HARMFUL ORGANISMSS CONTAINING THEM TECHNICAL FIELD The present invention relates to substituted benzene derivatives, processes for their production, biocidal compositions for control of harmful organisms containing them as active ingredients and intermediates thereof.

BACKGROUND ART Many carbamate compounds derived from physostig ine have been practically used as insecticides. These carbamate insecticides are nervous system distracting agents having acetylcholine esterase inhibitory activities, but they have not been used as fungicides. Whereas, the compounds of the present invention are different in the chemical structure from these carbamate compounds.

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide novel substituted benzene derivatives which are useful as biocidal agents for control of harmful organisms, particularly as agricultural or horticultural biocidal agents for control of harmful organisms, processes for their production, intermediates thereof, etc. As a

result of extensive research on a wide range of compounds, the present inventors have found that substituted benzene derivatives having a certain specific structure such as a carbamate, carbonate or thiocarbamate structure, exhibit excellent biocidal activities agains± harmful organisms. The present invention has been accomplished on the basis of this discovery.

Thus, the present invention provides a substituted benzene derivative of the formula (I)

wherein A is an aryloxy group which may be substituted, an arylthio group which may be substituted or -ON=C(R ¹ )R ² , each of R ¹ and R ² which are independent of each other is an alkyl group which may be substituted, or an aryl group which may be substituted, 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 from 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, processes for its production, a biocidal composition for control of harmful organisms

containing it as an active ingredient, and an intermediate thereof.

DETAILED DESCRIPTION OF THE INVENTION The aryl moiety or the aryl group for A, B or each of R ¹ and R ² in the formula (I) includes, for example, phenyl, pyridyl, thienyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, indanyl, pirazinyl, isoxazolyl and isothiazolyl. The substituents for the aryloxy group which may be substituted or the arylthio group which may be substituted in the definition of A or for the aryl group which may be substituted in the definition of each of R ¹ and R ² include, for example, halogen atoms; C _1-4 alkyl groups which may be substituted by halogen or C ₁ _ ₄ alkoxy; aryl groups which may be substituted by halogen or C _χ _ ₄ alkoxy; a nitro group; a cyano group; C _1-4 alkoxy groups which may be substituted by halogen; C ₁ _ ₄ alkylthio groups; an amino group; άi-C ₁ _ ₄ alkylamino groups; and methylenedioxy groups which may be substituted by halogen. The number of substituents may be one or more, and when the number of substituents is more than one, the plurality of substituents may be the same or different.

The alkyl group which may be substituted in the definition of each of R ¹ and R ² may be a C ₁ _ ₆ linear or branched alkyl group, such as methyl, ethyl, propyl, butyl, pentyl or hexyl. Its substituents include, for example, halogen atoms; a cyano group; C _1-4 alkoxy

groups; and C-^ alkylthio groups. The number of substituents may be one or more, and when the number of substituents is more than, one, the plurality of substituents may be the same or different. In this specification, the halogen atom, the halogen atom in the haloalkyl or haloalkyloxy group, or the halogen atom constituting a substituent, includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the definition of B, the alkyl group or the alkyl moiety in each of the alkoxy group, the haloalkyl group or the haloalkyloxy group, may be a C ₁ _ ₆ linear or branched alkyl group. In the definition of B, the cycloalkyl group or the cycloalkyl moiety in the cycloalkyloxy group, may be the one having from 3 to 8 carbon atoms. Further, with respect to substituents defined by B, when m is two or more, the plurality of the substituents may be the same or different.

In the definition of Y, the alkyl moiety in each of the alkoxy group, the alkylthio group, the alkylamino group and the dialkylamino group, may be a C _λ _ _B linear or branched alkyl group. Further, in the case of the dialkylamino group, the number of carbon atoms in the two alkyl moieties may be the same or different.

Among compounds represented by the formula (I), the following compounds are preferred:

(1) A substituted benzene derivative of the formula (I), wherein the aryl moiety in the aryloxy group which

may be substituted or the arylthio group which may be substituted, for A, the aryl group which may be substituted, for each of R ¹ and R ² , or the aryl group for B, is phenyl, pyridyl, thienyl, furanyl, pirrolyl, pirazolyl, imidazolyl, indanyl, pyrazinyl, isooxazolyl or isothiazolyl; the aryloxy group which may be substituted, or the arylthio group which may be substituted, for A, or the aryl group which may be substituted for each of R ¹ and R ² , may have one or more substituents selected from the group consisting of halogen atoms; C _1-4 alkyl groups which may be substituted by halogen or C _1-4 alkoxy; aryl groups which may be substituted by halogen or C _1-4 alkoxy; a nitro group; a cyano group; C _j ^ alkoxy groups which may be substituted by halogen; C ₁ _ ₄ alkylthio groups; an amino group; di-C ₁ _ ₄ alkylamino groups; and methylenedioxy groups which may be substituted by halogen, provided that when the number of substituents is more than one, the plurality of substituents may be the same or different; and the alkyl group which may be substituted, for each of R ¹ and R ² , may have one or more substituents selected from the group consisting of halogen atoms; a cyano group; C ₁ _ ₄ alkoxy groups; and C _χ _ ₄ alkylthio groups.

(2) A substituted benzene derivative of the formula (I), wherein A is -ON=C(R ¹ )R ² wherein R ¹ and R ² are as defined above, X is an oxygen atom, n is 1, and m is 0.

(3) A substituted benzene derivative of the formula

(I), which is 0-(2-methylaminocarbonyloxybenzyl)-3- methylacetophenone oxime, 0-(2- methylaminocarbonyloxybenzyl)-3-methoxyacetophenone oxime or 0-(2-methylaminocarbonyloxybenzyl)-3,4- dimethylacetophenone oxime.

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

X-H

(ID

Hai-CO-Y ¹ Y ¹ -CO-Y ¹ (1II-J) or (III-2)

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

Method (A) is carried out usually in the presence of a solvent and a base. The solvent may, for example, be an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; a halogenated aliphatic hydrocarbon such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane or trichloroethane; a cyclic or

non-cyclic aliphatic hydrocarbon such as n-hexane or cyclohexane; an ether such as diethyl ether, dioxane or tetrahydrofuran; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a nitrile such as acetonitrile or propionitrile; or an aprotic polar solvent such as dimethylformamide, N-methyl-2- pyrrolidone, dimethylsulfoxide or sulfolane.

The base may be an inorganic base or an organic base. The inorganic base may, for example, be an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; a carbonate of an alkali metal or an alkaline earth metal, such as anhydrous potassium carbonate or anhydrous calcium carbonate; an alkali metal hydride such as sodium hydride; or an alkali metal such as sodium metal. The organic base may, for example, be pyridine, triethylamine or diisopropylethylamine.

The reaction temperature is usually from -20°C to the boiling point of the solvent, preferably from 0 to 50°C, and the reaction time is usually from 0.5 to 24 hours.

(11)

( 1 - 2 )

wherein A, n, B, m and X are as defined above, M-OCN represents a cyanate, M is an alkali metal, R-NCO represents an isocyanate, and R is an alkyl group.

