JPH08134037A - 2,2-dichlorocyclopropanehydroxamic acid derivative and agricultural disinfectant containing same - Google Patents

Abstract

PURPOSE: To obtain the subject derivative having a cyclopropanehydroxamic acid part substituted with chlorine atom, excellent in a fungicide, not exhibiting phytotoxicity to Oryza sativa and exhibiting excellent controlling effect, especially on rice blast disease.

CONSTITUTION: This compound is represented by formula I {R₁ to R₃ are each H or a lower alkyl; A is H or OR₄ (R₄ is H or a lower alkyl, lower acyl or lower alkylsulfonyl which may be substituted); when A is H, B is a group of formula II [X is a halogen, a lower (halo)alkyl or a lower (halo)alkoxy; (n) is 0 or 1-3] and when A is OR₄, B is a group of formula}, e.g. N-1-(4- chlorophenyl)ethyl-N-methoxy-2,2-dichloro-1-methyl-2-trans- methylcyclopropanecarboxamide. Furthermore, the objective derivative is preferably used by reacting, e.g. 2,2-dichlorocyclopropanecarboxylic chloride of formula IV with a hydroxylamine derivative of formula V in a solvent or without solvent by using an acid binding agent.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel 2,2-dichlorocyclopropanehydroxamic acid derivative not described in the literature and an agricultural fungicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication No. 63-54949 discloses the following general formulas (A) and (A ') as novel cyclopropanecarboxamide derivatives having antibacterial activity:

[0003]

[Chemical 7]

[In the formula, X represents halogen, alkyl, cyano, nitro, haloalkyl, alkoxy or haloalkoxy, n represents 0, ¹ , 2 or 3, and R ¹ represents a hydrogen atom, halogen, alkyl or cyclo. Alkyl, R ² , R ³ , R ⁶ , R ⁷ , and R ⁸ each represent a hydrogen atom or alkyl, provided that R ⁷ and R ⁸ do not simultaneously represent a hydrogen atom, and R ¹ and R ² Each may form a ring with each adjacent carbon atom, and R ²
And R ³ together with adjacent carbon atoms may form a ring, and R ⁴ and R ⁵ each represent a halogen atom. ] Cyclopropanecarboxamides represented by the following are disclosed, but those having the hydroxamic acid derivative having the general formula (A ′) and the general formula (A), wherein R ₆ is bound through an oxygen atom: Is not mentioned at all.

[0005]

Many compounds have been used as agricultural fungicides so far, but by continuously using the same drug for many years, it is possible to obtain fungicidal effects due to the emergence of bacteria that have acquired resistance to the drug. The decline is a problem. Therefore, regarding agricultural and horticultural fungicides, it is expected to create compounds having a new structure having a strong bactericidal effect.

The present invention is intended to provide a novel fungicide for agricultural and horticultural use which satisfies these needs.

[0007]

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted diligent research, and as a result,
2-dichlorocyclopropane hydroxamic acid derivative,
They have found that they have an excellent bactericidal action, and have completed the present invention.

The novel 2,2-dichlorocyclopropane hydroxamic acid derivative of the present invention is represented by the following general formula (1). In addition, the 2,2-dichlorocyclopropane hydroxamic acid derivative in the present invention is not only the compound represented by the following general formula (1), but also its racemic form or a mixture of optical isomers, or a pure enantiomer or diastereomer. Derivatives in the form of mers are also included.

[0009]

Embedded image

[Wherein R ₁ , R ₂ and R ₃ are each a hydrogen atom or a lower alkyl group, A is a hydrogen atom or OR ₄ (in the formula, R ₄ is a hydrogen atom and may be substituted). A lower alkyl group, a lower acyl group or a lower alkylsulfonyl group), and when A is a hydrogen atom, B
Is

[0011]

[Chemical 9]

(Wherein X represents a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a lower haloalkoxy group, and n represents 0, 1, 2 or 3), and A is OR. _{When 4} is B

[0013]

[Chemical 10]

(Wherein X and n are the same as defined above). Examples of the substituent of the optionally substituted lower alkyl group in the definition of the above general formula (1) include a halogen atom, a lower alkoxy group, a carboxyl group, a lower alkoxycarbonyl group and a cyano group.

