JP4007378B2 - Rice blast control agent containing amide compound - Google Patents

Description

The present invention relates to the use of amide compounds.

Conventionally, N- [1- (substituted phenyl) ethyl] -2-cyano-3,3-dimethylbutanamide described in JP-A-2-76846 is effective for controlling rice blast. ing.
Japanese Patent Laid-Open No. 2-76846

However, this compound is not always perfect as an active ingredient of a rice blast control agent because it is difficult to say that the effect of controlling rice blast disease is sufficient depending on the treatment method such as seed treatment.

In view of such circumstances, the present inventors have conducted extensive studies to develop a compound having an excellent control effect against rice blast, and as a result, the benzyl position has an absolute configuration of (R). It has been found that optically active N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide has an excellent control effect against rice blast, Further, N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide and an active ingredient of a specific insecticide or a specific plant disease control agent are mixed. As a result, it was found that a better control effect against rice blast was obtained, and the present invention was achieved.
That is, the present invention relates to N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide (hereinafter referred to as the present compound),
(A) 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (trifluoromethyl) sulfinyl-1H-pyrazole-3-carbonitrile,
(B) 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine and (c) ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl ( A method for controlling rice blast, characterized by using an insecticide active ingredient selected from the group consisting of (methyl) aminothio] -N-isopropyl-β-alaninate; and a compound of the present invention,
(A) Diisopropyl 1,3-dithiolane-2-ylidene malonate,
(B) 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole,
(C) 3-allyloxy-1,2-benzisothiazole-1,1-dioxide,
(D) 1,2,5,6-tetrahydro-4H-pyrrolo [3,2,1-ij] quinolin-4-one,
(E) (Z) -2′-methylacetophenone 4,6-dimethylpyrimidin-2-ylhydrazone,
(F) O-ethyl S, S-diphenyl phosphorodiothiate,
(G) 4,5,6,7-tetrachlorophthalide,
(H) Kasugamycin,
(I) α, α, α-trifluoro-3′-isopropoxy-o-toluanilide,
(J) 1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea,
(K) Validamycin,
(L) 3'-isopropoxy-o-toluanilide,
(N) N- (1,3-dihydro-1,1,3-trimethylisobenzofuran-4-yl) -5-chloro-1,3-dimethylpyrazole-4-carboxylic acid amide,
(Q) (E) -4-chloro-α, α, α-trifluoro-N- (1-imidazol-1-yl-2-propoxyethylidene) -o-toluidine,
(R) N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] imidazole-1-carboxamide,
(S) 2-[(4-chlorophenyl) methyl] -5- (1-methylethyl) -1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol,
(T) Pent-4-enyl N-furfuryl-N-imidazol-1-ylcarbonyl-DL-homoalaninate and (V) dimethyl 4,4 ′-(o-phenylene) bis (3-thioallophanate)
There is provided a rice blast control method comprising using a plant disease control agent active ingredient selected from the group consisting of:

  According to the present invention, rice blast can be controlled extremely effectively.

The compound of the present invention has an absolute configuration of (R) at the benzyl position on the amine side, but the optical purity of the moiety does not need to be 100% ee (enantiomeric excess). An optically active substance rich in the (R) isomer having an optical purity of, for example, 75% ee [ie (R) :( S) = 87.5: 12.5] or higher is included, but the optical purity is 85 for the part. An optically active substance rich in (R) isomer of% ee [ie (R) :( S) = 92.5: 7.5] or more is preferable. In addition, the α-position on the acid side of the compound of the present invention is likely to undergo racemization (epimerization), and the configuration of such sites does not significantly affect the control efficacy in the practical situation of rice blast control. (R) isomer, (S) isomer or a mixture of any proportion thereof may be used, but from the industrial standpoint, (RS) isomer is usually used.
The compound of the present invention shows a particularly excellent control effect against rice blast (Pyricularia oryzae), which is an important disease of rice, but when mixed with other appropriate plant disease control agents, the control is achieved by a synergistic action. Not only will it become more effective, it will also show the effect of more efficient control of other important diseases of rice such as rice idiot (Gibberella fujikuroi).

The compound of the present invention comprises a C2 -C4 alkyl (for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc.) ester of (alpha) -cyano-tert-butylacetic acid and (R) -1- (2,4-dichlorophenyl). It can be efficiently produced by reacting ethylamine with 130-250 ° C.
The reaction consists of C2-C4 alkyl (which may be racemic or optically active) of α-cyano-tert-butylacetic acid and (R) -1- (2,4-dichlorophenyl) ethylamine (optical purity 100%). ee (enantiomeric excess) is not necessary. For example, an optically active substance rich in (R) -form having an optical purity of 75% ee or more may be used in the absence of a solvent or in a solvent. The reaction can be carried out usually at 0.5 to 24 hours at a reaction temperature of 130 to 220 ° C. The amount of reactant used is usually 0.9 to 1.2 moles of (R) -1- (2,4-dichlorophenyl) ethylamine per mole of C2 to C4 alkyl of α-cyano-tert-butylacetic acid. Is the ratio. The solvent used as necessary is not particularly limited as long as it is inert in the reaction and has a boiling point of 130 to 250 ° C., but examples thereof include hydrocarbon solvents such as xylene, cumene, mesitylene, chlorobenzene, diethylene, and the like. Examples thereof include halogenated aromatic hydrocarbon solvents such as chlorobenzene, ether solvents such as diglyme and triglyme, or mixtures thereof.
The reaction solution after completion of the reaction is usually cooled to room temperature, and the resulting crystals are collected by filtration, washed with n-hexane or the like, and then dried to obtain the compound of the present invention.

(R) -1- (2,4-dichlorophenyl) ethylamine used as one raw material compound for producing the compound of the present invention is, for example, a method described in Organic Reaction Vol 5,301 to 330 (1949), etc. The (RS) -body obtained by the above can be produced by optical resolution by, for example, the method described in JP-A-2-306942.
C2-C4 alkyl of α-cyano-tert-butylacetic acid used as another raw material compound for producing the compound of the present invention is described in, for example, J. Org. Am. Chem. Soc. 72, 4791 (1950) and the like, but can be efficiently obtained by the following raw material production method a.

