JPH0912551A - Iminothioether compounds, their manufacturing methods and intermediates, and bactericides and acaricides - Google Patents

Abstract

(57) [Summary] [Constitution] The following formula Embedded image [In the formula, W is CH or N; R¹Is a C1-4 alkyl group;
R^TwoIs OR^FiveOr NHR ⁶(R^FiveAnd R⁶Is C1-4
Alkyl group); R^ThreeIs a C3-8 cycloalkyl group; R^Four
Is a nitrogen atom or sulfur atom that may be condensed with the benzene ring
4 to 8 members having one or two heterocyclic ring atoms selected from
Represents a heterocyclic ring. ] The iminothioether system shown by
Compound Manufacturing method and sterilization and acaricide containing it as an active ingredient
Agent. [Effect] It has excellent bactericidal and acaricidal efficacy.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel iminothioether compound useful as a bactericide, acaricide, etc.

[0002]

Description of the Prior Art As iminothioether compounds similar to the present invention, the following formulas disclosed in JP-A-2-288806 are disclosed.

[0003]

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(In the formula, W represents CH or N. R ¹ represents an alkyl group, an alkoxy group or an alkylthio group.
² represents a heteroaryl group, a non-aromatic heterocyclic group, or a phenyl group. The symbols of the various substituents defined by this formula are:
Limit to this formula only. It is described that the compound shown by the above) is effective as a fungicide. However,
Disclosure of an iminothioether compound in which the substituent of the carbon atom at the iminomethylthio group site is a cycloalkyl group as in the present invention is not recognized. Therefore, since the iminothioether compound of the present invention is a novel compound, it has not been known that it has not only a further excellent effect as a bactericide but also an excellent migration and acaricidal effect.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel iminothioether compound, a process for producing the same, and a bactericidal and acaricidal agent containing the compound as an active ingredient.

[0006]

Means for Solving the Problems As a result of studies to solve the above problems, the present inventors have found that the novel iminothioether compounds have excellent bactericidal and acaricidal activity, and It came to completion. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0007]

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[In the formula, W represents CH or N.] R¹Is charcoal
It represents an alkyl group having a prime number of 1 to 4. R ^TwoIs OR^FiveOr N
HR⁶Represents (where R^FiveAnd R⁶Can be different
Represents an alkyl group having 1 to 4 carbon atoms. ). R^ThreeIs carbon
It represents a cycloalkyl group of the number 3 to 8. R^FourIs benzene
Selected from nitrogen and sulfur atoms which may be fused with the ring
4- to 8-membered heterocycle having one or two heterocyclic ring atoms
Represents ] Relating to an iminothioether compound
Is what you do. The second invention is the following formula (2):

[0009]

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[In the formula, R ³ and R ⁴ have the same meanings as described in claim 1. However, N- (2-methoxy-5-pyridyl) cyclopropanethiocarboxamide is excluded. ] It is related with the thioamide type compound shown by these. Third
Of the invention, a thioamide compound represented by the above formula (2) and the following formula (3):

[0011]

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(Wherein R ¹ , R ⁵ and W have the same meanings as defined above) and R ² is OR ⁵ in the above formula (1), which is characterized by reacting with a compound represented by the above formula. The following equation (1-
1):

[0013]

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(In the formula, R ¹ , R ^{3 to} R ⁵ and W have the same meanings as described above.) The present invention relates to a process for producing an iminothioether compound. The fourth invention is the following formula (1-2):

[0015]

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(In the formula, R ¹ , R ³ , R ⁴ and R ⁵ have the same meanings as described above.) And an iminothioether compound represented by the following formula (4):

[0017]

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(Wherein R ⁶ has the same meaning as described in claim 1) and R ² in the above formula (1) is NHR ⁶ , W. Is the following equation (1-3) where N:

[0019]

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(In the formula, R ¹ , R ³ , R ⁴ and R ⁶ have the same meanings as described above.) The present invention relates to a process for producing an iminothioether compound. The fifth invention is
The following equation (5):

[0021]

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The compound represented by the formula (wherein R ³ and R ⁴ have the same meanings as described above) is converted to an imino chloride, and then sulfurized.
A method for producing a thioamide compound represented by: A sixth invention is the following formula (6):

[0023]

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(Wherein R ⁴ has the same meaning as described above) and a cyclopropylmagnesium bromide are reacted with each other, and the thioamide compound represented by the above formula (2) is reacted. It relates to the manufacturing method of. The seventh invention relates to a bactericidal and acaricidal agent containing the iminothioether compound represented by the formula (1) as an active ingredient.

