JPH11209352A - Thiosemicarbazones and pest-controlling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having excellent biological activity and useful as a pest-controlling agent. SOLUTION: This compound is shown by formula I [R<1> is H, a 1-6C alkyl, 3-8C cycloalkyl or (substituted) phenyl; R<3> is a (substituted) phenyl, (substituted) 2-pyridyl or (substituted) pyrazinyl; Het is a (substituted) five-membered heterocycle or benzocondensed heterocycle having five-membered heterocycle], e.g. 3-[2-pyridyl-1-(1,3-thiazol-2-yl)methanone]-1-pyrrolidinethicarbonylhy drazone. It is recommended that the compound of formula I is obtained, for example, by reaction between a compound of formula II and a compound of formula III in a diluent such as ethanol at about -20 to about 150 deg.C under normal pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to novel thiosemicarbazones, a method for producing the same, and use as a pesticide.

[0002]

BACKGROUND OF THE INVENTION WO85 / 00955,
DE-A-4207400 and DE-A-42074
No. 01 describes certain thiosemicarbazones and their use as microbicides. Also, Journal
of Medical Chemistry, 1979, Vol. 22, No. 7, p. 855 and Vol. 22, No. 11, p. 1367, describe thiosemicarbazones having an antimalarial action.

[0003] The present inventors have been conducting research for many years in order to develop excellent pesticides, and in order to create compounds having higher effects and higher safety, many compounds are synthesized and their properties are evaluated. Have been considering.

[0004]

As a result, a novel thiosemicarbazone represented by the following formula (I) having excellent biological activity has been found.

[0005]

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Wherein R ¹ and R ² are each independently
Hydrogen atom, C ₁ - ₆ alkyl, C ₃ - ₈ cycloalkyl or represents an phenyl optionally substituted, or R
¹ and R ² together with the nitrogen atom to which they are attached represent an optionally substituted 5- or 6-membered saturated heterocyclic group; R ³ is optionally substituted phenyl,
Represents optionally substituted 2-pyridyl or optionally substituted 2-pyrazinyl, wherein the substituents on these cyclic groups are cyano, halogen, C _1-4 alkyl, C _1-4 alkoxy and C _1-4 Het is at least one selected from the group consisting of haloalkyl, and Het represents an optionally substituted 5-membered heterocyclic group or a benzo-fused heterocyclic group having a 5-membered heterocyclic ring.

The compound of the above formula (I) of the present invention can be synthesized by any of the following production methods (a) to (d). That is, the production method (a) : Formula

[0008]

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Wherein R ³ and Het are as defined above,

[0010]

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In the formula, R ¹ and R ² are as defined above.
A method of reacting with a compound represented by the formula:

Production method (b) : Formula

[0013]

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Wherein R ³ and Het are as defined above,

[0015]

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In the formula, R ¹ and R ² are as defined above,
A method of reacting with a compound represented by the formula:

Production method (c) : when R ¹ represents a hydrogen atom

[0018]

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Wherein R ³ and Het have the same meaning as defined above, and a compound represented by the formula R ² -NCS (VII) wherein R ² has the same meaning as defined above. How to let.

Production method (d) : The compound of the above formula (VI) is

[0021]

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In the formula, R ¹ and R ² are as defined above,
A method of reacting with a compound represented by the formula:

The thiosemicarbazones of the formula (I) of the present invention exhibit an excellent microbicidal action.

The thiosemicarbazones of the formula (I) provided by the present invention exhibit a stronger microbicidal action than the compounds described in the above-mentioned prior art documents.

In the present specification, the halogen in "halogen" and "haloalkyl" represents fluoro, chloro, bromo or iodo, preferably fluor, chloro or bromo.

"Alkyl" can be linear or branched, and includes, for example, methyl, ethyl, propyl, isopropyl, n-, iso-, sec- or tert-butyl.

“Alkoxy” can be straight-chain or branched and is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-, sec- or ter-
t-butoxy and the like.

As the "cycloalkyl", for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like can be mentioned.

"Haloalkyl" can be straight-chain or branched and includes, for example, trifluoromethyl, 2,2
2,2-trifluoroethyl and the like.

"Phenyl" may be substituted by one or more substituents, and when substituted by more than one substituent, those substituents may be the same or different. Good. Examples of the substituent on phenyl include halogen such as fluoro, chloro, bromo, and iodo; methyl, ethyl, propyl, isopropyl, n
Alkyl such as-, tert-, sec- or iso-butyl; methoxy, ethoxy, propoxy, isopropoxy, n-, tert-, sec- or iso-
Alkoxy such as butoxy and the like can be mentioned.