Specific examples of each group and atom in the definition of the above general formula (1) are as follows.

Halogen atom : for example, fluorine, chlorine, bromine, iodine.

Lower alkyl group : an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, A group such as i-pentyl and n-hexyl.

Lower haloalkyl group : an alkyl group substituted with the above halogen atom, for example, a group such as chloromethyl, chloroethyl, dichloroethyl, difluoromethyl, trifluoromethyl, trifluoroethyl and the like.

Lower alkoxy group : an alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy,
A group such as i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, i-pentyloxy and n-hexyloxy.

Lower haloalkoxy group : an alkoxy group substituted with the above halogen atom, for example, difluoromethoxy, trifluoromethoxy, trifluoroethoxy, pentafluoroethoxy and the like.

Lower acyl group : an acyl group having 1 to 6 carbon atoms, such as acetyl, propanoyl, butanoyl or pentanoyl.

Lower alkylsulfonyl group : 1 to 1 carbon atoms
6 is an alkylsulfonyl group of 6 and is a group such as methanesulfonyl, ethanesulfonyl, and propanesulfonyl.

Lower alkoxycarbonyl group : 1 to 1 carbon atoms
6 alkoxycarbonyl group, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,
i-propoxycarbonyl, n-butoxycarbonyl,
i-butoxycarbonyl, s-butoxycarbonyl, t
Groups such as -butoxycarbonyl, n-pentyloxycarbonyl, i-pentyloxycarbonyl.

X in the above general formula is preferably a chlorine atom, a bromine atom, a methyl group, a methoxy group or a trifluoromethyl group.

R ₁ is preferably a hydrogen atom or a methyl group, R ₂ is preferably a methyl group, ethyl group, n-propyl group, i-propyl group or the like, and R ₃ is a methyl group, ethyl group, i -Propyl group and the like are preferable.

Specific examples of the compound of the present invention represented by the above general formula (1) include the compounds shown in Tables 1 to 10 below, but the present invention is limited thereby. Not a thing.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

[Table 5]

[0032]

[Table 6]

[0033]

[Table 7]

[0034]

[Table 8]

[0035]

[Table 9]

[0036]

[Table 10]

[0037]

[Table 11]

[0038]

[Table 12]

[0039]

[Table 13]

[0040]

[Table 14]

[0041]

[Table 15]

[0042]

[Table 16]

[0043]

[Table 17]

[0044]

[Table 18]

[0045]

[Table 19]

[0046]

[Table 20]

[0047]

[Table 21]

[0048]

[Table 22]

[0049]

[Table 23]

[0050]

[Table 24]

[0051]

[Table 25]

[0052]

[Table 26]

[0053]

[Table 27]

[0054]

[Table 28]

[0055]

[Table 29]

[0056]

[Table 30]

[0057]

[Table 31]

[0058]

[Table 32]

[0059]

[Table 33]

[0060]

[Table 34]

[0061]

[Table 35]

[0062]

[Table 36]

[0063]

[Table 37]

[0064]

[Table 38]

[0065]

[Table 39]

[0066]

[Table 40]

[0067]

[Table 41]

[0068]

[Table 42]

[0069]

[Table 43]

[0070]

[Table 44]

[0071]

[Table 45]

[0072]

[Table 46]

[0073]

[Table 47]

[0074]

[Table 48]

[0075]

[Table 49]

[0076]

[Table 50]

[0077]

[Table 51]

[0078]

[Table 52]

[0079]

[Table 53]

[0080]

[Table 54]

[0081]

[Table 55]

[0082]

[Table 56]

[0083]

[Table 57]

[0084]

[Table 58]

[0085]

[Table 59]

[0086]

[Table 60]

The compound (1) of the present invention can be produced, for example, by the following method (method A or A ', method B or B'). These can be modified appropriately and combined appropriately.

