JPH07179402A - Substituted benzene derivative, its production and pest-controlling agent containing the same - Google Patents

Abstract

PURPOSE:To obtain a new substituted benzene derivative having excellent pest- controlling activity, esp. useful as an agricultural/horticultural pest-controlling agent. CONSTITUTION:This substituted benzene derivative is represented by formula I [A is an aryloxy, an arylthio or ON=C(R<1>)R<2>(R<1> and R<2> are each an alkyl or an aryl); n is 1 or 2; B is a halogen, an alkyl, an aryl, an alkoxyl, a cycloalkyl, a cycloalkyloxy, a haloalkyl, a haloalkyloxy, cyano or nitro; m is 0-4; X is O or S; Y is an alkoxyl, an alkylthio, amino, an alkylamino or dialkylamino], e.g. o-(2-methylaminocarbonyloxybenzyl)-3- methylacetophenonoxime. The compound of formula I (where, Y is an alkoxyl, an alkylthio or a dialkylamino) can be obtained by reaction between a new compound of formula II and a compound of formula III (Hat denotes a halogen) or formula IV.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a substituted benzene derivative, a method for producing the same, a pest control agent containing the derivative as an active ingredient, and an intermediate thereof.

[0002]

2. Description of the Related Art Many carbamate compounds derived from physostigmine have been put to practical use as insecticides. These carbamate insecticides are nervous system disruptors having an acetylcholinesterase inhibitory action, but they are not used as fungicides. on the other hand,
The compounds of the present invention differ in chemical structure from these carbamate compounds.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel substituted benzene derivative useful as a pest control agent, particularly an agricultural and horticultural pest control agent, a process for producing the same, an intermediate and the like. .

[0004]

In the search for a wide range of compounds, the present inventors have found that a substituted benzene derivative having a certain skeleton such as carbamate, carbonate or thiocarbamate exhibits an excellent pest control effect. And completed the present invention. That is, the present invention has the general formula (I)

[0005]

[Chemical 8]

(In the formula, A is an optionally substituted aryloxy group, an optionally substituted arylthio group or -ON =
A C (R ¹ ) R ² group, R ¹ and R ² are independently an optionally substituted alkyl group or an optionally substituted aryl group, n is 1 or 2, B is a halogen atom, Alkyl group, aryl group, alkoxy group, cycloalkyl group,
A cycloalkyloxy group, a haloalkyl group, a haloalkyloxy group, a cyano group or a nitro group, and m is 0 to 4
Is an integer, X is an oxygen atom or a sulfur atom, and Y is an alkoxy group, an alkylthio group, an amino group, an alkylamino group or a dialkylamino group, a method for producing the same, and a method for producing the same. The present invention relates to a pest control agent and an intermediate thereof contained as components.

In the general formula (I), A, B or R ¹ and R ²
Examples of the aryl group or aryl moiety of phenyl, pyridyl, thienyl, furanyl, pyrrolyl, pyrazolyl,
It includes imidazolyl, indanyl, pyrazinyl, isoxazolyl, isothiazolyl and the like. Examples of the substituent of the optionally substituted aryloxy group or the optionally substituted arylthio group in the definition of A or the optionally substituted aryl group in the definition of R ¹ and R ² include a halogen atom and a halogen atom. Or a (C _1-4 ) alkyl group which may be substituted with C _1-4 alkoxy; a halogen atom or C _1-4
An aryl group which may be substituted with alkoxy; a nitro group;
Cyano group; C _1-4 alkoxy group which may be substituted with a halogen atom; C _1-4 alkylthio group; amino group; di C _1-4
An alkylamino group; a methylenedioxy group which may be substituted with a halogen atom and the like can be mentioned. Substitution number is 1 or 2
It may be more than one, and in the case of two or more, they may be the same or different.

The alkyl group which may be substituted in the definition of R ¹ and R ² may be a linear or branched alkyl group having 1 to 6 carbon atoms. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like can be mentioned.
Examples of the substituent include a halogen atom; a cyano group; a C _1-4 alkoxy group; a C _1-4 alkylthio group; The number of substitutions may be 1 or 2 or more,
In the case of two or more, they may be the same or different.

In the present specification, examples of the halogen atom described as the halogen atom, the haloalkyl group or the haloalkyloxy group or the halogen atom constituting the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Each alkyl moiety of the alkyl group, alkoxy group, haloalkyl group or haloalkyloxy group in the definition of B may be a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group in the definition of B or the cycloalkyl moiety of the cycloalkyloxy group may be one having 3 to 8 carbon atoms. Further, the substituents defined by B may be the same or different when m is 2 or more.

Each alkyl moiety of the alkoxy group, alkylthio group, alkylamino group or dialkylamino group in the definition of Y may be a linear or branched alkyl group having 1 to 8 carbon atoms. In the case of a dialkylamino group, the carbon numbers of the two alkyl moieties may be the same or different.

Among the compounds represented by the general formula (I), the following compounds are desirable.

(1) In the above general formula (I), the aryl moiety of the optionally substituted aryloxy group or the optionally substituted arylthio group, the optionally substituted aryl group of R ¹ and R ² , or The aryl group of B is phenyl, pyridyl, thienyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, indanyl, pyrazinyl, isoxazolyl or isothiazolyl, and the optionally substituted aryloxy group or optionally substituted arylthio group or R ¹ And when each substituent of the optionally substituted aryl group of R ² is 1 or 2 or more and 2 or more, the same or different halogen atom; halogen atom or C _1-4 alkoxy may substitute (C _1-4 ) alkyl group; a halogen atom or a C _1-4 aryl group which may be substituted by alkoxy; nitro group; cyano group Substituted by a halogen atom which may C _1-4 alkoxy groups; C _1-4 alkylthio group; an amino group; a di C _1-4 alkylamino group or methylenedioxy group optionally substituted a halogen atom (s), R ¹ or 2 in which the substituent of the optionally substituted alkyl group of R ² is 1 or 2
Above, in case of 2 or more, the same or different halogen atom
Cyano group: a substituted benzene derivative which is a C _1-4 alkoxy group or a C _1-4 alkylthio group.

(2) In the general formula (I), A is-
A substituted benzene derivative which is an ON = C (R ¹ ) R ² group (R ¹ and R ² are as described above), X is an oxygen atom, n is 1, and m is 0.

(3) The compound of the general formula (I) is O-
(2-Methylaminocarbonyloxybenzyl) -3-
A substituted benzene derivative which is methylacetophenone oxime, O- (2-methylaminocarbonyloxybenzyl) -3-methoxyacetophenone oxime or O- (2-methylaminocarbonyloxybenzyl) -3,4-dimethylacetophenone oxime.

The substituted benzene derivative represented by the general formula (I) can be produced by the following method (A) or (B).

[0016]

[Chemical 9]

(Wherein A, n, B, m and X are as described above, Y ¹ is an alkoxy group, an alkylthio group or a dialkylamino group, and Hal is a halogen atom).

The method (A) is usually carried out in the presence of a solvent and a base. As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; chloroform, carbon tetrachloride, methylene chloride, dichloroethane,
Halogenated aliphatic hydrocarbons such as trichloroethane;
Cyclic or acyclic aliphatic hydrocarbons such as n-hexane and cyclohexane; ethers such as diethyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Nitriles such as acetonitrile and propionitrile;
Dimethylformamide, N-methyl-2-pyrrolidone,
Examples include aprotic polar solvents such as dimethyl sulfoxide and sulfolane.

The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as anhydrous potassium carbonate and anhydrous calcium carbonate. Metal or alkaline earth metal carbonates; alkali metal hydrides such as sodium hydride; alkali metals such as sodium metal; and organic bases such as pyridine, triethylamine, and diisopropylethylamine. The reaction temperature is generally -20 ° C to the boiling point of each solvent (preferably 0 to 50 ° C), and the reaction time is generally 0.5 to 24 hours.

[0020]

[Chemical 10]

(Wherein A, n, B, m and X are as described above, M-OCN represents a cyanate salt, M is an alkali metal, and R-NCO represents an isocyanate ester, R is an alkyl group)

The method (B) is usually carried out in the presence of a solvent, and a catalyst may be optionally used. Examples of the solvent include the same as those used in the method (A). As catalyst, acids such as boron trifluoride, hydrochloric acid, aluminum chloride, alkyl tin chloride, alkyl tin acetate,
Triethylamine, pyridine, dimethylaniline, dimethylaminopyridine, 1,4-diazabicyclo (2.
2.2) Bases such as octane, N-methylpiperidine, sodium acetate and the like can be mentioned. Reaction temperature is usually -20 ° C
~ Solvent boiling point temperature, reaction time is 0.5 to 24 hours.