As the “5- or 6-membered saturated heterocyclic group”, for example, a monovalent group derived from a saturated heterocyclic compound such as pyrrolidine, imidazolidine, pyrazolidine, piperidine, piperazine, morpholine and the like can be mentioned. Can be These heterocyclic groups include, for example, hydroxy, halogen (eg, fluoro, chloro, bromo, etc.), alkyl (eg, methyl, ethyl, propyl, isopropyl, n-,
sec-, iso- or tert-butyl, etc.), alkoxy (for example, methoxy, ethoxy, propoxy,
Isopropoxy), alkylthio (eg, methylthio, ethylthio, propylthio, isopropylthio, etc.), alkylthioalkyl (eg, methylthiomethyl, ethylthiomethyl, etc.), and when there are a plurality of substituents , They may be the same or different.

The "5-membered heterocyclic group" includes, for example, thiophene, thiazole, isothiazole, furan, pyrrole, oxazole, isoxazole, imidazole, pyrazole, pyrazine, triazole, thiadiazole,
1 derived from a heterocyclic compound such as oxadiazole
Valence groups. These heterocyclic groups include, for example, cyano, nitro, halogen (eg, fluoro, chloro,
Bromo, etc.), alkyl (for example, methyl, ethyl, propyl, isopropyl, n-, sec-, iso- or tert-butyl), alkoxy (for example, methoxy, ethoxy, propoxy, isopropoxy, etc.), alkylthio (for example, methylthio) , Ethylthio, propylthio, isopropylthio, etc.), haloalkyl (for example,
Trifluoromethyl, etc.), haloalkoxy (eg, trifluoromethoxy, etc.), cyanoalkyl (eg, cyanomethyl, 1-cyanoethyl, 1-cyanopropyl, etc.), alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl, etc.), alkylthioalkyl (Eg, methylthiomethyl, ethylthiomethyl, etc.), and when there are a plurality of substituents, they may be the same or different.

The “benzo-fused heterocyclic group having a 5-membered heterocyclic group” is a cyclic group having a structure in which a heterocyclic ring and a benzene ring exemplified in the above “5-membered heterocyclic group” are condensed, Examples include benzo [b] thiophene, benzothiazole, benzimidazole and the like. These fused heterocyclic groups include cyano, nitro, halogen (eg, fluoro, chloro, bromo, etc.), alkyl (eg, methyl, ethyl, propyl, isopropyl, n-, sec.
-, Iso- or tert-butyl), alkoxy (for example, methoxy, ethoxy, propoxy, isopropoxy), alkylthio (for example, methylthio, ethylthio, propylthio, isopropylthio, etc.), alkylthioalkyl (for example, methylthiomethyl, ethyl) Thiomethyl or the like), and when there are a plurality of substituents, they may be the same or different.

In the compound of the formula (I), preferably, R ¹ and R ² are each independently a hydrogen atom,
_{Represents 1-4} alkyl or C _5-6 cycloalkyl, represents phenyl optionally substituted by at least one substituent selected from the group consisting of halogen, methyl and methoxy, or represents R ¹ and R ^2, together with the nitrogen atom to which they are attached, a pyrrolidinyl, shows a morpholino or piperidino, these saturated heterocyclic group may be substituted by hydroxy or C _1-4 alkyl, R ³ is Represents optionally substituted phenyl, optionally substituted 2-pyridyl or optionally substituted 2-pyrazinyl, and the substituent in these cyclic groups is cyano, fluoro, chloro, bromo, methyl, ethyl Represents at least one selected from the group consisting of propyl, isopropyl, methoxy and trifluoromethyl, And Het is optionally substituted 1,2,4-triazolyl, optionally substituted imidazolyl, optionally substituted thiazolyl, optionally substituted oxazolyl, optionally substituted isoxazolyl, Benzothiazolyl which may be substituted, isothiazolyl which may be substituted, pyrazolyl which may be substituted, thienyl which may be substituted, furyl which may be substituted, pyrrolyl which may be substituted or substituted be indicative of good thiadiazolyl, substituents halogen in these heterocyclic groups, C _1-4 alkyl, C _1-4 cyanoalkyl, C _1-4 alkoxycarbonyl, C ₁ -4 haloalkyl and C ₁ -4
It is at least one selected from the group consisting of haloalkoxy.

In the compounds of the above formula (I), it is particularly preferred that R ¹ and R ² each independently represent C _1-4 alkyl or cyclohexyl, or R ¹ and R ² Taken together with the nitrogen atom present represents pyrrolidinyl, morpholino or piperidino, R ³ represents phenyl, 2-pyridyl or 2-pyrazinyl and Het is optionally substituted 1,
Represents 2,4-triazolyl, optionally substituted thiazolyl, optionally substituted imidazolyl, optionally substituted thienyl or optionally substituted thiadiazolyl, and the substituent in these heterocyclic groups is It is at least one selected from the group consisting of fluoro, chloro, bromo, methyl, cyanomethyl, ethyl, propyl, isopropyl, trifluoromethyl, trifluoromethoxy and ethoxycarbonyl.

