JPS59101462A - Carboxylic acid 2,2-dichloro-3,3- dimethylcyclopropylmethyl ester compound and agricultural fungicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (m and n are 0 or 1; R<1> and R<2> are H, or may together form a single bond when both m and n are 1; Q is heterocyclic group having O, S, N, etc.). EXAMPLE:2,2-Dichloro-3,3-dimethylcyclopropylmethyl furan-2-carboxylate. USE:An agricultural fungicide exhibiting especially excellent effect against rice blast. PROCESS:The compound of formula I can be prepared, e.g. by reacting the compound of formula II with the compound of formula III (M<1> is halogen or OH) in an inert solvent at 0-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel carboxylic acid 2,2-dichloro-3,3
- Dimethylcyclopropyl methyl ester compound and agricultural fungicide.

More specifically, the present invention relates to a carboxylic acid 2,2-dichloro-3,3-dimethylcyclopropylmethyl ester compound represented by the following general formula (I).

General formula: %Formula% In the formula, m and n each represent 0 or 1, and R1 and R
2 each represents a hydrogen atom, where m and n are both 1, R1 and R2 may be taken together to form a single bond, and Q represents a heteroatom such as oxygen or sulfur. ,
Indicates a saturated or unsaturated heterocyclic group having at least one nitrogen (however, in the case of two or more nitrogen atoms, they may be of the same type or different polarity), and the heterocyclic group may be benzo-fused. , Furthermore, the heterocyclic group may optionally contain at least one of a halogen atom, a nitro group, a lower alkyl group, a benzyloxy group, a carbonyl group, and a keto group (however,
In the case of two or more, they may be of the same type or different types), provided that ml and n are 0 at the same time, and Q
is a benzo-fused heterocyclic group containing a nitrogen atom, and in that case, excluding the case where the nitrogen atom of Q is directly bonded to the throat in the formula.

Furthermore, the present invention provides carboxylic acids 2, 2 of the general formula (1)
The present invention also relates to an agricultural fungicide containing a -dichloro-3,6-dimethylcyclopropyl methyl ester compound as an active ingredient.

Dutch Patent No. 7205298 (known before the application of the present invention)
Corresponding West German Patent No. 2219710) has the general formula: (wherein, Mal is a l-rogen atom, R1 is a hydrogen atom, an alkyl group, or a phenyl group, R2 and R3 are a hydrogen atom,
or an alkyl group, R4 is a cyano group, a carboxyl group,
Indicates a thiocarboxyl group, a salt thereof, an ester thereof, or an N-substituted amide thereof. It is stated that the cyclopropane carboxy derivative represented by ) has bactericidal activity. However, this prior art publication does not mention the presence of the compound of formula (I) at all. The present inventors have conducted research on the development of agricultural fungicides. As a result, it was found that the carboxylic acid 2,2-dichloro-5,3-dimethylcyclopropyl methyl ester compound represented by the above formula (1), which has not been described in the prior literature, can be easily produced, and that the compound of formula (I) is It was discovered that it has an excellent bactericidal effect on bacteria and is useful as an agricultural fungicide.

The compound of formula (I) of the present invention has the advantage that it can be easily produced. That is, the production of the compound disclosed in the Dutch patent requires, for example, the reaction under anhydrous conditions, the reaction involves multiple steps, and the reaction time is very long. It has manufacturing disadvantages such as skin irritation, hygroscopicity, requiring expensive raw materials, and very low yields. In contrast, the compound of formula (I) of the present invention has the following advantages: the reaction can be carried out at room temperature, the reaction process is carried out in one step, the raw materials are cheap and easily available, and the
It was found that this compound is a compound that has not been previously described in any literature and can be produced by a method that is significantly advantageous for industrial implementation, such as the ability to produce the desired product with a high yield.

Furthermore, according to the research conducted by the present inventors, the compound of formula (I) of the present invention has the advantage that it can be produced industrially with remarkable advantage as compared to the conventional compound disclosed in the Dutch patent, as mentioned above. In addition, compared to the compounds disclosed in the Dutch patent,
It has been found that it exhibits excellent fungicidal activity and is also useful for controlling plant diseases caused by a wide range of plant pathogenic bacteria, and is particularly effective against rice blast.

