. A composition comprising a bioavailable amount of a compound of formula (I) as described in claim 1 and at least one additional biocompatible compound selected from fungicides, insecticides, nematicides, miteicides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients. A method for protecting crops from insect and mite pests includes: bringing the crop into contact with a compound of formula (I) as claimed in claim 1 or a salt thereof, a stereoisomer, a polymorph, a metal complex or an N-oxide, or with a composition as claimed in claim 11 or with a composition as claimed in claim 14. The method of claim 15, wherein the method comprises: applying an effective amount of the compound of formula (I) to an agricultural or horticultural crop, the effective amount being from 1 gram of active ingredient per hectare to 5,000 grams of active ingredient per hectare. A method for protecting seeds, plants, and plant parts from soil insects and for protecting seedling roots and buds from soil and leaf insects, comprising: contacting the seeds with a compound of formula (I) as claimed in claim 1 or a salt thereof, a stereoisomer, a polymorph, a metal complex or an N-oxide, or a composition as claimed in claim 11 or a composition as claimed in claim 14, before sowing and/or after pre-germination. Use of a compound of formula (I) as described in claim 1, or a salt thereof, stereoisomer, polymorph, metal complex or N-oxide thereof, or a composition as described in claim 11 or a composition as described in claim 14, for the control of insects and mites in crops and horticultural crops, and for the control of household and vector-borne parasites and animal parasites. A seed comprising a compound of formula (I) as claimed in claim 1, or a salt thereof, a metal complex, an N-oxide, a stereoisomer, a polymorph, or a composition as claimed in claim 11 or a composition as claimed in claim 14, wherein the amount of the compound of formula (I) in the seed is from 0.0001% to 1% by weight. A compound of formula (Z), ^R1 , Q, ^R2 and ^R2x are as defined in claim 1, provided that 2-(ethylthio)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine is excluded from the definition of compounds of formula (Z).