Hereinafter, the present invention will be described in detail.Target compounds and raw material compounds Novel iminothioether compounds that are target compounds
(1) [Compounds (1-1) to (1-3)] and raw materials for producing the same
W and R represented by [compounds (2) to (6)]¹~ R
⁶Is as follows. Examples of [W] W include CH and N. [R¹] R¹Is an alkyl group having 1 to 4 carbon atoms.
Can you name some? As an alkyl group, straight chain
Or branched ones; preferably
It is a methyl group.

[R ² ] R ² is OR ⁵ , NHR ⁶
And the like. R ⁵ and R ⁶ are alkyl groups having 1 to 4 carbon atoms which may be different from each other. The alkyl group may be a linear or branched alkyl group; CH ₃ is preferable. [R ³ ] Examples of R ³ include cycloalkyl groups having 3 to 8 carbon atoms. The cycloalkyl group may be a linear or branched one, and is preferably a cyclopropyl group.

[R ⁴ ] R ⁴ is a 4- to 8-membered ring having one or two heterocyclic ring atoms selected from a nitrogen atom and a sulfur atom which may be condensed with a benzene ring, preferably 5 Alternatively, a 6-membered heterocycle can be mentioned. Examples of the heterocycle having only a nitrogen atom as a heterocyclic ring include a pyrrole group, an imidazole group, a pyrazole group, a 1,2,3-triazole group, a 1,2,4-triazole group, a pyridine group, a pyrimidine group and a pyridazine group. , Pyrazine group, 1,
3,5-triazine group, 1,2,4-triazine group, indole group, benzimidazole group, quinoline group, phthalazine group, naphthyridine group, isoquinoline group, quinazoline group and the like can be mentioned; preferably pyridyl group, It is a pyrimidine group. Examples of the pyridyl group include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group and the like; which may have a substituent. Examples of the substituent of the pyridyl group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom and the like. The alkyl group may be a linear or branched one, but is preferably a methyl group; its substitution position is not particularly limited, but in the case of a 2-pyridyl group, preferably a 4-position, They are 5-position and 6-position.

The alkoxy group may be a linear or branched one, but is preferably a methoxy group; its substitution position is not particularly limited, but in the case of a 3-pyridyl group, it is preferably 6 -It is the place. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like, but a chlorine atom, an iodine atom and a bromine atom are preferable; the substitution position thereof is not particularly limited, but a 2-pyridyl group is preferable. In the case of, it is preferably 3-position and 5-position. Examples of the pyrimidine group include a 2-pyrimidyl group, a 4-pyrimidyl group and a 5-pyrimidyl group; a 2-pyrimidyl group is preferable. The pyrimidine group may have a substituent. Examples of the substituent of the pyrimidine group include a linear or branched alkyl group having 1 to 4 carbon atoms and the like;
It is preferably a methyl group; its substitution position is not particularly limited, but in the case of a 2-pyrimidyl group, it is preferably 2-
4th place.

Examples of the heterocyclic ring having only a sulfur atom as a heterocyclic ring atom include a benzothiophene group and a thiophene group, but a thiophene group is preferable. Examples of the thiophene group include a 2-thiophene group and a 3-thiophene group; preferably 3
A thiophene group. The thiophene group may have a substituent. Examples of the substituent of the thiophene group include a linear or branched alkoxycarbonyl group having a carbon number of 2 to 5; preferably a methoxycarbonyl group; its substitution position is not particularly limited,
It is preferably the 2-position in the case of a 3-thiophene group.
Examples of the heterocycle having both a nitrogen atom and a sulfur atom as a heterocyclic ring atom include an isothiazole group, a thiazole group, a thiadiazole group, a benzisothiazole group, a benzothiazole group, and a benzothiadiazole group; A thiazole group and a benzothiazole group. As the thiazole group, 2-thiazole group, 4
-Thiazole group and the like can be mentioned; preferably 2-thiazole group. The thiazole group may have a substituent. As the benzothiazole group, 2-
Examples thereof include a benzothiazole group and a 4-benzothiazole group; and a 2-benzothiazole group is preferable. The benzothiazole group may have a substituent. As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned, and preferable compounds from the viewpoint of drug efficacy are as follows.

(A) W is CH, R ¹ is a methyl group, R ² is an alkoxy group having 1 to 4 carbon atoms, and R ³
Is a cycloalkyl group having 3 to 8 carbon atoms, and R ⁴ is a pyridyl group. (b) W is CH, R ¹ is a methyl group, R ² is an alkoxy group having 1 to 4 carbon atoms, and R ³ is 3 to 3 carbon atoms.
A compound wherein 8 cycloalkyl groups and R ⁴ is a thiazole group. (c) W is CH, R ¹ is a methyl group, R ² is an alkoxy group having 1 to 4 carbon atoms, and R ³ is 3 to 3 carbon atoms.
A compound which is 8 cycloalkyl groups and R ⁴ is a thiophene group. (d) W is CH, R ¹ is a methyl group, R ² is an alkoxy group having 1 to 4 carbon atoms, and R ³ is 3 to 3 carbon atoms.
A compound wherein 8 cycloalkyl groups and R ⁴ is a pyrimidine group.

