JP2026514063A - Imidazo[1,2-a]pyrazine derivatives - Google Patents

Abstract

The present invention relates to formula (I)
[Chemical formula 1]
The present invention relates to compounds of formula (I) (wherein the formula the substituents are as defined in claim 1), processes and methods for preparing compounds of formula (I), pesticide compositions comprising compounds of formula (I) as defined in claim 1, preparation of these compositions, and the use of compounds or compositions in agriculture or horticulture for controlling, preventing or controlling ectoparasitism of plants, harvested food crops, seeds or non-biological materials by plant pathogenic microorganisms, particularly fungi.

Description

This invention relates to imidazo[1,2-a]pyrazine derivatives having microbial activity, particularly fungicidal activity, and more specifically activity against oomycetes, for example, as an active ingredient. This invention also relates to the preparation of these imidazo[1,2-a]pyrazine derivatives, intermediates useful for the preparation of these imidazo[1,2-a]pyrazine derivatives, the preparation of these intermediates, pesticide compositions containing at least one imidazo[1,2-a]pyrazine derivative, the preparation of these compositions, and the use of imidazo[1,2-a]pyrazine derivatives or compositions in agriculture or horticulture for controlling, preventing, or preventing ectoparasitism of plants, harvested food crops, seeds, or non-biological materials by plant pathogenic microorganisms, particularly fungi, and more specifically oomycetes.

Surprisingly, it was discovered that certain novel imidazo[1,2-a]pyrazine derivatives possess particularly advantageous fungicidal properties against oomycetes.

Therefore, in the first aspect, the present invention relates to formula (I):
(wherein Z is O or S, preferably Z is O;
^A1 is CH or N, preferably N;
R ^1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _{C1-6 alkyl} ;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl;
^A2 is independently ^CR2 or N, provided that three or fewer ^A2s are N, preferably two or fewer ^A2s are N, preferably one or fewer ^A2s are N, and more preferably four ^A2s are ^CR2 ;
^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where _{C1-6 alkyl} , _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl} , C Each of the _3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs;
A ³ is independently CR ³ or N;
^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C Each of the _1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, C1-6 alkylsulfinyl- _C1-6 alkyl, C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl _{-C1-6 alkyl} , _C1-6 alkylaminocarbonyl- _C1-6 alkyl, _diC1-6 alkylaminocarbonyl _{-C1-6 alkyl, and CN, where C1-6 alkyl, C1-6 alkoxy-C1-6 alkyl , C3-6 cycloalkyl , C3-6} cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, C Each of the _2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, _C1-6 alkylsulfinyl- _C1-6 alkyl, _C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl- _C1-6 alkyl, _C1-6 alkylaminocarbonyl- _{C1-6 alkyl, and diC1-6 alkylaminocarbonyl-C1-6 alkyl may} be optionally substituted with one to three substituents independently selected from halogens and CN;
Here, ^A3 and ^R4 may optionally combine to form a ring, more preferably a 5- to 8-membered heterocycle, more preferably a 6-membered heterocycle; and ^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl _{- C1-6} alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino, _diC1-6 alkylamino, and _C1-6 alkylC1-6 alkoxyamino, where each of the groups may optionally be substituted with 1 to ₃ substituents independently selected from halogens and CNs);
The present invention provides compounds of the same; or salts or N-oxides thereof.

In a second aspect, the present invention provides a pesticide composition comprising a compound of formula (I), more specifically, a pesticide composition comprising a fungicidal effective amount of a compound of formula (I). The composition may further comprise at least one compound selected from additional active ingredients, suitable inactive ingredients, carriers, auxiliaries, and any mixtures thereof.

The compound of formula (I) can be used to control plant pathogenic microorganisms. Therefore, to control plant pathogens, the compound of formula (I) according to the present invention, or a composition containing the compound of formula (I), can be applied directly to plant pathogens, to the habitat of plant pathogens, to plants particularly susceptible to attack by plant pathogens, or to plant reproductive material.

Therefore, in a third aspect, the present invention provides the use of a compound of formula (I), or a composition containing a compound of formula (I), as described herein, for the eradication, prevention, or control of plant pathogens.

In a fourth aspect, the present invention provides a method for eradicating, preventing, or controlling plant pathogens, comprising applying a compound of formula (I) or a composition containing a compound of formula (I), as described herein, to the plant pathogens, to the habitat of the plant pathogens, particularly to plants susceptible to attack by the plant pathogens, or to the reproductive material of plants.

Compounds of formula (I) are particularly effective in eradicating, preventing, or controlling plant pathogenic fungi, especially oomycetes. Therefore, in a fifth aspect, the present invention provides the use of compounds of formula (I), or compositions containing compounds of formula (I), as described herein, for controlling plant pathogenic fungi, especially oomycetes.

In a sixth aspect, the present invention provides a method for eradicating, preventing, or controlling plant pathogenic diseases, such as those caused by plant pathogenic fungi, comprising applying a compound of formula (I), or a composition containing a compound of formula (I), as described herein, to the plant pathogenic fungi, or to the habitat of the plant pathogenic fungi, particularly to plants susceptible to attack by plant pathogenic fungi, especially oomycetes, or to plant reproductive materials.

When one group, for example, an alkyl group, is indicated as substituted, this includes those groups that are part of the other groups, for example, the alkyl group in an alkylthio group.

Definition:
- The terms "halogen" or "halo" refer to fluorine (fluoro or F), chlorine (chloro or Cl), bromine (bromo or Br), or iodine (iod or I), preferably fluorine, chlorine, or bromine.
The term "amino" refers to _two NH groups.
- In this specification, the term "alkyl" used alone or as part of a chemical group preferably refers to a linear or branched hydrocarbon having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, and 2-ethylbutyl. A alkyl group having 1 to 4 carbon atoms is preferred, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl.
- The term "alkenyl," either alone or as part of a chemical group, preferably refers to a linear or branched hydrocarbon having 2 to 6 carbon atoms and at least one double bond, such as vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl- 2-Pentenyl, 4-Methyl-2-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-2-Butenyl, 1,2-Dimethyl-3-Butenyl, 1,3-Dimethyl-2-Butenyl This represents methyl-2-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, and 1-ethyl-2-methyl-2-propenyl. An alkenyl group having 2 to 4 carbon atoms is preferred, for example, 2-propenyl, 2-butenyl, or 1-methyl-2-propenyl.
- The term "alkynyl," either alone or as part of a chemical group, preferably refers to a linear or branched hydrocarbon having 2 to 6 carbon atoms and at least one triple bond, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl This represents 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-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl, and 2,5-hexadynyl. Alkynnyls having 2 to 4 carbon atoms are preferred, for example, ethynnyl, 2-propynyl, or 2-butynyl-2-propenyl.
- The term "haloalkyl" refers to the alkyl groups as generally defined above, substituted with one or more identical or different halogen atoms, such as fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, or 2,2,2-trifluoroethyl.
-As used herein, the term "cyanoalkyl" refers to an alkyl group generally defined above, which is substituted with one or more cyano groups.
- The term "cycloalkyl," either alone or as part of a chemical group, preferably refers to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic hydrocarbon having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, or adamantyl. Cycloalkyls having 3, 4, 5, 6, or 7 carbon atoms are preferred, such as cyclopropyl or cyclobutyl.
-As used herein, the term "halocycloalkyl" refers to a cycloalkyl group as generally defined above, which is substituted with one or more identical or different halogen atoms.
- The term "cyanocycloalkyl" refers to a cycloalkyl group that is substituted with one or more cyano groups, as generally defined above.
The term "alkoxy" refers to the group of formula -OR _a , where R _a refers to the alkyl group as generally defined above. Examples of alkoxys include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and tert-butoxy. The term "alkoxyalkyl" refers to an alkyl group substituted with the alkoxy group (as described above). Examples include methoxymethyl, methoxyethyl, ethoxymethyl, and propoxymethyl.
The term "alkylsulfanyl" refers to the group of formula -SR _a , where R _a is an alkyl group as generally defined above.
The term "alkylsulfinyl" refers to the group of the formula -S(O)R _a , where R _a is an alkyl group as generally defined above.
The term "alkylsulfonyl" refers to the _group of the formula -S(O) _2Ra , where _Ra is an alkyl group as generally defined above.
The term "alkylcarbonyl" refers to a group of the formula _Ra C(O)-, where _Ra is an alkyl group as generally defined above.
The term "alkoxycarbonyl" refers to the group of the formula _RaOC (O), where _Ra is an alkyl group as generally defined above.
The term "alkylamino" refers to the group of the formula _RaNH- , where _Ra is an alkyl group as generally defined above.
The term "cycloalkylamino" refers to the group of the formula _RaNH- , where _Ra is a cycloalkyl group as generally defined above.
The term "alkoxyamino" refers to the group of formula _RaNH- , where _Ra is an alkoxy group as generally defined above.
The term "alkylaminocarbonyl" refers to the group of the formula R _a NHC(O)-, where R _a is an alkyl group as generally defined above.
-Hydroxyl or hydroxyl represents the -OH group.

The terms "exterminate," "prevent," or "control," and their variations, in relation to the present invention, mean reducing pathogenicity, more specifically plant pathogenicity, particularly any undesirable effects such as fungal infections including oomycetes, extrinsic parasitism or attack on plants or plant-derived products, and pathogenic damage, to a level in which improvement is demonstrated.

As used herein, the term "effective amount" refers to the amount of a compound, its salt, or N-oxide that produces the desired effect through one or more applications.

The effective dose can be readily determined by those skilled in the art by observing the results obtained using known techniques and under similar circumstances. Several factors are considered in determining the effective dose, including, but not limited to, the type of plant or derivative product to which it is applied; the pathogen being controlled and its life cycle; the specific compound being applied; the type of application; and other relevant circumstances.

A compound of formula (I) having at least one basic center can, for example, form an acid addition salt with a strong inorganic acid, such as a mineral acid, such as perchloric acid, sulfuric acid, nitric acid, nitrite, phosphoric acid, or hydrohalic acid, or with a strong organic carboxylic acid, such as an unsubstituted or substituted _C1 - _C4 alkane carboxylic acid, such as acetic acid, or with a strong organic carboxylic acid, such as an unsubstituted or halogen-substituted _C1 - _C4 alkane carboxylic acid, such as acetic acid, or with a strong organic carboxylic acid, such as an unsubstituted or halogen-substituted C1-C4 alkane or aryl sulfonic acid, such as methane or p-toluenesulfonic acid. A compound of formula (I) having at least one acidic group can form, for example, a salt with a base, for example an inorganic salt, for example an alkali metal or alkaline earth metal salt, for example sodium, potassium or magnesium salt, or a salt with ammonia or an organic amine, for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy lower alkylamine, for example mono-, di- or triethanolamine.

In each case, the compound of formula (I) according to the present invention exists in a free form, an oxidized form as an N-oxide, a covalently hydrated form, or a salt form, for example, an agrochemically usable or agrochemically acceptable salt form. The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. These are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. The compound of formula (I) according to the present invention also includes hydrates that may be formed during salt formation.

The compounds of formula (I) according to the present invention also include hydrates that may be formed during salt formation.

In further embodiments, compounds of formula (I) according to the present invention are provided, wherein R ^1a is selected from _C1-6 alkyl, _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, preferably from _C1-6 alkyl.

In further embodiments, compounds of formula (I) according to the present invention are provided, wherein ^R1b and ^R1c are independently selected from hydrogen, _C1-6 alkyl, _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy; preferably hydrogen.

In certain embodiments, compounds of formula (I) according to the present invention are provided, wherein R ^1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; and R ^1b and R ^1c are hydrogen.

In further embodiments, a compound of formula (I) according to the present invention, wherein ^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where each of the _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy _{- C1-6} alkyl, _C1-6 alkoxy- _C1-6 alkoxy, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally selected by 1 to 3 substituents independently selected from halogen, hydroxyl, and CN; preferably, R ^R2 is independently selected from hydrogen, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, where each of the _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxy, and CN; more preferably, compounds are provided in which ^R2 is independently selected from hydrogen, halogen, CN, _C1-6 alkyl, and _C1-6 alkoxy.

In further embodiments, the compound of formula (I) according to the present invention is selected from hydrogen, ^hydroxyl , halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, amino, C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, amino, _C1-6 alkylamino, _{diC1-6 -} alkylamino, and C Compounds are provided in which each of _{the 3-6} cycloalkylamino groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs. In one preferred embodiment, ^R3 may be hydrogen.

In a further embodiment, a compound of formula (I) according to the present invention is provided, wherein four ^A2s are ^CR2s and ^A3s are N.

In further embodiments, the compound of formula (I) according to the present invention is:
but
The present invention provides a compound in which, preferably, three ^A2s are ^CR2s and ^A3 is ^CR3 .

In further embodiments, the compound of formula (I) according to the present invention is:
but
The present invention provides a compound in which, preferably, three ^A2s are ^CR2s and ^A3 is ^CR3 .

In further embodiments, the compound of formula (I) according to the present invention is wherein four ^A2s are ^CR2s and ^A3s are ^CR3s , preferably
but
A compound is provided.

In a particular embodiment,
but
^R2 is as defined in the present invention; preferably, ^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and C1-6 alkylcarbonyl, where _{C1-6 alkyl} , _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C3-6 cycloalkyl, _{C3-6 cycloalkyl} - _C1-6 alkyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and C Each of the _1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; preferably, ^R2 is independently selected from hydrogen, halogens, CNs, _C1-6 alkyls, _C1-6 alkoxys, _C1-6 alkoxy- _C1-6 alkyls, and _C1-6 alkoxy- _C1-6 alkoxys, where each of the _C1-6 alkyls, _C1-6 alkoxys, _C1-6 alkoxy- _C1-6 alkyls, and _C1-6 alkoxy- _C1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; more preferably, ^R2 is independently selected from hydrogen, halogens, CNs, _C1-6 alkyls, and _C1-6 alkoxys.

In further embodiments, a compound of formula (I) according to the present invention, wherein ^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, and _C1-6 alkoxy, where each of the _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _{C2-6 alkynyl, and C1-6 alkoxy} groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; preferably ^R4 is _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and C Selected from _1-6 alkoxy groups, where each of the _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN;
Herein, compounds are provided in which ^A3 and ^R4 can optionally combine to form a ring, more preferably a 5- to 8-membered heterocycle, and more preferably a 6-membered heterocycle.

In further embodiments, compounds of formula (I) according to the present invention are provided, wherein ^A3 is ^CR3 , and ^R3 and ^R4 together form a ring, preferably a 5- to 8-membered heterocycle, preferably a 6-membered heterocycle, and more preferably one of W1, W2, or W3 as described in the following compounds of formula (I):

The carbon and/or nitrogen atoms forming the ring (W1, W2, or W3) may be substituted in particular with an R ^3' group, where R ^3' is selected from hydrogen, _C1-6 alkyl, and _C3-6 cycloalkyl, and each of the _C1-6 alkyl and _C3-6 cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN. For example, the compound of formula (I-W3) may be as follows:

In preferred embodiments, the compounds of formulas (I-W1), (I-W2), and (I-W3) may be as described below.

The carbon and/or nitrogen atoms forming the ring (W1, W2, or W3) may be substituted in particular with an R ^3' group, where R ^3' is selected from hydrogen, _C1-6 alkyl, and _C3-6 cycloalkyl, where each of the _C1-6 alkyl and _C3-6 cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN. For example, the compound of formula (I-W3) may be as follows:

In further embodiments, compounds of formula (I) according to the present invention are provided, wherein ^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, and _C1-6 alkoxyC1-6 alkyl, where each of the groups may be optionally substituted with ₁ to 3 substituents independently selected from halogens and CN.

In a particular embodiment, the compound of formula (I) according to the present invention is,
Z is O;
^A1 is N;
R ^1a is selected from C _1-6 alkyl, C _3-6 cycloalkyl, C _1-6 alkoxy-C _1-6 alkyl, C _3-6 cycloalkyl-C _1-4 alkyl, and C _1-6 alkoxy, preferably from C _1-6 alkyl;
^R1b is selected from hydrogen, _C1-6 alkyl, _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, preferably hydrogen;
^R1c is selected from hydrogen, _C1-6 alkyl, _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, preferably hydrogen;
Four ^A2s are ^CR2 ; ^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkyl sulfanyl, _C1-6 alkyl sulfinyl, and _C1-6 alkyl sulfonyl, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl _{-C1-6 alkyl} , _{C1-6 alkyl} sulfanyl, C Each of _{the 1-6} alkylsulfinyl and _C1-6 alkylsulfonyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; preferably, ^R2 is independently selected from hydrogen, halogens, CNs, _C1-6 alkyls, _C1-6 alkoxys, _C1-6 alkoxy- _C1-6 alkyls, and _C1-6 alkoxy- _C1-6 alkoxys, where each of the _C1-6 alkyls, _C1-6 alkoxys, C1-6 alkoxy- _C1-6 alkyls, and _C1-6 alkoxy _{-C1-6 alkoxy} groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; more preferably, ^R2 is independently selected from hydrogen, halogens, CNs, _C1-6 alkyls, and _C1-6 alkoxys;
^A3 is ^CR3 , and ^R3 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl _{, C1-6} alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6- alkylamino, and _{C3-6 cycloalkylamino, where C1-6 alkyl} , _C1-6 alkoxy, _C1-6 alkoxy _{- C1-6} alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _{C3-6 cycloalkyl} , C Each of the _3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino and _C3-6 cycloalkylamino groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs; preferably ^R3 is hydrogen;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl, C3-6 cycloalkyl} - _C1-4 alkyl, and _C1-6 alkoxy, where each of the _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy groups may be optionally substituted with 1 _to 3 substituents independently selected from halogens and CN; ^A3 and ^R4 may optionally combine to form a ring, more preferably a 5-8 membered heterocycle, more preferably a 6 membered heterocycle;
A compound _of formula (I) is provided, in which ^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino, _diC1-6 alkylamino, and _{C1-6 alkylC1-6} alkoxyamino, where each of the groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN, preferably ^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, and _C1-6 alkoxyC1-6 alkyl, where each of the groups may be optionally substituted with ₁ to 3 substituents independently selected from halogens and CN.

In a preferred embodiment,
teeth
^R2 is as defined in the present invention, and preferably ^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and C1-6 alkylcarbonyl, where _{C1-6 alkyl} , _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C3-6 cycloalkyl, _{C3-6 cycloalkyl} - _C1-6 alkyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and C Each of the _1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; preferably, ^R2 is independently selected from hydrogen, halogens, CNs, _C1-6 alkyls, _C1-6 alkoxys, _C1-6 alkoxy- _C1-6 alkyls, and _C1-6 alkoxy- _C1-6 alkoxys, where each of the _C1-6 alkoxys, _C1-6 alkoxy- _C1-6 alkyls, and _C1-6 alkoxy- _C1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs; more preferably, ^R2 is independently selected from hydrogen, halogens, CNs, _C1-6 alkyls, and _C1-6 alkoxys.

In further embodiments, the compounds according to the present invention are selected from the following:
Methyl N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[cyanomethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[ethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-(6-fluoro-3,4-dihydro-2H-quinoline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-fluoro-3-methylphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-fluorophenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-(methoxymethyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[allyl-(3-fluorophenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-methoxy-2-pyridyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[8-methyl-6-[methyl-(3-methylsulfonylphenyl)carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
3-[6-(cyclopropanecarbonylamino)-3-pyridyl]-N-(3,4-difluorophenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
3-[6-(ethylcarbamoylamino)-3-pyridyl]-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
N-(4-fluoro-3-methoxyphenyl)-3-[4-[(2-methoxyacetyl)amino]phenyl]-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
3-[4-(cyclopropanecarbonylamino)phenyl]-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
3-[4-(ethylcarbamoylamino)phenyl]-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
3-(4-acetamidophenyl)-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
3-(6-acetamido-3-pyridyl)-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
3-[6-(cyclopropanecarbonylamino)-3-pyridyl]-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
3-(6-acetamido-3-pyridyl)-N-(3,4-difluorophenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide;
Methyl N-[5-[8-acetamido-6-[ethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[8-acetamido-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[8-cyano-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[8-cyclopropyl-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[8-bromo-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[8-ethyl-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-chlorophenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(3,4-difluorophenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-(7-fluoro-2,3-dihydro-1,4-benzoxazine-4-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-cyano-3-methylphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-(6-cyano-3,4-dihydro-2H-quinoline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-cyanophenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[5-[6-[(4-cyano-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate;
Methyl N-[4-[6-[(4-cyano-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]phenyl]carbamate;
Methyl N-[4-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]phenyl]carbamate;
Methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-2-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate; and methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-2,8-dimethyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate.

The method according to the present invention has advantageous properties for protecting plants from pathogenic attacks or ectoparasites that cause disease and damage to plants, such as plant pathogenic fungi, particularly oomycetes. In particular, in the case of plants, the present invention can control, limit, or prevent pathogenic damage to plants, parts of plants, plant propagation materials, and/or grown plants.

The compounds listed in Tables 1.1 to 1.297 below exemplify specific compounds of the present invention.

Table 1.1 provides compounds E1.1 to E1.418 of formula (Ia).
(In the formula, ^R1a is _CH3 , ^R2 is H, ^R5 is _CH3 , and ^A1 , ^A2a , ^A2b , ^A3 , and ^R4 are as defined in Table Z). More specifically, Table Z also includes compounds in which ^A3 and ^R4 together form a ring. In this case, the ring is shown in the combined ^A3 and ^R4 columns (Table Z) along the amide atom linked to the bicyclic core of formula (Ia). See, for example, the ^A3 and ^R4 columns of compound E1.8.

Table 1.2 provides 418 compounds E2.1 to E2.418 of formula (Ia), where R ^1a CH ₃ And R ² H is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.3 provides 418 compounds E3.1 to E3.418 of formula (Ia), where R ^1a CH ₃ And R ² H is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.4 provides 418 compounds E4.1 to E4.418 of formula (Ia), where R ^1a CH ₃ And R ² H is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.5 provides 418 compounds E5.1 to E5.418 of formula (Ia), where R ^1a CH ₃ And R ² H is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.6 provides 418 compounds E6.1 to E6.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.7 provides 418 compounds E7.1 to E7.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.8 provides 418 compounds E8.1 to E8.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.9 provides 418 compounds E9.1 to E9.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.10 provides 418 compounds E10.1 to E10.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.11 provides 418 compounds E11.1 to E11.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.12 provides 418 compounds E12.1 to E12.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.13 provides 418 compounds E13.1 to E13.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.14 provides 418 compounds E14.1 to E14.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.15 provides 418 compounds E15.1 to E15.418 of formula (Ia), where R ^1a CH ₃ And R ² CH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.16 provides 418 compounds E16.1 to E16.418 of formula (Ia), where R ^1a CH ₃ And R ² F is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.17 provides 418 compounds E17.1 to E17.418 of formula (Ia), where R ^1a CH ₃ And R ² F is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.18 provides 418 compounds E18.1 to E18.418 of formula (Ia), where R ^1a CH ₃ And R ² F is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.19 provides 418 compounds E19.1 to E19.418 of formula (Ia), where R ^1a CH ₃ And R ² F is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.20 provides 418 compounds E20.1 to E20.418 of formula (Ia), where R ^1a CH ₃ And R ² F is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.21 provides 418 compounds E21.1 to E21.418 of formula (Ia), where R ^1a CH ₃ And R ² is Cl, and R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.22 provides 418 compounds E22.1 to E22.418 of formula (Ia), where R ^1a CH ₃ And R ² is Cl, and R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.23 provides 418 compounds E23.1 to E23.418 of formula (Ia), where R ^1a CH ₃ And R ² is Cl, and R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.24 provides 418 compounds E24.1 to E24.418 of formula (Ia), where R ^1a CH ₃ And R ² is Cl, and R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.25 provides 418 compounds E25.1 to E25.418 of formula (Ia), where R ^1a CH ₃ And R ² is Cl, and R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.26 provides 418 compounds E26.1 to E26.418 of formula (Ia), where R ^1a CH ₃ And R ² is Br, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.27 provides 418 compounds E27.1 to E27.418 of formula (Ia), where R ^1a CH ₃ And R ² is Br, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.28 provides 418 compounds E28.1 to E28.418 of formula (Ia), where R ^1a CH ₃ And R ² is Br, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.29 provides 418 compounds E29.1 to E29.418 of formula (Ia), where R ^1a CH ₃ And R ² is Br, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.30 provides 418 compounds E30.1 to E30.418 of formula (Ia), where R ^1a CH ₃ And R ² is Br, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.31 provides 418 compounds E31.1 to E31.418 of formula (Ia), where R ^1a CH ₃ And R ² is CN, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.32 provides 418 compounds E32.1 to E32.418 of formula (Ia), where R ^1a CH ₃ And R ² is CN, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.33 provides 418 compounds E33.1 to E33.418 of formula (Ia), where R ^1a CH ₃ And R ² is CN, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.34 provides 418 compounds E34.1 to E34.418 of formula (Ia), where R ^1a CH ₃ And R ² is CN, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.35 provides 418 compounds E35.1 to E35.418 of formula (Ia), where R ^1a CH ₃ And R ² is CN, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.36 provides 418 compounds E36.1 to E36.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.37 provides 418 compounds E37.1 to E37.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.38 provides 418 compounds E38.1 to E38.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.39 provides 418 compounds E39.1 to E39.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.40 provides 418 compounds E40.1 to E40.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.41 provides 418 compounds E41.1 to E41.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.42 provides 418 compounds E42.1 to E42.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.43 provides 418 compounds E43.1 to E43.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.44 provides 418 compounds E44.1 to E44.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.45 provides 418 compounds E45.1 to E45.418 of formula (Ia), where R ^1a CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.46 provides 418 compounds E46.1 to E46.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² H is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.47 provides 418 compounds E47.1 to E47.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² H is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.48 provides 418 compounds E48.1 to E48.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² H is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.49 provides 418 compounds E49.1 to E49.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² H is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.50 provides 418 compounds E50.1 to E50.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² H is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.51 provides 418 compounds E51.1 to E51.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.52 provides 418 compounds E52.1 to E52.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.53 provides 418 compounds E53.1 to E53.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.54 provides 418 compounds E54.1 to E54.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.55 provides 418 compounds E55.1 to E55.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.56 provides 418 compounds E56.1 to E56.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.57 provides 418 compounds E57.1 to E57.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.58 provides 418 compounds E58.1 to E58.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.59 provides 418 compounds E59.1 to E59.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.60 provides 418 compounds E60.1 to E60.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² CH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.61 provides 418 compounds E61.1 to E61.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² F is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.62 provides 418 compounds E62.1 to E62.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² F is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.63 provides 418 compounds E63.1 to E63.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² F is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.64 provides 418 compounds E64.1 to E64.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² F is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.65 provides 418 compounds E65.1 to E65.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² F is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.66 provides 418 compounds E66.1 to E66.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Cl, and R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.67 provides 418 compounds E67.1 to E67.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Cl, and R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.68 provides 418 compounds E68.1 to E68.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Cl, and R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.69 provides 418 compounds E69.1 to E69.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Cl, and R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.70 provides 418 compounds E70.1 to E70.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Cl, and R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.71 provides 418 compounds E71.1 to E71.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Br, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.72 provides 418 compounds E72.1 to E72.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Br, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.73 provides 418 compounds E73.1 to E73.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Br, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.74 provides 418 compounds E74.1 to E74.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Br, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.75 provides 418 compounds E75.1 to E75.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is Br, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.76 provides 418 compounds E76.1 to E76.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is CN, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.77 provides 418 compounds E77.1 to E77.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is CN, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.78 provides 418 compounds E78.1 to E78.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is CN, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.79 provides 418 compounds E79.1 to E79.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is CN, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.80 provides 418 compounds E80.1 to E80.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² is CN, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.81 provides 418 compounds E81.1 to E81.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.82 provides 418 compounds E82.1 to E82.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.83 provides 418 compounds E83.1 to E83.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.84 provides 418 compounds E84.1 to E84.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.85 provides 418 compounds E85.1 to E85.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.86 provides 418 compounds E86.1 to E86.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.87 provides 418 compounds E87.1 to E87.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.88 provides 418 compounds E88.1 to E88.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.89 provides 418 compounds E89.1 to E89.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.90 provides 418 compounds E90.1 to E90.418 of formula (Ia), where R ^1a CH ₂ CH ₃ And R ² OCH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.91 provides 418 compounds E91.1 to E91.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² H is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.92 provides 418 compounds E92.1 to E92.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² H is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.93 provides 418 compounds E93.1 to E93.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² H is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.94 provides 418 compounds E94.1 to E94.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² H is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.95 provides 418 compounds E95.1 to E95.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² H is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.96 provides 418 compounds E96.1 to E96.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.97 provides 418 compounds E97.1 to E97.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.98 provides 418 compounds E98.1 to E98.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.99 provides 418 compounds E99.1 to E99.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.100 provides 418 compounds E100.1 to E100.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.101 provides 418 compounds E101.1 to E101.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.102 provides 418 compounds E102.1 to E102.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.103 provides 418 compounds E103.1 to E103.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.104 provides 418 compounds E104.1 to E104.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.105 provides 418 compounds E105.1 to E105.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² CH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.106 provides 418 compounds E106.1 to E106.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² F is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.107 provides 418 compounds E107.1 to E107.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² F is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.108 provides 418 compounds E108.1 to E108.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² F is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.109 provides 418 compounds E109.1 to E109.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² F is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.110 provides 418 compounds E110.1 to E110.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² F is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.111 provides 418 compounds E111.1 to E111.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Cl, and R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.112 provides 418 compounds E112.1 to E112.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Cl, and R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.113 provides 418 compounds E113.1 to E113.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Cl, and R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.114 provides 418 compounds E114.1 to E114.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Cl, and R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.115 provides 418 compounds E115.1 to E115.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Cl, and R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.116 provides 418 compounds E116.1 to E116.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Br, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.117 provides 418 compounds E117.1 to E117.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Br, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.118 provides 418 compounds E118.1 to E118.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Br, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.119 provides 418 compounds E119.1 to E119.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Br, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.120 provides 418 compounds E120.1 to E120.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is Br, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.121 provides 418 compounds E121.1 to E121.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is CN, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.122 provides 418 compounds E122.1 to E122.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is CN, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.123 provides 418 compounds E123.1 to E123.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is CN, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.124 provides 418 compounds E124.1 to E124.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is CN, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.125 provides 418 compounds E125.1 to E125.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² is CN, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.126 provides 418 compounds E126.1 to E126.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.127 provides 418 compounds E127.1 to E127.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.128 provides 418 compounds E128.1 to E128.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.129 provides 418 compounds E129.1 to E129.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.130 provides 418 compounds E130.1 to E130.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.131 provides 418 compounds E131.1 to E131.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.132 provides 418 compounds E132.1 to E132.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.133 provides 418 compounds E133.1 to E133.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.134 provides 418 compounds E134.1 to E134.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.135 provides 418 compounds E135.1 to E135.418 of formula (Ia), where R ^1a CH ₂ OCH ₃ And R ² OCH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.136 provides 418 compounds E136.1 to E136.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² H is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.137 provides 418 compounds E137.1 to E137.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² H is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.138 provides 418 compounds E138.1 to E138.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² H is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.139 provides 418 compounds E139.1 to E139.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² H is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.140 provides 418 compounds E140.1 to E140.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.141 provides 418 compounds E141.1 to E141.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.142 provides 418 compounds E142.1 to E142.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.143 provides 418 compounds E143.1 to E143.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.144 provides 418 compounds E144.1 to E144.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² CH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.145 provides 418 compounds E145.1 to E145.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² CH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.146 provides 418 compounds E146.1 to E146.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² CH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.147 provides 418 compounds E147.1 to E147.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² CH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.148 provides 418 compounds E148.1 to E148.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² F is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.149 provides 418 compounds E149.1 to E149.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² F is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.150 provides 418 compounds E150.1 to E150.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² F is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.151 provides 418 compounds E151.1 to E151.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² F is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.152 provides 418 compounds E152.1 to E152.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is Cl, and R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.153 provides 418 compounds E153.1 to E153.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is Cl, and R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.154 provides 418 compounds E154.1 to E154.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is Cl, and R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.155 provides 418 compounds E155.1 to E155.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is Cl, and R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.156 provides 418 compounds E156.1 to E156.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is Br, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.157 provides 418 compounds E157.1 to E157.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is Br, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.158 provides 418 compounds E158.1 to E158.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is Br, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.159 provides 418 compounds E159.1 to E159.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is Br, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.160 provides 418 compounds E160.1 to E160.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is CN, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.161 provides 418 compounds E161.1 to E161.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is CN, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.162 provides 418 compounds E162.1 to E162.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is CN, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.163 provides 418 compounds E163.1 to E163.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² is CN, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.164 provides 418 compounds E164.1 to E164.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² OCH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.165 provides 418 compounds E165.1 to E165.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² OCH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.166 provides 418 compounds E166.1 to E166.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² OCH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.167 provides 418 compounds E167.1 to E167.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² OCH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.168 provides 418 compounds E168.1 to E168.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² OCH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.169 provides 418 compounds E169.1 to E169.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² OCH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.170 provides 418 compounds E170.1 to E170.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² OCH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.171 provides 418 compounds E171.1 to E171.418 of formula (Ia), where R ^1a It is cyclopropyl, and R ² OCH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.172 provides 418 compounds E172.1 to E172.418 of formula (Ia), where R ^1a teeth
And R ² H is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.173 provides 418 compounds E173.1 to E173.418 of formula (Ia), where R ^1a teeth
And R ² H is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.174 provides 418 compounds E174.1 to E174.418 of formula (Ia), where R ^1a teeth
And R ² H is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.175 provides 418 compounds E175.1 to E175.418 of formula (Ia), where R ^1a teeth
And R ² H is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.176 provides 418 compounds E176.1 to E176.418 of formula (Ia), where R ^1a teeth
And R ² CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.177 provides 418 compounds E177.1 to E177.418 of formula (Ia), where R ^1a teeth
And R ² CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.178 provides 418 compounds E178.1 to E178.418 of formula (Ia), where R ^1a teeth
And R ² CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.179 provides 418 compounds E179.1 to E179.418 of formula (Ia), where R ^1a teeth
And R ² CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.180 provides 418 compounds E180.1 to E180.418 of formula (Ia), where R ^1a teeth
And R ² CH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.181 provides 418 compounds E181.1 to E181.418 of formula (Ia), where R ^1a teeth
And R ² CH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.182 provides 418 compounds E182.1 to E182.418 of formula (Ia), where R ^1a teeth
And R ² CH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.183 provides 418 compounds E183.1 to E183.418 of formula (Ia), where R ^1a teeth
And R ² CH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.184 provides 418 compounds E184.1 to E184.418 of formula (Ia), where R ^1a teeth
And R ² F is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.185 provides 418 compounds E185.1 to E185.418 of formula (Ia), where R ^1a teeth
And R ² F is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.186 provides 418 compounds E186.1 to E186.418 of formula (Ia), where R ^1a teeth
And R ² F is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.187 provides 418 compounds E187.1 to E187.418 of formula (Ia), where R ^1a teeth
And R ² F is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.188 provides 418 compounds E188.1 to E188.418 of formula (Ia), where R ^1a teeth
And R ² is Cl, and R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.189 provides 418 compounds E189.1 to E189.418 of formula (Ia), where R ^1a teeth
And R ² is Cl, and R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.190 provides 418 compounds E190.1 to E190.418 of formula (Ia), where R ^1a teeth
And R ² is Cl, and R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.191 provides 418 compounds E191.1 to E191.418 of formula (Ia), where R ^1a teeth
And R ² is Cl, and R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.192 provides 418 compounds E192.1 to E192.418 of formula (Ia), where R ^1a teeth
And R ² is Br, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.193 provides 418 compounds E193.1 to E193.418 of formula (Ia), where R ^1a teeth
And R ² is Br, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.194 provides 418 compounds E194.1 to E194.418 of formula (Ia), where R ^1a teeth
And R ² is Br, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.195 provides 418 compounds E195.1 to E195.418 of formula (Ia), where R ^1a teeth
And R ² is Br, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.196 provides 418 compounds E196.1 to E196.418 of formula (Ia), where R ^1a teeth
And R ² is CN, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.197 provides 418 compounds E197.1 to E197.418 of formula (Ia), where R ^1a teeth
And R ² is CN, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.198 provides 418 compounds E198.1 to E198.418 of formula (Ia), where R ^1a teeth
And R ² is CN, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.199 provides 418 compounds E199.1 to E199.418 of formula (Ia), where R ^1a teeth
And R ² is CN, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.200 provides 418 compounds E200.1 to E200.418 of formula (Ia), where R ^1a teeth
And R ² OCH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.201 provides 418 compounds E201.1 to E201.418 of formula (Ia), where R ^1a teeth
And R ² OCH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.202 provides 418 compounds E202.1 to E202.418 of formula (Ia), where R ^1a teeth
And R ² OCH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.203 provides 418 compounds E203.1 to E203.418 of formula (Ia), where R ^1a teeth
And R ² OCH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.204 provides 418 compounds E204.1 to E204.418 of formula (Ia), where R ^1a teeth
And R ² OCH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.205 provides 418 compounds E205.1 to E205.418 of formula (Ia), where R ^1a teeth
And R ² OCH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.206 provides 418 compounds E206.1 to E206.418 of formula (Ia), where R ^1a teeth
And R ² OCH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.207 provides 418 compounds E207.1 to E207.418 of formula (Ia), where R ^1a teeth
And R ² OCH ₂ CH ₃ And R ⁵ , NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is as defined in Table Z.
Table 1.208 provides 418 compounds E208.1 to E208.418 of formula (Ia), where R ^1a is NHAc, R ² H is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.209 provides 418 compounds E209.1 to E209.418 of formula (Ia), where R ^1a is NHAc, R ² H is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.210 provides 418 compounds E210.1 to E210.418 of formula (Ia), where R ^1a is NHAc, R ² H is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.211 provides 418 compounds E211.1 to E211.418 of formula (Ia), where R ^1a is NHAc, R ² H is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.212 provides 418 compounds E212.1 to E212.418 of formula (Ia), where R ^1a is NHAc, R ² H is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.213 provides 418 compounds E213.1 to E213.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.214 provides 418 compounds E214.1 to E214.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.215 provides 418 compounds E215.1 to E215.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.216 provides 418 compounds E216.1 to E216.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.217 provides 418 compounds E217.1 to E217.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.218 provides 418 compounds E218.1 to E218.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.219 provides 418 compounds E219.1 to E219.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.220 provides 418 compounds E220.1 to E220.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.221 provides 418 compounds E221.1 to E221.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.222 provides 418 compounds E222.1 to E222.418 of formula (Ia), where R ^1a is NHAc, R ² CH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.223 provides 418 compounds E223.1 to E223.418 of formula (Ia), where R ^1a is NHAc, R ² F is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.224 provides 418 compounds E224.1 to E224.418 of formula (Ia), where R ^1a is NHAc, R ² F is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.225 provides 418 compounds E225.1 to E225.418 of formula (Ia), where R ^1a is NHAc, R ² F is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.226 provides 418 compounds E226.1 to E226.418 of formula (Ia), where R ^1a is NHAc, R ² F is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.227 provides 418 compounds E227.1 to E227.418 of formula (Ia), where R ^1a is NHAc, R ² F is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.228 provides 418 compounds E228.1 to E228.418 of formula (Ia), where R ^1a is NHAc, R ² is Cl, and R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.229 provides 418 compounds E229.1 to E229.418 of formula (Ia), where R ^1a is NHAc, R ² is Cl, and R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.230 provides 418 compounds E230.1 to E230.418 of formula (Ia), where R ^1a is NHAc, R ² is Cl, and R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.231 provides 418 compounds E231.1 to E231.418 of formula (Ia), where R ^1a is NHAc, R ² is Cl, and R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.232 provides 418 compounds E232.1 to E232.418 of formula (Ia), where R ^1a is NHAc, R ² is Cl, and R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.233 provides 418 compounds E233.1 to E233.418 of formula (Ia), where R ^1a is NHAc, R ² is Br, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.234 provides 418 compounds E234.1 to E234.418 of formula (Ia), where R ^1a is NHAc, R ² is Br, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.235 provides 418 compounds E235.1 to E235.418 of formula (Ia), where R ^1a is NHAc, R ² is Br, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.236 provides 418 compounds E236.1 to E236.418 of formula (Ia), where R ^1a is NHAc, R ² is Br, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.237 provides 418 compounds E237.1 to E237.418 of formula (Ia), where R ^1a is NHAc, R ² is Br, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.238 provides 418 compounds E238.1 to E238.418 of formula (Ia), where R ^1a is NHAc, R ² is CN, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.239 provides 418 compounds E239.1 to E239.418 of formula (Ia), where R ^1a is NHAc, R ² is CN, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.240 provides 418 compounds E240.1 to E240.418 of formula (Ia), where R ^1a is NHAc, R ² is CN, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.241 provides 418 compounds E241.1 to E241.418 of formula (Ia), where R ^1a is NHAc, R ² is CN, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.242 provides 418 compounds E242.1 to E242.418 of formula (Ia), where R ^1a is NHAc, R ² is CN, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.243 provides 418 compounds E243.1 to E243.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.244 provides 418 compounds E244.1 to E244.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.245 provides 418 compounds E245.1 to E245.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.246 provides 418 compounds E246.1 to E246.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.247 provides 418 compounds E247.1 to E247.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.248 provides 418 compounds E248.1 to E248.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.249 provides 418 compounds E249.1 to E249.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.250 provides 418 compounds E250.1 to E250.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.251 provides 418 compounds E251.1 to E251.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.252 provides 418 compounds E252.1 to E252.418 of formula (Ia), where R ^1a is NHAc, R ² OCH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.253 provides 418 compounds E253.1 to E253.418 of formula (Ia), where R ^1a is CN, R ² H is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.254 provides 418 compounds E254.1 to E254.418 of formula (Ia), where R ^1a is CN, R ² H is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.255 provides 418 compounds E255.1 to E255.418 of formula (Ia), where R ^1a is CN, R ² H is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.256 provides 418 compounds E256.1 to E256.418 of formula (Ia), where R ^1a is CN, R ² H is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.257 provides 418 compounds E257.1 to E257.418 of formula (Ia), where R ^1a is CN, R ² H is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.258 provides 418 compounds E258.1 to E258.418 of formula (Ia), where R ^1a is CN, R ² CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.259 provides 418 compounds E259.1 to E259.418 of formula (Ia), where R ^1a is CN, R ² CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.260 provides 418 compounds E260.1 to E260.418 of formula (Ia), where R ^1a is CN, R ² CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.261 provides 418 compounds E261.1 to E261.418 of formula (Ia), where R ^1a is CN, R ² CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.262 provides 418 compounds E262.1 to E262.418 of formula (Ia), where R ^1a is CN, R ² CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.263 provides 418 compounds E263.1 to E263.418 of formula (Ia), where R ^1a is CN, R ² CH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.264 provides 418 compounds E264.1 to E264.418 of formula (Ia), where R ^1a is CN, R ² CH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.265 provides 418 compounds E265.1 to E265.418 of formula (Ia), where R ^1a is CN, R ² CH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.266 provides 418 compounds E266.1 to E266.418 of formula (Ia), where R ^1a is CN, R ² CH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.267 provides 418 compounds E267.1 to E267.418 of formula (Ia), where R ^1a is CN, R ² CH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.268 provides 418 compounds E268.1 to E268.418 of formula (Ia), where R ^1a is CN, R ² F is R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.269 provides 418 compounds E269.1 to E269.418 of formula (Ia), where R ^1a is CN, R ² F is R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.270 provides 418 compounds E270.1 to E270.418 of formula (Ia), where R ^1a is CN, R ² F is R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.271 provides 418 compounds E271.1 to E271.418 of formula (Ia), where R ^1a is CN, R ² F is R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.272 provides 418 compounds E272.1 to E272.418 of formula (Ia), where R ^1a is CN, R ² F is R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.273 provides 418 compounds E273.1 to E273.418 of formula (Ia), where R ^1a is CN, R ² is Cl, and R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.274 provides 418 compounds E274.1 to E274.418 of formula (Ia), where R ^1a is CN, R ² is Cl, and R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.275 provides 418 compounds E275.1 to E275.418 of formula (Ia), where R ^1a is CN, R ² is Cl, and R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.276 provides 418 compounds E276.1 to E276.418 of formula (Ia), where R ^1a is CN, R ² is Cl, and R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.277 provides 418 compounds E277.1 to E277.418 of formula (Ia), where R ^1a is CN, R ² is Cl, and R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.278 provides 418 compounds E278.1 to E278.418 of formula (Ia), where R ^1a is CN, R ² is Br, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.279 provides 418 compounds E279.1 to E279.418 of formula (Ia), where R ^1a is CN, R ² is Br, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.280 provides 418 compounds E280.1 to E280.418 of formula (Ia), where R ^1a is CN, R ² is Br, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.281 provides 418 compounds E281.1 to E281.418 of formula (Ia), where R ^1a is CN, R ² is Br, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.282 provides 418 compounds E282.1 to E282.418 of formula (Ia), where R ^1a is CN, R ² is Br, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.283 provides 418 compounds E283.1 to E283.418 of formula (Ia), where R ^1a is CN, R ² is CN, R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.284 provides 418 compounds E284.1 to E284.418 of formula (Ia), where R ^1a is CN, R ² is CN, R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.285 provides 418 compounds E285.1 to E285.418 of formula (Ia), where R ^1a is CN, R ² is CN, R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.286 provides 418 compounds E286.1 to E286.418 of formula (Ia), where R ^1a is CN, R ² is CN, R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.287 provides 418 compounds E287.1 to E287.418 of formula (Ia), where R ^1a is CN, R ² is CN, R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.288 provides 418 compounds E288.1 to E288.418 of formula (Ia), where R ^1a is CN, R ² OCH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.289 provides 418 compounds E289.1 to E289.418 of formula (Ia), where R ^1a is CN, R ² OCH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.290 provides 418 compounds E290.1 to E290.418 of formula (Ia), where R ^1a is CN, R ² OCH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.291 provides 418 compounds E291.1 to E291.418 of formula (Ia), where R ^1a is CN, R ² OCH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.292 provides 418 compounds E292.1 to E292.418 of formula (Ia), where R ^1a is CN, R ² OCH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.293 provides 418 compounds E293.1 to E293.418 of formula (Ia), where R ^1a is CN, R ² OCH ₂ CH ₃ And R ⁵ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.294 provides 418 compounds E294.1 to E294.418 of formula (Ia), where R ^1a is CN, R ² OCH ₂ CH ₃ And R ⁵ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.295 provides 418 compounds E295.1 to E295.418 of formula (Ia), where R ^1a is CN, R ² OCH ₂ CH ₃ And R ⁵ It is cyclopropyl, and A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.296 provides 418 compounds E296.1 to E296.418 of formula (Ia), where R ^1a is CN, R ² OCH ₂ CH ₃ And R ⁵ CH ₂ OCH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.
Table 1.297 provides 418 compounds E297.1 to E297.418 of formula (Ia), where R ^1a is CN, R ² OCH ₂ CH ₃ And R ⁵ NHCH ₂ CH ₃ A ¹ A ^2a A ^2b A ³ , R ⁴ This is defined in Table Z.

