JPH08295661A - Amide compound and its use - Google Patents

Abstract

PURPOSE: To obtain an amide compound having an excellent control potency against rice blast and having the potency over a long period also on seed treatment. CONSTITUTION: An optically active amide compound wherein the benzyl position has the absolute steric configuration of (R), e..g N-[(R)-1-(2,4-dichlorophenyl) ethyl]-2-cyano3,3,-dimethylbutaneamide. The compound is obtained by reacting 1 mole of a 2-4C alkyl ester of α-cyano-tert-butylacetic acid (e.g. ethyl or n- propyl ester) with 0.9-1.2 moles of (R)-1-(2,4-dichlorophenyl)ethyleneamine preferably at 130-220 deg.C for 0.5-24hrs. Therein, the optically active compound rich in the (R) steric configuration has an optical purity of >=75%ee, preferably >=85%ee, on the amine side.

Description

Detailed Description of the Invention

[0001]

This invention relates to amide compounds and their uses.

2. Description of the Related Art Conventionally, a type of N- [1- (substituted phenyl) ethyl] -2-cyano-3,3-dimethylbutanamide described in JP-A-2-76846 is effective for controlling rice blast disease and the like. It is stated that there is.

However, this compound cannot be said to have sufficient rice blast control effect depending on the treatment method such as seed treatment, so that it is not always used as an active ingredient of a rice blast control agent. It's not always perfect.

[0002]

In view of such a situation, the inventors of the present invention have conducted extensive studies to develop a compound having a superior control effect against rice blast, and as a result,
An optically active N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide having an absolute configuration in which the benzyl position is (R) is
The present inventors have found that not only a better control effect on blast of rice blast by foliar spraying etc., but also a superior control effect on seed treatment over a long period of time, the present invention has been completed. That is, the present invention is N-[(R) -1- (2,4
-Dichlorophenyl) ethyl] -2-cyano-3,3-
Dimethyl butanamide (hereinafter referred to as the compound of the present invention), a rice blast control agent containing the same as an active ingredient, and a rice blast disease characterized by treating the rice seed with the control agent. Provide a control method. The compound of the present invention has the absolute configuration at the benzyl position on the amine side is (R), but the optical purity at this site is 1
It does not have to be 00% ee (enantiomeric excess),
In the present invention, the optical purity of the site is, for example, 75% e.
e [that is, (R) :( S) = 87.5: 12.5] or more of (R) -enriched optically active substance is contained, but the optical purity of the site is 85% ee [that is, (( R) :( S) =
92.5: 7.5] or more, and an optically active substance rich in the (R) form 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 in practical use of rice blast control, the configuration of such a site does not significantly affect the control efficacy. For the above, the (R) form, the (S) form, or a mixture thereof in any proportion may be used, but from the industrial viewpoint, the (RS) form is usually used. The compound of the present invention is a rice blast (Pyric blast) which is an important disease of rice.
(ularia oryzae) shows a particularly excellent controlling effect, but by mixing with other suitable plant disease controlling agents, not only the controlling becomes more effective by a synergistic action,
Another important disease of rice, rice scabbard disease (Gibberella f
It also has the effect of making ujikuroi) control more efficient.