The compound represented by the general formula (II) can be obtained, for example, by the following reactions (C) to (E). (When n = 1 and X = oxygen atom)

[0024]

[Chemical 11]

(Wherein B, m, R ¹ and R ² are as described above, Ac is acetyl, and Ar is an optionally substituted aryl).

In the method (C), the two OH groups of the substituted or unsubstituted saligenin are acetylated, and then the compound of the formula (V-
This can be achieved by reacting the compound of 1), (V-2) or (V-3) with a base such as sodium hydride or butyllithium to form an alkali metal salt, and reacting in the presence of a solvent.

As the solvent, the same solvents as those used in the above method (A) can be mentioned. Reaction temperature is usually -2
The temperature is 0 ° C to the boiling point of the solvent, and the reaction time is 0.5 to 24 hours. (When n = 1 and X = sulfur atom)

[0028]

[Chemical 12]

(In the formula, A, B and m are as described above, and R is an alkyl group.)

The compound of the above formula (II-4) can be obtained by a 5-step reaction. In the first step and the second step, a substituted or unsubstituted thiosalicylic acid is reacted with a protecting group. That is, in the first step, the carboxyl group of thiosalicylic acid is esterified with an alcohol such as methanol, and in the second step, the SH group of the esterified product is sulfided with dihydropyran. Each reaction may be carried out under the conditions usually used for esterification or sulfidation. The third step is a reduction reaction of the carbonyl group of this sulfide. A reducing agent such as lithium aluminum hydride is used for the reduction reaction. The reaction conditions may be those normally used. The fourth step is a condensation reaction of the substituent A of this reduced product. This reaction is achieved by the following method.

[0031]

[Chemical 13]

(In the formula, B, m, R ¹ and R ² are as described above, and Ar is an optionally substituted aryl group.)

The above reaction is carried out in the presence of a solvent and an alkyl and aryl phosphine such as tributylphosphine and an azocarboxylic acid ester such as diethyl azodicarboxylate. As the solvent, the same ones as those used in the above method (A) can be mentioned. The reaction temperature is usually -78 ° C to + 70 ° C, and the reaction time is 0.5 to 24 hours.

The fifth step is the elimination reaction of the tetrahydropyranyl group. Iodine is used in this reaction. The reaction proceeds at room temperature, and after passing through the dimer of the compound of formula (II-4) formed by a disulfide bond, the compound of formula (II-4) is obtained with a reducing agent such as lithium aluminum hydride. Alternatively, the compound of formula (II-4) can be obtained by removing the tetrahydropyranyl group as silver mercapto using silver nitrate or the like and then hydrolyzing it with a weak acid. (When n = 2 and X = oxygen atom)

[0035]

[Chemical 14]

(Wherein A, B and m are as described above, and R is an alkyl group) The compound of the above formula (II-5) can be obtained by a five-step reaction. In the first step and the second step, a substituted or unsubstituted O-hydroxyphenylacetic acid is reacted with a protecting group. That is, in the first step, as in the case of thiosalicylic acid described above, the carboxyl group is esterified, and in the second step, the OH group of this esterified product is etherified with benzyl bromide. The reaction conditions for this etherification reaction may be those normally used. The third step is a reduction reaction of the carbonyl group of this etherified product, and the same method as the third step of the above-mentioned method (D) is used. The fourth step is a condensation reaction of the substituent A. This reaction is achieved by the following method.

[0037]

[Chemical 15]

(In the formula, B, m, R ¹ and R ² are as described above, and Ar is an optionally substituted aryl group.)

In the above reaction, the compound of the formula (IV-3) is once reacted with p-toluenesulfonyl chloride or methanesulfonyl chloride serving as a leaving group in the presence of a base such as triethylamine and a solvent to obtain the compound of the formula (IV -3) Compound tosylate or mesylate is produced. Then, the formula (V-
1), a compound obtained by reacting the compound of (V-2) or (V-3) with sodium hydride, butyllithium, or the like,
The compound of formula (IV-3) is reacted with tosylate or mesylate in the presence of a solvent. As the solvent used in this reaction, the same solvent as in the above method (A) can be mentioned. The reaction temperature is generally -20 ° C to the boiling point of the solvent, and the reaction time is 0.5 to 24 hours.

The fifth step is a benzyl group elimination reaction. Palladium-carbon, platinum oxide or the like is used as a catalyst in this reaction, and the compound of formula (II-5) can be easily obtained by stirring in a hydrogen atmosphere.

The compound of the present invention represented by the general formula (I) is useful as an active ingredient of a pest controlling agent. Examples of agricultural and horticultural fungicides include rice blast, rice blight, rice sesame leaf blight, cucumber anthracnose, cucumber powdery mildew, cucumber downy mildew, tomato blight, tomato ring spot, citrus black spot disease. , Citrus green mold, apple and pear scab, apple leaf spot, grape downy mildew, various types of gray mold, sclerotium, rust and other diseases, and Fusarium bacterium, Pythium bacterium, Rhizoctonia cinerea, verti It shows an excellent control effect against soil diseases caused by plant pathogenic fungi such as Syrium and Plasmodiophora. Especially rice blast disease, various powdery mildew diseases, various gray mold diseases, sclerotial diseases,
It shows an excellent control effect against downy mildew of cucumber and grape, and plague of tomato and potato. Since the compound of the present invention has a long residual effect and an excellent preventive effect as well as an excellent therapeutic effect, it is possible to control diseases by treatment after infection. Further, disease control by soil treatment is also possible. The compound of the present invention is effective not only against susceptible bacteria but also against various resistant bacteria (benomyl resistant powdery mildew, metalaxyl resistant downy mildew, benomyl and / or dicarboximide compound resistant gray mold).

The compound of the present invention also has an insecticidal activity, an acaricidal activity and a nematicidal activity, and is effective against various pests which pose a problem of control.

When the compound of the present invention is used, it may be formulated into various forms such as emulsions, powders, wettable powders, liquids, granules and suspensions together with auxiliary agents, as in the case of conventional pesticide formulations. You can In the actual use of these preparations, they can be used as they are or diluted with a diluent such as water to a predetermined concentration and used. Examples of the auxiliary agent here include a carrier, an emulsifying agent, a suspending agent, a dispersing agent, a spreading agent,
Examples include penetrants, wetting agents, thickeners, stabilizers, and the like, which may be appropriately added as necessary.

The carrier is divided into a solid carrier and a liquid carrier. As the solid carrier, starch, sugar, cellulose powder, cyclodextrin, activated carbon, soybean powder, wheat flour, chaff powder, wood flour, fish meal, milk powder and other animal and plant powders; talc, kaolin, bentonite, organic bentonite, calcium carbonate, Calcium sulfate, sodium bicarbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, silica, mineral powders such as sulfur powder, and the like, and liquid carriers include water; soybean oil, cottonseed oil, corn oil, and the like. Animal and vegetable oils; alcohols such as ethyl alcohol and ethylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran; aliphatic hydrocarbons such as kerosene, kerosene and liquid paraffin; xylene, trimethylbenzene, tetramethyl Benzene, sikh Aromatic hydrocarbons such as hexane and solvent naphtha; halogenated hydrocarbons such as chloroform and chlorobenzene; acid amides such as dimethylformamide; esters such as ethyl acetate and glycerin ester of fatty acids; nitriles such as acetonitrile; Sulfur-containing compounds such as dimethylsulfoxide; N-methylpyrrolidone and the like.

A suitable compounding weight ratio of the compound of the present invention to the auxiliary is generally 0.05: 99.95 to 90:10, preferably 0.2: 99.8 to 80:20.

The use concentration / use amount of the compound of the present invention varies depending on the target crop, use method, formulation form, application amount and the like and cannot be specified unconditionally, but in the case of foliar treatment, it is usually 0.1 to 0.1 per active ingredient. It is 10,000 ppm, preferably 1 to 2,000 ppm. In the case of soil treatment,
Usually 10 to 100,000 g / ha, preferably 200
~ 20,000 g / ha.

