JPH0386855A - Cyanoacetic acid amide derivative, its production and plant-blight controlling agent containing the derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is 3-6C secondary alkyl, 4-6C secondary or tertiary alkenyl or 4-6C secondary or tertiary alkynyl; X, Y and Z are H, Cl, Br, methyl, ethyl, lower alkoxy, trifluoromethyl, lower fluoroalkoxy, etc.). EXAMPLE:N-[1-(4-chloro-2-methoxyphenyl)ethyl]-2-cyano-3,3-dimethyl-4- pentenamide. USE:A plant-blight controlling agent. It exhibits excellent effect especially against rice blast and causes low phytotoxicity to crops. PREPARATION:The compound of formula I can be produced by reacting an alpha-methylbenzylamine derivative of formula II with an alpha-substituted cyanoacetic acid of formula III or its reactive derivative in a solvent (e. g. THF) at 0-200 deg.C for 0.1-24hr.

Description

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

<Conventional technology> Various plant disease control agents have been developed so far.
It is difficult to say that it is necessarily fully satisfactory in terms of efficacy, etc.

By the way, many cyanoacetate amide derivative compounds have been synthesized so far.

For example, JP-A-68-72668 has the following format (however,
R1 represents an alkyl group, R1, R1 and R4 each represent the same or different hydrogen atom or alkyl group,
Xi, X, and Xa each represent the same or different hydrogen atom, alkyl group, halogen atom, halogenoalkyl group, alkoxy group, alkylthio group, alkoxyalkyl group, nitro group, or cyano group.

The compounds shown are examples and herbicidal activity) It is stated that it has.

<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 Problem> In order to achieve the above object, the present inventors have made extensive studies and found that - form [wherein R is a secondary alkyl group having 3 to 6 carbon atoms] , represents a secondary or 8th class alkenyl group having 4 to 6 carbon atoms, or a secondary or 8th class alkynyl group having 4 to 6a carbon atoms.

X1Y and Z are the same or different and represent a hydrogen atom, a chloro atom, a bromine atom, a methyl group, an ethyl group, a lower alkoxy group, a trifluoromethyl group, or a lower fluoroalkoxy group. However, when X and Y are the same or different and represent a hydrogen atom or a chloro atom,
Z is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group,
Not a trifluoromethyl group or lower fluoroalkoxy group. It has been discovered that the cyanoacetamide derivative represented by (hereinafter referred to as the compound of the present invention) has excellent foliar and foliar preventive disease control efficacy and systemic disease control efficacy, and has led to the present invention.

Furthermore, it has also been found that the compound of the present invention has extremely low phytotoxicity to rice even at high concentrations.

The compound of the present invention is particularly useful for rice blast disease (Pyri-cu).
laria oryzae), but other plant diseases that can be controlled include rice sesame leaf blight (Cochliobolus m1ya).
beanus), apple scab (Venturia
1naequalis), pear scab (Ventu
ria nashicola), oyster anthracnose (Glo
eosporium kaki), anthracnose of cucurbits (
Coll-etotrichum lagenariu
m), common bean anthracnose (CCo11etotri
chu lindemuthianum), groundnut black bitter disease (Mycosphaerella pers)
onatum), Cercospora a
rachidicola), tobacco anthracnose (CCo
11 etotrichu tabacum), brown spot disease of sugar beet (Cercospora beticola)
) etc.

Among the compounds of the present invention, those that are more preferable in terms of their plant disease control efficacy and phytotoxicity are those having the -form [wherein, X' represents a lower alkoxy group, and Z' represents a chloro atom, a bromine atom,
Represents a lower alkoxy group or a trifluoromethyl group. It is a cyanoacetamide derivative represented by [.

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

The compound of the present invention has the form - [wherein X%Y and 2 represent the same meanings as above. ] An a-methylbenzylamine derivative represented by the general formula % formula % ( ) [wherein R represents the same meaning as above. ] denoted by α
It can be obtained by reacting -substituted cyanoacetic acid or a reactive derivative thereof in the presence of a reaction aid if necessary.

In the above reaction, the α-substituted cyanoacetic acid represented by the -form (III) or its reactive derivative may be the corresponding carboxylic acid, acid anhydride, acid chloride, acid bromide, carboxylic acid methyl ester, or carboxylic acid ethyl ester. Examples of reaction aids include dicyclohexylcarbodiimide, 1- Ethyl-8-(8-dimethylaminopropyl) carboxylic acid hydrochloride, 1,1-carbonylciimidazole, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, phosgene, sodium hydroxide, potassium hydroxide, Examples include sodium methylate, sodium ethylate, triethylamine, pyridine, quinoline, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine.