Method (B) is carried out usually in the presence of a solvent. In some cases, a catalyst may be used. The ^' solvent may be the same as used for the above-mentioned method (A). The catalyst may, for example, be an acid such as boron trifluoride, hydrochloric acid, aluminum chloride, an alkyltin chloride or an alkyltin acetate, or a base such as triethylamine, pyridine, dimethylaniline, dimethylaminopyridine, l,4-diazabicyclo(2,2,2)octane, N- piperidine or sodium acetate. The reaction temperature is usually from -20°C to the boiling point of the solvent, and the reaction time is usually from 0.5 to 24 hours.

The compound of the formula (II) can be prepared, for example, by the following reactions (C) to (E) . Where n = 1, and X = oxygen atom

(n - i )

(V- 2) (11 - 2 )

⁽ V- 3) (fl - ;0

wherein B, m, R ¹ and R ² are as defined above, Ac represents acetyl, and Ar represents an aryl group which may be substituted. Method (C) can be carried out by acetylating two OH groups in substituted or unsubstituted saligenin, followed by the reaction with a compound of the formula (V-1), (V-2) or (V-3) and a base such as sodium hydride or butyl lithium, to obtain an alkali metal salt. The reaction is conducted in the presence of a solvent. The solvent may be the same as used in the above method (A) . The reaction temperature is usually from -20°C to the boiling point of the solvent, and the reaction time is usually from 0.5 to 24 hours. Where n = 1, and X = sulfur atom

wherein A, B and m are as defined above, and R is an alkyl group.

The compound of the formula (II-4) can be prepared by the five step reactions. In the first and second steps, substituted or unsubstituted thiosalicylic acid is reacted with protecting agents. Namely, in the first step, the carboxyl group of the thiosalicylic acid is esterified with an alcohol such as methanol, and in the second step, the SH group of this esterified product is converted to sulfide with dihydropyran. The respective

reactions can be conducted under the conditions commonly employed for the esterification and the sulfide- conversion, respectively. The third step is a reduction of the carbonyl group of this sulfide compound. For the reduction, a reducing agent such as lithium aluminum hydride is applied. The reaction condition may be the one commonly used. The fourth step is a condensation reaction of the substituent A of this reduced product. This reaction can be accomplished by the following method.

(VI- 1 )

(V- 2 ) (VI- 2 )

(V- 3 ) 071- 3 )

wherein B, m, R ¹ and R ² are as defined above, and Ar represents an aryl group which may be substituted.

The above reaction is carried out in the presence of a solvent as well as an alkyl or aryl phosphine such as tributyl phosphine and an azocarboxylic acid ester such ^" as diethyl azodicarboxylate. The solvent may be the same as used in the above-mentioned method (A) . The reaction temperature is usually from -78°C to +70°C, and the reaction time is usually from 0.5 to 24 hours. The fifth step is a reaction for removing the tetrahydropyranyl group. For this reaction, iodine is employed. The reaction proceeds at room temperature, whereby a dimer of the compound of the formula (II-4) is formed by a disulfide bond and then converted by a reducing agent such as lithium aluminum hydride to the compound of the formula (II-4). Otherwise, silver nitrate or the like may be employed to convert it to silver mercaptide, whereupon the tetrahydropyranyl group is removed, followed by hydrolysis with weak acid, to obtain the free compound of the formula (II-4). Where n = 2, and X = oxygen atom

( E )

(11 - 5 )

wherein A, B and m are as defined above, and R is an alkyl group.

The compound of the above formula (II-5) can be prepared by the five step reactions.

In the first and second steps, substituted or unsubstituted O-hydroxyphenylacetic acid is protected with appropriate masking group, respectively. Namely, in the first step, the carboxyl group is esterified in the

same manner as in the above-mentioned thiosalicylic acid, and in the second step, the OH group of this esterified product is etherified with benzyl bromide. The reaction condition for this etherification reaction may be that one commonly used. The third step is a reduction of the carbonyl group of this etherified product, and the same method as in the third step of the above-mentioned method (D) may be employed. The fourth step is a condensation reaction of the substituent A. This reaction can be accomplished by the following method.

(IV-3)

^(1V - ^{3 )} ÷ HS-A r - ^{→ (} B

(V- 3 )

wherein B, m, R ¹ and R ² are as defined above, and Ar represents an aryl group which may be substituted.

In the above reaction, a compound of the formula (IV- 3) is once reacted with p-toluenesulfonyl chloride or methanesulfonyl chloride in order to make it leaving group, in the presence of a base such as triethylamine and a solvent, to obtain a tosylate or mesylate of the compound of the formula (IV-3). Then, the tosylate or mesylate of the compound of the formula (IV-3) is reacted with a compound obtained by reacting a compound of the formula (V-1), (V-2) or (V-3) with sodium hydride or butyl lithium, in the presence of a solvent. The solvent to be used for this reaction, may be the same as used in the above-mentioned method (A) . The reaction temperature is usually from -20°C to the boiling point of the solvent, and the reaction time is usually from 0.5 to 24 hours.

The fifth step is a reaction for removing the benzyl group. For this reaction, palladium-carbon or platinum oxide may, for example, be used as the catalyst, and by stirring under a hydrogen atmosphere, the compound of the

formula (II-5) can readily be obtained.

The compound of the formula (I) according to the present invention is useful as an active ingredient of biocidal compositions for control of harmful organisms. For example, the compound of the formula (I) can be used as the active ingredient of agricultural and horticultural fungicides to exhibit an excellent effect of controlling plant diseases such as rice blast, rice sheath blight, rice helminthosporium leaf spot, cucumber anthracnose, cucumber powdery mildew, cucumber downy mildew, tomato late blight, tomato early blight, citrus melanose, citrus common green mold, apple and pear scab, apple alternaria blotch, grape downy mildew, and gray mold, sclerotinia rot and rust of various crops; and soil diseases caused by phytopathogenic fungi such as Fusarium, Pythium,- Rhizoctonia, Verticillium, and Plasmodiophora. The compound of the formula (I) exhibits an especially excellent effect of controlling rice blast, powdery mildew of various crops, gray mold of various crops, sclerotinia rot of various crops, cucumber and grape downy mildew, and tomato and potato late blights. The compound of the present invention exhibits not only a long-term residual effect and an excellent preventive effect, but also has a curative effect to enable disease control to be effected through treatment therewith after infection. Furthermore, disease control is possible through soil treatment with the compound of the present

invention. The compound of the present invention is effective not only against sensitive strains but also against various resistant strains such as Benomyl- resistant powdery mildew, Metalaxyl-resistant downy mildew, and Benomyl-and/or dicarboximide-resistant gray mold.

The compound of the present invention has an insecticidal, acaricidal and nematocidal activities as well and hence are effective against a variety of vermin in question.