(E) W is CH, R ¹ is a methyl group, R ² is an alkoxy group having 1 to 4 carbon atoms, and R ³
Is a cycloalkyl group having 3 to 8 carbon atoms and is an R ⁴ benzothiazole group. (f) W is N, R ¹ is a methyl group, R ² is an alkoxy group having 1 to 4 carbon atoms, and R ³ is ³ to 8 carbon atoms.
A cycloalkyl group and R ⁴ is a benzothiazole group. (g) W is N, R ¹ is a methyl group, R ² is an alkoxy group having 1 to 4 carbon atoms, and R ³ is ³ to 8 carbon atoms.
A cycloalkyl group and R ⁴ is a pyridyl group. (h) W is N, R ¹ is a methyl group, and R ² is NH
A R ⁶ (R ⁶ represents 1-4 alkoxy group having a carbon number.), R ³ is a cycloalkyl group having 3 to 8 carbon atoms, a compound wherein R ⁴ is a pyridyl group.

(I) W is N, R ¹ is a methyl group, R ² is an alkoxy group having 1 to 4 carbon atoms, and R ³
Is a cycloalkyl group having 3 to 8 carbon atoms, and R ⁴ is a thiophene group. (j) W is N, R ¹ is a methyl group, and R ² is NH
A R ⁶ (R ⁶ represents 1-4 alkoxy group having a carbon number.), R ³ is a cycloalkyl group having 3 to 8 carbon atoms, a compound wherein R ⁴ is a thiophene group. Examples of W and R ^{1 to} R ⁴ of the compound (1) represented by (a) to (j), which are composed of these preferable combinations, include the preferable ones and more preferable ones shown in the above description. . Specific examples of these compounds (1) include compounds 1 to 24 shown in chemical formulas and physical properties shown in Tables 6 to 9 below.

The compound (1) can be synthesized by the following synthetic method 1 or 2. [Synthesis Method 1] Compound (1-1) [R ² in Compound (1)
Is a compound in which is OR ⁵ . Compound containing compound (1-2)]
Can be produced by reacting the compound (2) with the compound (3) in a solvent as shown below. This reaction can be accelerated in the presence of a base.

[0034]

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(In the formula, R ¹ , R ^{3 to} R ⁵ and W have the same meanings as above.) The kind of the solvent is not particularly limited as long as it does not directly participate in the reaction, and for example, benzene. Chlorinated or unchlorinated aromatic, aliphatic or cycloaliphatic carbonizations such as, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, cyclohexane Hydrogens; diethyl ether, tetrahydrofuran,
Ethers such as dioxane; ketones such as acetone, methyl ethyl ketone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and the like; Triethylamine, pyridine,
Organic bases such as N, N-dimethylaniline and the like;
Mention may be made of 3-dimethyl-2-imidazolidone; dimethylsulfoxide; alcohols such as methanol, t-butanol; mixtures of the solvents mentioned.

The solvent is used in an amount of 0.1 to 0.1% for compound (2).
Can be used up to 80% by weight;
0.1 to 40% by weight is preferable. As the type of base,
There is no particular limitation, and for example, potassium-t-butoxide,
Examples thereof include potassium hydride, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like; preferably potassium-t-
Butoxide. The amount of the base used is 1 to 3 times mol of the compound (2). The reaction temperature is -10 to 130.
℃, but preferably 10 to 80 ℃. The reaction time varies depending on the above concentration and temperature; usually 0.5.
~ 8 hours. The amount of the raw material compound used is the compound (2)
Compound (3) is 0.1 to 4 times by mole; preferably 0.5 to 1.5 times by mole. Compound (2)
Can be synthesized by converting compound (5) to imino chloride and then sulfurizing it.

In the reaction of sulfurization after conversion to imino chloride, phosphorus chloride and inorganic hydrosulfide, trialkylsulfine, alkyl halide and inorganic hydrosulfide can be used. Examples of phosphorus chlorides include phosphorus pentachloride. As inorganic hydrosulfide,
Examples thereof include sodium hydrosulfide. Examples of trialkylsulfine include tributylsulfin and the like. Examples of the alkyl halide include carbon tetrachloride and the like. Alternatively, compound (2) can be produced by reacting compound (6) with cyclopropylmagnesium bromide. Examples of the compound (2) are shown in Tables 1 to 3 below.
Compounds represented by the chemical formula and physical properties described in (2-1) ~ (2-1
5) etc. can be mentioned.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

The compound (5) is described in New Experimental Chemistry Course, 14
Vol. II, p. 1143 (Maruzen), cyclopropylcarbonyl chloride and the corresponding amine in the presence of an organic base such as triethylamine or pyridine or a base such as sodium hydride in the presence of dichloromethane or chloroform. Alternatively, it can be produced by heating reaction in a solvent such as tetrahydrofuran, if necessary. Examples of the compound (5) include compounds (5-1) to (5-15) shown in Tables 4 and 5 below.