The compound of the present invention comprises a C ₂ -C ₄ alkyl (eg ethyl, n-propyl, isopropyl, n-butyl, isobutyl etc.) ester of α-cyano-tert-butylacetic acid and (R) -1- ( It can be efficiently produced by reacting with 2,4-dichlorophenyl) ethylamine at 130 to 250 ° C. The reaction is α-cyano-
C ₂ -C ₄ alkyl of tert-butylacetic acid (racemic form or optically active form) and (R) -1- (2,
4-dichlorophenyl) ethylamine (optical purity 100
% Ee (enantiomeric excess) is not required, and for example, an optically active substance rich in (R) -form with an optical purity of 75% ee or higher may be used. ) And with or without solvent, 130
~ 250 ° C, preferably at a reaction temperature of 130-220 ° C,
Usually, it can be carried out by reacting for 0.5 to 24 hours. The amount of reactants used for C ₂ -C ₄ alkyl 1 mole of α- cyano -tert- butyl acetate (R) -
1- (2,4-dichlorophenyl) ethylamine is usually 0.
It is a ratio of 9 to 1.2 mol. The solvent used as necessary is inert in the reaction and is 130 to 25
There is no particular limitation as long as it has a boiling point of 0 ° C.,
Examples thereof include hydrocarbon solvents such as xylene, cumene and mesitylene, halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, ether solvents such as diglyme and triglyme, and a mixture thereof. The reaction liquid after the reaction is usually cooled to room temperature, and then the generated crystals are collected by filtration, washed with n-hexane or the like, and dried to obtain the compound of the present invention.

(R) -1- (2,4-dichlorophenyl) ethylamine, which is used as one of the starting compounds for producing the compound of the present invention, is, for example, Organic Reaction.
Vol. 5,301 to 330 (1949) and the like, the (RS) -form obtained by the method and the like are described in, for example, JP-A-2-30694.
It can be manufactured by optical division by the method described in Japanese Patent Publication No. 2 or the like. The C ₂ -C ₄ alkyl of α-cyano-tert-butylacetic acid, which is used as the other starting compound in the production of the compound of the present invention, is described in, for example, J. Am. Chem. Soc. 72 , 4791 (1
Although it can be produced by the method described in 950) or the like, it can be efficiently obtained by the following production method a of raw materials.

(Production Method a) 2-Cyano-3-methyi
Lu-2-butenoic acid C₂~ C_FourAlkyl ester and meth
With rumagnesium halide in the presence of copper catalyst
To give C of α-cyano-tert-butylacetic acid
₂~ C_FourA method for obtaining an alkyl ester. Below is the raw material
The construction method a will be described in detail. 2-cyano-3-used
C of methyl-2-butenoic acid₂~ C_FourWith alkyl ester
For example, 2-cyano-3-methyl-2-butenoic acid
Ethyl, 2-cyano-3-methyl-2-butenoic acid n-type
Ropil, isop-2-cyano-3-methyl-2-butenoate
Ropil, 2-cyano-3-methyl-2-butenoic acid n-bu
Chill, isobutyl 2-cyano-3-methyl-2-butenoate
Le etc. Methyl magnesium hara used
As the id, methyl magnesium chloride (CH₃
MgCl), methyl magnesium bromide (CH₃M
gBr), methylmagnesium iodide (CH₃M
gI), which are commercially available products or
Alternatively, magnesium and methyl halide may be
It can be prepared according to the method. As a copper catalyst,
Usually, a monovalent copper salt is used, for example, copper (I) chloride (Cu
Cl), copper (I) bromide (CuBr) or copper (I) iodide
(CuI). The reaction is usually performed in an organic solvent.
As the organic solvent used, for example, tetrahydr
Rofuran (hereinafter referred to as THF), diethyl ether
Ether, ether solvent such as dibutyl ether, toluene,
Aromatic hydrocarbon solvent such as siren, benzene, etc.
Examples include mixed solvents of a medium and an aromatic hydrocarbon solvent. Anti
The reaction temperature is usually 10 to 60 ° C, and the reaction time is usually 0.5 to 1
It is 0 hours, and the amount of the reactant used in the reaction is
C of ano-3-methyl-2-butenoic acid₂~ C _FourAlkyl
Methyl magnesium halide is equivalent to 1 mol of ester.
Usually in the proportion of 1 to 2 mol, 2-cyano-3-methyl-2-bu
C of tenenoic acid₂~ C_FourCopper to 1 part by weight of alkyl ester
The catalyst is usually 0.0005 to 0.1 part by weight.
The reaction solution after the reaction is usually, for example, water or ammonium chloride.
After treating with water, dilute sulfuric acid, etc., concentrate the organic layer and
If the purification operation such as distillation is further performed,
C of α-cyano-tert-butylacetic acid₂~ C_FourA
The ruquil ester can be isolated.