The compound of the present invention may be used in combination with an adjuvant(s) to prepare various formulations such as an emulsifiable concentrate, a dust, a wettable powder, an aqueous solution, granules, a suspension concentrate, etc. like in the case of conventional agricultural chemical formulations. These formulations can be practically used either as such or after diluted with a diluent such as water to a predetermined concentration. As the adjuvant, there can be mentioned carriers, emulsifying agents, suspending agents, dispersants, spreaders, penetrating agents, wetting agents, thickening agents, and stabilizing agents, which may be appropriately added to the compound of the present invention as desired. Carriers are classified into solid carriers and liquid carriers. Examples of solid carriers include animal or vegetable powders such as starch, sugar,

cellulose powder, cyclodextrin, activated carbon, soybean powder, wheat powder, chaff powder, wood powder, fish powder, and powdery milk; and mineral powders such as talc, kaolin, bentonite, bentonite-alkylamine complex, calcium carbonate, calcium sulfate, sodium bicarbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, silica, and sulfur powder. Examples of liquid carriers include water; animal or vegetable oils such as soybean oil, cotton seed oil, and corn oil; 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 kerosine, lamp oil, and liquid paraffin; aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane and solvent naphtha; halogenated hydrocarbons such as chloroform and chlorobenzene; acid amides such as dimethylformamide; esters such as ethyl acetate and fatty acid glycerin esters; nitriles such as acetonitrile; sulfur-containing compounds such as dimethylsulfoxide; and N- methoxypyrrolidone.

The suitable blending weight ratio of the compound of the present invention to the adjuvant(s) is generally in the range of 0.05:99.95 to 90:10, and preferably in the range of 0.2:99.8 to 80:20.

The concentration of the compound of the present invention at the time of application varies depending on

the crop as the object of application treatment, the way of application, the form of a formulation, the dose, etc., and hence cannot be generically determined. In the case of foliar application treatment, however, the concentration of the compound of the present invention as the active ingredient may usually be in the range of 0.1 to 10,000 ppm, and preferably in the range of 1 to 2,000 ppm. In the case of soil application treatment, the dose may usually be in the range of 10 to 100,000 g/ha (hectare), and preferably in the range of 200 to 20,000 g/ha.

A description will now be made of Formulation Examples of the biocidal composition of the present invention for control of harmful organisms, which comprises the compound of the present invention as the active ingredient. FORMULATION EXAMPLE 1

(1) Compound No. 1 50 parts by weight

(2) kaolin 40 parts by weight (3) sodium lignosulfonate 7 parts by weight

(4) a polyoxyethylene alkylphenyl ether sulfate

3 parts by weight The above components are uniformly mixed to obtain a wettable powder. 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 lignosulfonate 4 parts by weight

(5) a polyoxyethylene alkylaryl ether

4 parts by weight The above components are uniformly mixed to obtain a wettable powder. 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) a dialkylsulfosuccinate 1 part by weight

(5) a polyoxyethylene alkylphenyl ether sulfate

3 parts by weight

(6) sodium ?-naphthalenesulfonate-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) a dialkylsulfosuccinate 2 parts by weight

(4) a polyoxyethylene alkylphenyl ether sulfate

4 parts by weight The above components are uniformly mixed to obtain a wettable powder.

FORMULATION EXAMPLE 5

(1) Compound No. 6 0.5 part by weight

(2) talc 99.0 parts by weight

(3) phosphate of a lower alcohol

0.5 parts by weight The above components are uniformly mixed to obtain a dust.

FORMULATION EXAMPLE 6

(1) Compound No. 7 0.2 part by weight

(2) calcium carbonate powder 98.8 parts by weight

(3) phosphate of a lower alcohol 1 part by weight

The above components 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) a polyoxyethylene alkylaryl ether

20 parts by weight The above components are mixed and dissolved to obtain an emulsifiable concentrate. 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 lignosulfonate 5 parts by weight The above components are admixed with a suitable amount of water for granulation and granulated to obtain granules.

FORMULATION EXAMPLE 9

(1) Compound No. 4 10 part by weight

(2) isoparaffin saturated hydrocarbons (fraction: 210-265°C) 79 parts by weight (3) a mixture of a polyoxyethylene phenylphenol derivative and a polyoxyethylene sorbitan alkylate

10 parts by weight (4) a bentonite-alkylamine complex

1 part by weight The above components are mixed and finely pulverized to obtain a suspension concentrate. FORMULATION EXAMPLE 10

(1) Compound No. 5 40 parts by weight

(2) an oxyethylated polyarylphenol phosphate neutralized with triethanolamine

2 parts by weight

(3) a silicone

0.2 part by weight

(4) xanthan gum 0.1 part by weight (5) ethylene glycol 5 parts by weight

(6) water 52.7 part by weight

The above components are mixed and finely pulverized to obtain an aqueous suspension concentrate. 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 part by weight

(5) a sodium alkylsulfonate 1 part by weight The above components are placed in a high-speed mixing granulator, admixed with 20% water, granulated, and dried to obtain water-soluble granules.

If desired, the compound of the present invention may be used in mixture or combination with other agricultural chemical(s), examples of which include insecticides, acaricides, nematocides, fungicides, antiviral agents, attractants, herbicides, and plant growth regulators. in this case, the effect of the compound or biocidal composition of the present invention may sometimes be enhanced.

Specific examples of active ingredients of such insecticides, acaricides or nematocides include the following compounds: Organic phosphate compounds

O-(4-bromo-2-chlorophenyl)O-ethyl S-propyl phosphorothioate (common name: Profenotos), 0-(2,2-dichlorovinyl)0,0-dimethylphosphate (common name: Dichlorvos),

O-ethyl 0-{3-methyl-4-(mthylthio)phenyl]N-isopropyl phosphoroamidate (common name: Fenamiphos),

0,0-dimethyl 0-(4-nitro-m-tolyl)phosphorothioate (common name: Fenitrothion) ,

O-ethyl 0-(4-nitrophenyl)phenyl phosphonothioate (common name: EPN) ,

0,0-diethyl 0-(2-isopropyl-6-methylpyrimidin-4- yl)phosphorothioate (common name: Diazinon),

0,O-dimethyl 0-(3,5,6-trichloro-2- pyridyl)phosphorothioate (common name: Chloropyrifos- methyl) ,

0,S-dimethyl N-acetylphosphoramiothioate (common name: Acephate),

0-(2,4-dichlorophenyl) O-ethyl S-propyl phosphorodithioate (common name: Prothiofos), and (RS)-S-sec-butyl O-ethyl 2-oxo-l,3-thiazolidin-3-yl phosphonothioate (disclosed in U.S. Patent No. 4,590,182); Carbamate compounds

1-naphthyl N-methylcarbamate (common name: Carbaryl), 2-isopropoxyphenyl N-methylcarbamate (common name: Propoxur) ,

2-methy1-2-(methylthio)propionaldehyde 0- methylcarbamonyloxime (common name: Aldicarb), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- methylcarbamate (common name: Carbofuran), dimethyl N,N'- [ (thiobis. (methylimino)carbonyloxy] ]bisethanimidothioate (common name: Thiodicarb),

S-methyl N-(methylcarbamoylox )thioacetimidate (common name: Methomyl),

N, -dimethy1-2-methylcarbamoyloxyimino-2-( ethylthio) acetamide (common name: Oxamyl),

2-(ethylthiomethyl)phenyl N-methylcarbamate (common name: Ethiofencarb) ,

2-dimethylamino-5,6-dimethylpyrimidin-4-yl N,N- dimethylcarbamate (common name: Pirimicarb), and 2-sec-butylphenyl N-methylcarbamate (common name: Fenobucarb) ; Nereistoxin derivatives

S,S'-2-dimethylaminotrimethylenebis(thiocarbamate) (common name: Cartap) , and N,N-dimethyl-l,2,3-trithian-5-ylamine (common name: Thiocyclam) ; Organic chlorine compounds