The compounds according to the present invention may have several advantages, including, in particular, advantageous levels of biological activity for protecting plants from fungal diseases, or excellent properties for use as agricultural chemical active ingredients (e.g., higher biological activity, advantageous activity spectrum, increased safety profile, improved physicochemical properties, or increased biodegradability). The compounds according to the present invention have particularly advantageous levels of biological activity for protecting plants from oomycetes such as Phytophthora, Plasmopara, and Pythium.

Compounds of formula (I) where Z is O can be prepared as shown in schemes 1 to 18 below, in which case, unless otherwise specified, the definition of each variable site is as defined in this invention.

Compounds of formula (I) can be prepared by Suzuki cross-coupling of a compound of formula (II), where X _{is Cl} , _{Br ,} or _I , in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, in the presence of a base such as Cs₂CO₃, K₂CO₃, or NaOtBu, and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(diphenylphosphine)palladium(II) chloride, palladium chloride, or palladium acetate, with a compound of formula (III), where R ⁶ is independently hydrogen, C₁ _{- 6} alkyl, or two R ^6s together form a C₃ _-8 cycloalkyl. Compounds of formula (III), where R ⁶ is independently hydrogen, C₁-6 alkyl, or two R ^6s together form a C₃ _-8 cycloalkyl, can be prepared by known methods or are commercially available. This transformation is shown in Scheme 1.
Scheme 1

Alternatively, the compound of formula (I) can be prepared by directly arylating the compound of formula (IV) with the compound of formula (V) (wherein X is Cl, Br, or I) in the presence of a catalyst such as palladium diacetate, a ligand such as triphenylphosphine or (dicyclohexylphosphino)biphenyl, and a base such as cesium carbonate or potassium carbonate. The compound of formula (V) where X is Cl, Br, or I can be prepared by known methods or is commercially available. This coupling reaction is shown in Scheme 2.
Scheme 2

Compounds of formula (II) (wherein X is Cl, Br, or I) can be prepared by reacting a compound of formula (VI) (wherein X is Cl, Br, or I) with a reagent of formula (VII) ( _{wherein X is a good leaving group such as Cl, Br, I, triflate, tosyl, or mesyl) in the presence of a base such as Cs₂CO₃, K₂CO₃} ^, _{NaH , or} NaOtBu. Compounds of formula (VIII) in which ^Rₙ is an electron-withdrawing group such as a cyano or ester can alternatively be used to functionalize the amide nitrogen in the presence of a base such as triethylamine or 1,8-diazabicyclo[5.4.0]undeca-7-ene. Compounds of formula (VI) where X is Cl, Br, or I can be prepared by a peptide coupling reaction between a compound of formula (IX) where X is Cl, Br, or I and ^X2 is OH and an amine of formula (X), and by activating the carboxylic acid functional group of the compound of formula (IX), which is a process usually carried out by converting the -OH of the carboxylic acid to a good leaving group such as a chloride group by using, for example, (COCl)2 or SOCl2, in a suitable solvent (e.g., 25°C to 60°C), preferably in the presence of a base such as triethylamine or N,N-diisopropylethylamine, before treatment with the amine of formula (X); or optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), in a suitable solvent (e.g., acetonitrile), under conditions described in the literature for amide coupling such as 1-propanephosphonic acid cyclic anhydride (T3P), for example, (COCl) ₂ or _SOCl2 . For example, Chem. See Soc. Rev. 2009, 38, 606 and Chem. Soc. Rev. 2011, 40, 5084. Alternatively, compounds of formula (II) where X is Cl, Br, or I can be obtained using the above conditions by amide coupling transformation of a compound of formula (IX) where X is Cl, Br, or I and ^X2 is OH, with an amine of formula (XI). These transformations are shown in Scheme 3.
Scheme 3

The compound of formula (XI) is commercially available or can be obtained by reacting the compound of formula (X) with the compound of formula (VII) (wherein ^X1 is a good leaving group such as Cl, Br, I, triflate, tosyl _{, or mesyl) in the presence of a base such as Cs₂CO₃, K₂CO₃ , NaH ,} or NaOtBu. Alternatively, the compound of formula (XI) can be synthesized by reacting the compound of formula (X) with the compound of formula (VIII) (wherein ^R7 is an electron-withdrawing group such as cyano or ester) in the presence of a base such as triethylamine or 1,8-diazabicyclo[5.4.0]undeca-7-ene, optionally. Alternatively, the compound of formula (XI) may be used in a suitable solvent, for example, in the presence of NaBH(OAc) ₃ or _NaBH3CN , and optionally in the presence of a Brønsted or Lewis acid such as acetic acid, to produce an aldehyde of formula (XII) (wherein R ⁸ is _C1-5 alkyl, _C1-6 alkoxy- _C1-5 alkyl, _C3-6 cycloalkyl- _C1-3 alkyl, _C1-5 alkenyl, _C1-5 alkynyl, _C1-5 alkoxy, _C1-6 alkylsulfanyl- _C1-5 alkyl, _C1-6 alkylsulfanyl- _C1-5 alkyl, _C1-6 alkylsulfonyl- _C1-5 alkyl, _C1-6 alkoxycarbonyl-C1-5 alkyl, _C1-6 alkylaminocarbonyl- _C1-5 alkyl, _diC1-6 alkylaminocarbonyl- _C It can be obtained from the amine of formula (X) by reductive amination with _{a 1-5} alkyl group (selected from 1-5 alkyl groups). Alternatively, another reagent system for reductive amination uses a combination of titanium isopropoxide and _NaBH4 . The synthesis of the compound of formula (XI) from the amine of formula (X) is described in Scheme 4.
Scheme 4

Alternatively, the compound of formula (II), where X is Cl, Br, or I, can be prepared by reacting the compound of formula (IV) with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, or bromine in a suitable solvent such as dichloromethane, chloroform, tetrahydrofuran, or acetonitrile. The compound of formula (IV) can be obtained by amide coupling conversion of the amine of formula (XI) with the compound of formula (XIII) (wherein ^X2 is OH), and by activating the carboxylic acid functional group of the compound of formula (XIII), which is a process usually carried out by converting the -OH of the carboxylic acid to a good leaving group such as a chloride group by using, for example, (COCl)2 or SOCl2, under conditions described in the literature for amide coupling such as 1-propanephosphonic acid cyclic anhydride (T3P) in a suitable solvent (e.g., acetonitrile) in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), preferably at a temperature of 25°C to 60°C, before treatment with the amine of formula (XI); or optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), using, for example, (COCl) ₂ or _SOCl2 , to a good leaving group such as a chloride group. Alternatively, the compound of formula (IV) can be obtained by alkylating the compound of formula (XIV) with the compound of formula (VII) (wherein ^X1 is a good leaving group such _{as Cl, Br, I, triflate, tosyl, or mesyl) in the presence of a base such as Cs₂CO₃, K₂CO₃ , NaH ,} or NaOtBu. Alternatively, the compound of formula (IV) can also be synthesized by reacting the compound of formula (XIV) with the compound of formula (VIII) (wherein ^R7 is an electron-withdrawing group such as cyano or ester) in the presence of a base such as triethylamine or 1,8-diazabicyclo[5.4.0]undeca-7-ene, optionally. The compound of formula (XIV) can be prepared using the above conditions by peptide coupling transformation from the compound of formula (XIII) (wherein ^X2 is OH) with the amine of formula (X). These transformations are shown in Scheme 5.
Scheme 5

Alternatively, the compound of formula (IV) can be synthesized by reacting the compound of formula (XV) (wherein X is Cl, Br, or I) with the amine of formula (XI) and carbon monoxide in the presence of a catalyst such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) and optionally a base such as triethylamine. This transformation is shown in Scheme 6.
Scheme 6

Alternatively, the compound of formula (IV) can be obtained from the compound of formula (XVI), where X is _Cl , Br, or I, by a cross-coupling transformation with the compound of formula (XVII) (Suzuki cross-coupling) or the compound of formula (XVIII) (Still coupling), where R ⁶ is independently hydrogen, _C1-6 alkyl, or two _R ^6s together form a C3-8 cycloalkyl, or by a palladium-catalyzed cyanation reaction. The Suzuki cross-coupling can be achieved in the presence of a base such as _Cs2CO3 , _K2CO3 , or _NaOtBu , in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, using a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(diphenylphosphine)palladium(II) chloride, palladium chloride, or palladium acetate. Still coupling can be achieved using _a suitable palladium catalyst, such as tetrakistriphenylphosphine palladium, tris(dibenzylideneacetone)dipalladium, palladium chloride, or palladium acetate, in the presence of a base such as _Cs₂CO₃ or sodium acetate, in a suitable solvent such as dimethylformamide, dioxane, or acetonitrile. Palladium-catalyzed cyanation can be achieved by using a suitable catalyst such as tris(dibenzylideneacetone)dipalladium(O), palladium acetate, or [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II), optionally together with a suitable ligand such as 5-diphenylphosphanyl-9,9-dimethylxanthene-4-yl)-diphenylphosphan (xanthophos), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (Xphos), and a cyanidating agent such as zinc cyanide, potassium cyanide, or potassium hexacyanoferrate(II), in the presence of a base such as potassium acetate or cesium carbonate, in a suitable solvent such as dimethylformamide, dioxane, or tetrahydrofuran, with or without water as a cosolvent. Compounds of formula (XVII) and (XVIII) in which R ⁶ can independently be hydrogen, _C1-6 alkyl, or two R ^6s can combine to form a _C3-8 cycloalkyl group, are prepared by known methods or are commercially available. These transformations are shown in Scheme 7.
Scheme 7

Alternatively, the compound of formula (IV) can be obtained from the compound of formula (XIX) by reaction with the compound of formula (XX) (wherein X is Cl or Br and R ⁹ is C _1-6 alkyl) in the presence of a base such as pyridine or diisopropylethylamine. The amine of formula (XIX) can be prepared by treating the compound of formula (XXI) in a protic solvent such as methanol with an acid, typically hydrochloric acid, or with sodium acetate and hydroxyamine hydrochloride. The compound of formula (XXI) can be synthesized by reacting the compound of formula (XVI) (wherein X is Cl, Br, or I) with diphenylmethaneimine (CAS No. 1013-88-3) in the presence of a catalyst such as palladium acetate or tris(dibenzylideneacetone)dipalladium, and optionally a ligand such as 1,1'-[1,1'-binaphthalene]-2,2'-diylbis[1,1-diphenylphosphine] or (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), in the presence of a base such as cesium carbonate or sodium tert-butoxide. Alternatively, the compound of formula (IV) can be directly obtained by reacting the compound of formula (XVI) with the compound of formula (XXII) (wherein R ⁹ is C _1-6 alkyl) in a palladium-catalyzed coupling reaction (Buchwald-Hartwig reaction). This reaction can be achieved by using a suitable catalyst such as xanthophos-Pd-G2 (CAS 1375325-77-1), xanthophos-Pd G3 (CAS 1445085-97-1), or [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) in a suitable solvent such as dioxane, tetrahydrofuran, or toluene, in the presence of a base such as cesium carbonate, sodium tert-butoxide, or potassium phosphate. These transformations are shown in Scheme 8.
Scheme 8

The compound of formula (XIV) (wherein ^X2 is OH) can be synthesized from the compound of formula (XXIII) (wherein ^R9 is _C1-6 alkyl) by treatment with an acid or base. This conversion is well known to those skilled in the art. The compound of formula (XXIII) where ^R10 is _C1-6 alkyl can be obtained from the compound of formula (XXIV) (where X is Cl, Br, or I, and ^R10 is _C1-6 alkyl) by cross-coupling conversion with the compound of formula (XVII) (Suzuki cross-coupling) or the compound of formula (XVIII) (Still coupling) using the above conditions. These conversions are shown in Scheme 9.
Scheme 9

Alternatively, the compound of formula (XXIII), in which R ¹⁰ is C _1-6 alkyl, can be obtained from the compound of formula (XXV), in which R 10 is C _1-6 alkyl, by reaction with the compound of formula (XX), in which X is Cl or Br and R ⁹ is C _1-6 alkyl, in the presence of a base such as pyridine or diisopropylethylamine. The amine of formula (XXV), in which R ¹⁰ is C _1-6 alkyl, can be prepared by treating the compound of formula (XXVI), in which R ¹⁰ is ^C _1-6 alkyl, with an acid, typically hydrochloric acid, or sodium acetate and hydroxyamine hydrochloride, in a protic solvent such as methanol. Compounds of formula (XXVI) where R ¹⁰ is C _1-6 alkyl can be synthesized by reacting compound (XXIV) (wherein X is Cl, Br, or I, and R 10 is C 1-6 alkyl) with diphenylmethaneimine (CAS number 1013-88-3) in the presence of a catalyst such as palladium acetate or tris(dibenzylideneacetone)dipalladium, and optionally a ligand such as 1,1'-[1,1'-binaphthalene]-2,2'-diylbis[1,1-diphenylphosphine] or ( ^9,9 -dimethyl- _{9H-xanthene-4,5-} diyl)bis(diphenylphosphine), and a base such as cesium carbonate or sodium tert-butoxide. These transformations are shown in scheme 10.
Scheme 10

Compounds of formula (XV) (wherein X is Cl, Br, or I) can be prepared by cross-coupling of a hydrazone of formula (XXVII) (wherein X is Cl, Br, or I) with a compound of formula (XXVIII) (wherein _{R 6 is} independently hydrogen, _{C1-6 alkyl} , or two R ^6s together can form a _C3-8 cycloalkyl, and R ¹¹ is selected from _{C1-5 alkyl} , _C1-6 alkoxy- _C1-5 alkyl, and _C3-6 cycloalkyl- _C1-3 alkyl). Such transformations are described in the literature, e.g., Org. Lett. ²⁰²⁰ , 22, 2271. Alternatively, the compound of formula (XV) (wherein X is Cl, Br, or I) can be obtained by reacting the hydrazone of formula (XXVII) (wherein X is Cl, Br, or I) with the alkoxide of formula (XXIX) (wherein R ¹² is _C1-5 alkyl) in a protic solvent such as methanol or tert-butanol. The compound of formula (XXVIII) (wherein R ⁶ can be independently hydrogen, _C1-6 alkyl, or two R ^6s can together form a _C3-8 cycloalkyl, and R ¹¹ can be selected from _C1-5 alkyl, _C1-6 alkoxy- _C1-5 alkyl, and _C3-6 cycloalkyl- _C1-3 alkyl), and the compound of formula (XXIX) (wherein R ¹² is _C1-5 alkyl) are commercially available or can be prepared by known methods. A hydrazone of formula (XXVII) (wherein X is Cl, Br, or I) can be prepared by condensation of p-toluenesulfone hydrazide (CAS 1576-35-8) with an aldehyde of formula (XXX) (wherein X is Cl, Br, or I). Aldehydes of formula (XXX) (wherein X is Cl, Br, or I) are commercially available or can be prepared by condensation of a compound of formula (XXXI) (wherein X is Cl, Br, or I) with a compound of formula (XXXII) (wherein X is Cl, Br, or I) or its corresponding acetal of formula (XXXIII) (wherein X is Cl, Br, or I, and ^R13 is independently _C1-6 alkyl or the two ^R13s can together form a _C3-8 cycloalkyl). The reaction results can be improved by using a base such as sodium bicarbonate or potassium carbonate, or by using an acid such as p-toluenesulfonic acid or hydrogen bromide. The compounds of formula (XXXI) (wherein X is Cl, Br, or I), formula (XXXII) (wherein X is Cl, Br, or I), and formula (XXXIII) (wherein X is Cl, Br, or I) are commercially available or prepared using methods known to those skilled in the art. These conversions are shown in Scheme 11.
Scheme 11

The compound of formula (XVI) (wherein X is Cl, Br, or I) can be obtained by amide coupling conversion of the amine of formula (XI) with the compound of formula (XXXIV) (wherein X is Cl, Br, or I, and ^X2 is OH), and by activation of the carboxylic acid functional group of the compound of formula (XXXIV), which is preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, or tetrahydrofuran) at a temperature preferably between 25°C and 60°C, optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine; or optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine) in a suitable solvent (e.g., acetonitrile) under conditions described in the literature for amide coupling such as 1-propanephosphonic acid cyclic anhydride (T3P), for example, (COCl) ₂ or SOCl This is a process that is usually carried out by using ₂ to convert the -OH group of a carboxylic acid into a good leaving group such as a chloride group. The compound of formula (XXXIV) (wherein X is Cl, Br, or I, and ^X2 is OH) can be prepared by hydrolysis of the ester functional group of the compound of formula (XXXIV) (wherein X is Cl, Br, or I, and ^R10 is _C1-6 alkyl), which can be synthesized by condensation of the compound of formula (XXXV) (wherein X is Cl, Br, or I, and ^R10 is _C1-6 alkyl) with the compound of formula (XXXII) (wherein X is Cl, Br, or I) or its corresponding acetal of formula (XXXIII) (wherein X is Cl, Br, or I, and ^R13 is independently _C1-6 alkyl, or the two ^R13s together can form a _C3-8 cycloalkyl). Compounds of formula (XXXV) (wherein X is Cl, Br, or I, and R ¹⁰ is a _C1-6 alkyl group) are commercially available or prepared using methods known to those skilled in the art. These transformations are shown in Scheme 12.
Scheme 12

Alternatively, the compound of formula (I) can be prepared by amide coupling conversion of the amine of formula (XI) and the compound of formula (XXXVI) (wherein X is Cl, Br, or I, and ^X2 is OH), and by activating the carboxylic acid functional group of the compound of formula (XXXVI), which is a process usually carried out by converting the -OH of the carboxylic acid to a good leaving group such as a chloride group by using, for example, (COCl)2 or SOCl2, under conditions described in the literature for amide coupling such as 1-propanephosphonic acid cyclic anhydride (T3P), preferably in a suitable solvent (e.g., 25°C to 60°C) and preferably in the presence of a base such as triethylamine or N,N-diisopropylethylamine, before treatment with the amine of formula (XI); or optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine) in a suitable solvent (e.g., acetonitrile), for example, by using (COCl) ₂ or _SOCl2 , to convert the -OH of the carboxylic acid to a good leaving group such as a chloride group. Alternatively, the compound of formula (I) can _be prepared by alkylating the compound of formula (XXXVII) with the compound of formula (VII) (wherein ^X1 is a good leaving group such as Cl, _Br , _I , _triflate , tosyl, or mesyl) in the presence of a base such as Cs₂CO₃, K₂CO₃, NaH, or NaOtBu. Alternatively, the compound of formula (I) can be synthesized by reacting the compound of formula (XXXVII) with the compound of formula (VIII), where ^R7 is an electron-withdrawing group such as cyano or ester, in the presence of a base such as triethylamine or 1,8-diazabicyclo[5.4.0]undeca-7-ene, optionally. The compound of formula (XXXVII) can be synthesized by peptide coupling transformation from the compound of formula (XXXVI) (wherein ^X2 is OH) and the amine of formula (X) using the above conditions. These transformations are shown in Scheme 13.
Scheme 13

The compound of formula (XXXVI) (wherein ^X2 is OH) can be obtained by hydrolysis of the ester portion of the compound of formula (XXXVIII) (wherein ^R10 is _C1-6 alkyl). The compound of formula (XXXVIII) (wherein ^R10 is _C1-6 alkyl) can be prepared by direct arylation of the compound of formula (XXXIII) (wherein ^R10 is _{C1-6 alkyl) with the compound of formula (V) (wherein X is Cl, Br, or I) in the presence of a catalyst such as palladium diacetate, a ligand such as triphenylphosphine or (dicyclohexylphosphin} )biphenyl, and a base such as cesium carbonate or calcium carbonate. Alternatively, the compound of formula (XXXVIII) (wherein ^R10 is _C1-6 alkyl) may be obtained from a Suzuki coupling reaction between the compound of formula (XXXIX) (wherein _{X is} Cl, _Br , or _I , and R10 is C1-6 alkyl) and the compound of formula (III) (wherein R6 can independently be hydrogen, a C1-6 alkyl, or the two R6s can together form a ^C3-8 cycloalkyl) in the presence of a base such as Cs2CO3, K2CO3, or NaOtBu and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [ _1,1- bis(diphenylphosphine)ferrocene]dichloropalladium(II), bis(diphenylphosphine)palladium(II ⁾ chloride, _palladium chloride, or palladium acetate, in a suitable solvent such as dimethylformamide, ^dioxane _, tetrahydrofuran, ethanol, or water. Compounds of formula (XXXIX) (where X is Cl, Br, or I, and R ¹⁰ is _C1-6 alkyl) can be synthesized by reacting compound of formula (XXIII) (where R ¹⁰ is _C1-6 alkyl) with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, or bromine in a suitable solvent such as dichloromethane, chloroform, tetrahydrofuran, or acetonitrile. These transformations are shown in Scheme 14.
Scheme 14

Alternatively, the compound of formula (I) can be synthesized by reacting the compound of formula (XL) (wherein X is Cl, Br, or I) with the amine of formula (XI) and carbon monoxide in the presence of a catalyst such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) and optionally a base such as triethylamine. Compounds of formula (XL) (wherein X is Cl, Br, or I) can be prepared by Suzuki cross-coupling of compound (XLI) (wherein X is independently _Cl , _Br, or _I ) with compound (III) (wherein R ₆ is independently hydrogen, a C1-6 alkyl group, or the two R 6 groups can together form a C3-8 cycloalkyl group) in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, in the presence of a base such as Cs2CO3, K2CO3, or NaOtBu, and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [ _1,1- bis(diphenylphosphineno) ^ferrocene ]dichloropalladium( ^II ), bis _{(diphenylphosphine} )palladium(II) chloride, palladium chloride, or palladium acetate. These transformations are shown in Scheme 15.
Scheme 15

Alternatively, the compound of formula (I) can be prepared by the reaction of the compound of formula (XLII) and the compound of formula (XLIII) (wherein ^X2 is OH) in a peptide coupling transformation using the above conditions. The compound of formula (XLII) can be prepared by Suzuki cross-coupling of the compound of formula (II) (wherein _{X is Cl} , Br _, or _I ) and the compound of formula (XLIV) (wherein R 6 can be independently hydrogen, C1-6 alkyl, or the two R 6s can together form a C3-8 c cycloalkyl) in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, in the presence of a base such as Cs2CO3, K2CO3, or ^NaOtBu and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, [ _1,1- bis(diphenylphosphine)ferrocene]dichloropalladium(II), bis(diphenylphosphine) ^palladium _(II ) chloride, palladium chloride, or palladium acetate. Compounds of formula (XLIV) (wherein ^R6 can be independently hydrogen, _C1-6 alkyl, or the two ^R6s can together form a _C3-8 cycloalkyl group) are prepared by known methods or are commercially available. These transformations are shown in Scheme 16.
Scheme 16

Compounds of formula (Ib) where Z is S can be prepared by reacting a compound of formula (I) where Z is O with phosphorus pentasulfide or Lawson's reagent (CAS: 19172-47-5) in a suitable solvent such as toluene, xylene, or dichloromethane. This conversion is shown in Scheme 17.
Scheme 17

Alternatively, the compound of formula (Ib) where Z is S can be prepared by reacting the compound of formula (XLIIb) with the compound of formula (XLIII) (wherein ^X2 is OH) in a peptide coupling transformation using the above conditions. The compound of formula (XLIIb) can be prepared by reacting the compound of formula (XLII) with phosphorus pentasulfide or Lawson's reagent (CAS: 19172-47-5) in a suitable solvent such as toluene, xylene, or dichloromethane. This transformation is shown in Scheme 18.
Scheme 18

It will be understood by those skilled in the art that the amide coupling reactions described above between acids, amines, and coupling agents can also be carried out using the corresponding acid chlorides and amines. The conversion of acids to their corresponding acid chlorides is well known to those skilled in the art.

When the term "compound according to the present invention" is used, it refers to the compound according to the present invention.

Alternatively, the compounds according to the present invention can be obtained by using standard synthetic techniques known to those skilled in the art. Non-exclusive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions, olefination reactions, oxime formation, alkylation, and halogenation reactions.

The compounds according to the present invention can be converted to other compounds according to the present invention in a manner known by conventional means by substituting one or more substituents of the starting compound according to the present invention with other substituents according to the present invention.

Depending on the appropriate reaction conditions and selection of starting materials in each case, it may be possible, for example, to substitute only one substituent with another substituent according to the present invention in a single reaction step, or to substitute multiple substituents with other substituents according to the present invention in the same reaction step.

Salts of the compounds according to the present invention can be prepared by methods known in themselves. Therefore, for example, acid addition salts of the compounds according to the present invention can be obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with a base can be obtained by treatment with a suitable base or a suitable ion exchange reagent.

Salts of the compounds according to the present invention can be converted to the free compound by conventional methods, acid addition salts can be converted, for example, by treatment with a suitable basic compound or a suitable ion exchange reagent, and salts with a base can be converted, for example, by treatment with a suitable acid or a suitable ion exchange reagent.

The salts of the compounds according to the present invention can be converted to other salts of the compounds according to the present invention, or acid addition salts, for example, other acid addition salts, by methods known in themselves, for example, by treatment of an inorganic acid salt, such as a silver acetate hydrochloride, with a suitable metal salt of the acid, such as a sodium, barium, or silver salt of the acid, in a suitable solvent (for example, an inorganic salt that forms silver chloride insoluble therein and therefore precipitates from the reaction mixture).

Depending on the procedure or reaction conditions, the compound according to the present invention, which has salt-forming properties, can be obtained in either a free form or a salt form.

In each case, the compounds according to the present invention, in free or salt form, and, where appropriate, their tautomers, may exist in one form of possible isomers or as mixtures thereof, depending on the number, absolute and relative configuration of chiral carbon atoms present in the molecule, and/or the stereoconfiguration of non-aromatic double bonds present in the molecule, in the form of pure isomers, such as anticarpone and/or diastereomers, or as stereoisomer mixtures, such as enantiomer mixtures, such as racemic compounds, diastereomer mixtures, or racemic compound mixtures; the present invention relates to pure stereoisomers and to all possible isomer mixtures, and in all cases above and below, even where stereochemical details are not specifically described, they should be understood in this sense.

The diastereomer or racemic mixture of the compounds according to the present invention, in the free or salt form obtained depending on the selected starting materials and procedure, can be separated into pure diastereomers or racemic compounds based on the physicochemical differences of the components by known methods, such as fractional crystallization, distillation, and/or chromatography.