(Raw material production method a)
C2-C4 alkyl ester of α-cyano-tert-butylacetic acid is obtained by reacting C2-C4 alkyl ester of 2-cyano-3-methyl-2-butenoic acid with methylmagnesium halide in the presence of a copper catalyst. Method.
Hereinafter, the raw material production method a will be described in detail.
Examples of the C2-C4 alkyl ester of 2-cyano-3-methyl-2-butenoic acid used include ethyl 2-cyano-3-methyl-2-butenoate and 2-cyano-3-methyl-2-butenoic acid. n-propyl, isopropyl 2-cyano-3-methyl-2-butenoate, n-butyl 2-cyano-3-methyl-2-butenoate, isobutyl 2-cyano-3-methyl-2-butenoate, etc. It is done.
Examples of the methylmagnesium halide used include methylmagnesium chloride (CH3MgCl), methylmagnesium bromide (CH3MgBr), and methylmagnesium iodide (CH3MgI), which are either commercially available or magnesium and methyl. It can be prepared by reacting a halide with a conventional method.
As the copper catalyst, a monovalent copper salt is usually used, and examples thereof include copper chloride (I) (CuCl), copper bromide (I) (CuBr), and copper iodide (I) (CuI).
The reaction is usually carried out in an organic solvent. Examples of the organic solvent to be used include ether solvents such as tetrahydrofuran (hereinafter referred to as THF), diethyl ether and dibutyl ether, and aromatic hydrocarbon solvents such as toluene, xylene and benzene. And a mixed solvent of an ether solvent and an aromatic hydrocarbon solvent.
The reaction temperature is usually 10 to 60 ° C., the reaction time is usually 0.5 to 10 hours, and the amount of the reactant used for the reaction is C2-C4 alkyl ester of 2-cyano-3-methyl-2-butenoic acid. Methyl magnesium halide is usually in a ratio of 1 to 2 moles per mole, and the copper catalyst is usually from 0.0005 to 0.1 per 1 part by weight of C2-C4 alkyl ester of 2-cyano-3-methyl-2-butenoic acid. It is the ratio of parts by weight.
The reaction solution after the reaction is usually treated with, for example, water, aqueous ammonium chloride, dilute sulfuric acid, etc., and the organic layer is concentrated. If necessary, the target α-cyano- The C2 -C4 alkyl ester of tert-butylacetic acid can be isolated.

The C2-C4 alkyl ester of 2-cyano-3-methyl-2-butenoic acid, which is a raw material used in the raw material production method a, can be efficiently produced by the following raw material production method b.
(Raw material production method b)
A method for obtaining C2-C4 alkyl ester of 2-cyano-3-methyl-2-butenoic acid by reacting acetone with C2-C4 alkyl ester of cyanoacetic acid in the presence of a catalyst using n-hexane as a main solvent. .
Hereinafter, the raw material production method b will be described in detail.
Examples of the C2 -C4 alkyl ester of cyanoacetic acid used include ethyl cyanoacetate, n-propyl cyanoacetate, isopropyl cyanoacetate, n-butyl cyanoacetate, isobutyl cyanoacetate, and the like. It can be used or can be produced by a conventional method.
As the catalyst, usually substituted aniline and carboxylic acid are used.
Examples of the substituent in the optionally substituted aniline include a hydroxyl group, a methyl group, and a methoxy group. Examples of the optionally substituted aniline include aminophenol (p-aminophenol, o-amino). Phenol, m-aminophenol, etc.) and toluidine (p-toluidine, o-toluidine, m-toluidine).
Examples of carboxylic acids include, for example, lower (for example, C1 to C4) fatty acids (for example, acetic acid, formic acid, propionic acid, etc.) and benzoic acid.
As a reaction solvent, n-hexane is used as a main solvent. More specifically, the use ratio of n-hexane to the total solvent is usually 50 to 100% by weight, and the reaction solvent can be used by mixing with n-hexane. Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene.
The reaction temperature is usually 50 to 100 ° C., the reaction time is usually 5 to 20 hours, and the reaction is usually carried out while removing water generated during the reaction.
The amount of the reactant used in the reaction is usually 1 to 4 moles of acetone and 1 mole of 0.001 to 0.2 moles of catalyst per mole of C2 -C4 alkyl ester of cyanoacetic acid (even if substituted). Good anilines are usually in the proportion of 0.001 to 0.1 mol; carboxylic acids are usually in the proportion of 0.01 to 0.2 mol).
The reaction solution after the reaction is usually concentrated under reduced pressure or normal pressure and distilled as it is, or dissolved in a solvent such as ethyl acetate, toluene, xylene and washed with water, the solution is concentrated under reduced pressure to remove the solvent, and if necessary Furthermore, the target C2-C4 alkyl ester of 2-cyano-3-methyl-2-butenoic acid can be isolated by performing a purification operation such as distillation.

The compound of the present invention reacts (R) -1- (2,4-dichlorophenyl) ethylamine with a reactive derivative other than α-cyano-tert-butylacetic acid or its ester, if necessary, in the presence of a reaction aid. Can also be manufactured.
In the above reaction, examples of the reactive derivative of α-cyano-tert-butylacetic acid include the corresponding acid anhydride, acid chloride, acid bromide, etc., and the reaction aid is α-cyano-tert-butylacetic acid or its Depending on the reactive derivative, for example dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1,1'-carbonyldiimidazole, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, chloride Examples include thionyl, phosgene, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, triethylamine, pyridine, quinoline, N, N-dimethylaniline, N, N-diethylaniline, N-methylmorpholine and the like.
In the above reaction, the reaction temperature is typically 0 to 200 ° C., the reaction time is 0.1 to 24 hours, and the amount of the reagent used for the reaction is α-cyano-tert-butylacetic acid or a reactive derivative thereof. (R) -1- (2,4-dichlorophenyl) ethylamine is usually in a proportion of 1 to 1.2 mol per 1 mol, and the reaction aid used as necessary is usually 1 mmol to 5 mol. Is the ratio.
In the above reaction, a reaction solvent is not necessarily required, but it is generally carried out in the presence of a solvent.
Solvents that can be used include aliphatic hydrocarbons such as hexane, heptane and ligroin, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and diethylene glycol dimethyl ether, Examples thereof include halogen-containing solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, solvents such as dimethylformamide, dimethyl sulfoxide, acetonitrile, water, and mixtures thereof.
After completion of the reaction, the reaction mixture is subjected to usual post-treatments such as organic solvent extraction and concentration, and if necessary, subjected to operations such as column chromatography and recrystallization to isolate the target compound of the present invention. be able to.
Α-Cyano-tert-butylacetic acid or a reactive derivative thereof, which is a raw material compound for producing the compound of the present invention, is obtained by a usual derivatization method, that is, a carboxylic acid ester is hydrolyzed to obtain a carboxylic acid The obtained carboxylic acid can be produced by an acid halide to obtain a carboxylic acid halide.