[0042]

[Table 4]

[0043]

[Table 5]

The compound (6) is described in New Experimental Chemistry Course, 14
Volume, III, page 1506 (Maruzen)
The corresponding amine is reacted with carbon disulfide in a solvent such as toluene or xylene at room temperature in the presence of a base such as triethylamine or triethylenediamine, and the obtained salt and methyl chloroformate are dissolved in a solvent such as dichloromethane. It can be produced by reacting in a room temperature at room temperature.

Examples of the compound (6) include compounds having R ⁴ shown in Tables 6 to 8 below. When W is CH, the compound (3) is, for example,
According to the method described in JP-A-61-28042,
Methyl-2-methoxy-1- (2-methylphenyl)-
It can be prepared by treating an acrylate with a halogenating agent such as N-bromosuccinimide. When W is N in the compound (3), (E) can be prepared according to the method described in JP-A-2-221253, for example.
-Methyl-2-methylphenylglyoxylic acid can be prepared by treating O-methyloxime with a halogenating agent such as N-bromosuccinimide.

Target compound produced as described above
After completion of the reaction, (1-1) can be subjected to usual post-treatments such as extraction, concentration, filtration and the like, and if necessary, can be appropriately purified by a known means such as recrystallization or various chromatography.
Examples of the compound (1-1) include compounds 1 to 17, 19, 21, 23 and 24 shown in Tables 6 to 8 below.

[Synthesis Method 2] Compound (1-3) [Compound (1)
In which W is N and R ² is NHR ⁶ ]
Can be produced by reacting the compound (1-2) with the compound (4) in a solvent or without solvent, as shown below.

[0048]

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(In the formula, R ¹ and R ^{3 to} R ⁶ have the same meanings as described above.) Examples of the solvent include the solvents described in the method of synthesizing compound (1); It is methanol. The solvent may be used in an amount of 1 to 80% by weight of compound (1-2); preferably 1 to 50% by weight. The reaction temperature is not particularly limited, but -3
Within a temperature range from 0 ° C. to the boiling point of the solvent used;
It is preferably 0 to 80 ° C. The reaction time varies depending on the above concentration and temperature; it is usually 1 to 30 hours. As the compound (4), a commercially available product [methylamine / methanol solution 40% (manufactured by Wako Pure Chemical Industries, product number 131
-10395)] can be used.

Target compound produced as described above
After completion of the reaction, (1-3) can be subjected to usual post-treatments such as extraction, concentration, filtration, etc., and if necessary, can be appropriately purified by a known means such as recrystallization or various chromatography.
As the compound (1-3), the compound 1 shown in Table 8 below is used.
8, 20, 22, etc. can be mentioned.

Bactericidal / Acaricidal Agents [Controlling Effect] The compounds (1) of the present invention which have a controlling effect include agricultural and horticultural pests [for example, mites (Mikanidae of the mite family, citrus mites, etc.). Rust etc.), and agro-horticultural pathogens (eg, wheat leaf rust, barley powdery mildew, cucumber downy mildew, cucumber gray mold, rice blast, tomato epidemic, etc.).

[Bactericidal / Acaricidal Agent] The bactericidal / acaricidal agent of the present invention contains at least one compound (1) as an active ingredient. The compound (1) can be used alone, but it is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent and the like (for example, a powder, an emulsion, a fine granule, a granule, a hydrate) by an ordinary method. Agents, oily suspensions, aerosols and the like).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbonization. Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection), and the like.

Examples of surfactants and dispersants that can be used to improve the performance of the present agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading and the like include, for example, alcohol sulfates and alkyls. Examples thereof include sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent. In the production of the present agent, the above-mentioned carrier, surfactant, dispersant, and auxiliary can be used alone or in appropriate combination according to the respective purposes. When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% for wettable powders.
% By weight, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0055]

EXAMPLES The present invention will be specifically described below with reference examples and examples. Note that these examples do not limit the scope of the present invention. Reference Example 1 [Synthesis of Compound (6)] (1) Synthesis of 2-pyridyl isothiocyanate

[0056]

