WO1998031665A1

WO1998031665A1 - N-phenylthioura derivatives, process for the preparation thereof, fungicides for agricultural and horticultural use containing the same as the active ingredient, and intermediates for the preparation thereof

Info

Publication number: WO1998031665A1
Application number: PCT/JP1998/000049
Authority: WO
Inventors: Shinya Henmi; Seiji Kakinuma; Kiyoshi Takasuka; Hideyo Fujii; Syuichi Usui; Noriyoshi Katsuyama; Shunnosuke Watanabe
Original assignee: Agro-Kanesho Co., Ltd.
Priority date: 1997-01-16
Filing date: 1998-01-09
Publication date: 1998-07-23
Also published as: AU5342598A

Abstract

N-phenylthiourea derivatives useful as fungicides for agricultural and horticultural use which exhibit excellent activities particularly even at low concentrations. The derivatives are represented by general formula (I) with compounds represented thereby wherein A is CH2-O-A2; A2 is represented by formula (1) and V is -(R5)=NOR6 being particularly preferable.

Description

Specification

N-phenylthioperia derivative, its production method,

Agricultural and horticultural fungicides containing this as an active ingredient, and intermediates for the production thereof

The present invention relates to an N-phenylthiourea derivative, a method for producing the same, an agricultural and horticultural fungicide containing the same as an active ingredient, and an intermediate for producing the same. Background technology

Agricultural and horticultural fungicides relating to N-phenyl perylene-related compounds or N-phenyl thioperrea-related compounds have been known. Previously unknown. Accordingly, it is an object of the present invention to provide an N-phenylthioperylene derivative having an excellent bactericidal effect, particularly at a low concentration. Disclosure of the invention

The present inventor has conducted extensive research and research on agricultural and horticultural fungicides, and as a result, found that among compounds having an N-fuunyl thiourea skeleton, compounds having a specific structure exhibit excellent fungicidal activity at low concentrations. The invention has been completed.

That is, an object of the present invention is to provide a compound represented by the following general formula (I).

(In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, an alkyl group, a halogenated aralkyl kill group, an alkoxy group, a halogenated C alkoxy group, C ₃ - a ₅ alkynyl group, - ₅ alkenyl group or C ₃

R ′ ² is a hydrogen atom or a C, _—3 alkyl group,

R ³ is a d- ₃ alkyl group;

X and Y are independently hydrogen, halogen, On alkyl, halogenated

A C alkyl group, a d alkoxy group, a halogenated alkoxy group, a cyano group, or a nitro group;

A represents — 0— A ¹ , — CH ₂ — 0— A ² or — CH ₂ ON2 C (R ⁴ ) —A ³ ,

R 'is a C, _-3 alkyl group;

A ¹ is

And Here, X ′ and Y ′ are independently a hydrogen atom, a halogen atom, c, — _:

Halogenated ₃ alkyl _{group,: 1} alkoxy group, halogenated C an alkoxy group, an Shiano group or a nitro group,

A ²

Or — Aa

Z ヽ, Aa

Where Z is N or CH;

U represents a hydrogen atom, a halogen atom, _alkyl group, halogenated C doctor ₆ alkyl group, ₆ alkoxy group, halogenated - ₆ alkoxylated group, Shiano group, a nitro group or A a,

V is a hydrogen atom, a halogen atom, a Ci alkyl group, a halogenated alkyl group, a d alkoxy group, a dogenated d alkoxy group, a cyano group, a nitro group, an alkylcarbonyl group, a Ci ₆ alkoxycarbonyl group or —C (R ⁵ ) = NOR ⁶ groups,

R ⁵ is a hydrogen atom, C, - ₆ alkyl group, a halogenated 0 ₆ alkyl group or A a,

R ⁶ is a hydrogen atom, an alkyl group, a halogenated d alkyl group, (: ₃ _-5 alkenyl group, halogenated C ₅ alkenyl group, C _{3 5} alkynyl group or a halogen of C _{3 5} alkynyl, W is a hydrogen atom, a halogen atom, C, - _t; alkyl group, a halogenated ds alkyl le group, C, - an e alkoxy group or a halogenated C Bok ₆ alkoxy group,

A ³ is one C (R ⁵ ) = NOR ⁶ , Aa or

Is shown. DESCRIPTION OF EXEMPLARY EMBODIMENTS

Hereinafter, the present invention will be described in detail.

The meanings of the groups in the Ν-phenylthioperia derivative of the above formula (I) are as follows.

R ¹ is a hydrogen atom, a hydroxyl group, a C, _-3 alkyl group, a nitrogenated d- ₃ alkyl group,

A C alkoxy group, a halogenated d alkoxy group, a C ₃ -alkenyl group or

Ca is an alkynyl group. Here, the alkyl group having 1 to 3 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Accordingly, examples of the halogenated C ₃ alkyl include a trifluoromethyl group, a difluoromethyl group, a 2-trifluoroethyl group, a 2-chloroethyl group, and the like. Examples of the ₃ alkoxy include a methoxy group, an ethoxyquin group, an n- or isopropoxy group, and the like. Further, as the halogenated ₃ alkoxy, for example, and Jifurorome butoxy group, 2-click Roroetokin group. The alkenyl group having 3 to 5 carbon atoms may be linear or branched, and includes, for example, an aryl group, a 2-butenyl group, 1-methyl-2-propenyl and the like.

The alkynyl group having 35 carbon atoms may be linear or branched, and examples thereof include a propargyl group and a 2-butynyl group.

The alkoxy group having 13 carbon atoms is an alkoxy group of an alkyl group having 13 carbon atoms, and the range of the alkyl group is as described above.

R ² is a hydrogen atom or a _3-alkyl group. The range of the Ci- ₃ alkyl group is as described above. R ² is preferably a hydrogen atom.

Is a d alkyl group, the range of which is as described above.

X and Y are independently a hydrogen atom, a halogen atom, a _—3 alkyl group, a halogenated

A C alkyl group, a C, _-3 alkoxy group, a halogenated alkoxy group, a cyano group or a group; Here, the ranges of the C alkyl group and the halogen atom are as described above.

A is represented by one 0—A ¹ , one CH ₂ —0—A ² or one CH ₂ ON = C (R ⁴ ) —A ³ . Here, R ⁴ is a C, _-3 alkyl group, and its range is as described above.

A ¹ is a group represented by the following formula.

(Aa)

Here, X ′ and Y ² independently represent a hydrogen atom, a halogen atom, a ₃ alkyl group, a halogenated ₃ alkyl group, a ₃ alkoxy group, a halogenated ₃ A oxy group, a cyano group, or a nitro group ₍ the range of a halogen atom, an alkyl group, an alkoxy group, etc. is as defined above ₍

A ² is the following functional group.

Aa,

Or one Aa

Z ヽ, Aa

Here, Z is N or CH, U is a hydrogen atom, a halogen atom, d - s § alkyl group, a halogenated - ₆ alkyl group, - ₆ alkoxy groups, halogenated C i alkoxylated group, Shiano group, It is a nitro group or Aa. Examples of the alkyl group include a methyl group, an ethyl group, an n- or isopropyl group, an n-, iso-, s- or t-butyl group, and neopentyl. The range of the halogen atom is as described above. Therefore, a halogenated C, - as the _s alkyl, for example, Torifuruoro or methyl, trichloromethyl, 2-Kuroroechiru, 3 black port propyl, 3-Bed Romopuropiru, 5-bromopentyl, like hexyl group into 6- black port No. Examples of the ₆ alkoxy group include a methoxy group, an ethoxyquin group, an n- or isopropoxy group, _n- , an iso-, s-, or t-butoxy group, and a neopentoxy group. Examples of the nodulated d-s alkoxy include, in particular, trifluoromethoxy, difluoromethoxy, 2-chloroethoxy, 2-trifluoroethoxy, 3-chloropropyloxy, 3-bromopropyloxy and the like.

V is a hydrogen atom, a halogen atom, a ds s alkyl group, a halogenated C ₆ alkyl group, a ₆ alkoxy group, a halogenated _s alkoxy group, a cyano group, a nitro group. —C, — «alkylcarbonyl group, d—s alkoxycarbonyl group, —C (R ⁵ ) = N 0 R ″. C i— ₁ in d—s alkylcarbonyl group and C n alkoxycarbonyl group _;.! range alkyl groups are as previously described C - ₆ the alkyl force Ruponiru group, for example, a methyl group, E chill carbonyl group, flop port pills carbonyl group, an isopropyl group, a butyl group, Examples include an isobutylcarbonyl group, an S-butylcarbonyl group, a t-butylcarbonyl group, an n-heptylcarbonyl group, an isoheptylcarbonyl group, a hexylcarbonyl group, etc. Particularly, a methylcarbonyl group and an ethyl group A carbonyl group is preferred.

Examples of the C, -6 alkoxycarbonyl group include those corresponding to the above ₆ alkylcarbonyl group. The range of the other functional groups is as described above.

R ⁵ is a hydrogen atom, a ds alkyl group, a halogenated C ₆ -6 alkyl group or A a. The ranges of the Ci- ₆ alkyl group and the halogenated Ci-6 alkyl group are as described above.

A a

Is a functional group represented by The ranges of X ′ and Y ² are as described above.

R ⁶ is a hydrogen atom, _d-6 alkyl group, a halogenated C, -6 alkyl group, C 5 alkenyl group, halogenated C 3-5 alkenyl group, C _{3 5} alkynyl group or a halogen of C 3-5 alkynyl And the range of these functional groups is clear from the above. Here, the halogenated C _{3 5} alkenyl group, e.g., 3-Kuroroari Le and the like. Examples of the halogenated C _{3 5} alkynyl group, for example, 3- ® chromatography Dopronogill can be mentioned.

w is a hydrogen atom, a halogen atom, a ₆ alkyl group, a halogenated C alkyl group, a C, —s alkoxy group or a halogenated C ₆ alkoxy group, and the range of these functional groups is clear from the above. It is.

A ³ is — C (R ⁵ ) = 0 R ⁶ , A a or the following group.

, 丫 1

Here, X 'and Upsilon ² ranges are as described above.

Among the diphenylthiourea derivatives of the present invention, particularly, one CH: 0—A, and A ² is

U

And N-phenylthiodialea derivatives which are -C (R ⁵ ) 2 NOR ⁶ groups are preferred.For example, even at a low concentration of 64 ppm or less, preferably 16 ppm J It has an excellent germicidal effect for agriculture and horticulture as compared with the above compound.

The N-phenylthioperia derivative of the present invention can be produced by a known method. In addition, the N-phenylthioperia derivative of the present invention can be produced as a mixture of E / Z isomers, geometric isomers, optical isomers, diastereomers, and the like. In the case where the N-fluorothiodiarea derivative of the present invention is obtained as a mixture of isomers, it may be obtained by an ordinary method, for example, by recrystallization or chromatography. Can be separated into various isomers ₍

Method for producing N-phenylthiodiarea derivative

Manufacturing route (A)

1)

NHR.