In the above reaction, the reaction temperature is typically 0 to 200°
C1 reaction time is 0.1 to 24 hours, and the amount of reagents used in the reaction is - per mole of α-substituted cyanoacetic acid or its reactive derivative represented by the form (fil).
The α-methylbenzylamine derivative represented by format (II) is 1 to 1.2 mol, and the reaction aid is 1 mmol to 1.2 mol.
It is 5 moles.

In the above reaction, a reaction solvent is not necessarily required, but it is carried out in the presence of a solvent in boat fishing.

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, solvents such as dimethylformamide, dimethylsulfoxide, acetonitrile, and water, and mixtures thereof.

After completion of the reaction, the desired compound of the present invention can be obtained by performing usual post-treatments such as extraction, concentration, and filtration, and subjecting it to operations such as column chromatography and recrystallization, if necessary. Note that the α-methylbenzylamine derivative represented by the general formula [■], which is one of the raw material compounds for producing the compound of the present invention, is, for example, an organic
React-ions, Vol, 5.801-88
0 (1949), the -form [wherein, X%Y and 2 represent the same meanings as above. ] It can be synthesized from the compounds shown in the following.

The other raw material compound, α-substituted cyanoacetic acid represented by the general formula (III) or its reactive derivative, is, for example, disclosed in J, Organomet, Chem, 2g5
．． 895 (1985), J. Am. Chem.
Soc, 108.1089 (1986) 1, or J. Am. Chem. Soc.

66.886 (1944) and the usual derivatization method, that is, hydrolyzing a carboxylic acid ester to obtain a carboxylic acid, and converting the obtained carboxylic acid into an acid halide to obtain a carboxylic acid halide. It can be synthesized by various methods.

Furthermore, among the compounds of the present invention, in -format CI), R is a secondary alkyl group, a secondary alkenyl group, or a secondary
A compound representing an alkynyl group of -formula [wherein, X, Y and 2 represent the same meanings as above]. ] A cyanoacetamide derivative represented by the general formula % ([wherein R' is a secondary alkyl group having 8 to 6 carbon atoms, a secondary alkenyl group having 4 to 6 carbon atoms, or Carbon number 4
~6 secondary alkynyl groups, and L represents a chloro atom, bromo atom, iodo atom, or a leaving group such as a methanesulfonyloxy group or a p-toluenesulfonyloxy group. ] It can also be obtained by reacting the compound shown in the following in the presence of a base or the like.

Examples of the base used in the above reaction include alkali metal hydrides such as sodium hydride.

In the above reaction, the reaction temperature is typically -10 to 10
0°C, the reaction time is 0.1 to 24 hours, and the amount of reagent used for the reaction is represented by the -format CD for 1 mole of the cyanoacetamide rust conductor shown by the -format (N). The compound is 1-1.5 mol and the base is 1-1.2 mol.

Examples of solvents that can be used in the above reaction include aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as tetrahydrofuran, dioxane, and 1,2-dimethoxyethane, and dimethylformamide. Examples include aprotic polar solvents.

After the reaction is completed, the product is subjected to usual post-treatments such as extraction, concentration, and filtration, and if necessary, subjected to operations such as column chromatography and recrystallization.

The desired compound of the present invention can be obtained.

In addition, the cyanoacetamide derivative represented by the general formula (ff), which is one of the raw material compounds in the production of the compound of the present invention, is an α-methylbenzyladensine derivative represented by the -form [■], cyanoacetic acid or It can be obtained by reacting the reactive derivative thereof in the presence of a reaction aid if necessary.

In addition, the compound represented by the general formula [ma], which is the other raw material compound, can be obtained by using a commercially available one or by synthesizing it from a commercially available raw material by a normal derivatization method. .

The compound of the present invention has at least four stereoisomers (optical isomers) derived from its asymmetric carbon atoms, and the present invention also includes these isomers and mixtures thereof.

Some examples of the compounds of the present invention that can be obtained by such a production method are illustrated below.

No.! Table When using the compound of the present invention 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 a solid carrier, liquid carrier, surfactant, or other formulation aid. It is used by mixing it with a drug and preparing it 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 96%.

Examples of solid carriers include fine particles 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 hydrous silicon oxide. Powders or granules may be mentioned, and 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, and soybean oil. , vegetable oils such as cottonseed oil, dimethyl sulfoxide, acetonitrile, water, etc.