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2-aminopyridine (9.4 g, 0.1 m)
ol) and triethylenediamine (22.4 g, 0.2 m)
was dissolved in toluene (200 ml), carbon disulfide (14.3 ml, 0.3 mol) was added dropwise with stirring, and the mixture was stirred at room temperature for 24 hours. The reaction solution is filtered,
The solid collected by filtration is washed with toluene and hexane to give yellow 2
-Pyridyldithiocarbamate triethylenediamine salt was obtained. Obtained salt (10.7g, 0.037mo
l) was dissolved in methylene chloride (100 ml) and cooled under water,
Methyl chloroformate (4.2 g, 0.044 with stirring)
(mmol) and then stirred at room temperature for 2 hours. After completion of the reaction, the mixture was filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was subjected to column chromatography (MS-Gel 150-6).
(0A, eluted with toluene) to obtain 2.5 g of the oily target product. CI-MS (isobutane m / z) 137 (M + 1) IR (liquid film cm ^-1 ) 3150, 2000

Reference Example 2 (1) Synthesis of N- (2-methoxy-5-pyridyl) cyclopropanethiocarboxamide

[0059]

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Under a nitrogen stream, phosphorus pentachloride (PCl ₅ )
(1.2 g, 5.5 mmol) was added to methylene chloride (30 m
l) and dissolved with stirring with N- (2-methoxy-5-
Pyridyl) cyclopropanecarboxamide (1.0 g,
(5 mmol) of methylene chloride solution was added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, 70% with stirring under water cooling
Sodium hydrosulfide (NaSH) (3.72 g, 50 mm
ol) in dimethylformamide and stirred at room temperature for 1 hour. After the reaction was completed, water was added to separate the organic layer,
This layer was washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was subjected to column chromatography [MS-Gel 150-60A, toluene:
By elution with ethyl acetate = (1: 0) to (3: 2)], 0.3 g of the oily target product was obtained.

¹ H-NMR (CDCl ₃ , 270 MH
z, 297 K, TMS, δ ppm) 7.8 to 7.5 (1
H, brs), 7.3 to 6.8 (2H, m), 6.7 to
6.4 (1H, m), 3.9 (3H, s), 2.0-
1.8 (1H, m), 1.8-0.8 (4H, m)

Example 1 [Synthesis of Compound (2)] (1) Synthesis of N- (2-pyrimidyl) cyclopropanethiocarboxamide [Compound (2-14)]

[0063]

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N- (2-pyrimidyl) cyclopropanecarboxamide (0.9 g, 5.3 mmol) was dissolved in acetonitrile and stirred with tributylphosphine (1.2 g, 5.8 mmol) and carbon tetrachloride (0.9 mg).
g, 5.8 mmol) was added and the mixture was stirred at room temperature for 1 hour, and then heated under reflux for 2 hours. After cooling this to room temperature,
70% sodium hydrosulfide (1.40 g, 15.9 mmo)
l) was added and the mixture was heated under reflux for 1 hour. After completion of the reaction, the reaction solution was filtered and concentrated under reduced pressure. Toluene was added to the obtained residue, the toluene layer was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. This is subjected to column chromatography [MS-Gel 150-60
A, eluted with toluene: ethyl acetate = (4: 1) to (1: 1)] to give 0.3
g was obtained.

(2) Synthesis of N- (3-pyridyl) cyclopropanethiocarboxamide [Compound (2-8)]

[0066]

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Under a nitrogen stream, magnesium (3.45 g,
0.14 mmol), iodine (1 piece) and tetrahydrofuran (small amount) were mixed, and then cyclopropyl bromide (several drops) was added. When the reaction started violently, a tetrahydrofuran solution (20 ml) of cyclopropyl bromide (6.48 g, 54 mmol) was added dropwise, and the mixture was stirred at room temperature for 30 minutes. The obtained cyclopropyl magnesium bromide (5.7 g, 40 mmol) was added dropwise to a tetrahydrofuran solution (30 ml) in which 3-pyridyl isothiocyanate (5.0 g, 36 mmol) was dissolved, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, saturated saline was added, and then ethyl acetate was added to separate the ethyl acetate layer. This was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was washed with hexane to obtain 4.0 g of the desired product as brown powder crystals.

(3) N- (1,3-thiazol-2-yl) cyclopropanethiocarboxamide [Compound (2-1
1)] Synthesis

[0069]

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N- (1,3-thiazol-2-yl) cyclopropanecarboxamide (1.0 g, 5.9 mmo
Toluene (50 ml) was added to 1) and completely dissolved at 50 ° C., and then Lawesson's reagent (720 mg, 1.7 mmo).
1) was added, and the mixture was heated under reflux for 2 days. After the reaction,
The residue obtained by concentration under reduced pressure was purified by column chromatography [MS-Gel 150-60A, eluted with toluene: ethyl acetate = (1: 0) to (9: 1)] to give the desired product in an amount of 0. 44 g was obtained.

(4) Other compounds in Tables 1 and 2 (2)
Synthesis of Other compounds (2) in Tables 1 and 2 were synthesized according to the methods described in (1) to (3) above. The compounds synthesized as described above are as shown in Tables 1 to 3 above.