Furthermore, the compound of formula (1) has the advantage that it has low toxicity to warm-blooded animals and does not cause any phytotoxicity to parent crops at the usual concentration used, and It has also been found that it exhibits a remarkable penetrative action, and has the advantage of being able to be applied in a water surface (medium) manner, for example, when controlling rice blast. Therefore, the object of the present invention is to provide a novel carboxylic acid 2,2-dichloro-3,3- of the general formula (I).
The present invention provides a dimethyl-cyclopropyl methyl ester compound and its use as an agricultural fungicide.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

The bactericidal spectrum of the compound of formula (I) of the present invention is wide, for example, against archaeal bacteria [Archimycetes].
)], algae [Phycomycetes
s) : ], 5 progeny bacteria [Ascomycetes (Ascomycetes)
cetes), Basidiomycetes [Basidiomycetes]
idiomycetes), Fungi imperfecti (Fungi imperfecti)
:], and can be effectively used against various plant diseases caused by other bacteria.

The compound of formula (I') of the present invention can be prepared, for example, by the following method 1),
11) and 11).

Manufacturing method 1); CI CI (1) In the formula, m, n, R1, R2, and Q are the same as above.

Ml represents a halogen atom or a hydroxyl group.

In the above reaction formula, m and n each represent 0 or 1, R1 and R2 each represent a hydrogen atom, and when m and n are both 1, R1 and R2 are taken together. A single bond may be formed, and Q is a saturated or unsaturated heterocycle having at least one layer of oxygen, sulfur, and nitrogen (however, in the case of two or more, the same or different types may be used) as a petro atom. wherein the heterocyclic group may be benzo-fused, and
The heterocyclic group may optionally be a halogen atom such as fluoro; chloro; bromo; iodo; a nitro group; methyl: ethyl; propyl; isopropyl; The substituent may be substituted with at least one of a group, a benzyloxycarbonyl group, and a keto group (however, in the case of two or more groups, the same or different types may be used).

However, this excludes cases where m and n are both 0, Q is a benzo-fused heterocyclic group containing a nitrogen atom, and the nitrogen atom of Q is directly bonded to and in the formula.

Specifically, M1 represents a hydroxyl group or a halogen atom as mentioned above, preferably chloro or bromine.

In the method for producing the compound of formula (1) of the present invention shown in the above reaction formula, specific examples of the compound of general formula (II) as a raw material include 2-furancarboxylic acid, 3-furancarboxylic acid, 5-bromocarboxylic acid, -2-Furancarboxylic acid, 5-nitro-2-furancarboxylic acid, nathiophenecarboxylic acid, 5-chloro-2-thiophenecarboxylic acid, 3,-chlorobenzothiophene-2-carboxylic acid, 2-pyrrolecarboxylic acid , pyrrolidin-5-one-2-carboxylic acid, N
-benzyloxycarbonylpyrrolidine-2-carboxylic acid, indole-3-carboxylic acid, indolizine-2-
Carboxylic acid, 3-methyl-isoxazole-5-carboxylic acid, benzoxazole-2-carboxylic acid, benzothiazole-2-carboxylic acid, 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid,
Pyridine-4-carboxylic acid N-oxide, 2-chloropyridine-3-carboxylic acid, 5-chloropyridine-3-carboxylic acid, 2-pyrazinecarboxylic acid, α-pyridone-6
-carboxylic acid, α-pyrone-5-carboxylic acid, 4,6-
Dimethyl-α-pyrone-5-carboxylic acid, 3-quinolinecarboxylic acid, 1-quinolinecarboxylic acid, 2-quinoxalinecarboxylic acid, chromone-2-carboxylic acid, chromone-3-carboxylic acid, γ-pyrone-2-carboxylic acid acid, 3
-coumarincarboxylic acid, 1-pyrrolidineacetic acid, 1-piperidineacetic acid, 1-morpholineacetic acid, 1-pyrazoleacetic acid, 1-imidazoleacetic acid, 1-(1,2,4-triazole)acetic acid, 2-thiopheneacetic acid, 2- Pyridineacetic acid, 3-pyridineacetic acid, 2(IH)-pyridone-1-acetic acid, phthalimidoacetic acid, (benzointhiazolin-3-one-1,1-dioxide)-2-acetic acid, 3,5-dichloro-2(IH) )-pyridone-1-acetic acid, β-(2-furan)propionic acid, β-(2-thiophene)propionic acid, β-(3-pyridine)propionic acid, β-(5-imidazole)acrylic acid, β- Examples include (2-thiophene)acrylic acid, and acid halides thereof, such as acid chlorides and acid bromides.