2,2,2-trichloro-l,1-bis(4-chlorophenyl)ethanol (common name: Dicofol), and 4-chlorophenyl-2,4,5-trichlorophenylsulfone (common name: Tetradifon); Orqanometallic compounds bis[tris(2-methyl-2-phenylpropyl)tin]oxide (common name: Fenbutatin oxide); Pyrethroid compounds

(RS)-α-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)- 3-methylbutylate (common name: Fenvalerate) ,

3-phenoxybenzyl (IRS)-cis,trans-3-(2,2- dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (common name: Permethrin),

(RS)-α-cyano-3-phenoxybenzyl (IRS)-cis,trans-3-(2,2- dichorovinyl)-2,2-dimethylcyclopropanecarboxylate (common

name: Cypermethrin) ,

(S)-c-cyano-3-phenoxybenzyl (IR)-cis-3-(2,2- dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (common name: Deltamethrin) , (RS)-__~cyano-3-phenoxybenzyl (lRS)-cis,trans-3-(2- chloro-3,3,3-trifluoropropenyl)-2,2-dimethyl- cyclopropanecarboxylate (common name: Cyhalothrin) ,

4-methyl-2,3,5,6-tetrafluorobenzyl-3-(2-chloro-3,3,3- trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (common name: Tefluthrin) , and

2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (common name: Ethofenprox) ; Benzoylurea compounds

1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (common name: Diflubenzuron) ,

1-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2- pyridyloxy)phenyl]3-(2,6-difluorobenzoyl)urea (common name: Chlorfluazuron) , and

1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6- difluorobenzoyl)urea (common name: Teflubenzuron), Juvenile hormone-like compounds isopropyl(2E,4E)-ll-methoxy-3,7-ll-trimethyl-2,4- dodecadienoate (common name: Methoprene); Pyridazinone compounds 2-t-butyl-5-(4-t-butylbenzylthio)-4-chloro- 3(2H)pyridazinone (common name: Pyridaben); Pyrazole compounds

t-butyl 4[ (1,3-dimethyl-5-phenoxypyrazol-4-yl)- methyleneamino-oxymethyl]benzoate (common name: Fenpyroximate) ; Nitro compounds 1(6-chloro-3-pyridylmethyl)-N-nitro-imidazolidin-2- yideneamine (common name: Imidacloprid),

1-[ -(6-chloro-3-pyridylmethyl)-N-ethylamino]-1- methylamino-2-nitroethylene (European Patent Laid-Open No. 302,389), 2-methylamino-2-[N-methyl]-N-(6-chloro-3- pyridylmethyl)amino]-l-nitroethylene (European Patent Laid-Open No. 302,389),

1-(6-chloro-3-pyridylmethyl)amino-l-dimethylamino-2- nitroethylene (European Patent Laid-Open No. 302,389), 1-(6-chloro-3-pyridylmethyl)-2-(1-nitro-2- allylthioethylidene)imidazolidine (European Patent Laid- Open No. 437,784),

1-(6-chloro-3-pyridylmethyl)-2-(l-nitro-2- ethylthioethylidene)imidazolidine (European Patent Laid- Open No. 437,784),

1-(6-chloro-3-pyridylmethyl)-2-(l-nitro-2- methylallylthioethylidene)imidazolidine (European Patent Laid-Open No. 437,784), l-(6-chloro-3-3-pyridylmethyl)-3-methyl-2- nitroguanidien (European Patent Laid-Open No. 383,091),

1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2- nitroguanidine (European Patent Laid-Open No. 383,091),

3-(6-chloro-3-pyridylmethyl_2-nitromethylene- thiazolidine (European Patent Laid-Open No. 192,060),

1-(6-chloro-3-pyridylmethyl) -2- (nitromethylene)imidazolidine (European Patent Laid-Open No. 163,855),

6-(6-chloro-3-pyridylmethylamino)-1,3-dimethyl-5- nitro-l,2,3,4-tetrahydropyrimidine (European Patent Laid- Open No. 366,085), and

1-(6-chloro-3-pyridylmethyl)-5-nitro-3-methyl-6- methylamino-l,2,3,4-tetrahydropyrimidine (European Patent Laid-Open No. 366,085); Dinitro compounds Organic sulfur compounds Urea compounds Triazine compounds Hydrazine compounds Other compounds

2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6- tetrahydro-2H-l,3,5-thiadiazin-4-one (common name: Buprofezin), trans-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2- oxothiazolidinone-3-carboxamide (common name: Hexythiazox) ,

N-methylbis(2,4-xylyliminomethyl)amine (common name: Amitraz),

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine (common name: Chlordimeform) , and

(4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl)- propyl] (dimethylJsilane (common name: Silafluofen) ,

The compound of the present invention may also be used in mixture or combination with microbial agricultural chemicals such as B.T. and insect viruses, and antibiotics such as avermectin and milbemycin.

Specific Examples of active ingredients of the aforementioned fungicides include the following compounds. Pyrimidinamine compounds

2-anilino-4-methyl-6-(1-propynyl)pyrimidine (common name: Mepanipyrim) ,

4,6-dimethyl-N-phenyl-2-pyrimidinamine (common name: Pyrimethanil) Azole compounds

1-(4-chlorophenox )-3,3-dimethyl-l-(1H-1,2,4-triazol- l-yl)butanone (common name: Triadimefon) ,

1-(biphenyl-4-yloxy)-3,3-dimethyl-l-(1H-1,2,4- triazol-l-yl)butan-2-ol (common name: Bitertanol), l-[N-(4-chloro-2-trifluoromethylphenyl)-2- propoxyacetimidoyl]imidazole (common name: Triflumizole) ,

1-[2-(2,4-dichlorophenyl)-4-ethyl-l,3-dioxolan-2-yl- methyl]-lH-l,2,4-triazole (common name: Etaconazole) ,

1-[2-(2,4-dichlorophenyl)-4-propyl-l,3-dioxolan-2-yl- methyl]-lH-l,2,4-triazole (common name: Propiconazole),

1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole (common name: Penconazole) ,

bis(4-fluorophenyl) (methyl) (lH-l,2,4-triazol-l-yl- methyl)silane (common name: Flusilazole) ,

2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-l-yl- methyl)hexanenitrile (common name: Myclobutanil) , (2RS, 3RS)-2-(4-chlorophenyl)-3-cyclopropyl-l-(lH- l,2,4-triazol-l-yl)butan-2-ol (common name: Cyproconazole) ,

(RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4- triazol-l-ylmethyl)pentan-3-ol (common name: Terbuconazole) ,

(RS)-2(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1- yl)hexan-2-ol (common name: Hexaconazole) ,

(2RS,5RS)-5-(2,4-dichlorophenyl)tetrahydro-5-(1H- 1,2,4-triazol-1-ylmethyl)-2-furyl 2,2,2-trifluoroethyl ether (common name: Furconazole-cis) , and

N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]- imidazole-1-carboxamide (common name: Prochloraz); Quinoxaline compounds

6-methyl-l,3-dithiolo[4,5-b]quinoxalin-2-one (common name: Quinomethionate) ;

Dithiocarbamate compounds manganese ethylenebis(dithiocarbamate) polymer (common name: Maneb), zinc ethylenebis(dithiocarbamate) polymer (common name: Zineb), complex of zinc with manganese ethylenebis(dithiocarbamate (Maneb) (common name:

Mancozeb) , dizinc bis(dimethyldithiocarbamate)ethylenebis(dithiocarbamate) (common name: Polycarbamate) , and zinc propylenebis(dithiocarbamate) polymer (common name: Propineb); Organic chlorine compounds

4,5,6,7-tetrachlorophthalide (common name: Fthalide), tetrachloroisophthalonitrile (common name: Chlorothalonil) , and pentachloronitrobenzene (common name: Quintozene); Benzi idazole compounds methyl 1-(butylcarbamoyl)benzimidazol-2-yl-carbamate (common name: Benomyl) , dimethyl 4,4'-(o-phenylene)bis(3-thioallophanate) (common name: Thiophanate-Methyl) , and methyl benzimidazol-2-ylcarbamate (common name: Carbendazim) ; Pyridinamine compounds 3-chloro-N-(3-chloro-2,6-dinitro-4-<_.,<_.,<_.- trifluorotolyl)-5-trifluoromethyl-2-pyridinamine (common name: Fluazinam) ; Cyanoacetamide compounds

1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (common name: Cymoxanil);

Phenylamide compounds methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate

(common name: Metalaxyl),

2-methoxy-N-(2-oxo-l,3-oxazolidin-3-yl)aceto-2 ^■ ,6'- xylidide (common name: Oxadixyl),

(±)-<_.-2-chloro-N-(2,6-xylylacetamido)-7-butyrolacto ne (common name: Ofurace), methyl N-phenylacetyl-N-(2,6-xylyl)-DL-alaninate (common name: Benalaxyl), methyl N-(2-furoyl)-N-(2,6-xylyl)-DL-alaninate (common name: Furalaxyl), and (±) -a- [N-3-chlorophenyl)cyclopropanecarboxamido] -γ- butyrolactaone (common name: Cyprofuram) ; Sulfenic acid copmounds

N-dichlorofluoromethylthio-N' ,N'-dimethyl-N- phenylsulfamide (common name: Dichlofluanid) ; Copper compounds cupric hydroxide (common name: cupric hydroxide), and copper 8-quinolinolate (common name: Oxine-Copper) ; Isoxazole compounds

5-methylisoxazol-3-ol (common name: Hydroxyisoxazole) ;

Orqanophosphorus compounds aluminum tris(ethyl phosphonate) (common name: Fosetyl-Al),

0-2,6-dichloro-p-tolyl-0,0-dimethyl phosphorothioate (common name: Tolcofos-methyl) ,

S-benzyl 0,0-diisopropyl phosphorothioate,

O-ethyl S,S-diphenyl phosphorodithioate, and aluminum

ethyl hydrogenphosphonate; N-Haloqenothioalkyl compounds

N-(trichloromethylthio)cyclohex-4-ene-l,2- dicarboximide (common name: Captan) , N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-l,2- dicarboximide (common name: Captafol), and

N-(trichloromethylthio)phthalimide (common name: Folpet) ;

Dicarboximide copmounds N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-l,2- dicarboximide (common name: Procymidone) ,

3-(3,5-dichlorophenyl)-N-isopropyl-2,4- dioxoimidazolidine-1-carboxamide (common name: Iprodione), and (RS)-3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-l,3- oxazolidine-2,4-dione (common name: Vinclozolin) ; Benzanilide compounds , ,α-trifluoro-3'-isopropoxy-o-toluanilide (common name: Flutolanil), and 3'-isopropoxy-o-toluanilide (common name: Mepronil); Benzamide compounds

2-(1,3-dimethylpyrazol-4-ylcarbonylamino)-4-methyl-3- pentenenitrile (disclosed in British Patent no. 2,190,375), and a-(nicotinylamino)-(3-fluorophenyl)acetonitrile (disclosed in Japanese Patent Laid Open No. 135,364/1988);

Piperazine compounds

N,N'-[piperazine-l,4- diylbisftrichloromethyl)methylene] jdiformamide (common name: Triforine); Pyridine compounds

2' ,4'-dichloro-2-(3-pyridyl)acetophenone O- methyloxime (common name: Pyrifenox); Carbinol compounds

(±)-2,4'-dichloro- _< _.-(pyrimidin-5-yl)benzhydryl alcohol (common name: Fenarimol), and

(±)-2,4'-difluoro-σ-(1H-1,2,4-triazol-1-yl- methyl)benzhydryl alcohol (common name: Flutriafol); Piperidine compounds

(RS)-l-[3-(4-tert-butylphenyl)-2- methylpropyl.piperidine (common name: Fenpropidine) ; Morpholine compounds

(±)-cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]- 2,6-dimethylmorpholine (common name: Fenpropimorph) ; Orqanotin compounds triphenyltin hydroxide (common name: Fentin Hydroxide), and triphenyltin acetate (common name: Fentin Acetate); Urea compounds

1-(4-chlorobenzyl)-l-cyclopentyl-3-phenylurea (common name: Pencycuron) ;

Cinnamic acid compounds

(E,Z)4-[3-(4-chlorophenyl)-3-(3,4-

dimethoxyphenyl)acryloyl]morpholine (common name: Dimetho orph) ; Phenylcarbamate compounds isopropyl 3,4-diethoxycarbanilate (common name: Diethofencarb) ;

Cyanopyrrole compounds

3-cyano-4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole (common name: Fludioxonil) , and

3-(2' ,3'-dichlorophenyl)-4-cyanopyrrole (common name: Fenpiclonil) .

Other active ingredients of the fungicides include anthraquinone compounds, crotonic acid copmounds and antibiotics.

The suitable blending weight ratio of the substituted benzene derivative of the present invention represented by the formula (I) to the other agricultural chemical(s) when used in mixture or combination may generally be in the range of 1:300 to 300:1, and preferably in the range of 1:100 to 100:1. Especially when the substituted benzene derivative of the present invention is combined with a pyrimidinamine compound, an organic chlorine compound, a pyridinamine compound or a cyanopyrrole compound, excellent effects can be expected for control of various gray mold diseases.

Now, specific Synthesis Examples for preparation of the compounds of the present invention will be described.

However, it should be understood that the present invention is by no means restricted by such specific Examples.

SYNTHESIS EXAMPLES 1 Synthesis of 0-(2-methylaminocarbonyloxybenzyl)-3- methylacetophenone oxime (Compound No. 17)