Specific examples of the compound of the formula (I) of the present invention include the compounds shown in Table 1 below.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

[Table 6]

[0043]

[Table 7]

In the production method (a), as a raw material, for example,
Methyl 3- [1- (2-pyridyl) -1- (1,3-
When thiazolyl-2-yl) methylidene] hydrazine carbodithioate and pyrrolidine are used, they are represented by the following reaction formula.

[0045]

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In the production method (b), for example,
When 2-pyridyl- (1,3-thiazol-2-yl) methanone and 1-pyrrolidinethiocarbohydrazide are used, they are represented by the following reaction formula.

[0047]

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In the production method (c), as a raw material, for example,
When [2-pyridyl- (1,3-thiazol-2-yl) methanone] hydrazone and 4-chlorophenylisothiocyanate are used, they are represented by the following reaction formula.

[0049]

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In the production method (d), as a raw material, for example,
[2-Pyridyl- (1-1,3-thiazol-2-yl) methanone] When hydrazone and N, N-dimethylthiocarbamoyl chloride are used, they are represented by the following reaction formula.

[0051]

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In the above-mentioned production method (a), the compound of the formula (II) used as a raw material is, for example, a compound of the formula (IV) and methyl hydrazine carbodithioate, which is the same as in the production method (b) described later. It can be produced by reacting under conditions.

Examples of compounds of formula (II) include methyl
3- [1- (2-pyridyl) -1- (1,3-thiazolyl-2-yl) methylidene] hydrazine carbodithioate and the like.

In the above process (a), the compound of the formula (III) used as a raw material is well known in the field of organic chemistry, and examples thereof include morpholine, pyrrolidine, piperidine, dimethylamine and diethylamine. And the like.

In the above production method (b), the compound of the formula (IV) used as a raw material is, for example, a compound of the formula Br-Het wherein Het has the same meaning as described above. formula

[0056]

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In the formula, R ³ can be obtained by reacting with a compound represented by the same definition as described above. This synthesis method is well known as aromatic acylation using an organometallic compound.

Examples of the compound of the formula (IV) include 2-phenyl- (1,3-thiazol-2-yl) methanone,
Examples thereof include 2-pyridyl- (1,3-thiazol-2-yl) methanone and 2-pyrazinyl- (1,3-thiazol-2-yl) methanone.

In the above-mentioned production method (b), the compound of the formula (V) as a raw material is, for example, Journal of Medicinal Chem
istry, Vol. 22, No. 11, 1979, 1367-1373
It is described on the page together with the production method. Examples of compounds of formula (V) include 1-pyrrolidinethiocarbohydrazide,
Examples thereof include 2,2-dimethylthiosemicarbazide, 2,2-diethylthiosemicarbazide, 2-ethyl-2-methylthiosemicarbazide, 1-piperidinethiosemicarbazide and the like.

In the above-mentioned production methods (c) and (d), the compound of the formula (VI) used as a starting material is, for example, a compound of the above-mentioned formula (IV) and hydrazine in a production method (b) described later. The reaction can be carried out according to the following. Examples of compounds of formula (VI) include:
[2-pyridyl- (1,3-thiazol-2-yl) methanone] hydrazone, [2-pyridyl- (4-methyl-
[1,3-thiazol-2-yl) methanone] hydrazone, [2-pyridyl- (5-methyl-1,3-thiazol-2-yl) methanone] hydrazone, [2-pyridyl- (5-chlorothiphen-2- Il) methanone] hydrazone.

In the above process (c), the compound of the formula (VII) used as a raw material is a compound well known in the field of organic chemistry, and examples thereof include 4-chlorophenylisothiocyanate and 4-fluorophenyl. Isothiocyanate and the like can be mentioned.

In the above production method (d), the compound of the formula (VIII) used as a raw material is a compound well known in the field of organic chemistry, and examples thereof include N, N-dimethylthiocarbamoyl chloride, N , N-diethylthiocarbamoyl chloride, N-pyrrolidinethiocarbamoyl chloride and the like.

The reaction of the above process (a) can be carried out in a suitable diluent, and examples of the diluent used in this case include water; aliphatic, cycloaliphatic and aromatic hydrocarbons. (Optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene Etc .; ethers such as ethyl ether, methyl ethyl ether,
Isopropyl ether, butyl ether, dioxane,
Dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc .; nitriles, such as acetonitrile, propionitrile, acrylonitrile, etc .; alcohols, such as methanol, ethanol, isopropanol, butanol, ethylene glycol, etc .; esters Classes, for example, ethyl acetate,
Amyl acetate and the like; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA) and the like Sulfones, sulfoxides, for example, dimethyl sulfoxide (D
MSO), sulfolane and the like; bases such as pyridine and the like.

