JPS59101438A - 2,2-dichloro-3,3-dimethyl-cyclopropane-methanol derivative - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R<1> is H, halogen, or acetyloxy; R<2> is H; with the proviso that R<1> and R<2> together with C linked form carbonyl or saturated hydrocarbon ring; R<3> is cyano, thiocyanamido, acetyl, lower alkoxycarbonyl, substituted phenoxy, lower alkoxy, substituted amino, etc.; with the proviso that R<1>-R<3> together with C linked form partially saturated hydrocarbon ring). EXAMPLE:2,2-Dichloro-3,3-dimethylcyclopropylmethyl alpha-methoxyacetate. USE:A fungicide for agriculture. Showing improved antimicrobial effect on pathogenic germs of plant such as Archimycetes, Phycomycetes, Fungi Imperfecti, etc., having low toxicity to warm-blooded animal, no phytotoxicity to cultivated crops, useful for controlling blights of plant, especially blast of rice plant. PROCESS:For example, a compound shown by the formula II is reacted with a compound shown by the formula III(R<3>' is R<3> except thiocyanato, acylamino, etc.; Hal is halogen), to give a compound shown by the formula I where R<3> is R<3>'.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel 2,2-dichloro-3,8-dimethyl-
The present invention relates to a cyclopropane-methanol derivative and an agricultural fungicide containing the compound as an active ingredient.

More specifically, the present invention provides 2 represented by the following formula (1),
The present invention relates to a 2-dichloro-8,8-dimethyl-cyclopropane-methanol derivative. That is, the general formula: In the formula, RI represents a hydrogen atom, a halogen atom, or an acetyloxy group, R2 represents a hydrogen atom, and RI and R1 together represent, for example, a carbonyl group together with the carbon atom to which they are bonded. Furthermore, RI and R1 together with the carbon atoms to which they are bonded can represent a saturated hydrocarbon ring, and Bs represents a cyano group, a thiocyanato group, an acetyl group, a lower alkoxycarbonyl group, substituted phenoxy group (the substituent may be the same or different, and represents at least one selected from the group consisting of halogen; nitro; lower alkoxy), lower alkoxy group, halo-lower alkenylthio group,
benzylthio group, di-lower alkylphosphono group, acylamino group, substituted amino group (the fl[% group may be the same or different selected from the following 9 groups, such as lower alkyl; phenyl; formyl; benzyl; methanesulfonyl). ), a phenyl group which may be substituted (the substituent is at least one group which may be the same or different selected from the group consisting of halogen; lower alkyl; lower alkoxy; nitro), where Rs means a phenyl group, R1 and R2 are not hydrogen atoms at the same time), lower alkylthio-lower alkyl group, 2.2
1-dichloro-8,8- to dimethylcyclopropylmethoxycarbonyl group, or /R4 R4 and RI are a hydrogen atom, a lower alkyl group, a lower alkoxycarbonyl group, an optionally substituted phenyl group (the substituent is a halogen; R1, R1 and Rs together with the carbon atoms to which they are bonded represent a partially unsaturated hydrocarbon ring. A 2,2-dichloro-8,8-dimethyl-cyclopropane-methanol derivative represented by:

The present invention also provides 2,2-dichloro-
The present invention also relates to an agricultural fungicide characterized by containing a 1,8-dimethyl-cyclopropane-methanol derivative as an active ingredient.

Dutch Patent No. 72052 general formula known before filing of the present invention: (In the formula, Hal is) a rogen atom, R1 is a hydrogen atom, an alkyl group, or a phenyl group, R1 and Rs 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 a cyclopropane carboxy derivative represented by the following formula has bactericidal activity. However, this prior art publication, of course, makes no mention of the existence of the compound of formula (1).

The present inventors have conducted research on the development of agricultural fungicides. As a result, the 2,2-dichloro-8,8-dimethyl-cyclopropane-methanol derivative represented by the above formula (1), which has not been described in any prior literature, can be easily produced.
It was also discovered that the compound of formula (1) exhibits an excellent bactericidal effect against plant pathogen traps and is useful as an agricultural fungicide.

According to the research conducted by the present inventors, the chemical structure of the compound of the present invention is that the compound of the above formula (1 ), when it has the chemical structure of the group R1:1, it can exhibit an excellent bactericidal effect as an agricultural fungicide.

In addition, in terms of production, the production of the compound disclosed in the Dutch patent requires, for example, a reaction under anhydrous conditions, the reaction involves multiple steps, and furthermore, the reaction time is very long. There are manufacturing disadvantages such as the use of expensive and skin irritating compounds such as sodium trichloroacetate as raw materials and very low yields. In contrast, the compound of formula (1) of the present invention has the following advantages: the reaction can be carried out at room temperature, the reaction process is completed in one step, the raw materials are cheap and easily available, and about 80%
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 the above-mentioned high yield.

Furthermore, according to the research conducted by the present inventors, the compound of formula (1) 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 bactericidal 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 of being of low toxicity to warm-blooded animals, and does not cause any phytotoxicity to cultivated crops at the usual concentration of use; It has also been found that it has the advantage of being able to be applied on the water surface (in the middle) when controlling rice blast, for example.