When the compound of the present invention is used as an active ingredient of a rice blast control agent, it may be used as it is without adding any other components, but is usually used as a solid carrier, liquid carrier, surfactant or other preparation. It is mixed with adjuvants and formulated into emulsions, wettable powders, suspensions, granules, powders, etc.
These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99%, preferably 0.2 to 95%.
Examples of solid carriers include fine powders such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic silicon hydroxide. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, soybean oil, cottonseed oil, and the like Vegetable oil, dimethyl sulfoxide, acetonitrile, water and the like.
Examples of surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene. Nonionic surfactants such as anionic surfactants such as sulfonic acid formalin condensate, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like.
Examples of the formulation adjuvant include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), PAP (isopropyl acid phosphate) and the like.

These preparations can be used as they are, or diluted with water and sprayed with foliage, or powdered and sprinkled on the soil surface and water surface, or powdered and sprinkled on the soil surface, mixed or mixed in a seedling box Treat or seed.
Seed treatment methods include seed soaking treatment, seed spraying treatment, seed dressing treatment, and the like. In seed treatment, powder seeding or coating can be performed together with calcium peroxide or the like.
Moreover, it can also be used by mixing with other plant disease control agents, insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, soil conditioners and the like.

Examples of other plant disease control agents that can be mixed are shown below together with compound symbols.
(A) Diisopropyl 1,3-dithiolane-2-ylidene malonate (generic name isoprothiolane),
(B) 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole [generic name tricyclazole],
(C) 3-allyloxy-1,2-benzisothiazole-1,1-dioxide [general name probenazole],
(D) 1,2,5,6-tetrahydro-4H-pyrrolo [3,2,1-ij] quinolin-4-one [generic name pyroquilon],
(E) (Z) -2′-methylacetophenone 4,6-dimethylpyrimidin-2-ylhydrazone [generic name: ferimzone],
(F) O-ethyl S, S-diphenyl phosphorodiothiate [generic name edifenphos],
(G) 4,5,6,7-tetrachlorophthalide [generic name phthalide],
(H) Kasugamycin [generic name kasugamycin],
(I) α, α, α-trifluoro-3′-isopropoxy-o-toluanilide (generic name: flutolanil),
(J) 1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea (generic name pencycuron),
(K) Validamycin [generic name: validamycin],
(L) 3'-isopropoxy-o-toluanilide [generic name mepronil],
(M) 6- (3,5-dichloro-4-methylphenyl) -3 (2H) -pyridazinone [generic name diclomezine],
(N) N- (1,3-dihydro-1,1,3-trimethylisobenzofuran-4-yl) -5-chloro-1,3-dimethylpyrazole-4-carboxylic acid amide [generic name furametpyr],
(O) Methyl (E) -2- {2- [6- (2-Cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate [ICIA5504]
(P) 5-ethyl-5,8-dihydro-8-oxo-1,3-dioxolo [4,5-g] quinoline-7-carboxylic acid [generic name oxolinic acid],
(Q) (E) -4-chloro-α, α, α-trifluoro-N- (1-imidazol-1-yl-2-propoxyethylidene) -o-toluidine [generic name triflumizole],
(R) N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] imidazole-1-carboxamide [generic name prochloraz],
(S) 2-[(4-chlorophenyl) methyl] -5- (1-methylethyl) -1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol [generic name ipconazole],
(T) Pent-4-enyl N-furfuryl-N-imidazol-1-ylcarbonyl-DL-homoalaninate [generic name pefurazoate],
(U) methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate [generic name benomyl],
(V) Dimethyl 4,4 ′-(o-phenylene) bis (3-thioallophanate) [generic name thiophanate-methyl],
(W) 2- (thiazol-4-yl) benzimidazole [generic name thiabendazole],
(X) Bis (dimethylthiocarbamoyl) disulfide [generic name thiram],
(Y) 4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine [CGA219417, proposed general name cyprodinil],
(Z) 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile [generic name fludioxonil].
The mixing ratio in the case of using the compound of the present invention and the active ingredient of the other plant disease control agent mixed varies depending on the type of the plant disease control agent to be mixed, etc., but with respect to 1 part by weight of the compound of the present invention, The plant disease control agent can usually take 0.01 to 100, preferably 0.2 to 20 by weight ratio.

Examples of insecticides that can be mixed are shown below with compound symbols.
(A) 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (trifluoromethyl) sulfinyl-1H-pyrazole-3-carbonitrile [generic name fipronil],
(B) 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine (generic name imidacloprid),
(C) ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate (generic name benfuracarb),
(D) S, S ′-(2-dimethylaminotrimethylene) bis (thiocarbamate) [generic name cartap],
(E) 4- (methylthio) phenyl dipropyl phosphate [generic name propaphos],
(F) 2,3-dihydro-2,2-dimethylbenzofuran-7-yl (dibutylaminothio) methylcarbamate [generic name carbosulfan],
(G) (E) -N- (6-Chloro-3-pyridylmethyl) -N-ethyl-N′-methyl-2-nitrovinylidenediamine (generic name nitenpyram),
(H) (E) -4,5-dihydro-6-methyl-4- (3-pyridylmethyleneamino) -1,2,4-triazin-3 (2H) -one [generic name pimetrozine]
(I) O, O-dimethyl O-4-nitro-m-tolyl phosphorothioate [generic name fenitrothion]
Etc.
The mixing ratio when the compound of the present invention and the active ingredient of the insecticide are mixed varies depending on the kind of the insecticide to be mixed, etc., but the weight ratio of the insecticide is 1 part by weight of the compound of the present invention. In general, it can be 0.01 to 100, preferably 0.2 to 20.

When the compound of the present invention is used as an active ingredient of a rice blast control agent, the treatment amount varies depending on weather conditions, formulation form, treatment time, treatment method, treatment place, etc., but usually 0.05 to 200 g per are. When the emulsion, wettable powder, suspending agent and the like are diluted with water and applied, the applied concentration is 0.00005 to 0.5%, preferably 0.0001 to 0.2%. Yes, granules, powders, etc. are applied as they are without dilution.
In the treatment of the seedling box, the amount of the active ingredient is usually about 0.1 to about 100 g, preferably about 0.5 to about 10 g per box (30 cm × 60 cm × 3 cm) of the size normally used. be able to.
In the seed treatment, the amount of the active ingredient is usually about 0.001 to about 50 g, preferably about 0.01 to about 10 g, per 1 kg of the seed. Soak in a high concentration chemical solution of usually about 5000 to about 50,000 ppm in a proportion of 3 kg, usually for a short time of about 5 minutes to about 30 minutes, or a low concentration chemical solution of usually about 20 to about 4000 ppm in a proportion of usually 1 to 3 kg. For about 6 hours to about 48 hours.