Next, the above manufacturing method 1) will be specifically explained using a representative example.

The above manufacturing method can be carried out desirably using a solvent or a diluent. All inert solvents and diluents can be used for this purpose.

Such solvents or diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene,
Methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and v-chloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, so-propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydro-7 Ran; ketones such as acetone,
Methyl ethyl ketone, methyl-is.

-propyl ketone, methyl-1so-butyl ketone; nitriles such as acetonitrile, gropionitrile,
Acrylonitrile; alcohols such as methanol,
Ethanol, 1so-propanol, phthanol, ethylene glycol: Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethylformamide, dimethylacetamide; Sulfones, Sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine, etc. can be given.

Furthermore, as described above, the reaction of the present invention can also be carried out in the presence of an acid binder. Such acid binders include commonly used alkali metal hydroxides, carbonates, bicarbonates, alcolades, etc., and tertiary amines such as triethylamine, diethylaniline, pyridine, etc. .

Further, in the above method, it is possible to use a dehydrating binder, and an example thereof is dicyclohexylcarbodiimide.

The method of the invention can be carried out within a wide temperature range. It is generally carried out between about -20°C and the boiling point of the mixture, preferably between about 0 and about 100°C. In addition, it is preferable to carry out the reaction under normal pressure, but
It is also possible to operate under elevated or reduced pressure.

Manufacturing method 11) (III) (IV) + A-8-O
H In the formula, m, n, R1, R2, and Q are the same as above, and A represents a lower alkyl group or an aryl group.

In the above reaction formula, m, n, R1, R2, and Q have the same meanings as described above, and A specifically represents the same lower alkyl tetra, phenyl; 〇-(m- or p −
) represents an aryl group such as tolyl.

In the method for producing the compound of formula (1) of the present invention represented by the above reaction formula, specific examples of the compound of general formula (I[l) as a raw material include, for example, 2,2-dichloro-3,3-dimethylcyclopropylene Examples include p-toluesulfonate, 2,2-dichloro-3,6-dimethylcyclopropylmethyl benzenesulfonate, and 2,2-dichloro-43-dimethylcyclopropylmethyl methanesulfonate.

Similarly, specific examples of the compound of general formula (IV) as a raw material include carboxylic acids similar to the compound of general formula (It) exemplified in the production method 1).

Next, the above manufacturing method 11) will be specifically explained using a representative example.

When carrying out the above method, in the presence of a base such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc., and in the presence of a phase transfer catalyst, an inert solvent or diluent similar to that described above is added. can be used to obtain the desired product with high purity and high yield.

Specific examples of such phase transfer catalysts include tetramethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium iodite, trioctyl-methylammonium chloride, triethyl-benzylammonium chlorite, triether-benzylammonium bromide. , trimethyl-decylammonium chloride, trimethyl-dodecylammonium chloride, trimethyl-hexadecyl ammonium chloride, trimethyl-hexadecyl ammonium bromide, tetraphenylphosphonium chloride, triphenyl-methylphosphonium iodite, tetrabutylphosphonium chloride, etc. Mention may be made of tanamides and tetraalkylphosphonium halotanides.

The above method can be carried out within a wide temperature range. Generally, it can be carried out between about -20<0>C and the boiling point of the mixture, preferably between about 0 and about 100<0>C.

The reaction is preferably carried out under normal pressure, but it is also possible to carry out the reaction under increased pressure or reduced pressure.

Manufacturing method 1ii); (m=1, n=0 or m=0, n-1)
CH3(V)(M)cH3(1') In the formula, Hal is the same as above, t represents a hydrogen atom or an alkali metal atom such as sodium or potassium, and Q' is the heterocyclic group of Q defined above. The group is a heterocyclic group containing at least one nitrogen atom as a petro atom, where the nitrogen atom is directly bonded to y in formula (■).