Therefore, the object of the present invention is to provide novel 2 compounds of the general formula (I).
．． The present invention provides a 2-dichloro-8,8-dimethylcyclopropane-methanol derivative 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 effect of the compound of formula (I) of the present invention is wide, for example, against archaeal bacteria [Archimycetes].
) J, algae [phycomycetes (Ph'/comJcet
ets) J, Ascomycetes [Ascomycetes]
cgtes) J, Basidiomycetes (Hast
diomJcetes) J, Deuteromycetes [pungiJrn, perf ec
tt) 3 and other various plant diseases caused by paper fungi.

The novel compound of formula (1) of the present invention can be prepared, for example, by the following method i).
, ii), 111) and iv).

Manufacturing method j); H・Ila 1 In the formula, RI and R1 are the same as above.

R3° is a thiocyanato group, a substituted amine group, an acylamino group, and a group among the above definitions of R3, and R1 is)
In the case of S-logen atom, it means excluding a lower alkoxycarbonyl group, and Hal indicates a no-logen atom.

In the second reaction described above, RI specifically represents a hydrogen atom, a norogen atom such as fluoro; chlorine; bromo; iodine, or an acetyloxy group, and R1 represents a hydrogen atom. RI and 82 together can also represent a carbonyl group together with the carbon atom to which they are attached. Furthermore, yc, Bl and RI together with the carbon atom to which they are attached may represent a saturated hydrocarbon ring, for example a saturated hydrocarbon ring having 8 to 7 carbon atoms.

E" specifically includes a cyano group, an acetyl group, a lower alkoxycarbonyl group, a substituted phenoxy group [the substituents are the same as above], rogene; nitro; methyl, ethyl, furoyl, isopropyl, and -1 or t
At least one member selected from the group consisting of lower alkoxy having a lower alkyl group such as ert-)butyl, which may be the same or different, lower alkoxy groups similar to those exemplified above, and halogen atom traps similar to those exemplified above. polysubstituted lower alkenyl groups such as vinyl, allyl, and 1-proynyl; benzylthio groups; di-lower alkylphosphono groups having lower alkyl groups similar to those exemplified above; optionally substituted phenyl groups (the substituents are halogen atom as above; lower alkyl group as above; lower alkoxy group as above; (If R and R1 are not hydrogen atoms at the same time), lower alkylthio-lower alkyl group having the same lower alkyl group as above, or Gt2,2-dichloro-8,8-dimethylcyclopropylmethoxy RI, R1 and Rs' together with the carbon atom to which they are bonded represent a carbonyl group, and RI, R1 and Rs', together with the carbon atom to which they are bonded, represent a partially unsaturated hydrocarbon ring, such as a partially unsaturated hydrocarbon ring having 5 to 7 carbon atoms, such as cyclopentene, It can represent cyclohexene, cycloheptene, etc. 1fal represents the same nitrogen atom as described 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 (n) as a raw material include cyanoacetyl chloride, acetoacetyl chloride, ethoxycarbonylacetyl chloride,
2-(8- or 4-) chlorphenoxyacetyl chloride, 2-(or 4-) fluorophenoxyacetyl chloride, 2-methoxyphenoxyacetyl chloride, 2
-(8-1 or 4-)nitrophenoxyacetyl chloride, 2,4-dichlorophenoxyacetyl chloride%2
-Chlor-p-)lyloxyacetyl chloride, methoxyacetyl chloride, 2,8.8-)lychlorallylthioacetyl chloride, benzylthioacetyl chloride, diethylphosphonoacetyl chloride, 2-(or 4-)chlorphenylacetyl Chloride, 2-(or 4-)fluorophenylacetyl chloride, 4-bromphenylacetyl chloride, etc.-(father is p-))lylacetyl chloride, 2-(8-, father is 4-)methoxyphenylacetyl chloride , 4-ethoxyphenylacetylchloride IJ
2- (also 114) nitrophenylacetyl chloride, α-ria-α-phenylacetyl chloride,
α-Bromo-α-phenylacetyl chloride, α-acetoxy-phenylacetyl chloride, benzoylformyl chloride, ethyloxalyl chloride, 2,2-dichloro-8°8-)methylcyclopropylmethylmalonyl chloride, (1-cyanocyclo Examples include (propane)-carbonyl chloride, (l-cyclohexene)carbonyl chloride, and their bromides.

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

H3 +HC1 The method for producing the compound of the present invention can be carried out desirably using a solvent or diluent. Therefore, all inert solvents and diluents can be used as K.

Such solvents or diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (which may be chlorinated depending on the pressure), such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene. ,
Methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso-furobyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl is.

-propyl ketone, methyl-1so-butyl ketone; nitriles such as acetonitrile, propionitrile,
Acrylonitrile; alcohols such as methanol,
Ethanol, tso-furopanol, butanol, 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. I can give it to you.