Formulation examples of pest control agents containing the compound of the present invention as an active ingredient are shown below.

Formulation Example 1 (1) Compound No. 1 ... 50 parts by weight (2) Kaolin ... 40 parts by weight (3) Sodium lignin sulfonate ... 7 parts by weight (4) Polyoxyethylene alkylphenyl ether sulphate ... 3 parts by weight The above ingredients are uniformly mixed to obtain a wettable powder. Is obtained.

Formulation Example 2 (1) Compound No. 17: 20 parts by weight (2) White carbon: 10 parts by weight (3) Kaolin: 62 parts by weight (4) Sodium lignin sulfonate: 4 parts by weight (5) Polyoxyethylene alkylaryl ether:
A wettable powder is obtained by uniformly mixing 4 parts by weight or more.

Formulation Example 3 (1) Compound No. 21: 10 parts by weight (2) Diatomaceous earth: 15 parts by weight (3) Calcium carbonate powder: 69 parts by weight (4) Dialkylsulfosuccinate: 1 part by weight (5) Polyoxyethylene alkylphenyl ether sulfate: 3 parts by weight (6) ) Β-Naphthalenesulfonic acid soda formalin condensate: 2 parts by weight The above components are uniformly mixed to obtain a wettable powder.

Formulation Example 4 (1) Compound No. 23 ... 6 parts by weight (2) Diatomaceous earth ... 88 parts by weight (3) Dialkylsulfosuccinate ... 2 parts by weight (4) Polyoxyethylene alkylphenyl ether sulphate ... 4 parts by weight The above ingredients are uniformly mixed to obtain a wettable powder. Is obtained.

Formulation Example 5 (1) Compound No. 6 ... 0.5 parts by weight (2) Talc ... 99.0 parts by weight (3) Lower alcohol phosphate ester ... 0.5 parts by weight The above ingredients are uniformly mixed to obtain a dust.

Formulation Example 6 (1) Compound No. 7: 0.2 parts by weight (2) Calcium carbonate powder: 98.8 parts by weight (3) Lower alcohol phosphate ester: 1 part by weight The above ingredients are uniformly mixed to obtain a dust.

Formulation Example 7 (1) Compound No. 2 ... 20 parts by weight (2) Xylene ... 60 parts by weight (3) Polyoxyethylene alkylaryl ether ...
20 parts by weight or more of the respective components are mixed and dissolved to obtain an emulsion.

Formulation Example 8 (1) Compound No. 3 ... 1 part by weight (2) Bentonite ... 33 parts by weight (3) Kaolin ... 61 parts by weight (4) Sodium lignin sulfonate ... 5 parts by weight Add an appropriate amount of water required for granulation to the above components, and mix and granulate. Then, granules are obtained.

Formulation Example 9 (1) Compound No. 4 ... 10 parts by weight (2) Saturated isoparaffin hydrocarbon (fractions 210-2
65 ° C.) 79 parts by weight (3) Mixture of polyoxyethylene phenylphenol derivative and polyoxyethylene sorbitan alkylate ...
10 parts by weight (4) Organic bentonite ... 1 part by weight The above components are mixed and finely pulverized to obtain a suspension agent.

Formulation Example 10 (1) Compound No. 5 ... 40 parts by weight (2) Oxyethylated polyarylphenol phosphate-triethanolamine ... 2 parts by weight (3) Silicone ... 0.2 parts by weight (4) Zansan gum ... 0.1 parts by weight (5) Ethylene glycol 5 parts by weight (6) Water 52.7 parts by weight The above components are uniformly mixed and ground to give an aqueous suspension.

Formulation Example 11 (1) Compound No. 8 ... 75 parts by weight (2) Sodium polycarboxylate ... 13.5 parts by weight (3) Anhydrous sodium sulfate ... 10 parts by weight (4) Dextrin ... 0.5 parts by weight (5) Sodium alkyl sulfonate ... 1 parts by weight or more Put each of the ingredients in a high-speed mixing granulator, and further 20
% Water is added, and the mixture is granulated and dried to obtain a wettable granule.

If necessary, the compound of the present invention is mixed with other pesticides such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides and plant growth regulators. , Can be used in combination, and in this case, a more excellent effect may be exhibited.

Examples of the active ingredient compound of the above insecticide, acaricide or nematicide include, for example, O- (4-bromo-2).
-Chlorophenyl) O-ethyl S-propyl phosphorothioate (generic name: profenophos), O- (2,2-
Dichlorovinyl) O, O-dimethyl phosphate ((generic name: dichlorvos), O-ethyl O- [3-
Methyl-4- (methylthio) phenyl] N-isopropyl phosphoramidate (generic name: fenamiphos),
O, O-dimethyl O- (4-nitro-m-tolyl) phosphorothioate (generic name: fenitrothion), O-
Ethyl O- (4-nitrophenyl) phenylphosphonothioate (generic name: EPN), O, O-diethyl O
-(2-isopropyl-6-methylpyrimidin-4-yl) phosphorothioate (generic name: diazinon),
O, O-dimethyl O- (3,5,6-trichloro-2
-Pyridyl) phosphorothioate (generic name: chlorpyrifosmethyl), O, S-dimethyl N-acetylphosphoramidothioate (generic name: acephate), O-
(2,4-dichlorophenyl) O-ethyl S-propyl phosphorodithioate (generic name: prothiophos),
An organic phosphate ester compound such as (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate (a compound described in US Pat. No. 4,590,182);

1-naphthyl N-methylcarbamate (generic name: carbaryl), 2-isopropoxyphenyl N-methylcarbamate (generic name: propoxur),
2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyl oxime (generic name: aldicarb), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate (generic name: carbofuran), Dimethyl N, N '-[thiobis {(methylimino) carbonyloxy}] bisethaneimidothioate (generic name: thiodicarb), S-methyl N-
(Methylcarbamoyloxy) thioacetimidate (generic name: Mesomel), N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide (generic name: oxamyl), 2- (ethylthiomethyl) phenyl N-methyl carbamate (generic name: etiophencarb), 2-dimethylamino-5,6-dimethylpyrimidin-4-yl N, N-dimethylcarbamate (generic name: pyrimicarb), 2-sec-butylphenyl N-methylcarbamate ( Generic name: carbamate compounds such as Fenobucarb);

S, S'-2-dimethylaminotrimethylene bis (thiocarbamate) (generic name: cartap),
Nereistoxin derivatives such as N, N-dimethyl-1,2,3-trithian-5-ylamine (generic name: thiocyclam); 2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol (Generic name: dicofol), 4-chlorophenyl-2,4,5-trichlorophenyl sulfone (generic name: tetradiphone) such as an organic chlorine compound; bis [tris (2-methyl-2-phenylpropyl) tin] oxide An organometallic compound such as (generic name: fenbutatin oxide);

(RS) -α-cyano-3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate (generic name: fenvalerate), 3-phenoxybenzyl (1RS) -cis, Transformer-3-
(2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (generic name: permethrin),
(RS) -α-cyano-3-phenoxybenzyl (1R
S) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (generic name: cypermethrin), (S) -α-cyano-
3-phenoxybenzyl (1R) -cis-3- (2,2
-Dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (generic name: deltamethrin), (R
S) -α-Cyano-3-phenoxybenzyl (1RS)
-Cis, trans-3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate (generic name: cyhalothrin), 4-
Methyl-2,3,5,6-tetrafluorobenzyl-3
-(2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (generic name: tefluthrin), 2- (4-ethoxyphenyl) -2-methylpropyl 3 -Pyrethroid compounds such as phenoxybenzyl ether (generic name: Etofenprox);

1- (4-chlorophenyl) -3- (2,
6-difluorobenzoyl) urea (generic name: diflubenzuron), 1- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3- (2,6- Difluorobenzoyl) urea (generic name: chlorfluazuron), 1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6
-Difluorobenzoyl) urea (generic name: teflubenzuron) benzoylurea compound; isopropyl (2E, 4E) -11-methoxy-3,7,11
-Trimethyl-2,4-dotecadienoate (generic name:
Juvenile hormone-like compounds such as methoprene);