C2-C of ₂ -cyano-3-methyl-2-butenoic acid which is a raw material used in the production method a of raw material
_{The 4-} alkyl ester can be efficiently produced by the following production method b of raw materials. (Manufacturing method b of raw material) C _{2 to} C ₄ of acetone and cyanoacetic acid
A method for obtaining a C ₂ -C ₄ alkyl ester of 2-cyano-3-methyl-2-butenoic acid by reacting an alkyl ester with n-hexane as a main solvent in the presence of a catalyst. Hereinafter, the raw material manufacturing method b will be described in detail. Examples of the C ₂ -C ₄ alkyl ester of cyanoacetic acid used include ethyl cyanoacetate and cyanoacetic acid n-
Examples thereof include propyl, isopropyl cyanoacetate, n-butyl cyanoacetate, isobutyl cyanoacetate, and the like, which are commercially available or can be produced by a conventional method. As the catalyst, aniline and carboxylic acid which may be substituted are usually used. Examples of the substituent in the optionally substituted aniline include a hydroxyl group, a methyl group and a methoxy group, and 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 (eg C
₁ -C ₄₎ fatty acids (e.g., acetic acid, formic acid, and propionic acid) and benzoic acid. As a reaction solvent, n-hexane is used as a main solvent, and more specifically, the ratio of n-hexane to the total solvent is usually 50 to 100% by weight.
Examples of the reaction solvent that can be used as a mixture with n-hexane include aromatic hydrocarbon solvents such as toluene and xylene. Reaction temperature is usually 50
The reaction time is usually 5 to 20 hours, and the reaction is usually carried out while removing water produced during the reaction. The amount of the reaction agent used in the reaction is usually 1 to 4 mol of acetone and 0.001 to 0.2 mol of the catalyst for 1 mol of the C ₂ -C ₄ alkyl ester of cyanoacetic acid (substituted). The aniline which may be used is usually in the proportion of 0.001 to 0.1 mol; the carboxylic acid is usually in the proportion of 0.01 to 0.2 mol). The reaction solution after the reaction is usually concentrated under reduced pressure or atmospheric pressure and distilled as it is, or dissolved in a solvent such as ethyl acetate, toluene, xylene and washed with water, and the solution is concentrated under reduced pressure to remove the solvent, and if necessary. By further performing a purification operation such as distillation, the desired 2-cyano-3-methyl-2
- the butenoic acid C ₂ -C ₄ alkyl ester can be isolated.