Furthermore, as described above, the reaction of the present invention can be carried out in the presence of an acid binder. Examples of such acid binders include commonly used alkali metal hydroxides, carbonates, bicarbonates, alcolades, etc., and 8th class amines such as triethylamine, diethylaniline, pyridine, etc. .

The method of the invention can be carried out within a wide temperature range. It is generally carried out between about -20<0>C and the boiling point of the mixture, preferably between about 0<0>C and about 100<0>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) (R1=H1R1-H) CHs (1-ii) M-Ha 1 In the formula, Hal is the same as above.

M represents a hydrogen atom or an alkali metal atom.

Bs" represents a thiocyanato group, an acylamino group, a substituted amino group, or a group (as defined above for Rj).

In the above reaction formula, HaL specifically represents the same thing as above, and M represents a hydrogen atom or an alkali metal atom such as lithium, sodium, potassium, etc.

Specifically, R3" is a thiocyanato group, methyl, ethyl, furoyl, isopropyl, n-(iso-1sec
-, or tart-) A lower alkylcarbonylamino group having a lower alkyl group such as butyl, or an acylamino group such as a benzoylamino group, a substituted amino group (the substituent is specifically the same lower alkyl as above; phenyl; formyl; benzyl; methanesulfonyl, which may be the same or different; or specifically, each independently represents a hydrogen atom, a lower alkyl group similar to the above, A lower alkoxycarbonyl group having a lower alkyl group, an optionally substituted phenyl group (specifically, the substituent may be the same halogen atom as mentioned above; the same kind selected from the group consisting of 9, such as the same lower alkyl group as above) at least -ke).

In the method for producing the compound of the formula (1-ii) of the present invention represented by the above reaction formula, specific examples of the compound having the general formula (plane) as a raw material include, for example, 2,2-dichloro-8,8-dimethyl-cyclopropyl Methyl α-chloroacetate, 2,2-dichloro-8
, 8-dimethyl-cyclopropylmethyl α-bromoacetate and the like.

Specific examples of compounds of general formula (IV) which are also raw materials include, for example, isobutyraldoxime, acetoxime, 8-entanone oxime, benzaldoxime, 2-chlorobenzaldoxime, 2-methylbenzaldoxime. , 2-bromobenzaldoxime, acetophenone oxime, ethyl 2-hydroxyiminopropionate, potassium thiocyanate, dimethylamine, N-methyl-methanesulfamide-Nα salt, N-methylaniline, acetamide, benzamide, formanilide, Examples include N-benzyl-methylamine.

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

CH.

+ 11Br In order to carry out the above 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.

Manufacturing method 111); (RI=)・rogen atom, R”=II)
CH3(V) (Vl)u-iii) H-11'cL l'+ SOx In the formula, RII'' represents a lower alkoxycarbonyl group.

In the above reaction formula, Rs"' specifically represents a lower alkoxycarbonyl group having a lower alkyl group as described above.

Specifically, Hal' represents a fluorine atom such as fluor, chloro, bromine, or iodine.

In the method for producing the compound of formula (I-Ill) of the present invention shown in the above reaction formula, the compound of general formula (V) as a raw material is also a compound of the present invention, and specific examples thereof include, for example, ethyl 9,2-dichloro -13,8-dimethylcyclopropylmalonate, methyl 2,2-dichloro-8,
8-dimethylcyclopropyl malonate, propyl 2
, 2-dichloro-8,8-dimethylcyclopropyl malonate, isopropyl 2,2-dichloro-8,8-dimethylcyclopropyl malone), n-j thyl 2.2-
Dichloro-8,8-dimethylcyclopropylmalonate and the like can be exemplified.

Similarly, specific examples of the compound of general formula (Vl) which is a raw material include sulfuryl chloride, sulfuryl bromide, and the like.

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

11CII + S O2 In order to carry out the above 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.

Manufacturing method 1); (Vll) In the formula, R1, R2 and Rs are the same as above.

In the above reaction formula, R' and Rz specifically represent the same thing as described above, and R8 specifically represents the same meaning as R'' and R3'' described above.