In the method for producing the compound of the formula (■') of the present invention represented by the above reaction formula, specific examples of the compound of the general formula (■) as a raw material include, for example, 2,2-dichloro-3,6-dimethylcycloprobyl Examples include methyl α-bromoacetate, 2,2-dichloro-3,3-dimethylcyclopropylmethyl α-chloroacetate, and the like.

Further, as specific examples of the compound of general formula (Vl) which is also a raw material, for example, pyrrolidine, piperidine, morpholine, imidazole, IH-1,2,4-triazole, α-pyridone, phthalimide, benzisothiazoline-3 -one-1,1-dioxide, 45-dichloro-α
Examples include -pyridone, and their alkali metal salts such as sodium and potassium.

Next, the above manufacturing method 111) will be specifically explained using a representative example.

In order to carry out the method, for example, the same inert solvent or diluent as described above can be used, and the desired product can be obtained with high purity and high yield.

The above method can be carried out within a wide temperature range. Generally, it can be carried out between about -20<0>C and the boiling point of the mixture, preferably between about 0 and about 100<0>C.

The reaction is preferably carried out under normal pressure, but it is also possible to carry out the reaction under increased pressure or reduced pressure.

In addition to the above-mentioned production methods 1), 11) and 11D, the compound of formula (I) of the present invention can also be synthesized by the production method represented by the following reaction formula.

(I) 10M3.Mal In the formula, m, n, R1, R2, and Q are the same as above, and rabbit represents an alkali metal atom.

When the compound of the present invention is used as an agricultural fungicide,
It can be used as it is or diluted directly with water, or it can be used in various formulations using agrochemical adjuvants by methods commonly used in the field of agrochemical manufacturing. In actual use, these various formulations can be used directly as they are or diluted with water to a desired concentration. Examples of pesticide adjuvants mentioned here include diluents (solvents, fillers, carriers), surfactants (
Examples include solubilizers, emulsifiers, dispersants, wetting agents), stabilizers, fixing agents, aerosol propellants, and synergists.

Solvents include water: organic solvents; hydrocarbons [e.g.
-Hexane, petroleum ether, naphtha, petroleum fractions (paraffin wax, kerosene, light oil, medium oil, benzene in heavy oil, toluene, xylenes), /10-genich hydrocarbons [e.g.
Chlormethylene, quaternary carbon, trichlorethylene,
Ethylene chloride, tooled ethylene, chlorobenzene, chloroform], alcohols (e.g. ttf, methyl alcohol, ethyl alcohol, flobyl alcohol, ethylene glycol), ethers C, t, ethyl ether, ethylene oxide, dioxane], alcohol ethers MC examples, ethylene glycol monomethyl ether], ketones [e.g. acetone, isophorone], esters [e.g. ethyl acetate, amyl acetate], amides [e.g. dimethylformamide, dimethylacetamide], sulfoxides [e.g. , dimethyl sulfoxide].

Inorganic granules such as slaked lime, magnesium lime, gypsum, calcium carbonate, sand stone, perlite, pumice, calcite, diatomaceous earth, amorphous silicon oxide,
Alumina, zeolite, clay minerals (e.g. pyrophyllite, talc, montmorillonite, beidellite, vermiculite, kaolinite, mica); vegetable granules such as grain flour, starch, modified starch, sugar, glucose, crushed plant matter; synthesis Examples of resin powders include powders of phenol resins, urea resins, and vinyl chloride resins.

Examples of surfactants include anionic surfactants such as alkyl sulfate esters (e.g., sodium lauryl sulfate), aryl sulfonic acids (e.g., alkylaryl sulfonate, sodium alkylnaphthalene sulfonate), succinates, and polyethylene glycols. Alkylaryl ether sulfate salts; cationic surfactants such as alkylamines [e.g. laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride], polyoxyethylene alkylamines; nonionic surfactants such as Polyoxyethylene glycol ethers [e.g., polyoxyethylene alkylaryl ethers and condensates thereof], polyoxyethylene glycol esters [e.g., polyoxyethylene fatty acid esters], polyhydric alcohol esters [
Examples include polyoxyethylene sorbitan monolaurate]; amphoteric surfactants, and the like.