Method A Synthesis Route by Method A

[0089]

[Chemical 11]

(Wherein X, R ₁ , R ₂ , R ₃ , R ₄ and n have the same meanings as described above.) In the reaction formula of the above Method A, the compound represented by the formula (1-1) is 2,2-dichlorocyclopropanecarboxylic acid chloride of the above formula (2), in the presence of a solvent-free or a suitable solvent, with a suitable acid binder, in the temperature range of -78 ° C to the boiling point of the solvent, It can be produced by reacting with the hydroxylamine derivative of the formula (3) for 0.1 to 24 hours.

The compound (2), which is the starting material for this reaction, can be easily obtained by the reaction of 2,2-dichlorocyclopropanecarboxylic acid with thionyl chloride described in JP-A-63-54349. In addition, the compound (3) may be prepared, for example, by using the corresponding acetophenone oxime derivative as
n Letters 3331 (1981), 3755 (1986) and the like can be obtained by reduction by a known method.

Examples of the acid binder used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate; organic bases such as pyridine, triethylamine and dimethylaminopyridine. Is mentioned.

This reaction is preferably carried out in the presence of a solvent,
The solvent used is not particularly limited as long as it does not participate in the reaction, and examples thereof include ethers such as diethyl ether, tetrahydrofuran, dioxane; ketones such as acetone and methyl ethyl ketone; aromatic carbonization such as benzene, toluene and xylene. Hydrogens; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide, water and the like, and mixed solvents thereof.

The reaction temperature is not particularly limited and may be appropriately selected. For example, the reaction temperature may be -20 ° C to the reflux temperature of the solvent.

The reaction time varies depending on the reaction temperature, the type of reagent used, etc., but can be exemplified by a reaction time of about 1 to several hours.

After completion of the reaction, the desired compound (1-1) can be isolated from the reaction mixture by a conventional method.

A'method A'synthesis route by method '

[0098]

[Chemical 12]

(In the formula, X, R ₁ , R ₂ , R ₃ , R ₄ and n have the same meanings as described above.) In the reaction formula of Method A ′, the compound represented by the formula (1-2) Is 2,2-dichlorocyclopropanecarboxylic acid chloride of the above formula (2) in the temperature range of -78 ° C to the boiling point of the solvent in the presence of a suitable acid binder in the absence of a solvent or a suitable solvent. It can be produced by reacting with the hydroxylamine derivative of the above formula (3 ′) for 0.1 to 24 hours.

The compound (2) which is the starting material for this reaction is 2,2-described in, for example, JP-A-63-54349.
It can be easily obtained by the reaction of dichlorocyclopropanecarboxylic acid with thionyl chloride or the like. The compound (3 ′) is
For example, the corresponding 1-bromoethylbenzene derivative and N-
It can be obtained by treating an intermediate obtained from hydroxyphthalimide with hydrazine or the like.

Examples of the acid binder used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate; organic bases such as pyridine, triethylamine and dimethylaminopyridine. Is mentioned.

This reaction is preferably carried out in the presence of a solvent,
The solvent used is not particularly limited as long as it does not participate in the reaction, and examples thereof include ethers such as diethyl ether, tetrahydrofuran, dioxane; ketones such as acetone and methyl ethyl ketone; aromatic carbonization such as benzene, toluene and xylene. Hydrogens; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide, water and the like, and mixed solvents thereof.

The reaction temperature is not particularly limited and may be appropriately selected. For example, the reaction temperature may be -20 ° C to the reflux temperature of the solvent.

The reaction time varies depending on the reaction temperature, the type of reagent used, etc., but can be exemplified by a reaction time of about 1 to several hours.

After completion of the reaction, the desired compound (1-2) can be isolated from the reaction mixture by a conventional method.

Method B Synthesis route by method B

[0107]

[Chemical 13]

(Wherein X, R ₁ , R ₂ , R ₃ , R ₄ and n have the same meanings as described above, and Y represents a halogen atom, an acyloxy group or an alkylsulfonyloxy group). In the compound represented by the formula (1-1), the 2,2-dichlorocyclopropanehydroxamic acid derivative of the formula (4) can be prepared by using a suitable acid binder in the presence of no solvent or a suitable solvent. , -78 ° C to the boiling point of the solvent in the temperature range of 0.1 to 24 hours with the alkyl halide of the above formula (5).