(Wherein, the meaning of the group is as described above.) A-one way

In this method, the compound represented by the formula (II) is reacted with the compound represented by the formula (II) usually in the presence of a solvent and a base. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and benzene; halogenated aliphatic hydrocarbons such as carbon form, carbon tetrachloride, methylene chloride, dichloroethane, and trichloroethane; Cyclic or acyclic aliphatic hydrocarbons such as n-hexane and cyclohexane; ethers such as getyl ether, dioxane, and tetrahydrofuran; ketones such as acetoneton, methyl ethyl ketone, and methyl isobutyl ketone

Nitriles such as acetate nitrile and propionitrile; and aprotic polar solvents such as dimethylformamide, N-methyl-12-pyrrolidone, dimethyl sulfoxide and sulfolane.

The base may be either an inorganic base or an organic base. As the inorganic base, for example, sodium hydroxide, potassium hydroxide metal oxide such as potassium hydroxide hydroxide; sodium carbonate carbonate free, potassium hydroxide metal such as anhydrous calcium carbonate or potassium earth metal Carbonates; alkaline metal hydrides such as sodium hydride; alkaline metals such as sodium metal, and the like.

Examples of the organic base include, for example, pyridine, triethylamine, diisopropylethylamine and the like.

The reaction temperature is usually from 120 ° C to the boiling point of each solvent, preferably from 0 to

50 ° C. The reaction time is generally 0.1 to 24 hours, preferably 0.5 to 12 hours.

A—Method 2

In this method, the compound represented by the formula (II) is reacted with thiophosgene, usually in the presence of a solvent, optionally in combination with a base. Solvent and base The same ones used in the method (A-1) can be used. The reaction temperature and reaction time are also the same as those described above.

The product thus obtained is isolated or purified or reacted with the conjugate (IV) without isolation and purification to produce the compound of the formula (I).

A-one three way

In this method, the compound represented by the formula (II) is usually reacted with an isothiosocyanate represented by the formula (V) in the presence of a solvent and optionally in the presence of a catalyst to obtain the compound represented by the formula (II). One of the compounds represented by I) (1-1) is produced. Examples of the solvent include the same solvents as those used in the above-mentioned method (A-1). Examples of the catalyst include boron trifluoride, acids such as hydrochloric acid, aluminum chloride, alkyltin chloride, and alkyltin acetate; triethylamine, pyridine, dimethylaniline, dimethylaminopyridine, 1,4-diazabicyclo (2.2). .2) Bases such as octane, N-methylbiperidine, sodium acetate and the like. The reaction temperature is usually from 120 ° C to the boiling point of the solvent, preferably from 0 to 50 ° C, and the reaction time is preferably from 0.5 to 24 hours, particularly preferably from 1 to 12 hours. Time is appropriate.

The intermediate represented by the general formula (II) can be produced according to the following production route (B) or (C).

Manufacturing route (B)

Examples of the production route include those represented by the following formula ₍

B-1 way

In this production route, nitrobenzene derivatives obtained by standard methods are reduced, for example, using hydrogen or a hydrogen source such as ammonium formate in the presence of a catalyst such as Pd, Pt or Ni. , then _c Anirin derivative (II one 1) is obtained, resulting Anirin derivative (II- 1), by reaction with R ¹ '-Hal in the usual manner to obtain compound (pi-2) be able to. Wherein, R ¹ '- R "s is Hal, preferably, C, - ₃ alkyl group, a halogenated C ₃ alkyl group, C ₃ - 5 alkenyl group or C ₃ -. Shows the ₅ alkynyl group other functional groups , X, Y, A, and Hal are as described above.

B—Method 2

In this method, except that the aniline derivative (II-11) is obtained by reacting a phthalanilide derivative with hydrazine or monomethylamine, etc. Same as 1 ₍ Production route (C)

(In the formula, R ¹ ″ represents a _3- alkyl group or a halogenated C alkyl group, and the range is as described above. Other X, Y, A, and Hal are as described above.) For example, it can be reacted with ammonium chloride in the presence of zinc to obtain a phenylhydroxyamine derivative (III-3) (Organic Syntheses Collective Vol III p668 (1955)). Then, formylation is performed with formic acid and acetic anhydride to obtain an N-hydroxyformanilide derivative (other than a formyl group, if appropriate as a protecting group).

Next, the N-hydroxyformanilide derivative is reacted with R '"-Hal to obtain an N-alkoxyformanilide derivative, which is then hydrolyzed under alkaline or acidic conditions to give N-hydroxyformanilide derivative. An alkoxyaniline derivative (II-4) can be obtained. As described above, an N-alkoxyanilin derivative can be easily and inexpensively produced from an N-alkoxyformanilide derivative. Conventional methods have not found such a simple and inexpensive manufacturing method.

In this hydrolysis reaction, an organic solvent mixture of an aqueous solution is preferable. Examples of such an organic solvent include methanol, ethanol, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, acetonitrile, and dimethylformamide. , N-methyl-12-pyrrolidone, dimethylsulfoxide, sulfolane and the like.

The aqueous solution of sodium hydroxide includes sodium hydroxide, potassium hydroxide, carbonate carbonate, sodium carbonate, monomethylamine, etc., for example, 0.1 to 50%, preferably 1 to 30%. % Solutions are used. As the acidic aqueous solution, it is suitable to use hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, phosphoric acid, etc., for example, having a concentration of 0.1 to 50%, preferably 1 to 30%. It is.

The hydrolysis is preferably carried out at a temperature of from −20 ° C. to the boiling point of the solvent, particularly preferably from 0 to 50 ° C., and the reaction time is, for example, from 0.1 to 24 hours, preferably from 0.1 to 24 hours. 1 to 12 hours is appropriate.

The N-alkoxyaniline derivative (II-4) can be produced, for example, according to the following production route (D). .

(Wherein, A '= A ² or N double C (R ⁴⁾ shows an ^{^{^{A 3, A 2, A 3}}} , R 4, R 1 ", Hal are as defined above.)

This route can be produced from a nitrobenzene derivative to an N-alkoxyformylaniline derivative by the same method as in Production Route C.

Then, in the presence of a free-radical initiator, for example, azobisdisoptyronitrile, for example, with N-promosuccinimid, bromine, chlorine or SO ₂ C ₁₂ , or by free-radical halogen exposure to ultraviolet light Thus, a hydride derivative can be obtained.

Then, it is reacted with A'-OH by a usual method, and N-alkoxyaniline (Π-4) can be obtained by hydrolysis.

The N-funinylthioperia derivative represented by the general formula (I) of the present invention is useful as a fungicide for agricultural and horticultural use, for example, rice blast (Pyricularia oryzae), rice sheath blight (Rhizoctonia solani), and rice Sesame leaf blight (Chochl iobolus miyabeanus), oats, oat spot disease (Pseudocercosporel la herpotrichoides; oats, barley powdery mildew (Erysip he graminis), powdery mildew (Sphaerotheca ful iginea), buttocks (Uncinula necator), powdery mildew on various host plants, crown rust of enbac (Puccinia coronata) and Rust on other plants, Botryt is cinerea on grape and Botryt is cinerea on other plants, Sclerot i nia sclerot iorum and Scab on other plants, Phytophthora on potato infesta ns) and other plant plague, cucumber downy mildew (Pseudoperonospora cubens is), budo downy mildew (Plasmopara vi U cola) and other plant downy mildews, apple scab (Venturia inaequal is), Various plants such as pear scab (Venturia nashi cola) and other scabs, apple spot leaf rot (Al ternaria mal i), pear black scab (Al ternaria kikuc hiana) and other plants Alternaria disease and apple monilia disease (Moni l inia mal i), 祧星 (Moni l ini a fruct i cola) and Monilia's disease of fruit trees, citrus black spot (Di aporthe ci tr i) ヽ Very high control effect against diseases such as citrus blue mold (Penici 11 ium i tal i cum), especially at low concentrations Has an excellent control effect.

The fungicide for agricultural and horticultural use of the present invention has a remarkable bactericidal effect on the above-mentioned diseases that damage paddy field crops, field crops, fruit trees, vegetables, other crops, flowers and the like. Treatment of paddy fields, fields, fruit trees, vegetables, other crops, flowers and other paddy water, foliage or soil, seeds, and bulbs before or at the time when the disease is predicted By doing so, the desired effect of the agricultural and horticultural fungicide of the present invention is exhibited.

The concentration of the compound of the present invention used Z varies depending on the target crop, the method of use, the formulation form, the application rate, etc., and cannot be specified unconditionally. However, in the case of foliage treatment, it is usually 0.1 to 10 per active ingredient. It is in the range of 0.000 ppm, preferably 1-2 ppm.

The compound of the present invention may be used in combination with other pesticides, if necessary, such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, plant growth regulators, etc. In this case, the effect may be even better. Examples of the active ingredient compound of the insecticide, acaricide, or nematicide include, for example, 1- (4-bromo-12-chlorophenyl) 0-ethyl S-propylphosphorothioate (generic name: profenophos) , Poly (2,2-dichlorovinyl) 0,0-Dimethylphosphonate (generic name: dichlorvos), 0-Ethyl 0— [3-Methyl 4- (methylthio) phenyl] N-Isopropyl phosphoramidate Generic name: phenamiphos), 〇, 0-dimethyl 0— (412-m-tolyl) phosphorothioate (generic name: dinitrothion), 0-ethyl 0— (4-nitrophenyl) phenylphosphonothio Aeto (generic name: EPN), 0, 0—Jetil

0-(2-Isopropyl-6-methylpyrimidine-14-yl) phosphorothioate (generic name: diazinon), 0,0-dimethyl 0- (3,5,6-trichloro-1-2-pyridyl) phosphoro Thioate (generic name: chlorpyrifosmethyl), 0, S-dimethyl N-acetyl phosphoroamidothioate (generic name: acephate), 0— (2,4-dichlorophenyl) 0-ethyl S-propylphospho dithioate Organics (generic name: protifos), (RS) —S—sec—butyl diethyl 2—oxo-1,3—thiazolidine-13—ylphosphonothioate (generic name: phosthiazate) Phosphate ester compounds;

1-naphthyl N-methylcarbamate (generic name: valvalyl), 2-isopropoxyphenyl N-methylcarbamate (generic name: propoxur), 2-methyl-2- (methylthio) propionaldehyde 0-methylcarbamoyloxysim (Generic name: aldicarp), 2,3-dihydro-1,2,2-dimethylbenzofuran-7-yl N-methylcarbamate (generic name: carbofuran), dimethyl

N, Ν '-[Thiobis ((methylimino) carbonyloxy)] bisethaneimido thioate (generic name: thiodicarb), S-methyl Ν— (methylcarbamoyloxy) thioacetimidate (generic name: mesomemil), Ν, Ν _Dimethyl 2

—Methylcarbamoyloxyiminow 2— (methylthio) acetamide (generic name : Oxamil), 2- (ethylthiomethyl) phenyl N-methylcarbamate (generic name: ethiofencarp), 2-dimethylamino-5,6-dimethylpyrimidine-14-yl N, N-dimethylcarbamate (generic name) : Pirimi curve),

Carbamate compounds such as 2-sec-butylphenyl N-methylcarbamate (generic name: phenocarb);