Example 2 [Synthesis of Compound (1)] (1) 3-Methoxy-2-('2- (cyclopropyl ("2-
Methoxy- "5-pyridylimino) methylthiomethyl)
Synthesis of phenyl) -methyl acrylate [compound 3]

[0073]

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N- (2-methoxy-5-obtained in Reference Example 1
Pyridyl) cyclopropane thiocarboxamide (0.5
g, 2.4 mmol) in tetrahydrofuran (20 m
l) and dissolved in methyl 3-methoxy-2-('2-bromomethylphenyl) -acrylate (0.68 g, 2.4 m
mol), and potassium-t-butoxide (0.27 g, 2.4 mmol) was added with stirring to obtain 3 at room temperature.
Stirred for hours. After the reaction was completed, saturated saline and ethyl acetate were added to separate the ethyl acetate layer. This layer was further washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by column chromatography [MS-Gel 150-60A, eluted with toluene: ethyl acetate = (1: 0) to (7: 3)] to obtain 0.3 g of an oily desired product. It was

(2) Synthesis of Methyl E-3-methoxy-2-('2- (cyclopropyl ("2-methoxy-" 5-pyridylimino) methylthiomethyl) phenyl) -2-iminoacetate [Compound 19]

[0076]

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N- (2-methoxy-5-obtained in Reference Example 1
Pyridyl) cyclopropane thiocarboxamide (1.0
g, 4.8 mmol) to tetrahydrofuran (20 m
l) and dissolved in methyl E-3-methoxy-2-('2-bromomethylphenyl) -2-iminoacetate (1.21 g,
4.8 mmol), and potassium -t- with stirring.
Butoxide (0.53 g, 4.8 mmol) was added, and the mixture was stirred at room temperature for 3 hours. After the reaction is completed, cool to room temperature,
Saturated saline and ethyl acetate were added and the ethyl acetate layer was separated. This layer was further washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained residue is subjected to column chromatography [MS-Gel
150-60A, toluene: ethyl acetate = (9: 1)-
By elution with (1: 1)], 0.3 g of the oily target product was obtained.

(3) N-methyl-E-3-methoxy-2
Synthesis of-('2- (cyclopropyl ("2-methoxy-" 5-pyridylimino) methylthiomethyl) phenyl) -2-iminoacetic acid amide [Compound 20]

[0079]

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Methyl E-3-methoxy-2-('2- (cyclopropyl ("2-methoxy-" 5-pyridylimino) methylthiomethyl) phenyl) -2-iminoacetate (0.
16 g, 0.4 mmol) was dissolved in methanol (10 ml), and 40% methylamine-methanol solution (0.3
g, 4 mmol) was added, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure, and the obtained residue was subjected to column chromatography [MS-Gel 150-60A, toluene:
By eluting with ethyl acetate = (4: 1) to (1: 1)], 0.1 g of the oily target product was obtained.

(4) Synthesis of other compounds (1) in Tables 6 to 8 Other compounds (1) in Tables 6 to 8 were synthesized according to the methods described in (1) to (3) above. did. The compounds synthesized as described above and their physical properties are shown in Tables 6-9.

[0082]

[Table 6]

[0083]

[Table 7]

[0084]

[Table 8]

[0085]

[Table 9]

Example 3 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium lignin sulfonate were uniformly mixed, and then a small amount of water was added and kneaded, and then granulated and dried to obtain granules.

(2) Preparation of Wettable Powder 10 parts by weight of compound 1, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of neoperex powder (trade name; manufactured by Kao Corporation) and demol (product) Name; made by Kao Co., Ltd.) and 0.5 parts by weight, and
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of Compound 1 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Kasei Co., Ltd.) were added and mixed uniformly to obtain an emulsion. .

(4) Preparation of powder preparation 5 parts by weight of compound 1, 50 parts by weight of talc and 4 of kaolin
5 parts by weight were uniformly mixed to obtain a powder.

Example 4 [Efficacy test] (1) Efficacy test against adult females of the genus Acarina The compounds (1) shown in Tables 6 to 8 prepared according to Example 3
Each wettable powder of 3 with water containing surfactant (0.01%)
Each bean leaf (20 m in diameter) diluted to 00 ppm and infested with 10 adult female spider mites in each of these chemicals.
m) for 15 seconds. Next, each leaf piece was left in a constant temperature room at 25 ° C., and after 3 days, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate. Evaluation of the acaricidal effect
Four stages (A: 100%, B:
Less than 100 to 80%, C: less than 80 to 60%, D: 60
%). In addition, as shown in Table 10, Japanese Patent Laid-Open No.
Comparative compound 3 described in JP-A-992929 was examined in the same manner as in the case of compound (1) and used as a comparative example.