The production method (a) can be carried out within a substantially wide temperature range. Generally, about -20 to about 1
It can be carried out at a temperature of 50C, preferably between about 0 and about 100C. The reaction is desirably performed under normal pressure, but may be optionally performed under elevated or reduced pressure.

In carrying out the production method (a), for example, 0.1 mol to 20 mol of the compound of the formula (III) in a diluent such as ethanol is reacted with 1 mol of the compound of the formula (II). By doing so, the target compound of the formula (I) can be obtained.

The reaction of the above process (b) can be carried out in a suitable diluent, and examples of the diluent used in this case include aliphatic, cycloaliphatic and aromatic hydrocarbons (in some cases). May be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and the like; Ethers, for example, ethyl ether, methyl ethyl ether,
Isopropyl ether, butyl ether, dioxane,
Dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc .; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, etc .; esters, such as ethyl acetate, amyl acetate, etc .; acid amides ,
For example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2
-Imidazolidinone, hexamethylphosphoric triamide (HMPA) and the like; sulfones and sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolane; and bases such as pyridine.

The production method (b) can be carried out in the presence of an acid catalyst. Examples of the acid catalyst that can be used include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, sodium bisulfite and the like; Organic acids such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like; organic amine hydrochlorides such as pyridine hydrochloride, triethylamine hydrochloride and the like; aminesulfonic acid Salts, for example, pyridine p-toluenesulfonic acid salt, triethylaminesulfonic acid and the like can be mentioned.

The production method (b) can be carried out within a substantially wide temperature range. Generally, about -20 to about 1
It can be carried out at a temperature of 50C, preferably between about 0 and about 100C. The reaction is desirably performed under normal pressure, but may be optionally performed under elevated or reduced pressure.

In carrying out the production method (b), for example, 0.5 mol to 10 mol of the compound of the formula (V) in a diluent such as ethanol is added to 1 mol of the compound of the formula (IV), By reacting in the presence of an acid catalyst,
The desired compound of formula (I) can be obtained.

The reaction of the above process (c) can be carried out in a suitable diluent, and examples of the diluent used in this case include water; aliphatic, cycloaliphatic and aromatic hydrocarbons. (Optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene Etc .; ethers such as ethyl ether, methyl ethyl ether,
Isopropyl ether, butyl ether, dioxane,
Dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc .; nitriles, such as acetonitrile, propionitrile, acrylonitrile, etc .; alcohols, such as methanol, ethanol, isopropanol, butanol, ethylene glycol, etc .; esters Classes, for example, ethyl acetate,
Amyl acetate and the like; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA) and the like Sulfones, sulfoxides, for example, dimethyl sulfoxide (D
MSO), sulfolane and the like; bases such as pyridine and the like.

The production method (c) can be carried out in the presence of an acid binder. Examples of the acid binder that can be used include inorganic bases such as hydrides, hydroxides and carbonates of alkali metals and alkaline earth metals. , Bicarbonates and the like, for example, sodium hydride, lithium hydride, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; inorganic alkali metals Amides such as lithium amide, sodium amide, potassium amide and the like; organic bases such as alcoholates, tertiary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMED
A), N, N-dimethylaniline, N, N-diethylaniline,
Pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and the like; Organic lithium compounds, for example, methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, dimethylkappa-lithium, lithium diisopropylamide, lithium cyclohexylisopropylamide, lithium dicyclohexylamide, n-
Butyl lithium DABCO, n-butyl lithium DBU, n-butyl lithium TMEDA and the like can be mentioned.

The production method (c) can be carried out within a substantially wide temperature range. Generally, about -70 to about 1
It can be carried out at a temperature of 50C, preferably between about 0 and about 100C. The reaction is desirably performed under normal pressure, but may be optionally performed under elevated or reduced pressure.

In carrying out the production method (c), for example, 0.1 mol to 20 mol of the compound of the formula (VII) in a diluent such as tetrahydrofuran is added to 1 mol of the compound of the formula (VI) for triethylamine. The target compound of the formula (I) in which R ¹ represents a hydrogen atom can be obtained by reacting in the presence of

The reaction of the above production method (d) can be carried out in a suitable diluent, and examples of the diluent used in this case include aliphatic, cycloaliphatic and aromatic hydrocarbons (in some cases). May be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and the like; Ethers, for example, ethyl ether, methyl ethyl ether,
Isopropyl ether, butyl ether, dioxane,
Dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like; ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (M
Nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc .; esters, for example, ethyl acetate, amyl acetate, etc .; acid amides, for example,
Dimethylformamide (DMF), dimethylacetamide (DM
A), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide
(HMPA) and the like; sulfones, sulfoxides, for example, dimethyl sulfoxide (DMSO), sulfolane and the like; bases, for example,
Pyridine and the like can be mentioned.