S, S '— 2-dimethylamino trimethylenebis (thiocarbamate) (general name: cartap), N, N-dimethyl_1,2,3-trithian-15-ylamine (generic name: thiocyclam) Nereistoxin derivative;

2,2,2-Trichloro-1,1-bis (4-chlorophenyl) ethanol (generic name: dicophor), 4-chlorophenyl-1,2,4,5-trichloromethylphenyl sulfone (generic name: tetradiphone) Such organochlorine compounds;

Organometallic compounds such as bis [tris (2-methyl-2-phenylpropyl) tin] oxide (generic name: fenbutatin oxide);

(RS) —α-cyano 3-phenoxybenzyl (RS) — 2- (4-chlorophenyl) -1,3-methylbutyrate (generic name: fenvalerate), 3-phenylquinbenzyl (1RS) —Cis, trans-1— (2,2-dichlorovinyl) -1,2,2-dimethylpropanecarboxylate (generic name: permethrin), (RS) -1-α-cyano-3-phenoxybenzyl (1 RS) ) —Cis, trans

3- (2,2-dichlorovinyl) -1,2,2-dimethylcyclopropanecarboxylate (generic name: cypermethrin), (S) —Hycyan-1-3-phenyloxybenzyl (1R) —cis-13 — (2,2-dibutyric vinyl) 1,2,2-dimethylcyclopropanecarboxylate (generic name: deltamethrin), (RS) —α-cyano 3-phenoxybenzyl (1RS) —cis, trans One 3— (2—Black mouth one)

3,3,3-Trifluoropropynyl) 1,2,2-dimethylcyclopropanecarboxylate (generic name: cyhalothrin), 4-methyl-2,3,5,6-tetra Fluorobenzyl-1- (2-chloro-1,3,3,3-trifluoro-1-propenyl) -1,2-dimethylcyclopropanecarboxylate (generic name: tefluthrin), 2- (4-ethoxyphenyl) A) pyrethroid compound such as 1-methylpropyl 3-phenoxybenzyl ether (generic name: ethoproplon);

1— (4—Chlorophenyl) 1— (2,6-Difluobenzoyl) ゥ rea (generic name: difluvenzuron), 1— [3,5-dichloro4-1 (3-—Chloro-1-5- Trifluoromethyl-1-2-pyridyloxy) phenyl] 1-3- (2,6-difluorobenzoyl) ゥ rea (generic name: chlorofluazuron), 1- (3,5-dichloro-1 2,4- Benzoyl perylene compounds such as difluorophenyl) 1- (2,6-difluorobenzoyl) perylene (generic name: tefluvenzuron); isopropyl (2E, 4E) — 11 1-methoxy-1 3, Juvenile hormone-like compounds such as 7,1 1-trimethyl-2,4-dodecadienoate (common name: methoprene);

Pyridazinone compounds such as 2 — t-butyl-5 — (4 — t — butylbenzylthio) 1-4 1-chloro-3 (2 H) — pyridazinone (generic name: pyridaben); t-butyl 4 _ [ Pyrazole-based compounds such as (1,3-dimethyl-15-phenoxyvirazole-4-yl) methyleneaminooxymethyl] benzoate (generic name: phenylpyroximate);

1— (6—black 3—pyridylmethyl) 1 N—nitro 1 imidazolidine 1 2

—Ilideneamine (generic name: imidacloprid), 1— [N_ (6-chloro-3

—Pyridylmethyl) 1-N-ethylamino] 1-methylamino-2-ditrothylene (published No. 302398), 2-methylamino 1 2— [N-methyl-N— (6— 1-nitroethylene 3- (pyridylmethyl) amino

(European publication No. 3 02 3 8 9), 1— (6—Black mouth 3-Pyridylmethi A) Amino-1-dimethylamino-1-nitroethylene (European publication No. 302 389), 1- (6-chloro-3-pyridylmethyl) 1-2- (1-nitro-2-arylthioethylidene) ) Imidazolidine (European publication No. 4 3 7 7 8 4), 1- (6-chloro-1-3-pyridylmethyl) 1-2- (1-nitro-2-ethylthiochiethylidene) imidazolidine Open mouth N 0. 4 3 7 7 8 4), 1- (6-chloro-3-pyridylmethyl) 1-2- (1-nitro-1-2-3-methylarylthioethylidene) imidazolidine No. 4 3 7 7 8 4), 1- (6-chloro-1-3-pyridylmethyl) 1-3-methyl-1-2-nitroguanidine

(European publication No. 383091), 1- (6-chloro-3-pyridylmethyl) 1,3-dimethyl-2--2-troganidine (European publication No. 3830091), 3- (6-cyclo-1--3-pyridylmethyl) 1-2-nitromethylene-thiazolidine (European publication No. 192600), 1- (6-cyclo-1-3-pyridylmethyl) 1-2- (nitro Methylene) 1-imidazolidin (N. 1 6 3 8 5 5), 6- (6-chloro-1-3-pyridylmethylamino) 1,3-dimethyl-1-5-nitro-1, 2,3,4-tetrahydropyrimidine (published in Europe), 1- (6-chloro-3-pyridylmethyl) -1,5-nitro-13-methyl-1-6-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, and other compounds such as 2-tert-butylimino-13-isopropyl-1-5-phenyl-1,3,5,6- Tetrahi draw 2 H— 1, 3,

5-Thiadiazine 4-one (generic name: bubrophedin), trans- (4-chlorophenyl) -1-N-cyclohexyl-1-4-methyl-1-2-oxothiazolidinone

— 3-Carboxamide (generic name: hexthiazox), N-methylbis (2, 4

—Xylyliminomethyl) amine (generic name: amitraz), N '-(4—black mouth — O—tolyl) 1 N, N-dimethylformamidine (general name: chlordimeform). (4-ethoxyphenyl) 1 [3- (4-fluoro-3-phenoxyphenyl) propyl] (dimethyl) silane (generic name) : Silafluofone); and the like. Furthermore, it can be mixed or used in combination with microbial pesticides such as BT agents and entomopathogenic virus agents, and antibiotics such as avermectin and milbemycin.

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

1- (4-Chlorophenoxy) -1,3-dimethyl-11- (1H-1,2,4-triazole-1-yl) butanone (generic name: triadimefon), 1- (biphenyl-1-4 1,3,3-dimethyl_1- (1H, 1,2,4-triazole-1-yl) butan-2-ol (generic name: bitertanol)

[N- (4-chloro-2-trifluoromethylphenyl) -2-propoxyacetoimidyl] imidazole (generic name: trifrenolemizole), 1— [2- (2,4-dichloromethylphenyl) 1-4 1-ethyl-1,3-dioxolan-2-ylmethyl] -1H-1, 2,4-triazolyl (generic name: etaconazole), 1- [2-

(2,4-dichlorophenyl) 1-4-propyl-1 1,3-dioxolan-2-ylmethyl] 1 1H—1,2,4-triazol (generic name: propiconazole), 1- [2 -— (2 , 4-Dichlorophenyl) pentyl] 1 1H-1,2,4-triazole (generic name: penconazole), bis (4-fluorophenyl) (methyl)

(1H-1,2,4-triazole-1-ylmethyl) silane (generic name: flusilazole), 2- (4-chlorophenol) 2- (1H-1,2,4-triazo-1) L-ylmethyl) Hexane nitrile (generic name: microbutanyl), 2 RS, 3 RS) — 2— (4-chlorophenyl) 1 3-cyclopropyl 1 11

(1H-1, 2,4-triazole-1 yl) butane-1-ol (generic name: cyproconazole), (RS) — 1- (4-chlorophenyl) 1-4,4-dimethyl 3- (1H—1,2,4,1-triazole-1-ylmethyl) pentane-3-ol (generic name: terbuconazole), (RS) —2— (2,4-dichlorophenyl) — 1— (1 H— 1, 2, 4, 1-triazole— 1-yl) Hexane-1 2 —ol (generic name: hexaconazole), (2RS, 5RS)-5-(2 , 4-Dichlorophenyl) tetrahydro-5- (1H-1,2,4-triazol-1-ylmethyl) -12-furyl 2,2,2-trifluoroethyl ether (generic name)

: Farconazole cis), N-propyl-N- [2- (2,4,6-trichloromethylphenoxy) ethyl] Izazole-based compounds such as 11-carboxamide (general name: prochloraz) ;

6-Methyl-1,3-dithio-mouth [4,5-b] Quinoxaline-based compounds such as quinoxaline-2-one (generic name: quinomethionate); polymer of manganese ethylene bis (dithiocarbamate) (generic name: Maneb, a polymer of zinc ethylene bis (dithiocarbamate) (general name: zineb), complex compound of zinc (zinc) and manganez ethylene bis (dithiocarbamate) (manneb)

: Manzeb), dizinc bis (dimethyl dithiocarbamate) Ethylene bis (dithiocarbamate) (generic name: polycarbamate), dithiocarbamate-based compound such as zinc propylene bis (dithiocarbamate) polymer (generic name: provineb) ;

Organochlorines such as 4,5,6,7-tetrachlorophthalide (generic name: fusaride), tetrachloride isophthalonitrinole (generic name: chlorothalonil), and pentachloroditrobenzen (generic name: kintozen) Compounds: Methyl 11- (putilcalbamoyl) Benzimidazo-l- 2-ilka-bamate (generic name: benomyl) Benzi midazo such as dimethyl 4,4 '-(o-phenylene) bis (3-thioallophanate) (generic name: thiophane-methyl), methylbenzimidazo-l-2-carbamate (generic name: carbendazim) -Based compounds;

Pyridinamides such as 3-chloro-N— (3-chloro-2,6-dinitro-141-a, a, trifluorotrifluoro) -5-trifluoromethyl-12-pyridinamine (generic name: fludinam) Cyanoacetamide compounds such as 1_ (2-cyano-2-methoxyiminoacetyl) -13-ethylethylurea (generic name: simoxanil);

Methyl N— (2-Methoxyacetyl) 1 N— (2,6-xylyl) 1 DL—araninate (general name: metalaxyl), 2—Methoxy 1 N— (2-oxo-1,3-oxazolidine 13 _ 2), 6'-kinlidide (generic name: oxadixyl), (±) 2-chloro-N- (2,6-xylylacetoamide) -butyrolactone (generic name: off-race) , Methyl Ν-phenylacetyl- チル-(2,6-xylyl) -DL-alaninate (generic name: benalaxyl) methyl Ν- (2-furoyl) -Ν- (2,6-xylyl) -DL-araranine A phenylamide compound such as i-to (general name: flaxyl), (c) i-ct-CN- (3-chlorophenyl) cyclopropanecarboxamide] -arptyrolactone (generic name: cyprofuran); .