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 (Vll) as a raw material include N-isobutylideneaminooxyacetic acid, N-ethylideneaminooxyacetic acid, , #-(2-henteridene)aminooxyacetic acid, N-(2-chlorobenzylidene)aminooxyacetic acid, N-(2-methylbenzylidene)aminooxyacetic acid r11. N-C2-brombenzylidene)aminooxyacetic acid, 7V-(1-phenylethylidene)aminooxyacetic acid, #-(1-carboethoxyethylidene)aminooxyacetic acid, cyanacetic acid, thiocyanatoacetic acid, acetoacetic acid, ethylmalonic acid1. Ethylchloromalonic acid, (2-chlorophenoxy)acetic acid, (8-chlorophenoxy)acetic acid, (4-chlorophenoxy)acetic acid,
(2-fluorophenoxy)acetic acid, (4-fluorophenoxy)acetic acid, B-methoxyphenoxy)acetic acid, (2-
(nitrophenoxy)acetic acid, (8-nitronenoxy)acetic acid, (2゜4-dichlorophenoxy)acetic acid, (2-chloro-4-methylphenoxy)acetic acid, methoxyacetic acid, (2
,8,8-)lichlorallylthio)acetic acid, benzylthioacetic acid, diethylphosphonoacetic acid, N,N-dimethylglycine, N-methylphenylalanine, acetylglycine,
Benzoylglycine, N-formylphenylalanine,
N-Benzylalanine, N-methylsulfonylalanine, (2-chlorophenyl)acetic acid, (4-10ruphenyl)vinegar 1! , (2-fluorophenyl)acetic acid, (4-fluorophenyl)acetic acid, (4-7'romphenyl)acetic acid,
m-)lylacetic acid, p-tolylacetic acid, (2-methoxyphenyl)acetic acid, (8-methoxyphenyl)i[, (4-meth)xyphenyl)acetic acid% (4-ethoxyphenyl)acetic acid, (2-nitrophenyl) ) Acetic acid, (4-nitrophenyl) acetic acid, α-chloro-phenylacetic acid, α-bromo-phenylacetic acid, 2゜2-dichloro-8,8-dimethylcyclopropylmethylmalonic acid, l-cyanocyclopropanecarboxylic acid , ■-cyclohexenecarboxylic acid, acetoxy-phenylacetic acid, phenylketoic acid, monoethyl oxalate, and the like.

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

Htr tO In order to carry out the above method, the same inert solvent or diluent as described above is used in the presence of a dehydration condensation agent, and the desired product can be obtained with high purity and high yield.

A specific example of such a dehydration condensation agent is dicyclohexylcarbodiimide.

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.

Above manufacturing methods 1), 11), 111), K iv) and other K
For example, compound /168 of the present invention described below can also be synthesized by the reaction of 2,2-dichloro-8,8-dimethylcyclopropylmethanol and malonyl chloride, as shown in Example 8 below. In addition, as shown in Example 101C below, Compound 457 below is 2,2-dichloro-8,8-dimethylcyclopropylmethanol,
It can also be synthesized by reaction with diketene.

When the compound of the present invention is used as an agricultural fungicide,
It can be used directly as it is after being diluted with water, or it can be used in various formulations using a method commonly used in the field of agricultural chemical manufacturing using agricultural chemical adjuvants. In actual use, these various formulations can be used directly 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 distillates (paraffin wax, kerosene, light oil, middle oil, heavy oil), benzene, toluene, xylenes], halogenated hydrocarbons [e.g. chlormethylene, carbon tetrachloride, trichlorethylene, Ethylene chloride, ethylene tribromide, chlorobenzene, chloroform], Flu:IA [(e.g. tij, methyl alcohol, ethyl alcohol, flobyl alcohol, ethylene glycol]), ethers [e.g. ethyl ether, ethylene oxide, dioxane] , alcohol ethers C example (e.g. ethylene glycol monomethyl ether), ketones [e.g. acetone, isophorone], esters [e.g. ethyl acetate, amyl acetate], amides [e.g. dimethylformamide, dimethylacetamide], sulfoxides [For example, dimethyl sulfoxide] can be mentioned.

As fillers or carriers, inorganic powders such as slaked lime, magnesium lime, gypsum, calcium carbonate, silica stone,
Perlite, pumice, calcite, diatomaceous earth, amorphous silicon oxide, alumina, zeolite, clay minerals (e.g. pyrophyllite, talc, montmorillonite, beidellite, vermiculite, kaolinite, mica); vegetable powders such as grain flour , starch, modified starch, sugar, glucose, crushed plant stems; synthetic resin granules; phenol resins, urea resins, vinyl chloride resins, and the like.

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-)lichloro-1.1.2-)lifluoroethane, chlorobenzene,
LNG, lower ether〕=(for smoking agent) Combustion regulator〔
For example, nitrite, zinc powder, dicyandiamide]: Oxygen supply agent [e.g., chlorate, dichromate]: Efficacy extender: Dispersion stabilizer [e.g., casein, tragacanth, carboxymethyl cellulose (CMC), folihinyl] Alcohol (PVA)]: A synergist can be mentioned.

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

Forms of preparations include emulsions, oils, wettable powders, aqueous solutions, suspensions, powders, granules, powders, smoking agents, tablets, aerosols, pastes, capsules, etc. can.

The agricultural fungicide of the present invention may contain from about 0.1 to about 95% by weight of the active ingredient, preferably from about 0.5 to about 90% by weight.

In actual use, the various formulations and spray preparations described above (read, y-to-use-prepared)
The active compound content in cation) is generally about 0.00
01 to about 20% by weight, preferably about 0.005 to about 1O
A range of weight percent 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 occurrence 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. .

Various formulations or dispersion preparations containing the active ingredients of the invention (read/-to-rbse-7r)
Application methods, spraying, spraying, spraying, spraying, misting, ato-mtting, dusting, granulation, and water surface application are commonly used in the agricultural chemical manufacturing field. , poring]: smoke: doming application, [e.g., mixing, spring ring (sprinkl)
ing), fumigation (vapo-ring), irrigation] two-surface application [e.g.
Powder coating, coating]: Can be applied by dipping, etc. Also, the so-called ultra-high concentration small amount spraying method (rbltr5L-1ow
-volv, m, e) It can also be used from K.