Enantiomer mixtures such as racemates obtained by similar methods can be separated into optically enantiomers by known methods, for example, by recrystallization from an optically active solvent, by chromatography in a chiral adsorbent, for example by high-performance liquid chromatography (HPLC) in acetylcellulose using suitable microorganisms, by cleavage by specific immobilized enzymes via the formation of inclusion compounds using a chiral crown ether into which only one enantiomer is combined, or by conversion to a diastereomer salt. For example, the basic final product racemate can be reacted with an optically active acid such as a carboxylic acid, e.g., camphoric acid, tartaric acid, or malic acid, or a sulfonic acid, e.g., camphor sulfonic acid. The diastereomer mixture thus obtained can then be separated, for example by fractional crystallization based on different solubility, and the desired enantiomer can be released from there by the action of a suitable agent, e.g., a basic agent, thereby obtaining a diastereomer from which the desired enantiomer is released.

Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating a suitable mixture of stereoisomers, but also by generally known diastereoselective or enantioselective synthesis methods, such as the method according to the present invention using suitable stereochemical starting materials.

N-oxides can be prepared by reacting the compounds according to the present invention with a suitable oxidizing agent, such as an H2O2/urea adduct, in the presence of an acid anhydride, such as trifluoroacetic anhydride. Such oxidation is known from the literature, e.g., J. Med. Chem., 32(12), 2561-73, 1989, or International Publication No. 00/15615.

When individual components possess different biological activities, it is advantageous to isolate or synthesize the biologically more effective stereoisomers, such as enantiomers or diastereomers, or stereoisomer mixtures, such as enantiomer mixtures or diastereomer mixtures, in each case.

The compounds according to the present invention, and optionally their tautomers, may be obtained in their respective free or salt forms, and optionally in hydrate forms, and/or may contain other solvents, such as solvents that may have been used to crystallize compounds existing in solid form.

The following examples illustrate, but are not limited to, the present invention.

The present invention also provides intermediates useful for the preparation of compounds according to the present invention.

The following intermediates form further embodiments of the present invention.

Formula (IV)
(wherein Z is O or S, preferably Z is O;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl, preferably ^R1a is selected from _{C1-6 alkyl} , _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^A2 is independently ^CR2 or N, provided that three or fewer ^A2s are N, preferably two or fewer ^A2s are N, preferably one or fewer ^A2s are N, and more preferably four ^A2s are ^CR2 ;
^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where _{C1-6 alkyl} , _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl} , C Each of the _3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxyl, and CN; preferably, ^R2 is independently selected from hydrogen, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy-C Each of the _1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs;
A ³ is independently CR ³ or N;
^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C Each of the _1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN; preferably, ^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl, where each of the _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, C1-6 alkylsulfinyl- _C1-6 alkyl, C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl _{-C1-6 alkyl} , _C1-6 alkylaminocarbonyl- _C1-6 alkyl, _diC1-6 alkylaminocarbonyl _{-C1-6 alkyl, and CN, where C1-6 alkyl, C1-6 alkoxy-C1-6 alkyl , C3-6 cycloalkyl , C3-6} cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, C Each of the _2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, _C1-6 alkylsulfinyl- _C1-6 alkyl, _C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl- _C1-6 alkyl, C1-6 alkylaminocarbonyl- _C1-6 alkyl and _diC1-6 alkylaminocarbonyl- _C1-6 alkyl may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; preferably, ^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, where _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _{C3-6 cycloalkyl} -C Each of the _1-4 alkyl and _C1-6 alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CNs; and ^A3 and ^R4 may optionally combine to form a ring, more preferably a 5-8 membered heterocycle, more preferably a 6 membered heterocycle);
A compound of the same, or its salt or N-oxide.

Formula (II)
(wherein Z is O or S, preferably Z is O;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1a is selected from _C1-6 alkyl, _C3-6 cycloalkyl, _C1-6 alkoxy- _{C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^A2 is independently ^CR2 or N, provided that three or fewer ^A2s are N, preferably two or fewer ^A2s are N, preferably one or fewer ^A2s are N, and more preferably four ^A2s are ^CR2 ;
^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where _{C1-6 alkyl} , _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl} , C Each of the _3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxyl, and CN, preferably ^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, where _C1-6 alkyl, _C1-6 alkoxy, C1-6 alkoxy- _C1-6 alkyl, _{and C1-6 alkoxy} -C Each of the _1-6 alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs;
A ³ is independently CR ³ or N;
^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl, C3-6 cycloalkyl} , _{C3-6 cycloalkyl} -C Each of the _1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN, preferably ^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl, where each of the _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, C1-6 alkylsulfinyl- _C1-6 alkyl, C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl _{-C1-6 alkyl} , _C1-6 alkylaminocarbonyl- _C1-6 alkyl, _diC1-6 alkylaminocarbonyl _{-C1-6 alkyl, and CN, where C1-6 alkyl, C1-6 alkoxy-C1-6 alkyl , C3-6 cycloalkyl , C3-6} cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, C Each of the _2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, _C1-6 alkylsulfinyl- _C1-6 alkyl, _C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl- _C1-6 alkyl, C1-6 alkylaminocarbonyl- _C1-6 alkyl and _diC1-6 alkylaminocarbonyl- _C1-6 alkyl may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; preferably, ^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, where _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _{C3-6 cycloalkyl} -C Each of _{the 1-4} alkyl and _C1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens and CN;
^A3 and ^R4 may optionally combine to form a ring, more preferably a 5- to 8-membered heterocycle, and more preferably a 6-membered heterocycle; and X is Cl, Br, or I;
A compound of the same, or its salt or N-oxide.

Formula (XXXVI)
(wherein ^A1 is CH or N, preferably N;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl, preferably ^R1a is selected from _{C1-6 alkyl} , _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _{C1-6 alkylsulfanyl, C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, C1-6 alkoxy , amino} , and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen; and ^R5 is _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino _{, diC1-6} alkylamino, and _C1-6 alkylC Selected from _1-6 alkoxyaminos, where each of the groups may be optionally substituted with 1-3 substituents independently selected from halogens and CNs;
A compound of the same, or its salt or N-oxide.

Formula (XXXVIII)
(wherein ^A1 is CH or N, preferably N;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, _C1-6 alkoxy, amino _{, and NHC(O)C1-6 alkyl; preferably, R1a is selected from C1-6 alkyl, C3-6 cycloalkyl, C1-6 alkoxy-C1-6 alkyl} ^, _{C3-6 cycloalkyl - C1-4 alkyl ,} and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl _{- C1-6} alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino, _diC1-6 alkylamino, and _{C1-6 alkylC1-6} alkoxyamino, where each of the above groups may be optionally substituted with one to three substituents independently selected from halogens and CN; and ^R10 is _C1-6 alkyl.
A compound of the same, or its salt or N-oxide.

Formula (XL)
(wherein ^A1 is CH or N, preferably N;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, _C1-6 alkoxy, amino _{, and NHC(O)C1-6 alkyl; preferably, R1a is selected from C1-6 alkyl, C3-6 cycloalkyl, C1-6 alkoxy-C1-6 alkyl} ^, _{C3-6 cycloalkyl - C1-4 alkyl ,} and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl _{- C1-6} alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino, _diC1-6 alkylamino, and _{C1-6 alkylC1-6} alkoxyamino, where each of the above groups may be optionally substituted with one to three substituents independently selected from halogens and CN;
X is Cl, Br, or I);
A compound of the same, or its salt or N-oxide.

Formula (XVI)
(wherein Z is O or S, preferably Z is O;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^A2 is independently ^CR2 or N, provided that three or fewer ^A2s are N, preferably two or fewer ^A2s are N, preferably one or fewer ^A2s are N, and more preferably four ^A2s are ^CR2 ;
^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where _{C1-6 alkyl} , _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl} , C Each of the _3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxyl, and CN; preferably, ^R2 is independently selected from hydrogen, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy-C Each of the _1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs;
A ³ is independently CR ³ or N;
^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C Each of the _1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN; preferably, ^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl, where each of the _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, C1-6 alkylsulfinyl- _C1-6 alkyl, C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl _{-C1-6 alkyl} , _C1-6 alkylaminocarbonyl- _C1-6 alkyl, _diC1-6 alkylaminocarbonyl _{-C1-6 alkyl, and CN, where C1-6 alkyl, C1-6 alkoxy-C1-6 alkyl , C3-6 cycloalkyl , C3-6} cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, C Each of the _2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, _C1-6 alkylsulfinyl- _C1-6 alkyl, _C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl- _C1-6 alkyl, C1-6 alkylaminocarbonyl- _C1-6 alkyl and _diC1-6 alkylaminocarbonyl- _C1-6 alkyl may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN; preferably, ^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, where _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _{C3-6 cycloalkyl} -C Each of _{the 1-4} alkyl and _C1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens and CN;
Here, ^A3 and ^R4 may optionally combine to form a ring, more preferably a 5- to 8-membered heterocycle, and more preferably a 6-membered heterocycle; and X is Cl, Br, or I).
A compound of the same, or its salt or N-oxide.

The compounds of formula (I) as defined in this invention can be used, for example, as active ingredients for controlling plant pathogens, or as non-living substances for controlling potentially harmful putrefactive microorganisms or organisms in the agricultural sector and related fields of use. Novel compounds are distinguished by their excellent activity at low application rates, the sufficient tolerance exhibited by plants, and their environmental safety. They possess highly useful curative, preventative, and systemic properties and can be used to protect numerous cultivated plants. The compounds of formula (I) as defined in this invention can be used, for example, to suppress or eradicate pathogens appearing on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants from plant pathogenic microorganisms, while simultaneously protecting those parts of the plant as they grow later.

Compounds of formula (I) as defined in this invention may also be used as fungicides. The term "fungicide" as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidal effective amount" means the amount of such compound or combination of such compounds that can produce an effect on fungal growth. Controlling or modifying effects include all deviations from natural occurrence, such as death or delay, while prevention includes the formation of barriers or other defenses in or on plants to prevent fungal infection.

For protection against fungal infections and plant pathogenic fungi in the soil, a mixture of formula (I) as defined in this invention may also be used as a coating agent for treating plant propagation materials, such as seeds, tubers, or grains, or plant cuttings (e.g., rice), such as fruits. The propagation material can be treated with a composition containing a compound of formula (I) as defined in this invention before planting: for example, seeds can be coated before sowing. The compound of formula (I) as defined in this invention can also be applied (coated) to grains, either by impregnating the seeds with a liquid formulation or by coating the seeds with a solid formulation. The composition can also be applied to the planting site when the propagation material is planted, for example, in the planting furrow during sowing. This invention also relates to such methods for treating plant propagation materials and to plant propagation materials treated in this manner.

Furthermore, compounds of formula (I) as defined in this invention can be used in related fields, for example, to control fungi in the protection of industrial materials, including wood and wood-related industrial products, in food storage, and in hygiene management.

Furthermore, the present invention can also be used to protect non-biological materials, such as sawn timber, wall coverings, and paints, from fungal attacks.

Compounds of formula (I) as defined in this invention, and fungicidal compositions containing them, can be used to control plant diseases caused by broad-spectrum fungal plant pathogens. They are effective in controlling broad-spectrum plant diseases such as those affecting ornamental plants, lawns, vegetables, fields, grains, and fruit crops.

Examples of disease-causing fungi and fungal vectors, as well as plant pathogenic bacteria and viruses, that can be controlled include the following:

Aspergillus species such as Absidia corymbifera, Alternaria sp., Aphanomyces sp., Ascochyta sp., A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, and A. Species of the genus Aureobasidium such as A. pullulans, species of the genus Botryosphaeria such as Blastomyces dermatidis, Blumeria graminis, Bremia lactucae, species of Botryosphaeria such as B. dothidea, B. obtusa, species of Botrytis such as B. cinerea, C. albicans, C. Candida species such as C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis species, C. Cercospora species such as C. arachidicola, Cercosporidia personatum, Cladosporium species, Claviceps purpurea,
Coccidioides imtis, Cochliobolus sp., and Colletotrichum sp. such as C. musae,
Cryptococcus neoformans, species of the genus Diaporte, species of Didymella, species of Dretchlera, species of Elsinoe,
Species of the genus Epidermophyton, Erwinia amylovora, Erysiphe species such as E. cichoracearum,
Eutypa lata, F. culmorum, F. graminearum, F. langsetsiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. Fusarium species such as F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, and Gymnosporangium juniperi-virginiane. Juniperi virginianae), Helminthosporium sp., Hemileia sp., H. Species of the genus Histoplasma, such as H. Capsulatum, Laetisaria fuciformis, Leptogramium lindbergi, Leveillula taurica, Lophodermium seditisum, Microdochium nivale, species of the genus Microsporum, species of Monilinia, species of Mucor, M. Mycosphaerella species such as M. gramicola and M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides species, Penicillium species such as P. digitatum and P. italicum, Petriellidium species, P. maydis, P. Peronosclerospora species such as P. philippinensis and P. sorgi, Peronosclerospora species, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora species, Phoma species, Phomopsis viticola, P. This includes species of the genus Phytophthora, such as P. infestans; species of the genus Plasmopara, such as P. halstedii and P. viticola; species of the genus Pleospora; and P. Podosphaera species such as Leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotricoides, Pseudomonas species, P. cubensis, P. Pseudoperonospora species such as P. humuli, Pseudopeziza tracheiphylla, P. hordei, P. recondita, P. striiformis, P. triticina, Puccinia species such as P. triticina, Pyrenopeziza species, Pyrenophora species, P. Species of the genus Pyricularia, such as P. oryzae; species of the genus Pythium, such as P. ultimateum; species of Ramularia; species of Rhizoctonia; Rhizomucor pusilus; Rhizopus arrhizus; species of Rhynchosporium; S. apiospermum; and S. Species of the genus *Scedosporium*, such as *S. proliferans*, and *Schizothyrium pomi*,
Sclerotinia species (Sclerotinia sp.), Sclerotium species (Sclerotium sp.), S. nodorum, S. Septoria species such as S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerothex fuliginea), Sporothorix species, Stagonospora nodorum, Stemphylium species, Stereum hirsutum, Thanatophorus cucumeris Trichoderma species such as *T. cucumeris*, *T. basicola*, *Tilletia* sp., *T. harzianum*, *T. pseudokoningii*, and *T. viride*,
Species of the genera Trichophyton, Typhula, Uncinula necator, Urocystis, Ustilago, Venturia (including V. inaequalis), Verticillium, and Xanthomonas.

In particular, compounds of formula (I) as defined in the present invention, and fungicidal compositions containing them, can be used to control plant diseases caused by broad-spectrum fungal plant pathogens in basidiomycetes, ascomycetes, oomycetes and/or deuteromycetes, blasocladiomycetes, chytridiomycetes, glomeromycetes and/or mucormycetes. More specifically, compounds of formula (I) as defined in the present invention can be used to control oomycetes.

These pathogens may include the following:

Phytophthora capsisi, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophtra Phytophthora diseases, such as those caused by Pythium citrophora and Phytophthora erythroseptica; Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare, Pythium sylvaticum and Pythium urtimum Pythium diseases, such as those caused by *Pythium ultimum*; Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida, Sclerophora macrospora, and Bremia lactucae Diseases caused by Peronosporales, such as lactucae; and Oomycetes, including others such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghii, and Sclerospora graminicola.
Ascomycetes, for example, Pleosporales, for example, Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisisi, Pleospora herbarum, Phoma destructiva Destructiva, Phaeosphaeria herpotricoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium tritis triticirepentis), Setosphaeria turcica, Dretchlera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inequaris * Cladosporium carpophyllum, Cladosporium ephthum, etc. effusum), Passarola fulva, Cladosporium oxysporum, Dothstroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella coepkeii koepkeii), Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotricoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales, for example, Gaeumanmyces graminis, Magnaporte glycea Diaporthales, such as Pyricularia oryzae, Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporte phaseolu, Discula destructiva, Gnomonia fructicola, and Greeneria ubicola. * uvicola*, * Melanconium juglandinum*, * Phomopsis viticola*, * Sirococcus clavigignenti-juglandacearum*, * Tsubakia dryina*, * Dicarpella* species, * Valsa ceratosperma*, and others, such as * Actinothyrium graminis*, *Ascochyta* Aspergillus pisi), Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida species, Capnodium ramosum, Cephaloascus species, Cephalosporium gramineum Gramineum, Ceratocystis paradoxa, Chaetomium sp., Hymenoscyphus pseudoalbidus, Coccidioides sp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe amperina ampelina), Epicoccum nigram, Epidermophyton species, Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorgh, Gloeodes pomigena, Gloeosporium perenans Brown spot, spot disease, blast disease, or canker disease and/or rot caused by perennans, etc.; Gloeochinia
Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptogramium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditisum, Marssonina graminicola, Microdochium nivare Monilina fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus sp., Ophiostoma novo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri rhododendri, Petriellidium sp., Pezicula sp., Phyalophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pussulans * pustulans*, * Pseudopeziza medicaginis*, * Pyrenopeziza brassicae*, * Ramulispora sorgh*, * Rhabdocline pseudotsugae*, * Rhynchosporium secalis*, * Sacrocladium oryzae*, * Scedosporium spp.*, * Schizothyrium pomi* pomi), Sclerotinia sclerotiorum, Sclerotinia minor; Sclerotium species (Sclerotium spp.), Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma persea, Sporonema fascidioides Phacidioides, Stigmina palmivora, Tapesia yalundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; Erysiphales, e.g., Blumeria graminis, Erysiphe polygonii Polygoni), Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podosphaera macularis, Golovinomyces cichoracerum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossipii Powdery mildew caused by plants such as gossypii, Phyllactinia guttata, and Oidium arachidis; Botryosphaeriales, such as Dothiollella aromatica, Diprodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, and Botryotinia fabi Molds caused by species such as fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, and Phyllosticta cucurbitacearum; Glomerellales, for example, Colletotrichum gleosporioides, Colletotrichum lagenarium Anthracnose caused by plants such as Lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola; and Hypocreales, such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, and Fusarium graminearum. * graminea*, * Fusarium virguliforme*, * Fusarium oxysporum*, * Fusarium subglutinans*, * Fusarium oxysporum f. sp. cuben*, * Gerlacia nivale*, * Gibberella fujikuroi*, * Gibberella zeae*, * Gliocladium* species Wilt disease or canker disease caused by plants such as Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae.
The following are examples of smut fungi that cause smut, such as those belonging to the Basidiomycete class, including Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, and other species of the Ustilaginales order; for example, Cerotelium fici, Chrysomyxa arctostaphyli, and Coleosporium ipomoeae. Puccinia ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorgh, Puccinia hordei, Puccinia striiformis f. sp. Hordei, Puccinia striiformis f. sp. Puccinia striiformis f. sp. Secalis, Pucciniastrum coryli, and other species in the order Pucciniales, or Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum Caused by species of the order Uredinales, such as *Mucronatum*, *Physopella ampelosidis*, *Transchelia discolor*, and *Uromyces viciae-fabae*; as well as species of the genera Cryptococcus, *Exobasidium vexans*, *Marasmiellus inoderma*, *Mycena*, and *Sphacelotheca leiliana* reiliana), Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae Other rot and disease, such as those caused by *Tilletsia dahliae*, *Entylomella microspora*, *Neovossia moliniae*, and *Tilletsia caries*.
Blastocladiomycetes, such as Physoderma maydis.
Mucormycetes include species of the genus Mucor, such as Coanephora cucurbitarum, Mucor sp., and Rhizopus arrhizus.
Furthermore, diseases caused by other species and genera closely related to those listed above.

In addition to their fungicidal activity, the compounds, and compositions comprising the compound of formula (I) as defined in this invention, may also be active against bacteria such as *Erwinia amylovora*, *Erwinia caratovora*, *Xanthomonas campestris*, *Pseudomonas syringae*, *Streptomyces scabies*, and other related species, as well as certain protozoa.

Within the scope of the present invention, target crops and/or useful plants to be protected are typically berry plants, e.g., blackberries, blueberries, cranberries, raspberries and strawberries; cereals, e.g., barley, corn, millet, oats, rice, rye, sorghum, rye and wheat; fiber plants, e.g., cotton, flax, hemp, jute and sisal; crops, e.g., sugar and fodder beets, coffee, hops, mustard, rapeseed (canola), poppies, sugarcane, sunflowers, tea and tobacco; fruit trees, e.g., apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears and plums; grasses, e.g., Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and zoysia grass; herbs, e.g., basil, borage, chives, coriander, lavender, lavage, mint, oregano, parsley and rosemary , sage and thyme; legumes, e.g., kidney beans, lentils, peas and soybeans; nuts, e.g., almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms, e.g., oil palm; ornamental plants, e.g., flowers, shrubs and trees; other trees, e.g., cocoa, coconut, olive and rubber; vegetables, e.g., asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, mallow, melon, okra, onions, pepper, potatoes, pumpkins, rhubarb, spinach and tomatoes; and climbing plants, e.g., grapes, including perennial and annual crops.

Useful plants and/or target crops according to the present invention include conventional varieties, as well as genetically enhanced or genetically modified varieties, such as those with insect resistance (e.g., Bt. and VIP varieties), disease resistance, herbicide tolerance (e.g., glyphosate and glufosinate-tolerant maize varieties, commercially available under trade names RoundupReady® and LibertyLink®), and nematode resistance. Examples of suitably genetically enhanced or genetically modified varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.

The terms “useful plants” and/or “target crops” should be understood to include useful plants that have been conferred resistance to herbicides such as bromoxynil or several types of herbicides (e.g., HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron, and trifloxysulfuron, EPSPS (5-enol-pyruvir-sikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors, or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional breeding methods or genetic engineering. An example of a crop conferred resistance to imidazolinones, such as imazamox, by conventional breeding (muta introduction) methods is Clearfield® summer rapeseed (canola). Examples of crops genetically modified to be resistant to herbicides or several herbicides include glyphosate- and glufosinate-resistant maize varieties marketed under trade names RoundupReady®, Herculex I®, and LibertyLink®.

The terms “useful plants” and/or “target crops” should be understood to include those that naturally exhibit or have been conferred resistance to harmful insects. This includes plants transformed, for example, by the use of recombinant DNA technology to enable the synthesis of one or more selectively acting toxins, such as those known from toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxin, vegetative insecticidal proteins (Vip), insecticidal proteins from nematode-symbiotic bacteria, and toxins produced by scorpions, arachnids, wasps, and fungi. An example of a crop modified to express Bacillus thuringiensis toxin is Bt maize KnockOut® (Syngenta Seeds). An example of a crop containing two or more genes that encode insecticidal resistance and therefore express two or more toxins is VipCot® (Syngenta Seeds). Crops or their seed materials can also be resistant to multiple pests (so-called superimposed transgenic events produced by genetic modification). For example, a plant, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International), can be both herbicide resistant and capable of expressing insecticidal proteins.

The terms “useful plants” and/or “target crops” should be understood to also include useful plants transformed using recombinant DNA technology to enable the synthesis of selectively acting antipathogenic substances, such as so-called “infection-specific proteins” (PRPs, see, e.g., European Patent Application Publication No. 0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such substances are known, for example, from European Patent Application Publication No. 0392225, International Publication No. 95/33818, and European Patent Application Publication No. 0353191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

Toxins that may be expressed by transgenic plants include, for example, insecticidal proteins derived from Bacillus cereus or Bacillus popilliae; or insecticidal proteins derived from Bacillus thuringiensis, such as δ-endotoxins like Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C; or vegetative insecticidal proteins (Vip) such as Vip1, Vip2, Vip3 or Vip3A; or Photorhabdus luminescence Insecticidal proteins of nematode-symbiotic bacteria such as *Luminescens*, *Xenorhabdus nematophyllus*, and other species of the genera *Photorhabdus* or *Xenorhabdus*; toxins produced by animals such as scorpion toxin, spider toxin, large wasp toxin, and other insect-specific neurotoxins; toxins produced by fungi such as *Streptomycete* toxin, plant lectins such as pea lectin, barley lectin, or snowdrop lectin; aglutinin; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patain, cystatin, and papain inhibitors; lysine, corn Examples include ribosome-inactivating proteins (RIPs) such as locosy-RIP, abrin, rufin, saporin, or briodin; steroid metabolic enzymes such as 3-hydroxysteroid xidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, and HMG-COA-reductase; ion channel blockers such as sodium or calcium channel blockers; juvenile hormone esterase, diuretic hormone receptor, stilbenzyl synthase, bibenzyl synthase, chitinase, and glucanase.

Furthermore, it should be understood that in connection with the present invention, there exist δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, as well as explicitly hybrid toxins, cleavage toxins, and modified toxins. Hybrid toxins are produced by recombinant synthesis through novel combinations of different domains of these proteins (see, for example, International Publication No. 02/15701). Cleavage toxins, such as cleavage Cry1Ab, are known. In the case of modified toxins, one or more amino acids of a naturally occurring toxin are replaced. In such amino acid substitutions, preferably, a protease recognition sequence that does not naturally exist is inserted into the toxin. For example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see International Publication No. 03/018810).

Additional examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in European Patent Publication No. 0374753, International Publication No. 93/07278, International Publication No. 95/34656, European Patent Publication No. 0427529, European Patent Publication No. 451878, and International Publication No. 03/052073.

The preparation processes for such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acid and their preparations are known, for example, from International Publication 95/34656, European Patent Application Publication 0367474, European Patent Application Publication 0401979, and International Publication 90/13651.

Toxins contained in transgenic plants confer resistance to harmful insects. Such insects can exist in any insect taxonomy, but are typically found in beetles (Coleoptera), dipterans (Diptera), and butterflies (Lepidoptera).

Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants include: YieldGard® (a maize variety expressing Cry1Ab toxin); YieldGard Rootworm® (a maize variety expressing Cry3Bb1 toxin); YieldGard Plus® (a maize variety expressing Cry1Ab and Cry3Bb1 toxins); Starlink® (a maize variety expressing Cry9C toxin); Herculex I® (a maize variety expressing Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing Cry1Ac toxin); and Bollgard. These include I (registered trademark) (cotton variety expressing Cry1Ac toxin); Bollgard II (registered trademark) (cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot (registered trademark) (cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf (registered trademark) (potato variety expressing Cry3A toxin); NatureGard (registered trademark), Agrisure (registered trademark) GT Advantage (GA21 glyphosate-tolerant trait), Agrisure (registered trademark) CB Advantage (Bt11 corn borer (CB) trait), and Protecta (registered trademark).

Further examples of such transgenic crops are as follows:
1. Bt11 maize, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31, 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified maize (Zea mays) conferred resistance to attacks by the European corn borer (Ostrinia nubilaris and Sesamia nonagrioides) through transgenic expression of cleavage-type Cry1Ab toxin. Bt11 maize has also acquired resistance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.
2. Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Bt176 maize, registration number C/FR/96/05/10. Genetically modified maize (Zea mays) conferred resistance to attacks by the European corn borer (Ostrinia nubilaris and Sesamia nonagrioides) through transgenic expression of Cry1Ab toxin. Bt176 maize has also acquired resistance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.
3. Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, MIR604 maize, registration number C/FR/96/05/10. Maize conferred with insect resistance by transgenic expression of modified Cry3A toxin. This toxin is Cry3A055, modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in International Publication No. 03/018810.
4. MON 863 maize, manufactured in Monsanto Europe S. A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects.
5. Monsanto Europe S. A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, IPC 531 cotton, registration number C/ES/96/02.
6. 1507 maize, registration number C/NL/00/10, manufactured by Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium. Genetically modified maize for the expression of the protein Cry1F to acquire resistance to certain Lepidopteran insects and the expression of the PAT protein to acquire resistance to the herbicide glufosinate ammonium.
7. NK603 x MON810 corn, registration number C/GB/02/M3/03, manufactured at Monsanto Europe S. A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. This is a conventional hybrid corn variety resulting from a cross between the genetically modified varieties NK603 and MON 810. NK603×MON 810 corn genetically recombinantly expresses the protein CP4 EPSPS, obtained from the Agrobacterium sp. strain CP4, which confers resistance to the herbicide Roundup® (which contains glyphosate), and the Cry1Ab toxin, obtained from the Bacillus thuringiensis subsp. kurstaki, which provides resistance to certain Lepidoptera, including the European corn borer.

As used herein, the term “habitat” means cultivated land on which plants grow, or on which seeds of cultivated plants are sown, or on which seeds will be sown in the soil. It includes the soil, seeds and seedlings, and established vegetation.

The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

The term "plant propagation material" is understood to refer to plant materials, such as seeds and other reproductive parts, as well as cuttings or tubers, that can be used for plant propagation, such as potatoes. Examples include plant seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts. Germinated plants and seedlings that will be transplanted after germination or emergence from the soil may also be included. These seedlings may be protected before transplantation by complete or partial treatment by immersion. Preferably, "plant propagation material" is understood to mean seeds.

The pesticides referred to herein by their common names are, for example, publicly known from "The Pesticide Manual," 19th Ed., British Crop Protection Council 2021.

Compounds of formula (I), as defined in this invention, may be used in their unmodified form or, preferably, in combination with auxiliaries conventionally used in the art of formulation. For this purpose, they may be appropriately formulated by known methods into emulsifiable concentrates, coating pastes, ready-to-spray or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, powders for spraying, granules, and also, for example, encapsulations in polymeric substances. As with the type of composition, the method of application, such as spraying, misting, powdering, granulation, coating, or pouring, is selected according to the intended purpose and the circumstances at hand. The composition may also contain further auxiliaries such as stabilizers, defoamers, viscosity modifiers, binders, or tackifiers, as well as fertilizers, micronutrient donors, or other formulations for obtaining special effects.

For example, suitable carriers and/or auxiliary agents for agricultural applications may be solids or liquids and are substances useful in formulation techniques, such as natural or recycled inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders, or fertilizers. Such carriers are described, for example, in International Publication No. 97/33890.

A suspension concentrate is an aqueous formulation in which finely ground solid particles of an active compound are suspended. Such formulations contain anti-settling agents and dispersants, and may further contain wetting agents, defoamers, and crystal growth inhibitors to enhance activity. When used, these concentrates are diluted with water and typically applied as a spray to the area to be treated. The amount of the active ingredient may range from 0.5% to 95% of the concentrate.

Wettable powders are in the form of finely ground particles that disperse easily in water or other liquid carriers. The particles contain the active ingredient held within a solid matrix. Typical solid matrices include Fuller's earth, kaolin clay, silica, and other easily hygroscopic organic or inorganic solids. Wettable powders typically contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersants, or emulsifiers.

Emulsifying concentrates are homogeneous liquid compositions that are dispersible in water or other liquids, and may consist solely of the active compound and a liquid or solid emulsifier, or they may also contain liquid carriers such as xylene, high-boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquids and are typically applied as a spray to the area to be treated. The amount of the active ingredient may range from 0.5% to 95% of the concentrate.

Granular formulations, comprising both extruded materials and relatively coarse particles, are typically applied undiluted to the area requiring treatment. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, crushed corn cobs, crushed peanut shells, sugars, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium dioxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations typically contain 5% to 25% active ingredients, which may include surfactants such as heavy aromatic naphtha, kerosene, and other petroleum fractions, or vegetable oils; and/or stickers such as dextrin, glue, or synthetic resins.

Powder for scattering is a free-flowing mixture of the active ingredient and finely ground solids such as talc, clay, powder, and other organic and inorganic solids that act as a dispersant and carrier.

Microcapsules are typically droplets or granules of an active ingredient encapsulated in an inert, porous shell that allows for the release of the encapsulated material into the surroundings at a controlled rate. Encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically constitutes 50 to 95% of the capsule's weight and may include a solvent in addition to the active compound. Encapsulated granules are generally porous granules having a porous membrane that seals the pore openings of the granules, retaining the active species in liquid form within the granular pores. Granules are typically in the range of 1 millimeter to 1 centimeter in diameter, preferably 1 to 2 millimeters. Granules are formed by extrusion, agglomeration, or prilling, or they exist naturally. Examples of such materials include vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubber, cellulose-based materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthetes.

Other useful formulations for agricultural applications include simple solutions of the active ingredient in a solvent in which the active ingredient is completely dissolved at the desired concentration, such as acetone, alkylated naphthalene, xylene, and other organic solvents. Pressurized sprayers may also be used, in which the active ingredient is dispersed in a finely pulverized form as a result of evaporation of a low-boiling point dispersible solvent carrier.

Suitable agricultural additives and/or carriers useful for formulating the compositions of the present invention using the above-described formulation types are well known to those skilled in the art.

Examples of liquid carriers that can be used include water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, and diethylene glycol methyl ether. Lu ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, Glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PE) Examples include G400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol and amyl alcohols, tetrahydrofurfuryl alcohol, hexanol, octanol and other high molecular weight alcohols, ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. Water is generally the optimal carrier for diluting concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide, pyroferrite clay, silica, attapulgite clay, diatomaceous earth (kieselguhr), white pigment, diatomaceous earth (diatomaceous earth), lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, and lignin.

A wide range of surfactants are advantageously used in both the liquid and solid compositions, particularly those designed to be diluted with a carrier before application. These agents, when used, typically constitute 0.1% to 15% by mass of the formulation. They may be anionic, cationic, nonionic, or polymeric in nature, and can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfate salts, e.g., diethanolammonium lauryl sulfate; alkylaryl sulfonates, e.g., calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, e.g., nonylphenol-C. sub. 18 ethoxylate; and alcohol-alkylene oxide addition products, e.g., tridecyl alcohol-C. sub. Examples include 16 ethoxylates; soaps, e.g., sodium stearate; alkylnaphthalene sulfonate salts, e.g., sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinate salts, e.g., sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, e.g., sorbitol oleate; quaternary amines, e.g., lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, e.g., polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

Other commonly used additives in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoaming agents, light-shielding agents, compatibilizers, metal ion chelating agents, neutralizing agents and buffering agents, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, mitigating agents, lubricants and adhesives.

In addition, other biocides or compositions may be combined with the composition of the present invention and used in the method of the present invention, and may be applied simultaneously with or sequentially to the composition of the present invention. When applied simultaneously, these further active ingredients may be formulated together with the composition of the present invention, or mixed, for example, in a spray tank. These further biocides may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, plant growth regulators, and/or biological formulations.