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

Isoxazole-based compounds such as 5-methylisoxazol-3-ol (generic name: hydroxyisoxazole); aluminum tris (ethylphosphonate)

(Generic name: fosetyl aluminum), 0-2, 6-dichloro_p-tolyl-1 0, 0-dimethyl phosphorothioate (generic name: phosphoric acid methyl phosphate), S-benzyl 〇, 0-diisopropyl phosphorothioate, 0-ethyl S, S-diphenyl phosphorodithioate, aluminum Organophosphorus compounds such as chillhydrogen phosphonate;

N- (trichloromethylthio) cyclohexyl 4--1,2-dicarboximide (generic name: captan), N— (1,1,2,2-tetrachloroethylthio) cyclohexyl 4 N-halogenothioalkyl compounds such as 1,2-dicarboxymide (generic name: captaphol) and N- (trichloromethylthio) phthalimid (generic name: phthalide);

N- (3,5-dichloromethyl) 1-1,2-dimethylcyclopropane 1,1,2-dicarboximide (generic name procymidone), 3- (3,5-dichlorophenyl) -1-N-isopropyl 1,2,4-Dioxoimidazolidin-11-carboxamide (generic name: iprodione), (RS) —3- (3,5-dichlorophenyl)

Dicarboxyimide compounds such as 5-methyl-5-vinyl-1,3-oxazolidine-12,4-dione (generic name: vinclozolin);

Benzanilide compounds such as a, a, 1-trifluoro-3 '-isopropoxy-o-toluanilide (generic name: flutolanil) and 3'-isopropoxy-o-toluanilide (generic name: mepronil) ;

2- (1,3-Dimethylvirazole-14-ylcarbonylamino) -14-methyl-3-penteneditrile (compound described in British Patent No. 2190375), α- ( Nicotinylamino 1- (3-fluorophenyl) acetonitrile

Benzamide-based compounds such as the compounds described in JP-A-63-135354; Ν, Ν '-[piperazine-11,4-diylbis [(trichloromethyl) methylene] diformamide (generic name) : Piperazine compounds such as trifolin); 2 ',

4'-Dichro 1- (3-pyridyl) acetophenone 0-Methyloxime Pyridine compounds such as (generic name: pyrifinox);

(Sat) 1, 2, 4 '-Dichroic Ichiichi (Pyrimidine 1-5-yl) Benzhydryl alcohol (generic name: finalimol), (±)-2, 4'-Difluoro-α-(1 Η- Carbinol compounds such as 1,2,4-triazo-1-ylmethyl) benzhydryl alcohol (generic name: furtriafol);

(RS) — 1- [3- (4-tert-butylphenyl) -12-methylpropyl] piperidine-based compound such as piperidine (generic name: phenylpropyl);

(Sat) One cis-one 4-1 [3- (4-shallow butylphenyl) -12-methyl propyl] 1,2,6-dimethyl morpholine such as morpholine (generic name: propane morph) Compound;

Trifiniltin hydroxide (generic name: pentine hydroxide): an organic tin-based compound such as triphenylnitine acetate (generic name: fentin acetate);

Urea compounds such as 1- (4-cyclopentyl) 1-1-cyclopentyl-3-phenylperyl (generic name: peniculone);

(Ε, Ζ) 4- (3- (4-chlorophenyl) -1-3- (3,4-dimethoxyphenyl) acryloyl) cinamic acid-based compounds such as morpholine (generic name: dimethomorph);

Phenylcarbamate-based compounds such as isopropyl 3,4-ethoxycarbanilate (generic name: jetfancarb);

3-cyano 4- (2,2-difluoro-1,3-benzodioxo-1-yl) pyrrol (generic name: fludioxonil), 3- (2 ', 3'-dichlorophenyl) 1-4 Cyanopyrrole compounds such as cyanopyrole (generic name: phanpiclonil);

Anthraquinone compounds; crotonic acid compounds; antibiotics and the like. The appropriate mixing weight ratio of the N-phenylthiourea derivative represented by the general formula (I) and the counterpart agent to be used in combination is generally 1: 300 to 300: 1. Or 1: 100 to 100: 1. In particular, when this benzyloquinbenzene derivative is mixed with a pyrimidinamine-based compound, an organochlorine-based compound, a pyridinamine-based compound or a cyanopyrrole-based compound, an excellent effect of controlling various types of gray mold can be expected.

When the N-phenylthioperia derivative of the present invention is actually used as an active ingredient of a bactericide, it is usually mixed with a solid carrier, a solvent, a surfactant, and other pharmaceutical auxiliaries to form a powder, emulsion, or microparticle. They can be formulated into capsules, microemulsions, wettable powders, aqueous and oily suspensions, wettable powders and the like. These preparations contain the N-phenylthiodiurea derivative used in the present invention as an active ingredient in an amount of 0.002 to 80% by weight, preferably 0.01 to 70% by weight. Is appropriate.

Examples of the solid carrier include fine powders and granules such as kaolin clay, attapuljait clay, bentonite, acid clay, virofluorite, talc, diatomaceous earth, calcite, walnut shell powder, urea, ammonium sulfate, and synthetic hydrated silica. Can be Solvents include aromatic and aliphatic hydrocarbons such as quinylene, naphthas, methylnaphthalene, paraffins, and machine oil; alcohols such as isopropanol, butanol, propylene glycol, ethylene glycol, cellosolve, and carbitol; Examples include ketones such as acetone, cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, and acetonitrile.

Surfactants used for emulsification, dispersion, wet spreading, etc. include lignin sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, alkyl sulfate ester salt, alkyl sulfonate , Alkyali

—Sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl Aryl ether sulfuric acid or sulfonic acid or phosphate, polyoxyethylene alkyl ether sulfuric acid or phosphoric acid or sulfonate, phosphoric acid or sulfuric acid or sulfonic acid of polyoxyethylene styrenated and benzylated vinyl ether Anionic surfactants such as salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene propylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorby Nonionic surfactants such as fatty acid esters, polyoxyethylene styrenated and benzylated phenyl ethers, and polyoxyethylene castor oil.

Other formulation aids include alginates, polyvinyl alcohol, arabic gum, carboxymethylcellulose, xanthan gum, peran gum, isopropyl phosphate and the like.

As a typical example of a formulation, a water-dispersible powder contains about 5 to 70 parts by weight of the N-phenylthiodiurea derivative of the present invention, 2 to 5 parts by weight of an anionic surfactant, and 5 to 5 parts by weight of a synthetic hydrous silicate carrier. It is prepared by mixing and grinding with 20 parts by weight and a solid carrier in an amount sufficient to make the whole 100 parts by weight.

The emulsion contains 1 to 70 parts by weight of the N-phenylthiourea derivative of the present invention, 5 to 15 parts by weight of a nonionic surfactant, 1 to 10 parts by weight of an anionic surfactant, and the whole. Can be prepared by mixing with an inert pharmaceutically acceptable liquid diluent in an amount sufficient to make up to 100 parts by weight.

The aqueous suspension contains 5 to 50 parts by weight of the N-phenylthioperia derivative of the present invention, 1 to 5 parts by weight of a nonionic surfactant or anionic surfactant, and 0.1 to 1 part by weight of a thickener. 0.3 parts by weight and a sufficient amount of water to make the whole 100 parts by weight, and wet-pulverize to a particle size of 0.1 to 3 urn, preferably 0.5 to 2 m. Can be prepared with The water-dispersible granules may contain 5 to 50 parts by weight of a finely divided N-fluorothiourea derivative of the present invention, 90 to 40 parts by weight of inorganic salt mineral powder, 5 to 10 parts by weight of a binder and a surfactant. These granules, which disintegrate and disperse quickly when administered in water. Example

Next, the present invention will be specifically described with reference to Synthesis Examples and Application Examples. However, the scope of the present invention is not limited to these synthesis examples and application examples.

Synthesis example 1

Synthesis of N- [2- [2-Methyl-14-[(E)-11- (methoxyimino) ethyl] phenoxymethyl] phenyl] -N, -methylthiodiurea (No. 7)

N- [2- [2-Methyl-1-41 [(E)-1- (Methoxyimino) ethyl] phenoxymethyl] aniline 2.8 g of a 3 O ml tetrahydrofuran solution was cooled to 10 ° C or less, and tiophosgene was added. After adding 1.2 g, 1.5 g of triethylamine was added, and the mixture was returned to room temperature and stirred for 30 minutes. 5 ml of a 40% monomethylamine methanol solution was quickly added. After stirring for 1 hour, 100 ml of water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and evaporated. The residue was purified by silica gel chromatography (hexane: ethyl acetate) to obtain 3.0 g of the title compound. mP158-160 ° C.

Η-NMR (CDCl ₃ ) (ppm): 2.17 (3H, s), 2.27 (3H, s), 3.05 (3H, d), 3.95 (3H, s), 5. 0 7 (2H, s), 5.97 (1H, bs), 6.70-7.60 (7H, m), 8.08 (lH, bs) Synthesis example 2

Synthesis of N- [2- [2-Methyl-14-[(E)-1- (Methoxyimino) ethyl] [phenoxymethyl] phenyl] 1 N-Hydroxy-1N'-methylthiodiurea (No. 11)

i) 2-Methyl-41 [(E)-1-(Methoxyimino) ethyl] 50 g of phenyl 2-212 trobenzyl ether and 100 g of powdered zinc in 100 Oml of ethanol Heated to 0 ° C. A 50 ml aqueous solution of 9.4 g of ammonium chloride was slowly added dropwise thereto. After stirring at 70 to 80 ° C for 2 hours, the mixture was cooled to room temperature, filtered, the filtrate was concentrated and extracted with ether, and the organic layer was washed with water, dried over anhydrous magnesium sulfate, and evaporated. The residue was purified by silica gel chromatography (hexane: ethyl acetate), and N- [2- [2-methyl-1-41 [(E) -1]-(methoxyimino) ethyl] phenoxymethyl] phenyl] 30 g of N-hydroxyamine was obtained. m.p.96-98 ° C

'H-R (CDCl ₃ ) (ppin): 2.18 (3H, s), 2.21 (3H, s), 3.97 (3H, s), 4.46 (2H, s), 6.7 8-7.46 (8H, m) ii (1) To a solution of 6.2 g of the N-hydroxyamine compound obtained in i) in 3 Omi tetrahydrofuran was added 1.7 g of methyl isothiocyanate, and the mixture was stirred at room temperature for 8 hours. After adding 100 ml of water and extracting with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate and evaporated. The residue was purified by silica gel chromatography (hexane: ethyl acetate) to obtain 7.3 g of the title compound.

'HNR (CDCl ₃ ) (ppm): 2.11 (3H, s), 2.2K3H, s), 3.05 (3H, d), 3.88 (3H, s), 5.09 (2H, s), 6.70-7.60 ( 7H, m) IR (neat) (cm— ¹ ): 3382, 3058, 1605 Synthesis example 3

N— [2 -— [2-Methyl-1 4-((E) -1- (methoxymino) ethyl] phenoxymethyl] phenyl) —Synthesis of N-Methoxy-1-N'-methylthiodirea (Νο · _12)

After stirring a mixed solution of 100 ml of formic acid and 50 ml of acetic anhydride for 1 hour at 50 to 60 ° C, N- [2- [2-methyl-1-41 (: (E)- 1- (Methoxyimino) ethyl] phenoxymethyl] phenyl] 1 N-hydroxyamidine was added at 30 to 40 ° C. After stirring for 3 hours, the mixture was diluted with 300 ml of dichloromethane, and a 5% aqueous sodium hydroxide solution was added. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and evaporated to give N-hydroxy N- [2- [2-methyl-4. — (: (E) —1— (methoxymino) ethyl] phenoxymethyl]] formanilide 21 g of an oil was obtained.