The production method (d) can be carried out in the presence of an acid binder, and usable acid binders include inorganic bases such as hydrides, hydroxides and carbonates of alkali metals and alkaline earth metals. , Bicarbonates and the like, for example, sodium hydride, lithium hydride, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; inorganic alkali metals Amides such as lithium amide, sodium amide, potassium amide and the like; organic bases such as alcoholates, tertiary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMED
A), N, N-dimethylaniline, N, N-diethylaniline,
Pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and the like; Organic lithium compounds, for example, methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium,
Phenyllithium, dimethylkappa-lithium, lithium diisopropylamide, lithium cyclohexylisopropylamide, lithium dicyclohexylamide, n
-Butyl lithium DABCO, n-Butyl lithium DBU, n-
Butyllithium and TMEDA can be mentioned.

Process (d) can be carried out in the presence of a catalyst, and examples of usable catalysts include triethylamine,
1,8-diazabicyclo [5,4,0] undec-7-ene (DBU),
Pyridine, 4- (N, N-dimethylamino) pyridine and the like can be mentioned.

Process (d) can be performed within a substantially wide temperature range. Generally, about -70 to about 1
It can be carried out at a temperature of 50C, preferably between about 0 and about 100C. The reaction is desirably carried out under normal pressure, but may be operated under pressure or under reduced pressure in some cases.

In carrying out the production method (d), for example, 0.1 mol to 20 mol of the compound of the formula (VII) in a diluent such as acetonitrile is added to 1 mol of the compound of the formula (VI).
The target compound of the formula (I) can be obtained by reacting the compound of the formula (I) in the presence of triethylamine.

The compounds of the formula (I) according to the invention have a strong microbicidal action. And the active compound of the formula (I) of the present invention exerts an accurate control effect on pests without causing phytotoxicity to cultivated plants. Thus, they can be used as pesticides, in particular as pesticides.

The active compounds according to the invention have a strong bactericidal action and can be advantageously used, for example, for controlling unwanted phytopathogenic microorganisms.

The active compounds according to the invention are generally used as microbicidal (mold) agents, for example, Plasmiophoromycetes.
s), Oomycetes, Chytridiomycetes,
It can be used against various plant diseases caused by Zygomycetes, Ascomycetes, Basidiomycetes or Deuteromycetes, and can also be used as a microbicide (e. , Rhizobiaceae, Enterobacteriaceae, Corynebacteriaacea
e) or Streptomyces (Streptomycaceae)
etaceae) can be used against various plant diseases caused by bacteria.

The active compound of the present invention exhibits a good affinity for plants at the concentration of the active compound necessary for controlling the above-mentioned phytopathogenic microorganisms. Chemical treatment of rootstocks and seeds, and soil treatment are possible.

When the active compound of the present invention is used as a pesticide, it can be formulated into a usual preparation. As the formulation form, for example, liquids, wettable powders, emulsions, suspensions, powders, foams, pastes, tablets, granules,
Aerosols, active compound infiltration-natural and synthetic, microcapsules, seed coatings, ULV [cold mist, warm mist
mist)].

These preparations can be prepared by a method known per se. For example, an active compound can be used as a developing agent,
That is, it can be prepared by mixing with a liquid diluent, a solid diluent or a carrier, and in some cases, a surfactant, ie, an emulsifier and / or dispersant and / or a foam-forming agent.

As the liquid diluent or carrier, generally,
Aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [ For example, paraffins such as cyclohexane (for example, mineral oil fractions)
Etc.], alcohols (eg, butanol, glycol) and their ethers and esters, ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and strong polar solvents (eg, dimethylformamide, dimethyl sulfoxide, etc.) , Water and the like. When water is used as the developing agent, for example, an organic solvent can be used as an auxiliary solvent.

Examples of the solid diluent include soil natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite, diatomaceous earth, etc.)
Soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicate, etc.) and the like can be mentioned.

Examples of solid carriers for granules include:
Crushed and sorted rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic or organic powder,
Fine particles of organic substances (eg, sawdust, coconut, corn cob, tobacco stem, etc.) can be mentioned.

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (eg, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate) , Arylsulfonates, etc.], and albumin hydrolysis products.

The dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Fixing agents can also be used in the preparations (powder, granules, emulsions).
For example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate, etc.) and the like can be mentioned. Coloring agents can also be used, such as inorganic pigments (eg, iron oxide, titanium oxide, Prussian blue, etc.), organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and iron, Mention may be made of trace elements such as manganese, boron, copper, cobalt, molybdenum, zinc and salts of these metals.

The preparation generally contains the active ingredient in an amount of 0.1%.
To 95% by weight, preferably 0.5 to 90% by weight.

The active compounds according to the invention can be incorporated in the abovementioned formulations or in various use forms with other known active compounds, such as fungicides (fungicides, bactericides, etc.), insecticides,
Acaricides, nematicides, herbicides, bird repellents, growth regulators, fertilizers and / or soil conditioners can also be present.