The following combinations of the compound of formula I and another active substance in a 1:1 weight ratio are preferred (where the abbreviation "TX" means "one compound selected from the compounds defined in Tables 1.1 to 1.297 and Table A"):
(7E,9Z)-Dodeca-7,9-diene-1-ylacetate + TX, (9Z,11E)-Tetradeca-9,11-diene-1-ylacetate + TX, (9Z,12E)-Tetradeca-9,12-diene-1-ylacetate + TX, (E)-6-methylhepta-2-en-4-ol + TX, (E)-Deca-5-en-1-ylacetate and (E)-Deca-5-en-1-ol + TX, (E)-Trideca-4-en-1-ylacetate + TX, (E,Z)-Tetradeca-4,10-diene-1- Illacetate + TX, (Z)-Dodeca-7-En-1-Illacetate + TX, (Z)-Hexadeca-11-En-1-Illacetate + TX, (Z)-Hexadeca-11-Enal + TX, (Z)-Hexadeca-13-En-11-In-1-Illacetate + TX, (Z)-Icosa-13-En-10-On + TX, (Z)-Tetradeca-7-En-1-R + TX, (Z)-Tetradeca-9-En-1-All + TX, (Z)-Tetradeca-9-En-1-Illacetate + TX, 1,2-Jib Romo-3-chloropropane + TX, 1,2-dichloropropane + TX, 1,2-dichloropropane and 1,3-dichloropropane + TX, 1,3-dichloropropane + TX, 14-methyloctadeca-1-ene + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 2-(octylthio)ethanol + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + TX, 5-methyl-6-thioxo-1,3,5-thiadiadinane-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, abamectin + TX, acequinosyl + TX, acetamiprid + TX, acetoprol + TX, acrinatrin + TX, acinonapil + TX, Adoxophyes Orana orana) GV + TX, afidopiropene + TX, afoxolaner + TX, Agrobacterium radiobacter + TX, AKD-3088 + TX, alanicarb + TX, aldicarb + TX, aldoxycarb + TX, allethrin + TX, α-cypermethrin + TX, alphamethrin + TX, alpha-multistriatin + TX, Amblyseius spp. + TX, amidoflumet + TX, amino acids + TX, aminocarb + TX, Anagrapha falcifera NPV + TX, Anagrus atomus Atomus) + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Apholate + TX, Autographa californica NPV + TX, AZ 60541 + TX, Azadirachtin + TX, Azocyclotin + TX, Bacillus aizawai + TX, Bacillus chitinosporus Bacillus chitinosporus AQ746 (NRRL accession number B-21 618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL accession number B-21664) + TX, Bacillus pumilus (NRRL accession number B-30087) + TX, Bacillus pumilus AQ717 (NRRL accession number B-21662) + TX, Bacillus sp. AQ175 (ATCC accession number 55608) + TX, Bacillus sp. AQ177 (ATCC accession number 55609) + TX, Bacillus sp. AQ178 (ATCC accession number 53522) + TX, Bacillus sphaericus Neide + TX, Bacillus subtilis AQ153 (ATCC accession number 55614) + TX, Bacillus subtilis AQ30002 (NRRL accession number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL accession number B-50455) + TX, Bacillus subtilis AQ713 (NRRL accession number B-21661) + TX, Bacillus subtilis AQ743 (NRRL accession number B-21665) + TX, Bacillus subtilis subtilis) Details unknown + TX, Bacillus thuringiensis AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis Berliner + TX, Bacillus thuringiensis subsp. Aizawai + TX, Bacillus thuringiensis subsp. islaerensis Bacillus thuringiensis subsp. Israelensis) + TX, Bacillus thuringiensis subspecies Japonensis + TX, Bacillus thuringiensis subspecies kurstaki + TX, Bacillus thuringiensis subspecies Tenebrionis + TX, Bacillus thuringiensis subspecies kurstaki BMP 123+TX, Beauveria bassiana+TX, Beauveria brongnatiii+TX, Bencrotiaz+TX, Benomyl+TX, Bensultap+TX, Benzoximate+TX, Benzpyrimoxane+TX, Beta-cyfluthrin+TX, Beta-cypermethrin+TX, Betoxazine+TX, Bifenazette+TX, Bifenthrin+TX, Binapacril+TX, Biorethrin+TX, Biorethmetrin+TX, Bis(tributyltin)oxide+TX, Bisagil+TX, Bistriflurone+TX, Bisulfurfen+TX, Brevicomin+TX, Proflanilide+TX, Broflusrinate+TX, Bro Moacetamide + TX, Bromophos-ethyl + TX, Bronopol + TX, Busulfan + TX, Butocarboxime + TX, Butopyronoxyl + TX, Butoxy (Polypropylene Glycol) + TX, Butylpyridaben + TX, Kazsaphos + TX, Calcium Arsenate + TX, Carbaryl + TX, Carbofuran + TX, Carbon Disulfide + TX, Carbosulfan + TX, Cartap + TX, CAS No.: 1594624-87-9 + TX, CAS No.: 1922957-47-8 + TX, CAS No.: 1255091-74-7 + TX, CAS No.: 1365070-7 2-9+TX, CAS number: 1445683-71-5+TX, CAS number: 1445684-82-1+TX, CAS number: 159462 6-19-3+TX, CAS number: 1594637-65-6+TX, CAS number: 1632218-00-8+TX, CAS number: 180 8115-49-2+TX, CAS number: 1922957-46-7+TX, CAS number: 1922957-48-9+TX, CAS number: 1956329-03-5+TX, CAS number: 1990457-52-7+TX, CAS number: 1990457-55-0+TX, CAS Number: 1990457-57-2+TX, CAS number: 1990457-66-3+TX, CAS number: 1990457-77-6+TX, CAS number: 1990457-85-6+TX, CAS number: 2032403-97-5+TX, CAS number: 2044701-44-0+ TX, CAS number: 2095470-94-1+TX, CAS number: 2128706-04-5+TX, CAS number: 2128706-05 -6+TX, CAS number: 2133042-31-4+TX, CAS number: 2133042-44-9+TX, CAS number: 2171099-
09-3+TX, CAS number: 2220132-55-6+TX, CAS number: 2396747-83-2+TX, CAS number: 2408220-91-5+TX, CAS number: 2408220-94-8+TX, CAS number: 2415706:16-8+TX, piperfuranilide (CAS number: 2615135-05-0)+TX, CAS number: 2719848-60-7+TX, CAS number: RNA (Leptinotarsa desemlineata) Decemrineata-specific recombinant double-strand interference GS2) + TX, Chlorantraniliprole + TX, Chlordane + TX, Chlorfenapyr + TX, Chloropicrin + TX, Chloroprallethrin + TX, Chlorpyrifos + TX, Chromafenozide + TX, Chrysoperla carnea + TX, Clempyrin + TX, Chloetocarb + TX, Clothianidin + TX, Codrelle + TX, Codremon + TX, Copper acetoarsenite + TX, Copper dioctanoate + TX, Copper hydroxide + TX, Copper sulfate + TX, Cresol + TX, Culfomate + TX, Cryptolamus montorghini Montrouzieri) + TX, Kyurua + TX, Cyanophenphos + TX, Cyantraniliprole + TX, Sibutrin + TX, Cyclaniliprole + TX, Cyclobtriflurum + TX, Cycloprotrin + TX, Cycloxapride + TX, Cydia pomonella GV + TX, Cyenopyrafen + TX, Cietopyrafen + TX, Cyflumetofen + TX, Cyfluthrin + TX, Cyhalodiamide + TX, Cylohalothrin + TX, Cypermethrin + TX, Cyphenothrin + TX, Cypuprofuranilide + TX, Cyromazine + TX, Cytokinin + TX, Dacnusa sibirica sibirica) + TX, dazomet + TX, DBCP + TX, DCIP + TX, deltamethrin + TX, diafenthiuron + TX, dialiphos + TX, diamidaphos + TX, dibrom + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diclofenthion + TX, diclofenthion + TX, diclofen + TX, dichlorophene + TX, dicliphos + TX, dichloromesothiaz + TX, diethyltoluamide + TX, diflubenzuron + TX, Diglyphus isaea ISAEA + TX, Dimatif + TX, Dimethoate + TX, Dimethylcalvert + TX, Dimethyl phthalate + TX, Zinpropyridaz + TX, Dinactin + TX, Dinocap + TX, Dinotefuran + TX, Dioxabenzophos + TX, Dipirithione + TX, Disparure + TX, D-Limonene + TX, Dodeca-8-en-1-ylacetate + TX, Dodeca-9-en-1-ylacetate + TX, Dodeca-8,10-dien-1-ylacetate + TX, Dodicine + TX, Dominicalle + TX, Doramectin + TX, Emamectin + TX, Emamectin benzoate + TX, Empenthrin + TX, Encarsia formosa (formosa) + TX, Endotar + TX, Endrin + TX, Eprinomectin + TX, Epsilon-Monfluorothrin + TX, Epsilon-Metofluthrin + TX, Eretmoserus elemicus Eremicus + TX, Esfenvalerate + TX, Ethion + TX, Ethiprole + TX, Etoprophos + TX, Ethyl 4-methyloctanoate + TX, Ethyl hexanediol + TX, Ethylene dibromide + TX, Etofenprox + TX, Ethoxazole + TX, Etopyrafen + TX, Eugenol + TX, Fermented products from seaweed extract and molasses + TX, Fermented products from seaweed extract and molasses containing urea + TX, Fermented plant products from seaweed extract and fermented plant products containing seaweed extract and plant hormones, vitamins, EDTA-chelated copper, zinc, and iron + TX, Famfur + TX, Fena Minosulf + TX, Fenamifos + TX, Phenazaquin + TX, Fenflusrin + TX, Fenitrothion + TX, Fenmezoditiaz + TX, Phenobucarb + TX, Phenothiocarb + TX, Phenoxycarb + TX, Fenpropathrin + TX, Fenpyrad + TX, Fenpyroximate + TX, Fensulfothion + TX, Fenthion + TX, Fentin + TX, Fentin acetate + TX, Fenvalerate + TX, Iron(III) phosphate + TX, Fipronil + TX, Flomethoquin + TX, Flonicamide + TX, Fluacrypyrim + TX, Fluazindolidine + TX, Fluazuron + TX, Flubenji Amide + TX, Flubendimine + TX, Fluchlordiniliprole + TX, Flucitrinate + TX, Flucycloxurone + TX, Flucitrinate + TX, Fluensulfone [318290-98-1] + TX, Fluensulfone + TX, Fluphenelim + TX, Flufenprox + TX, Flufiprole + TX, Fluhexafone + TX, Flumethrin + TX, Fluopyram + TX, Flupyradiflon + TX, Flupyrimine + TX, Flupyroxytribin + TX, Fluralaner + TX, Fluvalinate + TX, Fluxamethamide + TX, Form Aldehyde + TX, Fosthiazate + TX, Fosthiethane + TX, Frontalin + TX, Furfural + TX, Gamma-cyhalotrin + TX, Gossyplure (registered trademark) (1:1 mixture of (Z,E) and (Z,Z) isomers of hexadeca-7,11-dien-1-yl acetate) + TX, Grandorule + TX, Grandorule I + TX, Grandorule II + TX, Grandorule III + TX, Grandorule IV + TX, Granulosis virus + TX, Guadipyr + TX, GY-81 + TX, Halfenprox + TX, Halofenozide + TX, Harpin + TX, Helicoverpa almigera Armigera) Polyhedrosis virus + TX, Helicoverpa zea NPV + TX, Helicoverpa zea Polyhedrosis virus + TX, Heliotis punctigera Polyhedrosis virus + TX, Heliotis virescens Polyhedrosis virus + TX, Hemel + TX, Hempa + TX, Heptafluthrin + TX, Heterophos + TX, Heterorhabditis bacteriophagora and H. H. megidis + TX, Hexalua + TX, Hexamide + TX, Hexythiazox + TX, Hippodamia convergens + TX, Hydramethylnon + TX, Hydralgafen + TX, Slaked lime + TX, Imisiaphos + TX, Imidacloprid + TX, Imiprothrin + TX, Indazapiroxameth + TX, Indoxacarb + TX, Iodomethane + TX, Iprodione + TX, Ipsdienol + TX, Iposenol + TX, Isamidophos + TX, Isazofos + TX, Isocycloserum + TX, Isofluara Nam (CAS number: 2892524-05-7) + TX, Isothioate + TX, Ivermectin + TX, Japonilua + TX, Kappa-bifenthrin + TX, Kappa-tefluthrin + TX, Kasugamycin + TX, Kasugamycin hydrochloride hydrate + TX, Kinetin + TX, Lambda-cyhalotrin + TX, Redoprona + TX, Lepimectin + TX, Leptomastic Dactylopia dactylopii) + TX, lineatin + TX, litolua + TX, lupulua + TX, rotilaner + TX, lufenuron + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, mecarfone + TX, medolua + TX, megatomoic acid + TX, metaflumizone + TX, metaldehyde + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisoplie var. acridam (Metarrhizium anisoplie) Metallidium anisopliae var. acridum) + TX, Metallidium anisopliae var. anisopliae (Metarlidium anisopliae var. anisopliae) + TX, Metallidium species (Metarlidium spp.) + TX, Metepa + TX, Methiocarb + TX, Methiotepa + TX, Methomyl + TX, Methquin-butyl + TX, Methoxyphenozide + TX, Methylphorate + TX, Methyl bromide + TX, Methyl eugenol + TX, Methyl isothiocyanate + TX, Methyl neodecanamide + TX, Metofluthrin + TX, Metolcarb + TX, Mexacalbate + TX, Milbemectin + TX, Milbemycin oxime + TX, Monfluorothrin + TX, Morzide + TX, Moxidectin + TX, Muscarle + TX, Muscodor albus 620 (NRRL accession number 30547) + TX, Muscodor roseus (Muscodor roseus) A3-5 (NRRL accession number 30548) + TX, Myrothecium verrucaria composition + TX, Narbam + TX, NC-184 + TX, Neem tree-based product + TX, Neodiprion celtifer N. lecontei NPV + TX, Nickel bis(dimethyldithiocarbamate) + TX, Niclosamide + TX, Niclosamide-olamine + TX, Nicofluprole + TX, Nitenpyram + TX, Nichiazine + TX, Nitrapyrine + TX, Octadeca-2,13-dien-1-ylacetate + TX, Octadeca-3,13-dien-1-ylacetate + TX, Octylinone + TX, Omethoate + TX, Orflurua + TX, Orius species spp.) + TX, orictalure + TX, ostramonene + TX, oxamate + TX, oxamyl + TX, oxazosulfyl + TX, oxolinic acid + TX, oxytetracycline + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, parathion-ethyl + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa ramosa) + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, Penflurone + TX, Pentachlorophenol + TX, Permethrin + TX, Phenothrin + TX, Phorate + TX, Phosphamidone + TX, Phosphocarb + TX, Phytoseulus persimilis + TX, Picalidine + TX, Pioxaniliprole + TX, Piperazine + TX, Piperonyl butoxide + TX, Pyrimicarb + TX, Pyrimiphos-ethyl + TX, Pyrimiphos-methyl + TX, Plutella xylostera Plutella xylostella granulopathy virus + TX, Plutella xylostella nuclear polyhedron disease virus + TX, nuclear polyhedron disease virus + TX, potassium and molybdenum and EDTA chelated manganese + TX
Potassium ethylxanthogenic acid + TX, potassium hydroxyquinoline sulfate + TX, prallethrin + TX, probenazole + TX, profenofos + TX, profluthrin + TX, propargit + TX, propethamfos + TX, propoxul + TX, prothiofos + TX, protrefene bute + TX, piflubmid + TX, pymetrozine + TX, pyraclofos + TX, pyrafulprole + TX, pyridaben + TX, pyridaryl + TX, pyridine-4-amine + TX, pyrifluquinazone + TX, pyrimidifen + TX, pyriminostrobin + TX, pyriprole [394730-71-3] + TX, pyriprole + TX, pyriproxyfen + TX, QRD 420 (terpenoid mixture) + TX, QRD 452 (terpenoid mixture) + TX, QRD 460 (terpenoid mixture) + TX, Quillaya saponaria + TX, Quinoclamine + TX, Quinonamide + TX, Resmethrin + TX, Rhodococcus globerulus AQ719 (NRRL accession number) B-21663) + TX, Saloraner + TX, S-Bioarethrin + TX, Cebuphos + TX, Selamectin + TX, Siguru + TX, Silafluofen + TX, Simazine + TX, Sodium Pentachlorophenoxide + TX, Solzidine + TX, Spidoxamato + TX, Spinetoram + TX, Spinosad + TX, Spirobudifen + TX, Spirodiclofen + TX, Spiromesifen + TX, Spiropidione + TX, Spirotetramato + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus + TX, Spodoptera flugyperda frugiperda nuclear polyhedron disease virus + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapteris scapterisci) + TX, Steinernema spp. + TX, Streptomyces galbus (NRRL accession number 30232) + TX, Streptomyces sp. (NRRL accession number B-30145) + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Strychnine + TX, Sulcatol + TX, Sulfiflumin (CAS number: 2377084-09-6) + TX, Sulfoxaflor + TX, Tadimucarb + TX, Tebufenozide + TX, Tebufenpyrad + TX, Tebupirimiphos + TX, Tecrophthalam + TX, Tefluthrin + TX X, Temephos + TX, Tepa + TX, Turbam + TX, Terbuphos + TX, Terpenoid mixture + TX, Tetrachlorolantraniliprole + TX, Tetrachlorothiophene + TX, Tetradeca-11-en-1-yl acetate + TX, Tetradiphon + TX, Tetramethrin + TX, Tetramethylfluthrin + TX, Tetranactin + TX, Tetraniliprole + TX, Theta-Sipel Metrine + TX, Thiacloprid + TX, Thiafenox + TX, Thiamethoxam + TX, Thiocyclam + TX, Thiodicarb + TX, Thiofanox + TX, Thiohempa + TX, Thiomersal + TX, Thiometon + TX, Thionadin + TX, Thiophanate + TX, Thiosultap + TX, Thiotepa + TX, Tigolaner + TX, Thiolantranilipro Lu + TX, Thioxazafen + TX, Tolfenpyrad + TX, Toxafen + TX, Tralomethrin + TX, Transfluthrin + TX, Tretamine + TX, Triazamate + TX, Triazophos + TX, Triazurone + TX, Tributyltin oxide + TX, Trichlorfon + TX, Trichloronate + TX, Trichlorfon + TX, Trichogramma species spp.) + TX, Triphenmorph + TX, Trifluenfronate + TX, Triflumezopyrim + TX, Trimedrua + TX, Trimedrua A + TX, Trimedrua B1 + TX, Trimedrua B2 + TX, Trimedrua C + TX, Trimetacarb + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Tranquol + TX, Cyclopyrazoflor + TX, Typhlodromeus occidentalis + TX, Uredepa + TX, Verticillium lecanii + TX, Verticillium species spp.) + TX, xylenol + TX, YI-5302 + TX, zeatin + TX, zeta-cypermethrin + TX;
N-[(1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds (The compound may be prepared from the method described in International Publication No. 2019/110427) + TX, (3',4',5'-trifluorobiphenyl-2-yl)amide + TX, (3-methylisoxazole-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone (These compounds may be prepared from the method described in International Publication No. 2017/220485) + TX, (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate (this compound can be prepared from the method described in International Publication No. 2014/006945) + TX, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone + TX, (7E,9Z)-dodeca-7,9-diene-1-ylacetate + TX, (9Z,11E)-tetradeca-9,11-diene-1-ylacetate + TX, (9Z,12E)-tetradeca-9,11-diene-1-ylacetate Deca-9,12-dien-1-yl acetate + TX, (E)-6-methylhepta-2-en-4-ol + TX, (E)-deca-5-en-1-yl acetate and (E)-deca-5-en-1-ol + TX, (E)-trideca-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, (Z)-Dodeca-7-En-1-Ilacetate + TX, (Z)-Hexadeca-11-En-1-Ilacetate + TX, (Z)-Hexadeca-11-Enal + TX, (Z)-Hexadeca-13-En-11-In-1-Ilacetate + TX, (Z)-Icosa-13-En-10-On + TX, (Z)-Tetradeca-7-En-1-R + TX, (Z)-Tetradeca-9-En-1-All + TX, (Z)-Tetradeca-9-En-1-Ilacetate + TX, (Z,2E) -5-[1-(2,4-dichlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide (this compound can be prepared from the method described in International Publication No. 2018/153707) + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazole-1 [-yl]acetyl]-4-piperidyl]thiazole-4-yl]-4,5-dihydroisoxazole-5-yl]-3-chlorophenyl]methanesulfonate + TX, 1-(4,5-dimethylbenzimidazole-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(4,5-dimethylbenzimidazole-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridine- 3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridine-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6-chloro-7-methylpyrazolo[1,5-a]pyridine-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline (These compounds may be prepared from the methods described in International Publication No. 2017/025510) + TX, 1,1-bis(4- Chlorophenyl)-2-ethoxyethanol + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dibromo-3-chloropropane + TX, 1,2-dichloropropane and 1,3-dichloropropane + TX, 1,3-dichloropropane + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 1-[2-[[1-(4-chlorophenyl)pyrazole-3-yl [Oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazole-5-one + TX, 10-diene-1-ylacetate + TX, 14-methyloctadeca-1-ene + TX, 1-bromo-2-chloroethane + TX, 1-dichloro-1-nitroethane + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 1-methyl- 4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazole-1-yl)phenoxy]methyl]phenyl]tetrazole-5-one + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(1,3-dithiolan-2-yl)phenyldimethyl Lucarbamate + TX, 2-(2-butoxyethoxy)ethylpiperonylate + TX, 2-(2-butoxyethoxy)ethylthiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3 R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared from the method described in International Publication No. 2014/095675) + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2-(octylthio) Ethanol + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c '] dipyrrole-1,3,5,7(2H,6H)-tetron (this compound can be prepared from the method described in International Publication No. 2011/138281) + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (this compound can be prepared from the method described in International Publication No. 2017/02 (This compound may be prepared from the method described in International Publication No. 9179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (This compound may be prepared from the method described in International Publication No. 2017/029179) + TX, 2-chlorovinyl diethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2-imidazolidone + TX, 2-isovalerylindan-1, 3-Dione + TX, 2-Methyl(propane-2-inyl)aminophenylmethylcarbamate + TX, 2-Oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide (this compound can be prepared from the method described in International Publication No. 2018/065414) + TX, 2-Thiocyanatoethyl laurate + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-Cyc Lopenta[e]benzimidazole (these compounds may be prepared from the method described in International Publication No. 2016/156085) + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinoline-1-yl)quinolone + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound may be prepared from the method described in International Publication No. 2016/156290) + TX, 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound may be prepared from the method described in International Publication No. 2016/156290) + TX, 3-bromo-1-chloropropa-1-ene + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-tri Fluorophenyl)pyridazine + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 3-methyl-1-phenylpyrazole-5-yldimethylcarbamate + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine-3-carbonitrile + TX, 4-(2-bromo-4- Fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethylpyrazole-3-amine + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazole-1-yl)-3,3-dimethylisoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridine-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridine-3-yl)isoquinoline + TX, 4,4-dimethyl-2-[[4-[5-(triflu Oromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-
3-(5-thioxo-4H-1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazine-3-one + TX, 4-chlorophenylphenyl sulfone + TX, 4-methyl(propane-2-inyl)amino-3,5-xylylmethylcarbamate + TX, 4-methylnonan-5-ol and 4-methyl Tyrnonan-5-one + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexa-2-eneone + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 5,5-dimethyl-3-oxocyclohexa-1-enyldimethylcarbamate + TX, 5-amino-1,3,4-thiadiazole-2-thiol Zinc salt (2:1) + TX, 5-methyl-6-thioxo-1,3,5-thiadiadinane-3-ylacetic acid + TX, 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (can be prepared from the method described in International Publication No. 2020/109391) + TX, 6-chloro-3-(3-cyclopropyl-2-fluoro- Phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (which can be prepared from the method described in International Publication No. 2020/109391) + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazole-1-yl)isoquinoline + TX, 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoroethyl] ]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide (which can be prepared from the method described in International Publication No. 2020/109391) + TX, 6-ethyl-5,7-dioxopyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitride + TX, 6-isopentenylaminopurine + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]- 1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-hydroxyquinoline sulfate + TX, acetylone + TX, acetoprol + TX, acibenzol + TX, acibenzol-S-methyl + TX, acrylonitrile + TX, Adoxophyes Orana orana) GV + TX, Agrobacterium radiobacter + TX, Aldoxycarb + TX, Aldrin + TX, Allosamidin + TX, Alixicarb + TX, α-Chlorohydrin + TX, α-Ecdysone + TX, α-Multistriatin + TX, Aluminum phosphide + TX, Amblyseius species spp.) + TX, amectotractin + TX, ametoctrazine + TX, amidithione + TX, amidothioate + TX, aminocarb + TX, aminopyriphen + TX, amisulbrom + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, anabasin + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, ancimidor + TX, anilazine + TX, anisifuruprin + TX, anthraquinone + TX, antu + TX, Aphelinus abdominalis abdominalis) + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, aramite + TX, arsenite + TX, atidathion + TX, Autographa californica NPV + TX, azaconazole + TX, azamethiphos + TX, azobenzene + TX, azothoate + TX, azoxystrobin + TX, Bacillus sphaericus Neide + TX, Bacillus thuringiensis Thuringiensis) Delta Endotoxin + TX, Barium Carbonate + TX, Barium Hexafluoridosalic Acid + TX, Barium Polysulfide + TX, Bartholin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, Beauveria bronchiniatii (brongniartii) + TX, Benalaxyl + TX, Bencrotiaz + TX, Benomyl + TX, Benoxaphos + TX, Bentiavaricarb + TX, Benzothiostrobin + TX, Benzovindiflupir + TX, Benzyl benzoate + TX, Beta-cyfluthrin + TX, Beta-cypermethrin + TX, Betoxazine + TX, Bioetanomethrin + TX, Biopermethrin + TX, Bis(2-chloroethyl) ether + TX, Bis(tributyltin) oxide + TX, Bisagil + TX, Bisthiosemi + TX, Vitertanol + TX, Bixa Fen + TX, Blastocidine-S + TX, Borax + TX, Bordeaux mixture + TX, Boscalid + TX, Brevicomin + TX, Brodifacum + TX, Brofenvalerate + TX, Bromadiolon + TX, Bromethalin + TX, Bromufenbinphos + TX, Bromoacetamide + TX, Bromocyclene + TX, Bromo-DDT + TX, Bromophos + TX, Bromopropylate + TX, Bromuconazole + TX, Bronopol + TX, Bufencarb + TX, Bupirimate + TX, Buprofezin + TX, Busulfan + TX, Buta-3-inyl N-[6-[[(Z)-[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, Butacarb + TX, Butathiophos + TX, Butocarboxime + TX, Butonate + TX, Butopyronoxyl + TX, Butoxy(polypropylene glycol) + TX, Butoxycarboxime + TX, Butylpyridaben + TX, Arsenic acid Calcium + TX, Calcium cyanide + TX, Calcium polysulfide + TX, Camfecrol + TX, Captahole + TX, Captan + TX, Carbanolate + TX, Carbendazim + TX, Carbon disulfide + TX, Carbon tetrachloride + TX, Carbophenothion + TX, Carboxone + TX, Cartap hydrochloride + TX, CAS number: 2132414-04-9 + TX, CAS number: 2344721 -61-3 + TX, Sebadin + TX, Quinomethionate + TX, Chloralose + TX, Chlorbenside + TX, Chlorbicyclene + TX, Chlordane + TX, Chlordecone + TX, Chlorodimeform + TX, Chlorodimeform hydrochloride + TX, Chlorphenetol + TX, Chlorfensone + TX, Chlorfensulfide + TX, Chlorobenzylate + TX, Chloroform + TX, C Loloinconazide + TX, Chloromebform + TX, Chloromethirone + TX, Chloroneb + TX, Chlorophacinone + TX, Chloropicrin + TX, Chloropropylate + TX, Chlothalonil + TX, Chlorphoxime + TX, Chlorprazophos + TX, Chlorthiophos + TX, Clozolinate + TX, Cholecalciferol + TX, Chrysoperia carnea carnea) + TX, Synerin I + TX, Synerin II + TX, Synerin + TX, cismethrin + TX, cis-resmethrin + TX, clocythrin + TX, closantel + TX, kodrelle + TX, kodremon + TX, copper acetarsenite + TX, copper arsenate + TX, copper dioctanoate + TX, copper hydroxide + TX, copper naphthenate + TX, copper oleate + TX, copper oxide + TX, copper oxychloride + TX, copper sulfate + TX Coumacryl + TX, Coumafryl + TX, Coumaphos + TX, Coumatetralyl + TX, Cumithoxystrobin (Diaxiangjunzhi) + TX, Cumithoate + TX, Comoxystrobin + TX, Cresol + TX, Crimidine + TX, Crotamiton + TX, Clothoxyphos + TX, Cluthomate + TX, Cryolite + TX, Cryptraemus montorgiensis Montrouzieri) + TX, CS 708 + TX, Kyurua + TX, Cufraneb + TX, Cyanophenphos + TX, Cyanophos + TX, Cyanthoate + TX, Cyazofamide + TX, Sibutrin + TX, Cycloresrin + TX, Cyclobtrifluram + TX, Cydia pomonel GV + TX, Cyflufenamid + TX, Simiazole + TX, Cymoxanil + TX, Cyproconazole + TX, Cyprodinil + TX, Cithioate + TX, Cytokinin + TX, Dacnusa sibirica sibirica + TX, DAEP + TX, dazomet + TX, DCIP + TX, DCPM + TX, DDT + TX, debacarb + TX, decarbofuran + TX, demefion + TX, demefion-O + TX, demefion-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methylsulfone + TX, diamidaphos + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dicapton + TX, diclobentiazox + TX, diclofenthion + TX X, Diclofluanide + TX, Diclon + TX, Dichlorophene + TX, Dichlorvos + TX, Diclozoline + TX, Dicriphos + TX, Diclosimet + TX, Diclomedin + TX, Dichloran + TX, Dicrezyl + TX, Dicyclanil + TX, Dicyclopentadiene + TX, Dieldrin + TX, Dienochlor + TX, Dietofencarb + TX, Diethyl 5-methylpyrazole-3-ylphosphate + TX, Diethyltoluamide + TX, Diphenacome + TX, Difenoconazole + TX, Difethiaron + TX, Diflovidazine + TX, Diglyphus isaea ISAEA) + TX, Dilor + TX, Dimatif + TX, Dimefluthrin + TX, Dimefox + TX, Dimethane + TX, Dimethyrimol + TX, Dimethomorph + TX, Dimethrin + TX, Dimethylcalvert + TX, Dimethyl phthalate + TX, Dimethylvinphos + TX, Dimethilane + TX, Dimoxystrobin + TX, Dynex + TX, Dynex-Dicrexin + TX, Diniconazole + TX, Dinocap-4 + TX, Dinocap-6 + TX, Dinocton + TX, Dinopenton + TX, Dinoprop + TX, Dinosam + TX, Dino Cebu + TX, Dinosulfone + TX, Dinoterbone + TX, Geophenolan + TX, Dioxabenzophos + TX, Dioxathion + TX, Diphacinone + TX, Diphenylsulfone + TX, Dipimethitron + TX, Dipirithione + TX, Disparure + TX, Disulfiram + TX, Dithianone + TX, Diticlophos + TX, DNOC + TX, Dodeca-8-en-1-ylacetate + TX, Dodeca-9-en-1-ylacetate + TX, Dodeca-8 + TX, Dodemorph + TX, Dodicine + TX, Dozin + TX, Dofenapine + TX, Dominicalle
+TX, Doramectin +TX, DSP +TX, d-Tetramethrin +TX, Ecdysterone +TX, Edifenphos +TX, EI 1642 +TX, EMPC +TX, Encarsia formosa +TX, Endotar +TX, Endothion +TX, Enestrobrin +TX, Enoxastrobin +TX, EPBP +TX, Epoxyconazole +TX, Eprinomectin +TX, Eretomocerus eremicus +TX, Ergocalciferol +TX, Etaphos +TX, Etaboxam +TX, Ethiofencarb +TX, Ethyrimol +TX, Ethoate-methyl +TX, Ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoropropane-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the method described in International Publication No. 2020/056090) + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the method described in International Publication No. 2020/056090) + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared from the method described in International Publication No. 2018/158365) + TX, ethyl 4-methyloctanoate + TX, ethyl formate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, etridiazole + TX, etrimphos + TX, eugenol + TX, EXD + TX, famoxadone + TX, farnesol + TX, farnesol and Loridol + TX, Fenamidom + TX, Phenaminosulf + TX, Phenaminestrobin + TX, Phenalimol + TX, Phenazaflor + TX, Fenbuconazole + TX, Fenbutatine oxide + TX, Fenchlorfos + TX, Phenetacarb + TX, Fenflam + TX, Fenhexamide + TX, Fenitrothion + TX, Phenotiocarb + TX, Phenoxacrim + TX, Phenoxanil + TX, Fenpiclonil + TX, Fenpicoxamide + TX, Fenpyritrin + TX, Fenpropidine + TX, Fenpropimorph + TX, Fenpyrad + TX X, Fenpyrazamine + TX, Fenpyroximate + TX, Fenson + TX, Fensulfothione + TX, Fenthion + TX, Fenthion-ethyl + TX, Fentin + TX, Fentriphanil + TX, Ferbam + TX, Ferimzon + TX, Iron(III) phosphate + TX, Furocumafen + TX, Floryl picoxamide + TX, Fluazinam + TX, Flubeneteram + TX, Flubendimine + TX, Flucoflon + TX, Flucycloxurone + TX, Fludioxonil + TX, Fluenetil + TX, Fluphenoxadiazam + TX, Fluphenoxystrobin + TX, Fluindapir + TX, Flumethylsulfolim + TX, Flumorph + TX, Fluopicolide + TX, Fluopimomide + TX, Fluopyram + TX, Fluolbenzide + TX, Fluoroacetamide + TX, Fluoroimide + TX, Fluoxapiproline + TX, Fluoxastrobin + TX, Fluoxythioconazole + TX, Flupropazine + TX, Flupropazine hydrochloride + TX, Fluquinconazole + TX, Flusilazole + TX, Flusulfamide + TX, Fluthianil + TX, Flutolanil + TX, Flutriafor + TX, Fluxapiroxad + TX, FMC 1137+TX, Forpet+TX, Formaldehyde+TX, Formetanate+TX, Formetanate hydrochloride+TX, Formparanate+TX, Fosetyl-aluminum+TX, Fosmethilan+TX, Fosspire+TX, Fosthietan+TX, Frontalin+TX, Fuberidazole+TX, Flalaxil+TX, Flamethopyr+TX, Flathiocarb+TX, Furethrin+TX, Furfural+TX, Ga Nma-HCH+TX, Gliodin+TX, Grandolure+TX, Grandolure I+TX, Grandolure II+TX, Grandolure III+TX, Grandolure IV+TX, Guazatin+TX, Guazatin Acetate+TX, Halfenprox+TX, HCH+TX, Hemel+TX, Hempa+TX, HEOD+TX, Heptachlor+TX, Heterophos+TX, Heterorhabditis bacteriophagora and H. H. megidis + TX, hexaconazole + TX, hexadecylcyclopropane carboxylate + TX, hexalua + TX, hexamide + TX, HHDN + TX, Hippodamia conbergensis (convergens) + TX, Hydralgafen + TX, Slaked lime + TX, Hydrogen cyanide + TX, Himexazole + TX, Hikincarb + TX, Imanin + TX, Imazalil + TX, Imibenconazole + TX, Iminoctadine + TX, Impulfluxam + TX, Ipconazole + TX, Ipfentrifluconazole + TX, Ipflufenoquine + TX, Iprobenphos + TX, Iprodione + TX, Iprovalicarb + TX, Ipsdienol + TX, Iposenol + TX, IPSP + TX, Isamidophos + TX, Isazofos + TX, Isobenzane + TX, Isocarbophos + TX, Isodrine + TX X, Isofenphos + TX, Isofetamide + TX, Isoflucipram + TX, Isolan + TX, Isoprothiolan + TX, Isopyrazam + TX, Isothianil + TX, Isoxathion + TX, Japonilua + TX, Jasmolin I + TX, Jasmolin II + TX, Iodophenphos + TX, Juvenile Hormone I + TX, Juvenile Hormone II + TX, Juvenile Hormone III + TX, Cadeslin + TX, Kasugamycin + TX, Kasugamycin Hydrochloride Hydrate + TX, Kereban + TX, Kinetin + TX, Quinoprene + TX, Kresoxim-Methyl + TX, Lead Arsenate + TX, Leptomastic Dactylopia dactylopii) + TX, leptophos + TX, linden + TX, lineatin + TX, lilimphos + TX, litolua + TX, lupulua + TX, rubenmixianan + TX, lithidathione + TX, Macrolophus caliginosus + TX, magnesium phosphide + TX, maronoben + TX, Mamestra brassicae Brassicae) NPV + TX, Mankapper + TX, Mancozeb + TX, Mandestrobin + TX, Mandipropamide + TX, Maneb + TX, Magidox + TX, m-Cumenylmethylcarbamate + TX, Mecarbam + TX, Mecarfon + TX, Medrua + TX, Mefentrifluconazole + TX, Megatomoic acid + TX, Menazone + TX, Mepanipyrim + TX, Meperfluthrin + TX, Mephosphoran + TX, Mepronil + TX, Mercury(II) oxide + TX, Mercury chloride + TX, Mesulfen + TX, Mesulfenphos + TX, Metalaxyl + TX, Metam + TX, Metam-potassium + TX, Metam-sodium + TX, Metaphycus herborus Helvolus) + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Metallyl picoxamide + TX, Metconazole + TX, Metepa + TX, Methacryphos + TX, Methanesulfonyl fluoride + TX, Metasulfocarb + TX, Methiotepa + TX, Metoclotophos + TX, Methoprene + TX, Methquin-butyl + TX, Methotrin + TX, Methoxychlor + TX, Methyl(Z)-2-(5-cyclohexyl-2-methylphenoxy)- 3-Methoxypropa-2-enoate + TX, Methyl(Z)-2-(5-cyclopentyl-2-methylphenoxy)-3-Methoxypropa-2-enoate (These compounds can be prepared from the method described in International Publication No. 2020/193387) + TX, Methyl(Z)-2-[5-(3-isopropylpyrazole-1-yl)-2-methylphenoxy]-3-Methoxypropa-2-enoate + T X, Methyl(Z)-3-Methoxy-2-[2-Methyl-5-(3-Propylpyrazole-1-yl)phenoxy]prop-2-enoate + TX, Methyl(Z)-3-Methoxy-2-[2-Methyl-5-(4-Propyltriazole-2-yl)phenoxy]prop-2-enoate + TX, Methyl(Z)-3-Methoxy-2-[2-Methyl-5-[3-(Trifluoromethyl)pyrazole-1-yl]pheno [Xy]propa-2-enoate (these compounds can be prepared from the method described in International Publication No. 2020/079111) + TX, methyl(Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazole-2-yl]phenoxy]propa-2-enoate + TX, methyl aphorate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazole-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared from the method described in International Publication No. 2020/097012) + TX, methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazole-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared from the method described in International Publication No. 2020/097012) + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazole-2-yl]-2-methylphenyl]methyl]carbamate + TX, methylchloroform + TX, methylene chloride + TX, methylneodecanamide + TX, methylam + TX, methylcarb + TX, metminostrobin + TX, methoxadiazone + TX, metraphenone + TX, methyltetraprole + TX, MGK 264 + TX, milbemycin oxime + TX, mipahox + TX, myrex + TX, monoclotophos + TX, morphothion + TX, molzide + TX, moxidectin + TX, muscarle + TX, mycrobutanil + TX, microzoline + TX, Myrothecium vercaria Verrucaria composition + TX, N-((1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl)-8-fluoroquinoline-3-carboxamide (These compounds may be prepared from the method described in International Publication No. 2017/153380) + TX, N-((1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl)-8-fluoroquinoline-3-carboxamide (These compounds may be prepared from the method described in International Publication No. 2017/153380) + TX, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamide Zin + TX, N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]-1,2,4-triazole-3-amine (These compounds are described in International Publication No. 2017/055473, International Publication No. 2017/055469, International Publication No. 2017/093348)
(Can be prepared from the method described in International Publication No. 2017/118689) + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX , N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1, 2,4-Oxadiazole-3-yl]benzamide + TX, N-[(Z)-Methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]benzamide + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N-[2-[2,4-Dichlorophenoxy]phenyl]-3-(Difluoromethyl)-1-Methylpyrazole-4-Carboxa Mid + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared from the method described in International Publication No. 2016/202742) + TX, N'-[4-(4,5-dichlorothiazole-2-yl)oxy-2,5 [dimethylphenyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (These compounds may be prepared from the method described in International Publication No. 2015/155075) (This compound can be prepared from the method described in IPCOM000249876D) + TX,N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX,N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX,N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2- [Propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide (These compounds are described in International Publication No. 2018/202428) (These compounds can be prepared from the method described in International Publication No. 2018/228896) + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (These compounds can be prepared from the method described in International Publication No. 2018/228896) + TX, Narbam + TX, Naphthalophos + TX, Nared + TX, Naphthalene + TX, NC-170 + TX, Neodiprion sertifer NPV and N. N. lecontei NPV + TX, nerolidol + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, nickel bis(dimethyl) Dithiocarbamate) + TX, Niclosamide-olamine + TX, Nicotine + TX, Nicotine sulfate + TX, Nifluridide + TX, Nikkomycin + TX, N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, Nichiazine + TX, Nitrapyrine + TX, Nitrilacarb + TX, Nitrilacarb 1 : Zinc chloride complex + TX, Nitrotar-isopropyl + TX, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole Zoll-3-yl]benzenecarbothioamide + TX, norbolmid + TX, nualimol + TX, O,O,O',O'-tetrapropyldithiopyrophosphate + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octylinone + TX, offlace + TX, oleic acid + TX, omethoate + TX, orflourua + TX, Orius species spp.) + TX, Orictalua + TX, Orysastrobin + TX, Ostramon + TX, Oxadixyl + TX, Oxamate + TX, Oxatiapiproline + TX, Oxine Copper + TX, Oxolinic Acid + TX, Oxycarboxyne + TX, Oxideprophos + TX, Oxydisulfon + TX, Oxytetracycline + TX, Paclobutrazol + TX, Pesilomyces fumosoroseus Phytoseurus persimilis + TX, para-dichlorobenzene + TX, parathion + TX, parathion-methyl + TX, pefurazoate + TX, penconazole + TX, pencyclon + TX, penflufen + TX, penflulon + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, penthiopyrad + TX, permethrin + TX, PH 60-38 + TX, phenamacryl + TX, fencapton + TX, fosacetim + TX, fosalon + TX, phosdiphen + TX, phospholan + TX, phosglycine + TX, fosniclor + TX, phosphamidone + TX, phosphine + TX, phosphorus + TX, phoxim-methyl + TX, phthalide + TX, Phytoseurus persimilis Persimilis) + TX, Picarbutrazox + TX, Picalidine + TX, Picoxystrobin + TX, Pindone + TX, Piperazine + TX, Piperonyl butoxide + TX, Piprotal + TX, Pyrimethaphos + TX, Polychlorodicyclopentadiene isomer + TX, Polychloroterpene + TX, Polynactin + TX, Polyoxin + TX, Potassium arsenite + TX, Potassium ethylxanthogenicate + TX, Potassium hydroxyquinoline sulfate + TX, Potassium thiocyanate + TX, pp'-DDT+TX, Precosen I+TX, Precosen II+TX, Precosen III+TX, Primidophos+TX, Probenazole+TX, Prochloraz+TX, Proclonol+TX, Procymidone+TX, Profluthrin+TX, Promacil+TX, Promecarb+TX, Propamocarb+TX, Propiconazole+TX, Propineb+TX, Propoxul+TX, Propropyl isomer+TX, Proquinazide+TX, Protidathion+TX, Prothioconazole+TX, Prothiophos + TX, Protoate + TX, Pidiflumetofen + TX, Piraclostrobin + TX, Piramethostrobin + TX, Piraoxystrobin + TX, Pirapropoin + TX, Pyraziflumid + TX, Pirazophos + TX, Pyrethmetrin + TX, Pyrethrin I + TX, Pyrethrin II + TX, Pyrethrin + TX, Pyribencarb + TX, Pyridaclomethyl + TX, Pyridafenthion + TX, Pyridine-4-amine + TX, Pyriphenox + TX, Pyrimethanil + TX , Pirimitate + TX, Pirimorph + TX, Pyrinulone + TX, Pyriophenone + TX, Pyrisoxazole + TX, Pyrroquilon + TX, Quasia + TX, Quinalphos + TX, Quinalphos-methyl + TX, Quinoclamine + TX, Quinofumerine + TX, Quinonamide + TX, Quinotion + TX, Quinoxifen + TX, Quinthiophos + TX, Quintozen + TX, R-1492 + TX, Lafoxanide + TX, Resmethrin + TX, Reynoutria saccharinensis Sachalinensis extract + TX, Ribavirin + TX, R-metalaxyl + TX, Rotenone + TX, Lianya + TX, Lianodine + TX, S421 + TX, Sabajira + TX, Shuladan + TX, Siriloside + TX, Seboctylamine + TX, Sebufos + TX, Sedaxane + TX, Selamectin + TX, Sesamex + TX, Sesasmolin + TX, SI-0009 + TX, Siguru + TX, Simazine + TX, Simeko Nasol + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium fluoroacetate + TX, Sodium hexafluorosilicate + TX, Sodium pentachlorophenoxide + TX, Sodium selenate + TX, Sodium tetrathiocarbonate + TX, Sodium thiocyanate + TX, Sofamide + TX, Solzidine + TX, Spiroxamine + TX, SSI-121 + TX, Steinernema viviones bibionis) + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema species (spp.) + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Strychnine + TX, Sulcatol + TX, Sulcoflon + TX, Sulcoflon-sodium + TX, Sulfiram + TX, Sulfuramide + TX, Sulfotep + TX, Sulfoxide + TX, Sulfur + TX, Sulfuryl fluoride + TX, Sulprophos + TX, Tar oil + TX, Tau-fluvalinate + TX, Tadimucarb + TX, TDE + TX, Tebuconazole + TX, Tebufloquine + TX, Tebupyrimphos + TX, Tecrophthalam + TX, Temephos + TX, Tepa + TX, TEPP + TX, Teraret Phosphorus + TX, Turbam + TX, tert-butyl N-[6-[[[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, tetrachloroethane + TX, tetrachlorothiophene + TX, tetraconazole + TX, tetradeca-11-en-1-yl acetate + TX, tetradiphon + TX, tetramethylfluthrin + TX, tetrasul + TX, thallium sulfate + TX, thiabendazole + TX, thiaphenox + TX, thiapronil + TX, ticlophos + TX, tifluzamide + TX, thiocarboxime + TX, thiocycline
Ram + TX, Thiocyclam hydrogen oxalate + TX, Thiodiazole copper + TX, Thiofanox + TX, Thiohempa + TX, Thiomersal + TX, Thiometon + TX, Thionadin + TX, Thiophanate + TX, Thiophanate-methyl + TX, Thioquinox + TX, Thiosultap + TX, Thiosultap-sodium + TX, Thiotepa + TX, Thyram + TX, Turingiencin + TX, Thiazinyl + TX, Torcrophos-methyl + TX, Tol Procarb + TX, Trilfluanide + TX, Tralomethrin + TX, Transpermethrin + TX, Tretamine + TX, Triadimephon + TX, Triadimenol + TX, Triamiphos + TX, Triatene + TX, Triazamate + TX, Triazophos + TX, Triazoxide + TX, Triazurone + TX, Tributyltin oxide + TX, Trichlormethaphos-3 + TX, Trichloronate + TX, Trichogramma species spp.) + TX, Triclopyricarb + TX, Tricyclazole + TX, Tridemorph + TX, Triphenmorph + TX, Triphenofos + TX, Trifloxystrobin + TX, Triflumizole + TX, Triforine + TX, Trimedrua + TX, Trimedrua A + TX, Trimedrua B1 + TX, Trimedrua B2 + TX, Trimedrua C + TX, Trimetacarb + TX, Trinactin + TX, Trinexapac + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Triplene + TX, Triticonazole + TX, Tranquol + TX, Typhlodromeus osidentalis occidentalis + TX, uredepa + TX, validamycin + TX, valifenarate + TX, bamidthion + TX, vaniliprole + TX, veratridine + TX, veratrin + TX, berbutin + TX, Verticillium lecanii + TX, vinclozoline + TX, warfarin + TX, XMC + TX, xylenol + TX, zeatin + TX, zetametrin + TX, zhongshenmycin + TX, zinc naphthenate + TX, zinc phosphide + TX, thiazole zinc + TX, zineb + TX, ziraprofos + TX;