The compound of the present invention is (R) -1- (2,4-
Dichlorophenyl) ethylamine and α-cyano-te
It can also be produced by reacting rt-butylacetic acid or a reactive derivative other than the ester thereof in the presence of a reaction aid, if necessary. In the above reaction, the reactive derivative of α-cyano-tert-butylacetic acid may be a corresponding acid anhydride, acid chloride, acid bromide or the like, and the reaction aid may be α-cyano-tert-butylacetic acid or its derivative. Depending on the reactive derivative, for example, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1,
1'-Carbonyldiimidazole, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, phosgene, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, triethylamine, pyridine, quinoline, N, N- Dimethylaniline, N, N-diethylaniline, N-methylmorpholine and the like can be mentioned. In the above reaction, the reaction temperature is normally 0 to 20.
The reaction time is 0 ° C and the reaction time is 0.1 to 24 hours. The amount of the reagent to be used in the reaction is (R) -l-based on 1 mol of α-cyano-tert-butylacetic acid or its reactive derivative.
(2,4-dichlorophenyl) ethylamine is usually 1
The amount of the reaction aid used as needed is usually 1 mmol to 5 mol. In the above reaction, a reaction solvent is not always necessary, but it is generally carried out in the presence of a solvent. As the solvent that can be used, hexane, heptane, aliphatic hydrocarbons such as ligroin, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, ethers such as diethylene glycol dimethyl ether, Examples thereof include halogen atom-containing solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, solvents such as dimethylformamide, dimethylsulfoxide, acetonitrile, water and mixtures thereof. The reaction solution after completion of the reaction is subjected to usual post-treatments such as extraction with an organic solvent 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. The α-cyano-tert-butylacetic acid or its reactive derivative, which is a starting compound for producing the compound of the present invention, can be obtained by a conventional derivatization method, that is, by hydrolyzing a corresponding carboxylic acid ester to obtain a carboxylic acid. It can be produced by a method of converting the obtained carboxylic acid into 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 ingredients, but it is usually a solid carrier, a liquid carrier, a surfactant or the like. It is mixed with the auxiliary agent for formulation and prepared into an emulsion, wettable powder, suspension, granule, powder or the like for use. In these preparations, the compound of the present invention as an active ingredient,
It is contained in a weight ratio of 0.1 to 99%, preferably 0.2 to 95%. As the solid carrier, for example, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, fine powder of synthetic silicon oxide hydroxide, etc. Alternatively, a granular material may be used, and examples of the liquid carrier 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 and cottonseed oil. Vegetable oil, dimethyl sulfoxide, acetonitrile, water and the like. Examples of the surfactant used for emulsification, dispersion, wet extension and the like include, for example, alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkylsulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene. Examples thereof include anionic surfactants such as sulfonic acid formalin condensates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters. As a formulation auxiliary agent,
Examples thereof include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like.

These formulations may be used as they are,
Alternatively, it is diluted with water and sprayed on foliage, scattered on the surface of the soil or water, dispersed, dispersed on the surface of the soil and mixed, treated with a nursery box, or treated with seeds.
Examples of the seed treatment method include seed dipping treatment, seed spraying treatment, and seed dressing treatment. In the seed treatment, direct seeding may be performed by dressing or coating with calcium peroxide or the like. In addition, other plant disease control agents, insecticides,
Acaricide, nematicide, herbicide, plant growth regulator, fertilizer,
It can also be used as a mixture with a soil conditioner or the like.

Examples of other plant disease controlling 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 [generic 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 fe
rimzone], (F) O-ethyl S, S-diphenyl phosphorodiothioate [generic name edifenphos], (G)
4,5,6,7-Tetrachlorophthalide [generic name phth
alide], (H) Kasugamycin [generic name kasugamyci
n], (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 furametyr], (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 triflumizol
e], (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-triazole-1
-Ylmethyl) cyclopentanol [generic name ipconazol
e], (T) pento-4-enyl N-furfuryl-
N-imidazol-1-ylcarbonyl-DL-homoalaninate [generic name pefurazoate], (U) methyl
1- (Butylcarbamoyl) benzimidazole-2-
Ilcarbamate [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 generic name cyprodini
l], (Z) 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile [generic name fludioxonil], the compound of the present invention and the above other plant disease control The mixing ratio when the active ingredients of the agent are mixed and used varies depending on the kind of the plant disease controlling agent to be mixed, etc., but with respect to 1 part by weight of the compound of the present invention, the plant disease controlling agent is usually 0 in weight ratio. 0.01 to 100, preferably 0.
It can take 2 to 20.