Hereinafter, the present invention will be described in more detail with reference to production examples, formulation examples, test examples, and the like, but the present invention is not limited to these examples.
First, the manufacture example of this invention compound is shown.
Production Examples 1-5
Production Examples 1 to 5 of the present compound according to the following production method A or B are summarized in Table 1.
Hereinafter, the following stereoisomers are referred to as X1, X2, Y1, and Y2, respectively.
N-[(R) -1- (2,4-dichlorophenyl) ethyl]-(R) -2-cyano-3,3-dimethylbutanamide: X1.
N-[(S) -1- (2,4-dichlorophenyl) ethyl]-(S) -2-cyano-3,3-dimethylbutanamide: X2.
N-[(S) -1- (2,4-dichlorophenyl) ethyl]-(R) -2-cyano-3,3-dimethylbutanamide: Y1.
N-[(R) -1- (2,4-dichlorophenyl) ethyl]-(S) -2-cyano-3,3-dimethylbutanamide: Y2.
Each of these isomers can be obtained by fractionating the racemate (X1 body + X2 body + Y1 body + Y2 body) under the conditions described in * 4 in the column of Table 1 below. The absolute configuration of each of these was determined by X-ray structural analysis of each of the X1 body and the Y body (Y1 + Y2).
(Production method A)
A C2-C4 alkyl ester of (RS)-. Alpha.-cyano-tert-butylacetic acid and (R) -1- (2,4-dichlorophenyl) were added to a four-necked flask equipped with a Bigru type rectification column, a thermometer and a mechanical stirrer. ) A predetermined amount of ethylamine was charged.
After heating up to 180 degreeC, it reacted for 5 to 10 hours, distilling the produced | generated alcohol at 180-190 degreeC. After completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting crystals were collected by filtration and washed twice with n-hexane. The obtained compound was dried under reduced pressure to obtain the compound of the present invention.
(Production method B)
A rectifying column (20 cm) packed with a helicoil, a four-necked flask equipped with a thermometer and a mechanical stirrer was added with (RS) -α-cyano-tert-butylacetic acid C 2 -C 4 alkyl ester and (R) -1- ( A predetermined amount of 2,4-dichlorophenyl) ethylamine was charged and 50 ml of a predetermined solvent was added. This solution was heated and refluxed for 8 to 20 hours while distilling the produced alcohol together with the solvent (about 30 ml). After completion of the reaction, the reaction mixture was cooled to room temperature, 50 ml of n-hexane was added, and the resulting crystals were collected by filtration and washed twice with n-hexane. The obtained compound was dried under reduced pressure to obtain the compound of the present invention.

[Table 1]
┌──────────────────────────────────┐
│Production Yield Stereoisomer│
│ Manufacturing R * 1 CYBR * 2 DCEA * 3 Solvent yield (vs. ratio │
│Example (g) (g) (g) CYBR) X1 / Y2 * 4 │
│ Law │
├──────────────────────────────────┤
│1 * 13 B Et 20.0 27.0 * 5 Xylene 35.3 95.4% 50/50 * 8 │
│2 A Et 20.0 23.6 * 5 None 33.6 90.8% 49/51 * 9 │
│3 A Bu 19.7 20.2 * 5 None 28.6 90.0% 50/50 * 10 │
│4 A Et 20.0 23.6 * 6 None 33.8 91.3% 46/46 * 11 │
│5 A Et 17.0 20.0 * 7 None 27.2 86.7% 44/44 * 12 │
└──────────────────────────────────┘
* 1. Alkyl of α-cyano-tert-butyl acetate (Et represents ethyl, Bu represents n-butyl).
* 2. Alkyl α-cyano-tert-butyl acetate.
* 3. Optically active 1- (2,4-dichlorophenyl) ethylamine rich in (R) -form.
* 4. Calculate the ratio using the high-performance liquid chromatogram analysis area comparison method [High-performance liquid chromatography (HPLC) analysis conditions are as follows;
Equipment: Hitachi L-6200
Column: SUMIPAX YMC-GEL SIL + SUMICHIRAL OA-4700
(5 μm, diameter 4 mm × length 25 cm) (5 μm, diameter 4.6 mm × length 25 cm)
Mobile phase: n-hexane / ethanol / trifluoroacetic acid = 240: 10: 1
Detection: UV254nm]
* 5. (R) -1- (2,4-dichlorophenyl) ethylamine having an optical purity of 99.8% ee or higher was used.
* 6. (R) -1- (2,4-dichlorophenyl) ethylamine having an optical purity of 84% ee was used.
* 7. (R) -1- (2,4-dichlorophenyl) ethylamine having an optical purity of 76% ee was used.
* 8. X2 / Y1 = <0.1 / <0.1
* 9. X2 / Y1 = <0.1 / <0.1
* 10. X2 / Y1 = <0.1 / <0.1
* 11. X2 / Y1 = 4/4
* 12. X2 / Y1 = 6/6
* 13. The physical properties of the compound of the present invention obtained in Production Example 1 (hereinafter referred to as (1)) are as follows.
m. p. 160 to 161 ° C
[Α] D 20 = + 18.0 ° (c = 1.01, CH 2 Cl 2)

Next, a production example of the raw material production method a is shown.
Reference production example a-1
After adding 6.0 g of copper (I) iodide at 35-40 ° C. to a solution of methyl magnesium chloride prepared from 119 g of methyl chloride, 49.6 g of magnesium and 509 g of THF, 2-cyano-3-methyl-2- A solution prepared by dissolving 240 g of ethyl butenoate in 480 g of toluene was added dropwise at the same temperature over about 1 hour. After completion of the dropwise addition, the reaction was further continued at the same temperature for 1 hour. The reaction mixture was cooled to 20-30 ° C. and then poured into 1742 g of 20% aqueous ammonium chloride at 10-20 ° C. After standing at room temperature and liquid separation, the aqueous layer was extracted twice with 480 ml of ethyl acetate, and the organic layers were combined and washed twice with 480 g of saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was distilled as it was (boiling point of main fraction: 80 to 86 ° C./12 to 15 mmHg) to obtain the desired product. The yield of α-cyano-tert-butyl ethyl acetate after distillation was 249 g, and the yield was 94%.

  In Reference Production Example a-1, the results of the reaction carried out in the same manner as in Raw Material Production Example a-1 except that the type or amount of the catalyst are changed are shown in Table 2. The yield in the table represents the ratio of 2-cyano-3-methyl-2-butenoic acid to the alkyl ester.