'H-NMR (CDCl3) (ppm): 2.09 (3H, s), 2.22 (3H, s), 3.94 (3H, s), 5.12 (2H, s), 6.70 -7.94 (8H.m) ii) i To a solution of 21 g of the N-hydroxyformanilide compound obtained in) in 200 ml of dimethylformamide, 18 g of methyl iodide and 13 g of anhydrous potassium carbonate were added, and the mixture was stirred at room temperature for 6 hours. . 300 ml of ether was added, washed with water, dried over anhydrous magnesium sulfate and evaporated. The residue was purified by silica gel chromatography (hexane: ethyl acetate), and N-methoxy-1-N- [2- [2-methyl-41-((E)-11- (methoxyimino) ethyl] phenoxymethyl) was obtained. ]] 18 g of formanilide crystals were obtained. m.p. 6 2—64 ° C

'H-NMRCCDChXppm): 2.17 (3H, s), 2.28 (3H, s), 3.74 (3H, s), 3.96 (3H, s), 5.09 (2H, s), 6.72-7.72 (8H, m), 8.42 (1H, bs) 贿 Br) (cm— '): 1683 iii) To a solution of 0.342 g of the N-methoxyformanilide compound obtained in ii) in 5 ml of ethanol, 0.4 ml of a 10% aqueous sodium hydroxide solution was added at room temperature. One hour later, the mixture was diluted with water and extracted with ether. It was dried over anhydrous magnesium sulfate and evaporated. Purified by silica gel chromatography (hexane: ethyl acetate), N- [2-

[2-Methyl-4-C (E) —1- (methoxyimino) ethyl] phenoxymethyl] phenyl] 1 N-methoxyamine 0.30 g was obtained.

'H-NMR (CDCl3) (ppm): 2.17 (3H, s), 2.23 (3H, s), 3.70 (3H, s), 3.94 (3H, s), 4.96 (2H, s), 6.72-7.72 ( 7H.m), IR (neat) (cm- ¹ ): 3316, 1608, 1242, 1140 iv) A solution of 0.30 g of the N-methoxyamine compound obtained in iii) in 5 ml of tetrahydrofuran at 10 ° After cooling to below C, 0.12 g of thiophosgene was added, 0.12 g of triethylamine was added, and the mixture was returned to room temperature and stirred for 30 minutes. ImI of 40% monomethylamine methanol solution was quickly added. After stirring for 1 hour, 100 ml of water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and evaporated. The residue was purified by silica gel chromatography (hexane: ethyl acetate) to obtain 0.240 g of an oily substance of the title compound.

'H-R (CDCl ₃ ) (ppm): 2.13 (3H, s), 2.25 (3H, s), 3.15 (3H, d), 3.62 (3H, s), 3.91 (3H, s), 5.18 (2H , s), 6.70-7.60 (7H, m)

In the same manner as above, the compounds shown in the following Tables 1 to 3 were synthesized.

table 1

Compound

_n ^ -mouth

¾-^ "X Υ R 'R ² R ³

Η Η 0CH ₃ H CH ₃ O-CH: i

3 Η Η 0CH ₃ H CHa 2-cH3-5-ci-c ₆ H ₃

4 Η Η HH CH ₃ 2, 5- (CH ₃ ) ₂ -C ₆ H ₃

5 Η Η 0CH ₃ H CH ₃ 2, 5- (CH ₃ ) ₂ -C ₆ H ₃

6 Η Η 0CH _a H CH ₃ 2, 4- (CH ₃ ) ₂ -C _S H ₃

7 Η Η HH CH ₃ 2-CH ₃ -4- [C (CH ₃ ) = N0CH ₃ ]

-C (E)

_{_{8 Η Η CH 3 H CH 3}} 2- CH 3 - 4- [C (CH 3) = N0CH 3]

-C _S H ₃ (E)

_{9 Η Η CH 2 C≡: CH} H CH 3 2_CH 3 - 4- [C (CH 3) = N0CH 3]

-H ₃ (E)

10 Η Η CH ₂ CH2: CH ₂ H CH ₃ 2-CH, -4- [C (CH ₃ ) = N0CH ₃ ]

-C (E)

_{11 Η Η OH H CH 3 2-} CH 3 - 4- [C (CH 3) = N0CH 3]

-C ₆ H ₃ (E) _{_{12 HH 0CH 3 H CH 3 2}} -CH 3 - -4- [C (CH 3) = N0CH 3]

(Continued)

^{¾ 1¾ 1}

Compound

XYR ¹ R ² R ³ A ²

13 HHHH CH ₃ 2-CH3 -4-Acetyl-C ₆ H ₃

_{_{16 HHHH CH a 2- CH 3 -}} 4- [C (CH 3) = N0- iso -

C ₃ H ₇ ] _C ₆ H ₃ (E)

17 HHHH CH ₃ 2-CH ₃ -4- [C (CH ₃ ) = N0CH ₂ CH =

CHC1 (trans)] -C ₆ H ₃ (E)

18 HHHH CH _a 2-CH ₃ -4- [C (CH ₃ ) = N0CH ₂ C≡

CH] -C ₆ H ₃ (E)

19 HHHH CH ₃ 2-CH ₃ -4- [C (CH ₃ ) = N0-n-

C]-C ₆ H ₃ (E)

20 HHHH CH ₃ 2-CH ₃ -4- [C (CH ₃ ) = N0-sec-

C ₄ H ₉ ]-C ₆ H ₃ (E)

_{_{21 HHHH CH 3 2- CH 3 -}} 4- (CH = N0CH 3) - C 6 H 3

(E)

_{_{22 HHHH CH 3 2,5- (CH 3}} ) 2 - 4- [C (CH 3) =

N0CH ₃ ] -C ₆ H ₂ (E) _{_{HHHH CH S 2 - CH 3 -}} 4- [C (C 2 H 5) = N0CH 3]

-C (E)

_{_{HHHH CH 3 2_CH 3 - 4- [}} C (iso- C 3 H 7) =

N0CH ₃ ] -C ₆ H ₃ (E: Z = 1: 1 mixture)

HH OCH _: H CH ₃ 3-CI-5-CF ₃ —pyridine

2--

HHHH CH ₃ 2-C1-Pyridine- ₃ -yl HH 0CH ₃ H CH _a 1-C ₆ H ₅ —Virazol-3-yl

HHHH CH ₃ l- (4-Cl-C ₆ H ₄ ) -pyrazol—3-yl

HH OCH3 H CH ₃ l- (4-Cl- C ₆ H ₄ ) -pyrazol

_{HHHH CH 3 1 - (4- CI-} C 6 H 4) - 1,2,4- tri § zone one rule 3 I le _{HH OCH3 H CH 3 1- (4-} CI- C 6 H 4) - 1 , 2,4-Triazole-3-yl HHHH CH ₃ l- (4-Cl-C ₆ H ₄ ) -pyrimidine-4-yl

_{HH OCH3 H CH 3 2 - CH} 3 - 4- (4 '-CH 3 -C 6 H

Table 2

Compound

jp.

XYR ¹ R ² R ³ A ³

34 HHHH CH, 4-Cl-C _fi H

35 HH OH H CH ₃ 4-C to C

_{_{36 "HH 0CH 3 H CH 3}} 4 - C Bok C ₆ H.,

39 HH 0CH ₃ H CH ₃

40 HHHH CH, 4- 0C ₂ H ₅ -pyrimidine 1 2

_{41 HH OCH3 H CH 3 4 -} 0C 2 H 5 - pyrimidone Jin one 2 Inore

_{_{_{42 HHHH CH 3 4-0CH 2 CF 3}}} - pyrimidone Jin

2--

43 HHHH CH ₃ -C (CH ₃ ) = N0CH ₃ (E)

44 HH 0CH ₃ H CH ₃ -C (CH ₃ ) = 0CH ₃ (E)

45 HHHH CH,-C (C ₆ H ₅ ) = N0CH ₃

(E: Z = 1: 1 mixture) 46 HH OCH :, H CH ₃ -C (CH ₃ ) = N0C, H ₅ (E)

Five

48 HHHH CH _;) 2-Viradinyl

Compound

XYRR ^; A

_{49 HHHH CH 3 6- (2-} CN-C 6 H,.) - 0- pyrimidine one 4- I le

_{50 HH 0CH = H CH 3 6-} (2-CN-C 6 H,.) - 0- pyrimidine one 4 -

H H H H CH [

52 HH OCHc H CH _: C

Table 4

Compound

Physical properties

No. I m. P. 108-109 ° C

'H-MR (CDCl ₃ ) (ppm); 2.27 (3H, s), 3.02 (3H, d), 5.0l (2H, s), 5.96 (1H, bs), 6.84-8.16 (8H, m)

o. 4 mp. 114.5- 116 ° C

'HNR (CDCl ₃ ) (ppm); 2.20 (3H, s), 2.30 (3H, s), 3.17 (3H, d), 5.00

(2H, s), 6.60-8.10 (7H, m)

o. 5 Oil

'H-NMR (CDCl ₃ ) (ppm); 2.21 (3H, s), 2.25 (3H, s), 3.18 (3H, d), 3.65

(3H, s), 5.12 (2H, s), 6.70-8.00 (7H, m)

o.7 nup.158-160 ° C

'H-NMR (CDCl ₃ ) (ppm); 2.17 (3H, s), 2.27 (3H, s), 3.05 (3H, d), 3.95

(3H, s), 5.07 (2H, s), 5.97 (1H, bs), 6.70-7.60 (7H, m), 8.08 (1H, bs)

No. 8 D. 96- 99 ° C

'H-NMR (CDCl ₃ ) (ppm); 2.19 (3H, s), 2.39 (3H, s), 3.0K3H, d), 3.61 (3H, s), 3.96 (3H, s), 4.92 (2H, s), 6.72-7.80 (7H, m)

No.11 oil

'H-NMR (CDCl ₃ ) (ppm); 2.11 (3H, s), 2.2K3H, s), 3.05 (3H, d), 3.88 (3H, s), 5.09 (2H, s), 6.70-7.60 ( 7H, m)

IR _{(neat) (cm - '); 3382} , 3058, 1605

No.12 oil

'H-NMR (CDCl ₃ ) (ppm); 2.13 (3H, s), 2.25 (3H, s), 3.15 (3H, d), 3.62 (3H, s), 3.9K3H, s), 5.18 (2H, s), 6.70-7.60 (7H, m)

No. 13 p. 120-122 ° C

'H-MR (CDCl ₃ ) (ppm); 2.25 (3H, s), 2.45 (3H, s), 3.02 (3H, d), 5.10 (2H, s), 6.10 (1H, bs), 6.78-7.80 (7H, m), 8.30 (1H, s)