Pyridazinone compounds such as 2-t-butyl-5- (4-t-butylbenzylthio) -4-chloro-3 (2H) -pyridazinone (generic name: pyridaben); t-butyl 4- [ (1,3-Dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl] benzoate (generic name: fenpyroximate)
A pyrazole compound such as;

1- (6-chloro-3-pyridylmethyl)
-N-nitro-imidazolidine-2-ylideneamine (generic name: imidacloprid), 1- [N- (6-chloro-3-pyridylmethyl) -N-ethylamino] -1-
Methylamino-2-nitroethylene (European publication N
o. 302389), 2-methylamino-2- [N-methyl-N- (6-chloro-3-pyridylmethyl) amino] -1-nitroethylene (European publication No. 30).
2389), 1- (6-chloro-3-pyridylmethyl)
Amino-1-dimethylamino-2-nitroethylene (European publication No. 302389), 1- (6-chloro-3-pyridylmethyl) -2- (1-nitro-2-allylthioethylidene) imidazolidine (European publication) N
o. 437784), 1- (6-chloro-3-pyridylmethyl) -2- (1-nitro-2-ethylthioethylidene) imidazolidine (European Publication No. 43778).
4), 1- (6-chloro-3-pyridylmethyl) -2-
(1-Nitro-2-β-methylallylthioethylidene)
Imidazolidine (European publication No. 43778
4), 1- (6-chloro-3-pyridylmethyl) -3-
Methyl-2-nitroguanidine (European publication No.
383091), 1- (6-chloro-3-pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (European Publication No. 383091), 3- (6-chloro-).
3-pyridylmethyl) -2-nitromethylene-thiazolidine (European publication No. 192060), 1- (6
-Chloro-3-pyridylmethyl) -2- (nitromethylene) -imidazolidine (European publication No. 1638)
55), 6- (6-chloro-3-pyridylmethylamino) -1,3-dimethyl-5-nitro-1,2,3,4
-Tetrahydropyrimidine (European publication No. 36
6085), 1- (6-chloro-3-pyridylmethyl)
-5-nitro-3-methyl-6-methylamino-1,
Nitro compounds such as 2,3,4-tetrahydropyrimidine (European publication No. 366085);

Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazine compounds,
In addition, as other compounds, 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,5
6-Tetrahydro-2H-1,3,5-thiadiazine-
4-one (generic name: bubrofedin), trans- (4
-Chlorophenyl) -N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide (generic name: hexithiazox), N-methylbis (2,4-
Xylyliminomethyl) amine (generic name: amitraz), N ′-(4-chloro-o-tolyl) -N, N-dimethylformamidine (generic name: chlordimeform),
(4-Ethoxyphenyl)-[3- (4-fluoro-3
-Phenoxyphenyl) propyl] (dimethyl) silane (generic name: silafluophene); and the like. Further, they can be mixed and used together with microbial agents such as BT agents and insect pathogenic virus agents, antibiotics such as avermectin and milbemycin.

Examples of the active ingredient compound of the bactericide include 2-anilino-4-methyl-6- (1-propynyl) pyrimidine (generic name: mepanipyrim), 4,6-dimethyl-N-phenyl-2- Pyrimidinamine (generic name:
Pyrimidinamine-based compounds such as pyrimethanil);

1- (4-chlorophenoxy) -3,3-
Dimethyl-1- (1H-1,2,4-triazole-1
-Yl) butanone (generic name: triadimefon), 1-
(Biphenyl-4-yloxy) -3,3-dimethyl-
1- (1H, 1,2,4-triazol-1-yl) butan-2-ol (generic name: bitertanol), 1-
[N- (4-chloro-2-trifluoromethylphenyl) -2-propoxyacetimidoyl] imidazole (generic name: triflumizole), 1- [2- (2,4-
Dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole (generic name: etaconazole), 1- [2- (2,4-
Dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole (generic name: propiconazole), 1- [2- (2,2
4-dichlorophenyl) pentyl] -1H-1,2,4
-Triazole (generic name: penconazole), bis (4
-Fluorophenyl) (methyl) (1H-1,2,4-
Triazol-1-ylmethyl) silane (generic name: flusilazole), 2- (4-chlorophenyl) -2- (1
H-1,2,4-triazol-1-ylmethyl) hexanenitrile (generic name: microbutanyl), (2R
S, 3RS) -2- (4-chlorophenyl) -3-cyclopropyl-1- (1H-1,2,4-triazole-
1-yl) butan-2-ol (generic name: cyproconazole), (RS) -1- (4-chlorophenyl) -4,
4-Dimethyl-3- (1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol (generic name: turbuconazole), (RS) -2- (2,4-dichlorophenyl) -1 -(1H-1,2,4-triazole-
1-yl) hexan-2-ol (generic name: hexaconazole), (2RS, 5RS) -5- (2,4-dichlorophenyl) tetrahydro-5- (1H-1,2,4-
Triazol-1-ylmethyl) -2-furyl 2,2
2-trifluoroethyl ether (generic name: farconazole cis), N-propyl-N- [2- (2,4,6)
-Trichlorophenoxy) ethyl] imidazole-1-
Azole compounds such as carboxamide (generic name: prochloraz);

6-methyl-1,3-dithiolo [4,5-
b] A quinoxaline compound such as quinoxalin-2-one (general name: quinomethionate); a polymer of manganese ethylenebis (dithiocarbamate) (general name: manneb), zinc ethylenebis (dithiocarbamate)
Polymer (generic name: Zineb), complex compound of zinc (zinc) and Manganese ethylenebis (dithiocarbamate) (manneb) (generic name: Manzeb), dizincbis (dimethyldithiocarbamate) ethylenebis (dithiocarbamate) (general) Name: polycarbamate), dithiocarbamate compound such as zinc propylene bis (dithiocarbamate) polymer (general name: probineb);

Organochlorine compounds such as 4,5,6,7-tetrachlorophthalide (generic name: phthalide), tetrachloroisophthalonitrile (generic name: chlorothalonil), pentachloronitrobenzene (generic name: quintozene) Methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate (generic name: benomyl), dimethyl 4,4 ′-(o-phenylene) bis (3
Thioallophanate) (generic name: thiophanate methyl), methylbenzimidazol-2-ylcarbamate (generic name: carbendazim) such as benzimidazole compounds;

3-chloro-N- (3-chloro-2,6-
Dinitro-4-α, α, α-trifluorotolyl) -5
A pyridinamine-based compound such as trifluoromethyl-2-pyridinamine (generic name: fluazinam); 1- (2
A cyanoacetamide compound such as -cyano-2-methoxyiminoacetyl) -3-ethylurea (generic name: cimoxanil);

Methyl N- (2-methoxyacetyl)-
N- (2,6-xylyl) -DL-alaninate (generic name: metalaxyl), 2-methoxy-N- (2-oxo-1,3-oxazolidin-3-yl) aceto-2 ',
6'-xylidide (generic name: oxadixyl), (±)
-Α-2-chloro-N- (2,6-xylylacetamide) -γ-butyrolactone (generic name: offlace), methyl N-phenylacetyl-N- (2,6-xylyl) -DL-alaninate ( (Generic name: benalaxyl),
Methyl N- (2-furoyl) -N- (2,6-xylyl) -DL-alaninate (generic name: furaraxyl),
(±) -α- [N- (3-chlorophenyl) cyclopropanecarboxamide] -γ-butyrolactone (generic name:
Phenylamide compounds such as cyprofuran);

N-dichlorofluoromethylthio-N ',
N'-dimethyl-N-phenylsulfamide (generic name:
Sulfenic acid compounds such as diclofluanid); cupric hydroxide (generic name: cupric hydroxide), copper 8-
Copper-based compounds such as quinolinoleate (generic name: organic copper);

Isoxazole compounds such as 5-methylisoxazol-3-ol (generic name: hydroxyisoxazole); aluminum tris (ethylphosphonate) (generic name: fosetylaluminum), O-2,
6-dichloro-p-tolyl-O, O-dimethylphosphorothioate (generic name: tolclofos-methyl), S-benzyl O, O-diisopropylphosphorothioate,
Organophosphorus compounds such as O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate;

N- (trichloromethylthio) cyclohex-4-ene-1,2-dicarboximide (general name: captan), N- (1,1,2,2-tetrachloroethylthio) cyclohex-4-ene-1 , 2-dicarboximide (generic name: captafol), N- (trichloromethylthio) phthalimide (generic name: folpet), N-halogenothioalkyl compounds;