(1) 12.4 g (0.1 mol) of saligenin and 30.6 g (0.3 mol) of acetic anhydride were dissolved in 47.5 g (0.6 mol) of pyridine and left to stand still overnight at room temperature. 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) 5.37 g (40 mmol) of 3'-methylacetophenone, 3.06 g (44 mmol) of hydroxylamine hydrochloride and 4.45 g (44 mmol) of triethylamine were dissolved in 40 ml of methanol and stirred overnight at room temperature. Methanol was distilled off under reduced pressure, and 100 ml of water was added to the residue, whereupon the formed crystalline product was collected by filtration and thoroughly washed with water, to obtain 5.60 g (94%) of 3'-methylacetophenone oxime. From the NMR analysis, this product was found to be substantially pure. (3) 1.35 g (33.6 mmol) of 60% sodium hydride was suspended in 30 ml of tetrahydrofuran and cooled by ice bath. A solution having 4.77 g (32 mmol) of the 3'-

methylacetophenone oxime obtained in the above step (2) dissolved in 10 ml of tetrahydrofuran, was dropwise added thereto under cooling with ice, and the mixture was stirred for 30 minutes. Then, 10 ml of a tetrahydrofuran solution of 3.33 g (16 mmol) of the bisacetylsaligenin ^' obtained in the above step (1) was added thereto, and the mixture was stirred for 30 minutes under cooling. Then, the cooling bath was removed, and the mixture was stirred overnight at room temperature. The reaction mixture was added to 100 ml of 3N hydrochloric acid, and the mixture was extracted with methylene chloride. Then, the extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was dissolved in 80 ml of methanol, and a small amount of lithium hydroxide was added thereto. The mixture was stirred overnight at room temperature. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography with a solvent mixture of methylene chloride/hexane, to obtain 1.81 g (45%) of 0-(2- hydroxybenzyl)-3-methylacetophenone oxime. NMR (CDC ₃ )5 2.24(s,3H), 2.38(s,3H), 5.15(S,2H), 6.7- 7.5(m,8H), 9.02(brs,lH)

(4) 0.91 g (3.56 mmol) of 0-(2-hydroxybenzyl)-3- methylacetophenone oxime was dissolved in 30 ml of methylene chloride, and under cooling with ice, 0.22 g (3.74 mmol) of methyl isocyanate and then two drops of

triethylamine were added thereto. The mixture was stirred overnight at room temperature, and then the solvent was distilled off. 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 ( CDC ₃ ) δ 2.22(s,3H), 2.34(s,3H), 2.78(d,3H,J=5Hz) , 5.22(s,2H), 6.9-7.7(m,8H) SYNTHESIS EXAMPLE 2 Synthesis of 0-(2-methoxycarbonyloxybenzyl)-3- methylacetophonone oxime (Compound No. 13)

0.91 g (3.56 mmol) of 0-(2-hydroxybenzyl)-3- methylacetophenone oxime obtained in Synthesis Example 1 (3) was dissolved in 30 ml of acetonitrile, and under cooling with ice, 0.40 g (4.28 mmol) of methyl chlorocarbonate and 0.43 g (4.28 mmol) of triethylamine were sequentially added thereto. The mixture was stirred overnight at room temperature. Then, the solvent was distilled off, and the residue was dissolved in methylene chloride, washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 1.09 g (98%) of the desired product (Compound No. 13). NMR (CDC ₃ )r$ 2.21(s,3H), 2.35(s,3H), 3.84(s,3H), 5.26(s,2H), 7.0-7.6(m,8H) SYNTHESIS EXAMPLE 3

Synthesis of 2-(2,4-dimethylphenyl)oxymethyl-S- methylaminocarbonyl thiophenol (Compound No. 8)

(1) 10 ml of acetyl chloride was dropwise added to 100 ml of dry methanol'under cooling with ice, and the mixture was stirred for 30 minutes. Then, 15.4 g (0.1 mol) of thiosalicylic acid was gradually added thereto, and the mixture was stirred overnight at room temperature. Then, the solvent was distilled off under reduced pressure, and the residue was purified by short silica gel column chromatography (hexane/ethyl acetate = 2/1).

(2) Methyl thiosalicylate obtained in the above step (1) and 8.41 g (0.1 mol) of dihydropyran were dissolved in dry ethyl ether, and under cooling with ice, a boron trifluoride-ethyl ether complex (47% solution, 30.2 g

(0.1 mol)) was added thereto. The mixture was stirred at the same temperature for 30 minutes. The mixture was further reacted at room temperature for one hour and again cooled with ice. To this mixture, 60 ml of a 20% sodium hydroxide aqueous solution and then 60 ml of water were added. The ether layer was separated, and the aqueous layer was extracted with ethyl ether. The ether layers were put together and washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure.

(3) Methyl S-tetrahydropyranylthiosalicylate obtained in the above step (2) was dissolved in 50 ml of dry ethyl

ether, and under cooling with ice, the solution was added to a suspension of 5.7 g (0.15 mol) of lithium aluminum hydride in 150 ml of dry ethyl ether. Further, 1.9 g (0.05 mol) of lithium aluminum hydride was added thereto, and the mixture was stirred at the same temperature for ^' 10 minutes. Then, the mixture was reacted overnight at room temperature. To the mixture, 8 ml of water, 8 ml of 15% sodium hydroxide, and 24 ml of water were sequentially gradually added under cooling with ice to destroy an excess reducing agent. Then, sodium sulfate was added thereto, and the mixture was filtered through on the pat of Celite. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane/ethyl acetate = 3/1) to obtain 17.5 g (three step over all yield: 78%) of 2- tetrahydropyranylthiobenzyl alcohol.

(4) 6.73 g (30 mmol) of 2-tetrahydropyranylthiobenzyl alcohol obtained in the above step (3) and 3.85 g (31.5 mmol) of 2,4-xylenol were dissolved in 100 ml of dry tetrahydrofuran, and under cooling with ice, 25 ml of a tetrahydrofuran solution of 6.37 g (31.5 mmol) of tributylphosphine and 25 ml of a tetrahydrofuran solution of 5.49 g (31.5 mmol) of diethyl azodicarboxylate were sequentially added thereto, and the mixture was stirred for 30 minutes with ice bath. Then, the mixture was stirred overnight at room temperature, and the reaction mixture was concentrated under reduced pressure to a

volume of about 50 ml and diluted with 200 ml of ethyl acetate. The mixture was washed twice with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography

(hexane/ethyl acetate = 20/1 to 10/1) to obtain 8.12 g (82%) of 2-(2,4-dimethylphenyl)oxymethyl-S- tetrahydropyranyl thiophenol. NMR (CDC^ ₃ )S 2.25(s,6H), 1.4-2.3(m,6H) , 3.3-3.8(m,2H) , 5.13(t,lH,J=4Hz), 5.17(s,2H), 6.7-7.8(m,7H)

(5) 100 ml of a methanol solution of 8.12 g (24.7 mmol) of 2-(2,4-dimethylphenyl)oxymethyl-S- tetrahydropyranyl thiophenol obtained in the above step (4), was slowly dropwise added to 200 ml of a methanol solution of 15.7 g (61.8 mmol) of iodine at room temperature over a period of about 70 minutes. Then, the mixture was stirred for 80 minutes and then cooled with ice. Then, 0.5M sodium thiosulfate was slowly dropwise added thereto until the red color of iodine disappeared. The amount of the dropwise addition was about 200 ml.

Further, 100 ml of water was added thereto, whereupon the formed crystals were collected by filtration and washed with water. The crystals were dissolved in ethyl ether and then dried over anhydrous sodium sulfate. Then, the ether was distilled off under reduced pressure to obtain 5.71 g of crystals.