No. 14 mp 122-125. C 'H-NMR (CDCl ₃ ) (ppm); 1.3K3H, t), 2.17 (3H, s 2.27 (3H, s), 3.07 (3H, d 4.23 (2H, q), 5.09 (2H, s), 6.04 (1H, bs), 6.78-7.64 (7H, m), 8.12C1H, s)

m. 141-142 ° C

'H-NMR (CDC1 ₃ ) (PPIII); 0.97 (3H, t 1.74 (2H, q 2.18 (3H, s 2.27 (3H, s), 3.03 (3H, d), 4.11 (2H, t), 5.05 (2H, s 6.01 (1H, bs), 6.78-7.72C7H, m), 8.26 (lH, bs)

m.p. 138.5- 139 ° C

'H-MR (CDCl ₃ ) (ppm); 1.30 (6H, d 2.16 (3H, s 2.27 (3H, s 3.03 (3H, d), 4.12-4.64 (1H, m), 5.05 (2H, s), 6.02 (1H, bs), 6.77-7.67 (7H, m 8.26 (1H, bs)

mp. 149-150 ° C

'H-NMR (CDCl ₃ ) (ppm); 2.20 (3H, s 2.29 (3H, s 3.08 (3H, d 4.66 (2H, d 5.07 (2H, s 5.85-6.31 (3H, m), 6.80-7.65 ( 7H, m), 8.16 (IH, bs)

m.p. 126-127 ° C

'H-NMR (CDCl ₃ ) (ppm); 2.20 (3H, s 2.28 (3H, s 2.45 (1H, t 3.04 (3H, d 4.75 (2H, d), 5.05 (2H, s 6.00 (1H, bs)) , 6.79-7.64 (7H, m), 8.23 (lH, bs)

mp.137-138 ° C

'H-MR (CDCl ₃ ) (ppm); 0.96 (3H, t 1.28-1.85 (4H, m 2.19 (3H, s 2.28 (3H, s 3.05 (3H, d), 4.16 (2H, t 5.06 (2H, s), 5.99 (1H, b), 6.79-7.63 (7H, m 8.20 (1H, bs)

m.p. 101-105 ° C

'H-MR (CDCl ₃ ) (ppni); 0.98 (3H, t), 1.30 (3H, d 1.53-1.85 (2H, m), 6 ε

(sq Ή,) 2Α "8

'Ο "' Η8 8ΑΑ2ε · '(s' HZ) 9 S' (s Ήε) ΐΟΐΟε: (indd) (ao ^£ aO) HWN-H,

Bulge '2 ·. . 8SJ OS ON (ω Ή6) 96 "Α-Οΐ Ί '(ω Ήΐ) 50" 9- 9Α * S' (s 'HZ) 8 S' (s Ήε) 89 · ε '(Ρ' HS) 8T: ( ) 13 Go -Η,

62 "O

(sq 'Ηΐ) 098' (in 'H6) Si

'(ω' ΗΖ) 0Ζ'9_0 丄 'S' (s 'HZ) S' CP 'HS) 90' £: (). ) Translation _{H |}

(ΉΑ) ΐ8 "8-06'9

'(sq Ήΐ) 00 "9' (s Ή2) 20" 9 '(s'HS) 68'S' SA * C '(Ρ Έε) 66' Ζ '('

Ηΐ) 09 "ε-5ΐ 'Ζ' (s ^l H8) S2 'Ζ' (Ρ 'Η9) 9ΐ · ΐ '80 · ΐ: ((3 (Ι3)-Η,

(ια

'Η) Ζΐ' 8-08 · 9 '(sq Ήΐ) 00 "9' (s Ή2) Α0" S '(s' HS) 96 'ξ' (Ρ Ήε)

90 'ε' (b 'Η2) 0 丄 · 2' (s ¾8) 8S "Ζ '(1 Ήε) 0ΐ · ΐ:

(Ή9) 00 "8-22 '9' (sq Ήΐ) 96 'S' (s' H2) T0" 9 '(s ¾) £ 6 "8' (Ρ ΉΟ

90 '8' (s Ήθοε "Z '(s Ήε) 022' (s Ήε) ΐΐ 'Z: (indd) (M3ao) HW -H,

ZZ ON

0 "ΉΑ) 86 Ί-6Γ9 '(sq ΉΤ) 88" 9' (s Ή2)

90 "S '(s Ήε) 2626ε' (P 'He) 90 Έ' (s 'H8) 92' Z: (uidd) (3aa) N-H,

Q. 8 T_SM "d'ui IZ" ON (sq 'HT) S2'8' (丄 8 · 丄 -99 · 9 '(sq' Ηΐ) 80 '9' (s Ή

Z) 60'9 '(ω' HS) ^-10 '(Ρ' HS) 80 "S '(s' Hg) 0S * 2 '(s' HS) 0Z'2 ^ 000 / 86df / X3d S99 OA 0

((ΐ: ΐ =

ζ: 3) Ηε) 6 · ε '68 · ε '(ρ Ήε) ε8' ζ '(s Ήε) ΐο · 2' _Ι3α3 ) leakage — _Ηι

m ^ · ^Ο Ν

(ω 'm OL Ί- Ζ Ί' (s ¾2) 08 -9 '(s Ή8) 96 "8' (s) ζι" ε 'CP Ήε) ^ · ε' (s ⁴ HS) SO 'Z' ( S 'HS) S6'I: () ( ^ε ΐ3α3) translation-H'

(sq 'Ηΐ) 6ε8' (in 'H) 0 丄' 丄 -02 丄丄 (sq Ήΐ) 20 '9' (s Ή2) 'S' (s' Ηε) ΐ6Έ '(P' H8) 60 '"8' (s Ή9) ΐΟ2: (indd) (0a0) HWN-H,

Dinοθεΐ-82ΐ * din ε 〇Ν (Ρ Ήΐ) 99'8 '(' Η) 06 '8- OS · 丄' (Ρ 'Ηΐ) 6 · 9' (s Ή2)

OS'S '(b Ή2) 00 * S' CP Ήε) 92 '2' (s' H £) 6S 'Z' · () () (13)

Οοθεΐ-82ΐ 'dz "ON (P' Ηΐ '8 ⁴ (« I

OA 'ί-ΟΖ Ί' (Ρ 'Ηΐ) ε9 ・ 9' (s' HS) 8 S '(b' H2) 0L '-OZ' (s Ή8)

OL'S '(p Ήε) 6Γε' (s Ήε) 9ε 'ζ Ό Ήε) 6ε * ΐ'. ( ^{Ω (Ι (ί} ) (3αο) ΜΜ -Η,

^ ON

(Ή8) 0ΐ '8-

02 Ί '(S Ή2) 0Ζ * 9' (Ρ Ή8) 0ΐ "8 '(s Ήε) 82' Ζ: (uidd) (M3aO) HWN-H,

(ui 'H8) 08 · 丄-S6 · 9' (s Ή2)

ZZ "S '(s Ήε) 89' (P 'HS rS' (s 'HE) ZS' Z :( ^UIdd ) (0a0) HWN-H,

i¾ ^; ^ 98 · 0Ν (Ή8) 08 'λ-

06 '9' (s Ή2) 9ΐ '5' (Ρ Ήδ) 0Τ 'S' (s' HS) S2'S: (uidd) (0a3) HWN-H,

tO00 / 86Jf / XDJ 5.95 (1H bs), 7.20-7.70 (9H, m)

8.14 (1H, bs)

No.49 glassy material

'H-NMR (CDC) (ppm); 3.03 (3H, d), 6.65 (1H, bs), 7.20-8.90

(8H, m), 8.28 (1H, s)

No.51 oil

^ H-NMR (CDCl ₃ ) (ppin); 3.07 (3H, d), 6.26 (1H, bs), 6.35-7.80 (9H, m) Synthesis example 4 (production of intermediate)

The following intermediates were synthesized according to the steps of i) to iii) of Synthesis Example 3.

Table 5

Intermediate

-.

XYR ⁷ R ⁸ A

a-1 HH CH ₃ CHO A— 1

a-2 HH CH ₃ CHO A- 2

a- 3 HH CH ₃ CHO A- 3

a-4 HH CH ₃ CHO A— 4

a-5 HH CH ₃ H A-5

a-6 H H CH. H A- 6

a-7 HH CH ₃ CHO A-7

The structure of group A is as follows (

)

Table 6

Intermediate

Physical properties

a-1 m.p. 62- 64 ° C

^, H-NMR (CDCl3) (ppm): 2.17 (3H, s), 2.28 (3H, s), 3.74 (3H, s), 3.96 (3H, s), 5.09 (2H, s), 6.72-7.72 ( 8H, m), 8.42 (1H, bs)

a-2 oil

¹ H-MR (CDCl ₃ ) (ppm); 2.2K3H, s), 3.76 (3H, s), 5.27 (2H, s), 7.20

-7.60 (7H, m), 8.36 (1H, bs)

a-3 oil

'Η-NR (CDCl ₃ ) (ppm); 1.42 (3H, t), 2.39 (3H, s), 3.78 (3H, s),

4.49 (2H, q), 5.44 (2H, s), 6.64 (1H, d), 7.35-7.73 (4H, m),

8.46 (1H, d)

a-4 oil

'H-NMR (CDCl ₃ ) (ppm); 2.22 (3H, s), 2.29 (3H, s), 3.75 (3H, s), 5.04 (2H, s), 6.70-7.70 (7H, m), 8.40 (1H, bs)

a-5 oil

'Η-hear (CDCl ₃ ) (ppm); 2.17 (3H, s), 2.23 (3H, s), 3.70 (3H, s), 3.94 (3H, s), 4.96 (2H, s), 6.72-7.72 (7H, m)

IR neat ( _Cffl- '); 3316, 1608, 1242, 1140

a-6 oil

'H-NMR (CDCl ₃ ) (ppm); 2.18 (3H, s), 3.74 (3H, s), 3.9K3H, s), 5.10 (2H, s), 6.90-8.11 (8H, m)

a-7 oil

lH-NMR (CDCl ₃ ) (ppm); 1.92 (3H, s), 2.01 (3H, s), 3.74 (3H, s), 3.91 (3H, s), 5.20 (2H, s), 7.25-7. 70 (4H, m), 8.37 (1H, bs) IR unit (cm- ¹ ); 1689, 1368, 1044, 885 Next, examples of preparations using the N-phenylthiodiarea derivative of the present invention as a bactericide are shown. However, in the formulation examples, parts means parts by weight. Formulation Example 1 (Wettable powder)

Compound (No. 1 or No. 7) finely pulverized with a hammer mill to a particle size of 10 m (50 parts), sodium ligninsulfonate (3 parts), sodium lauryl sulfate (2 parts), synthetic hydrous silicic acid (10 parts) and clay (3) After well mixing 5 parts, the mixture was pulverized by a jet mill to obtain wettable powders for each. Formulation Example 2 (emulsion)

5 parts of compound (No. 5, 11 or 12), 9 parts of polyoxyethylene styrenated phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene were uniformly dissolved to obtain emulsions, respectively. Was. Formulation Example 3 (Suspension)

25 parts of compound (No. 1 or No. 7) finely pulverized to a particle size of 10 m with a hammer mill, 3 parts of polyoxetylene styrenated phenyl ether sulfate ammonium salt, 3 parts of water And wet-pulverized to an average particle size of 2ζπι, and then mixed with 10 parts of a previously prepared solution consisting of 2 parts of xantham, 1 part of preservative, 50 parts of ethylene glycol and 47 parts of water. Each suspension was obtained. Formulation Example 4 (Water dispersible granules)

Compound (No. 1 or No. 7) finely pulverized with a hammer mill to a particle size of 10 zm (40 parts), fine clay 23 parts, ammonium sulfate powder 20 parts, sodium lignin sulfonate 5 parts and sodium peryl sulfate 2 After mixing the parts, the mixture was further pulverized by a jet mill. After adding 15 parts of water and mixing, the 0.8 screen was extruded into granules, which were dried at 70 ° C. 1 to i. Cut into lengths of about 5 MI and sieved to obtain wettable powders for each.