Examples of pesticides 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-nitroimidazolidine -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) phenyldipropyl phosphate [generic name propaphos
], (F) 2,3-dihydro-2,2-dimethylbenzofuran-7-yl (dibutylaminothio) methyl carbamate [generic name carbosulfan], (g) (E)
-N- (6-chloro-3-pyridylmethyl) -N-ethyl-N'-methyl-2-nitrovinylidene diamine [generic name nitenpyram], (h) (E) -4,5-dihydro-6-methyl -4- (3-pyridylmethyleneamino)-
1,2,4-triazin-3 (2H) -one [generic name py
metrozine] (i) O, O-dimethyl O-4-nitro-m-tolyl phosphorothioate [generic name fenitrothion] and the like. The mixing ratio when the compound of the present invention and the active ingredient of the insecticide described above are mixed and used varies depending on the kind of the insecticide to be mixed, but the weight ratio of the insecticide is 1 part by weight of the compound of the present invention. It is usually 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 amount to be treated varies depending on weather conditions, formulation form, treatment time, treatment method, treatment location, etc. The amount is from 05 to 200 g, preferably from 0.1 to 100 g, and when the emulsion, wettable powder, suspending agent and the like are diluted with water and applied, the application concentration is 0.00005 to 0.10 g.
5%, preferably 0.0001 to 0.2%, and granules, powders, etc. are applied as they are without any dilution. In treating the nursery 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 1 box (30 cm × 60 cm × 3 cm) of a commonly used size. be able to. In the seed treatment, the amount of the active ingredient can be usually about 0.001 to about 50 g, preferably about 0.01 to about 10 g, per 1 kg of seeds. 3 kg
Is usually immersed in a high-concentration drug solution of about 5,000 to about 50,000 ppm for a short time, usually about 5 minutes to about 30 minutes, or
Alternatively, usually about 20 to about 400 at a rate of usually 1 to 3 kg.
It is immersed in a low-concentration chemical solution of 0 ppm for a long time, usually about 6 hours to about 48 hours.

[0013]

The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown. Production Examples 1 to 5 Production Examples 1 to 5 of the compound of the present invention according to the following Production Method A or B are summarized in Table 1. In the following, the following stereoisomers will be 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 is a racemate (X1 body + X2 body + Y1 body).
Body + Y2 body) can be obtained by HPLC fractionation under the conditions described in * 4 of the margin of Table 1 below. Then, the absolute configuration of each of these was determined by the X-ray structural analysis of each of the X1 body and the Y body (Y1 + Y2). (Production method A) (RS) -α-in a four-necked flask equipped with a Vigreux-type rectification column, a thermometer and a mechanical stirrer.
Were charged C ₂ -C ₄ alkyl esters of cyano -tert- butyl acetate and (R) -1- (2,4- dichlorophenyl) a predetermined amount of ethylamine. After the temperature was raised to 180 ° C., the reaction was carried out at 180 to 190 ° C. for 5 to 10 hours while distilling the produced alcohol. After completion of the reaction, the reaction mixture was cooled to room temperature, the generated crystals were collected by filtration and washed twice with n-hexane. The compound of the present invention was obtained by drying the obtained crystals under reduced pressure. (Production method B) Fractionation tower filled with helicoil (20c
m), a 4-necked flask equipped with a thermometer and a mechanical stirrer, was added with C of (RS) -α-cyano-tert-butylacetic acid.
₂ -C ₄ alkyl ester and (R) -1- (2,4-
A predetermined amount of dichlorophenyl) ethylamine was charged, and 50 ml of a predetermined solvent was added. While heating this solution, distilling the produced alcohol together with the solvent (about 30 ml)
Refluxed for 8-20 hours. After the reaction is complete, cool to room temperature,
50 ml of n-hexane was added, the resulting crystals were collected by filtration, and n-
It was washed twice with hexane. The compound of the present invention was obtained by drying the obtained crystals under reduced pressure.

[0014]

[Table 1] * 1. Alkyl of α-cyano-tert-butylacetate (Et represents ethyl, Bu represents n-butyl, respectively). * 2. Alkyl α-cyano-tert-butylacetate. * 3. Optically active 1- (2,4-dichlorophenyl) ethylamine rich in (R) -form. * 4. Calculate the ratio by the area comparison method by high performance liquid chromatogram analysis [The analysis conditions of high performance liquid chromatography (HPLC) 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: UV 254 nm] * 5. Optical purity (R) -1- (2,4-dichlorophenyl) ethylamine with 99.8% ee or more 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 (hereinafter referred to as (1)) obtained in Production Example 1 are as follows. is there. 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 will be described. Reference Production Example a-1 Copper (I) iodide was added to a solution of methylmagnesium chloride prepared from 119 g of methyl chloride, 49.6 g of magnesium and 509 g of THF at 35 to 40 ° C.
After adding 0 g, a solution of 240 g of ethyl 2-cyano-3-methyl-2-butenoate in 480 g of toluene was added dropwise at the same temperature over about 1 hour. After the dropping was completed, the reaction was further performed at the same temperature for 1 hour. 20-30 reaction mixture
After cooling to ℃, 20% ammonium chloride water 174
Poured into 2 g 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 saline. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure, and the residue was distilled as it was (boiling point of main fraction: 80-86).
(° C / 12 to 15 mmHg) to obtain the desired product. The yield of ethyl α-cyano-tert-butyl acetate after distillation is 249.
The yield was 94%.