Other stabilizers, fixing agents [e.g., agricultural soap, casein lime, sodium alginate, polyvinyl alcohol (
PVA), vinyl acetate adhesive, acrylic adhesive],
Aerosol propellants [e.g., trichlorofluoromethane, dichlorofluoromethane, 1.2.2-trichlor.1.1.2-trifluoroethane, chlorobenzene,
LNG1 lower ether]: Combustion modifier (for smoking agents) [e.g. nitrite, zinc dust, dicyandiamide]: Oxygen supply agent [e.g. chlorate, dichromate]: Efficacy extender Bidispersion stabilizer [ Examples include casein, tragacanth, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA)): synergists.

The compound of the present invention can be manufactured into various formulations by methods generally practiced in the agricultural chemical manufacturing field.

Forms of preparations include: emulsion: oil: wettable powder: aqueous solution: @
Clouding agent: Powder: Granule: Powder: Smoking agent: Tablet: Smoking agent: S
Forms: Capsules, etc. can be mentioned.

The agricultural fungicide of the present invention contains the active ingredient from about 0.1 to about 9
It can be contained in an amount of 5% by weight, preferably about 0.5 to about 9% by weight.

In actual use, the various formulations and spray preparations described above are used.
The active compound content in cation) is generally about 0.000
1 to about 2 aM amount, preferably about [10]55 to 11
A range of 0 weight is suitable.

The content of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, and the incidence of crop diseases.

The compound of the present invention may further be used, if necessary, with other agricultural chemicals, such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant growth regulators, attractants [e.g. Organic phosphoric acid ester compounds, carbamate compounds, dithio(
or thiol) carbamate compounds, organic chlorine compounds, dinitro compounds, organic (sulfur or metal compounds, antibiotics, substituted diphenyl ether compounds, urea compounds, triazine compounds) or/and fertilizers, etc. can.

Various formulations or ready-to-use preparations containing the active ingredients of the invention.
ti on) is a method of application, spraying, spraying, spraying, misting, atomizing, etc., which are commonly used in the agricultural chemical manufacturing field.
tomizing), dusting, granulation, water surface application, poring]: smoking: soil application, [e.g., mixing, sprinkling,
fumigation (vaporing, irrigation) dual surface application (e.g. painting, banding, dressing, coating):
This can be done by immersion or the like. Also, the so-called ultra-high concentration small volume spraying method (ultra-1ow-volume)
It can also be used by In this way, 100% active ingredient content is possible.

The application rate per unit area is from about [105 to about 10 Kg of active compound per hectare, preferably from about 0.3 to about 10 Kg of active compound per hectare.
Approximately 6Ko≠; used. However, in special cases it is possible, and even necessary, to exceed or fall below these ranges.

According to the invention, the compound comprises a compound of general formula (I) as an active ingredient, and also diluents (solvents and/or fillers and/or carriers) and/or surfactants, and if necessary, e.g. stabilizers. An agricultural fungicidal composition can be provided which includes a fixing agent, a synergist, and a synergist.

Furthermore, according to the present invention, the compound of the general formula (I) is applied alone or in combination with a diluent (solvent and/or filler and/or carrier) and the site of occurrence of pathogens and/or their outbreaks and crop diseases. A crop disease control method can be provided in which a surfactant and, if necessary, a stabilizer, a fixing agent, and a synergist are mixed and applied.

Next, the content of the present invention will be specifically explained with reference to Examples.
The present invention should not be limited to this only.

Example 1 1.71 2-dichloro-3,3-dimethylcyclopropylmethanol and 1.07 pyridine were added to 50 d of toluene.
20% of a toluene solution containing 1.62% of 2-furoyl chloride was added dropwise under water cooling. After stirring for 5 hours, the reaction solution was poured into ice water and the toluene layer was separated. The toluene layer is washed successively with 1% aqueous hydrochloric acid and 1% bicarbonate (I) aqueous rum solution and water, and dried over anhydrous sodium sulfate. When toluene is distilled off under reduced pressure and the residual liquid is vacuum distilled, the desired 2
．． 2.17 of 2-dichloro-3,3-dimethylcyclopropylmethylfuran-2-carboxylate is obtained.