In this way it is possible to contain 100 grams of active ingredient.

The application rate per unit area is about 0.08 to about 10 kg of active compound per hectare, preferably about 0.8 to about 10 kg.
Approximately 6 kg can be used. However, in special cases it is possible, and sometimes even necessary, to exceed or fall below these ranges.

According to the present invention, the compound of the general formula (1) is included as an active ingredient, and a diluent (solvent and/or filler and/or carrier) and/or surfactant, and if necessary, for example, a stabilizer. An agricultural fungicidal composition can be provided which includes a fixing agent, a synergist, and a synergist.

Further, according to the present invention, the compound of the general formula (1) is applied alone or as a diluent (solvent and/or filler and/or carrier) to the site of pathogenic bacteria and/or their outbreak and crop disease. A crop disease control method can be provided in which a mixture of a surfactant and/or a stabilizer, a fixing agent, and a synergist is applied if necessary.

Next, the content of the present invention will be specifically explained using examples.
The present invention should not be limited to this only.

Example 1 2.2-dichloro-8,8-dimethylcyclopropylmethanol 60f and pyridine, 241 and hexane 200r
Dissolve dK, and while cooling with ice water, a solution of methoxyacetyl chloride and BOW dissolved in hexane and 20017 is added dropwise over 2 hours while stirring. After dropping, 00C~2
After stirring for a further 5 hours at 0° C., the salts are removed from the oven and washed with hexane and 200°C. Solution F was 1% aqueous hydrochloric acid solution, 19
g Wash sequentially with an aqueous sodium carbonate solution and water, and dry over anhydrous sodium sulfate. After removing the solvent under reduced pressure, distillation yields the target product 2,2-dichloro-8,8-dimethylcyclopropylmethyl α-methoxyacetate 85
Get an F. bp, 186-b Example 2 ('3 (Compound Demon 2) 2.
Dissolve 2-dichloro-8,8-dimethylcyclopropylmethyl α-bromoacetate, 2.68F topenzaldoxime, 1.1f) toluene, 20WLtK, and add 0.6F potassium carbonate to this solution.

Potassium hydroxide 0.6F and triethylbenzylammonium chloride, 501! Add l1il and stir at room temperature for 8 hours. Pour 50 dK of water into the reaction solution, separate the toluene layer, and wash the aqueous layer with 20 ml of toluene.

The toluene layers are combined, washed with water, and dried over anhydrous sulfuric acid. When toluene is distilled off under reduced pressure and the remaining oil is distilled, the target product, 2,2-dichloro-8,8-
1.85 fdj of dimethylcyclopropylmethyl α-(N-penzylidene ξnooxy)acetate is obtained.

6p, 180-181'c/　U　, 4　ym　Ih.

In Examples 2.2-dichloro-8,8-dimethylcyclopropylmethyl α-chloroacetate 2.9of and potassium thiocyanate, 2. Of is suspended in 20 WLtK of ethyl alcohol and heated under reflux for 12 hours. Ethyl alcohol is distilled off and the residue is extracted with toluene. Wash the toluene layer with water,
Dry over anhydrous sulfuric acid (IJum). When toluene is distilled off under reduced pressure and the remaining oil is distilled, the target product 2,2
-dichloro-8,8-dimethylcyclopropylmethyl
α-thiocyanatoacetate, 2.6 fbE is obtained.

bp.

148℃10.4Hf0 Example 4 Toluev solution 2 of 2.9f of 2.2-dichloro-8,8-dimethylcyclopropylmethyl α-bromoacetate 2
0 dVc, under ice cooling, 50% dimethylamine aqueous solution 1
Drop 0ml. After 10 minutes, the reaction was stirred at room temperature for 70 hours. The reaction solution was mixed with 50 dl of water ([', Separate the toluene layer. Wash the aqueous layer once with 20 toluene, combine with the previous toluene layer, wash 8 times with 201 d of water, and add anhydrous sulfuric acid). Dry on top. Toluene was distilled off under reduced pressure and the remaining oil was distilled under vacuum to obtain 2.81 of the target N-methylalanine 2,9-dichloro-8,8-dimethylcyclopropylmethyl ester. bp.

112℃/0.4mmHf.

Example 5 0° (compound/l65)2
．． 2-dichloro-8,8-dimethylcyclopropylmethyl α-bromoacetate, 2.9f, N-methyl-methanesulfamide-Ha salt 1. fl potassium carbonate 0.
51, triethylbenzylammonium chloride 0.2
1 was suspended in a mixed solvent of 80 parts of toluene and 2 parts of methylene chloride, and stirred for 40 hours. Add 80ml of toluene and remove the insoluble portion. The organic solvent layer is washed with water and dried over anhydrous sodium sulfate. The organic solvent is distilled off under reduced pressure, and the residual liquid is recrystallized from hexano, to obtain 8.2 v of the target product, N-(methanesulfonyl)alanine 2,2-dichloro-8,8-dimethylcyclopropylmethyl ester. mp
, 78-76°C.