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

[Table 2] * 1. Weight ratio. * 2. Amount of catalyst (parts by weight) relative to 1 part by weight of alkyl ester of 2-cyano-3-methyl-2-butenoic acid. * 3. Alkyl 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 will be described.
The reaction rate is a value obtained by the following equation 1.

## EQU00001 ## Reaction rate = 100-GC area ratio (%) of residual cyanoacetic acid alkyl ester (%) Gas chromatographic (GC) analysis conditions; Shimadzu GC-7A, column: 10% DEXSIL 300GC, diameter 3 mm
× Length 1 m UNIPORT HP 100-200 mesh Column temperature: Temperature was raised to 70-150 ° C. at a rate of 5 ° C./min Reference Production Example b-1 Ethyl cyanoacetate 50.0 g, acetone 51.34 g, acetic acid
1.99 g, p-aminophenol 0.24 g and n-hexane 41 ml were charged, and the mixture was heated under 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 is concentrated under reduced pressure to give hexane,
After removing acetic acid and unreacted acetone, the residue was rectified as it was under reduced pressure of 20 mmHg using a 30 cm rectification column packed with a helicoil, and fractions at 110 to 113 ° C. were 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 performed in the same manner as in Production Example b-1 of the raw material except that the type of reaction solvent, the type of catalyst, the type of alkyl of the alkyl ester of cyanoacetic acid, or the reaction time was changed. The results are summarized in Table 3
Shown in The yield in the table represents the ratio of cyanoacetic acid to alkyl ester.

[Table 3] * 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, parts represent parts by weight, and the compound (1) of the present invention was obtained in the above Production Example 1. Formulation Example 1 50 parts of the present compound (1), 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain a wettable powder. Formulation Example 2 25 parts of the compound (1) of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and wet pulverized until the particle size of the active ingredient becomes 5 microns or less, and a suspension agent. To get Formulation Example 3 2 parts of the compound (1) of the present invention, 87 parts of kaolin clay and 10 parts of talc are well pulverized and mixed to obtain a dust. Formulation Example 4 20 parts of the present compound (1), 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate and 60 parts of xylene are mixed well to obtain an emulsion. Formulation Example 5 10 parts of the present compound (1), 1 part of synthetic hydrous silicon oxide,
Calcium lignin sulfonate 2 parts, bentonite 30
And 73 parts of kaolin clay are well pulverized and mixed, water is added and kneaded well, and then granulated and dried to obtain granules.
Each of the compounds (A) to (Z) and (a) to (h), and a mixture of each of these compounds and the compound (1) of the present invention are also prepared according to the above Preparation Examples 1 to 5. be able to.

Next, it is shown in Test Examples that the compound of the present invention is useful as a rice blast disease controlling agent and the like. The compound (1) of the present invention was obtained in Production Example 1, and other plant disease controlling agents and insecticides are indicated by the above-mentioned compound symbols. The compounds used for comparison and control are 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 test reagent preparation made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and 2 kg of rice husk (Nihonbare) was added to the solution. Immersion treatment was performed for 10 minutes at a rate of 1 kg seed. The treated rice husks were air-dried and then sown in a seedling raising box at a rate of 160 g seeds / box and raised for 20 days. Then, 5 rice seedlings were transplanted to a 1/5000 ares Wagner pot filled with soil and filled with water. Cultivation was continued in the greenhouse while continuing water leakage treatment from the bottom of the Wagner pot at a rate of 3 cm per day. Six weeks after the transplantation, the rice blast fungus was placed in a greenhouse together with another rice blast seedling, and kept in a humid condition to infect the blast fungus. Eleven days after the inoculation of the bacteria, the disease index of leaf blast was investigated according to the following criteria, and the control value was calculated from the formulas 2 and 3. The disease severity in the untreated plot was 58%.