N- (3,5-dichlorophenyl) -1,
2-Dimethylcyclopropane-1,2-dicarboximide (generic name: procymidone), 3- (3,5-dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide (generic name: Iprodione), (RS) -3- (3,5-dichlorophenyl)-
5-methyl-5-vinyl-1,3-oxazolidine-
Dicarboximide compounds such as 2,4-dione (generic name: vinclozolin);

Benzanilide compounds such as α, α, α-trifluoro-3'-isopropoxy-o-toluanilide (generic name: flutolanil), 3'-isopropoxy-o-toluanilide (generic name: mepronil);

2- (1,3-dimethylpyrazole-4-
Ilcarbonylamino) -4-methyl-3-pentenenitrile (compound described in British Patent No. 2190375), α- (nicotinylamino)-(3-fluorophenyl) acetonitrile (JP-A 63-135364).
Benzamide-based compounds such as compounds described in 1.);

Piperazine compounds such as N, N '-[piperazine-1,4-diylbis [(trichloromethyl) methylene]] diformamide (generic name: triphorine); 2', 4'-dichloro-2- ( Pyridine compounds such as 3-pyridyl) acetophenone O-methyloxime (generic name: pyriphenox);

(±) -2,4'-Dichloro-α- (pyrimidin-5-yl) benzhydryl alcohol (generic name: phenalimol), (±) -2,4'-difluoro-
Carbinol compounds such as α- (1H-1,2,4-triazol-1-ylmethyl) benzhydryl alcohol (generic name: flutriafol);

A piperidine compound such as (RS) -1- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine (generic name: phenpropidin);

(±) -cis-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6
-Morpholine compounds such as dimethylmorpholine (generic name: fenpropimorph); such as triphenyltin hydroxide (generic name: fentin hydroxide), triphenyltin acetate (generic name: fentine acetate) Organic tin compounds;

Urea compounds such as 1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea (generic name: Pensiculone);

Cynamic acid compounds such as (E, Z) 4- [3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acryloyl] morpholin (generic name: dimethomorph);

Phenylcarbamate compounds such as isopropyl 3,4-diethoxycarbanilate (generic name: dietofencarb);

3-Cyano-4- (2,2-difluoro-
Cyanopyrrole systems such as 1,3-benzodioxol-4-yl) pyrrole (generic name: fludioxonil), 3- (2 ', 3'-dichlorophenyl) -4-cyano-pyrrole (generic name: fenpiclonyl) Compound;

Anthraquinone compounds; crotonic acid compounds; antibiotics and the like. Further, a suitable mixing weight ratio of the partner agent to be mixed with and used in combination with the substituted benzene derivative represented by the general formula (I) is generally 1: 300 to 3.
00: 1, preferably 1: 100 to 100: 1.
In particular, when the substituted benzene derivative is mixed with a pyrimidinamine-based compound, an organic chlorine-based compound, a pyridinamine-based compound or a cyanopyrrole-based compound, an excellent effect for controlling various Botrytis cinerea can be expected.

[0089]

EXAMPLES Next, specific synthesis examples of the compound of the present invention will be described.

Synthesis Example 1 O- (2-methylaminocarbo
Nyloxybenzyl) -3-methylacetophenone
Synthesis of oxime (Compound No. 17) (1) Saligenin 12.4 g (0.1 mol) and acetic anhydride 30.6 g (0.3 mol) were added to pyridine 47.5 g.
(0.6 mol) and dissolved at room temperature overnight. The volatile substances were distilled off under reduced pressure, and the residue was purified by silica gel column chromatography with hexane-ethyl acetate to obtain bisacetylsaligenin almost quantitatively.

(2) 3'-Methylacetophenone 5.3
7 g (40 mmol), hydroxylamine hydrochloride 3.
06 g (44 mmol) and triethylamine 4.45
g (44 mmol) was dissolved in 40 ml of methanol, and the mixture was stirred at room temperature overnight. Methanol was distilled off under reduced pressure, 100 ml of water was added to the residue, and the resulting crystal product was collected by filtration and thoroughly washed with water. A yield of 5.60 g (94%) gave 3'-methylacetophenone oxime. This was almost pure by NMR analysis.

(3) 1.35 g of 60% sodium hydride
(33.6 mmol) was suspended in 30 ml of tetrahydrofuran and cooled in an ice bath. 3′-obtained in (2) above
Methyl acetophenone oxime 4.77g (32mm
ol) dissolved in 10 ml of tetrahydrofuran was added dropwise under ice cooling, and the mixture was stirred for 30 minutes. Then, 3.33 g of bisacetylsaligenin obtained in (1) above
A solution of (16 mmol) in 10 ml of tetrahydrofuran was added, and the mixture was stirred for 30 minutes under cooling. Then, the cooling bath was removed, and the mixture was stirred at room temperature overnight. The reaction mixture was mixed with 3N hydrochloric acid 10
The mixture was added to 0 ml, extracted with methylene chloride, washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in 80 ml of methanol, a small amount of lithium hydroxide was added, and the mixture was stirred at room temperature overnight. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using a methylene chloride-hexane mixed solvent to obtain O- (2-hydroxybenzyl) -3-methylacetophenone oxime 1.81 g (45%). It was

NMR (CDCl ₃ ) δ 2.24 (s,
3H), 2.38 (s, 3H), 5.15 (s, 2)
H), 6.7 to 7.5 (m, 8H), 9.02 (br
s, 1H)

(4) O- (2-hydroxybenzyl)-
3-methylacetophenone oxime 0.91 g (3.
56 mmol) was dissolved in 30 ml of methylene chloride and 0.22 g (3.74 mmo) of methyl isocyanate under ice cooling.
l), followed by 2 drops of triethylamine. After stirring overnight at room temperature, the solvent was evaporated and the residue was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 0.92 g (83%) of the desired product (Compound No. 17). m. p. 77-79 ° C,

NMR (CDCl ₃ ) δ 2.22 (s,
3H), 2.34 (s, 3H), 2.78 (d, 3H,
J = 5 Hz), 5.22 (s, 2H), 6.9 to 7.7.
(M, 8H)

Synthesis Example 2 O- (2-methoxycarbonyl)
Oxybenzyl) -3-methylacetophenone oxy
Synthesis of Compound (Compound No. 13) O- (2-hydroxybenzyl) -3-methylacetophenone oxime 0.9 obtained in Synthesis Example 1 (3) above.
1 g (3.56 mmol) was dissolved in 30 ml of acetonitrile, and 0.40 g (4.28 g) of methyl chlorocarbonate under ice cooling.
mmol), 0.43 g of triethylamine (4.28 m)
mol) were added sequentially. After stirring overnight at room temperature, the solvent was distilled off, the residue was dissolved in methylene chloride, washed with water and then dried over sodium sulfate, and the solvent was distilled off under reduced pressure. Silica gel column chromatography (hexane / ethyl acetate)
1.09 g of the desired product (Compound No. 13) after purification by
(98%) obtained.

NMR (CDCl ₃ ) δ 2.21 (s,
3H), 2.35 (s, 3H), 3.84 (s, 3)
H), 5.26 (s, 2H), 7.0 to 7.6 (m, 8)
H)

Synthesis Example 3 2- (2,4-dimethylphenyi)
) Oxymethyl-S-methylaminocarbonylthiof
Synthesis of enol (Compound No. 8) (1) 10 ml of acetyl chloride was added dropwise to 100 ml of anhydrous methanol under ice cooling, followed by stirring for 30 minutes. To this product, 15.4 g (0.1 mol) of thiosalicylic acid was gradually added and then stirred overnight at room temperature. The solvent was distilled off under reduced pressure,
The residue was purified by short silica gel column chromatography (hexane: ethyl acetate = 2: 1).

(2) The thiosalicylic acid methyl ester obtained in the above (1) and dihydropyran (8.41 g, 0.
1 mol) was dissolved in anhydrous ether, and boron trifluoride ether complex (47% solution, 30.2 g (0.1 m) under ice cooling.
ol)) was added and the mixture was stirred at the same temperature for 30 minutes. The mixture was further reacted at room temperature for 1 hour, and cooled again with ice. 20% to this
60 ml of an aqueous solution of sodium hydroxide and then 60 ml of water were added. The ether layer was separated, the aqueous layer was extracted with ether, the ether layers were combined, washed with water, and dried over sodium sulfate. The solvent was distilled off under reduced pressure.