hp, 169°C/20 run Hg Example 2 2.2-dichloro-6-dimethylcyclopropyl)l
/-le 1.70r and 2-? 'Role carboxylic acid 111
2 was dissolved in 30ml of toluene at 1K, and while stirring, 1.90f of dicyclohexylcarbodiimide was added, followed by 4-N,N-
Add 200 μm of dimethylaminopyridine and continue stirring for 10 hours. The toluene-insoluble portion is removed and washed with 20 toluene, and the solution F is sequentially washed with a dihydrochloric acid aqueous solution, a 1% sodium bicarbonate aqueous solution, and water, and then the toluene solution is dried over anhydrous sodium sulfate. Toluene is distilled off under reduced pressure and the residue is recrystallized from ethanol to obtain 2.19M' of the desired 2,2-dichloro-3,3-dimethylcyclopropylmethylvirol-2-carboxylate. mp
, 103-104°C Example 3 2,2-cyclo-3,3-dimethylcyclopropylmethyl p-toluenesulfone) i23F, 4-pyridinecarboxylic acid 1.52, potassium hydroxide 1.07
, potassium carbonate 1. The mixture is heated under reflux for 12 hours in a toluene solution containing 50 mg of Of and triethylbenzylammonium chloride. After cooling, the toluene-insoluble part was removed and washed with 60 ml of toluene, and the furnace liquid was mixed with 1 ml of aqueous sodium carbonate solution and 2 ml of 0.5 ml of hydrochloric acid aqueous solution. , followed by washing with water and then drying over anhydrous sulfuric acid (IJ). Toluene is distilled off under reduced pressure and the residual liquid is distilled under vacuum to obtain 2.29 g of the desired 2,2-dichloro-43-dimethylcyclopropylmethyl pyridine-4-carboxylate. bp, 120℃70.5a
mHg Example 4 2,2-') 1.825 y of 3.3-dimethylcyclopropylmethyl α-bromoacetate and 1.8 y of imidazole are dissolved in 20 ml of methyl ethyl ketone and heated under reflux for 40 hours. The solvent was distilled off under reduced pressure, the residue was extracted with toluene, the toluene solution was thoroughly washed with water,
Dry over anhydrous sodium sulfate. Toluene was distilled off under reduced pressure and the residue was recrystallized from ether to obtain the desired 2.2
-dichloro-3,3-dimethylcyclopropylmethyl α
-(1-imidazolyl)acetate 2.41 is obtained. mp, 89.5-9 Q, 5°C Compounds of the formula (1) of the present invention synthesized by substantially the same method as in Examples 1 to 4 above are shown in Table 1 below.

Table 1 In addition to the above compounds of the present invention, the following compounds of the present invention were synthesized.

Compound No. 49: 2.2-dichloro-3,3-dimethylcyclopropylmethyl β-(2-chenyl)propionate, H3 Compound No. 50: 2.2-dichloro-6,6-dimethylcyclopropylmethyl β-(2 -furyl) phyllobiotin, Compound N [LSI: 2,2-dichloro-3,6-dimethylcyclopropylmethyl β-(3-pyridyl)propionate, Next, Examples of formulations and biological tests of the compounds of the present invention A specific example is given below.

Example 5 (Irrigation agent) 1.15 parts of the compound of the present invention, a mixture of white carbon (hydrated amorphous silicon oxide fine powder) and powdered clay (1:
5) 80 parts, sodium alkylbenzenesulfonate,
2 parts and 3 parts of a sodium alkylnaphthalene sulfonate formalin condensate were pulverized and mixed to obtain an irrigation agent. This is diluted with water and sprayed onto pathogenic bacteria and/or locations where pathogens and/or crop diseases occur.

Example 6 (Emulsion) 2.30 parts of the compound of the present invention Nα, 55 parts of xylene, 8 parts of holoxyethylene alkylphenyl ether, and 7 parts of calcium alkylbenzenesulfonate were mixed and stirred to prepare an emulsion. This is diluted with water and sprayed on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 7 (Powder) 6.2 parts of the compound of the present invention and 98 parts of powdered clay were pulverized and mixed to prepare a powder. This is sprinkled on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 8 (Powder) 50 parts of the present compound Nα, 1.5 parts, Improvir hydrogen phosphate (PAP), 5 parts α, powdered clay,
Grind and mix 98 parts to make a powder, and sprinkle it on areas where pathogenic bacteria and/or spread, their outbreaks, and crop diseases occur.