[Table 2]
┌──────────────────────────────────┐
│Raw material production Reaction solvent Catalyst Reaction time Yield * 4│
│Example a THF: Toluene (parts by weight) * 2 Alkyl * 3 (hr) (%) |
├──────────────────────────────────┤
│ 1 1: 1: 1 CuI (0.025) Ethyl 1 94 │
│ 2 1: 1 * 1 CuCl (0.025) Ethyl 1 91 │
│ 3 1: 1 * 1 CuCl (0.013) Ethyl 1 91 │
│ 4 1: 1 * 1 CuCl (0.006) Ethyl 1 91 │
│ 5 1: 1 * 1 CuCl (0.002) Ethyl 1 89 │
│ 6 1: 1: 1 CuCl (0.001) Ethyl 1 89 │
└──────────────────────────────────┘
* 1. Weight ratio.
* 2.2 Amount of catalyst (parts by weight) based on 1 part by weight of alkyl ester of 2-cyano-3-methyl-2-butenoic acid.
* 3. Alkyl ester of alkyl ester of 2-cyano-3-methyl-2-butenoic acid.
* 4. Yield after distillation.

Next, a production example of the raw material production method b is shown.
The reaction rate is a value obtained by the following equation (1).

[Equation 1]
Reaction rate = 100-remaining alkyl ester of cyanoacetic acid
(%) GC area ratio (%)
Gas chromatographic (GC) analysis conditions;
Shimadzu GC-7A,
Column: 10% DEXIL 300GC Diameter 3mm x Length 1m
UNIPORT HP 100-200 mesh
Column temperature: 70 to 150 ° C. at a rate of 5 ° C./min. Reference production example b-1
50.0 g of ethyl cyanoacetate, 51.34 g of acetone, 1.99 g of acetic acid, 0.24 g of p-aminophenol and 41 ml of n-hexane were charged, and the mixture was heated to reflux for 9 hours while azeotropically removing water produced during the reaction. When analyzed by gas chromatography, the reaction rate of ethyl cyanoacetate was 99%. After completion of the reaction, the reaction solution was concentrated under reduced pressure to remove hexane, acetic acid and unreacted acetone, and the residue was rectified using a 30 cm rectification column packed with helicoil under a reduced pressure of 20 mmHg. A 113 ° C. fraction was collected. The yield of ethyl 2-cyano-3-methyl-2-butenoate after distillation was 63.6 g, and the yield was 94%.

  In Reference Production Example b-1, the reaction was carried out in the same manner as in Production Example b-1 except that the type of reaction solvent, the type of catalyst, the type of alkyl of alkyl ester of cyanoacetic acid, or the reaction time were changed. Are summarized in Table 3. The yield in the table represents the ratio of cyanoacetic acid to alkyl ester.

[Table 3]
┌──────────────────────────────────┐
│Production of raw materials Reaction solvent Catalyst R * 1 Reaction time Reaction rate Yield * 2│
│Example b Hexane: Toluene (hr) (%) (%) │
├──────────────────────────────────┤
│ 1 Hexane only C * 4 Et 9 99 94 │
│ 2 Hexane only C * 4 Bu 9 99 93 │
│ 3 Hexane only D * 5 Et 12 96 87 │
│ 4 Hexane only E * 6 Et 8 99 95 │
│ 5 Hexane only F * 7 Et 10 99 95 │
│ 6 2: 1 * 3 E * 6 Et 10 99 92 │
└──────────────────────────────────┘
* 1. Alkyl of alkyl ester of cyanoacetic acid (Et represents ethyl and Bu represents butyl).
* 2. Yield after distillation.
* 3. Weight ratio.
* 4. C: p-aminophenol and acetic acid * 5. D: p-Toluidine and acetic acid * 6. E: p-aminophenol and benzoic acid * 7. F: p-aminophenol and propionic acid

Next, formulation examples are shown. In addition, a part represents a weight part and this invention compound (1) was obtained in the said manufacture example 1.
Formulation Example 1
50 parts of the compound (1) of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic silicon hydroxide are thoroughly pulverized and mixed to obtain a wettable powder.
Formulation Example 2
This invention compound (1) 25 parts, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water are mixed, and it wet-grinds until the particle size of an active ingredient will be 5 microns or less, and a suspension agent is obtained.
Formulation Example 3
This invention compound (1) 2 parts, 87 parts of kaolin clay, and 10 parts of talc are well ground and mixed to obtain a powder.
Formulation Example 4
The present compound (1) 20 parts, polyoxyethylene styryl phenyl ether 14 parts, calcium dodecylbenzenesulfonate 6 parts and xylene 60 parts are mixed well to obtain an emulsion.
Formulation Example 5
The compound (1) of the present invention (10 parts), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 73 parts of kaolin clay are thoroughly pulverized and mixed. To obtain granules.
Each of the compounds (A) to (Z) and (a) to (h) and the mixture of each of these compounds and the compound of the present invention (1) is also formulated according to the above Formulation Examples 1 to 5. be able to.

Next, test examples show that the compounds of the present invention are useful as rice blast control agents and the like. In addition, this invention compound (1) was obtained in the said manufacture example 1, and other plant disease control agents and insecticides are shown with the said compound symbol. Moreover, the compound used for the comparison control is shown by the following compound numbers.
(2) N-[(RS) -1- (2,4-dichlorophenyl) ethyl]-(RS) -2-cyano-3,3-dimethylbutanamide [specifically described in JP-A-2-76846 Compound (6)]

Test Example 1 Rice Blast Control Test (Seed Dipping Treatment)
A reagent provided as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and rice fir (Nipponbare) was soaked at a ratio of 2 kg chemical solution / 1 kg seed for 10 minutes.
The treated fir was air-dried and sown in a seedling box at a rate of 160 g seeds / box and nurtured for 20 days. After that, five rice seedlings were transplanted into a 1/5000 Earl Wagner pot filled with soil and watered. Cultivation was continued in the greenhouse while continuing water leakage treatment at a rate of 3 cm per day from the bottom of the Wagner pot. Six weeks after transplantation, they were placed in a greenhouse together with another rice seedling that had developed blast, and infected with blast fungus in a humidified state. Eleven days after the inoculation, the disease index of leaf blast was examined according to the following criteria, and the control value was calculated from Equation 2 and Equation 3. The disease severity in the untreated area was 58%.
Disease index Incidence of lesion area ratio 0 0
11-5%
2 6-25%
4 26-50%
8 51% or more

[Equation 2]
(1 × n1) + (2 × n2) + (4 × n3) × (8 × n4)
Disease severity (%) = ─────────────────────────────
8 x N
N: Number of leaves surveyed n1 to n4: Number of leaves on disease index 1, 2, 4, 8

[Equation 3]
Disease severity of untreated areas-Disease control value (%) of treated areas = ──────────────────── × 100
Table 4 shows the disease severity of the untreated group.