(3) The methyl S-tetrahydropyranylthiosalicylate obtained in (2) above was treated with anhydrous ether 50
The solution dissolved in ml was cooled with ice and lithium aluminum hydride (5.7 g, 0.15 mol) in anhydrous ether 15 was added.
In addition to the 0 ml suspension, lithium aluminum hydride (1.9 g, 0.05 mol) was further added, and the mixture was stirred at the same temperature for 10 minutes. Then, the mixture was reacted overnight at room temperature. The mixture was successively cooled under ice-cooling with water (8 ml), 15% sodium hydroxide (8 ml) and water (24 ml).
After slowly adding ml to deactivate the excess reducing agent, sodium sulfate was added and the mixture was filtered through Celite. After distilling off the solvent, silica gel column chromatography (hexane:
The product was purified with ethyl acetate = 3: 1) to obtain 17.5 g of 2-tetrahydropyranylthiobenzyl alcohol (total yield of 3 steps: 78%).

(4) 6.73 g (30%) of 2-tetrahydropyranylthiobenzyl alcohol obtained in the above (3)
3.85 g of 2,4-xylenol (31.
(5 mmol) dried tetrahydrofuran 100 ml
And dissolve in ice-cold water, and then sequentially under ice-cooling, tributylphosphine 6.3
A solution of 7 g (31.5 mmol) in 25 ml of tetrahydrofuran, 5.49 g of diethyl azodicarboxylate (31.
A solution of 5 mmol) in 25 ml of tetrahydrofuran was added, and the mixture was stirred in an ice bath for 30 minutes. Then, the mixture was stirred overnight at room temperature, the reaction mixture was concentrated under reduced pressure to a volume of about 50 ml, and diluted with 200 ml of ethyl acetate. It was washed twice with water, dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was directly purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1-10: 1) to give 2- ( 2,4-Dimethylphenyl) oxymethyl-S-
8.12 g of tetrahydropyranyl thiophenol (8
2%) was obtained.

NMR (CDCl ₃ ) δ 2.25 (s,
6H), 1.4 to 2.3 (m, 6H), 3.3 to 3.8.
(M, 2H), 5.13 (t, 1H, J = 4Hz),
5.17 (s, 2H), 6.7 to 7.8 (m, 7H)

(5) 2- (2,4) obtained in (4) above
-Dimethylphenyl) oxymethyl-S-tetrahydropyranylthiophenol 8.12 g (24.7 mmo)
1 ml of a methanol solution of 1) was added to 15.7 g of iodine.
To 200 ml of a methanol solution of (61.8 mmol) was slowly added dropwise at room temperature over about 70 minutes. Then, after stirring for 80 minutes, the mixture was cooled with ice, and 0.5 M sodium thiosulfate was slowly added dropwise until the red color of iodine disappeared. About 2 drops
It was 00 ml. Further, 100 ml of water was added, and the resulting crystals were collected by filtration and washed with water. After dissolving in ether, it was dried over sodium sulfate, then the ether was distilled off under reduced pressure,
5.71 g of crystals were obtained.

The solution obtained by dissolving 5.71 g of the crystals obtained above in 150 ml of anhydrous ether was used as a solution of 0.23 g (5.87 mmol) of lithium aluminum hydride in ether 10.
The mixture was slowly added to the 0 ml suspension under ice cooling. Further, lithium aluminum hydride 0.23 g (5.87 mmo
1) was added, and the mixture was stirred in an ice bath for 4 hours. 0.5 ml of water, 1
5% sodium hydroxide (0.5 ml), then water 1.5
After adding ml to deactivate the excess reducing agent, it was dried over sodium sulfate and the ether was distilled off under reduced pressure.

The obtained oil was purified by short silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 4.25 g of 2- (2,4-dimethylphenyl) oxymethylthiophenol. NMR (CDCl ₃ ) δ 2.25 (s, 6H), 5.
14 (s, 2H), 6.6 to 7.8 (m, 7H)

(6) 2- (2,4) obtained in (5) above
-Dimethylphenyl) oxymethylthiophenol 1.
50 g (6.14 mmol) of dry methylene chloride 25 m
Dissolve in 1, and under ice cooling, methylisocyanate 0.37 g
(6.45 mmol), followed by 2 drops of triethylamine. After stirring overnight at room temperature, the solvent was distilled off under reduced pressure,
The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1 to 2: 1) to obtain 1.64 g (89% yield) of the desired product (Compound No. 8).
Melting point 114-115 ° C

NMR (CDCl ₃ ) δ 2.23 (s,
6H), 2.78 (d, 3H, J = 5Hz), 5.15
(S, 2H), 5.4 (bs, 1H), 6.6 to 7.8.
(M, 7H)

Synthesis Example 4 2- (2,4-dimethylphenyi)
) Oxymethyl-S-methoxycarbonyl thiophene
2. Synthesis of Noll (Compound No. 7) 1.50 g of 2- (2,4-dimethylphenyl) oxymethyl thiophenol obtained in Synthesis Example 3 (5) above
(6.14 mmol) and triethylamine 0.75 g
(7.37 mmol) was dissolved in 25 ml of anhydrous acetonitrile, and 0.70 g of methyl chlorocarbonate (7.3 g) under ice cooling.
7 mmol) was added. After stirring overnight at room temperature, it was diluted with methylene chloride, washed twice with water, dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (hexane: ethyl acetate 20: 1-10:
Purification in 1) yielded 1.67 g (90% yield) of the desired product. Melting point 39-41 ° C

NMR (CDCl ₃ ) δ 2.25 (s,
6H), 3.77 (s, 3H), 5.16 (s, 2)
H), 6.6 to 7.7 (m, 7H)

Synthesis Example 5 2- (2,4-dimethylphenyi)
) Oxyethyl-O-methylaminocarbonylpheno
Under ice cooling Synthesis (1) in anhydrous methanol 130ml of Lumpur (Compound No.12), acetyl chloride 13ml, and the mixture was stirred for 1 hour at room temperature. 25.6 g (168 mmo) of 2-hydroxyphenylacetic acid
1) was gradually added, and the mixture was stirred overnight at room temperature. The solvent was distilled off under reduced pressure, the residue was again dissolved in 350 ml of ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate three times, and then washed with water. The extract was dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the obtained crystals were collected by filtration and sufficiently washed with hexane to obtain 26.3 g of methyl 2-hydroxyphenylacetate (94% yield).

(2) 13.3 g (80 mmol) of methyl 2-hydroxyphenylacetate obtained in the above (1) was dissolved in 100 ml of dimethylformamide, 12.3 g (88.8 mmol) of potassium carbonate was added, and the mixture was stirred at room temperature for 1 hour. It was stirred. Benzyl bromide 15.4 g (87.2 mmo
A solution of 1) in 50 ml of dimethylformamide was gradually added, and the mixture was stirred overnight at room temperature. The reaction mixture is ice water 500m
The mixture was poured into 1 and then extracted with ethyl acetate three times. The combined ethyl acetate layers were washed 4 times with water and once with saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1 to 5: 1), and methyl 2-benzyloxyphenylacetate was 18.2.
g (89% yield) was obtained.

NMR (CDCl ₃ ) δ 3.59 (s,
3H), 3.67 (s, 2H), 5.07 (s, 2)
H), 6.7 to 7.6 (m, 9H)

(3) 18.2-g (71 mmol) of methyl 2-benzyloxyphenylacetate obtained in (2) above
100 ml of the anhydrous ether solution of was added to a suspension of 4.04 g (106 mmol) of lithium aluminum hydride in 250 ml of ether under ice cooling, and the mixture was stirred at the same temperature for 1 hour and then at room temperature overnight. The mixture was treated with an ordinary method under ice cooling to give 2-benzyloxyphenylethanol as an oily substance.