When the active compounds of the present invention are used, they are used directly as they are or in the form of preparations for spraying, emulsions, suspensions, powders, tablets, pastes, microcapsules, granules and the like. Or a further diluted preparation for use. The active compound can then be prepared in the customary manner, for example by spraying a solution.
g), dipping, spraying, atomization
ng, misting), irrigation, suspension formation, application, dusting, dusting, dusting, wet coating, wet coating, pasty coating, feather coating and the like.

In treating each part of the plant, the active compound concentration in the actual use forms can be varied within a substantial range. And generally 0.0001-1
%, Preferably in the range of 0.001 to 0.5% by weight.

For seed treatment, the active compound is added to the seed 1
0.001 to 50 g per kg, preferably 0.01 to 1
It can be used within the range of 0 g.

In soil treatment, the point of action is set at 0.
00001 to 0.1% by weight, especially 0.0001 to 0.0
Concentrations of active compound in the range of 2% by weight can generally be used.

Next, the present invention will be described more specifically with reference to examples, but the present invention should not be limited to these examples.

[0098]

EXAMPLES Synthesis Example 1

[0099]

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Methyl 3- [1- (2-pyridyl) -1
-(1,3-thiazol-2-yl) methylidene] hydrazine carbodithioate (2.06 g) was dissolved in ethanol (30 ml), pyrrolidine (0.60 g) was added, and the mixture was stirred with heating at 70 to 80 ° C. for 8 hours. did. The ethanol was distilled off and the residue was purified by silica gel column chromatography (eluent: chloroform) to give 3 as yellow crystals.
-[2-Pyridyl-1- (1,3-thiazol-2-yl) methanone] -1-pyrrolidine thiocarbonylhydrazone (1.60 g) was obtained.

Melting point 156-160 ° C. Synthesis Example 2

[0102]

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2-pyrazinyl- (1,3-thiazole-
2-yl) methanone (0.7 g), 1-pyrrolidine thiocarbahydrazide (0.64 g) and p-toluenesulfonic acid (0.1 g) were dissolved in ethanol (30 ml) for 7 minutes.
The mixture was heated and stirred at 0 to 80 ° C. for 8 hours. The ethanol was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform) to give 3-powder as a yellow powder.
[2-pyrazinyl- (1,3-thiazol-2-yl)
[Methanone] -1-pyrrolidine thiocarbonylhydrazide (0.75 g) was obtained.

Melting point: 158-162 ° C. Synthesis Example 3

[0105]

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2-pyridyl- (1,3-thiazole-2
-Yl) methanone (0.76 g), 4-n-butylthiosemicarbazide (0.71 g) and p-toluenesulfonic acid (0.1 g) in ethanol (20 ml) were used for 70-
The mixture was heated and stirred at 80 ° C. for 8 hours. Ethanol is distilled off, and silica gel column chromatography (elution solvent:
And purified as yellow crystals of 2-pyridyl- (1,3-thiazol-2-yl) methanone 4-.
There was obtained n-butylthiosemicarbazone (0.9 g).

Melting point 100-101 ° C. Synthesis Example 4

[0108]

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2-pyridyl- (1,3-thiazole-2
-Yl) methanone hydrazone (0.71 g), 4-chlorophenylisothiocyanate (0.59 g) and dimethylaminopyridine (0.1 g) were heated and refluxed in anhydrous ether for 4 hours, and allowed to cool. The crystals were collected by filtration and further recrystallized using a mixed solvent of hexane / ethyl acetate to give 2-pyridyl- (1,3-thiazol-2-yl).
Methanone 4- (4-chlorophenyl) -thiosemicarbazone (0.5 g) was obtained.

Melting point: 225-229 ° C. The compound obtained in the same manner as in Examples 1 to 4
Table 2 below shows the compounds synthesized in Nos. 1 to 4.

[0111]

[Table 8]

[0112]

[Table 9]

[0113]

[Table 10]

[0114]

[Table 11]

[0115]

[Table 12]

Preparation of Intermediate Synthesis Example 5: Raw Material of Compound of Synthesis Example 1

[0117]

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2-pyridyl- (1,3-thiazole-2
-Yl) methanone (1.9 g), methylhydrazinecarbodithioate (1.22 g) and p-toluenesulfonate (0.1 g) were stirred in 2-propanol (20 ml) at room temperature for 24 hours. The precipitated crystals are collected by filtration,
After washing with a small volume of cold 2-propanol, methyl 3- [1
-(2-pyridyl) -1- (1,3-thiazole-2-
Yl) methylidene] hydrazinecarbodithioate (1.83 g).