Example 6 2,2-dichloro-8,8-dimethylcyclopropyl
α-bromoacetate 2.89. Formanilide 1.1
F, potassium carbonate 2.5F, )ethylbenzyl ammonium chloride 1009)) Suspend in 3Qdl of toluene and heat under reflux for 20 hours. After cooling, add 20ml of toluene and pour in 50111VC of water.

Wash the toluene layer with water and dry over anhydrous sodium sulfate. Toluene was distilled off under reduced pressure and the residue was recrystallized from ether to yield the target product, N-formylphenylalanine.
2r,2-dichloro-8,8-dimethylcyclopropylmethyl ester 2.7F is obtained. mp, 84.
5-85.5°C.

Example 7 0° (Compound A67)2.
2-dichloro-8,8-dimethylcyclopropylmethanol 2.9t and cyanoacetic acid 0.9f toluene, 40d
Dissolve dicyclohexylcarbodiimide 2. with stirring. Process Of, then add 4-dimethylaminopyridine, 50q.

After stirring at room temperature for 12 hours, insoluble matter was removed, and toluene 40
Wash with 1 tl of toluene solution, wash with l-dihydrochloric acid aqueous solution, l-bicarbonate aqueous solution, and water in order, and dry on anhydrous sulfuric acid solution.

Toluene is distilled off under reduced pressure, and the residue is recrystallized from ether to obtain the target product, 2.2-dichloro-8,8-dimethylcyclopropylmethyl α-cyanoacetate, 2.4f. mp, 70-72°C.

Example 8 (Compound A68) Under water cooling, 2,2-dichloro-8,8-dimethylcyclopropylmethanol lO- was added to 8.7f of malonyl dichloride.
drip. After the dropwise addition, the mixture was gradually returned to room temperature, stirred at room temperature for 72 hours, and then heated at 100° C. for 5 hours. The reaction solution is cooled, 5Qa/d of water and 50d of toluene are added at the same time, and the toluene layer is separated. The toluene layer was washed successively with a 1% aqueous sodium carbonate solution and water, and dried over 17 um of anhydrous sulfuric acid. Toluene was distilled off under reduced pressure, and the remaining oil was fractionally distilled to obtain the target product, bis-(2,2-dichloro-8,8-diJ thylcyclopropyl)malonate, 7.
4f is obtained. hp,';? , 00-205℃10.
4mwHy Example 9 (Compound 7% 6) Ethyl 2.2-dichloro-8,8-dimethylcyclopropylmalone), 8.15F sulfuryl chloride,
8. Drop Of. After dropping, heat at 60°C for 1 hour. After cooling, extract with toluene, wash with water, 1% aqueous sodium bicarbonate solution, water, and dry over anhydrous sodium sulfate. The toluene was distilled off under reduced pressure and the remaining oil was distilled under vacuum to obtain the target product, ethyl 2,2-dichloro-8,8-
dimethylcyclopropylmethyl chlormalone) Z,
Get 6r. bp, 185 DEG C. 10.4 H1 DEG Compounds shown in Table 1 below were produced according to the methods of Examples 1 to 7 above.

Example 10 CB'' (compound position 57) 2.2
I-dichloro-8,8-dimethylcyclopropylmethanol17. Dissolve 1 ooyK of Of in acetone, and add 1 tnl of triethylamine to the solution.

While cooling in a water bath, diketene 11. 20- of acetone containing Of is added dropwise. After the dropwise addition, the mixture was heated under reflux for 2 hours.

The reaction solution was cooled with ice water, diluted hydrochloric acid 1001 was added, and extracted with toluene. Wash the toluene layer with water and add anhydrous sulfuric acid)
Dry on Jum. When toluene is distilled off under reduced pressure and the residual liquid is vacuum distilled, the desired product 2. Z-dichloro-8,8-
dimethylcyclopropylmethyl acetoacetate) 1
6,8 f is obtained. hp, 115℃/0.4
trvnlly 0 Next, formulation examples of the compounds of the present invention,
and specific examples of biological test examples.

Example 11 (Wettable powder) 15 parts of the compound of the present invention Al, a mixture of white carbon (hydrated amorphous silicon oxide fine powder) and powdered clay (
1:5), 2 parts of sodium alkylbenzenesulfonate, and 8 parts of sodium alkylnaphthalenesulfonate 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 12 (emulsion) 420.80 parts of the compound of the present invention, xylene, 55 L, t!
IJ oxyethylene alkyl phenyl ether, 8 parts,
7 parts of calcium alkylbenzenesulfonate were mixed and stirred to form an emulsion. This is diluted with water and sprayed on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 18 (Powder) 41.2 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 14 (Powder) 25.1.5 parts of the compound of the present invention, 0.5 parts of isoprobyl-hydrogen phosphatide (7'AP), and 98 parts of powdered clay were pulverized and mixed to make a powder. /Or dusting the outbreak and areas where the crop disease occurs.