Examples of the acid binder used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate; organic bases such as pyridine, triethylamine and dimethylaminopyridine. Is mentioned.

This reaction is preferably carried out in the presence of a solvent,
The solvent used is not particularly limited as long as it does not participate in the reaction, and examples thereof include ethers such as diethyl ether, tetrahydrofuran, dioxane; ketones such as acetone and methyl ethyl ketone; aromatic carbonization such as benzene, toluene and xylene. Hydrogens; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide, etc., and mixed solvents thereof.

There are no particular restrictions on the reaction temperature, but examples include -20 ° C to the reflux temperature of the solvent. Also, the reaction time varies depending on the reaction reagent, reaction temperature, etc.,
For example, a reaction time of about 1 to several hours can be exemplified.

[0112] synthetic route by B 'method B' method

[0113]

Embedded image

(Wherein X, R ₁ , R ₂ , R ₃ and n have the same meanings as described above, and Y represents a halogen atom, an acyloxy group or an alkylsulfonyloxy group) In the reaction formula of the B'method, The compound represented by the formula (1-2) is obtained by using the 2,2-dichlorocyclopropanehydroxamic acid derivative of the above formula (4 ′) without a solvent or in the presence of a suitable solvent and using a suitable acid binder. , -78 ° C. to the boiling point of the solvent in the temperature range, the compound can be produced by reacting with the alkyl halide of the above formula (5 ′) for 0.1 to 24 hours.

Examples of the acid binder used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate; organic bases such as pyridine, triethylamine and dimethylaminopyridine. Is mentioned.

This reaction is preferably carried out in the presence of a solvent,
The solvent used is not particularly limited as long as it does not participate in the reaction, and examples thereof include ethers such as diethyl ether, tetrahydrofuran, dioxane; ketones such as acetone and methyl ethyl ketone; aromatic carbonization such as benzene, toluene and xylene. Hydrogens; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide, etc., and mixed solvents thereof.

The reaction temperature is not particularly limited, and examples thereof include −20 ° C. to the reflux temperature of the solvent. Also, the reaction time varies depending on the reaction reagent, reaction temperature, etc.,
For example, a reaction time of about 1 to several hours can be exemplified.

The bactericide of the present invention contains the novel 2,2-dichlorocyclopropanehydroxamic acid derivative of the above general formula (1) as an active ingredient.

When the compound of the present invention is used as a bactericidal agent, it is mixed with a carrier or diluent, an additive, an auxiliary agent, etc. by a known method to prepare a formulation form usually used as an agricultural chemical, for example, powder or granule. It is used as a wettable powder, a flowable powder, etc. Further, it can be used as a mixture or in combination with other agricultural chemicals such as fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and soil conditioners.

In particular, when used in combination with other bactericides, not only the pesticides used are reduced and labor is saved, but also a broader bactericidal spectrum due to the synergistic action of both drugs and a higher effect due to a synergistic action are expected. it can.

Examples of carriers or diluents used in the preparation include solid or liquid carriers generally used.

Examples of the solid carrier include clays represented by kaolinite group, montmorillonite group, illite group, polygloskite group and the like, more specifically, pyroflight, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica and the like. Talc, etc .; gypsum, calcium carbonate, dolomite, diatomaceous earth,
Magnesium lime, phosphorus lime, zeolite, silicic acid anhydride,
Other inorganic substances such as synthetic calcium silicate; vegetable organic substances such as soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch and crystalline cellulose; coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol Examples thereof include synthetic or natural polymer compounds such as ketone resins, ester gums, cobal gums, and dammal gums; waxes such as carnauba wax and beeswax, and urea.

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as xylene, ethylbenzene, cumene and methylnaphthalene;
Chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene, orthochlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; ethyl acetate,
Amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate and other esters; methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol and other alcohols; ethylene glycol ethyl ether, diethylene glycol butyl ether Examples thereof include ether alcohols; polar solvents such as dimethylformamide and dimethylsulfoxide, and water.