[Table 4]
┌─────────┬────────────────┬──────┐
│ Reagents │ Active ingredient treatment concentration (ppm) │ Control value (%) │
├─────────┼────────────────┼──────┤
│ (1) │ 10000 │ 86 │
│ │ 5000 │ 74 │
│ │ 2500 │ 65 │
├─────────┼────────────────┼──────┤
│ (2) │ 10000 │ 61 │
│ │ 5000 │ 41 │
│ (B) │ 10000 │ 0 │
│ (T) │ 10000 │ 0 │
│ (U) │ 10000 │ 0 │
└─────────┴────────────────┴──────┘
As described above, the compound (1) of the present invention exhibits excellent control efficacy even under severe conditions, and surprisingly, the compound (1) of the present invention is 1/4 of the compound of the comparative compound (2). The control effect was almost the same in amount.

Test Example 2 Rice Blast Control Test (Seed Spray Treatment)
The reagent provided as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and this was sprayed onto rice fir (Nipponbare) at a dose of 30 ml / 1 kg seed. The treated fir was air-dried, filled with sand loam in a plastic pot, seeded, and grown in a greenhouse for 20 days. After that, they were placed in a greenhouse together with another rice seedling that developed blast, and kept in a humidified state to infect blast fungus. 10 days after the inoculation, the disease index of leaf gluten was investigated according to Test Example 1 and the control value was determined. The disease severity in the untreated area was 100%.
The results are shown in Table 5.

[Table 5]
┌───────┬───────────────┬──────────┐
│ Test │ Active ingredient treatment concentration │ Control value (%) │
│ Drug │ (ppm) │ │
├───────┼───────────────┼──────────┤
│ (1) │ 2000 │ 86 │
│ (1) + (Q) │ 2000 + 2000 │ 100 │
│ (1) + (R) │ 2000 + 2000 │ 100 │
│ (1) + (S) │ 2000 + 2000 │ 100 │
│ (1) + (T) │ 2000 + 2000 │ 100 │
│ (1) + (V) │ 2000 + 2000 │ 100 │
├───────┼───────────────┼──────────┤
│ (2) │ 2000 │ 48 │
│ (Q) │ 2000 │ 0 │
│ (R) │ 2000 │ 0 │
│ (S) │ 2000 │ 15 │
│ (T) │ 2000 │ 0 │
│ (V) │ 2000 │ 0 │
└───────┴───────────────┴──────────┘

Test Example 3 Rice idiot disease control test (seed spraying treatment)
To rice fir (Nipponbare) contaminated with rice idiot (Gibberella fujikuroi), a reagent prepared as a wettable powder according to Formulation Example 1 is diluted with water to a predetermined concentration. The rice paddy was sprayed at a dose. The treated fir was air-dried, then filled with sand loam in a plastic pot, sown at a rate of 50 grains per pot, and grown in a greenhouse for 21 days. The disease state was investigated by the following equation (4), and the percentage of healthy seedlings was determined.

[Equation 4]
Number of healthy seedlings in each treatment area Healthy seedling rate (%) = ──────────────────── × 100
Table 6 shows the results of the number of healthy seedlings in the untreated and uninoculated areas.

[Table 6]
┌───────┬───────────────┬──────────┐
│ Test │ Active ingredient treatment concentration │ Healthy seedling rate (%) │
│ Drug │ (ppm) │ │
├───────┼───────────────┼──────────┤
│ (1) + (Q) │ 10000 + 10000 │ 100 │
│ (1) + (R) │ 10000 + 10000 │ 100 │
│ (1) + (S) │10000 + 10000 │ 100 │
│ (1) + (T) │10000 + 10000 │ 100 │
│ (1) + (V) │10000 + 10000 │ 100 │
├───────┼───────────────┼──────────┤
│ (1) │ 10000 │ 10 │
│ (Q) │ 10000 │ 78 │
│ (R) │ 10000 │ 88 │
│ (S) │ 10000 │ 93 │
│ (T) │ 10000 │ 84 │
│ (V) │ 10000 │ 70 │
│Bacteria inoculation / No treatment│-│ 0 │
│No inoculation / No treatment│-│ 100 │
└───────┴───────────────┴──────────┘

Test Example 4 Rice Blast Control (Stem and Leaf Spray)
A plastic pot was filled with sandy loam, sown with rice (Nihonbare), and grown in a greenhouse for 20 days. The reagent provided as a suspension according to Formulation Example 2 is diluted with water to a predetermined concentration, and the amount of the solution is such that the leaves are slightly wetted by the rice seedlings (30 liter / 10 are) Sprayed with foliage. After spraying, the plants were air-dried and sprayed and inoculated with a spore suspension of blast fungus. After inoculation, the plants were grown for 4 days at 28 ° C. in the dark and under high humidity, and the disease index of leaf blast was investigated according to Test Example 1 to determine the control value. The disease severity in the untreated area was 100%.
The results are shown in Table 7.

[Table 7]
┌──────┬───────────┬───────┐
│ Reagents │ Active ingredient treatment concentration (ppm) │ Control value (%) │
├──────┼───────────┼───────┤
│ (1) │ 100 │ 100 │
│ │ 50 │ 99 │
│ │ 25 │ 94 │
└──────┴───────────┴───────┘

Test Example 5 Rice Blast Control (Stem and Leaf Spray)
A plastic pot was filled with sandy loam, sown with rice (Nihonbare), and grown in a greenhouse for 20 days. The reagent provided as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and sprayed on the foliage so that it was sufficiently attached to the leaf surface of the rice seedling. Immediately after the chemical solution was air-dried in the preventive effect test, and after 7 days in the greenhouse in the residual effect test, a spore suspension of blast fungus was spray-inoculated. After inoculation, it was kept at 24 ° C. under high humidity for 10 days, and the control effect was examined by the following index.

Control index Control effect ────────────────
5 Healthy 4 Control effect 90% or more 3 Control effect 70-89%
2 Control effect 41-69%
1 Control effect 1-40%
0 Control effect 0%
The results are shown in Table 8 and Table 9.