(4) Half of 2-benzyloxyphenylethanol obtained in the above (3) and a solution of 4.48 g (44.3 mmol) of triethylamine in methylene chloride were cooled with ice to obtain p-toluenesulfonyl chloride 8.10.
g (42.5 mmol) was added slowly. The mixture was stirred under ice cooling for 30 minutes and then at room temperature overnight. Because the reaction has not ended,
Further, 4.48 g of triethylamine and 8.10 g of sulfonyl chloride were added, and the reaction was continued at room temperature overnight. The reaction mixture was poured into 200 ml of ice water, the methylene chloride layer was separated, washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, water and saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (methylene chloride / hexane) to obtain 12.3 g of 2-benzyloxyphenylethanol p-toluenesulfonate.

NMR (CDCl ₃ ) δ 2.37 (s,
3H), 2.98 (t, 2H, J = 7Hz), 4.24
(T, 2H, J = 7Hz), 4.94 (s, 2H),
6.6-7.7 (m, 13H)

(5) Sodium hydride 0.66 g (1
6.5 mmol) was suspended in 30 ml of dimethyl sulfoxide, and 1.83 g (15 mmo) of 2,4-xylenol was suspended.
A solution of l) in 10 ml of dimethyl sulfoxide was added, and the mixture was stirred for 20 minutes under ice cooling (until solidification). 2-
A solution of 5.16 g (13.5 mmol) of benzyloxyphenyl ethanol p-toluene sulfonate in 10 ml of dimethyl sulfoxide was added, and the mixture was stirred at room temperature overnight.
The reaction mixture was poured into 300 ml of ice water, and ethyl acetate 1 was added.
Extraction was performed 3 times for each 00 ml. The ethyl acetate layers were combined, washed 3 times with water and then with saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. Purified by silica gel column chromatography (ethyl acetate / hexane), 2
-(2,4-Dimethylphenyl) oxyethyl O-benzylphenol was obtained.

(6) 2- (2,4) obtained in the above (5)
-Dimethylphenyl) oxyethyl O-benzylphenol was dissolved in 150 ml of ethyl acetate, 1 g of 5% palladium-carbon was added, and the mixture was reacted overnight under a hydrogen atmosphere. The catalyst was filtered through Celite, the filtrate was concentrated under reduced pressure, and further purified by silica gel column chromatography (ethyl acetate: hexane = 1: 10 to 1: 5) to give 2- (2,4-dimethylphenyl) oxyethylphenol. 1.76 g (2
Step 54% yield) was obtained.

NMR (CDCl ₃ ) δ 2.28 (s,
6H), 3.17 (t, 2H, J = 6Hz), 4.25
(T, 2H, J = 6 Hz), 6.6 to 7.5 (m, 7
H)

(7) 2- (2,4-dimethylphenyl)
Oxyethylphenol 0.88g (3.63mmo
l) was dissolved in 25 ml of dry methylene chloride, 0.23 g (3.99 mmol) of methyl isocyanate under ice-cooling and then 2 drops of triethylamine were added. After stirring overnight at room temperature, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (methylene chloride / hexane) to obtain 0.86 g of the desired product (79% yield). Melting point 10
3 ~ 105 ℃

NMR (CDCl ₃ ) δ 2.27 (s,
3H), 2.36 (s, 3H), 2.98 (d, 3H,
J = 5 Hz), 3.39 (t, 2H, J = 7.5H)
z), 4.25 (t, 2H, J = 7.5 Hz), 5.0
1 (brs, 1H), 6.7 to 7.6 (m, 7H)

Synthesis Example 6 2- (2,4-dimethylphenyi)
) Oxyethyl-O-methoxycarbonylphenol
Synthesis of (Compound No. 11) 0.88 g (3.63 m) of 2- (2,4-dimethylphenyl) oxyethylphenol obtained in Synthesis Example 5 (6)
mol) and 0.44 g of triethylamine (4.36 m)
(mol) was dissolved in 25 ml of anhydrous acetonitrile, and 0.41 g (4.36 mmol) of methyl chlorocarbonate was added under ice cooling. After stirring overnight at room temperature, dilute with 150 ml of methylene chloride, wash with water, dry over sodium sulfate, evaporate the solvent under reduced pressure, and purify the residue by silica gel column chromatography (hexane / ethyl acetate) to obtain the desired product. 0.97
g (89% yield) were obtained.

NMR (CDCl ₃ ) δ 2.13 (s,
3H), 2.24 (s, 3H), 3.08 (t, 2H,
J = 7 Hz), 3.87 (s, 3H), 4.16 (t,
2H, J = 7 Hz), 6.6 to 7.5 (m, 7H) Specific examples of the compounds of the present invention are shown in Tables 1 to 4.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

Next, test examples of the compounds of the present invention as agricultural and horticultural fungicides will be described. The evaluation criteria were as follows, unless otherwise specified. [Evaluation Criteria] The control effect was obtained by visually observing the degree of disease of the test plant at the time of the investigation and determining the control index on the following five levels. [Control index] [Extent of disease] 5: No lesions are observed at all 4: Lesion area, lesion number or lesion length is less than 10% of untreated section 3: Lesion area, lesion number or disease The spot length is less than 40% of the untreated section 2: The lesion area, number of lesions or lesion length is less than 70% of the untreated section 1: The lesion area, number of lesions or lesion length is untreated 70% or more of ward

Test Example 1. Cucumber powdery mildew prevention effect test Cucumber (variety: four leaves) is cultivated in a plastic bowl with a diameter of 7.5 cm, and 10 ml of a chemical solution in which the active ingredient compound is adjusted to a predetermined concentration when the one-leaf stage is reached is used with a spray gun. Sprayed. After kept in a thermostatic chamber at 22 to 24 ° C. for about 24 hours, conidia of powdery mildew fungi were sprinkled and inoculated. The lesion area of the first leaf was examined 8 days after the inoculation, and the control index was determined according to the above evaluation criteria. 1 is 500ppm
With a control index of 4, and compound No. No. 4 had a control index of 5 at 250 ppm.

Test Example 2. Cucumber downy mildew prevention effect test Cucumber (cultivar: four leaves) is cultivated in a plastic bowl with a diameter of 7.5 cm, and 10 ml of a chemical solution in which the active ingredient compound is adjusted to a predetermined concentration when the two-leaf stage is reached is sprayed using a spray gun. did. After keeping it in a thermostatic chamber at 22 to 24 ° C. for about 24 hours, it was spray-inoculated with a spore suspension of downy mildew. The lesion area of the first leaf was examined 5 to 7 days after the inoculation, and the control index was determined according to the evaluation criteria. 7, 8, 13, 1
Nos. 4, 17 and 18 had a control index of 5 at 500 ppm, and compound No. 2, 15, 16, 19, 20 and 23 are 50
A control index of 4 was shown at 0 ppm.

Test Example 3. Rice blast preventive effect test Rice (cultivar: Koshihikari) was cultivated in a plastic bowl with a diameter of 7.5 cm, and 20 ml of a chemical solution in which the active ingredient compound was adjusted to a predetermined concentration when the 4-leaf stage was reached was sprayed using a spray gun. . After being kept in a thermostatic chamber at 22 to 24 ° C for about 24 hours, a spore suspension of blast fungus was spray-inoculated. The number of lesions was examined 5 to 7 days after the inoculation, and the control index was determined according to the evaluation criteria. 1 and 9 have a control index of 5 at 500 ppm, and Compound No. 11, 19 and 22
Showed a control index of 4 at 500 ppm.

Test Example 4. Tomato epidemic preventive effect test Tomato (cultivar: Ponteroza) was cultivated in a plastic bowl with a diameter of 7.5 cm, and when the 4-leaf stage was reached, 10 ml of a chemical solution in which each test compound was adjusted to a predetermined concentration was sprayed using a spray gun. . After keeping it in a constant temperature room at 22 to 24 ° C. for about 24 hours, it was spray inoculated with a suspension of zoospores of Phytophthora. Inoculation 3 ~
After 4 days, the lesion area was investigated and the control index was determined according to the above evaluation criteria. 6, 9 and 10 had a control index of 5 at 500 ppm, and Compound No. Two
2, 24 and 25 each showed a control index of 4 at 500 ppm.