Others Emulsification, dispersion, wetting, spreading, spreading, binding, control of disintegration, stabilization of active ingredient of the compound of the present invention,
Surfactants and other auxiliary agents can be used for the purpose of improving fluidity, preventing rust, and preventing freezing.

Examples of the surfactant to be used include nonionic, anionic, cationic and zwitterionic ones, but usually nonionic and / or anionic. Ionic ones are used.

Suitable nonionic surfactants include, for example, compounds obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; isooctylphenol,
Compounds obtained by polymerizing addition of ethylene oxide to alkylphenols such as nonylphenol; Compounds obtained by polymerizing addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Polymerization addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid Compounds: higher fatty acid esters of polyhydric alcohols such as sorevitan, compounds obtained by polymerizing addition of ethylene oxide thereto, compounds obtained by block polymerization addition of ethylene oxide and propylene oxide, and the like.

Suitable anionic surfactants include, for example, alkyl sulphate salts such as sodium lauryl sulphate, oleyl alcohol sulfuric acid ester amine salts, etc., alkyl sulphonates such as sodium sulfosuccinate dioctyl ester, sodium 2-ethylhexene sulphonate. Examples thereof include aryl sulfonates such as acid salts, sodium isopropylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.

Further, the bactericide of the present invention contains casein, gelatin, gelatin for the purpose of improving the properties of the preparation and enhancing the bactericidal effect.
High molecular compounds such as albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol and the like and other auxiliary agents can be used together.

The above-mentioned carrier and various auxiliary agents are in the dosage form of the preparation,
Depending on the application and the like, they may be used alone or in combination depending on the purpose.

The content of the active ingredient of the compound of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, preferably 1 to 99% by weight. 60% by weight is most suitable.

In the case of a wettable powder, for example, the active ingredient compound is usually contained in an amount of 10 to 90% by weight, the balance being a solid carrier and a dispersion wetting agent, and if necessary, a protective colloid agent, a defoaming agent and the like are added. To be

In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance is a solid carrier, a surfactant and the like. The active ingredient compound is uniformly mixed with the solid carrier, or uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm.

In the case of an emulsion, for example, the active ingredient compound is usually contained in an amount of 5 to 30% by weight, and about 5 to 20% by weight is contained therein.
A weight% emulsifier is contained, and the rest is a liquid carrier, and a spreading agent, an anticorrosive agent and the like are added if necessary.

In the case of a flowable agent, for example, the active ingredient compound is usually contained in an amount of 5 to 50% by weight, which contains a dispersion wetting agent in an amount of 3 to 10% by weight, and the balance is water, which may be protected as necessary. Colloid agents, antiseptics, antifoaming agents and the like are added.

The 2,2-dichlorocyclopropanehydroxamic acid derivative of the present invention can be used as an agent as it is in the compound of the general formula (1) or in any of the above-mentioned preparation forms.

The use concentration of the compound of the present invention varies depending on the target crop, the method of use, the form of preparation, the amount applied, etc. and cannot be specified unconditionally, but in the case of foliar treatment, 0.1 to 10,000 ppm per active ingredient is desirable. Is 1 to 500 ppm. In the case of soil treatment, it is 10-100,000 g / ha, preferably 200 to 20,000 g / ha.

[0137]

EXAMPLES The present invention will be specifically described below with reference to examples.

