JPH01261357A - Optically active cyanoacetamide derivative, production thereof and plant disease injury controlling agent containing said derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is chlorine or bromine atom). USE:A controlling agent against plant disease injuries effective against blast and helminthosporium leaf spot of rice plant, scab of apple, etc. PREPARATION:An optically active alpha-methylbenzyl derivative expressed by formula II in which steric configuration of the benzyl position is R is reacted with alpha-cyano-tert-butylacetic acid or a reactive derivative thereof (e.g., the corresponding carboxylic acid, acid anhydride, etc.), as necessary, in the presence of a reaction assistant to afford the aimed compound expressed by formula I. The reaction assistant is, e.g., cyclohexylcarbodiimide, etc. The standard conditions of the reaction are 0-200 deg.C temperature for 0.1-24hr. The compound expressed by formula II is used in an amount of 1-1.2mol based on 1mol alpha-cyano-tert-butylacetic acid and the reaction assistant is used in an amount of 1mol-5mol based on 1mol alpha-cyano-tert-bytylacetic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel optically active cyanoacetate derivative, a method for producing the same, and a plant disease control agent using the same as an effective ingredient.

<Prior art> Various plant disease control agents have been developed up to now, but
It is difficult to say that this is necessarily completely satisfactory.

<Problems to be Solved by the Invention> The purpose of the present invention is to develop a compound having excellent control efficacy against plant diseases.

<Means for Solving the Problems> In order to achieve the above object, the present inventors have made extensive studies and found that the general formula [wherein X represents a chlorine atom or a bromine atom]. ] An optically active cyanoacetamide derivative (hereinafter referred to as the compound of the present invention) in which the configuration at the benzyl position is R.

) has been found to have excellent foliar preventive and disease control efficacy and systemic disease control efficacy, leading to the present invention.

Since the compound of the present invention also has an asymmetric carbon atom in its acid site, there are two types of diastereomers, and the present invention includes each diastereomer and a mixture thereof.

Plant diseases that can be controlled by the compounds of the present invention include rice blast (PVricularia or Yzae
), sesame leaf blight (Cochl 1obo lus m1
Yal)eanu8), apple scab disease (Ventu
ria 1naequalis), pear scab disease (Ve
njuria nashicola), oyster anthracnose (
Gloeosporium kaki), anthracnose of cucurbits (C011'!toiric11um lage)
narium), kidney bean anthracnose (Col 1 et
otr i cllum 1 indemuth ia
num), groundnut black bitter disease (MYe08phaer
ella personum), tillage spot disease (Cerc
ospora arachidicola), Tobacco anthracnose (Collet Otriehum ial) ac
um), sugar beet brown spot (Cercospora 1)
) eticola), etc.

Next, the method for producing the compound of the present invention will be explained in detail.

The compound of the present invention has the general formula [wherein, X represents the same meaning as above]. ] Reacting an optically active d-methylbenzyl derivative having R configuration at the benzyl position with σ-cyano-tert-butylacetic acid or a reactive derivative thereof in the presence of a reaction aid if necessary. By getting cloudy.

In the above reaction, α-cyano-tert-
Examples of butyl acetic acid or its reactive derivatives include the corresponding carboxylic acids, acid anhydrides, acid chlorides, acid bromides, carboxylic acid esters such as carboxylic acid methyl ester and carboxylic acid ethyl ester, and reaction aids. For example, dicyclohexylcarbodiimide, 1-ethyl-8-(8-dimethylaminopropyl)carbodiimide hydrochloride, i,t'-carbonyl dihydrochloride, d-cyano-tert-butylacetic acid or its reactive derivative, Imidazole, phosphorus pentachloride, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, phosgene, sodium hydroxide,
Potassium hydroxide, sodium methylate, sodium ethylate, triethylamine, pyridine, quinoline, N
, N-dimethylaniline, N,N-diethylaniline,
Examples include N-methylmorpholine.

In the above reaction, the standard reaction temperature is 0 to 200℃
, the reaction time is 0.1 to 24 hours, and the amount of reagent used in the reaction is expressed by the general formula [■] per mole of α-cyano-1eri-butylacetic acid or its reactive derivative. The σ-methylbenzylamine derivative is 1 to 1.
The amount of the reaction aid is 1 mol to 5 mol.

In the above reaction, a reaction solvent is not necessarily required, but -condensation is carried out in the presence of a solvent.

Usable solvents include aliphatic hydrocarbons such as hexane, heptane, and ligroin, aromatic hydrocarbons such as benzene, toluene, and xylene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane,
Ethers such as diethylene glycol dimethyl ether, dichloromethane, chloroform, carbon tetrachloride, 1,2
Examples include halogen atom-containing solvents such as dichloroethane and chlorobenzene, and solvents such as dimethylformamide, dimethyl sulfoxide and acetonitrile.