Test Example 5. Cucumber gray mold prevention effect test Cucumber (cultivar: four leaves) is cultivated in a plastic bowl with a diameter of 7.5 cm, and when the two-leaf stage is reached, 10 ml of a chemical solution in which each test compound is adjusted to a predetermined concentration is used with a spray gun. I sprayed it. After keeping it in a temperature-controlled room at 22 to 24 ° C for about 24 hours, benomyl and dicarboximide-sensitive gray mold fungal spores are suspended in the first leaf in potato-glucose decoction,
I inoculated. The lesion length was examined 3 days after the inoculation, and the control index was determined according to the above evaluation criteria. 7, 1
7 and 18 had a control index of 5 at 500 ppm, and Compound No. 3 and 8 showed a control index of 4 respectively.

Compound N is used as an active ingredient in the places where Botrytis cinerea fungi inhabit plants such as cucumber, eggplant and grapes.
o. 17, No. 18 or No. 23 to 25-200p
25 to 2 pm and fluazinam or chlorothalonil
By spraying an aqueous dispersion containing 00 ppm, the growth of Botrytis cinerea can be well controlled.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 249/12 251/54 8829-4H 251/58 255/38 9357-4H 269/02 271/44 323/16 7419-4H 323/18 7419-4H 329/06 7106-4H 329/10 7106-4H 333/04 7106-4H C07D 213/70 (72) Inventor Kanako Nakano Goryobetsusho, Yamashina-ku, Kyoto No. 138 No. 13 Crescent Rabbit 401

Claims (11)

[Claims] 1. A compound represented by the general formula (I): (In the formula, A is an optionally substituted aryloxy group, an optionally substituted arylthio group or -ON = C (R ¹ ) R ²
R ¹ and R ² are independently an optionally substituted alkyl group or an optionally substituted aryl group, and n is 1
Or 2, B is a halogen atom, an alkyl group, an aryl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, a haloalkyl group, a haloalkyloxy group,
A cyano group or a nitro group, m is an integer of 0 to 4, X is an oxygen atom or a sulfur atom, and Y is an alkoxy group, an alkylthio group, an amino group, an alkylamino group or a dialkylamino group). Substituted benzene derivative represented. 2. The general formula (I) according to claim 1, wherein the aryl moiety of the optionally substituted aryloxy group or the optionally substituted arylthio group of A and the optionally substituted aryl of R ¹ and R ^2. The group or the aryl group of B is phenyl, pyridyl, thienyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, indanyl, pyrazinyl, isoxazolyl or isothiazolyl, and the optionally substituted aryloxy group or optionally substituted arylthio group of A or When each substituent of the optionally substituted aryl group of R ¹ and R ² is 1 or 2 or more and 2 or more, the same or different halogen atom; halogen atom or C _1-4 alkoxy may substitute (C _{1 -4} ) Alkyl group; aryl group which may be substituted with halogen atom or C _1-4 alkoxy; nitro group; cyano group A C _1-4 alkoxy group which may be substituted with a halogen atom; a C _1-4 alkylthio group; an amino group; a di C _1-4 alkylamino group or a methylenedioxy group which may be substituted with a halogen atom, The substituent of the optionally substituted alkyl group of R ¹ and R ² is 1 or 2
Above, in case of 2 or more, the same or different halogen atom
Cyano group: a substituted benzene derivative which is a C _1-4 alkoxy group or a C _1-4 alkylthio group. 3. In the general formula (I) according to claim 1, A is a —ON═C (R ¹ ) R ² group (R ¹ and R ² are as described above), X is an oxygen atom, A substituted benzene derivative in which n is 1 and m is 0. 4. The compound of general formula (I) according to claim 1 is O
-(2-Methylaminocarbonyloxybenzyl) -3
A substituted benzene derivative which is -methylacetophenone oxime, O- (2-methylaminocarbonyloxybenzyl) -3-methoxyacetophenone oxime or O- (2-methylaminocarbonyloxybenzyl) -3,4-dimethylacetophenone oxime. 5. A compound represented by the general formula (I-1): (In the formula, A is an optionally substituted aryloxy group, an optionally substituted arylthio group or -ON = C (R ¹ ) R ²
R ¹ and R ² are independently an optionally substituted alkyl group or an optionally substituted aryl group, and n is 1
Or 2, B is a halogen atom, an alkyl group, an aryl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, a haloalkyl group, a haloalkyloxy group,
A cyano group or a nitro group, m is an integer of 0 to 4, X is an oxygen atom or a sulfur atom, and Y ¹ is an alkoxy group, an alkylthio group or a dialkylamino group)
A method for producing a substituted benzene derivative represented by:
General formula (II): (Wherein, A, n, B, m and X are as defined above) with a compound represented by the general formula (III -1) Hal-CO- Y 1 (III-1) or general formula (III- 2) Y
^A method for producing the above-mentioned substituted benzene derivative, which comprises reacting with a compound represented by ^1- CO-Y ¹ (wherein Y ¹ is as described above and Hal is a halogen atom). 6. A compound represented by the general formula (I-2): (In the formula, A is an optionally substituted aryloxy group, an optionally substituted arylthio group or -ON = C (R ¹ ) R ²
R ¹ and R ² are independently an optionally substituted alkyl group or an optionally substituted aryl group, and n is 1
Or 2, B is a halogen atom, an alkyl group, an aryl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, a haloalkyl group, a haloalkyloxy group,
A cyano group or a nitro group, m is an integer of 0 to 4, X is an oxygen atom or a sulfur atom, and Y ² is an amino group or an alkylamino group). Therefore, the general formula (II): The method for producing the substituted benzene derivative, which comprises reacting a compound represented by the formula (wherein A, n, B, m and X are as described above) with a cyanate or an isocyanate. 7. A compound represented by the general formula (I): (In the formula, A is an optionally substituted aryloxy group, an optionally substituted arylthio group or -ON = C (R ¹ ) R ²
R ¹ and R ² are independently an optionally substituted alkyl group or an optionally substituted aryl group, and n is 1
Or 2, B is a halogen atom, an alkyl group, an aryl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, a haloalkyl group, a haloalkyloxy group,
A cyano group or a nitro group, m is an integer of 0 to 4, X is an oxygen atom or a sulfur atom, and Y is an alkoxy group, an alkylthio group, an amino group, an alkylamino group or a dialkylamino group). A pest control agent comprising a substituted benzene derivative represented as an active ingredient and an auxiliary agent. 8. A substituted benzene derivative of the general formula (I),
Pyrimidinamine compounds, azole compounds, quinoxaline compounds, dithiocarbamate compounds, organic chlorine compounds, benzimidazole compounds, pyridinamine compounds, cyanoacetamide compounds, phenylamide compounds, sulfenic acid compounds, copper compounds, Isoxazole compounds, organic phosphorus compounds, N-halogenothioalkyl compounds, dicarboximide compounds,
Benzanilide compounds, benzamide compounds, piperazine compounds, pyridine compounds, carbinol compounds, piperidine compounds, morpholine compounds, organotin compounds, urea compounds, cinnamic acid compounds, phenylcarbamate compounds, cyano The pest control agent according to claim 7, which contains at least one compound selected from a pyrrole compound, an anthraquinone compound, a crotonic acid compound, and an antibiotic as an active ingredient. 9. A substituted benzene derivative of the general formula (I),
2-anilino-4-methyl-6- (1-propynyl) pyrimidine, 4,6-dimethyl-N-phenyl-2-pyrimidinamine, 4,5,6,7-tetrachlorophthalide,
Tetrachloroisophthalonitrile, pentachloronitrobenzene, 3-chloro-N- (3-chloro-2,6-dinitro-4-α, α, α-trifluorotolyl) -5
Trifluoromethyl-2-pyridinamine, 3-cyano-
Effective with at least one compound selected from 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole and 3- (2 ′, 3′-dichlorophenyl) -4-cyanopyrrole Claim 7 containing as a component
The pest control agent described in. 10. A pest control agent according to claim 7, wherein the pest is a plant pathogen. 11. A compound represented by the general formula (II): (In the formula, A is an optionally substituted aryloxy group, an optionally substituted arylthio group, or -ON = C (R ¹ ) R
² groups, R ¹ and R ² are independently an optionally substituted alkyl group or an optionally substituted aryl group, n is 1 or 2, B is a halogen atom, an alkyl group, an aryl group, It is an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, a haloalkyl group, a haloalkyloxy group, a cyano group or a nitro group, m is an integer of 0 to 4, X is an oxygen atom or a sulfur atom, and Y is an alkoxy. Group, an alkylthio group, an amino group, an alkylamino group or a dialkylamino group).