Production Example 1 (by Method A) N-1- (4-chlorophenyl) ethyl-N-methoxy-2,2-dichloro-1-methyl-2-trans-methylcyclopropanecarboxamide (Compound 3.4) Preparation of N-1- (4-chlorophenyl) ethyl-N-methoxyamine 1.86 g (10.0 mmol), triethylamine 1.
A solution of 2 g (12.0 mmol) dissolved in 30 ml of tetrahydrofuran was stirred under ice-cooling, and 2,2-dichloro-
A solution of 2.0 g (9.9 mmol) of 1-methyl-2-trans-methylcyclopropanecarbonyl chloride in 10 ml of tetrahydrofuran was added dropwise. After completion of dropping, the mixture was reacted with ice for 1 hour and further at room temperature for 1 hour, and then the reaction solution was poured into water,
Extract with ethyl acetate, dry over anhydrous magnesium sulfate,
The solvent was distilled off. The obtained oily substance was purified by silica gel column chromatography to give N-1- (4-chlorophenyl) ethyl-N-methoxy-2,2-dichloro-1.
2.7 g of -methyl-2-trans-methylcyclopropanecarboxamide was obtained (74% yield).

Production Example 2 (by Method A) N-1- (4-chlorophenyl) ethyl-N-hydroxy-2,2-dichloro-1-methyl-2-trans-methylcyclopropanecarboxamide (Compound 1.4) Preparation of N-1- (4-chlorophenyl) ethylhydroxylamine 1.71 g (10.0 mmol), triethylamine 1.2
While stirring a solution of g (12.0 mmol) dissolved in 30 ml of tetrahydrofuran under ice cooling, 2,2-dichloro-1 was added.
-Methyl-2-trans-methylcyclopropanecarbonyl chloride 2.0 g (9.9 mmol) of tetrahydrofuran 1
A 0 ml solution was added dropwise. After completion of the dropping, the mixture was reacted with ice for 1 hour and further at room temperature for 1 hour, the reaction solution was poured into water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained oily substance was purified by silica gel column chromatography to give N-1- (4-chlorophenyl) ethyl-N-hydroxy-2,2-dichloro-1-.
1.2 g of methyl-2-trans-methylcyclopropanecarboxamide was obtained (yield 36%).

Preparation Example 3 (by Method A ') Preparation of 1- (4-chlorophenyl) ethyl 2,2-dichloro-1-methyl-2-trans-methylcyclopropanehydroxamate (Compound 8.4) O -1- (4-chlorophenyl) ethylhydroxylamine 1.71 g (10.0 mmol), triethylamine 1.2
While stirring a solution of g (12.0 mmol) dissolved in 30 ml of tetrahydrofuran under ice cooling, 2,2-dichloro-1 was added.
A solution of 2.0 g (9.9 mmol) of methyl-2-trans-methylcyclopropanecarbonyl chloride in 10 ml of tetrahydrofuran was added dropwise. After completion of the dropping, the mixture was reacted with ice for 1 hour and further at room temperature for 1 hour, the reaction solution was poured into water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained oily substance was purified by silica gel column chromatography to give 1- (4-chlorophenyl) ethyl 2,2-dichloro-1-methyl-2-trans-methylcyclopropanehydroxamate 2.1.
g was obtained (yield 69%).

Production Example 4 (by Method A ') Production of 1- (4-chlorophenyl) ethyl 2,2-dichloro-1-ethyl-2-trans-methylcyclopropanehydroxamate (Compound 9.4) O -1- (4-chlorophenyl) ethylhydroxylamine 1.71 g (10.0 mmol), triethylamine 1.2
While stirring a solution of g (12.0 mmol) dissolved in 30 ml of tetrahydrofuran under ice cooling, 2,2-dichloro-1 was added.
A solution of 2.0 g (9.9 mmol) of -ethyl-2-trans-methylcyclopropanecarbonyl chloride in 10 ml of tetrahydrofuran was added dropwise. After completion of the dropping, the mixture was reacted with ice for 1 hour and further at room temperature for 1 hour, the reaction solution was poured into water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained oily substance was purified by silica gel column chromatography to give 1- (4-chlorophenyl) ethyl 2,2-dichloro-1-ethyl-2-trans-methylcyclopropanehydroxamate 2.2.
g was obtained (63% yield).