Example 15 (granules) Mixture K of 87.10 parts of the present compound, bentonite (montmorillonite), ao part, talc ('1 stone), 58 parts, lignin sulfonate, 2 parts, water, 25 parts. In addition, the mixture is thoroughly kneaded, made into granules of 10 to 40 mesh using an extrusion type granulator, and 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 16 (granules) Clay mineral particles having a particle size distribution of 0.2 to 2t1w, 95
of the present invention compound 4 in an oily state was put into a rotary mixer and rotated.
Spray 41.5 parts and absorb evenly to form granules. This is sprinkled on locations K where pathogens and/or their outbreaks and crop diseases occur.

Example 17 (Oil agent) 0.5 part of the compound of the present invention/1658.5 parts and 99.5 parts of kerosene were mixed and stirred to prepare an oil agent. This is sprayed on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 18 Preparation of test compound for foliar spray efficacy test against rice blast disease Active compound: 50 parts by weight Carrier; Mixture of diatomaceous earth and kaolin (1:5): 45 parts by weight Emulsifier; Pholyoxyethylene alkylphenyl ether = 5 A wettable powder is prepared by grinding and mixing the above-mentioned amounts of the active compound, carrier and emulsifier in parts by weight, and diluting the predetermined dosage with water.

Test Method Paddy rice (variety: Asahi) was cultivated in clay pots with a diameter of 12 Crn, and in the 8th to 4th periods, a diluted solution of a predetermined concentration of the test compound prepared in kg as described above was sprayed at 501 kg per 8 pots. The next day, a suspension of artificially cultured rice blast fungus spores was spray inoculated (twice) L.
The plants were 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 evaluated according to the following criteria, and the control value (%) was determined.

Morbidity Level Lesion area ratio 0 0.5 2 or less 1 8-5 2　　　　　　6～10 3 11-20 4 21-40 5 41 or more This test is the result of 8 pots in 1 section.

The results are shown in Table 2.

Table 2 [Note] 1. The compounding equipment was the same as described above.

2. Comparison A-1: (Compound described in Dutch Patent No. 7205298) 3. "-" in the drug damage column indicates that there is no drug damage.

Example 19 Test method for testing efficacy of water surface application against rice blast disease Paddy rice (variety: Asahi) was submerged in a white porcelain pot with a diameter of IZcm with 8 seeds, and at the early stage of tillering, a predetermined concentration of water was prepared in the same manner as in Test Example 1. Using a pipette, the chemical solution was poured onto the water surface so as not to directly contact the above-ground parts of the rice plants, but at the indicated amount. Four days later, a suspension of rice blast fungus spores was inoculated by spraying using a conventional method and kept in an inoculation chamber at a temperature of 28 to 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 18 to determine the control value (%).

As a result, Compound 1 of the present invention exhibited extremely superior effects compared to other compounds. For example, the compound of the present invention A6.
1, 2, this, 8.9.19-80.85.37-51 shows an active ingredient concentration Z U Om97 m"T:, the control value is close to 100%, and other The present compound of 800rn9. /m2, it exhibited an excellent control effect and control value of 100 cm.

Next, the present invention can be summarized as follows.

1) General formula: In the formula, RI represents a hydrogen atom, a halogen atom, or an acetyloxy group, Rz represents a hydrogen atom, and R1 and R2 are trapped together to form a carbonyl group together with the carbon atom to which they are bonded. Furthermore, R1 and R1 together with the carbon atoms to which they are bonded can represent a saturated hydrocarbon ring, and R3 is a cyano group, a thiocyanato group, an acetyl group, a lower alkoxycarbonyl x , is phenoxy group (the substituent may be the same or different, and represents at least one selected from the group consisting of... rogen; nitro; lower alkoxy), lower alkoxy group, halo lower alkenylthio group, benzylthio group, di-lower alkylphosphono group, acylamino group, substituted amine group (the substituent represents at least one group which may be the same or different selected from the group consisting of lower alkyl; phenyl; formyl; benzyl; methanesulfonyl) ), a phenyl group which may be substituted (the substituent is at least one of the same or different types selected from the group consisting of halogen; lower alkyl; lower alkoxy; nitro, and , R1 and R1 are not hydrogen atoms at the same time), lower alkylthio-lower alkyl group, 2,2-dichloro-8,8-dimethylcyclopropylmethoxy carbonyl group, or R4 and Rs represents a hydrogen atom, a lower alkyl group, a lower alkoxycarbonyl group, an optionally substituted phenyl group (the substituent is at least one of the same or different types selected from the group consisting of...rogen; lower alkyl); Also, B1. Bt and R3 may form a partially unsaturated hydrocarbon ring together with the carbon atom to which they are bonded, 2,Z-dichloro-13,B-dimethyl-
Cyclopropane-methanol derivative.

2) 2.2-Dichloro-8,8-dimethylcyclopropylmethanol is reacted with a compound represented by the general formula: where R1, R2, R'' and HaI are the same as above. General formula: In the formula, HI, Hz and R'' are the same as above.

A method for producing a 2,2-dichloro-8,8-dimethyl-cyclopropane-methanol derivative represented by:

8) General formula: In the formula, Hal is the same as above.