[Table 8]
┏━━━━━━━━━━━━┯━━━━━━━━┯━━━━━━━━━━━┓
有効 │ Active ingredient │ Control index ┃
┃ Test agent │ Treatment concentration ├─────┬─────┨
┃ (ppm) │Aftereffect │Preventive effect ┃
┠────────────┼────────┼┼─────┼─────┨
┃ (1) │ 2.5 │ 4 │ 4 ┃
│ │ 0.5 │ 2 │ 2 ┃
┃ (1) + (E) │2.5 + 5 │ 5 │ 5 ┃
┃ │0.5 + 3 │ 4 │ 4 ┃
┃ (1) + (F) │2.5 + 5 │ 5 │ 5 ┃
│ │0.5 + 3 │ 3 │ 3 ┃
┃ (1) + (G) │2.5 + 5 │ 5 │ 5 ┃
┃ │0.5 + 3 │ 4 │ 4 ┃
┃ (1) + (H) │2.5 + 5 │ 5 │ 5 ┃
┃ │0.5 + 3 │ 4 │ 4 ┃
┃ (1) + (N) │2.5 + 500 │ 5 │ 5 ┃
┃ │0.5 + 100 │ 4 │ 4 ┃
┃ (1) + (I) │2.5 + 500 │ 5 │ 5 ┃
┃ │0.5 + 100 │ 4 │ 4 ┃
┃ (1) + (J) │2.5 + 500 │ 5 │ 5 ┃
┃ │0.5 + 100 │ 4 │ 4 ┃
┃ (1) + (K) │2.5 + 500 │ 5 │ 5 ┃
┃ │0.5 + 100 │ 4 │ 4 ┃
┗━━━━━━━━━━━━┷━━━━━━━━┷━━━━━┷━━━━━┛

[Table 9]
┏━━━━━━━━━━━━┯━━━━━━━━┯━━━━━━━━━━━┓
有効 │ Active ingredient │ Control index ┃
┃ Test agent │ Treatment concentration ├─────┬─────┨
┃ (ppm) │Aftereffect │Preventive effect ┃
┠────────────┼────────┼┼─────┼─────┨
Ｅ (E) │ 5 │ 1 │ 2 ┃
┃ │ 3 │ 0 │ 1 ┃
┃ (F) │ 5 │ 1 │ 2 ┃
┃ │ 3 │ 0 │ 1 ┃
┃ (G) │ 5 │ 2 │ 3 ┃
┃ │ 3 │ 0 │ 1 ┃
┃ (H) │ 5 │ 1 │ 2 ┃
┃ │ 3 │ 0 │ 1 ┃
┃ (N) │ 500 │ 0 │ 0 ┃
┃ │ 100 │ 0 │ 0 ┃
┃ (I) │ 500 │ 0 │ 0 ┃
┃ │ 100 │ 0 │ 0 ┃
┃ (J) │ 500 │ 0 │ 0 ┃
┃ │ 100 │ 0 │ 0 ┃
┃ (K) │ 500 │ 0 │ 0 ┃
┃ │ 100 │ 0 │ 0 ┃
┗━━━━━━━━━━━━┷━━━━━━━━┷━━━━━┷━━━━━┛

Test Example 6 Rice blight control test (stem and leaf spraying)
A plastic pot was filled with sandy loam, sown with rice (Nihonbare), and grown in a greenhouse for 20 days. The reagent provided as a suspension according to Formulation Example 2 was diluted with water to a predetermined concentration, and sprayed on the foliage so that it was sufficiently attached to the leaf surface of the rice seedling. After the chemical solution was air-dried, the sclerotia of the mold blight fungus was inoculated to the stock. After inoculation, it was kept under high humidity at 27 ° C. for 10 days, and the control effect was investigated with the control index according to Test Example 5. The results are shown in Table 10.

[Table 10]
┏━━━━━━━━━━━━┯━━━━━━━━┯━━━━━━━━━━━┓
有効 │ Active ingredient │ ┃
┃ Test agent │ Treatment concentration │ Control index ┃
┃ │ (ppm) │ ┃
┠────────────┼────────┼┼───────────┨
┃ (1) + (I) │250 + 10 │ 4 ┃
│ │ 50 + 5 │ 2 ┃
┃ (1) + (J) │250 + 5 │ 4 ┃
│ │ 50 + 1.25│ 2 ┃
┃ (1) + (K) │250 + 10 │ 4 ┃
│ │ 50 + 5 │ 2 ┃
┃ (1) + (L) │250 + 30 │ 4 ┃
│ │ 50 + 10 │ 1 ┃
┠────────────┼────────┼┼───────────┨
┃ (1) │ 250 │ 0 ┃
│ │ 50 │ 0 ┃
┃ (I) │ 10 │ 3 ┃
│ │ 5 │ 1 ┃
┃ (J) │ 5 │ 3 ┃
│ │ 1.25 │ 1 ┃
┃ (K) │ 10 │ 3 ┃
│ │ 5 │ 1 ┃
┃ (L) │ 30 │ 3 ┃
│ │ 10 │ 0 ┃
┗━━━━━━━━━━━━┷━━━━━━━━┷━━━━━━━━━━━┛

Test example 7 Rice blast control test (nursing box treatment)
A rice seedling box (30 cm × 60 cm × 3 cm) was filled with artificial soil (Bonsol 2 manufactured by Koura Sangyo Co., Ltd.), and about 200 g of rice (Nipponbare) dry rice seeds were sown per box. Twenty days after sowing, the granules prepared according to Preparation Example 5 were uniformly sprayed on the soil surface of the seedling box. After lightly irrigating, 5 rice seedlings were transplanted into a 1/5000 Earl Wagner pot filled with sandy loam (from Takarazuka City, Hyogo Prefecture). Cultivation was continued in the greenhouse while continuing water leakage treatment at a rate of 3 cm per day from the bottom of the Wagner pot. Six weeks after transplantation, they were placed in a greenhouse together with another rice seedling that had developed blast, and infected with blast fungus in a humidified state. The disease index of leaf blast was investigated according to Test Example 1 11 days after the bacterial inoculation, and the control value was determined. The disease severity in the untreated area was 95%.
The results are shown in Table 11.