5.71 g of the crystals were dissolved in 150 ml of

dry ethyl ether, and the solution was slowly added to 100 ml of a suspension of 0.23 g (5.87 mmol) of lithium aluminum hydride in ethyl ether under cooling with ice. Further, 0.23 g (5.87 mmol) of lithium aluminum hydride was added thereto, and the mixture was stirred for 4 hours with ice bath. Then, 0.5 ml of water, 15% sodium hydroxide (0.5 ml) and then 1.5 ml of water were added thereto to destroy an excess reducing agent. Then, the mixture was dried over anhydrous 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)oxymethyl thiophenol. NMR ( CDC£ ₃ )δ 2.25(s,6H), 5.14(s,2H), 6.6-7.8(m,7H) (6) 1.50 g (6.14 mmol) of 2-(2,4- dimethylphenyl)oxymethylthiophenol obtained in the above step (5) was dissolved in 25 ml of dry methylene chloride, and under cooling with ice, 0.37 g (6.45 mmol) of methyl isocyanate and then two drops of triethylamine were added thereto. The mixture was stirred overnight at room temperature, and then 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 (yield: 89%) of the desired product (Compound No. 8). Melting point: 114-115°C NMR ( COC ₃ ) δ 2.23(s,6H) , 2.78(d,3H,J=5Hz) , 5.15(s,2H),

5.4(bs,lH), 6.6-7.8(m,7H) SYNTHESIS EXAMPLE 4

Synthesis of 2-(2,4-dimethylphenyl)oxymethyl-S- methoxycarbonyl thiophenol (Compound No. 7) 1.50 g (6.14 mmol) of 2-(2,4-dimethylphenyl)oxymethyl thiophenol obtained in Synthesis Example 3 (5) and 0.75 g (7.37 mmol) of triethylamine were dissolved in 25 ml of dry acetonitrile, and under cooling with ice, 0.70 g (7.37 mmol) of methyl chlorocarbonate was added thereto. The mixture was stirred overnight at room temperature, then diluted with methylene chloride, washed twice with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane/ethyl acetate = 20/1 to 10/1) to obtain 1.67 g

(yield: 90%) of the desired product. Melting point: 39-

41°C

NMR (CDC-^ ₃ )<52.25(S,6H), 3.77(s,3H), 5.16(s,2H), 6.6-

7.7(m,7H) SYNTHESIS EXAMPLE 5

Synthesis of 2-(2,4-dimethylphenyl)oxyethyl-0- methylaminocarbonylphenol (Compound No. 12)

(1) 13 ml of acetyl chloride was added to 130 ml of dry methanol under cooling with ice, and the mixture was stirred for one hour at room temperature. Then, 25.6 g (168 mmol) of 2-hydroxyphenylacetic acid was gradually added thereto, and the mixture was stirred overnight at

room temperature. The solvent was distilled off under reduced pressure, and the residue was dissolved again in 350 ml of ethyl acetate, washed three times with a saturated sodium bicarbonate aqueous solution and then with water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The obtained crystals were collected by filtration and thoroughly washed with hexane to obtain 26.3 g (yield: 94%) of methyl 2-hydroxyphenyl acetate. (2) 13.3 g (80 mmol) of methyl 2-hydroxyphenyl acetate obtained in the above step (1) was dissolved in 100 ml of di ethylformamide, and 12.3 g (88.8 mmol) of potassium carbonate was added thereto. The mixture was stirred for one hour at room temperature. A solution of 15.4 g (87.2 mmol) of benzyl bromide in 50 ml of dimethylformamide was gradually added thereto. The mixture was stirred overnight at room temperature. The reaction mixture was poured into 500 ml of ice water and then extracted three with ethyl acetate. The ethyl acetate layers were put together and washed four times with water and once with a saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue thereby obtained was purified by silica gel column chromatography (hexane/ethyl acetate = 10/1 to 5/1) to obtain 18.2 g (yield: 89%) of methyl 2- benzyloxyphenyl acetate.

NMR ( CDC^ ₃ )S 3 . 59 ( s , 3H) , 3 .67 ( s , 2H) , 5 . 07 ( s , 2H) , 6 . 7- 7 . 6 (m, 9H)

(3) 100 ml of a dry ethyl ether solution of 18.2 g (71 mmol) of methyl 2-benzyloxyphenyl acetate obtained in the above step (2) was added to a suspension of 4.04 g

(106 mmol) of lithium aluminum hydride in 250 ml of ethyl ether under cooling with ice, and the mixture was stirred for one hour at the same temperature and then overnight at room temperature. Under cooling with ice, the mixture was treated by a conventional method to obtain 2- benzyloxyphenyl ethanol as an oily substance.

(4) 8.10 g (42.5 mmol) of p-toluene sulfonyl chloride was gradually added to a methylene chloride solution of a half the amount of 2-benzyloxyphenyl ethanol obtained in the above step (3) and 4.48 g (44.3 mmol) of triethylamine, under cooling with ice. The mixture was stirred for 30 minutes under cooling with ice and overnight at room temperature. The reaction was not completed. Therefore, 4.48 g of triethylamine and 8.10 g of sulfonyl chloride were further added thereto, and the mixture was again reacted overnight at room temperature. The reaction mixture was poured into 200 ml of ice water, and the methylene chloride layer was separated, further washed with IN hydrochloric acid, a saturated sodium bicarbonate aqueous solution, water and a saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate. The solvent was distilled off

under reduced pressure. The residue thereby obtained was purified by silica gel column chromatography to obtain 12.3 g of 2-benzyloxyphenylethanol p-toluene sulfonate. NMR (CDC* ₃ )£ 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) 0.66 g (16.5 mmol) of sodium hydride was suspended in 30 ml of dimethylsulfoxide, and a solution of 1.83 g (15 mmol) of 2,4-xylenol in 10 ml of dimethylsulfoxide was added thereto. The mixture was stirred for 20 minutes under cooling with ice (until solidification). A solution of 5.16 g (13.5 mmol) of 2- benzyloxyphenylethanol p-toluene sulfonate in 10 ml of dimethylsulfoxide was added thereto, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into 300 ml of ice water and extracted three times with 100 ml of ethyl acetate. The ethyl acetate layers were put together, then washed three times with water and then with a saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to obtain 2-(2, - dimethylphenyl)oxyethyl O-benzylphenol.

(6) 2-(2,4-dimethylphenyl)oxyethyl O-benzylphenol obtained in the above step (5) was dissolved in 150 ml of ethyl acetate, and 1 g of 5% palladium-carbon was added thereto. The mixture was reacted overnight under a

hydrogen atmosphere. The catalyst was filtered off by Celite, and the filtrate was concentrated under reduced pressure and further purified by silica gel column chromatography (ethyl acetate/hexane = 1/10 to 1/5) to obtain 1.76 g (yield of two steps: 54%) of 2-(2,4- dimethylphenyl)oxyethylphenol. NMR (CDC ₃ )£ 2.28(s,6H), 3.17(t,2H,J=6Hz) , 4.25(t,2H,J=6Hz), 6.6-7.5(m,7H)

(7) 0.88 g (3.63 mmol) of 2-(2,4- dimethylphenyl)oxyethylphenol was dissolved in 25 ml of dry methylene chloride, and 0.23 g (3.99 mmol) of methyl isocyanate and then two drops of triethylamine were added thereto with cooling with ice. The mixture was stirred overnight at room temperature. Then, 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 (yield: 79%) of the desired product. Melting point: 103-105°C NMR ( CDC£ ₃ )δ 2.27(s,3H), 2.36(s,3H), 2.98(d,3H,J=5Hz) , 3.39(t,2H,J=7.5Hz), 4.25(t,2H,J=7.5Hz) , 5.01(brs,lH) , 6.7-7.6(m,7H) SYNTHESIS EXAMPLE 6