A compound represented by General formula: %formula%() In the formula, M and R3" are the same as in Nouki.

A general formula characterized by reacting with a compound represented by: In the formula, R3'' is the same as above.

A method for producing a 2,2-dichloro-8,8-dimethyl-cyclopropane-methanol derivative represented by:

Hs In the formula, R3'' is the same as above.

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

and a compound represented by the following general formula: In the formula, R1'' and Had' are the same as above.

A method for producing a 2,2-dichloro-8,8-dimethyl-cyclopropane-methanol derivative represented by:

5) 2.2-Dichloro-8,8-dimethyl-cyclopropylmethanol is reacted with a compound represented by the general formula: where RI, R2 and Rs are the same as above, A method for producing the 2,2-dichloro-8°8-dimethyl-cyclopropane-methanol derivative of the general formula (1).

6) An agricultural fungicide containing the 2,2-dichloro-8,8-dimethyl-cyclopropane-methanol derivative of the general formula (1) as an active ingredient.

7) The compound of general formula (1) may be used alone, or in the presence of a diluent (solvent and/or filler and/or carrier) and/or surfactant, and if necessary, a stabilizer, a fixing agent, and a co-proprietary agent. A crop disease control method that involves applying a mixture of

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

Patent applicant: 1 person other than Japan Special Pesticide Manufacturing Co., Ltd.

Claims (1)

[Claims] l) General formula: In the formula, RI represents a hydrogen atom, a halogen atom, or an acetyloxy group, R2 represents a hydrogen atom, and R1 and RI together represent R1 and R together with the carbon atoms to which they are bonded can represent a carbonyl group, and R1 and R together with the carbon atoms to which they are bonded can represent a saturated hydrocarbon ring, and R1 can represent a cyano group or a thiocyanato group. , acetyl group, lower alkoxycarbonyl group, substituted phenoxy group (the substituents may be the same or different selected from the group consisting of ), rogene, nitro, and lower alkoxy; at least one is shown), lower alkoxy group, halo lower alkenylthio group, benzylthio group, di-lower alkylphosphono group, acylamino group, substituted amino group (the 1f substituent is selected from the group consisting of lower alkyl; phenyl; formyl; benzyl; methanesulfonyl; , indicates at least one group which may be different types), a phenyl group which may be substituted (the substituent group is at least one group selected from the group consisting of halogen; lower alkyl; lower alkoxy; nitro, etc.), which may be the same or different types; , where R3 means a phenyl group, RI and R1 are not hydrogen atoms at the same time), lower alkylthio-lower alkyl group, 2. B-dichloro-8,8-dimethylcyclopropylmethoxycarbonyl group, or R4 and R6 are hydrogen atoms, lower alkyl groups, lower alkoxycarbonyl groups, optionally substituted phenyl groups (the substituents are...rogen; lower alkyl R1, R2 and R3, together with the carbon atoms to which they are bonded, may represent a partially unsaturated hydrocarbon ring. A 2,2-dichloro-8,8-dimethyl-cyclopropane-methanol ffj conductor can be represented by: 2) 2,2-dichloro-8,8-dimethylcyclopropylmethyl α-methoxyacetate according to claim 1, which is represented by the formula: 8) 2,2-dichloro-8,8-dimethylcyclopropylmethyl 2-methoxyphenylacetate according to claim 1, which is represented by the formula: General formula: In the formula, R1 represents a hydrogen atom, a halogen atom, or an acetyloxy group, R2 represents a hydrogen atom, and R1 and R1 together represent a carbonyl group together with the carbon atom to which they are bonded. Furthermore, %RI and R1 can be trapped together with the carbon atoms to which they are bonded to represent a saturated hydrocarbon ring, and Bs is a cyano group, a thiocyanato group, an acetyl group, a lower alkoxycarbonyl group. , substituted phenoxy group (the substituent may be the same or different, and represents at least one selected from the group consisting of halogen; nitro; lower alkoxy), lower alkoxy group, halo lower alkenylthio group,
benzylthio group, di-lower alkylphosphono group, acylamino group, substituted amino group (the fl substituent, at least one group selected from the group consisting of lower alkyl; phenyl; formyl; benzyl; methanesulfonyl, which may be the same or different); ), an optionally substituted phenyl group (the substituent is at least one of the same or different types selected from the group of halogen; lower alkyl; lower alkoxy; When meaning a phenyl group, R1 and R1 are not hydrogen atoms at the same time), lower alkylthio-lower alkyl group, z, 2-dichloro-8,8-dimethylcyclopropylmethoxycarbonyl R4 and RI are hydrogen atoms , a lower alkyl group, a lower alkoxycarbonyl group, a substituted phenyl group (the substituent is a halogen; the substituent is at least one selected from the group consisting of lower alkyl, which may be the same or different). , R1, R2 and R1 together with the carbon atom to which they are bonded can represent a partially unsaturated hydrocarbon ring, and 2,2-dichloro-8,8-dimethyl-cyclopropane- An agricultural fungicide containing methanol derivatives as all active ingredients.