[Table 11]
┌─────────┬────────────────┬──────┐
│ Reagents │ Amount of active ingredient processed (g / nursery box) │ Control value (%) │
├─────────┼────────────────┼──────┤
│ (1) │ 3 │ 98 │
│ │ 1.5 │ 92 │
│ │ 0.75 │ 80 │
├─────────┼────────────────┼──────┤
│ (B) │ 2 │ 39 │
└─────────┴────────────────┴──────┘

Test Example 8 Rice blast control test (nursing box treatment)
A rice seedling box (30 cm × 60 cm × 3 cm) was filled with artificial soil (Bonsol 2 manufactured by Koura Sangyo Co., Ltd.), and about 200 g of rice (Nipponbare) dry rice seeds were sown per box. Twenty days after sowing, the granules prepared according to Preparation Example 5 were uniformly sprayed on the soil surface of the seedling box. After lightly irrigating, 5 rice seedlings were transplanted into a 1/5000 Earl Wagner pot filled with sandy loam (from Takarazuka City, Hyogo Prefecture). Cultivation was continued in the greenhouse while continuing water leakage treatment at a rate of 3 cm per day from the bottom of the Wagner pot. Four weeks after transplantation, they were placed in a greenhouse together with another rice seedling that had developed blast, and infected with blast fungus in a humidified state. Eleven days after the inoculation, the disease index of rice cake was investigated according to Test Example 1 and the control value was determined. The disease severity in the untreated area was 91%.
The results are shown in Table 12.

[Table 12]
┌───────┬───────────────┬──────────┐
│ Test │ Active ingredient treatment amount │ Control value (%) │
│ Drug │ (g / nursery box) │ │
├───────┼───────────────┼──────────┤
│ (1) │ 1.5 │ 98 │
│ │ 0.75 │ 88 │
│ (1) + (a) │ 1.5 + 2 │ 100 │
│ │ 0.75 +1 1 │ 93 │
│ (1) + (b) │ 1.5 + 2 │ 100 │
│ │ 0.75 +1 1 │ 90 │
│ (1) + (c) │ 1.5 + 2.5 │ 100 │
│ │ 0.75 +1.25 │ 93 │
│ (1) + (N) │ 1.5 + 2.5 │ 100 │
│ │ 0.75 +1.25 │ 93 │
├───────┼───────────────┼──────────┤
│ (a) │ 2 │ 0 │
│ (b) │ 2 │ 0 │
│ (c) │ 2.5 │ 0 │
│ (N) │ 2.5 │ 0 │
└───────┴───────────────┴──────────┘

Test Example 9 Rice Blast Control Test (Water Treatment)
Sandy loam was filled in a 1/1000 Earl Wagner pot, water was poured, two-leaf rice (Nihonbare) was transplanted, and grown in a greenhouse for 7 days. Thereafter, the reagent provided in the form of granules according to Formulation Example 5 was water-treated in each pot, and cultivation was continued for 7 days (hereinafter referred to as test a) or 14 days (hereinafter referred to as test b). A spore suspension of rice blast fungus was spray-inoculated. After inoculation, it was kept at 24 ° C. under high humidity for 10 days, and the control effect was investigated with the control index according to Test Example 5. The results are shown in Table 13.

[Table 13]
┏━━━━━━━━━━━━┯━━━━━━━━┯━━━━━━━━━━━┓
│ │ Active ingredient treatment amount │ Control index ┃
┃ Test agent │ ├─────┬─────┨
┃ │ g / 10 are | Test a │ Test b ┃
┠────────────┼────────┼┼─────┼─────┨
┃ (1) │ 10 │ 3 │ 3 ┃
│ 2.5 │ 1 │ 1 ┃
┃ (1) + (A) │ 10 + 200 │ 5 │ 5 ┃
２．５ 2.5 + 50 │ 4 │ 3 ┃
┃ (1) + (B) │ 10 + 50 │ 5 │ 5 ┃
２．５ 2.5 + 10 │ 4 │ 3 ┃
┃ (1) + (C) │ 10 + 100 │ 5 │ 5 ┃
２．５ 2.5 + 30 │ 4 │ 3 ┃
┃ (1) + (D) │ 10 + 50 │ 5 │ 5 ┃
２．５ 2.5 + 10 │ 4 │ 3 ┃
┠────────────┼────────┼┼─────┼─────┨
┃ (A) │ 200 │ 2 │ 1 ┃
┃ │ 50 │ 1 │ 0 ┃
┃ (B) │ 50 │ 2 │ 1 ┃
│ │ 10 │ 1 │ 0 ┃
┃ (C) │ 100 │ 2 │ 1 ┃
│ │ 30 │ 1 │ 0 ┃
┃ (D) │ 50 │ 3 │ 2 ┃
│ │ 10 │ 1 │ 0 ┃
┗━━━━━━━━━━━━┷━━━━━━━━┷━━━━━┷━━━━━┛

According to the present invention, rice blast can be controlled extremely effectively.

Claims (4)

N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide;
5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (trifluoromethyl) sulfinyl-1H-pyrazole-3-carbonitrile,
1- (6-Chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine and ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N A method for controlling rice blast, which comprises using an active ingredient of an insecticide selected from the group consisting of isopropyl-β-alaninate. N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide The active ingredient of the insecticide is 0.2 to The rice blast control method according to claim 1, wherein the method is 20. N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide;
Diisopropyl 1,3-dithiolane-2-ylidene malonate,
5-methyl-1,2,4-triazolo [3,4-b] benzothiazole,
3-allyloxy-1,2-benzisothiazole-1,1-dioxide,
1,2,5,6-tetrahydro-4H-pyrrolo [3,2,1-ij] quinolin-4-one,
(Z) -2′-methylacetophenone 4,6-dimethylpyrimidin-2-ylhydrazone,
O-ethyl S, S-diphenyl phosphorodiothiate,
4,5,6,7-tetrachlorophthalide,
Kasugamycin,
α, α, α-trifluoro-3′-isopropoxy-o-toluanilide,
1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea,
Validamycin,
3′-isopropoxy-o-toluanilide,
N- (1,3-dihydro-1,1,3-trimethylisobenzofuran-4-yl) -5-chloro-1,3-dimethylpyrazole-4-carboxylic acid amide,
(E) -4-chloro-α, α, α-trifluoro-N- (1-imidazol-1-yl-2-propoxyethylidene) -o-toluidine,
N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] imidazole-1-carboxamide,
2-[(4-chlorophenyl) methyl] -5- (1-methylethyl) -1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol,
Pent-4-enyl N-furfuryl-N-imidazol-1-ylcarbonyl-DL-homoalaninate and dimethyl 4,4 ′-(o-phenylene) bis (3-thioallophanate)
A method for controlling rice blast, which comprises using a plant disease control agent active ingredient selected from the group consisting of: With respect to 1 part by weight of N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide, the plant disease control agent active ingredient is in a ratio by weight of 0. It is 2-20, The rice blast control method of Claim 3 characterized by the above-mentioned.