Acinetobacter lwoffii + TX, Acremonium alternatum + TX, Acremonium cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophies orana granulopathy virus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter Radiobacter strain K84 (Galltroll-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destrüens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus sp. + TX, Aureobasidium pullulans + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cyst (Bionatural Blooming) Blossoms® + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus circulans + TX, Bacillus filmus Bacillus firmus) (BioSafe®, BioNem-WP®) In particular strain CNMC1-1582 (e.g., VOTIVO® manufactured by BASF SE) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus licheniformis strain HB-2 (Biostart®, formerly Rhizoboost®) + TX, Bacillus macerans + TX, Bacillus marismorzii marismortui) + TX, Bacillus megatherium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus genus + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain GB34 (Yield) Shield® + TX, Bacillus pumilus strain QST 2808 (Sonata®, Ballad Plus®) + TX, Bacillus sphaericus (VectoLex®) + TX, Bacillus species + TX, Bacillus species AQ175 + TX, Bacillus species AQ177 + TX, Bacillus species spp.) stock AQ178 + TX, Bacillus subtilis stock AQ153 + TX, Bacillus subtilis stock AQ743 + TX, Bacillus subtilis stock QST 713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis stock QST 714 (JAZZ®) + TX, Bacillus subtilis Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®)+TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP®, Astuto®, Dipel WP (registered trademark), Biobit (registered trademark), Foray (registered trademark)) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone (registered trademark)) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF/3P (registered trademark)) + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis tenebrionis (Novodor®, BtBooster) + TX, Bacillus thuringiensis var. aizawai (XenTari®, DiPel®) + TX, Bacteria spp. (GROWMEND®, GROWSWEET®, Shootup®) + TX, Clavipacter misiganensis Bacteriophage of michiganensis (AgriPhage®, Bakflor®) + TX, Beauveria bassiana (Beaugenetic®, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES®, Mycotrol O®, BotaniGuard®) + TX, Beauveria brongnatiii (Engerlingspilz®, Schweizer) Beauveria (registered trademark), Melocont (registered trademark)) + TX, Beauveria species (Beauveria sp.) + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax (registered trademark)) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny (registered trademark), Intercept (registered trademark), Blue Circle (registered trademark)) + TX, Burkholderia gradi (Burkholderia Candida gladii) + TX, Burkholderia gladioli + TX, Burkholderia sp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata Candida glabrata) + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida cytoana (Candida) saitoana) (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea davisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum globesum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium chlorocephalum + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium species spp. ) + TX, Cladosporium tenuissimum (Cladosporium tenuissimum)
nuissimum) + TX, Chronostachys rosea (EndoFine®) + TX, Colletotrichum actatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola humicola) + TX, Cryptococcus infilmominiatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulosis virus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomononella granulosis virus (CYD-X®, Madex®, Madex® Plus, Madex Max, Carpovirusine (registered trademark)) + TX, Cylindrobasidium laeve (Stumpout (registered trademark)) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Dretchlera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophthora virlenta Virulenta (Vektor®) + TX, Epicoccum nigram + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum oxysporum) (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium species + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium species spp.) (SoilGard®) + TX, Gliocladium virens (SoilGard®) + TX, Granulopathy virus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola (Halomonas subglaciescola) + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nuclear polyhedron virus (Helicoverex®) + TX, Helicoverpa zea nuclear polyhedron virus (Gemstar®) + TX, Isaria fumosorosea (formerly Paecilomyces fumosoroseus) PFR-97 (registered trademark, PreFeRal (registered trademark)) + TX, isoflavone formononetin (Myconate (registered trademark)) + TX, Kloeckera apiculata + TX, Kloeckera sp. + TX, Lagenidium giganteum (Laginex (registered trademark)) + TX, Lecanicillium lecanii (formerly Verticillium lecanii) Conidia of strain KV01 (formerly known as lecanii) (Mycotal® registered trademark) (e.g., Vertalec® + TX by Koppert/Arista, Lecanicillium longisporum (Vertiblaster®)) + TX, Lecanicillium muscarium (Vertikil®)) + TX, Lymantria Dispar nuclear polyhedron disease virus (Disparvirus®) + TX, Marinococcus halophilus Halophilus) + TX, Meira geulakonigii + TX, Metalrhizium anisoplae (Destruxin WP®) + TX, Metalrhizium anisoplae (Met52®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium zimerum dimerum) (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscodor®) + TX, Muscodor roseus, especially strain A3-5 (accession number NRRL 30548) + TX, Mycorrhizae spp. (AMykor®, Root) Maximizer® + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®, BROS PLUS®) + TX, Ophiostomia piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paecilomyces linacinus linacinus) (Biostat WP®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BrightBan C9-1®) + TX, Pantoea species + TX, Pasteuria nishizawae, especially strain Pn1 (Syngenta/ChemChina CLARIVA); + TX, Pasteuria species spp.) (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purprogenum purpurogenum) + TX, Penicillium sp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, Phosphomeal® + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala anomala) + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less) Biofungicide® + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescein (Zequanox®) + TX, Pseudomonas fluorescein strain A506 (BrightBan) A506 (registered trademark) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save (registered trademark)) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex) L (registered trademark) + TX, Puccinia canaliculata + T
X, Puccinia thlaspes (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periprocum + TX, Ranella aquatilis + TX, Ranella species spp.) + TX, Rhizobia (Dormal®, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis graminis) + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp. + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor (SARRITOR®) + TX, Sclerotinia minor (Sclerotinia minor) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Soldaria fimicola + TX, Spodoptera exigua exigua) Polyhedra disease virus (Spod-X®, Spexit®) + TX, Spodoptera littoralis Polyhedra disease virus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotropomonas maltophilia + TX, Streptomyces albaduncus + TX, Streptomyces exafoliates exfoliates) + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces hygroscopicus + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus) WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma gamsii) (Tenet®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P®, PlantShield HC®, RootShield®, Trianum-G®) + TX, Trichoderma harzianum Harzianum) T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma species (Trichoderma sp.) LC 52 (Sentinel®) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp. + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum atrum) + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplemental micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibacrillus marismortzii marismortui) + TX, Xanthomonas campestris pv. poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophyllus + TX;
AGNIQUE® MMF + TX, Azadirachtin (PLASMA Neem Oil®, AzaGuard®, MeemAzal®, Molt-X®, e.g., Certis, US AZATIN XL) + TX, Vegetable IGR (Neemazad®, Neemix®) + TX, BugOil® + TX, Canola Oil (Lilly Miller Vegol®) + TX, American antlion (Chenopodium ambrosioides near Ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, Labiatae essential oil (Botania®) + TX, Neem oil extract (Trilogy®) + TX, Clove, rosemary, peppermint and thyme oil extract (Garden Insect Killer®) + TX, Garlic + TX, Glycine betaine (Greenstim®) + TX, Kaolin (Screen®) + TX, Lemongrass oil (GreenMatch®) + TX, Melaleuca alternifolia Alternifolia extract (also known as tea tree oil) (Timorex Gold®) + TX, clove peppermint garlic oil and mint mixture (Soil Shot®) + TX, clove rosemary and peppermint extract mixture (EF 400®) + TX, rosemary sesame peppermint thyme and cinnamon extract mixture (EF 300®) + TX, neem oil + TX, Nepeta cataria (catnip oil) + TX, Nepeta catalina (Nepeta Catarina) + TX, Nicotine + TX, Oregano oil (MossBaster®) + TX, Sesame oil (Nematon®) + TX, Pine oil (Retenol®) + TX, Pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia®, Sakalia®) + TX, Rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, Soybean oil (Ortho ecosense® + TX, brown algae storage glucam (Laminarin®) + TX, thyme oil + TX;
(E,Z)-7,9-dodecadiene-1-yl acetate + TX, (E,Z,Z)-3,8,11-tetradecatrieninyl acetate + TX, (Z,Z,E)-7,11,13-hexadecatrienal + TX, 2-methyl-1-butanol + TX, Biolure® + TX, blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, calcium acetate + TX, Check-Mate® + TX, Codling Moth pheromone (Paramound Dispenser-(CM)/Isomate C-Plus(registered trademark)) + TX, Entostat powder (extract from palm trees) (Exosex CM(registered trademark)) + TX, Grape Berry Moth pheromone (3M MEC-GBM Sprayable Pheromone(registered trademark)) + TX, Lavandryl senecioate + TX, Leafroller pheromone (3M MEC-LR Sprayable Pheromone(registered trademark)) + TX, Muscamone (Snip7 Fly Bait(registered trademark)) + TX, Pear fruit moth pheromone (Oriental Fruit Moth (3M Oriental Fruit Moth Sprayable Pheromone®) + TX, Peachtree Borer pheromone (Isomate-P®) + TX, Scenturion® + TX, Starbar Premium Fly Bait® + TX, Tomato Pinworm pheromone (3M Sprayable Pheromone®) + TX;
Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fusicoris fuscicollis) + TX, Amblyseius Andersoni (Anderline®, Andersoni-System®) + TX, Amblyseius californicus (Amblyline®, Spical®) + TX, Amblyseius cucumeris (Thripex®, Bugline cucumeris®) + TX, Amblyseius falakis (Amblylseius Fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii®, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fussiventris fuscientris) + TX, Anagyrus kamari + TX, Anagyrus loecki + TX, Anagyrus pseudococcus (Citripar®) + TX, Anicetus benefices + TX, Anisotroperomalus calandrae + TX, Anthocoris nemoralis nemoralis) (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline®, Aphiline®), + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Aphelinus-System®) + TX, Aphidius ervi) (Ervipar®) + TX, Aphysius gifuensis + TX, Aphysius matricariae (Aphipar-M®) + TX, Aphydoletes Aphidimyza (Aphidend®, Aphydoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hegenowii hagenowii) + TX, Atheta coriaria (Staphylline®) + TX, Bombus spp. + TX, Bombus terrestris (Bombus terrestris) (Beeline®, Tripol®) + TX, Bombus terrestris (Natupol Beehive®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus nigritus) + TX, Chrysoperla carnea (Chrysoline®, Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospirus ingenuus + TX, Cirrospirus quadristriatus + TX, Citrosticus phyllocnistoides + TX, Closterocerus chamaeleon chamaeleon) + TX, Closterocerus sp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lysimnia + TX, Cotesia flavipes + TX, Cotesia plutellae) + TX, Cryptoemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus psylus pusillus) + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicauda + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea (Diminex®, Miglyphus®, Digline®) + TX, Diversinervus genus spp.) + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max®, Encarline®, En-Strip®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini siphonini) + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Enermix®, Ercal®, Eretline e®, Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar®, Eretline m®) + TX, Eretmocerus siphonini (Eretmocerus siphonini) + TX, Exochomus quadripustulatus + TX, Feltielella acarisuga (Feltiline®) + TX, Feltielella acarisuga (Spiden®) + TX, Phopius arisanus + TX, Phopius ceratitivorus + TX, Formononetin (Wireless Beehome®) + TX, Franklinothrips Vespiformis (Vespop®) + TX, Gallendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis bacteriophaga (NemaShield) HB (registered trademark), Nemaseek (registered trademark), Terranem-Nam (registered trademark), Terranem (registered trademark), Larvanem (registered trademark), B-Green (registered trademark), NemAttack (registered trademark), Nematop (registered trademark)) + TX, Heterorhabditis megidis (Nemasys H (registered trademark), BioNem H (registered trademark), Exhibitline hm (registered trademark), Larvanem-M (registered trademark)) + TX, Heterorhabditis spp. (Lawn Patrol (registered trademark)) + TX, Hippodamia conbergensis (Hippodamia (convergens) + TX, Hypoaspis aculeifer (Aculeifer-System®, Entomite-A®) + TX, Hypoaspis miles (Hypoline m®, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus fluccissimus + TX, Lemophagus erabundus errabundus) + TX, Leptomastidea abnormis + TX, Leptomasticus dactylopii (Leptopar®) + TX, Leptomasticus epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia Caesar caesar) (Natury®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N®, Macroline c®, Mirical®) + TX, Mesoseirus
Mesoseulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameloni Cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug®, Nesibug®) + TX, Ophylla aenecens aenescens) (Biofly®) + TX, American dwarf stink bug (Orius insidiosus) (Thripor-I®, Oriline i®) + TX, El dwarf stink bug (Orius laevigatus) (Thripor-L®, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Continental dwarf stink bug (Orius strigicollis) (Thripor-S®) + TX, Pauesia juniperolum (Pauesia Juniperorum) + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymasticus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex®, Phytoline p(registered trademark)) + TX, Podisus maculiventris (Podisus(registered trademark)) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudreptomasticus mexicana Mexicana) + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrasticus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decolate + TX, Semielacher petiolatus + TX, Sitobion avenae avenae) (Ervibank®) + TX, Steinernema carpocapsae (Nematac C®, Millenium®, BioNem C®, NemAttack®, Nemastar®, Capsanem®) + TX, Steinernema feltiae (NemaShield®, Nemasys F®, BioNem F®, Steinernema-System®, NemAttack®, Nemaplus®, Exhibitline sf (registered trademark), Scia-rid (registered trademark), Entonem (registered trademark)) + TX, Steinernema kraussei (Nemasys L (registered trademark), BioNem L (registered trademark), Exhibitline srb (registered trademark)) + TX, Steinernema riobrave (BioVector (registered trademark), BioVektor (registered trademark)) + TX, Steinernema scapterisci (Nematac S (registered trademark)) + TX, Steinernema species ) + TX, Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctilum (Stethorus®) + TX, Tamarixia radiata + TX, Tetrastichus setifer + TX, Tripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma Trichogramma brassicae (Tricholine b (registered trademark)) + TX, Trichogramma brassicae (Tricho-Strip (registered trademark)) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma plethiosum (Trichogramma pretiosum) + TX, Xanthopimpla stemmator + TX;
Abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, CAS number: 2643947-26-4 + TX, Chondrostereum purpureum (Chontro Paste®) + TX, Colletotrichum gleosporioides (Collego®) + TX, Copper octanoate (Cueva®) + TX, Delta Trap (Trapline d®) + TX, Erwinia amyrobola amylovora) (Harpin) (ProAct® + TX, Ni-HIBIT Gold CST®) + TX, fatty acids derived from natural by-products of extra virgin olive oil (FLIPPER®) + TX, ferric phosphate (Ferri-phosphate) (Ferramol®) + TX, funnel trap (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, homo-brassonolide + TX, iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail) Bait (registered trademark) + TX, MCP hail trap (Trapline f (registered trademark)) + TX, Microctonus hyperodae + TX, Mycolectodiscus terrestris (Des-X (registered trademark)) + TX, Nosema locustae (Semaspore Organic Grasshopper Control (registered trademark)) + TX, Pheromone trap (Thripline ams® + TX, potassium bicarbonate (MilStop®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, potassium salt of fatty acid (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, spider venom + TX, sticky trap (Trapline YF® + TX, Rebell Amarillo®) + TX, SuffOil-X® + TX, trap (Takitrapline y+b®) + TX;
Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) (International Publication No. 2013/034938) + TX, Bacillus pumilus, in particular strain BU F-33 (BASF's CARTISA® registered trademark, EPA registration number 71840-19) + TX, Bacillus subtilis CX-9060, Bacillus sp., in particular accession number Strain D747 with FERM BP-8234 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), U.S. Patent No. 7,094,592 + TX, Bacillus subtilis strain BU1814, (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA of BASF SE) + TX, Bacillus subtilis variety amyloricephasiens with accession number DSM 10271 var. amyloliquefaciens) strain FZB24 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX, Bacillus subtilis, in particular strain QST713/AQ713 (having NRRL accession number B-21661, described in U.S. Patent No. 6,060,051, available from Bayer CropScience LP, U.S. as SERENADE® OPTI or SERENADE® ASO) + TX, Paenibacillus polymixa Paenibacillus strains, particularly strain AC-1 (e.g., TOPSEED® of Green Biotech Company Ltd.) + TX, accession number NRRL B-50972 or accession number NRRL B-67129, International Publication No. 2016/154297 + TX, Pantoea agglomerans, particularly strain E325 (accession number NRRL B-21856) (BLOOMTIME BIOLOGICAL® FD BIOPESTICIDE as Northwest Agri Products available) + TX, Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) + TX;
Aureobasidium pullulans, particularly spores of strain DSM14940, spores of strain DSM14941, or mixtures of spores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX; Pseudozyma aphidis (Yissum Research Development Company of the Hebrew University of (Disclosed in International Publication No. 2011/151819 by Jerusalem) + TX; Saccharomyces cerevisiae, in particular strains CNCM numbers 1-3936, 1-3937, 1-3938 or 1-3939 from Lesaffre et Compagnie, FR (International Publication No. 2010/086790) + TX;
Agrobacterium radiobacter strain K84 (e.g., AgBioChem, GALLTROL-A® of CA) + TX, Bacillus amyloricefaciens isolate B246 (e.g., AVOGREEN® of University of Pretoria) + TX, Bacillus amyloricefaciens strain F727 (also known as strain MBI110) (NRRL accession number) B-50768, International Publication No. 2014/028521 (STARGUS®, a registered trademark of Marrone Bio Innovations) + TX, Bacillus amyloricefaciens strain FZB42, accession number DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloricefaciens, in particular strain D747 (available as Double Nickel® from Kumiai Chemical Industry Co., Ltd., accession number FERM) Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP)) of FMC Corporation, having BP-8234 (US Patent No. 7,094,592) + TX, Bacillus licheniformis, in particular stock SB3086 having accession number ATCC 55406, International Publication No. 2003/000051 (from Novozymes) ECOGUARD® (available as Biofungicide and GREEN RELEAF®) + TX, Bacillus methylotropicus strain BAC-9912 (from Chinese Academy of Sciences' Institute of Applied Ecology) + TX, Bacillus mycoides, isolate with accession number B-30890 (available as BMJ TGAI® or WG and LifeGard® from Certis USA LLC) + TX, Bacillus pumilus Bacillus pumilus, in particular strain GB34 (available from Bayer AG, DE as Yield Shield®) + TX, Bacillus pumilus, in particular strain QST2808 (available from Bayer CropScience LP, US as SONATA®, with accession number NRRL B-30087, as described in US Patent No. 6,245,551) + TX, Bacillus subtilis CX-9060 + TX from Certis USA LLC, Bacillus subtilis IAB/BS03 (STK Bio-Ag Technologies' AVIV®, Idai Nature's PORTENTO® + TX, Bacillus subtilis KTSB strain (Donaghys' FOLIACTIVE®) + TX, Bacillus subtilis strain BU1814 (available as BASF SE's VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA) + TX, Bacillus subtilis strain GB03 (from Bayer AG, DE) (Available as Kodiak®) + TX, Bacillus subtilis strain MBI 600 (Available as SUBTIREX from BASF SE), having accession number NRRL B-50595, U.S. Patent No. 5,061,495 + TX, Bacillus subtilis strain Y1336 (Available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under registration numbers 4764, 5454, 5096 and 5277) + TX, Bacillus subtilis variety amyloricephaciens (Bacillus subtilis) having accession number DSM 10271 Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX, Bacillus subtilis Y1336 (available from Biobac® WP by Bion-Tech, Taiwan, registered in Taiwan as a biological fungicide with registration numbers 4764, 5454, 5096 and 5277) + TX, Paenibacillus epiphyticus of BASF SE Paenibacillus polymyxa ssp. plantarum (International Publication No. 2016/020371) + TX, Paenibacillus sp. strain with accession number NRRL B-50972 or accession number NRRL B-67129, International Publication No. 2016/154297 + TX, Pseudomonas chlororaphis strain AFS009, accession number NRRL International Publication No. 2017/019448 (e.g., AgBiome Innovations, HOWLER® and ZIO® in the US) + TX, Pseudomonas chlororaphis, particularly strain MA342 (e.g., CEDOMON®, CERALL® and CEDRESS® by Bioagri and Koppert) + TX, Pseudomonas fluorescens strain A506 (e.g., BLIGHTBAN® A506 by NuFarm) + TX, Pseudomonas proradicus PRORADIX) (e.g., PRORADIX® of Sourcon Padena) + TX, Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession number DSM 7206) (See MYCOSTOP® of Verdera, PREFENCE® of BioWorks, Crop Protection 2006, 25, 468-475) + TX, Streptomyces lidicus Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (Novozymes' ACTINO-IRON® and ACTINOVATE® registered trademarks) + TX;
Trichoderma atroviride strain T11 (IMI352941/CECT20498) + TX, Ampelomyces quisqualis strain AQ10 (e.g., AQ 10® by IntrachemBio Italia) + TX having accession number CNCM 1-807, Ampelomyces quisqualis, especially strain AQ 10 (e.g., AQ 10® by IntrachemBio Italia) + TX, Aspergillus flavus Aureobasidium pullulans, particularly strain DSM 14941 budding spores + TX, Aureobasidium pullulans, particularly strain DSM 14940 budding spores + TX, Aureobasidium pullulans, particularly strain DSM 14940 and DSM 14941 Budding spore mixture (e.g., bio-ferm, Botector® of CH) + TX, Chaetomium cupreum (accession number CABI 353812) (e.g., BIOKUPRUM® of AgriLife) + TX, Chaetomium globosum (available as RIVADIOM® by Rivale) + TX, Cladosporium cladosporioides, accession number Strain H39 having CBS122244, U.S. Patent Application Publication No. 2010/0291039 (by Stichting Dienst Landbouwkundig Onderzoek) + TX, Coniothyrium minitans, in particular strain CON/M/91-8 (accession number DSM9660, e.g., Contans® of Bayer CropScience Biologics GmbH) + TX, Cryptococcus flavecens, strain 3C (NRRL Y-50378), + TX, Dactylaria candida Candida), Dilophosphora alopecuri (available as TWIST FUNGUS®), Fusarium oxysporum, strain Fo47 (available as FUSACLEAN® by Natural Plant Protection) + TX, Gliocladium catenulatum (synonym: Chronostachys rosea f. catenulate), strain J1446 (e.g., by Lallemand) Prestop® + TX, Gliocladium roseum (also known as Chronostachys rosea f rosea) strain IK726 (Jensen DF, et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Chronostachys rosea strain 'IK726', Australian Plant) Pathol. 2007, 36(2):95-101) + TX, Gliocladium roseum (also known as Chronostachys rosea f rosea), particularly strain 321U from Adjuvants Plus, Xue A.G. (Efficacy of Chronostachys rosea strain ACM941 and fungide seed treatments for controlling the root to complex of field pea + TX, Can Jour Plant Strains such as ACM941+TX, Metschnikowia fructicola, particularly strain NRRL Y-30752+TX, Microsphaeropsis ochracea, Penicillium steckii (DSM 27859, International Publication No. 2015/067800)+TX, and Trichoderma asperelm with accession number CABI CC IMI 392716, as disclosed in Sci 2003+TX, 83(3):519-524. A mixture of strain ICC 012 (also known as Trichoderma harzianum, ICC012) and strain ICC 080 (e.g., BIO-TAM® of Isagro USA, Inc. or BIODERMA® of Agrobiosol de Mexico, S.A. de C.V.) of Trichoderma gamsii (formerly T. viride) with accession number IMI 392151 + TX, Penicillium vermiculum vermiculatum) + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C of Danstar Ferment) + TX, Pseudozyma flocculosa strain PF-A22 UL (available as SPORODEX® L of Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell wall (CEREVISANE® of Lesaffre, BASF SE's ROMEO (registered trademark)) + TX, Lesaffre et Compagnie, FR's Saccharomyces cerevisiae strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (International Publication No. 2010/086790) + TX, Saccharomyces cerevisiae, especially strain LASO2 (from Agro-Levures et Derives) + TX, Simplicillium lanosoniveum lanosoniveum) + TX, strain T34 (e.g., T34 Biocontroll by Biocontroll Technologies S.L., ES) or strain ICC 012 of Isagro + TX, strain WRL-076 (NRRL Y-30842), U.S. Patent No. 7,579,183 + TX, Talaromyces flavus strain V117b + TX, Trichoderma asperelloides JM41R (accession number NRRL B-50759) (TRICHO of BASF SE) PLUS (registered trademark)) + TX, Trichoderma asperellum, in particular strain SKT-1 having accession number FERM P-16510 (e.g., ECO-HOPE (registered trademark) of Kumiai Chemical Industry Co., Ltd.) + TX, Trichoderma asperellum, in particular strain kd (e.g., T-Gro of Andermatt Biocontrol) + TX, Trichoderma atroviride strain 77B (T77 of Andermatt Biocontrol) + TX, Trichoderma atroviride strain ATCC 20476 (IMI 206040) + TX, Trichoderma atroviride strain LC52 (e.g., Tenet from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain LU132 (e.g., Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain NMI no. V08/002388 + TX, Trichoderma atroviride Trichoderma atroviride strain NMI no. V08/002389 + TX, Trichoderma atroviride strain NMI no. V08/002390 + TX, Trichoderma atroviride strain no. V08/002387 + TX, Trichoderma atroviride strain SKT-1 (FERM P-16510), Japanese Patent Publication (Published) No. 11-253151 + TX, Trichoderma atroviride strain SKT-2 (FERM P-16511), Japanese Patent Publication No. 11-253151 + TX, Trichoderma atroviride strain SKT-3 (FERM P-17021), Japanese Patent Publication No. 11-253151 + TX, Trichoderma atroviride, in particular strain SC1 (accession number CBS 122089, International Publication No. 2009/116106 and U.S. Patent No. 8,431,120 (from Bi-PA)) + TX, Trichoderma atroviride, strain CNCM 1-1237 (e.g., Agrauxine, FR's Esquive® WP) + TX, Trichoderma fertil (e.g., BASF's product TrichoPlus) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (AGROBIOSOL DE MEXICO, S.A.DE) Available as BIODERMA (registered trademark) by C.V.), +TX, Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g., BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.) +TX, Trichoderma harmatum +TX, accessories
Trichoderma harmatum + TX, Trichoderma harzianum + TX, Trichoderma harzianum rifai T39 (e.g., Makhtesim, Trichodex® registered trademark of the US) + TX, Trichoderma harzianum strain Cepa Simb T5 (from Simbiose Agro) + TX, Trichoderma harzianum strain DB 103 (Dagutat) (Available from Biolab as T-GRO® 7456) + TX, Trichoderma harcianum strain ITEM 908 (e.g., Koppert's Trianum-P) + TX, Trichoderma harcianum strain T-22 (e.g., Andermatt Biocontrol or Koppert's Trianum-P) + TX, Trichoderma harcianum strain TH35 (e.g., Mycontrol's Root-Pro) + TX, Trichoderma polysporum Trichoderma stromaticum (Trichoderma virens) (also known as Gliocladium virens) particularly strain GL-21 (e.g., SoilGard by Certis, US) + TX, formerly known as Gliocladium virens Trichoderma virens strain G-41 (accession number ATCC 20906) (e.g., BioWorks, ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP in the US) + TX, Trichoderma viride strain B35 (Pietre et al., 1993, Zesz. Nauk. A R w Szczecinie 161:125-137) + TX, Trichoderma viride Verticillium audemansii strain U3 (e.g., BOTRY-ZEN® by Bottle-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.) + TX, accession number WCS850, deposited with the Central Bureau for Fungi Cultures, has the following characteristics: albo-atrum) (formerly V. dahliae) strain WCS850 (e.g., DUTCH TRIG® by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX;
A mixture of Azotobacter vinelandii and Clostridium pasteurianum (available from Agrinos as INVIGORATE®) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available from FMC Corporation as QUARTZO® (WG), PRESENCE® (WP)) + TX, Azorhizobium caurinodance Azospirillum caulinodans), especially strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR®, KALO, Inc.) + TX, Azospirillum lipoferum (e.g., VERTEX-IF®, TerraMax, Inc.) + TX, Azotobacter chlorococcum, especially strain H23 + TX, Azotobacter vinelandii, especially strain ATCC 12837+TX, Bacillus amyloricefaciens BS27 (Accession number NRRL B-5015)+TX, Bacillus amyloricefaciens, especially strain FZB42 (e.g., RHIZOVITAL® of ABiTEP, DE)+TX, Bacillus amyloricefaciens, especially strain IN937a+TX, Bacillus amyloricefaciens Bacillus amylolicefaciens pm414 (LOLI-PEPTA®, Biofilm Crop Protection) + TX, Bacillus amylolicefaciens SB3281 (ATCC # PTA-7542, International Publication No. 2017/205258) + TX, Bacillus amylolicefaciens TJ1000 (available from Novozymes as QUIKROOTS®) + TX, Bacillus cereus family member EE128 (NRRL No. B-50917) + TX, Bacillus cereus family member EE349 (NRRL No. B-50928) + TX, Bacillus cereus, especially strain BP01 (ATCC 55675, e.g., Arista Lifescience, MEPICHLOR® of the US) + TX, Bacillus mycoides BT155 (NRRL No. B-50921) + TX, Bacillus mycoides BT46-3 (NRRL No. B-50922) + TX, Bacillus mycoides EE118 (NRRL No. B-50918) + TX, Bacillus mycoides EE141 (NRRL No. B-50916) + TX, Bacillus pumilus, especially strain GB34 (e.g., Bayer Crop Science, DE's YIELD SHIELD®), + TX, Bacillus pumilus, especially strain QST2808 (Accession number NRRL No. B-30087) + TX, Bacillus siamensis, especially strain KCTC 13613T + TX, Bacillus subtilis, especially strain AQ30002 (accession number NRRL No. B-50421 and U.S. Patent Application No. 13/330,576) + TX, Bacillus subtilis, especially strain AQ30004 (NRRL No. B-50455 and U.S. Patent Application No. 13/330,576) + TX, Bacillus subtilis, especially strain MBI 600 (e.g., SUBTILEX® from BASF SE) + TX, Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE) + TX, Bacillus tequilensis strain NII-0943 + TX, Bacillus thuringiensis BT013A (NRRL) No. B-50924) Also known as Bacillus thuringiensis 4Q7+TX, Bradyrhizobium japonicum (e.g., Novozymes' OPTIMIZE®)+TX, Delftia acidovorans, especially strain RAY209 (e.g., Brett Young) Seeds' BIOBOOST®) + TX, Lactobacillus species (e.g., Lactopafi's LACTOPLANT®) + TX, Mesorhizobium cicer (e.g., BASF SE's NODULATOR) + TX, Paenibacillus polymyxa, especially strain AC-1 (e.g., Green Biotech Company Ltd.'s TOPSEED®) + TX, Pseudomonas erginosa aeruginosa) especially strain PN1 + TX, Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum especially bv. bv. viceae strain Z25 (accession number CECT 4585) + TX, Serratia marcescens strain SRM (accession number MTCC 8708) + TX, Sinorhizobium meliloti strain NRG-185-1 (Bayer CropScience's NITRAGIN® GOLD) + TX, Thiobacillus sp. (e.g., Cropaid Ltd UK's CROPAID®) + TX;
Myrothecium verrucaria strain AARC-0255 (e.g., DiTera® by Valent Biosciences) + TX, Penicillium bilaiii strain ATCC 22348 (e.g., JumpStart® by Acceleron BioAg) + TX, Penicillium bilaiii strain ATCC ATCC20851 + TX, Purpureocillium lilacinum (formerly Pesiliomyces lilacinus) (formerly known as lilacinus) strain 251 (AGAL 89/030550, e.g., BioAct of Bayer CropScience Biologics GmbH) + TX, Pythium oligandrum strain DV74 + TX, Pythium oligandrum strain M1 (ATCC 38472, e.g., Polyversum of Bioprepracy, CZ) + TX, Rhizopogon amylopogon (Agri-Enterprise, LLC, formerly Helena Chemical) Myco-Sol (from Company) + TX, Rhizopogon fulvigleba (e.g., Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Talaromyces flavus strain V117b + TX, Trichoderma asperellum strain (Plant Health Products, ZA) + TX, Trichoderma asperellum strain kd (e.g., Andermatt Biocontrol's T-Gro) + TX, Trichoderma atroviride, especially strain no. V08/002387+TX, Trichoderma atroviride strain CNCM 1-1237 (e.g., Agrauxine, Esquive® WP of FR)+TX, Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g., Sentinel of Agrimm Technologies Limited)+TX, Trichoderma atroviride strain no. NMI No. V08/002388+TX, Trichoderma atroviride strain no. NMI No. V08/002389+TX, Trichoderma atroviride strain no. NMI No. V08/002390 + TX, Trichoderma atroviride strain SC1 (described in International Publication No. 2009/116106) + TX, Trichoderma harcianum strain 1295-22 + TX, Trichoderma harcianum strain ITEM 908 + TX, Trichoderma harcianum strain T-22 (e.g., Andermatt Biocontrol or Koppert's Trianum-P from) + TX, Trichoderma harcianum Harzianum strain TSTh20 + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g., Certis, SoilGard® of the USA) + TX, Trichoderma viride strain B35 (Pietre et al., 1993, Zesz. Nauk. A R w Szczecinie 161:125-137) + TX, Verticillium arboatrum albo-atrum) (formerly V. dahliae) strain WCS850 (CBS 276.92, e.g., Dutch Trig from Tree Care Innovations) + TX;
Agrobacterium radiobacter strain K84 (Galltrol, AgBiochem Inc.) + TX, Bacillus amyloliquefaciens, particularly strain PTS-4838 (e.g., Valent Biosciences, AVEO, US) + TX, Bacillus mycoides, isolate J. (For example, BmJ from Certis USA LLC) + TX, Bacillus sphericus, especially serotype H5a5b strain 2362 (strain ABTS-1743) (for example, VECTOLEX® from Valent BioSciences, US) + TX, Bacillus thuringiensis israelensis strain BMP 144 (for example, AQUABAC® from Becker Microbial Products IL) + TX, Bacillus thuringiensis subspecies Aizawai Bacillus thuringiensis subsp. Aizawai strain GC-91 + TX, Bacillus thuringiensis subsp. Aizawai, especially serotype H-7 (e.g., Valent BioSciences, US FLORBAC® WG) + TX, Bacillus thuringiensis subsp. Aizawai, especially strain ABTS-1857 (SD-1372, e.g., Valent BioSciences XENTARI®) + TX, Bacillus thuringiensis subsp. islaerensis Bacillus thuringiensis subsp. Israelensis (serotype H-14) strain AM65-52 (accession number ATCC 1276) (e.g., Valent BioSciences, VECTOBAC®, US) + TX, Bacillus thuringiensis subsp. kurstaki strain ABTS 351 + TX, Bacillus thuringiensis subsp. kurstaki strain BMP 123 (Becker Microbial Products, IL, Bayer) CropScience's BARITONE) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (Certis, US's LEPINOX) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 7841 (Certis, US's CRYMAX) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g., Valent BioSciences (US DIPEL® ES) + TX, Bacillus thuringiensis subsp. kurstaki strain PB 54 + TX, Bacillus thuringiensis subsp. kurstaki strain SA 11 (Certis (US JAVELIN)) + TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (Certis, THURICIDE, US) + TX, Bacillus thuringiensis subsp. Tenebrionis strain NB 176 (SD-5428, e.g., NOVODOR® FC, BioFa DE) + TX, Bacillus thuringiensis var. colmeri (e.g., TIANBAOBTC, Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var. japonensis var. japonensis) strain Buibui + TX, Bacillus thuringiensis var. kurstaki strain EVB-113-19 (for example, AEF Global's BIOPROTEC®) + TX, Brevibacillus laterosporus + TX, Burkholderia species (especially Burkholderia rinogensis strain A396) (also known as Burkholderia rinogensis) rinojensis) strain MBI 305) (Accession number NRRL B-50319, International Publication No. 2011/106491 and International Publication No. 2013/032693, e.g., MBI206 TGAI and ZELTO® of Marrone Bio Innovations) + TX, Chromobacterium subtsugae in particular strain PRAA4-1T (e.g., MBI-203, e.g., GRANDEVO® of Marrone Bio Innovations) + TX, Lecanicillium mascarpum Muscarium Ve6 (Koppert's MYCOTAL) + TX, Paenibacillus popilliae (formerly Bacillus popilliae, e.g., St. Gabriel Laboratories' MILKY SPORE POWDER (trademark) or MILKY SPORE GRANULAR (trademark)) + TX, Serratia entomophila (e.g., Wrightson Seeds' INVADE (registered trademark)) + TX, Serratia marcescens marcescens) in particular strain SRM (accession number MTCC 8708) + TX, Trichoderma asperellum (TRICHODERMAX from Novozymes) + TX, Wolbachia pipientis ZAP strain (e.g., ZAP MALES® from MosquitoMate) + TX;
Beauveria bassiana strain ATCC 74040 (e.g., NATURALIS® from Intrachem Bio Italia) + TX; Beauveria bassiana strain ATP02 (acceptance number DSM24665), Apopka 97 (PREFERAL® from SePRO) + TX; Beauveria bassiana strain GHA (accession number ATCC74250, e.g., Laveriam International) Corporation's BOTANIGUARD® ES and MYCONTROL-O® + TX; Metalhizium anisopriae 3213-1 (deposited under NRRL access number 67074, disclosed in International Publication No. 2017/066094; Pioneer Hi-Bred International) + TX; Metalhizium robertsii 15013-1 (deposited under NRRL access number 67073) + TX; Metalhizium robertsii Robertsii) 23013-3 (deposited under NRRL acceptance number 67075) + TX; Paecilomyces lilacinus strain 251 (MELOCON® from Certis, US) + TX;
Cydia pomonelala (codling moth) granule virus (GV) + TX, Helicoverpa armigera (tobacco budworm) nuclear polyhedra virus (NPV) + TX, Adoxophyes Orana (summer fruit tortrix moth) granule virus (GV) + TX, Spodoptera exigua (white fall armyworm) mNPV + TX, Spodoptera frugiperda (sold armyworm) + TX;
Burkholderia species (especially Burkholderia cepacia) (formerly known as Pseudomonas cepacia) + TX, Gigaspora species + TX, Glomus species + TX, Laccaria species + TX, Lactobacillus buchneri + TX, Paraglomus species + TX, Pisolithus tinctorus tinctorus) + TX, Pseudomonas spp. + TX, Rhizobium spp. especially Rhizobium trifoli + TX, Rhizopogon spp. + TX, Scleroderma spp. + TX, Streptomyces spp. + TX, Suillus spp. + TX, Agrobacterium spp. * ) + TX, * Azorhizobium caulinodans + TX, * Azospirillum spp. + TX, * Azotobacter spp. + TX, * Bradyrhizobium spp. + TX, * Gigaspora monosporum + TX;
Allium sativum (NEMGUARD in Eco-Spray, BRALIC in ADAMA) + TX, Armour-Zen + TX, Artemisia absinthium + TX, Biokeeper WP + TX, Brassicaceae extract, especially rapeseed powder or mustard powder + TX, Cassia niglycans + TX, Cerastrus angulatus + TX, Chenopodium anselmitchcum Anthelminticum) + TX, Chenopodium quinoa saponin extract from quinoa seeds (e.g., Heads Up Plant Protectants, CA Heads Up® (Saponins of Quinoa)) + TX, Chitin + TX, Dryopteris filix-mas + TX, Equisetum arvense + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia Alternifolia extract (STK's TIMOREX GOLD) + TX, naturally occurring blad polypeptide extract from Lupin seeds (FMC's FRACTURE®) + TX, naturally occurring blad polypeptide extract from Lupin seeds (Certis EU's PROBLAD®) + TX, pyrethrin + TX, Auassia amara + TX, Quercus + TX, Quillaja extract (BASF's QL AGRI 35) + TX, Marrone Bio's REGALIA MAXX+TX, Requiem® insecticide+TX, Reynoutria sachalinensis extract (REGALLIA+TX), Riania/Ryanodine+TX, Symphytum officinale+TX, Tansy (Tanacetum vulgare)+TX, Thymol+TX, Thymol mixed with geraniol (Eden Research's CEDROZ)+TX, Thymol mixed with geraniol and eugenol (Eden Research's MEVALONE)+TX, Triact 70+TX, TriCon+TX, Tropaeulum majus) + TX, Urtica dioica + TX, Bellatrine + TX, Viscum album + TX;
Mercuric oxide + TX, octylinone + TX, thiophanate-methyl + TX;
MGK 264 + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-isovalerylindan-1,3-dione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexa-2-enone + TX, acibenzol + TX, acibenzol-S-methyl + TX, α-bromadiolone + TX, α-chlorohydrin + TX, aluminum phosphide + TX, anthraquinone + TX, antz + TX, arsenous acid + TX, barium carbonate + TX, benoxacol + TX, bisthiosemi + TX, brodifacum + TX Bromadiolon + TX, Bromethaline + TX, Calcium cyanide + TX, Chloralose + TX, Chlorophacinone + TX, Cholecalciferol + TX, Chloquintoset (including Chloquintoset-Mexyl) + TX, Copper naphthenate + TX, Copper oxychloride + TX, Coumacryl + TX, Coumafuryl + TX, Coumatetralyl + TX, Crimidine + TX, Cyprosulfamide + TX, Diazinon + TX, Dichlormid + TX, Dicyclopentadiene + TX, Diphenacome + TX, Difethiaron + TX, Diphacinone + TX, Ergocalciferol TX, Farnesol + TX, Farnesol and Nerolidol + TX, Fenchlorazole (containing Fenchlorazole-ethyl) + TX, Fenchlorim + TX, Furocumafen + TX, Fluoroacetamide + TX, Flupropazine + TX, Flupropazine hydrochloride + TX, Fluxofenim + TX, Frillazole + TX, Gamma-HCH + TX, Guazatin + TX, Guazatin acetate + TX, HCH + TX, Hydrogen cyanide + TX, Imanin + TX, Iodomethane + TX, Isoxadifen (containing Isoxadifen-ethyl) + TX, Linde +TX, Magnesium phosphide +TX, MB-599 +TX, Mefenydr (containing Mefenydr-diethyl) +TX, Metocamifen +TX, Methiocarb +TX, Methyl bromide +TX, Nerolidol +TX, Norbolmid +TX, Petroleum +TX, Fosacetim +TX, Phosphine +TX, Phosphate +TX, Phosphate +TX, Pindone +TX, Piperonyl butoxide +TX, Piprotal +TX, Potassium arsenite +TX, Probenazole +TX, Propyl isomer +TX, Pyridine-4-amine +TX, Pyrynulone +TX, Reynoutria saccharinensis Sachalinensis extract + TX, ribavirin + TX, S421 + TX, siriloside + TX, sesamex + TX, sesasmorin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thyram + TX, trimetacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, thyram + TX.