After completion of the reaction, the desired compound of the present invention can be obtained by performing usual post-treatments such as extraction and concentration, and subjecting it to operations such as column chromatography and recrystallization, if necessary. In addition, the optically active 11-methylbenzylamine derivative having the configuration f81R at the benzyl position represented by the general formula (II), which is one of the raw material compounds in the production of the compound of the present invention, can be used to convert the corresponding racemate into, for example, J, C)
Hem, Soc, @, 1971, 2418
It can be obtained by optical resolution using the method described in . In addition, the racemate, for example, or
ganic Reactions, Vol-6e 8
Leuck described in G1-880 (1949)
art reaction etc., - general formula [wherein, X represents the same meaning as above]. ] It can be synthesized from compounds shown in the following.

In addition, the other raw material compound, α-leanor-1ert-butyl acetic acid or its reactive derivative, can be used, for example, as J, Am
, Chem, Soc, 72, 4791 (1950
) or TuStu8 Liebigs Ann, C.
hem, 718, 101 (196g) and conventional derivatization methods, i.e. hydrolysis of carboxylic esters to give carboxylic acids (Arkiv K
ani, 2.821 (1950), converting the obtained carboxylic acid into an acid halide to obtain a carboxylic acid halide (T
etrahedron, 85 * 1965 (197
9)) It can be synthesized by the method etc.

When the compound of the present invention is used as an active ingredient in a plant disease control agent, it may be used as is without adding any other ingredients, but it is usually used in combination with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries. It is used in formulations such as emulsions, wettable powders, suspensions, granules, and powders.

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%.

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 hydrated silicon butyride. Alternatively, granular materials can be mentioned, and liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethyl-nonglycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, and large Examples include vegetable oils such as bean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, and water.

Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate salts, alkyl (aryl) sulfonate salts, dialkyl sulfonate salts, polyoxyethylene alkylaryl ether phosphate salts, Anionic surfactants such as naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isopropyl acid phosphate), etc.

These preparations can be used as they are, or diluted with water and sprayed on foliage, sprinkled or granulated on the soil, or applied to the soil. Furthermore, by mixing it with other plant disease control agents, it can be expected that the control efficacy will be enhanced.

Furthermore, it can be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, soil conditioners, and the like.

When the compound of the present invention is used as an active ingredient of a plant disease control agent, the amount to be treated depends on weather conditions, formulation form, treatment time,
Although it varies depending on the method, location, target disease, target crop, etc., it is usually 0.6 to 200F per are, preferably 1
~100i, and when applying emulsions, wettable powders, suspensions, etc. diluted with water, the application concentration is 0.005 to 0.5
% is preferably 0.01 to 0.2%, and granules, powders, etc. are applied as they are without any dilution.

<Effects of the Invention> Since the compound of the present invention has excellent effects against plant diseases caused by various plant pathogens, it can be used for various purposes as an active ingredient of plant disease control agents.

<Examples> The present invention will be explained in more detail below using production examples, formulation examples, and test examples. Note that the present invention is not limited to these examples.

First, a manufacturing example will be shown.

Production example (compounds (1) and (2)) α-cyano-1eri-butylacetic acid 1.55 F(1
To a solution of 0 mmof) dissolved in 6d of anhydrous tetrahydrofuran, t, 1'-carbonyldiimidazole 1
．． 78F (11 mmoj) was added little by little and stirred at room temperature for 1 hour. Add R-(t)-1-(4-1
0 Lofenyl) Ethylamine 1.56F (10 mmoj
) I took it easy. After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off to obtain a viscous liquid with a volume of 2.445'
I got it. This was carried out using silica gel column chromatography (
Elution solvent; toluene:ethyl acetate-20:1 then to
:i) to obtain Compound (1) 0.92 F and Compound (RI 0.46 F) as crystals. The obtained crystals were further purified by recrystallizing from diisopropyl ether.

Compound (1) rrQ l 56-157°C (a)%
” = +68° (C=xl, CH(7,)'H-NM
R (CDCJs/TMS, a (ppfn))1
．． 10 (8,9H), 1.44 (dtJ=7Hz, 8H
).

8.09 (8, IH), 4.65-5.25 (m, IE
I).

6.47 (br d, IH), 6.95-7.4 (m
, 411) Magis spectrum (”/eI 70 ev ) 278 (M
”), 221, 154, 189, 108 elemental analysis value (as Cf6HxsNzOC1) CHN
c1 Actual value 64.68 6.85 10.07 1
B, 2 calculated value 64.68 6.87 10.05
12.72 Compound (2) mp 140.5~
141.5t (g) %”; + 25° (c =
1, CHCf1s)'H-NMRMass spectrum similar to compound (1)Elemental analysis similar to compound (1)fi(C,,H,,N,OCJt,r)C
HN CJ Actual value 64.69 6.91 10.07 1
2.9 Calculated value 64.68 6.87 10. Q5
12.72 Some of the compounds of the invention that can be produced by such a production method are shown in Table 1.