Melting point: 158-159 ° C. Synthesis Example 6: Raw material of compound of Synthesis Example 5

[0120]

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An aqueous solution (80 ml) of potassium hydroxide (85%, 59.4 g) was added to an 85% hydrazine hydrate (57%).
ml) in 2-propanol (70 ml). Under ice-cooling and stirring, carbon disulfide (60.7 ml) was added at 10 ° C.
It was dropped so as not to exceed. After stirring was continued for further 1 hour under ice cooling, methyl iodide (93.5 ml) was similarly added dropwise. After the addition, the mixture was further stirred for 2 hours under ice cooling. The precipitated crystals were collected by filtration, washed with cold water, and recrystallized with dichloromethane to obtain methyl hydrazine carbodithioate (92.5 g).

Melting point: 80-82 ° C. Synthesis Example 7: Raw material of compound of Synthesis Example 2

[0123]

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Dissolve 85% hydrazine hydrate (25 g) in water (25 ml) and add carbon tetrachloride (20 ml). Under ice-cooling and stirring, a solution of pyrrolidinethiocarbonyl chloride (5.5 g) in carbon tetrachloride was added dropwise while maintaining the temperature at 10 ° C. or lower. After the addition, the mixture was stirred at room temperature for 6 hours. The precipitated crystals were collected by filtration and washed with a small amount of carbon tetrachloride to give 1-pyrrolidine thiocarbohydrazine (5 g) as white crystals.
I got

Melting point 170-171 ° C. Synthesis Example 8: Raw material of compound of Synthesis Example 4

[0126]

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2-pyridyl- (1,3-thiazole-2
-Yl) methanone (3.8 g), hydrazine hydrate (2
g) and P-toluenesulfonic acid (0.1 g) were heated under reflux in ethanol (40 ml) for 8 hours. After cooling down,
The solvent was distilled off, and the mixture was subjected to silica gel column chromatography (elution solvent: chloroform: ethanel = 100: 0).
-98: 2) to give 2-pyridyl- (1,3-thiazol-2-yl) methanone hydrazine (3.5
g) was obtained.

Melting point 60-63 ° C. Biological test Test example 1 (Spray test against gray mold) Preparation of active compound Active compound: 30 to 40 parts by weight Carrier: mixture of diatomaceous earth and kaolin (1: 5), 55 to 55
65 parts by weight Emulsifier: polyoxyethylene alkylphenyl ether, 5 parts by weight A wettable powder is prepared by pulverizing and mixing the above-mentioned amounts of the active compound, carrier and emulsifier, and diluting the prescribed dose with water for testing. Used for

Test Method Approximately three kidney beans (variety: Serena) were sowed in a 7 cm-diameter vinyl pot and grown in a greenhouse (15 to 25 ° C.). The test compound prepared as described above was diluted to a predetermined concentration in small seedlings having reached the primary leaves, and 25 per 3 pots.
ml. Gray mold fungus (Botr
One day after spraying, a mixture of spores of Ytis cinerea) with a PSA medium (potato sucrose agar medium) was inoculated into treated plants, and kept in a humid greenhouse at 20 ° C. Four days after inoculation,
The morbidity of each pot was classified and evaluated, and the control value was calculated.
The result is the average of three pots.

Disease degree Lesion area percentage (%) 0 0 0.5 Less than 2 1 Less than 2 to 5 25 Less than 5 10 3 Less than 10 to 20 4 Less than 20 to 40 5 40 or more Control value = (1- ｛) Degree of morbidity in treated plots {Degree of morbidity in untreated plots}) × 100 Results Compound No. 10, 12, 13, 16, 20, 22, 3
1, 34, 35 and 52 exhibited a control value of 90 or more at a concentration of 500 ppm.

Test Example 2 (Spray test on tomato late blight) Test method About 5 tomatoes (variety: Kurihara) were sowed in a 7 cm-diameter vinyl pot and raised in a greenhouse (15 to 25 ° C.). A test compound prepared in the same manner as in Test Example 1 was diluted to a predetermined concentration in small seedlings having reached four leaves, and 25 m per 3 pots was diluted.
1 sprayed. 10 days after spraying, the tomato blight (Phytophthorainfesta) which had been infected beforehand was developed.
The zoospores formed on the lesions of ns) were washed with distilled water in a distilled water to obtain a suspension. The suspension was sprayed and inoculated on the treated plants and kept in a greenhouse at 15 to 20 ° C. 7 days after inoculation,
The morbidity of each pot was classified and evaluated in the same manner as in Test Example 1, and the control value was calculated. The result is the average of three pots.

As a result, Compound Nos. 21, 26, 27,
Compounds 29, 31, 35, 43 and 49 showed a control value of 85 or more at the drug concentration (500 ppm).

Formulation Example 1 (granules) Compound No. 3 of the present invention (10 parts), bentonite (montmorillonite) (30 parts), talc (talc) (58 parts) and lignin sulfonate (2 parts) Add water (25
Part), knead well, and extrude 1
Granules of 0 to 40 mesh are formed and dried at 40 to 50 ° C. to obtain granules.