Synthesis of 2-(2,4-dimethylphenyl)oxyethyl-0- methoxycarbonylphenol (Compound No. 11) 0.88 g (3.63 mmol) of 2-(2,4- dimethylphenyl)oxyethylphenol obtained in Synthesis Example 5 (6) and 0.44 g (4.36 mmol) of triethylamine

were dissolved in 25 ml of dry acetonitrile, and 0.41 g (4.36 mmol) of methyl chlorocarbonate was added thereto under cooling with ice. The mixture was stirred overnight at room temperature, then diluted with 150 ml of methylene chloride, washed with water and dried over ^' anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 0.97 g (yield: 89%) of the desired product. NMR (CDC^ ₃ )£ 2.13(s,3H), 2.24(s,3H), 3.08(t,2H,J=7Hz) , 3.87(s,3H), 4.16(t,2H,J=7Hz), 6.6-7.5(m,7H)

Table 1

Table 2

( B) m

-OCH ₃ H ( α-methyl-3-me hylbenzylidene ) aminoxy

-OCH ₃ H ( α-methyl-3-methoxybenzylidene ) aminoxy

-OCH ₃ 6-OCH ₃ ( <_.-methyl-3-methylbenzylidene ) aminoxy

-OCH ₃ 6-OCH ₃ ( αr-methyl-3-methoxybenzylidene ) aminoxy

-NHCH ₃ H ( c.-methyl-3-methylbenzylidene ) aminoxy

-NHCH ₃ H ( α-methyl-3-methoxybenzylidene ) aminoxy

-NHCH ₃ 6-OCH ₃ ( αr-methyl-3-methylbenzylidene ) aminoxy

-NHCH ₃ 6-OCH ₃ ( α-methyl-3-methoxybenzylidene ) aminoxy

-NHCH-, H ( α-methyl-3 , 4-dimethylbenzylidene ) aminoxy

-OCH ₃ H ( α-methyl-3 , 4-dimethylbenzylidene ) aminoxy -NHCH, H ( α-methyl-3 , 4-dimethylbenzylidene ) aminoxy

Table 3

Table 4

A description will now be made of Test Examples of testing the compound of the present invention as an agricultural and horticultural fungicide. The evaluation of performance was made according to the following ratings unless otherwise specified. Criteria of evaluation

The control effect was visually observed in terms of the degree of disease outbreak on test plant on the day of observation to give one of the following five ratings as an index of control:

Rating Degree of disease outbreak

5 No lesions are recognizable at all.

4 The area, number or length of lesions is less than 10% of that in the non-treated plot. 3 The area, number or length of lesions is less than 40% of that in the non-treated plot.

2 The area, number or length of lesions is less than 70% of that in the non-treated plot.

1 The area, number or length of lesions is 70% or more of that in the non-treated plot.

TEXT EXAMPLE 1 (Test on preventive effect against cucumber powdery mildew)

Cucumber (cultivar: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When the cucumber reached a one-leaf stage, it was sprayed with 10 ml of a solution having predetermined active ingredient concentration through a spray gun. The pot was kept in a

constant-temperature chamber at 22 to 24°C for about 24 hours, after which the cucumber was dusted and inoculated with conidia of fungi of powdery mildew (Sphaerotheca fuliqinea) . Eighth day after the inoculation, the area of lesions on the first leaf was examined to find a rating as the index of control according to the above- mentioned criteria for evaluation. The results were as follows.

Compound No. 1 exhibited a rating of 4 as the index of control at a concentration of 500 ppm and Compound No. 4 exhibited a rating of 5 as the index of control at a concentration of 250 ppm.

TEXT EXAMPLE 2 (Test on preventive effect against cucumber downy mildew) Cucumber (cultivar: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When the cucumber reached a two-leaf stage, it was sprayed with 10 ml of a solution having a predetermined active ingredient concentration through a spray gun. The pot was kept in a constant-temperature chamber at 22 to 24°C for about 24 hours, after which the cucumber was sprayed and inoculated with a spore suspension of fungi of downy mildew (Pseudoperonospora cubensis) . Fifth to seventh day after the inoculation, the area of lesions on the first leaf was examined to find a rating as the index of control according to the aforementioned criteria for evaluation.

Compound Nos. 7, 8, 13, 14 17 and 18 exhibited a rating of 5 as the index of control at a concentration of 500 ppm, and Compound Nos. 2, 15, 16, 19, 20 and 23 exhibited a rating of 4 as the index of control at a concentration of 500 ppm.

TEXT EXAMPLE 3 (Test on preventive effect against rice blast)

Rice plant (cultivar: Koshihirakri) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When the rice plant reached a four-leaf stage, it was sprayed with 20 ml of a solution having a predetermined active ingredient concentration through a spray gun. The pot was kept in a constant-temperature chamber at 22 to 24°C for about 24 hours, after which the rice plant was sprayed and inoculated with a spore suspension of fungi of blast (Pyricularia oryzae) . Fifth to seventh day after the inoculation, the number of lesions was examined to find a rating as the index of control according to the aforementioned criteria for evaluation. Compound Nos. 1 and 9 exhibited a rating of 5 as the index of at a concentration of 500 ppm and Compound Nos. 11, 19 and 22 exhibited a rating of 4 as the index of control at a concentration of 500 ppm. TEST EXAMPLE 4 (Test on preventive effect against tomato late blight)

Tomato (cultivar: Ponderosa) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When the

tomato reached a four-leaf stage, it was sprayed with 10 ml of a solution having a predetermined active ingredient concentration through a spray gun. The pot was kept in a constant-temperature chamber at 22 to 24°C for about 24 hours, after which the tomato plant was sprayed and inoculated with a zoosporangia suspension of fungi of late blight (Phytophthora infestans) . Third to fourth day after the inoculation, the area of lesions was examined to find a rating as the index of control according to the aforementioned criteria for evaluation.

Compound Nos. 6, 9 and 10 exhibited a rating of 5 as the index of control at a concentration of 500 ppm and Compound Nos. 22, 24 and 25 exhibited a rating of 4 as the index of control at a concentration of 500 ppm. TEST EXAMPLE 5 (Test on preventive effect against cucumber gray mold)

Cucumber (cultivar: Suyo) was cultivated in a polyethylene pot having a diameter of 7.5 cm. When the cucumber reached a two-leaf stage, it was sprayed with 10 nil of a solution having predetermined active ingredient concentration through a spray gun. The pot was kept in a constant-temperature chamber at 22 to 24°C for about 24 hours, after which the first leaf was inoculated with a spore suspension of fungi of Benomyl- and dicarboximide- sensitive gray mold (Botrytis cinerea) in a potato glucose broth. Third day after the inoculation, the length of lesions was examined to find a rating as the

index of control according to the above-mentioned criteria for evaluation.

Compound Nos. 7, 17 and 18 exhibited a rating of 5 as the index of control at a concentration of 500 ppm, and Compound Nos. 3 and 8 exhibited a rating of 4 as the index of control at a concentration of 500 ppm.

An aqueous dispersion containing from 25 to 200 ppm of Compound No. 17, 18 or 23 and from 25 to 200 ppm of Fluazinam or Chlorophthalonil, as active ingredients, is applied to the locus of plants such as cucumber, egg plant and grape, where gray mold is infested, whereby the growth of the gray mold is excellently controlled.