A formulation was produced in the same manner as in the above Formulation Example, using a compound represented by the following formula described in JP-T-7-5202747 (W093 / 15046) as Comparative Compound A

Comparative Compound A The comparative compound A is not a thioperia compound but a mere perea compound.

The physical properties of the comparative compound are as follows.

m.p. 138-140 ° C

'HNR (CDCl ₃ ) (ppni): 2.13 (3H, s), 2.19 (3H, s), 2.70 (3H, d), 3.93 (3H, s), 4.99 (2H, s), 6.80-7.70 (7H, m)

Next, test examples of the bactericidal effect are shown. Test example 1

Effect on barley powdery mildew

A two-leaf barley (cultivar: Akagi nijo) grown in a pot with a diameter of 6 cm was uniformly sprayed with a water dilution of the compound of the present invention prepared in an emulsion using a spray gun. One day after natural drying, conidiospores of barley powdery mildew (Erys iphe graminis) were wiped off and inoculated, and maintained in a greenhouse. Seven days after inoculation, the number of lesions formed on the leaves was investigated.

The control rate was calculated from (a). Table 7 shows the results.

Control rate (%) = (1 number of lesions in one treatment area, number of non-treatment areas) X 100 (a) Table 7

—Compound No. Active ingredient concentration (ppm) Control rate (%)

1 2 5 6 7 5 5 2 5 6 9 6 7 2 5 6 1 0 0 7 6 4 1 0 0 7 1 6 1 0 0 8 2 5 6 9 4

1 1 2 5 6 1 0 0 1 1 6 4 9 4 1 1 1 6 8 9 1 2 2 5 6 1 0 0 1 2 6 4 1 0 0 1 2 1 6 1 0 0 1 3 2 5 6 9 0 1 4 2 5 6 9 5 1 5 2 5 6 9 1 1 6 2 5 6 9 9 1 7 2 5 6 9 9 1 8 2 5 6 9 5 1 9 2 5 6 9 0 2 0 2 5 6 9 6 1 2 5 6 9 1 2 2 2 5 6 9 0 2 3 2 5 6 1 0 0 2 3 6 4 9 8 2 3 1 6 4 0 2 4 2 5 6 9 3 2 9 2 5 6 9 8 2 9 6 4 9 4

2 9 1 6 9 2

3 4 2 5 6 7 8

3 7 2 5 6 9 5

4 3 2 5 6 8 3 4 4 2 5 6 9 6 4 4 6 4 9 4 4 4 1 6 6 3 4 5 2 5 6 8 4 Comparative compound A 2 5 6 9 5

6 4 9 2 1 6 1 8 Test example 2

Effect on wheat leaf rust

A water-diluted solution of the compound of the present invention prepared in an emulsion was evenly sprayed on wheat at the second leaf stage (cultivar: Norin 61) grown in a pot having a diameter of 6 cm using a spray gun. After natural drying 1, the uredospore suspension of wheat leaf rust (Pucci ni a recondi ta) was sprayed and inoculated, left in a room with a high humidity of 24 ° C for 24 hours, and then controlled in a greenhouse. Seven days after the inoculation, the number of lesions formed on the leaves was examined, and the control rate was calculated according to the formula (a) in Test Example 1. Table 8 shows the results. Table 8

Compound No. Active ingredient concentration (ppm) Control rate (%)

5 2 5 6 9 4 7 2 5 6 1 0 0 7 6 4 1 0 0 7 1 6 1 0 0 1 1 2 5 6 9 9 1 2 2 5 6 1 0 0 1 2 6 4 1 0 0 1 2 1 6 1 0 0 1 3 2 5 6 8 8 1 4 2 5 6 9 0 1 6 2 5 6 9 1 1 8 2 5 6 1 0 0 2 2 2 5 6 8 5 2 3 2 5 6 1 0 0 2 8 2 5 6 9 9 2 8 6 4 9 3

2 8 1 6 7 0

2 9 2 5 6 9 9

2 9 6 4 9 5

2 9 1 6 4 7

3 6 2 5 6 8 9

4 1 2 5 6 9 5

4 4 2 5 6 9 3

4 4 6 4 8 6

4 4 1 6 6 5 4 9 2 5 6 7 8Comparative compound A 2 5 6 7 6

6 4 6 8

1 6 1 5

Test example 3

Effect on tomato rickets

A two-leaf tomato (cultivar: large fukuju) grown in a pot with a diameter of 6 cm was uniformly sprayed with a water dilution of the compound of the present invention prepared in an emulsion using a spray gun. One day after natural drying, a zoospore suspension of the phytotoxin fungus (Phy tophthora inf estans) was spray-inoculated, left in a room with a high humidity of 20 ° C for 24 hours, and controlled in a greenhouse. Five days after the inoculation, the area ratio of lesions formed on the leaves was examined, and the control rate was calculated according to the following formula (b). Table 9 shows the results.

4 9 Control rate (%) = (1—area ratio of treated lesion area z area rate of untreated area) X 10 0 (b) Table 9

Compound No. Active ingredient concentration (ppm) Control rate (%)

1 2 5 6 8 1 4 2 5 6 8 1 5 2 5 6 8 6 7 2 5 6 9 7 7 6 4 9 1 7 1 6 6 3

1 1 2 5 6 9 1 1 2 2 5 6 9 7 1 2 6 4 9 7 1 2 1 6 9 4 1 3 2 5 6 7 5 1 4 2 5 6 9 1 1 4 6 4 8 1 1 4 1 6 6 3 1 5 2 5 6 8 1 1 6 2 5 6 8 8 1 8 2 5 6 8 1 1 9 2 5 6 7 5 2 0 2 5 6 7 5 2 1 2 5 6 9 1 2 1 6 4 7 5 2 1 1 6 5 0 2 2 2 5 6 8 8

2 3 2 5 6 9 1

2 4 2 5 6 8 1

2 8 2 5 6 7 9

2 9 2 5 6 9 8

2 9 6 4 9 5

2 9 1 6 8 9

3 4 2 5 6 7 5

3 6 2 5 6 8 9 4 1 2 5 6 9 5

4 4 2 5 6 8 3 Comparative compound A 2 5 6 3 8

6 4 3 1

1 6 0 Test example 4

Effect on rice blast

A water dilution of the compound of the present invention, formulated in an emulsion, was sprayed evenly onto a 4-leaf stage rice (cultivar: Koshihikari) grown in a pot with a diameter of 6 cm using a spray gun. One day after natural drying, a conidia suspension of rice blast fungus (Pyricularia oryzae) was spray-inoculated, left in a room with a high humidity of 24 ° C for 24 hours, and then maintained in a greenhouse. Seven days after the inoculation, the number of lesions formed on the leaves was examined, and the control rate was calculated according to the formula (a) in Test Example 1. The results are shown in Table 10. Table 10

Compound No. Active ingredient concentration (PPm) Control rate (%)

5 2 5 6 9 2 7 2 5 6 1 0 0 7 6 4 8 7 7 1 6 7 8

1 2 2 5 6 8 6

1 2 6 4 5 6 1 2 1 6 4 2 2 3 2 5 6 7 9 2 4 2 5 6 7 9 2 9 2 5 6 1 0 0 2 9 6 4 9 2 2 9 1 6 6 0 4 1 2 5 6 1 0 0 4 4 2 5 6 9 2Comparative compound A 2 5 6 1 2

6 4 1 9

1 6 0 Test example 5

Effect on rice sesame leaf blight

A four-leaf stage rice (cultivar: Koshihikari) grown in a pot with a diameter of 6 cm was uniformly sprayed with a water dilution of the compound of the present invention formulated in an emulsion using a spray gun. Natural drying

One day later, a conidia suspension of rice sesame leaf blight (Chochl i obol us mi yabeanus) is sprayed. The cells were inoculated, left in a room with a high humidity of 24 ° C for 24 hours, and then maintained in a greenhouse. Seven days after the inoculation, the number of lesions formed on the leaves was examined, and the control rate was calculated according to the formula (a) in Test Example 1. Table 11 shows the results. Table 11

Compound No. Active ingredient concentration (PPm) Control rate (%)

5 2 5 6 9 7 5 6 4 9 9 5 1 6 8 5 7 2 5 6 9 4 7 6 4 8 6 7 1 6 4 8

1 2 2 5 6 8 8 1 2 6 4 7 6 1 2 1 6 4 3 2 9 2 5 6 9 8 2 9 6 4 8 8 2 9 1 6 7 9 4 4 2 5 6 9 6 4 4 6 4 8 6 4 4 1 6 2 1 Comparative compound A 2 5 6 1 5

6 4 2 8

1 6 0 Test example 6

Effect on cucumber downy mildew

A water dilution of the compound of the present invention, formulated in an emulsion, was evenly sprayed on the cucumber in the 5-leaf stage (cultivar: Sagami semi-white cucumber) grown in a pot with a diameter of 6 cm using a spray gun. did. One day after natural drying, a zoospore suspension of cucumber downy mildew (Pseudoperonospora cubens is) was inoculated by spraying, left in a high humidity room at 24 ° C for 24 hours, and then controlled in a greenhouse. Seven days after the inoculation, the area ratio of lesions formed on the leaves was examined, and the control rate was calculated according to the formula (b) in Test Example 3. The results are shown in Table 12. Table 1 2

Compound No. Active ingredient concentration (PPm) Control rate (%)

7 2 5 6 1 0 0 7 6 4 8 8 7 1 6 7 5 1 2 2 5 6 1 0 0 1 2 6 4 1 0 0 1 2 1 6 9 4 Comparative compound A 2 5 6 1 0 0

6 4 0

1 6 0 Test example 7

Effect on tomato ring spot disease

A water-diluted solution of the compound of the present invention prepared in an emulsion was sprayed evenly onto a 5-leaf stage tomato (cultivar: large fukuju) grown in a 6 cm diameter bottle using a spray gun. Natural drying One day after drying, a conidia suspension of tomato ring spot fungus (Alternaria solani) was sprayed and inoculated, left in a room with a high humidity of 24 ° C for 24 hours, and then controlled in a greenhouse. Seven days after the inoculation, the area ratio of lesions formed on the leaves was examined, and the control rate was calculated according to the formula (b) in Test Example 3. Table 13 shows the results.