In addition, the composition of the present invention may be administered together with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known, for example, as described in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer acibenzolar-S-methyl.

The compounds of formula (I) as defined in this invention are typically used in the form of compositions and can be applied simultaneously with or consecutively to further compounds to a planted area or the plants to be treated. These further compounds may, for example, be fertilizers, sources of trace elements, or other preparations that affect plant growth. These may also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericidal agents, nematicides, molluskicides, or mixtures thereof, and may optionally include further carriers, surfactants, or application enhancers commonly used in the art of the formulations.

The compounds of formula (I) as defined in this invention can be used in the form of a (fungicidal) composition for the control or protection of plant pathogenic microorganisms, comprising, as an active ingredient, at least one compound of formula (I) as defined in this invention, or at least one preferred individual compound defined in free form or in an agrochemically usable salt form, and at least one of the above-mentioned auxiliary agents.

Therefore, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) as defined in the present invention, an agriculturally acceptable carrier, and optionally an auxiliary agent. The agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, the composition may, in addition to the compound of formula (I) as defined in the present invention, contain at least one or more pesticide compounds, such as additional fungicidal active ingredients.

Further aspects of the present invention relate to methods for controlling or preventing ectoparasitism by potentially harmful plant pathogenic or putrefactive microorganisms or organisms, particularly fungi, of plants, such as useful plants, such as crop plants, their reproductive materials, such as seeds, harvested crops, such as harvested food crops, or non-biological materials, the methods comprising the application of a compound of formula (I) as defined in the present invention, or any of the preferred individual compounds as defined above as active ingredients for plants, to plants, to parts of plants or their habitats, to their reproductive materials, or to any part of non-biological materials.

Control or prevention means reducing extrinsic parasitism by insects, plant pathogenic or putrefactive microorganisms, or organisms potentially harmful to humans, particularly fungi, to a level where improvement is demonstrated.

A preferred method for controlling or preventing ectoparasitism of crop plants by plant pathogenic microorganisms, particularly fungi, including the application of a compound of formula (I) as defined in this invention, or a pesticide composition containing at least one of the said compounds, is foliar application. The frequency and amount of application will depend on the risk of ectoparasitism by the corresponding pathogen or insect. However, the compound of formula (I) as defined in this invention can also be introduced into plants through the soil via the roots (osmotic action) by drenching the plant habitat with a liquid formulation or by applying the compound in solid form, such as granular form, to the soil (soil application). In rice crops, such granular material can be applied to flooded paddy fields. The compound of formula (I) as defined in this invention can also be applied to seeds (coating) by either impregnating the seeds or tubers with a liquid formulation of the fungicide or coating them with a solid formulation.

A composition containing, for example, a compound of formula (I) as defined in this invention, and, optionally, a solid or liquid additive or a monomer for encapsulating the compound of formula (I) as defined in this invention, can be prepared by known methods, typically by closely mixing and/or grinding the compound with an expander, such as a solvent, a solid carrier, and optionally, a surfactant.

Methods of application for the composition, i.e., methods for controlling the above-mentioned types of pathogens, such as spraying, misting, dusting, brushing, powdering, diffusion, or pouring (these should be selected according to the intended purpose of the general situation), and the use of the composition for controlling the above-mentioned types of pathogens are also subjects of the present invention. Typical concentration ratios are 0.1 to 1000 ppm, preferably 0.1 to 500 ppm of the active ingredient. The application rate per hectare is preferably 1 g to 2000 g of the active ingredient per hectare, more preferably 10 to 1000 g/ha, and most preferably 10 to 600 g/ha. When used as a seed drenching agent, a convenient application rate is 10 mg to 1 g of the active substance per kg of seed.

When using the combination of the present invention for seed treatment, a ratio of 0.001 to 50 g of the compound of formula (I) per kg of seed, preferably 0.01 to 10 g per kg of seed, is generally sufficient.

Preferably, a composition comprising the compound of formula (I) according to the present invention, as defined herein, is applied either preventively (meaning before the onset of disease) or therapeutically (meaning after the onset of disease).

The compositions of the present invention may be any of the conventional forms, for example, two-component systems, dry seed treatment powders (DS), seed treatment emulsions (ES), seed treatment fluid concentrates (FS), seed treatment solutions (LS), seed treatment water-dispersible powders (WS), seed treatment capsule suspensions (CF), seed treatment gels (GF), emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), or emulsifying granules. It can be used in the form of granules (EG), water-in-oil (EO) emulsions, oil-in-water (EW) emulsions, microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), industrial concentrates (TK), dispersible concentrates (DC), wettable powders (WP), or any technically feasible formulation combined with agriculturally acceptable auxiliaries.

Such compositions can be produced by conventional methods, for example, by mixing the active ingredient with a suitable formulation deactivator (diluent, solvent, filler, and optionally other formulation components such as surfactants, biocides, antifreezes, spreading agents, thickeners, and compounds providing auxiliary effects). Conventional sustained-release formulations can also be used when sustained effectiveness over a long period is desired. In particular, formulations applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, may contain condensation products of surfactants, such as wetting agents and dispersants, and other compounds providing auxiliary effects, such as formaldehyde, with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

The seed coating formulation is applied to seeds in a manner known to the present invention, utilizing the combination and diluent of the present invention in a preferred seed coating formulation form, such as an aqueous suspension or a dry powder form having good adhesion to seeds. Such seed coating formulations are known in the art. The seed coating formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example, as a slow-release capsule or microcapsule.

Generally, the formulation comprises 0.01 to 90% by weight of an active agent, 0 to 20% of an agriculturally acceptable surfactant, and 10 to 99.99% of a solid or liquid inert formulation and auxiliary agents. The active agent consists of at least a compound of formula (I) as defined in this invention, together with components (B) and (C), and optionally, other active agents such as particularly microbial agents or preservatives. The concentrated form of the composition generally contains about 2 to 80%, preferably about 5 to 70% by weight, of the activator. The application form of the formulation may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight, of the activator. Commercial products are preferably formulated as concentrates, but end users typically use diluted formulations.

While it is preferable to incorporate commercially available products as concentrates, end-users typically utilize dilute formulations.

The following examples illustrate the present invention. Certain compounds of the present invention can be distinguished from known compounds by their greater potency at lower doses, which can be verified by those skilled in the art using the experimental procedures outlined in the examples.

Combination example

By thoroughly mixing the active ingredient with an auxiliary agent and thoroughly grinding the mixture in a suitable pulverizer, a wettable powder can be obtained that can be diluted with water to form a suspension of the desired concentration.

By thoroughly mixing the active ingredient with an auxiliary agent and thoroughly grinding the mixture in a suitable grinder, a powder that can be used directly for seed treatment is obtained.

Emulsified concentrate active ingredient [compound of formula (I)] 10%
Octylphenol polyethylene glycol ether 3%
(4-5 mol of ethylene oxide)
Calcium dodecylbenzenesulfonate 3%
Castor oil polyglycol ether (ethylene oxide 35 mol) 4%
Cyclohexanone 30%
Xylene mixture 50%

Emulsions of any required dilution suitable for plant protection can be obtained from this concentrate by dilution with water.

Ready-to-use powders are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable pulverizer. Such powders can also be used for drying and coating seeds.

Extruded granules active ingredient [compound of formula (I)] 15%
Sodium lignin sulfonate 2%
Carboxymethylcellulose 1%
Kaolin 82%

The active ingredient is mixed with an auxiliary agent and ground, then the mixture is moistened with water. The mixture is extruded and then dried in an airflow.

Coated granules active ingredient [compound of formula (I)] 8%
Polyethylene glycol (molecular weight 200) 3%
Kaolin 89%

The finely ground active ingredient is uniformly added to kaolin moistened with polyethylene glycol in a mixer. A non-dusting coated granule is thus obtained.

Suspension concentrate active ingredient [compound of formula (I)] 40%
Propylene glycol 10%
Nonylphenol polyethylene glycol ether (ethylene oxide 15 mol) 6%
Sodium lignin sulfonate 10%
Carboxymethylcellulose 1%
Silicone oil (in the form of a 75% emulsion in water) 1%
Water 32%

By tightly mixing the finely ground active ingredient with an auxiliary agent, a suspension concentrate can be obtained, and a suspension of the desired dilution can be obtained by dilution with water. Using such a dilution, not only growing plants but also plant propagation materials can be treated by spraying, pouring, or immersion to protect them from microbial ectoparasitism.

Active ingredient in flowable formulation for seed treatment [compound of formula (I)] 40%
Propylene glycol 5%
Copolymer Butanol PO/EO 2%
Tristyrenephenol 2% with 10-20 moles of EO
1,2-Benzisothiazolin-3-one (20% aqueous solution) 0.5%
Monoazo pigment calcium salt 5%
Silicone oil (in the form of a 75% emulsion in water) 0.2%
Water 45.3%

By tightly mixing the finely ground active ingredient with an auxiliary agent, a suspension concentrate can be obtained, and a suspension of the desired dilution can be obtained by dilution with water. Using such a dilution, not only growing plants but also plant propagation materials can be treated by spraying, pouring, or immersion to protect them from microbial ectoparasitism.

A sustained-release capsule suspension is prepared by mixing 28 parts of the compound combination of formula (I) with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate/polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size is reached. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to this emulsion. The mixture is stirred until the polymerization reaction is complete.

The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of the active ingredient. The diameter of the capsules is 8 to 15 micrometers.

The resulting formulation is applied to seeds as an aqueous suspension using equipment suitable for the intended purpose.

Analytical Method Throughout this specification, temperature is expressed in degrees Celsius (°C), and "mp" indicates the melting point. LC/MS means liquid chromatography-mass spectrometry, and the apparatus and method are described below.

Method A:
Instrument: Shimadzu LCMS 2020 mass spectrometer; Column: HALOC ₁₈ 2.7 μm, 3.0 mm × 30 mm; Mobile phase: MeCN (containing either 0.05% HCOOH or 0.05% TFA) - Water (containing either 0.05% HCOOH or 0.05% TFA); Gradient: 5% to 95% MeCN over 1.4 min, hold for 0.6 min, total run time 2.5 min; Flow rate: 1.8 mL/min; Column temperature: 50°C; Wavelength: 214 and 254 nm PDA.

Method B:
Spectra were recorded using a Waters mass spectrometer (Acquity QDa mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch), capillary: 0.8 kV, cone range: 25 V, extractor: V (no extraction voltage for QDa detector), source temperature: 120 °C, desolvation temperature: 600 °C, cone gas flow rate: 50 L/h, desolvation gas flow rate: 1000 L/h, mass range: 110–850 Da), and a Waters Acquity UPLC: quaternary solvent vent manager, heated column compartment, and diode array detector. Column: Acquiity UPLC HSS T3 C18, 1.8 μm, 30 × 2.1 mm, Temperature: 40°C, DAD wavelength range (nm): 200-400, Solvent gradient: A = Water + 5% acetonitrile + 0.05% HCOOH, B = Acetonitrile + 0.1% HCOOH. Gradient: 10% B for 0 minutes; 10-50% B for 0-0.2 minutes; 50-100% B for 0.2-0.6 minutes; 100% B for 0.6-1.3 minutes; 100-10% B for 1.3-1.4 minutes; 10% B for 1.4-1.6 minutes; Flow rate (mL/min): 0.6.

Method C:
Spectra were recorded using the following: an ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) from Waters Corporation equipped with an electrospray source (polarity: positive and negative ions, capillary voltage: 3.0 kV, cone voltage: 30 V, extractor voltage: 3.00 V, source temperature: 150 °C, desolvation temperature: 400 °C, cone gas flow rate: 60 L/h, desolvation gas flow rate: 700 L/h, mass range: 140–800 Da), and an ACQUITY UPLC from Waters Corporation equipped with a solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm, Temperature: 60°C, DAD wavelength range (nm): 210–400, Solvent gradient: A = Water/Methanol 9:1 + 0.1% Formic Acid, B = Acetonitrile + 0.1% Formic Acid, Gradient: 0–100% B over 2.5 minutes; Flow rate (ml/min): 0.75.

Method D:
Spectra were recorded using Multimode-Electron Spray and APCI (polarity: positive and negative ions), capillary: 4.00 kV, corona current: 4.0 μA, charging voltage: 2.00 kV, nitrogen gas flow rate: 12.0 L/min, nebulizer pressure: 40 psig, mass range: 100–1000 m/z), dry gas temperature: 250 °C, vaporizer temperature: 200 °C, and a Waters UPLC: quaternary pump, heated column compartment and diode array detector. Column: X-Bridge BEH C18, 2.5 μm (2.1 × 50 mm), column temperature: ambient, wavelength (nm): 215 nm, gradient: A = 0.05% TFA in water, B = 0.05% TFA in acetonitrile. Gradient: Time/%B: 0/5, 1/5, 5/70, 7/95, 8.5/95, 8.6/5, 10/5; Flow rate: 0.6 mL/min.

Table A below summarizes the compounds of formula (I):
- LC/MS data, e.g., retention time (RT), [M + H] ⁺ etc.
- Type of method, and/or - Melting point (mp).

Example 1: Preparation of methyl N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (Compound 1)

Step A: Preparation of 6-bromo-3-iodo-8-methylimidazo[1,2-a]pyrazine
To a solution of 6-bromo-8-methylimidazo[1,2-a]pyrazine (CAS: 1073372-02-7) (1 g, 4.71 mmol, 1.00 equivalent) in acetonitrile (18.9 mL), N-iodosuccinimide (1.19 g, 5.18 mmol, _1.10 equivalent) was added. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, the residue was quenched with 10% NaOH, then quenched with a saturated solution _{of Na₂S₂O₃} , and extracted with chloroform. The combined organic layers were dried _{over Na₂SO₄} , filtered, and concentrated under reduced pressure to obtain 6-bromo-3-iodo-8-methylimidazo[1,2-a]pyrazine.
LC-MS (Method B): Rt 1.01 min, m/z = 338/340 (M+H) ⁺

Step B: Preparation of methyl N-[5-(6-bromo-8-methylimidazo[1,2-a]pyrazine-3-yl)-2-pyridyl]carbamate
A mixture of methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.36 g, 1.30 mmol, 1.10 equivalents), 6-bromo-3-iodo-8-methylimidazo[1,2-a]pyrazine (400 mg, 1.18 mmol, 1.10 equivalents), and potassium carbonate (0.25 g, 1.77 mmol, 1.5 equivalents) in 2-methyltetrahydrofuran (12 mL) was mixed with tetrakis(triphenylphosphine)palladium (0) (0.069 g, 0.059 mmol, 0.05 equivalents). The reaction mixture was degassed with argon and then stirred in a microwave at 80°C for 2 hours. After cooling to room temperature, the reaction mixture was filtered through a Celite pad and washed with methanol. The filtrate was washed with water, then with _brine , dried over _Na₂SO₄ , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (cyclohexane/ethyl acetate) to obtain methyl N-[5-(6-bromo-8-methylimidazo[1,2-a]pyrazine-3-yl)-2-pyridyl]carbamate.
LC-MS (Method B): Rt 1.02 min, m/z = 361 (MH) ^-
1H -NMR (400MHz, _CDCl3 , ppm) δ = 1.22-1.37 (m, 4H), 2.05 (s, 1H), 2.95 (s, 3H), 3.82 (s, 1H), 3.88 (s, 3H), 4.12 (d, J = 7.09Hz, 1H), 7.84 (s, 1H), 7.89 8dd, J = 8.68, 2.32Hz, 1H), 8.21 (s, 1H), 8.26 (d, J = 8.68Hz, 1H), 8.50-8.54 (m, 1H), 9.02 (s, 1H)

Step C: Preparation of 3-(4-fluoro-3-methoxy-anilino)propanenitrile
To a solution of 4-fluoro-3-methoxyaniline (CAS: 64465-53-8) (0.750 g, 4.78 mmol, 1.00 equivalent) in acetonitrile (4.78 mL), sodium iodide (0.755 g, 4.78 mmol, 1.00 equivalent), potassium carbonate (0.696 g, 4.78 mmol, 1.00 equivalent), and 3-bromopropanenitrile (CAS: 2417-90-5) (1.48 g, 10.5 mmol, _2.2 equivalents) were added. The reaction mixture was stirred at 60°C for 16 hours. The reaction mixture was cooled to room temperature, then dissolved in water and extracted with ethyl acetate. The combined organic layers were dried over _Na₂SO₄ , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (cyclohexane/ethyl acetate) to obtain 3-(4-fluoro-3-methoxyanilino)propanenitrile.
LC-MS (Method B): Rt 1.08 min, m/z = 195 (M+H) ^+
1H -NMR (400MHz, CDCl ₃ , ppm) δ = 2.63 (t, 2H), 3.45 (t, 2H), 3.87 (m, 3H), 3.93 (s, 1H), 6.08 (dt, J = 3.04, 8.71Hz, 1H), 6.26 (dd, J =2.69, 7.21Hz, 1H), 6.91 (dd, J=8.68, 11.25Hz, 1H)

Step D: Preparation of methyl N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 1) Methyl N-[5-(6-bromo-8-methyl-imidazo[1,2-a]pyrazine-3-yl)-2-pyridyl]carbamate (200 mg, 0.55 mmol, 1.00 equivalent), 3-(4-fluoro-3-methoxy-anilino)propanenitrile ( A mixture of CAS: 1073372-02-7 (0.118 g, 0.60 mmol, 1.1 equivalents), bis(benzonitrile)palladium chloride (0.022 g, 0.055 mmol, 0.10 equivalents), 4,5-bis(diphenylphosphin)-9,9-dimethylxanthene (0.032 g, 0.055 mmol, 0.10 equivalents), and triethylamine (0.116 mL, 0.82 mmol, 1.50 equivalents) in toluene (1.38 mL) was passed through a high-pressure vessel with nitrogen. The vial was pressurized with nitrogen and then with CO gas. The reaction mixture was stirred at 110°C for 6 hours. The reaction mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was purified by reverse-phase chromatography (C18 column, eluted with 5% to 90% MeCN/ _H2O ) to obtain methyl N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate.
LC-MS (Method B): Rt 1.07 min, m/z = 504 (M+H) ^+
1H -NMR (400MHz, CDCl ₃ , ppm) δ = 2.54 (m, 3H), 2.86 (t, J = 6.69Hz, 2H), 3.74 (m, 6H), 4.10 (t, J = 6.63Hz, 2H), 6.74 (br s, 1H), 7.07 (br s, 1H), 7.25-7.32 (m, 1H), 7.98-8.05 (m, 3H), 8.51 (br s, 2H), 10.54 (s, 1H).

Example 2: Preparation of methyl N-[5-[6-(6-fluoro-3,4-dihydro-2H-quinoline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 4)

Step A: Preparation of 6-bromo-8-methylimidazo[1,2-a]pyrazine
To a solution of 5-bromo-3-methylpyrazine-2-amine (10.00 g, 53.19 mmol, 1.00 equivalent) in ethanol (212 mL), a 50% aqueous solution of chloroacetaldehyde (20.27 mL, 159.6 mmol, 3.00 equivalent) was added. The reaction mixture was stirred at 78°C for 16 hours. The reaction mixture was quenched with saturated _NaHCO3 solution, extracted with ethyl acetate, washed with brine, dried _{over Na2SO4} , filtered, and concentrated under reduced pressure to obtain 6-bromo-8-methylimidazo[1,2-a]pyrazine.
LC-MS (Method B): Rt 0.36 min, m/z = 212/214 (M+H) ^+
1H -NMR (400MHz, DMSO-d ⁶ , ppm) δ = 2.74 (s, 3H), 7.79 (d, J = 0.88Hz, 1H), 8.08 (d, J = 0.88Hz, 1H), 8.83 (s, 1H).

Step B: Preparation of (6-fluoro-3,4-dihydro-2H-quinoline-1-yl)-(8-methylimidazo[1,2-a]pyrazine-6-yl)methanone
A mixture of 6-bromo-8-methylimidazo[1,2-a]pyrazine (1.00 g, 4.72 mmol, 1.00 equivalent), 6-fluoro-1,2,3,4-tetrahydroquinoline (0.720 g, 4.763 mmol, 1.01 equivalent), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.278 g, 0.471 mmol, 0.10 equivalent), bis(benzonitrile)palladium chloride (0.190 g, 0.471 mmol, 0.10 equivalent), and triethylamine (0.991 mL, 7.07 mmol, 1.50 equivalent) in toluene (10 mL) was stirred at 110°C for 6 hours in a high-pressure reactor filled with 10 bar CO gas. The mixture was filtered off, and the filtrate was concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (cyclohexane/ethyl acetate) to obtain (6-fluoro-3,4-dihydro-2H-quinoline-1-yl)-(8-methylimidazo[1,2-a]pyrazine-6-yl)methanone as a white solid.
LC-MS (Method B): Rt 1.07 min, m/z = 311 (M+H) ^+
1 H-NMR (400MHz, DMSO-d ⁶ , ppm) δ = 1.88-1.97 (m, 2H), 2.63 (s, 3H), 2.76-2.86 (m, 2H), 3.80 (t, J = 6.11Hz, 2H), 6.85 (br s, 1H), 7.03-7.33 (m, 2H), 7.76-7.83 (m, 1H), 8.17 (d, J=0.98Hz, 1H), 8.86 (s, 1H).

Step C: Preparation of (3-bromo-8-methylimidazo[1,2-a]pyrazine-6-yl)-(6-fluoro-3,4-dihydro-2H-quinoline-1-yl)methanone
To a solution of (6-fluoro-3,4-dihydro-2H-quinoline-1-yl)-(8-methylimidazo[1,2-a]pyrazine-6-yl)methanone (0.300 g, 0.966 mmol, 1.00 equivalent) stirred in acetonitrile (3.86 mL), N-bromosuccinimide (0.172 g, 0.966 mmol, 1.00 equivalent) was added at room temperature, and the reaction mixture was stirred for 1 hour. The reaction mixture was quenched with _a saturated aqueous solution of _{Na₂S₂O₃} and extracted with ethyl acetate. The combined organic layers were washed with brine, dried _{over Na₂SO₄} , filtered, and concentrated under reduced pressure to _obtain (3-bromo-8-methylimidazo[1,2-a]pyrazine-6-yl)-(6-fluoro-3,4-dihydro-2H-quinoline-1-yl)methanone.
LC-MS (Method B): Rt 1.10 min, m/z = 389/391 (M+H) ⁺

Step D: Methyl N-[5-[6-(6-fluoro-3,4-dihydro-2H-quinoline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 4)
(3-bromo-8-methylimidazo[1,2-a]pyrazine-6-yl)-(6-fluoro-3,4-dihydro-2H-quinoline-1-yl)methanone (0.300 g, 0.770 mmol, 1.00 equivalent) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.271 g, 0.924 mmol, 1.20 equivalent) were dissolved in acetonitrile (3 mL) and water (0.024 mL), to which sodium carbonate (0.257 g, 2.312 mmol, 3.00 equivalent) was added. The mixture was purged with argon for 5 minutes. Next, chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (0.063 g, 0.077 mmol, 10 equivalents) was added, and the mixture was irradiated in a microwave oven at 100°C for 1.25 hours. After cooling to room temperature, the reaction mixture was filtered through a Celite pad and washed with methanol. The filtrate was concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (cyclohexane/ethyl acetate) to obtain methyl N-[5-[6-(6-fluoro-3,4-dihydro-2H-quinoline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method B): Rt 1.03 min, m/z = 461 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 1.89-1.97 (m, 2H), 2.63-2.72 (m, 3H), 2.81 (t, J = 6.60Hz, 2H), 3.65-3.81 (m, 5H), 6.78-6.90 (m, 1H), 7.08 (dd, J = 9.23, 3.0 0Hz, 1H), 7.10-7.39 (m, 1H), 8.02-8.05 (m, 1H), 8.08 (s, 1H), 8.09-8.13 (m, 1H), 8.60 (d, J = 2.08Hz, 1H), 8.64 (s, 1H), 10.53 (s, 1H).