[Equation 2] N: Number of surveyed leaves n1 to n4: Number of leaves of disease index 1, 2, 4, 8 respectively

(Equation 3) The results are shown in Table 4.

[Table 4] 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 a 1/4 drug of the comparative compound (2). The amount showed almost the same control efficacy.

Test Example 2 Rice blast control test (seed spraying treatment) The reagent solution made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and this was used at a dose of 30 ml / 1 kg seed. Spray treatment was applied to rice fir (Nihonbare). After air-drying the treated chaff, a plastic pot was filled with sandy loam soil, seeded, and grown in a greenhouse for 20 days. Then, it was put in a greenhouse together with another rice seedling that had blast disease, kept in a humidified state, and infected with blast fungus. Ten days after the inoculation, the disease index of leaf fluff was investigated according to Test Example 1 to determine the control value. The disease severity in the untreated plot was 100%. The results are shown in Table 5.

[Table 5]

Test Example 3 Rice scabbard disease control test (seed spraying treatment) A test compound prepared as a wettable powder according to Preparation Example 1 was applied to rice chaff (Nipponbare) contaminated with rice scabbard disease (Gibberella fujikuroi). Is diluted with water to a specified concentration, which is
The rice was spray-treated with a dose of 1 kg of seeds. After air-drying the treated chaff, a plastic pot was filled with sandy loam soil, seeded at a rate of 50 grains per pot, and grown in a greenhouse for 21 days. The disease state was investigated by the following formula 4 and the rate of healthy seedlings was calculated.

[Equation 4] The results are shown in Table 6.

[Table 6]

Test Example 4 Rice blast control test (foliar application) Sand loam soil was filled in a plastic pot, and rice (Nihonbare) was sown and grown in a greenhouse for 20 days. A reagent solution made into a suspension in accordance with Formulation Example 2 is diluted with water to a predetermined concentration, and the rice seedlings are treated with an amount of a chemical solution (30 liters / 10 are) that leaves surfaces are slightly wet. The foliage was sprayed. After spraying, the plants were air-dried, and a spore suspension of blast fungus was sprayed and inoculated. After inoculation, the plant was grown at 28 ° C. in the dark and in high humidity for 4 days, and the disease index of leaf blast was examined according to Test Example 1 to determine the control value. In addition, the disease rate of untreated area is 100%
Met. The results are shown in Table 7.

[Table 7]

Test Example 5 Rice blast control test (spraying of foliage) A plastic pot was filled with sandy loam soil, seeded with rice (Nihonbare), and grown in a greenhouse for 20 days. A reagent solution made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the foliage was sprayed so as to sufficiently adhere to the leaf surface of the rice seedling. Immediately after the chemical solution was air-dried in the preventive effect test, and after being kept in the greenhouse for 7 days in the residual effect test, the spore suspension of blast fungus was spray-inoculated. After inoculation, 10 at 24 ° C and high humidity
It was kept for a day and the control effect was investigated by the following indexes. The results are shown in Tables 8 and 9.

[Table 8]

[Table 9]

Test Example 6 Rice Leaf Blight Control Test (Foliar Spraying) Sand loamy soil was filled in a plastic pot, and rice (Nihonbare) was sown and grown in a greenhouse for 20 days. The reagent solution made into a suspension according to Formulation Example 2 was diluted with water to a predetermined concentration, and the foliage was sprayed so as to sufficiently adhere to the leaf surface of the rice seedling. After air-drying with a chemical solution, the sclerotium of the wilt fungus was inoculated into the strain source. After inoculation, it was kept under high humidity at 27 ° C. for 10 days, and the control effect was investigated by the control index according to Test Example 5. The results are shown in Table 10.