Example 9 (granules) To a mixture of the present compound N [L 39, 10 parts, bentonite (montmorillonite), 30 parts, talc (talc)%, 58 parts, lignin sulfonate, 2 parts, 25 parts of water was added. , knead well and use an extrusion type granulator to make 10 to 40
The mesh is dried at 40 to 50°C to form granules. This is sprinkled on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 10 (granules) Clay mineral particles with a particle size distribution of 0.2 to 2 fins.

95 parts were placed in a rotary mixer, and while rotating, 5 parts of the oily compound of the present invention, N117, was sprayed and evenly absorbed to form granules. This is sprinkled on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 11 (Oil agent) 0.5 parts of the present compound N[L41 and 99.5 parts of kerosene are mixed and stirred to prepare an oil agent. This is sprayed on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 12 Test of foliar spray efficacy against rice blast disease Preparation of test compound Active compound: 50 parts by weight Carrier; Mixture of diatomaceous earth and kaolin (1:S): 45 parts by weight Emulsifier; Polyoxyethylene alkyl phenyl ether = 5 parts by weight The above-mentioned amounts of the active compound, carrier and emulsifier are ground and mixed to form an aquarium, and the prescribed amount is diluted with water to prepare.

Test Method Paddy rice (variety: Asahi) was grown in clay pots with a diameter of 12 crn, and during the 3rd to 4th period, a diluted solution of the test compound at a predetermined concentration prepared as described above was sprayed at 50 rnt per 3 pots. The next day, spray inoculation with a suspension of artificially cultured rice blast fungus spores (twice)
The plants were then kept in a greenhouse at 25°C and relative humidity of 100°C to allow infection. Seven days after inoculation, the degree of disease per pot was graded and evaluated according to the following criteria, and the control value (CH) was determined.

Morbidity Lesion area ratio (%) 0 0.5 2 or less 1 3-5 2 6-103
11-204 2
1 to 405 41 or more This test is the result of 3 pots in 1 section.

The compounds of the present invention (compounds 1 to 51 shown in Table 1 and Examples 1 to 4 above showed a control value of 100 cm at an active ingredient concentration of 500 ppm, and also showed a control value of 100 cm at an active ingredient concentration of 500 ppm. On the other hand, for example, in the Dutch patent disclosed above, the control value was shown, and at 250 ppm, the control value was only 50 or less.

Example 13 Water surface application efficacy test against rice blast Test method Paddy rice (variety: Asahi) was placed in a white porcelain pot with a diameter of 6 cr
Cultivation is carried out by submerged planting, and at the early stage of tillering, a chemical solution of a predetermined concentration prepared in the same manner as in Test Example 1 is irrigated onto the water surface using a pipette at the indicated amount without directly contacting the above-ground parts of the rice plant. did. Four days later, a suspension of rice blast fungus spores was spray-inoculated by a conventional method and kept in an inoculation chamber at a temperature of 26-25°C and a relative humidity of 100°C for 24 hours. Thereafter, the plants were transferred to a glass greenhouse at a temperature of 20 to 28° C., and 7 days after inoculation, the plants were investigated in the same manner as in Example 12 to determine the control value (chi).

The compound of the present invention has an excellent permeability and transfer effect, and when applied to the water surface, it exhibited a surprising effect on controlling rice blast disease. That is, it exhibited a complete control value of 100% at an active ingredient concentration of 800 .mu./m2, and also exhibited a 100% control effect at an active ingredient concentration of 200 .mu./m.sup.2. On the other hand, the compound disclosed in the Dutch patent cited in Example 12 exhibited a control effect of 200 cm/m2 or less than 50%.

The present invention can be summarized as follows.

1) A carboxylic acid 2,2-dichloro-3,6-dimethylcyclopropylmethyl ester compound represented by the general formula: where m, n, R", R" and Q are the same as above.

2) 2.2-cyclo-3.3-dimethylcyclopropylmethanol and the general formula: where m, n, R', R2, Q and Ml are the same as above.