Production Example 5 Production of 2,2-dichloro-1-methyl-2-trans-methylcyclopropanehydroxamic acid (according to Method A ') 10.35 g (148.9 mmol) of hydroxyamine hydrochloride was added to 100 ml of water and 100 ml of ether. It was dissolved in the mixed solution, 7.36 g (69.4 mmol) of sodium carbonate was added under ice cooling, and the mixture was stirred for 10 minutes. At the same temperature, 10.0 g of 2,2-dichloro-1-ethyl-2-trans-methylcyclopropanecarbonyl chloride dissolved in 50 ml of ether
(49.6 mmol) was added dropwise, and after stirring for 1 hour, the organic layer was separated. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 8.52 g of 2,2-dichloro-1-methyl-2-trans-methylcyclopropanehydroxamic acid (yield 94%).

Production Example 6 (by Method B) N-1- (4-chlorophenyl) ethyl-N-acetoxy-2,2-dichloro-1-methyl-2-trans-methylcyclopropanecarboxamide (Compound 2.4) Preparation of N-1- (4-chlorophenyl) ethyl-N-hydroxy-2,2-dichloro-1-methyl-2-trans-methylcyclopropanecarboxamide 0.67 g (2 mmo
l) and triethylamine (0.3 g, 3.0 mmol) dissolved in 10 ml of tetrahydrofuran were stirred under ice cooling, and a solution of 1.7 g (2.2 mmol) of acetyl chloride in 5 ml of tetrahydrofuran was added dropwise. 1 after cooling with ice
After further reacting for 1 hour at room temperature, the reaction solution was poured into water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained oily substance was purified by silica gel column chromatography to obtain 0.74 g of N-1- (4-chlorophenyl) ethyl-N-acetoxy-2,2-dichloro-1-methyl-2-trans-methylcyclopropanecarboxamide ( A yield of 98%) was obtained.

Production Example 7 (by Method B ') Production of 1- (2-chlorophenyl) ethyl 2,2-dichloro-1-methyl-2-trans-methylcyclopropanehydroxamate (Compound 8.2) 2 2.0 g (10.9 mmol) of 2,2-dichloro-1-methyl-2-trans-methylcyclopropanehydroxamic acid was dissolved in 20 ml of tetrahydrofuran, and the solution was added at 60C at 60 ° C.
% Sodium hydride 435 mg (10.9 mml) was added.
After stirring at the same temperature for 30 minutes, the mixture was stirred at room temperature for 30 minutes. After adding 2.39 g (10.9 mmol) of alpha-methyl-2-chlorobenzyl bromide at room temperature and heating at 60 ° C. for 5 hours, the reaction solution was poured into water and extracted with ethyl acetate.
After drying over anhydrous magnesium sulfate, the solvent was evaporated and the obtained oily product was purified by silica gel column chromatography to give 1- (2-chlorophenyl) ethyl 2,2-dichloro-1-methyl-2-trans-methylcyclo. 3.29 g of propane hydroxamate was obtained (yield 90
%).

Tables 11 to 12 show the compounds produced by the same method as in the above Production Examples.

[0146]

[Table 61]

[0147]

[Table 62]

[0148]

[Table 63]

[0149]

[Table 64]

[0150]

[Table 65]

Next, several embodiments of formulation examples using the compound of the present invention will be shown. The "parts" in the following preparations are based on weight.

Formulation Example 1 (emulsion) Compound No .: 2.4 or 9.4 10 parts Xylene 45 parts Calcium dodecylbenzenesulfonate 7 parts Polyoxyethylene styryl phenyl ether 13 parts Dimethylformamide 25 parts The above ingredients are uniformly mixed and dissolved. To obtain 100 parts of emulsion.

Formulation Example 2 (Wettable powder) Compound No .: 4.4 or 8.4 20 parts Diatomaceous earth 70 parts Calcium lignin sulfonate 5 parts Naphthalene sulfonate formalin condensate 5 parts 100 parts were obtained.

Formulation Example 3 (Granule) Compound No .: 7.98 or 8.2 5 parts Bentonite 50 parts Talc 42 parts Sodium lignin sulfonate 2 parts Polyoxyethylene alkylaryl ether 1 part After thoroughly mixing the above, An appropriate amount of water was added, the mixture was kneaded, and granulated using an extrusion granulator to obtain 100 parts of granules.