Example 3: Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (Compound 7)

Step A: Preparation of methyl 5-amino-6-bromopyrazine-2-carboxylate
N-bromosuccinimide (12.1 g, 68.2 mmol, 1.10 equivalent) was added to an ice-cold solution of methyl 5-aminopyrazine-2-carboxylate (10.0 g, 62.0 mmol, 1.00 equivalent) in acetonitrile (100 mL). The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was quenched with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried _{over Na₂SO₄} , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (cyclohexane/ethyl acetate) to obtain methyl 5-amino-6-bromopyrazine-2-carboxylate as a brown solid.
¹ H-NMR (400 MHz, DMSO-d ⁶ , ppm) δ = 3.81 (s, 3H), 7.68 (brs, 2H), 8.53 (s, 1H).

Step B: Preparation of methyl 5-amino-6-methylpyrazine-2-carboxylate
To a solution of methyl 5-amino-6-bromopyrazine-2-carboxylate (15.0 g, 61.4 mmol, 1.00 equivalent) and 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane (15.4 g, 123 mmol, 2.00 equivalent) in dioxane (150 mL), potassium carbonate (21.22 g, 153.5 mmol, 2.50 equivalent) was added, and the mixture was purged with argon for 5 minutes. Then, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (2.246 g, 3.070 mmol, 0.05 equivalent) was added, and the mixture was irradiated in a microwave oven at 110°C for 1 hour. The reaction mixture was concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (dichloromethane/methanol) to obtain methyl 5-amino-6-methylpyrazine-2-carboxylate as a white solid.
¹ H-NMR (400 MHz, DMSO-d ⁶ , ppm) δ = 2.31 (s, 3H), 3.78 (s, 3H), 7.13 (brs, 2H), 8.44 (s, 1H).

Step C: Preparation of ethyl 8-methylimidazo[1,2-a]pyrazine-6-carboxylate (compound X-1)
2-chloroacetaldehyde (2.32 g, 11.8 mmol, 2.00 equivalent) was added to a stirred solution of methyl 5-amino-6-methylpyrazine-2-carboxylate (1.10 g, 5.92 mmol, 1.00 equivalent) in ethanol (25.0 mL). The reaction mixture was stirred at 100 °C for 16 hours. The reaction mixture was concentrated under reduced pressure, then diluted with ethyl acetate and washed with a saturated solution of _NaHCO3 . The combined organic layers were washed with brine, dried _{over Na2SO4} , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (cyclohexane/ethyl acetate) to obtain a mixture (1:1) of ethyl 8-methylimidazo[1,2-a]pyrazine-6-carboxylate and methyl 8-methylimidazo[1,2-a]pyrazine-6-carboxylate as a brown solid.
¹ H-NMR (400 MHz, DMSO-d ⁶ , ppm) δ = 2.77 (s, 3H), 3.89 (s, 3H), 7.84 (s, 1H), 8.22 (s, 1H), 9.30 (s, 1H).

Step D: Preparation of N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide
To a stirred solution of ethyl 8-methylimidazo[1,2-a]pyrazine-6-carboxylate (compound X-1) (2.20 g, 9.65 mmol, 1.00 equivalent) and 4-fluoro-3-methoxyaniline (1.63 g, 11.6 mmol, 1.20 equivalent) in dry toluene (50.0 mL), trimethylaluminum (9.65 mL, 19.3 mmol, 2.00 equivalent) in toluene was added. The resulting reaction mixture was stirred at 80°C for 4 hours under a nitrogen atmosphere. The reaction mixture was cooled to 0°C, quenched with Rochelle salt aqueous solution, and diluted with ethyl acetate. The reaction mixture was filtered through a Celite pad and washed with ethyl acetate. The combined organic layers were washed with brine, dried _{over Na₂SO₄} , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (cyclohexane/ethyl acetate) to obtain N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide as a brown solid.
^1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 2.88 (s, 3H), 3.86 (s, 3H), 7.19-7.24 (m, 1H), 7.56-7.59 (m, 1H), 7.74-7.76 (dd, J =2.4, 8.0Hz, 1H), 7.86 (d, J = 0.8Hz, 1H), 8.29 (d, J = 0.8Hz, 1H), 9.26 (s, 1H), 10.40 (s, 1H).

Step E: Preparation of N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide
To an ice-cold solution of N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide (1.00 g, 3.16 mmol, 1.00 equivalent) in dry THF (20.0 mL), 60% sodium hydride (0.380 g, 9.49 mmol, 3.00 equivalent) in oil was added. After stirring for 30 minutes, iodomethane (0.591 mL, 9.49 mmol, 3.00 equivalent) was added dropwise, and the reaction mixture was stirred at room temperature for 6 hours. The reaction mixture was cooled to 0°C, quenched with _NH₄Cl solution, and extracted with ethyl acetate. The combined organic layers were washed with brine, dried _{over Na₂SO₄} , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (dichloromethane/methanol) to obtain N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide as a grayish-white solid.
^1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 2.46 (s, 3H), 3.40 (s, 3H), 3.74 (s, 3H), 6.68-6.70 (d, J = 7.6Hz, 1H), 7.03-7.08 (m, 1H) , 7.13-7.15 (dd, J=2.4, 7.6Hz, 1H), 7.75 (d, J=0.8Hz, 1H), 8.13 (d, J=1.2Hz, 1H), 8.80 (s, 1H).

Step F: Preparation of N-(4-fluoro-3-methoxyphenyl)-3-iodo-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide
To a stirred solution of N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (30.0 mg, 0.0859 mmol, 1.00 equivalent) in DMF (2 mL), N-iodosuccinimide (21.3 mg, 0.0945 mmol, 1.10 equivalent) was added at room temperature, and the mixture was stirred for 16 hours. The reaction mixture was quenched with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried _{over Na₂SO₄} , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (cyclohexane/ethyl acetate) to obtain N-(4-fluoro-3-methoxyphenyl)-3-iodo-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide as a grayish-white solid.
^1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 2.45 (s, 3H), 3.41 (s, 3H), 3.75 (s, 3H), 6.74 (s, 1H), 7.03-7.0 8 (m, 1H), 7.23-7.26 (dd, J=2.4, 8.0Hz, 1H), 7.90 (s, 1H), 8.37 (s, 1H).

Step G: Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 7)
To a stirred solution of N-(4-fluoro-3-methoxyphenyl)-3-iodo-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (400 mg, 0.818 mmol, 1.00 equivalent) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.273 g, 0.981 mmol, 1.20 equivalents) in 1,4-dioxane/water (3:1) (16.0 mL), cesium carbonate (0.533 g, 1.64 mmol, 2.00 equivalents) was added, and the mixture was purged with an argon stream for 2 minutes. cataCXium® A Pd G3 (29.8 mg, 0.0409 mmol, 0.05 equivalents) was added to the reaction mixture under an _N2 atmosphere. The resulting reaction mixture was irradiated in microwaves at 100°C for 1 hour. After cooling to room temperature, the reaction mixture was filtered through a Celite pad and washed with ethyl acetate. The filtrate was washed with water, then _brine , dried over _Na2SO4 , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (dichloromethane/methanol) to obtain methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a grayish-white solid.
^1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 2.56 (s, 3H), 3.38 (s, 3H), 3.71 (s, 3H), 3.73 (s, 3H), 6.75 (s, 1H), 7.03-7.08 (t, J = 9 .2Hz, 1H), 7.20-7.23 (dd, J=2.4, 8.0Hz, 1H), 7.98-8.05 (m, 3H), 8.52 (s, 2H), 10.50 (s, 1H).

Example 4: Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-(methoxymethyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 8)

Step A: Preparation of N-(4-fluoro-3-methoxyphenyl)-N-(methoxymethyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide
To an ice-cold solution of N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide (1.20 g, 3.80 mmol, 1.00 equivalent) in DMF (50.0 mL), 60% sodium hydride in oil (497 mg, 11.4 mmol, 3.00 equivalent) was added. After stirring for 30 minutes, chloro(methoxy)methane (611 mg, 7.59 mmol, 2.00 equivalent) was added dropwise, and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was cooled to 0°C, quenched with _NH₄Cl solution, and extracted with ethyl acetate. The combined organic layers were washed with brine, dried _{over Na₂SO₄} , filtered, and concentrated under reduced pressure. The crude residue was purified using silica gel cartridge C-18 (acetonitrile/water) to obtain N-(4-fluoro-3-methoxyphenyl)-N-(methoxymethyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide as a solid.
^1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 2.63 (s, 3H), 3.48 (s, 3H), 3.84 (s, 3H), 5.28 (s, 2H), 6.68 (s, 1H), 6.91-6.96 (m, 2H), 7.68 (s, 1H), 7.76 (s, 1H), 8.54 (s, 1H).

Step B: Preparation of N-(4-fluoro-3-methoxyphenyl)-3-iodo-N-(methoxymethyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide
To a stirred solution of N-(4-fluoro-3-methoxyphenyl)-N-(methoxymethyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide (0.500 g, 1.31 mmol, 1.00 equivalent) in 10 mL of DMF, N-iodosuccinimide (0.676 g, 3.01 mmol, 2.30 equivalents) was added at room temperature, and the mixture was stirred for 16 hours. The reaction mixture was quenched with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried _{over Na₂SO₄} , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge C-18 (acetonitrile/water) to obtain N-(4-fluoro-3-methoxyphenyl)-3-iodo-N-(methoxymethyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide as a solid.
^1H -NMR (400MHz, _CDCl3 , ppm) δ = 2.64 (s, 3H), 3.50 (s, 3H), 3.85 (s, 3H), 5.28 (s, 2H), 6.68 (brs, 1H), 6.91-6.98 (m, 2H), 7.81 (s, 1H), 8.47 (s, 1H).

Step C: Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-(methoxymethyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 8) N-(4-fluoro-3-methoxy-phenyl)-3-iodo-N-(methoxymethyl)-8-methyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.4 To a stirred solution of methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (255 mg, 0.919 mmol, 1.20 equivalents) in DMF (5.0 mL), cesium carbonate (499 mg, 1.53 mmol, 2.00 equivalents) was added, and the mixture was purged with an argon stream for 2 minutes. cataCXium® A Pd G3 (27.9 mg, 0.0383 mmol, 0.05 equivalents) was added to the reaction mixture under an _N2 atmosphere. The resulting reaction mixture was irradiated with microwaves at 100°C for 1 hour. After cooling to room temperature, the reaction mixture was filtered through a Celite pad and washed with ethyl acetate. The filtrate was washed with water, then _brine , dried over _Na₂SO₄ , filtered, and concentrated under reduced pressure. The crude residue was purified using a silica gel cartridge (dichloromethane/methanol) to obtain methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-(methoxymethyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a grayish-white solid.
^1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 10.50 (s, 1H), 8.62 (s, 1H), 8.51 (s, 1H), 8.07-7.99 (m, 3H), 7.23-7.19 (dd, J = 8.0, 2.4Hz, 1H ), 7.11-7.03 (t, J=9.2Hz, 1H), 6.78 (br.s, 1H), 5.20 (s, 2H), 3.72 (s, 3H), 3.33 (s, 3H), 2.50 (s, 3H).

Example 5: Preparation of 3-[6-(cyclopropanecarbonylamino)-3-pyridyl]-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound 19)

Step A: Preparation of ethyl 3-bromo-8-methylimidazo[1,2-a]pyrazine-6-carboxylate
To a solution of ethyl 8-methylimidazo[1,2-a]pyrazine-6-carboxylate (compound X-1) (5.40 g, 26.3 mmol) in dimethylformamide (60.0 mL), N-bromosuccinimide (5.62 g, 31.6 mmol) was added in small amounts at room temperature. The mixture was stirred at room temperature for 2 hours. After complete consumption of the starting materials, the reaction product was diluted with water. The precipitate was collected by filtration, washed with water, and concentrated under reduced pressure to obtain ethyl 3-bromo-8-methylimidazo[1,2-a]pyrazine-6-carboxylate as a brown solid.
LC-MS (Method A): Rt 1.04 min, m/z = 284 (M+H) ⁺

Step B: Preparation of 3-bromo-8-methylimidazo[1,2-a]pyrazine-6-carboxylic acid (compound X-2)
To a solution of ethyl 3-bromo-8-methylimidazo[1,2-a]pyrazine-6-carboxylate (6.50 g, 22.9 mmol) in tetrahydrofuran/ _H₂O (1:1, 70.0 mL), lithium hydroxide (1.10 g, 45.8 mmol) was added. The mixture was stirred at room temperature for 3 hours. The organic solvent was then removed under reduced pressure. The aqueous solution was adjusted to pH 2-3 with HCl aqueous solution (2N). The precipitate was collected by filtration and washed with water to obtain 3-bromo-8-methylimidazo[1,2-a]pyrazine-6-carboxylic acid as a white solid.
LC-MS (Method A): Rt 0.83 min, m/z = 256 (M+H) ⁺

Step C: Preparation of 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-3)
To a mixture of 3-bromo-8-methylimidazo[1,2-a]pyrazine-6-carboxylic acid (compound X-2) (0.800 g, 3.12 mmol) in dimethylformamide (10.0 mL), 1-methylimidazole (0.770 g, 9.37 mmol) and [chloro(dimethylamine)methylene]-dimethylammonium hexafluorophosphate (CAS 94790-35-9, 1.32 g, 4.68 mmol) were added at room temperature. The solution was stirred at room temperature for 5 minutes. Then, 4-fluoro-3-methoxy-N-methylaniline (0.0145 g, 0.0937 mmol) was added little by little. The resulting solution was stirred for 2 hours. The reaction mixture was diluted with ethyl acetate, washed with water and saturated aqueous NaCl solution, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a dichloromethane/methanol gradient to obtain 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide as a brown solid.
LC-MS (Method A): Rt 1.10 min, m/z = 393 (M+H) ⁺

Step D: Preparation of N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]cyclopropanecarboxamide
Under a nitrogen atmosphere, 2-aminopyridine-5-boronic acid pinacol ester, CAS 827614-64-2 (1.00 g, 4.31 mmol) was dissolved in ethyl acetate (50 mL). Then, pyridine (1.39 g, 17.3 mmol, 1.42 mL) was added. The reaction mixture was cooled to 0°C. Then, cyclopropane carbonyl chloride, CAS 4023-34-1 (1.84 g, 17.26 mmol, 1.60 mL) was added. The resulting mixture was stirred at room temperature for 1 hour. Cold water and ethyl acetate were added to the mixture. The layers were then separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was used directly in the following steps without further purification.

Step E: Preparation of 3-[6-(cyclopropanecarbonylamino)-3-pyridyl]-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound 19) Under an argon atmosphere, N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]cyclopropanecarboxamide (0.052 mmol), XPhos Pd G3, CAS 1445085-55-1 (3.455 mg, 0.004 mmol) were placed in vials. Next, a solution of 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-3) (0.040 mmol) in 1,4-dioxane (0.4 mL, degassed with argon) was added, followed by a solution of sodium carbonate (12.85 mg, 0.12 mmol) in water (0.1 mL, degassed with argon). The reaction mixture was stirred under argon at 100°C for 16 hours. The solvent was then evaporated. The residue was dissolved in dimethylacetamide (0.4 mL) and methanol (0.4 mL). The resulting suspension was filtered, and the filtrate was purified by reverse-phase chromatography to obtain the desired compound.
LC-MS (Method C): Rt 1.24 min, m/z = 474 (M+H) ⁺

Example 6: Preparation of methyl N-[5-[8-bromo-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 25)

Step A: Preparation of ethyl 8-bromoimidazo[1,2-a]pyrazine-6-carboxylate
To a solution of ethyl 5-amino-6-bromopyrazine-2-carboxylate (prepared as described in U.S. Patent No. 9,242,996, 2016, B2) (4.00 g, 16.3 mmol) in acetonitrile (60.0 mL), 2-bromo-1,1-dimethoxyethane (2.75 g, 16.3 mmol) was successively added. The mixture was heated at 140°C in a microwave reactor for 2 hours. After the reaction was complete, the resulting mixture was concentrated under vacuum. The crude product was purified by flash chromatography using a dichloromethane/methanol gradient to obtain ethyl 8-bromoimidazo[1,2-a]pyrazine-6-carboxylate as a yellow solid.
LC-MS (Method A): Rt 0.92 min, m/z = 270 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 9.46 (s, 1H), 8.40 (d, J = 1.0Hz, 1H), 7.96 (d, J = 1.0Hz, 1H), 4.38 (q, J = 7.0Hz, 2H), 1.36 (t, J = 7.0Hz, 3H).

Step B: Preparation of 8-bromoimidazo[1,2-a]pyrazine-6-carboxylic acid (compound X-4)
To a solution of ethyl 8-bromoimidazo[1,2-a]pyrazine-6-carboxylate (1.00 g, 3.70 mmol) in tetrahydrofuran (10.0 mL) and water (2.50 mL), lithium hydroxide (0.177 g, 7.41 mmol) was added. The mixture was stirred at room temperature for 3 hours. The mixture was diluted with water and extracted with ethyl acetate. The pH of the aqueous layer was adjusted to pH 4-5 with HCl aqueous solution (1 N), and the mixture was freeze-dried to obtain 8-bromoimidazo[1,2-a]pyrazine-6-carboxylic acid, which was used in the next step without further purification.
LC-MS (Method A): Rt 0.71 min, m/z = 244 (M+H) ⁺

Step C: Preparation of 8-bromo-N-(4-fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-5)
To a solution of 8-bromoimidazo[1,2-a]pyrazine-6-carboxylic acid (compound X-4) (0.130 g, 0.537 mmol) and 4-fluoro-3-methoxy-N-methylaniline (0.0917 g, 0.591 mmol) in pyridine (2.0 _mL ), propylphosphonic anhydride (50.0 wt.% ethyl acetate solution, 1.03 g, 1.61 mmol) was added dropwise at 65°C under a nitrogen atmosphere. The mixture was heated at 65°C for 2 hours. The final mixture was diluted with saturated NaHCO3 aqueous solution and extracted with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain 8-bromo-N-(4-fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide as a yellow oil.
LC-MS (Method A): Rt 1.07 min, m/z = 380 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 9.03 (s, 1H), 8.32 (s, 1H), 7.87 (s, 1H), 7.18 (dd, J = 7.8, 2.2Hz, 1H), 7.07 ( dd, J=11.0, 9.0Hz, 1H), 6.71 (d, J=8.2Hz, 1H), 3.76 (s, 3H), 3.40 (d, J=6.6Hz, 3H).

Step D: Preparation of 8-bromo-N-(4-fluoro-3-methoxyphenyl)-3-iodo-N-methylimidazo[1,2-a]pyrazine-6-carboxamide
8-bromo-N-(4-fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-5) (0.200 g, 0.527 mmol) was added dropwise to a solution of acetonitrile (2.0 mL) with N-iodosuccinimide (0.119 g, 0.527 mmol) at 0°C. The reaction mixture was stirred at 65°C for 16 hours. The resulting mixture was then diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain 8-bromo-N-(4-fluoro-3-methoxyphenyl)-3-iodo-N-methylimidazo[1,2-a]pyrazine-6-carboxamide as a yellow solid.
LC-MS (Method A): Rt 2.46 min, m/z = 505 (M+H) ^+
1H -NMR (400MHz, _CDCl3 , ppm) δ = 8.59 (s, 1H), 7.90 (s, 1H), 6.95 (d, J = 8.2Hz, 2H), 6.58 (s, 1H), 3.89 (d, J = 4.4Hz, 3H), 3.51 (s, 3H).

Step F: Preparation of methyl N-[5-[8-bromo-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 25) To a solution of 8-bromo-N-(4-fluoro-3-methoxyphenyl)-3-iodo-N-methylimidazo[1,2-a]pyrazine-6-carboxamide (0.120 g, 0.238 mmol) in dioxane (10.0 mL) and water (2.00 _mL ), methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.0991 g, 0.356 mmol), bis(diphenylphosphino)ferrocene-palladium(II) dichloride (0.0172 g, 0.0238 mmol), and _K₂CO₃ (0.0662 g, 0.475 mmol) were added. The mixture was stirred at room temperature under an _N₂ atmosphere for 2 hours. The mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by silica gel column chromatography (eluted with methanol/dichloromethane) to obtain methyl N-[5-[8-bromo-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method A): Rt 2.41 min, m/z = 529 (M+H) ^+
1H -NMR (400MHz, _CDCl3 , ppm) δ = 8.59 (s, 1H), 8.41 (s, 1H), 8.29-8.17 (m, 2H), 7.90 (s, 1H), 7.85 (d, J = 8.7H z, 1H), 6.95 (d, J=7.4Hz, 2H), 6.58 (s, 1H), 3.90 (s, 3H), 3.87 (s, 3H), 3.48 (s, 3H).

Example 7: Preparation of methyl N-[5-[8-cyano-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 23)

Step A: Preparation of 8-cyano-N-(4-fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide
To a solution of 8-bromo-N-(4-fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-5) (0.200 g, 0.527 mmol) in dimethylformamide (4.00 mL), zinc cyanide (0.124 g, 1.05 mmol), (5-diphenylphosphanyl-9,9-dimethyl-xanthene-4-yl)-diphenylphosphane (0.0610 g, 0.105 mmol) and _Pd2 (dba) ₃ (CAS 51364-51-3, 0.0483 g, 0.0527 mmol) were successively added. The mixture was heated in a microwave reactor at 100°C under an _N2 atmosphere for 1 hour. The resulting mixture was then diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain 8-cyano-N-(4-fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide as a yellow solid.
LC-MS (Method A): Rt 1.06 min, m/z = 326 (M+H) ⁺

Step B: Preparation of 3-bromo-8-cyano-N-(4-fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide
8-Cyano-N-(4-Fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide (0.150 g, 0.461 mmol) was added dropwise to a solution of acetonitrile (3.0 mL) with 1-bromopyrrolidine-2,5-dione (0.0821 g, 0.461 mmol) at 0°C. The reaction mixture was stirred at room temperature for 5 hours. The resulting mixture was then diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain 3-bromo-8-cyano-N-(4-Fluoro-3-methoxyphenyl)-N-methylimidazo[1,2-a]pyrazine-6-carboxamide as a yellow solid.
LC-MS (Method A): Rt 1.21 min, m/z = 406 (M+H) ⁺

Step C: Preparation of methyl N-[5-[8-cyano-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 23) 3-bromo-8-cyano-N-(4-fluoro-3-methoxyphenyl)-N-methyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.0700 g, 0.173 mmol) in dioxane/ _H₂O (4:1, 2.5 mL) is mixed with methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.0722 g, 0.260 _mmol ), _K₂CO₃ (0.0598 g, 0.433 mmol) and bis(diphenylphosphino)ferrocene-palladium(II) dichloride (0.0127 g, 0.0173 mmol) were added. The mixture was stirred at 50°C for 1.5 hours under an _N2 atmosphere. The resulting mixture was then concentrated under reduced pressure. The crude product was purified by flash chromatography using a dichloromethane/methanol gradient to obtain methyl N-[5-[8-cyano-6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a yellow solid.
LC-MS (Method A): Rt 1.16 min, m/z = 476 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 10.57 (s, 1H), 8.98 (s, 1H), 8.59 (s, 1H), 8.32 (s, 1H), 8.07 (s, 2H), 7.25 (d, J=5.8Hz, 1H), 7.08 (s, 1H), 6.78 (s, 1H), 3.74 (s, 6H), 3.41 (s, 3H).

Example 8: Preparation of methyl N-[5-[6-[cyanomethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 2)

Step A: Preparation of 2-(4-fluoro-3-methoxy-anilino)acetonitrile
To a solution of 4-fluoro-3-methoxyaniline (0.500 g, 3.188 mmol) in acetonitrile (3.18 mL), sodium iodide (0.503 g, 3.188 mmol) and 2-chloroacetonitrile (0.225 mL, 3.379 mmol) were added. The mixture was stirred at 70°C for 3 hours. The reaction was then cooled to room temperature and water was added. The aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was used as is, without further purification, in the following steps.
LC-MS (Method B): Rt 1.01 min, m/z = 181 (M+H) ⁺

Process B: N-(cyanomethyl)-N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide
A vial was filled with 6-bromo-8-methylimidazo[1,2-a]pyrazine, CAS 1159815-50-5 (0.300 g, 1.414 mmol), 2-(4-fluoro-3-methoxy-anilino)acetonitrile (0.267 g, 1.49 mmol), bis(benzonitrile)palladium chloride (0.057 g, 0.14 mmol), 4,5-bis(diphenylphosphin)-9,9-dimethylxanthene (0.083 g, 0.14 mmol), toluene (3.5 mL), and triethylamine (0.297 mL). Nitrogen was passed through the vial, then the vial was pressurized with nitrogen, then carbon monoxide was passed through twice, and finally the vial was pressurized with 10 bar of carbon monoxide. The pressurized vial was heated at 110°C for 7 hours. The mixture was then filtered through a Celite pad and concentrated under reduced pressure. The crude substance was purified by flash chromatography using a cyclohexane/ethyl acetate gradient to obtain N-(cyanomethyl)-N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide LC-MS (Method B): Rt 0.97 min, m/z = 340(M+H) ^+
1H -NMR (400MHz, CDCl ₃ , ppm) δ = 8.62 (br s, 1H), 7.66-7.75 (m, 2H), 6.84-6.97 (m, 2H), 6.60-6.73 (m, 1H), 4.68 (br s, 2H), 3.79 (s, 3H), 2.47 (s, 3H)

Step C: Preparation of 3-bromo-N-(cyanomethyl)-N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide
To a solution of N-(cyanomethyl)-N-(4-fluoro-3-methoxy-phenyl)-8-methyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.037 g, 0.11 mmol) in acetonitrile (0.43 mL), 1-bromopyrrolidine-2,5-dione (0.0213 g, 0.120 mmol) was added dropwise. The reaction mixture was stirred at room temperature for 3 hours. The resulting mixture was then diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a cyclohexane/ethyl acetate gradient to obtain 3-bromo-N-(cyanomethyl)-N-(4-fluoro-3-methoxy-phenyl)-8-methyl-imidazo[1,2-a]pyrazine-6-carboxamide.
LC-MS (Method B): Rt 1.03 min, m/z = 418 (M+H) ^+
1H -NMR (400MHz, CDCl ₃ , ppm) δ = 8.62 (br s, 1H), 7.76 (s, 1H), 6.90-7.08 (m, 2H), 6.74 (br s, 1H), 4.76 (br s, 2H), 3.87 (s, 3H), 2.54 (s, 3H)

Step D: Preparation of methyl N-[5-[6-[cyanomethyl-(4-fluoro-3-methoxy-phenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 2) 3-bromo-N-(cyanomethyl)-N-(4-fluoro-3-methoxy-phenyl)-8-methyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.23 g, 0.55 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.211 g, 0.715 mmol) were dissolved in acetonitrile (4.40 mL), to which sodium carbonate (0.175 g, 1.65 mmol) in water (2.19 mL) was added. The resulting solution was degassed with nitrogen for 15 minutes. Then, chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (CAS: 1310584-14-5) (0.044 g, 0.055 mmol) was added, and the vial was heated at 100°C in a microwave reactor for 2.5 hours. The reaction mixture was then diluted with methanol, filtered through a Celite pad, and the filtrate was evaporated under reduced pressure. The crude product was purified by flash chromatography using an ethyl acetate/methanol gradient to obtain methyl N-[5-[6-[cyanomethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method B): Rt 1.02 min, m/z = 490 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 10.52 (s, 1H), 8.66 (s, 1H), 8.55 (s, 1H), 8.03 (d, 3H), 7.30-7.32 (dd, 1H), 7.0 9-7.14 (m, 1H), 6.76-6.79 (m, 1H), 4.97 (s, 2H), 3.76 (s, 3H), 3.73 (s, 3H), 2.52 (s, 3H).

Example 9: Preparation of methyl N-[4-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]phenyl]carbamate (compound 36)
To a mixture of dioxane/ _H₂O (4:1, 5.0 mL), 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethyl-imidazo[1,2-a]pyrazine-6-carboxamide (compound X-3) (0.200 g, 0.509 mmol) and methyl N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamate, CAS 844500-75-0 (0.169 g, 0.610 mmol) were added, along with 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (0.0415 g, 0.0509 mmol) and potassium carbonate (0.211 g, 1.53 mmol). The mixture was stirred at 55°C for 2 hours under an _N2 atmosphere. The mixture was concentrated under reduced pressure, and the residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain the desired compound, which was triturated with acetonitrile/petroleum ether (2:1) to obtain methyl N-[4-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]phenyl]carbamate as a white solid.
LC-MS (Method A): Rt 1.14 min, m/z = 464 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 9.94 (s, 1H), 8.47 (s, 1H), 7.91 (s, 1H), 7.67 (d, J = 8.6Hz, 2H), 7.50 (d, J = 8.4Hz, 2H), 7.24 (dd, J=7.8, 2.4Hz, 1H), 7.08-7.03 (m, 1H), 6.74 (s, 1H), 3.73 (s, 3H), 3.71 (s, 3H), 3.39 (s, 3H), 2.55 (s, 3H).

Example 10: Preparation of methyl N-[5-[8-acetamido-6-[ethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 21)

Step A: Preparation of 8-bromo-N-ethyl-N-(4-fluoro-3-methoxyphenyl)imidazo[1,2-a]pyrazine-6-carboxamide
To a solution of 8-bromoimidazo[1,2-a]pyrazine-6-carboxylic acid (compound X-4) (0.440 g, 1.818 mmol) and N-ethyl-4-fluoro-3-methoxy-aniline (0.369 g, 2.18 mmol) in pyridine (5.0 mL), propylphosphonic anhydride (50.0 wt.% ethyl acetate solution, 5.78 g, 9.09 mmol) was added dropwise at 70°C under a nitrogen atmosphere. The mixture was heated at 70°C for 2 hours. The final mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain 8-bromo-N-(4-fluoro-3-methoxy-phenyl)-N-methyl-imidazo[1,2-a]pyrazine-6-carboxamide as a yellow solid.
LC-MS (Method A): Rt 1.12 min, m/z = 393 (M+H) ⁺

Step B: Preparation of 8-acetamido-N-ethyl-N-(4-fluoro-3-methoxyphenyl)imidazo[1,2-a]pyrazine-6-carboxamide
To a solution of 8-bromo-N-ethyl-N-(4-fluoro-3-methoxyphenyl)imidazo[1,2-a]pyrazine-6-carboxamide (0.400 g, 1.02 mmol) in dioxane (5.00 mL), acetamide (0.120 g, 2.03 mmol), Xantphos-Pd-G2 (CAS 1375325-77-1, 0.0904 g, 0.102 mmol) and cesium carbonate (0.497 g, 1.53 mmol) were added. The mixture was stirred at 70°C under an _N2 atmosphere for 2 hours. The mixture was diluted with water and extracted with ethyl acetate. The organic layer was concentrated under vacuum. The residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain 8-acetamido-N-ethyl-N-(4-fluoro-3-methoxyphenyl)imidazo[1,2-a]pyrazine-6-carboxamide as a white solid.
LC-MS (Method A): Rt 0.97 min, m/z = 372 (M+H) ⁺

Step C: 8-Acetamido-3-bromo-N-ethyl-N-(4-fluoro-3-methoxyphenyl)imidazo[1,2-a]pyrazine-6-carboxamide
To a solution of 8-acetamido-N-ethyl-N-(4-fluoro-3-methoxy-phenyl)imidazo[1,2-a]pyrazine-6-carboxamide (0.400 g, 1.077 mmol) in dichloromethane (10.0 mL), 1-bromopyrrolidine-2,5-dione (0.192 g, 1.077 mmol, 1.0 equivalent) was added in small increments at 0°C. The reaction mixture was stirred at room temperature for 4 hours. The resulting mixture was then diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain 8-acetamido-3-bromo-N-ethyl-N-(4-fluoro-3-methoxy-phenyl)imidazo[1,2-a]pyrazine-6-carboxamide as a white solid.
LC-MS (Method A): Rt 2.43 min, m/z = 452 (M+H) ⁺

Step D: Preparation of methyl N-[5-[8-acetamido-6-[ethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 21) To a solution of 8-acetamido-3-bromo-N-ethyl-N-(4-fluoro-3-methoxyphenyl)imidazo[1,2-a]pyrazine-6-carboxamide (0.180 g, 0.400 mmol) in dioxane (5.0 mL) and water (1.00 _mL ), methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.222 g, 0.800 mmol), bis(diphenylphosphino)ferrocene-palladium(II) dichloride (0.0293 g, 0.0400 mmol), and _K₂CO₃ (0.167 g, 1.20 mmol) were added. The mixture was stirred at 50°C under an _N₂ atmosphere for 2 hours. The mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by silica gel column chromatography (eluted with methanol/dichloromethane) to obtain methyl N-[5-[8-acetamido-6-[ethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method A): Rt 1.46 min, m/z = 522 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 10.10 (s, 1H), 9.75 (s, 1H), 8.49 (d, J = 2.3Hz, 1H), 8.33 (s, 1H) H), 7.98 (dt, J=8.6, 5.5Hz, 2H), 7.91 (s, 1H), 7.10 (dd, J=7.8, 2.5Hz, 1H), 7.01 (dd, J = 11.3, 8.5Hz, 1H), 6.77-6.69 (m, 1H), 3.88 (d, J = 7.1H z, 2H), 3.74 (s, 3H), 3.73 (s, 3H), 2.19 (s, 3H), 1.13 (t, J=7.1Hz, 3H).