[Table 10]

Test Example 7 Rice blast control test (treatment of seedling box) Rice seedling box (30 cm x 60 cm x 3 cm) was filled with artificial soil (Bonsol No. 2: Koura Sangyo Co., Ltd.) Approximately 200 g of dried rice (Nippon Hare) was sown. 20 days after sowing, the granules prepared according to Preparation Example 5 were uniformly sprayed on the soil surface of the nursery box. After light irrigation,
Five rice seedlings were transplanted into a 1/5000 ares Wagner pot filled with sandy loam soil (produced in Takarazuka City, Hyogo Prefecture). Cultivation was continued in the greenhouse while continuing water leakage treatment from the bottom of the Wagner pot at a rate of 3 cm per day. Transplant 6
After a week, they were placed in a greenhouse together with another rice seedling that had blast disease and kept in a humid condition to infect the blast fungus. 11 days after the inoculation of the bacteria, the disease index of leaf blast was investigated according to Test Example 1 to determine the control value. The disease severity in the untreated plot was 95%. The results are shown in Table 11.

[Table 11]

Test Example 8 Rice blast control test (treatment of seedling box) Rice seedling box (30 cm x 60 cm x 3 cm) was filled with artificial soil (Bonsol No. 2: Koura Sangyo Co., Ltd.) Approximately 200 g of dried rice (Nippon Hare) was sown. 20 days after sowing, the granules prepared according to Preparation Example 5 were uniformly sprayed on the soil surface of the nursery box. After light irrigation,
Five rice seedlings were transplanted into a 1/5000 ares Wagner pot filled with sandy loam soil (produced in Takarazuka City, Hyogo Prefecture). Cultivation was continued in the greenhouse while continuing water leakage treatment from the bottom of the Wagner pot at a rate of 3 cm per day. Transplant 4
After a week, they were placed in a greenhouse together with another rice seedling that had blast disease and kept in a humid condition to infect the blast fungus. 11 days after the inoculation of the bacteria, the disease index of rice cake was investigated in accordance with Test Example 1 to determine the control value. The disease incidence in the untreated plot was 91%. The results are shown in Table 12.

[Table 12]

Test Example 9 Rice blast control test (water surface treatment) 1/1000 ares Wagner pots were filled with sandy loam soil, watered, and two-leaf stage rice (Nihonbare) was transplanted and placed in a greenhouse 7
Nurtured for days. Thereafter, each pot was treated with water on the surface of each of the potting agents, which was made into granules according to Formulation Example 5, for 7 days (hereinafter, referred to as test a.
Cultivation) or 14 days (hereinafter referred to as test b), and the rice was spray-inoculated with a spore suspension of blast fungus. After inoculation, it was kept under high humidity at 24 ° C. for 10 days, and the control effect was investigated by the control index according to Test Example 5. The results are shown in Table 13.

[Table 13]

[0030]

INDUSTRIAL APPLICABILITY The present invention can control rice blast very effectively.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayuki Enomoto 3-1,98 Kasugadaka, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Chemical Co., Ltd. No. 1 in Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Yoshimi Yamada 4-2-1 Takashi Takarazuka, Hyogo Prefecture Sumitomo Kagaku Kogyo Co., Ltd.

Claims (4)

[Claims] 1. N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide. 2. Control of rice blast characterized by containing N-[(R) -1- (2,4-dichlorophenyl) ethyl] -2-cyano-3,3-dimethylbutanamide as an active ingredient. Agent. 3. A method for controlling rice blast, which comprises treating rice seeds with the rice blast control agent according to claim 2. 4. A method for controlling rice blast, which comprises treating rice seeds with the rice blast control agent according to claim 2 and sowing the seeds in a nursery box.