A method for producing a carboxylic acid 2,2-cy)10-3,3-dimethylcyclopropyl methyl ester compound represented by the general formula (1), the method comprising reacting the compound represented by the formula (1) with a compound represented by the formula (1).

3) General formula: In the formula, A is the same as above.

A compound represented by the general formula (I), characterized by reacting a compound represented by the general formula: where m, n, R1, R2 and Q are the same as above. A method for producing a carboxylic acid 2,2-cyclo-6,3-dimethylcyclopropylmethyl ester compound.

4) General formula: In the formula, Hal is the same as above, A compound represented by General formula: %formula%() In the formula, egg and Q' are the same as above.

A method for producing a carboxylic acid 2,2-dichloro-6,3-dimethylcyclopropylmethyl ester compound represented by the general formula: The method comprises reacting the compound represented by the formula:

4) An agricultural fungicide containing the 2,2-dichloro-3,3-dimethyl-cyclopropane-methanol derivative of the general formula (1) as an active ingredient.

5) The compound of general formula (I) may be used alone or in the presence of diluents (solvents and/or fillers and/or carriers) and/or surfactants, and if necessary, stabilizers, adhesion agents, synergists. A crop disease control method that involves applying a mixture of the following agents:

6) The crop disease control method according to item 7) above, which targets rice blast control.

Patent applicant: Japan Special Pesticide Manufacturing Co., Ltd. 263158
7330-4 C275106
7330-4C 277/687330-4C 295/10 6917-4
C307/68 6640-4
C307/71 6640-
4 C309/38 7169
-4 C311/12 716
9-4C-311/22 71
69-4 C333/24 8
214-4 C333/38
8214-4 C333/'70
'8214-4 C47] 704 10
2 6664. -4C□@Inventor Jun Saito- 3-7-12 Inuzawa, Mitaka City 0 Inventor Shinzo Ribe 47-15 Otani-cho, Hachioji City 0 Inventor Shin Sakawa 1-14-13 Tamadaira, Nihino City

Claims (1)

[Claims] General formula: In the formula, m and n each represent 0 or 1, and R1 and R2
each represents a hydrogen atom, where m and n are both 1
In the case of a saturated or unsaturated heterocyclic group, which may be benzo-fused, and further comprising:
The heterocyclic group may optionally be at least one of a halogen atom, a nitro group, a lower alkyl group, a benzyloxycarbonyl group, and a keto group (however, in the case of two or more groups, they may be the same or different). provided that m and n are simultaneously 0 and Q is a benzo-fused heterocyclic group containing a nitrogen atom, and in that case, the nitrogen atom of Q is directly bonded to and in the formula Carboxylic acid 2,2-dichlorok-3,3-, except when
Dimethylcyclopropyl methyl ester compound. 2) 2,2-dichloro-3,3-dimethylcyclopropylmethylfuran-2 according to claim 1, which is represented by the formula:
- Carboxylate. 3) 2,2-dichloro-6,3-dimethylcyclopropylmethylpyridine according to claim 1, which is represented by the formula:
4-carboxylate. 4) 42-dichloro-6,3-dimethylcyclopropylmethyl α-(2-chenyl)acet-1. according to claim 1, which is represented by the formula: 5) General formula: In the formula, m and η each represent 0 or 1, and R1 and R
2 each represents a hydrogen atom, where m and n are both 1, R1 and R2 may be taken together to form a single bond, and Q represents a heteroatom such as oxygen or sulfur. ,
Indicates a saturated or unsaturated heterocyclic group having at least one nitrogen (however, in the case of two or more, the same or different types may be present), and the heterocyclic group may be benzo-fused. , furthermore, the heterocyclic group may optionally contain at least one of a halogen atom, nitro group, lower alkyl group, benzyloxycarbonyl group, and keto group
(In the case of two or more groups, they may be the same or different types), provided that m and n are both 0 and Q is a benzo-fused heterocyclic group containing a nitrogen atom, and in that case, , except when the nitrogen atom of Q is directly bonded to 8 in the formula. An agricultural fungicide containing a carvone P2,2-dichloro-3,3-dimethylcyclopropyl methyl ester compound represented by the following as an active ingredient.