Example 11: Preparation of methyl N-[5-[6-[ethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 3)

Step A: Preparation of N-ethyl-N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide
A vial was filled with 6-bromo-8-methylimidazo[1,2-a]pyrazine (CAS1159815-50-5) (0.600 g, 2.83 mmol), N-ethyl-4-fluoro-3-methoxyaniline (0.484 g, 2.86 mmol), bis(benzonitrile)palladium chloride (0.114 g, 0.283 mmol), 4,5-bis(diphenylphosphin)-9,9-dimethylxanthene (0.167 g, 0.283 mmol), toluene (6.0 mL), and triethylamine (0.60 mL, 4.24 mmol). Nitrogen was passed through the vial, then the vial was pressurized with nitrogen, then carbon monoxide was passed through twice, and finally the vial was pressurized with 10 bar of carbon monoxide. The pressurized vial was heated at 110°C for 6 hours. The mixture was then filtered through a Celite pad and concentrated under reduced pressure. The crude material was purified by flash chromatography using a cyclohexane/ethyl acetate gradient to obtain N-ethyl-N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide as a brown solid.
LC-MS (Method B): Rt 0.84 min, m/z = 329 (M+H) ^+
1H -NMR (400MHz, DMSO-d ⁶ , ppm) δ = 8.38 (s, 1H), 8.12 (s, 1H), 7.75 (s, 1H), 7.00-7.15 (m, 2H), 6.65 (br s, 1H), 3.88 (q, J = 6.92Hz, 2H), 3.76 (s, 3H), 2.44-2.49 (m, 3H), 1.10-1.24 (m, 3H)

Step B: Preparation of 3-bromo-N-ethyl-N-(4-fluoro-3-methoxyphenyl)-8-methylimidazo[1,2-a]pyrazine-6-carboxamide
To a solution of N-ethyl-N-(4-fluoro-3-methoxy-phenyl)-8-methyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.600 g, 1.83 mmol) in acetonitrile (7.3 mL), 1-bromopyrrolidine-2,5-dione (0.325 g, 1.83 mmol) was added dropwise at 0°C. The reaction mixture was stirred at room temperature for 1 hour. The resulting mixture was then diluted with saturated thiosulfate solution and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a cyclohexane/ethyl acetate gradient to obtain 3-bromo-N-ethyl-N-(4-fluoro-3-methoxy-phenyl)-8-methyl-imidazo[1,2-a]pyrazine-6-carboxamide as a white solid.
LC-MS (Method B): Rt 1.07 min, m/z = 407 (M+H) ⁺

Step C: Preparation of methyl N-[5-[6-[ethyl-(4-fluoro-3-methoxy-phenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (Compound 3) 3-bromo-N-ethyl-N-(4-fluoro-3-methoxy-phenyl)-8-methyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.412 g, 1.01 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.355 g, 1.21 mmol) were dissolved in acetonitrile (4.12 mL), to which sodium carbonate (0.324 g, 3.04 mmol) in water (0.033 mL) was added. The resulting solution was degassed with nitrogen for 15 minutes. Next, chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (CAS: 1310584-14-5) (0.084 g, 0.101 mmol) was added, and the vial was heated at 100°C in a microwave reactor for 1.5 hours. The reaction mixture was then filtered through a Celite pad, and the filtrate was evaporated under reduced pressure. The crude product was purified by flash chromatography using an ethyl acetate/methanol gradient to obtain methyl N-[5-[6-[ethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method B): Rt 1.03 min, m/z = 479 (M+H) ^+
1 H-NMR (400 MHz, DMSO-d ⁶ , ppm) δ = 10.47 (s, 1H), 8.45 (br s, 2H), 7.95-8.00 (m, 1H), 7.93 (s, 2H), 7.13 (s, 1H), 6.91-7.06 (m, 1H), 6.63 (br s, 1H), 3.71-3.89 (m, 2H), 3.66 (s, 6H), 2.46-2.51 (m, 3H), 1.06 (t, J = 7.07Hz, 3H)

Example 12: Preparation of methyl N-[4-[6-[(4-cyano-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]phenyl]carbamate (compound 35)

Step A: Preparation of 3-bromo-N-(4-cyano-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-6)
A mixture of 3-bromo-8-methylimidazo[1,2-a]pyrazine-6-carboxylic acid (compound X-2) (0.700 g, 3.12 mmol) and 4-fluoro-3-methoxy-N-methylaniline (0.532 g, 3.28 mmol) in pyridine (10.0 mL) was to which 1-propanephosphonic acid cyclic anhydride (50% in ethyl acetate, 2.61 g, 8.20 mmol) was added. The resulting solution was stirred at 65°C for 2 hours. The reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a dichloromethane/methanol gradient to obtain 3-bromo-N-(4-cyano-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide as a yellow solid.
LC-MS (Method A): Rt 1.09 min, m/z = 401 (M+H) ⁺

Step B: Preparation of methyl N-[4-[6-[(4-cyano-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]phenyl]carbamate (compound 35) To a solution of 3-bromo-N-(4-cyano-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-6) (0.300 g, 0.750 mmol) in dioxane (8.0 mL) and water ( _2.0 mL), methyl N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamate (0.249 g, 0.899 mmol), bis(diphenylphosphin)ferrocene-palladium(II) dichloride ( _{0.0612 g} , 0.0750 mmol), and K₂CO₃ (0.104 g, 0.750 mmol) were added. The mixture was stirred at 55°C under an _N₂ atmosphere for 2 hours. The mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with methanol/dichloromethane), and the resulting product was further purified by trituration with acetonitrile/petroleum ether (2:1) to obtain methyl N-[4-[6-[(4-cyano-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]phenyl]carbamate as a white solid.
LC-MS (Method A): Rt 1.10 min, m/z = 471 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 9.95 (s, 1H), 8.59 (s, 1H), 7.94 (s, 1H), 7.69 (d, J = 8.6Hz, 2H), 7.57 (dd, J = 13.9, 8.4Hz, 3H), 7 .26 (d, J=1.5Hz, 1H), 6.90 (dd, J=8.3, 1.6Hz, 1H), 3.79 (s, 3H), 3.72 (s, 3H), 3.46 (s, 3H), 2.51 (s, 3H).

Example 13: Preparation of methyl N-[5-[6-[(4-cyano-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 34)
To a solution of 3-bromo-N-(4-cyano-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-6) (0.400 g, 0.999 mmol) in dioxane (4.0 mL) and water (1.0 mL), methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.278 _g , 0.999 mmol), bis(diphenylphosphin)ferrocene-palladium(II) dichloride (0.0816 g, 0.0999 mmol), and _K₂CO₃ (0.414 g, 3.00 mmol) were added. The mixture was stirred at 55°C under an _N₂ atmosphere for 2 hours. The mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with methanol/dichloromethane), and the resulting product was further purified by trituration with acetonitrile/petroleum ether (2:1) to obtain methyl N-[5-[6-[(4-cyano-3-methoxyphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method A): Rt 1.065 min, m/z = 472 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 10.52 (s, 1H), 8.63 (s, 1H), 8.56 (s, 1H), 8.04 (d, J = 5.0Hz, 3H), 7.58 (d, J = 8.3Hz, 1 H), 7.25 (s, 1H), 6.91 (d, J=8.3Hz, 1H), 3.78 (s, 3H), 3.73 (s, 3H), 3.46 (s, 3H), 2.51 (s, 3H).

Example 14: Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-2,8-dimethyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 38)

Step A: Preparation of ethyl 2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylate
A reaction mixture of 6-bromo-2,8-dimethylimidazo[1,2-a]pyrazine, prepared as described in International Patent Publication No. 2015/197503, 2015, A1 (0.800 g, 3.54 mmol), EtOH (10.0 mL), 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (CAS 95464-05-4, 0.289 g, 0.354 mmol), and N,N-diethylethaneamine (1.07 g, 10.62 mmol) was passed through which carbon monoxide was flowed. The vial was sealed and pressurized to 2.5 MPa with carbon monoxide. The reaction mixture was stirred at 100°C for 8 hours. The container was then cooled to room temperature and the pressure was released. The reaction mixture was concentrated, and the residue was purified by flash chromatography using a methanol/dichloromethane gradient to obtain ethyl 2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylate as a brown solid.
LC-MS (Method A): Rt 0.877 min, m/z = 220 (M+H) ⁺

Step B: Preparation of ethyl 3-bromo-2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylate
To a solution of ethyl 2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylate (0.800 g, 3.65 mmol) in acetonitrile (10.0 mL), 1-bromopyrrolidine-2,5-dione (0.779 g, 4.38 mmol) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 2 hours. The resulting mixture was then diluted with water. The precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain ethyl 3-bromo-2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylate as a brown solid.
LC-MS (Method A): Rt 1.218 min, m/z = 298 (M+H) ⁺

Step C: Preparation of 3-bromo-2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylic acid
To a solution of ethyl 3-bromo-2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylate (0.400 g, 1.34 mmol) in tetrahydrofuran/ _H₂O (1:1, 10.0 mL), lithium hydroxide (0.064 g, 2.7 mmol) was added. The mixture was stirred at room temperature for 3 hours. The organic solvent was then removed under reduced pressure. The aqueous solution was adjusted to pH 2-3 with HCl aqueous solution (2N). The precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain 3-bromo-2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylic acid as a white solid.
LC-MS (Method A): Rt 0.998 min, m/z = 270 (M+H) ⁺

Step D: Preparation of 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,2,8-trimethylimidazo[1,2-a]pyrazine-6-carboxamide
To a mixture of 3-bromo-2,8-dimethylimidazo[1,2-a]pyrazine-6-carboxylic acid (0.260 g, 0.963 mmol) in dimethylformamide (5.0 mL), 1-methylimidazole (0.237 g, 2.89 mmol) and [chloro(dimethylamine)methylene]-dimethylammonium hexafluorophosphate (CAS 94790-35-9, 0.405 g, 1.44 mmol) were added at room temperature. The solution was stirred at room temperature for 5 minutes. Then, 4-fluoro-3-methoxy-N-methylaniline (0.179 g, 1.16 mmol) was added little by little. The resulting solution was stirred for 2 hours. The reaction mixture was diluted with ethyl acetate, washed with water and saturated aqueous NaCl solution, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a dichloromethane/methanol gradient to obtain 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,2,8-trimethylimidazo[1,2-a]pyrazine-6-carboxamide as a brown solid.
LC-MS (Method A): Rt 1.170 min, m/z = 409 (M+H) ⁺

Step E: Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-2,8-dimethyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 38) To a solution of 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,2,8-trimethyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.240 g, 0.589 mmol) in dioxane (4.0 mL) and water (1.00 _mL ), methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.246 g, 0.884 mmol), bis(diphenylphosphino)ferrocene-palladium(II) dichloride (0.0431 g, 0.0589 mmol), and _K₂CO₃ (0.2447 g, 1.77 mmol) were added. The mixture was stirred at 55°C under an _N₂ atmosphere for 2 hours. The mixture was concentrated under vacuum. The residue was purified by silica gel column chromatography (eluted with methanol/dichloromethane) and further triturated with acetonitrile/petroleum ether (2:1) to obtain methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-2,8-dimethyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method A): Rt 1.09 min, m/z = 479 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ = 10.51 (s, 1H), 8.39 (s, 1H), 8.23 (s, 1H), 8.05 (d, J = 8.6Hz, 1H), 7.86 (d, J = 8.2Hz, 1H), 7.18 (dd, J = 7 .8, 2.3Hz, 1H), 7.04 (m, 1H), 6.70 (s, 1H), 3.73 (s, 3H), 3.71 (s, 3H), 3.36 (s, 3H), 3.32 (s, 3H), 2.40 (s, 3H).

Example 15: Preparation of methyl N-[5-[6-[(4-fluoro-3-methylphenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 5)

Step A: Preparation of N-(4-fluoro-3-methylphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide
A vial was filled with 6-bromo-8-methylimidazo[1,2-a]pyrazine (CAS 1159815-50-5) (0.700 g, 3.30 mmol), 4-fluoro-N,3-dimethylaniline (0.464 g, 3.33 mmol), bis(benzonitrile)palladium chloride (0.133 g, 0.330 mmol), 4,5-bis(diphenylphosphin)-9,9-dimethylxanthene (0.194 g, 0.330 mmol), toluene (7.0 mL), and triethylamine (0.694 mL). Nitrogen was passed through the vial, then the vial was pressurized with nitrogen, then carbon monoxide was passed through twice, and finally the vial was pressurized with 10 bar of carbon monoxide. The pressurized vial was heated at 110°C for 6 hours. The mixture was then filtered through a Celite pad and concentrated under reduced pressure. The crude substance was purified by flash chromatography using a cyclohexane/ethyl acetate gradient to obtain N-(4-fluoro-3-methylphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide LC-MS (Method B): Rt 0.96 min, m/z = 299(M+H) ^+
1H -NMR (400MHz, DMSO-d ⁶ , ppm) δ = 7.96 (s, 1H), 7.28 (d, J = 0.98Hz, 1H), 6.90 (s, 1H), 6.38 (br d, J = 7.21Hz, 1H), 6.15 (br d, J = 6.72Hz, 2H), 2.52 (s, 3H), 1.57-1.63 (br s, 3H), 1.27-1.34 (m, 3H)

Step B: Preparation of 3-bromo-N-(4-fluoro-3-methylphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide
To a solution of N-(4-fluoro-3-methylphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (0.680 g, 2.28 mmol) in acetonitrile (9.1 mL), 1-bromopyrrolidine-2,5-dione (0.406 g, 2.28 mmol) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hour. The resulting mixture was then diluted with saturated thiosulfate aqueous solution and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under vacuum. The residue was used in the next step without further purification.
LC-MS (Method B): Rt 1.05 min, m/z = 379 (M+H) ⁺

Step C: Preparation of methyl N-[5-[6-[(4-fluoro-3-methyl-phenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (Compound 5) 3-bromo-N-(4-fluoro-3-methyl-phenyl)-N,8-dimethyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.700 g, 1.86 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.652 g, 2.23 mmol) were dissolved in acetonitrile (7.00 mL), to which sodium carbonate (0.621 g, 5.57 mmol) in water (0.060 mL) was added. The resulting solution was degassed with nitrogen for 15 minutes. Next, chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (CAS: 1310584-14-5) (0.154 g, 0.186 mmol) was added, and the vial was heated at 100°C in a microwave reactor for 1.5 hours. The reaction mixture was then diluted with methanol, filtered through a Celite pad, and the filtrate was evaporated under reduced pressure. The crude product was purified by flash chromatography to obtain methyl N-[5-[6-[(4-fluoro-3-methyl-phenyl)-methyl-carbamoyl]-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method B): Rt 1.00 min, m/z = 449 (M+H) ^+
1H -NMR (400MHz, DMSO-d ⁶ , ppm) δ = 9.69 (s, 1H), 7.64-7.72 (m, 2H), 7.13-7.27 (m, 3H), 6.44-6.50 (m, 1H), 6.18 (br d, J = 8.88Hz, 2H), 2.90 (s, 3H), 2.52 (s, 3H), 1.70-1.74 (m, 3H), 1.33 (s, 3H)

Example 16: Preparation of 3-[4-(ethylcarbamoylamino)phenyl]-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound 16)
Under an argon atmosphere, 1-ethyl-3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)urea (0.052 mmol) and XPhos Pd G3 (CAS 1445085-55-1) (3.455 mg, 0.004 mmol) were placed in a vial. Next, a solution of 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide (compound X-3) (0.040 mmol) in 1,4-dioxane (0.4 mL, degassed with argon) was added, followed by a solution of sodium carbonate (12.85 mg, 0.12 mmol) in water (0.1 mL, degassed with argon). The reaction mixture was stirred under argon at 100°C for 16 hours. Next, the solvent was evaporated. The residue was dissolved in dimethylacetamide (0.4 mL) and methanol (0.4 mL). The resulting suspension was filtered, and the filtrate was purified by reverse-phase chromatography to obtain 3-[4-(ethylcarbamoylamino)phenyl]-N-(4-fluoro-3-methoxyphenyl)-N,8-dimethylimidazo[1,2-a]pyrazine-6-carboxamide.
LC-MS (Method C): Rt 1.15 min, m/z = 477 (M+H) ⁺

Example 17: Preparation of methyl N-[5-[6-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 29)

Step A: Preparation of (3-bromo-8-methylimidazo[1,2-a]pyrazine-6-yl)-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-yl)methanone
To a solution of 8-bromoimidazo[1,2-a]pyrazine-6-carboxylic acid (compound X-4) (0.140 g, 0.547 mmol) and 6-fluoro-4-methyl-2,3-dihydro-1H-quinoxaline (0.109 g, 0.656 mmol) in pyridine (5.0 mL), propylphosphonic anhydride (50.0 wt.% ethyl acetate solution, 0.522 g, 1.64 mmol) was added dropwise at 70°C under a nitrogen atmosphere. The mixture was heated at 70°C for 2 hours. The final mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, and concentrated under vacuum. The residue was purified by flash chromatography using a dichloromethane/methanol gradient, and then further purified by trituration with acetonitrile/petroleum ether (1:10) to obtain (3-bromo-8-methyl-imidazo[1,2-a]pyrazine-6-yl)-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-yl)methanone yellow oil.
LC-MS (Method A): Rt 1.22 min, m/z = 406 (M+2H) ²⁺

Step B: Preparation of methyl N-[5-[6-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 29) (3-bromo-8-methyl-imidazo[1,2-a]pyrazine-6-yl)-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-yl)methanone (0.130 g, 0.322 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.0894 g, 0.322 mmol) in acetonitrile/water (4.0 mL) were degassed with nitrogen for 15 minutes. Next, potassium carbonate (0.133 g, 0.965 mmol) and 1,1'-bis(diphenylphosphin)ferrocene-pallasium(II) dichloride dichloromethane complex (0.026 g, 0.032 mmol) were added, and the reaction mixture was heated at 50°C for 2.0 hours. The reaction mixture was then concentrated under reduced pressure. The crude product was purified by flash chromatography using a dichloromethane/methanol gradient to obtain methyl N-[5-[6-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-carbonyl)-8-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a pink solid.
LC-MS (Method A): Rt 1.19 min, m/z = 476 (M+H) ^+
1H -NMR (400MHz, DMSO- ^d6 , ppm) δ=10.08 (s, 1H), 8.53 (d, J=3.8Hz, 2H), 8.03-7.96 (m, 3H), 7.15 (s, 1H), 6.49 (dd, J=12.0, 2.7Hz, 1H), 6. 21 (td, J=8.5, 2.6Hz, 1H), 3.88 (t, J=5.3Hz, 2H), 3.73 (s, 3H), 3.41 (t, J=5.3Hz, 2H), 2.92 (s, 3H), 2.73 (s, 3H).

Example 18: Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-2-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 37)

Step A: Preparation of ethyl 3-bromo-2-methylimidazo[1,2-a]pyrazine-6-carboxylate
To a solution of ethyl 2-methylimidazo[1,2-a]pyrazine-6-carboxylate (CAS 1610666-95-9) (0.800 g, 3.90 mmol) in acetonitrile (10.0 mL), 1-bromopyrrolidine-2,5-dione (0.833 g, 4.68 mmol) was added in small amounts at room temperature. The reaction mixture was stirred at room temperature for 2 hours. The resulting mixture was then concentrated under vacuum. The residue was purified by flash chromatography using a petroleum ether/ethyl acetate gradient to obtain ethyl 3-bromo-2-methylimidazo[1,2-a]pyrazine-6-carboxylate as a yellow solid.
LC-MS (Method A): Rt 1.04 min, m/z = 284 (M+H) ⁺

Step B: Preparation of 3-bromo-2-methylimidazo[1,2-a]pyrazine-6-carboxylic acid
To a solution of ethyl 3-bromo-2-methylimidazo[1,2-a]pyrazine-6-carboxylate (0.600 g, 2.11 mmol) in tetrahydrofuran/ _H₂O (1:1, 10.0 mL), lithium hydroxide (0.101 g, 4.22 mmol) was added. The mixture was stirred at room temperature for 3 hours. The organic solvent was then removed under reduced pressure. The aqueous solution was adjusted to pH 2-3 with HCl aqueous solution (2N). The precipitate was collected by filtration and washed with water to obtain 3-bromo-2-methylimidazo[1,2-a]pyrazine-6-carboxylic acid as a white solid.
LC-MS (Method A): Rt 0.19 min, m/z = 254 (MH) ⁺

Step C: Preparation of 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,2-dimethylimidazo[1,2-a]pyrazine-6-carboxamide
To a mixture of 3-bromo-2-methylimidazo[1,2-a]pyrazine-6-carboxylic acid (0.020 g, 0.078 mmol) in acetonitrile (3.0 mL), 1-methylimidazole (0.019 g, 0.23 mmol) and [chloro(dimethylamine)methylene]-dimethylammonium hexafluorophosphate (CAS 94790-35-9, 0.0329 g, 0.117 mmol) were added at room temperature. The solution was stirred at room temperature for 5 minutes. Then, 4-fluoro-3-methoxy-N-methylaniline (0.0145 g, 0.0937 mmol) was added little by little. The resulting solution was stirred for 2 hours. The reaction mixture was diluted with ethyl acetate, washed with water and saturated NaCl aqueous solution, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a dichloromethane/methanol gradient to obtain 3-bromo-N-(4-fluoro-3-methoxyphenyl)-N,2-dimethylimidazo[1,2-a]pyrazine-6-carboxamide.
LC-MS (Method A): Rt 1.43 min, m/z = 394 (M+H) ⁺

Step D: Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-2-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate (compound 37) 3-bromo-N-(4-fluoro- ₃ -methoxyphenyl)-N,2-dimethyl-imidazo[1,2-a]pyrazine-6-carboxamide (0.400 g, 1.02 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (CAS) in a mixture of dioxane/H₂O (4:1, 10.0 mL) To a mixture of 844500-75-0 (0.424 g, 1.53 mmol), 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (0.0831 g, 0.102 mmol) and potassium carbonate (0.422 g, 3.05 mmol) were added. The mixture was stirred at 60°C for 2 hours under an _N2 atmosphere. The mixture was concentrated under reduced pressure, and the residue was purified by flash chromatography using a dichloromethane/methanol gradient to obtain the desired compound, which was triturated with acetonitrile/petroleum ether (2:1) to obtain methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-2-methyl-imidazo[1,2-a]pyrazine-3-yl]-2-pyridyl]carbamate as a white solid.
LC-MS (Method A): Rt 1.08 min, m/z = 465 (M+H) ^+
1 H-NMR (400 MHz, DMSO-d ⁶ , ppm) δ = 10.52 (s, 1H), 8.75 (br s, 1H), 8.40-8.46 (m, 2H), 8.06 (d, J = 8.8Hz, 1H), 7.81-8.03 (m, 1H), 7.18 (dd, J = 7.9, 2.4Hz, 1H), 6.93-7.15 (m, 1H), 6.72 (br s, 1H), 3.69-3.76 (m, 6H), 3.38 (s, 3H), 2.42 (s, 3H)

Biological examples:
The fungicidal activity of the compound of the present invention was tested as follows.

Phytophthora infestans / Tomato / Leaf blight preventative (leaf blight)
Tomato leaf fragments are placed on agar plates in a multi-well plate (24-well type), and a diluted test compound is sprayed onto them. One day after application, a fungal spore suspension is inoculated onto the leaf fragments. The inoculated leaf fragments are incubated in a climate cabinet at 16°C and 75% rh under a light environment of 24 hours in darkness followed by 12 hours of light/12 hours in darkness. The activity of the compound is evaluated as the disease control rate compared to untreated leaf fragments when an appropriate level of disease appears on untreated test leaf fragments (5-7 days after application).

The following compounds, at 200 ppm, resulted in at least 80% control of Phytophthora infestans when compared to an untreated control under identical conditions that exhibited widespread disease:
1, 2, 3, 4, 5, 7, 8, 12, 15, 16, 17, 18, 19, 21, 23, 24, 25, 26, 29, 31, 33, 34, 35, 36

Plasmopara viticola / Grape / Leaf blight preventative (leaf blight)
Grapevine leaflets are placed on agar plates in a multi-well plate (24-well type), and a test compound diluted with water is sprayed onto them. One day after application, a fungal spore suspension is inoculated onto the leaflets. The inoculated leaflets are incubated in a climate cabinet at 19°C and 80% rh under a 12-hour light/12-hour darkness environment. The activity of the compound is evaluated as the disease control rate compared to untreated leaflets when an appropriate level of disease appears on untreated test leaflets (6-8 days after application).

The following compounds, at 200 ppm, resulted in at least 80% control of Plasmopara viticola, which exhibited widespread disease development, compared to an untreated control under identical conditions:
1, 2, 3, 4, 6, 7, 8, 15, 16, 19, 23, 24, 25, 29, 30, 31, 34, 35, 36

Pythium ultimum / Liquid culture (Seedling blight)
Newly grown fungal mycelial fragments and oospores from liquid culture are directly mixed into a nutrient medium (PDB potato dextrose medium). After adding a solution of the test compound (DMSO) to a microtiter plate (96-well type), the nutrient medium containing the fungal mycelium/spore mixture is added. The test plate is incubated at 24°C, and the inhibition of growth is measured by photometry 2-3 days after application.

The following compounds, at 20 ppm, provided at least 80% control of Pythium ultimum when compared to an untreated control that exhibited widespread disease development under identical conditions.
1, 2, 3, 6, 7, 8, 14, 15, 16, 17, 19, 26, 29, 31, 34, 35, 36

Claims (18)

Equation (I)
(wherein Z is O or S, preferably Z is O;
^A1 is CH or N, preferably N;
R ^1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _{C1-6 alkyl} ;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl;
^A2 is independently ^CR2 or N, provided that three or fewer ^A2s are N, preferably two or fewer ^A2s are N, preferably one or fewer ^A2s are N, and more preferably four ^A2s are ^CR2 ;
^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _{C2-6 alkenyl} , _{C2-6 alkynyl} , C Each of the _3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs;
A ³ is independently CR ³ or N;
^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl, C3-6 cycloalkyl} , _{C3-6 cycloalkyl} -C Each of the _1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, C1-6 alkylsulfinyl- _C1-6 alkyl, C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl _{-C1-6 alkyl} , _C1-6 alkylaminocarbonyl- _C1-6 alkyl, _diC1-6 alkylaminocarbonyl _{-C1-6 alkyl, and CN, where C1-6 alkyl, C1-6 alkoxy-C1-6 alkyl , C3-6 cycloalkyl , C3-6} cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, C Each of the _2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, _C1-6 alkylsulfinyl- _C1-6 alkyl, _C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl- _C1-6 alkyl, _C1-6 alkylaminocarbonyl- _{C1-6 alkyl, and diC1-6 alkylaminocarbonyl-C1-6 alkyl may} be optionally substituted with one to three substituents independently selected from halogens and CN;
Here, ^A3 and ^R4 may optionally come together to form a ring, more preferably a 5- to 8-membered heteroring, more preferably a 6-membered heteroring;
^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl _{- C1-6} alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino, _diC1-6 alkylamino, and _{C1-6 alkylC1-6} alkoxyamino, where each of the above groups may be optionally substituted with one to three substituents independently selected from halogens and CNs;
A compound of the same, or its salt or N-oxide. The compound according to claim 1, wherein R ^1a is selected from C _1-6 alkyl, C _3-6 cycloalkyl, C _1-6 alkoxy-C _1-6 alkyl, C _3-6 cycloalkyl-C _1-4 alkyl, and C _1-6 alkoxy, and is preferably C _1-6 alkyl. The compound according to claim 1 or 2, wherein ^R1b and ^R1c are independently selected from hydrogen, _C1-6 alkyl, _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy. The compound according to claim 1, wherein R ^1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl, and R ^1b and R ^1c are hydrogen. _The compound according to any one of claims ^{1 to} ₄ , wherein R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, _{and C1-6} alkylcarbonyl, where each of the _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxyl, and CN. ^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _{C1-6 alkoxy, C1-6 alkoxy} - _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, amino, _{C1-6 alkylamino} , _diC1-6 -alkylamino, and C The compound according to any one of claims 1 to 5, wherein each of _{the 3-6} cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs. The compound according to any one of claims 1 to 6, wherein four ^A2s are ^CR2 and ^A3 is N. but
The compound according to any one of claims 1 to 6, wherein preferably three ^A2s are ^CR2s and ^A3s are ^CR3s . but
The compound according to any one of claims 1 to 6, wherein preferably three ^A2s are ^CR2s and ^A3s are ^CR3s . The four ^A2s are ^CR2s , and the ^A3s are ^CR3s , preferably
but
The compound according to any one of claims 1 to 6. The _compound according to any one of claims _{1 to 10} , wherein ^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, and _C1-6 alkoxy, where each of the _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, C3-6 cycloalkyl, _{C3-6 cycloalkyl-C1-4 alkyl} , _C2-6 alkenyl, C2-6 alkynyl, and _C1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens and CN. The compound according to any one of claims 1 to 11, wherein ^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, and _{C1-6 alkoxyC1-6} alkyl, where each of the groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN. A composition comprising the compound described in any one of claims 1 to 12 in an effective amount for fungicidal action. The composition according to claim 13, further comprising at least one compound selected from additional active ingredients, suitable inactive ingredients, carriers, auxiliaries, and any mixtures thereof. A method for eradicating, preventing, or controlling plant pathogenic diseases, comprising applying an effective fungicidal amount of the compound described in any one of claims 1 to 12, or a composition containing the compound described in any one of claims 1 to 12, or a composition described in claim 13 or 14, to a plant pathogen, the habitat of the plant pathogen, a plant susceptible to damage by the plant pathogen, or its plant propagation material. Formula (IV)
(wherein Z is O or S, preferably Z is O;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl, preferably ^R1a is selected from _{C1-6 alkyl} , _C3-6 cycloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^A2 is independently ^CR2 or N, provided that three or fewer ^A2s are N, preferably two or fewer ^A2s are N, preferably one or fewer ^A2s are N, and more preferably four ^A2s are ^CR2 ;
^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _{C2-6 alkenyl} , _{C2-6 alkynyl} , C Each of the _3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxyl, and CN; preferably, ^R2 is independently selected from hydrogen, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, where the _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy-C Each of the _1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs;
A ³ is independently CR ³ or N;
^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl, C3-6 cycloalkyl} , _{C3-6 cycloalkyl} -C Each of the _1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN; preferably, ^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl, where each of the _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, C1-6 alkylsulfinyl- _C1-6 alkyl, C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl _{-C1-6 alkyl} , _C1-6 alkylaminocarbonyl- _C1-6 alkyl, _diC1-6 alkylaminocarbonyl _{-C1-6 alkyl, and CN, where C1-6 alkyl, C1-6 alkoxy-C1-6 alkyl , C3-6 cycloalkyl , C3-6} cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, C Each of the _2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, _C1-6 alkylsulfinyl- _C1-6 alkyl, _C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl- _C1-6 alkyl, C1-6 alkylaminocarbonyl- _C1-6 alkyl and _diC1-6 alkylaminocarbonyl- _C1-6 alkyl may be optionally substituted with one to three substituents independently selected from halogens and CN; preferably, ^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, where the _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _{C3-6 cycloalkyl} -C Each of the _1-4 alkyl and _C1-6 alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CNs; and ^A3 and ^R4 may optionally combine to form a ring, more preferably a 5-8 membered heterocycle, more preferably a 6 membered heterocycle);
Compounds of or salts or N-oxides thereof;
Alternatively, equation (II)
(wherein Z is O or S, preferably Z is O;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, _C1-6 alkoxy, amino _{, and NHC(O)C1-6 alkyl; preferably, R1a is selected from C1-6 alkyl, C3-6 cycloalkyl, C1-6 alkoxy-C1-6 alkyl} ^, _{C3-6 cycloalkyl - C1-4 alkyl ,} and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^A2 is independently ^CR2 or N, provided that three or fewer ^A2s are N, preferably two or fewer ^A2s are N, preferably one or fewer ^A2s are N, and more preferably four ^A2s are ^CR2 ;
^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _{C2-6 alkenyl} , _{C2-6 alkynyl} , C Each of the _3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxyl, and CN; preferably, ^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, where _{the C1-6} alkyl, _C1-6 alkoxy, C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy-C Each of the _1-6 alkoxy groups may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs;
A ³ is independently CR ³ or N;
^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl, C3-6 cycloalkyl} , _{C3-6 cycloalkyl} -C Each of the _1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN; preferably, ^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl, where each of the _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, C1-6 alkylsulfinyl- _C1-6 alkyl, C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl _{-C1-6 alkyl} , _C1-6 alkylaminocarbonyl- _C1-6 alkyl, _diC1-6 alkylaminocarbonyl _{-C1-6 alkyl, and CN, where C1-6 alkyl, C1-6 alkoxy-C1-6 alkyl , C3-6 cycloalkyl , C3-6} cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, C Each of the _2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, _C1-6 alkylsulfinyl- _C1-6 alkyl, _C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl- _C1-6 alkyl, C1-6 alkylaminocarbonyl- _C1-6 alkyl and _diC1-6 alkylaminocarbonyl- _C1-6 alkyl may be optionally substituted with one to three substituents independently selected from halogens and CN; preferably, ^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, where the _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _{C3-6 cycloalkyl} -C Each of _{the 1-4} alkyl and _C1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens and CN;
Here, ^A3 and ^R4 may optionally come together to form a ring, more preferably a 5- to 8-membered heteroring, more preferably a 6-membered heteroring;
X is Cl, Br, or I);
A compound of the same, or its salt or N-oxide. Formula (XXXVI)
(wherein ^A1 is CH or N, preferably N;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, _C1-6 alkoxy, amino _{, and NHC(O)C1-6 alkyl; preferably, R1a is selected from C1-6 alkyl, C3-6 cycloalkyl, C1-6 alkoxy-C1-6 alkyl} ^, _{C3-6 cycloalkyl - C1-4 alkyl ,} and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _{C1-6 alkylsulfanyl, C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, C1-6 alkoxy , amino} , and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen; and ^R5 is _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino _{, diC1-6} alkylamino, and _C1-6 alkylC Selected from _1-6 alkoxyaminos, where each of the groups may be optionally substituted with 1-3 substituents independently selected from halogens and CNs.
Compounds of or salts or N-oxides thereof;
Alternatively, formula (XXXVIII)
(wherein ^A1 is CH or N, preferably N;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, _C1-6 alkoxy, amino _{, and NHC(O)C1-6 alkyl; preferably, R1a is selected from C1-6 alkyl, C3-6 cycloalkyl, C1-6 alkoxy-C1-6 alkyl} ^, _{C3-6 cycloalkyl - C1-4 alkyl ,} and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl _{- C1-6} alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino, _diC1-6 alkylamino, and _{C1-6 alkylC1-6} alkoxyamino, where each of the above groups may be optionally substituted with one to three substituents independently selected from halogens and CN;
^R10 is _C1-6 alkyl);
Compounds of or salts or N-oxides thereof;
Alternatively, formula (XL)
(wherein ^A1 is CH or N, preferably N;
^R1a is selected from hydroxy, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, C1-6 alkoxy- _C1-6 alkyl, _{C3-6 cycloalkyl} - _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, _C1-6 alkoxy, amino _{, and NHC(O)C1-6 alkyl; preferably, R1a is selected from C1-6 alkyl, C3-6 cycloalkyl, C1-6 alkoxy-C1-6 alkyl} ^, _{C3-6 cycloalkyl - C1-4 alkyl ,} and _C1-6 alkoxy;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^R5 is selected from _C1-6 alkyl, _C1-6 alkoxy, _C3-6 cycloalkyl, _C3-6 cycloalkyl _{- C1-6} alkyl, _C1-6 alkoxyC1-6 alkyl, _C1-6 alkylamino, _diC1-6 alkylamino, and _{C1-6 alkylC1-6} alkoxyamino, where each of the above groups may be optionally substituted with one to three substituents independently selected from halogens and CN;
X is Cl, Br, or I);
A compound of the same, or its salt or N-oxide. Formula (XVI)
(wherein Z is O or S, preferably Z is O;
^R1b and ^R1c are independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C3-6 cycloalkyl, _{C1-6 alkoxy-C1-6 alkyl} , _C3-6 cycloalkyl- _C1-4 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxy, amino, and NHC(O) _C1-6 alkyl; preferably, ^R1b and ^R1c are hydrogen;
^A2 is independently ^CR2 or N, provided that three or fewer ^A2s are N, preferably two or fewer ^A2s are N, preferably one or fewer ^A2s are N, and more preferably four ^A2s are ^CR2 ;
^R2 is independently selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _{C2-6 alkenyl} , _{C2-6 alkynyl} , C Each of the _3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, _C1-6 alkoxycarbonyl, _C1-6 alkylaminocarbonyl, _diC1-6 alkylaminocarbonyl, and _C1-6 alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxyl, and CN; preferably, ^R2 is independently selected from hydrogen, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy- _C1-6 alkoxy, where the _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, and _C1-6 alkoxy-C Each of the _1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs;
A ³ is independently CR ³ or N;
^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _C2-6 alkynyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino, where _C1-6 alkyl, _C1-6 alkoxy, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkoxy, _C2-6 alkenyl, _{C2-6 alkynyl, C3-6 cycloalkyl} , _{C3-6 cycloalkyl} -C Each of the _1-6 alkyl, _C1-6 alkylsulfanyl, _C1-6 alkylsulfinyl, _C1-6 alkylsulfonyl, amino, _C1-6 alkylamino, _diC1-6 -alkylamino, and _C3-6 cycloalkylamino groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN; preferably, ^R3 is selected from hydrogen, hydroxyl, halogen, CN, _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl, where each of the _C1-6 alkyl, _C1-6 alkoxy, and _C1-6 alkoxy- _C1-6 alkyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyl, and CN;
^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, _C2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, C1-6 alkylsulfinyl- _C1-6 alkyl, C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl _{-C1-6 alkyl} , _C1-6 alkylaminocarbonyl- _C1-6 alkyl, _diC1-6 alkylaminocarbonyl _{-C1-6 alkyl, and CN, where C1-6 alkyl, C1-6 alkoxy-C1-6 alkyl , C3-6 cycloalkyl , C3-6} cycloalkyl- _C1-4 alkyl, _C2-6 alkenyl, C Each of the _2-6 alkynyl, _C1-6 alkoxy, _C1-6 alkylsulfanyl- _C1-6 alkyl, _C1-6 alkylsulfinyl- _C1-6 alkyl, _C1-6 alkylsulfonyl- _C1-6 alkyl, _C1-6 alkoxycarbonyl- _C1-6 alkyl, C1-6 alkylaminocarbonyl- _C1-6 alkyl and _diC1-6 alkylaminocarbonyl- _C1-6 alkyl may be optionally substituted with one to three substituents independently selected from halogens and CN; preferably, ^R4 is selected from _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _C3-6 cycloalkyl- _C1-4 alkyl, and _C1-6 alkoxy, where the _C1-6 alkyl, _C1-6 alkoxy- _C1-6 alkyl, _C3-6 cycloalkyl, _{C3-6 cycloalkyl} -C Each of _{the 1-4} alkyl and _C1-6 alkoxy groups may be optionally substituted with one to three substituents independently selected from halogens and CN;
^A3 and ^R4 may optionally combine to form a ring, more preferably a 5- to 8-membered heteroring, more preferably a 6-membered heteroring;
X is Cl, Br, or I);
A compound of the same, or its salt or N-oxide.