[0091]

[Table 10]

The results are shown in Table 11.

[0093]

[Table 11]

(2) Control efficacy test against cucumber downy mildew One cucumber (cultivar: Sagamihanjiro) was cultivated in a plastic flower pot with a diameter of 6 cm, and seeded on a 1.5 leaf stage seedling. An acetone solution of the target compound (1) shown in 6 to 8 or a wettable powder prepared according to Example 3 was diluted to 200 ppm with water containing a surfactant (0.01%),
20 ml was applied per pot. After spraying, grow in a glass greenhouse for 2 days, then cucumber downy mildew (Pseudopero
zoosporangium of Nospora cubensis) was prepared from diseased leaves, and this was uniformly spray-inoculated on the back surface of plant leaves. After inoculation, the mixture was kept in the dark at 20 ° C. for 2 days and then grown in a glass greenhouse for 5 days to examine the degree of cucumber downy mildew lesions appearing on the first leaf.

The evaluation of the drug effect was carried out by calculating the control rate by comparing with the degree of lesions in the untreated section, and classified into 6 levels (0: control rate 31
%, 1: Control rate is less than 31-61%, 2: Control rate is less than 61-81%, 3: Control rate is less than 81-95%,
4: Control rate is less than 95-99%, 5: Control rate is 100
%). In addition, as shown in Table 10, Japanese Patent Laid-Open No. 2-2
Comparative Compounds 1, 2, or 3 described in JP-A-88806 and JP-A-6-92929 are converted into compound (1)
In the same manner as in the above case, the examination was carried out and it was set as a comparative example. Table 1 shows the results.
It is shown in FIG.

[0096]

[Table 12]

(3) Control efficacy test against cucumber gray mold The cotyledon of cucumber (variety: Sagamihanjiro) lined in a container lined with water-moistened paper is placed on the top, and the cucumber gray mold fungus (Botrytis cinerea) is placed. ) (5 × 10 ⁵ spores / ml) to 50
μl was dropped, and a paper disk was placed thereon, and immediately, an acetone solution of the compound (1) shown in Tables 6 to 8 or a wettable powder prepared according to Example 3 was added with a surfactant (0.01
%) And diluted with water to 500 ppm, and 90 μl of the solution was dropped on the paper disk. Then, after keeping in the dark at 20 ° C. for 4 days, the diameter of the lesions that appeared was investigated. The results are evaluated using the 6-step evaluation method described in (2) above.
It shows in Table 13.

[0098]

[Table 13]

(4) Control efficacy test against rice blast (preventive effect) Ten rice plants (cultivar: Nihonbare) were grown in a plastic flower pot with a diameter of 6 cm, and seedlings of 1.5 leaf stage were grown. The acetone solution of the target compound (1) shown in Tables 6 to 8 or each wettable powder prepared according to Example 3 was diluted to 40 ppm with water containing a surfactant (0.01%), and 20 ml was sprayed per pot. After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then a conidial suspension of rice blast fungus (Pyricularia oryzae) prepared from diseased leaves was uniformly spray-inoculated onto plant leaves. After inoculation, the plants were grown for 5 days in a humidified room at 28 ° C., and the degree of rice blast lesions appearing on the leaves was examined.
The results are shown in Table 14 by the 6-step evaluation method described in (2) above.

[0100]

[Table 14]

(5) Control efficacy test against barley powdery mildew (preventive effect) 10 barleys (cultivar: black wheat) were grown in a plastic flower pot with a diameter of 6 cm, and 1.5 leaf stage seedlings were grown. In addition, each of the acetone solutions of the target compound (1) shown in Tables 6 to 8 or each wettable powder prepared according to Example 3 was diluted to 200 ppm with water containing a surfactant (0.01%). Then, each of these chemical solutions was sprayed in an amount of 20 ml per pot. Grow these in a glass greenhouse for 2 days, then
Conidia of barley powdery mildew (Erysiphe graminis) were collected from the diseased leaves and sprinkled evenly over each plant to inoculate. Next, these were grown in a glass greenhouse for one week, and the degree of barley powdery mildew spots that appeared on each first leaf was investigated. The results are shown in Table 15 by the 6-step evaluation method described in (2) above.

[0102]

[Table 15]

(6) Control Efficacy Test for Wheat Leaf Rust (Preventive Effect) Ten wheat (cultivar: Kobushi Wheat) was cultivated in a plastic flower pot with a diameter of 6 cm, and 10 seeds were cultivated at 1.5 leaf stage. 1 of the target compound (1) shown in Tables 6 to 8
% Acetone solution or a wettable powder prepared according to Example 3 was diluted to 40 ppm with water containing a surfactant (0.01%) and sprayed at 20 ml per pot. After spraying, 2
The plants were cultivated in a glass greenhouse for one day, and then a spore suspension (7 × 10 ⁴ spores / ml) of wheat leaf rust (Puccinia recondita) was uniformly spray-inoculated on the plants. After inoculation, the plants were grown for one week in a glass greenhouse, and the degree of wheat leaf rust spots on the first leaves was examined. The results are shown in Table 16 by the 6-step evaluation method described in (2) above.