Table 13

Compound No. Active ingredient concentration (ppm) Control rate (%)

7 2 5 6 9 6 7 6 4 9 6 7 1 6 6 8

1 2 2 5 6 1 0 0 1 2 6 4 1 0 0 1 2 1 6 7 1 Comparative compound A 2 5 6 7 5

6 4 3 1

According to the present invention, an N-phenyl thioperrea derivative having an excellent agricultural and horticultural fungicide at a low concentration can be obtained.

Claims

The scope of the claims

1. N-phenylthioperia derivative represented by the following formula (1)

(In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, C, - ₃ alkyl group, a halogenated C § alkyl group, ₃ alkoxy group, a halogenated C, - _C3 alkoxy group, C ₃ - ₅ an alkenyl group or a C alkynyl Group,

R ² is a hydrogen atom or ₃ alkyl group,

R ³ is a d- ₃ alkyl group;

X and Y are independently a hydrogen atom, a halogen atom, a d alkyl group, a halogenated alkyl group, a d- ₃ alkoxy group, a halogenated d-alkoxy group, a cyano group or a nitro group;

A is, - 0- A ^1, CH ₂ one 0- A ² or _{- CH 2 0N = C (R} 1) shows the -A ^3,

R ⁴ is a d- ₃ alkyl group;

A ¹ is

Aa

And

Here, X ¹ and Y ′ independently represent a hydrogen atom, a halogen atom, C, 3

Group, halogenated C ₃ alkyl group, an alkoxy group, a halogenated C § alkoxy group, an Shiano group or a nitro group,

A ²

Aa

Where Z is N or CH;

U represents a hydrogen atom, a halogen atom, C, - ₆ alkyl group, a halogenated C _i-6 Al kill group, ₆ alkoxy group, a halogenated Ci ₆ alkoxylated group, Shiano group is a two-Toro group or A a,

V is a hydrogen atom, a halogen atom, a d-6 alkyl group, a halogenated d-6 alkyl group, a d- ₆ alkoxy group, a halogenated C, S alkoxy group, a cyano group, a dinitro group, an alkylcarbonyl group, C Bok S alkoxycarbonyl group or one C (R ⁵⁾ is a two NOR ^B group,

R ⁵ is a hydrogen atom, a C ₆ alkyl group, a halogenated ₆ alkyl group or A a,

R ⁶ is a hydrogen atom, C ₆ alkyl group, halogenated alkyl group, C ₃ —: alkenyl group, halogenated (: ₅ alkenyl group, C ₃ - _; -, alkynyl group or halo Gen of Cr> - a ₅ alkynyl group,

W is a hydrogen atom, a halogen atom, a C, _—S group, a halogenated _δ alkyl group, a ₆ alkoxy group or a halogenated C alkoxy group, and A ³ is one C (R ⁵ ) = NOR ⁶ , Aa or

-Υ

(However, R ⁵ , R ^s , X ′ and Y ′ have the above-mentioned meanings). )

2. The N-phenylthiourea derivative according to claim 1, which is A ² CH ₂ —0—A ² .

3. A ² is

U

3. The N-phenylthiodiurea derivative according to claim 2, which is:

4. N-Fuweniruchiou Rare derivative according to claim 3 which is V gar C (R ⁵⁾ = NOR ⁶ group.

5. Equation (Π):

(Wherein, A, X, Y, and R ′ are as defined in claim 1), and a compound represented by the formula ():

R 2

, R 3

H

a

(Wherein, and R ³ are as defined in claim 1, and Hal is a halogen atom cs =

I am a child. The method for producing an N-phenylthioperia derivative represented by the formula (I) according to claim 1, characterized by reacting with a compound represented by the following formula:

6. A Chikaraku, CH ₂ one 0- A ² is N- off We two thio urethane § derivative conductor method according to claim 5.

7. A ² is

U

8. The method for producing an N-phenylthiodiarea derivative according to claim 7, which is:

8. V gar C (R ⁵⁾ = method of manufacturing N- Fuweniruchiou rare derivative according to claim 7 is a NOR ⁶ group.

9. Formula (II):

(Wherein A, X, Y, and R ¹ are as defined in claim i.) And thiophosgene, and then the compound obtained is reacted with a compound of formula (IV) :

R ² (R ³ ) H (IV)

(Wherein R ² and R ³ are as defined above). The compound of claim 1, wherein the compound is reacted with an amide compound represented by the formula: Production method.

10. The method for producing an N-phenylthiourea derivative according to claim 9, wherein A is CH ₂ —0—A ² .

11. A ² is

U

11. The method for producing an N-phenylthiodialea derivative according to claim 10, wherein the derivative is:

12. V gar C (R ⁵⁾ = method of manufacturing N- phenylene Ruchiou Rare derivative according to claim 11 which is a NOR ⁶ group.

13. Formula (II):

(Where A, X, Y, and R ¹ are as defined in claim i.), And a compound represented by the formula (V): R ³ -NC S (V)

(Wherein, R ^{: i} is as defined above). A general formula (I-11):

A method for producing an N-phenylthioperia derivative represented by the formula:

14. The method for producing an N-phenylthiodialea derivative according to claim 13, wherein is CH ₂ -0-A ² .

15. A ² is

U

15. The method for producing an N-phenylthiodiurea derivative according to claim 14, which is:

16. The N-phenylthiourea derivative according to claim 15, wherein V is —C (R ⁵ ) = NOR ⁶ group.

17. A fungicide for agricultural and horticultural use, comprising the N-phenylthiodiurea derivative according to claim 1 as an active ingredient.

18. The fungicide for agricultural and horticultural use according to claim 17, wherein the N-phenylthioperylene derivative is used in an amount of 0.002 to 80% by weight.

19. The N-phenylthiodiurea derivative is used in an amount of 0.01 to 70% by weight. The fungicide for agricultural and horticultural use according to 1.

20. Intermediate for the synthesis of N-phenylthiodiarea derivative represented by the following formula (iV-1)

(Wherein, R ⁷ is a C, -alkyl group or a halogenated C ₃ alkyl group;

R ⁸ is a hydrogen atom or a —CHO group,

A, X and Y are as defined in claim 1. )

21. The above formula (IV-1) is obtained by hydrolyzing an N-alkoxyformanilide derivative in which R ⁸ in the formula (IV-1) according to claim 20 is —CHO group under acidic or alkaline conditions. )), Wherein an N-alkoxyaniline derivative wherein R ⁸ is a hydrogen atom is produced.

Claims of amendment

_{[1 9 9 8} November ₂₀₀₉ ₂ 1st (21. 05.98) International Bureau acceptance: the application range 1 and 17 of the original claims amended; range of other claims unchanged. (Page 6)]

Gen of C ₃ - a ₅ alkynyl group,

W is a hydrogen atom, a halogen atom, an alkyl group, a halogenated C, _—B alkyl group, a d-alkoxy group, or a halogenated (:, — alkoxy group;

A ³ is one C (R ⁵ ) = NOR ⁶ , Aa or

(However, R ⁵ , R ⁶ , X ¹ and Y ′ have the above-mentioned meanings.) However,

R ', R ² , and Y are hydrogen atoms, X is a 5-chloro group, R ³ is a methyl group, and A is a 2-phenoxy group.

2. The N-phenylthiourea derivative according to claim 1, wherein A is CH ₂ —0—A ² .

3. A ² is

3. The N-phenylthiodiarea derivative according to claim 2, which is:

4. The N-phenylthio group according to claim 3, wherein V is -C (R ⁵ ) = N0R ⁶ group.

63,

Amended paper (Article ⁹ of the Convention) Rare derivatives.

5. Equation (Π):

64

Amended paper (Article 19 of the Convention) R: '-NCS (V) (wherein, R ^{: l} is as defined above), and is reacted with a sheet represented by the following general formula (I-1):

14. The method for producing an N-phenylthiodialea derivative according to claim 13, wherein A is CH ₂ —〇—A ² .

15. A ² is

15. The method for producing an N_phenylthiodiarea derivative according to claim 14, which is:

17. A fungicide for agricultural and horticultural use containing an N-phenylthioperia derivative represented by the following formula (I) as an active ingredient.

65

Amended paper (Article 19 of the Convention)

(Wherein, R ¹ is a hydrogen atom, a hydroxyl group, a d-alkyl group, a halogenated C alkyl group, an alkoxy group, a halogenated C alkoxy group, a C alkenyl group or a C-alkynyl group,

R ² is a hydrogen atom or a _—3 alkyl group;

R ³ is a d-alkyl group;

X and Y are independently a hydrogen atom, a halogen atom, a C, _1-3 alkyl group, a halogenated C, _-3 alkyl group, a C, _-3 alkoxy group, a halogenated- ₃ alkoxy group, a cyano group or a nitro group. ,

A indicates — 0— A ¹ CH ₂ -0-A ² or — CH ₂ ON = C (R ⁴ ) —A:

R ⁴ is a d-alkyl group;

A ¹ is

66

Amended paper (Article 19 of the Convention) And

. In, X ¹ and Y 'are independently Korimoto atom, a halogen atom, an alkyl group, a halogenated alkyl group, c physician ₃ alkoxy group, a halogenated C,:., § alkoxy group, in Shiano group or a nitro group Yes,

A ²

Aa

Where Z is N or CH;

U is a hydrogen atom, a halogen atom, a Ci— _S alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated C, —alkoxy group, a cyano group, a nitro group, or A a;

67

Amended paper (Article 19 of the Convention) V represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated C _B Al kill group, d - ,; alkoxy group, halogenated alkoxy group, Shiano group, nitro group, C, - alkylcarbonyl group, an alkoxycarbonyl group, or one

C (R ⁵ ) = NOR ⁶ groups,

It is hydrogen, d-alkyl group, a halogenated c Bok ₆ alkyl group or

A a

R ⁶ is a hydrogen atom, d alkyl group, halogenated C, _—s alkyl group, alkenyl group, halogenated C alkenyl group, C ₃ alkynyl group or halogenated C alkynyl group;

W is a hydrogen atom, a halogen atom, a d-alkyl group, a halogenated C, -alkyl group, an alkoxy group or a halogenated C ₆ alkoxy group;

A ³ is one C (R ⁵ ) = NOR ⁶ , Aa or

(However, R ⁵ , R ⁶ , X ′ and Y ′ have the above-mentioned meanings.) )

18. The fungicide for agricultural and horticultural use according to claim 17, wherein the N-phenylthiodiurea derivative is used in an amount of 0.002 to 80% by weight.

19. The N-phenylthioperia derivative is used in an amount of 0.01 to 70% by weight.

68

Amended paper (Article 19 of the Convention) Statement under Article 19 (1) of the Convention

Claim 1 discloses in K. Nagarajan et al, "赚 spectra of 2-amino-4-phenylphenylazozoazoles", Indian J. Chem., (1973), No. 11, P. 879-881, N — [(2-Phenoxy) 5-cyclomouth] It has been clarified that phenyl-1-N, 1-methylthiourea (XXI) is clearly excluded.

Claim 17 clarifies that the compound is not excluded.