Formulation Example 4 (flowable agent) Compound No .: 1.4 or 8.16 30 parts Di-2-ethylhexyl sulfosuccinate sodium salt 2 parts Polyoxyethylene nonylphenyl ether 3 parts Defoamer 1 part Propylene glycol 5 Part water 59 parts The above components were uniformly pulverized and mixed with a wet ball mill to obtain 100 parts of a flowable agent.

The fungicides using the compounds of the present invention can be prepared according to the above-mentioned preparation examples.

Next, according to the test example, the bactericide of the present invention was used.
The effect of controlling various plant diseases will be specifically described.

Test Example (Control test against rice blast) Paddy rice (variety: Koshihikari) was sown in 7-piece plastic cups each having a diameter of 7 cm and grown in a greenhouse for 3 weeks. The reagent agent emulsified according to Formulation Example 1 was diluted with water so as to have a predetermined concentration, and sprayed so as to sufficiently adhere to the leaf surface of rice. One day after the application, a spore suspension of rice blast fungus was inoculated, kept in a humid chamber at 25 ° C for one day, and then sickened in a greenhouse. Seven days after the inoculation, the average number of lesions per leaf was investigated, and the control value was calculated by the following formula.

[0159]

[Equation 1]

The results are shown in Tables 13-14.

[0161]

[Table 66]

[0162]

[Table 67]

[0163]

The 2,2-dichlorocyclopropanehydroxamic acid derivative represented by the above general formula (1) of the present invention is a compound not described in the literature. This 2,2-dichlorocyclopropanehydroxamic acid derivative is characterized in that it has a cyclopropanehydroxamic acid moiety substituted with a chlorine atom.
It is considered that the excellent properties of the bactericide containing the dichlorocyclopropane hydroxamic acid derivative are exhibited.

The compound and fungicide of the present invention have an excellent controlling effect against blast disease occurring in paddy rice cultivation in foliar treatment and water surface application, and show no phytotoxicity to rice.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tokushige Tonoshima 8-3-1 Chuo, Ami-machi, Inashiki-gun, Ibaraki Prefecture Rhone Poulin Petrochemical Agro Co., Ltd. Ami Research Center (72) Inventor Yoshie Kirio Inashiki-gun, Ibaraki Prefecture 8-3-1 Chuo, Ami-machi Rhone Poulin Petrochemical Agro Co., Ltd. Ami Research Center (72) Inventor Bruce Milligan 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Rhone Poulin Petrochemical Agro Co., Ltd. In-house (72) Inventor Nobumitsu Sawai 8-3-1 Chuo, Ami-machi, Inashiki-gun, Ibaraki Rhone Poulin Petrochemical Agro Co., Ltd. Ami Research Center (72) Inventor Takako Maeda 8-3, Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture -1 Rhone Poulin Petrochemical Agro Co., Ltd. Ami Research Center

Claims (2)

[Claims] 1. The following general formula (1): [Wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a lower alkyl group, A represents a hydrogen atom or OR ₄ (in the formula, R ₄ represents a hydrogen atom or an optionally substituted lower alkyl group. , A lower acyl group or a lower alkylsulfonyl group), and when A is a hydrogen atom, B is (Wherein, X represents a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a lower haloalkoxy group, and n represents 0, 1, 2 or 3), and when A is OR ₄ . B is (In the formulae, X and n are the same as defined above.). ] The 2,2-dichloro cyclopropane hydroxamic acid derivative represented by these. 2. The following general formula (1): [Wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a lower alkyl group, A represents a hydrogen atom or OR ₄ (in the formula, R ₄ represents a hydrogen atom or an optionally substituted lower alkyl group. , A lower acyl group or a lower alkylsulfonyl group), and when A is a hydrogen atom, B is (In the formula, X represents a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a lower haloalkoxy group, and n represents 0, 1, 2 or 3.),
When A is OR ₄ , B is (In the formulae, X and n are the same as defined above.). ] The agricultural germicide containing the 2,2- dichloro cyclopropane hydroxamic acid derivative represented by these as an active ingredient.