[0104]

[Table 16]

(7) Efficacy test for transferability One cucumber (cultivar: Sagamihanjiro) was grown in a plastic flower pot with a diameter of 6 cm to grow the first leaf of a 1.5-leaf stage seedling. , The target compound (1) shown in Tables 6 to 8
1% acetone solution of was diluted to 1000 ppm with water containing a surfactant (0.01%), and 50 μl of the drug solution was added dropwise. Then, on top of that, an appropriate amount of carboxymethyl cellulose was added in order to prevent the chemical liquid from flowing out and to clarify the chemical liquid treated portion. The day after the chemical treatment, zoosporangia of cucumber downy mildew (Pseudoperonospora cubensis) was prepared from the diseased leaves, and this was uniformly spray-inoculated on the back surface of the plant leaves. After inoculation, the mixture was kept in the dark at 20 ° C. for 2 days and then grown in a glass greenhouse for 5 days to examine the degree of cucumber downy mildew lesions appearing on the first leaf. The comparative compound 3 and the commercial agent cimoxanil were examined in the same manner as in the case of the compound (1). The transferability was evaluated as + when the control effect was exerted only on the chemical solution-treated part and +++ when the control effect was exhibited from the chemical solution-treated part to the leaf edge. Table 17 shows the results.

[0106]

[Table 17]

[0107]

INDUSTRIAL APPLICABILITY The novel iminothioether compound of the present invention has excellent effects such as sterilization and acaricide.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area A01N 43/78 101 A01N 43/78 101 C07D 239/42 C07D 239/42 Z 277/42 277/42 277/82 277/82 333/38 333/38 (72) Inventor Hideaki Umeyama 5 1978, Koujigushi, Ube City, Yamaguchi Prefecture Ube Institute of Industrial Research Co., Ltd. Ube Laboratory

Claims (7)

[Claims] 1. The following formula (1):[In formula, W represents CH or N. R¹Is 1 to 4 carbon atoms
Represents an alkyl group. R ^TwoIs OR^FiveOr NHR⁶Represents
(Note that R^FiveAnd R⁶Is a carbon number which may be different from 1 to
Represents 4 alkyl groups. ). R^ThreeHas 3 to 8 carbon atoms
Represents a cycloalkyl group. R^FourIs condensed with the benzene ring
1 or 2 selected from nitrogen atom and sulfur atom
Represents a 4- to 8-membered heterocycle having a heterocyclic ring. 〕so
The iminothioether compounds shown. 2. The following formula (2): [In the formula, R ³ and R ⁴ have the same meanings as described in claim 1. However, N- (2-methoxy-5-pyridyl) cyclopropanethiocarboxamide is excluded. ] The thioamide type compound shown by these. 3. A thioamide compound represented by the formula (2) according to claim 2 and the following formula (3): (Wherein R ¹ , R ⁵ and W have the same meanings as described in claim 1) and R ^{2 in} the formula (1) according to claim 1, characterized in that the compound is reacted. Is an OR ⁵ in the following formula (1-1): (In the formula, R ¹ , R ^{3 to} R ⁵ and W have the same meanings as described in claim 1.) A process for producing an iminothioether compound. 4. The following formula (1-2): (In the formula, R ¹ , R ³ , R ⁴ and R ⁵ have the same meanings as described in claim 1.) and an iminothioether compound represented by the following formula (4): (Wherein R ⁶ has the same meaning as described in claim 1.) The compound of formula (1) according to claim 1, wherein R ² is NHR ⁶ , W Where N is N: (1-3): (In the formula, R ¹ , R ³ , R ⁴ and R ⁶ have the same meanings as defined in claim 1.) A process for producing an iminothioether compound. 5. The following formula (5): (In the formula, R ³ and R ⁴ have the same meanings as defined in claim 1.) After converting the compound represented by the formula 1 into an imino chloride,
Sulfuration, The manufacturing method of the thioamide type compound shown by Formula (2) of Claim 2 characterized by the above-mentioned. 6. The following formula (6): (In the formula, R ⁴ has the same meaning as described in claim 1.) The compound represented by formula (2) is reacted with cyclopropylmagnesium bromide, and the thioamide represented by formula (2) according to claim 2. Method of manufacturing system compounds. 7. A bactericidal and acaricidal agent containing an iminothioether compound represented by the formula (1) according to claim 1 as an active ingredient.