Formulation Example 2 (Granules) Clay mineral particles (95%) having a particle size distribution of 0.2 to 2 mm
Part) was placed in a rotary mixer, and while rotating, the compound of the present invention No. 1 was mixed with a liquid diluent. 1 (5 parts) is sprayed and moistened evenly, and then dried at 40 to 50 ° C. to obtain granules.

Formulation Example 3 (Emulsion) 3 (30 parts), xylene (5 parts),
Polyoxyethylene alkyl phenyl ether (8 parts)
And calcium alkylbenzene sulfonate (7 parts) are mixed and stirred to form an emulsion.

Formulation Example 4 (Wettable powder) 5 (15 parts), a mixture of white carbon (hydrated amorphous silicon oxide fine powder) and powdered clay (1: 5) (80 parts), sodium alkylbenzenesulfonate (2 parts) and sodium alkylnaphthalenesulfonate formalin polymer (3 parts) was powder mixed and wettable powder was added.

Formulation Example 5 (hydrated granules) 2 (20 parts), sodium lignin sulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) were sufficiently mixed, added with water, extruded through a 0.3 mm screen and dried, Hydrated granules.

[0138]

The novel thiosemicarbazides of the present invention are:
It has excellent microbicidal action as shown in the above biological test examples.

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁶ identifications FI C07D 401/06 207 C07D 401/06 207 211 211 231 231 233 233 249 249 405/12 207 405/12 207 409/12 207 409 / 12 207 413/12 207 413/12 207 417/12 207 417/12 207 (72) Inventor Keiko Tanaka 1-9-31, Wakagicho, Oyama City, Tochigi Prefecture (72) Inventor Taro Kanehara 1 -9-31

Claims (4)

[Claims] 1. The formula: embedded image In the formula, R ¹ and R ² are each independently a hydrogen atom,
_{Denotes 1-6} alkyl, C _3-8 cycloalkyl or optionally substituted phenyl, or R ¹ and R ² together with the nitrogen atom to which they are attached, are optionally substituted A 5- or 6-membered saturated heterocyclic group;
R ³ represents phenyl optionally substituted, an optionally substituted 2-pyridyl or optionally substituted 2-pyrazinyl, substituents cyano in these cyclic groups, halogen, C ₁ - ₄ alkyl , C ₁ - ₄ alkoxy and C _1-4 at least one selected from the group consisting of haloalkyl, and Het is optionally substituted 5
A thiosemicarbazone represented by the formula: which represents a membered heterocyclic group or a benzo-fused heterocyclic group having a 5-membered heterocyclic ring. 2. R ¹ and R ² each independently represent a hydrogen atom, C _1-4 alkyl or C _5-6 cycloalkyl, or at least one selected from the group consisting of halogen, methyl and methoxy Or R ¹ and R ² together with the nitrogen atom to which they are attached,
Represents pyrrolidinyl, morpholino or piperidino, and these saturated heterocyclic groups may be substituted by hydroxy or C _1-4 alkyl; R ³ may be substituted by phenyl; Represents pyridyl or optionally substituted 2-pyrazinyl, and the substituent in these cyclic groups is selected from the group consisting of cyano, fluoro, chloro, bromo, methyl, ethyl, propyl, isopropyl, methoxy and trifluoromethyl At least one kind of which is Het, optionally substituted 1,2,4-triazolyl, optionally substituted imidazolyl, optionally substituted thiazolyl, optionally substituted oxazolyl, substituted Isoxazolyl, optionally substituted benzothiazolyl, substituted Optionally isothiazolyl,
Represents an optionally substituted pyrazolyl, an optionally substituted thienyl, an optionally substituted furyl, an optionally substituted pyrrolyl or an optionally substituted thiadiazolyl, and a substituent in these heterocyclic groups Is halogen, C _1-4 alkyl, C _1-4 cyanoalkyl, C _1-4
Alkoxycarbonyl, C _1-4 haloalkyl and C _1-4
The compound according to claim 1, which is at least one member selected from the group consisting of haloalkoxy. 3. R ¹ and R ² are each independently C 2
_{Represents 1-4} alkyl or cyclohexyl, or R ¹ and R ² together with the nitrogen atom to which they are attached represent pyrrolidinyl, morpholino or piperidino, wherein R ³ is phenyl, 2-pyridyl or 2- Represents pyrazinyl, and Het is optionally substituted 1,
2,4-triazolyl, optionally substituted thiazolyl, optionally substituted imidazolyl, optionally substituted thienyl or optionally substituted thiadiazolyl, wherein the substituents in these heterocyclic groups are 3. The compound according to claim 1, which is at least one member selected from the group consisting of fluoro, chloro, bromo, methyl, cyanomethyl, ethyl, propyl, isopropyl, trifluoromethyl, trifluoromethoxy and ethoxycarbonyl. 4. A pesticidal composition comprising the thiosemicarbazone according to claim 1 as an active ingredient.