Table 1 *1 The above diastereomer shows a larger Rf value in silica gel thin layer chromatography developed with a mixed solvent of hexane-ethyl acetate (2:1) or hexane-toluene (5:1). In the system, diastereomer O exhibiting a smaller Rf value Next, formulation examples are shown. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight. Formulation Example 1 50 parts each of the compounds (1) to (3) of the present invention, 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed. A hydrating agent for each of the invention compounds is obtained.

Formulation Example 2 25 parts each of the compounds (1) to (3) of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 8 parts of 0M0, and 69 parts of water were mixed and wet-pulverized until the particle size of the active ingredient became 5 microns or less. A suspension of each of the compounds of the present invention is obtained.

Formulation Example 8 2 parts each of the compounds (1) to (8) of the present invention, 88 parts of kaolin clay and 10 parts of talc are thoroughly ground and mixed to obtain a powder of each of the compounds of the present invention.

Formulation Example 4 20 parts each of the compounds (1) to (3) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 60 parts of xylene were thoroughly mixed to form an emulsion of each of the compounds of the present invention. obtain.

Formulation Example 6 2 parts each of the compounds (1) to (3) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 66 parts of kaolin clay are thoroughly ground and mixed, and water may be added. After kneading, the mixture is granulated and dried to obtain granules of each compound of the present invention.

Next, test examples demonstrate that the compounds of the present invention are useful as plant disease control agents. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Control efficacy is determined by visually observing the diseased state of the test plants at the time of investigation, that is, the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, the rating is ``5''; If around 1096 copies are accepted, it's a "4", if around 80 copies are accepted, it's an "8", if around 50 copies are accepted, it's r2J, and if around 70 copies are accepted, it's a "1".
, if no difference is observed from the disease onset state when no compound is tested, it is evaluated as rOJ on a 6-level scale,
6.4.8.2.1,0 respectively.

Test Example 1 Rice blast control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Chika eBB) was sown and grown in a greenhouse for 20 days. A test chemical prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and sprayed on rice seedlings so as to sufficiently adhere to the leaf surface. After spraying, the plants were inoculated by spraying with an air-dried spore suspension of the blast fungus. After inoculation, the plants were grown for 4 days at 28° C. in darkness and high humidity, and their control efficacy was investigated. The results are shown in Table 3.

Test Example 2 Rice blast control test (osmotic transfer effect) Fill a plastic pot with sandy loam and plant rice (Kinki No. 88)
were sown and grown in a greenhouse for 14 days. For young rice seedlings,
The test drug made into an emulsion according to Formulation Example 4 was diluted with water,
The specified amount was irrigated into the soil. After irrigation, the plants were grown in a greenhouse for 7 days, and then sprayed and inoculated with a spore suspension of the blast fungus. After the solution was heated to 28° C., it was left in the dark and humid for 4 days, and then the pesticidal efficacy was investigated. The results are shown in Table 4.

Table 4 Test Example 8 Apple Scotch Disease Control Test (Preventive Effect) Plastic pots were filled with sandy loam, apples were sown, and grown in a greenhouse for 20 days. A test drug prepared as an emulsion according to Formulation Example 4 was diluted with water to a predetermined concentration and sprayed on apple seedlings so as to sufficiently adhere to the leaf surface.

After spraying, a spore suspension of apple scab was sprayed and inoculated. After inoculation, the seeds were left at 15° C. for 4 days under high humidity, and then grown under lighting for 15 days, and the pesticidal efficacy was investigated. The results are shown in Table 5.

Table 5 Test Example 4 Cucumber anthracnose control test (preventive effect) Fill plastic pots with sandy loam and place cucumbers (Sumo Hanpaku)
was heated and grown in a greenhouse for 14 days. A test drug prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed onto cucumber seedlings with developed cotyledons so as to sufficiently adhere to the leaf surface. After spraying, a spore suspension of cucumber anthracnose was sprayed and contacted. After inoculation, the seeds were left at 28° C. under humid conditions for 1 day, and then grown under lighting for 4 days to investigate the pesticidal efficacy. The results are shown in Table 6.

Table 6

Claims (3)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, X represents a chlorine atom or a bromine atom. ] An optically active cyanoacetamide derivative having R configuration at the benzyl position. (2) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, X represents a chlorine atom or a bromine atom. ] An optically active α-methylbenzylamine derivative in which the configuration at the benzyl position is R, and α-cyano-te
2. The method for producing a cyanoacetamide derivative according to item 1, which comprises reacting with rt-butylacetic acid or a reactive derivative thereof. (3) A plant disease control agent containing the cyanoacetamide derivative described in item 1 as an active ingredient.