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

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. It can also be used in combination with other plant disease control agents, insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

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 0.06 to 2 G Of per are, preferably 0.1 to 100 f, and emulsions, wettable powders, suspensions, etc. are mixed with water. When applied diluted, the application concentration is 0.00
005-0.54 preferably o, oooi-0.2%
Granules, powders, etc. are applied as is without any dilution.

<Effects of the Invention> The compound of the present invention has excellent effects on plant diseases caused by various plant pathogens, and has extremely low phytotoxicity to crops such as rice even at high concentrations, so it is useful for controlling plant diseases. It can be used for various purposes as an active ingredient of 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.

Manufacturing example! (Compound (2)) 2-cyano-8,8-dimethyl-4-pentenoic acid 0.4
To a solution of 61 (8 mmol) dissolved in anhydrous tetrahydrofuran 5-, 0.58 fl (8.6 mmol) of 1,1'-carbonyldiimidazole was added little by little, and the mixture was stirred at room temperature for 1 hour. Add 0.56 f of 1-(4-chloro-2-methoxyphenyl)ethylamine to this solution.
(8 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After the reaction, the solvent was distilled off and subjected to silica gel column chromatography (bathing solvent: hexane: ethyl acetate = 2: 1')
0,691 N-(1-(4-chloro-
2-methoxyphenyl)ethyl-2-cyano-8,8
-dimethyl-4-pentenamide was obtained.

ml) 142-147°C' H-NMR (CDCl5/TMS, δ (ppm)
) 1.0 to 1.7 (m, 9 H'), 8.16 and 8.18 (8 each, combined IH), 8.86 (8
11) I), 4.75-5.85 (m, 8H), 5.5
5-6.1 (m, IH), 6.7-7.8 (m,
4H) Mass spectrum (m/e, 708V) 820 (M”), 805.251, 184, 169°0
8 Production Example 2 (Compound (22)') N-(1-(4-chloro2-methoxy-phenyl)ethyl-2-cyanoacetamide 0,771 (8 mmol
) was dissolved in anhydrous dimethylformamide 5- and cooled on ice. Sodium hydride (60% 1noil) under nitrogen atmosphere
)0.181F (8.8 mmol) and cooled with water.
Stirred for 0 minutes. Subsequently, 5ec-butyl bromide 0.
After adding 49f (8.6 mmol) and stirring for 80 minutes under water cooling, the water cooling path was removed and the mixture was further stirred overnight. After the reaction, water was added to the reaction solution and extracted with ethyl acetate.
Washed twice with brine. After drying the organic layer, it was concentrated and purified by silica gel column chromatography (bathing solvent: hexane:ethyl acetate = 5:1'').
0.68f of N-(1-(4-chloro-2-methoxy-
Phenyl)ethyl]-2-cyano-8-methylpentanamide was obtained.

mp 90 N100℃'H-NMR (CDC11s/TMS, δ(ppm
)) 0.66-1.8 (m, IIH), 1.8-2.
4 (m, IH), 8.2-8.7 (m, IH
), 8.98 (8,8H), 4.9-6.65 (m, I
H), 6.7~'1. 'l (m, 4 H) Some of the compounds of the present invention that can be produced by such a production method are shown in the lit table.

Table 2 Next, production examples of the α-methylbenzylamine derivative represented by the general formula (n) are shown.

Reference production example 4-chloro-2-methoxyacetophenone 7, 48 f
l (40.8 mmol), formamide 7.489
(191.2 mmol) and 1 m of 90% formic acid was heated at 180-190°C for 6 hours and cooled. Water was added, extracted with chloroform, and then concentrated. Concentrated hydrochloric acid 4- was added to the obtained oily residue (9,87f) and heated at 100°C.
It was heated for 1 hour.

The mixture was cooled on ice, water was added, and the mixture was extracted twice with chloroform. The aqueous layer was made alkaline with a caustic soda water bath while cooling on ice, and then extracted twice with ether.

By drying with anhydrous magnesium sulfate and concentrating,
6.241 (70%) of almost pure 1-(4-chloro-2-methoxyphenyl)ethylamine was obtained by H-NMR.

α represented by the general formula (II) that can be produced in this way
- Some of the methylbenzylamine derivatives are shown below.

Table 8 Hs Next, a production example of the cyanoacetamide derivative represented by the general formula [■] is shown.

Reference production example Ethyl cyanoacetate 2. Of (20 mmol) and 1-(4-chloro-2-methoxy-phenyl)ethylamine 8.7 f (20 mmol) were mixed, heated and stirred at a pass temperature of 180°C for 2 hours while removing the generated ethanol, and then cooled. . The resulting crystals were recrystallized from ethanol to obtain 1.71f of N-[1-(4-10rho-2-methoxyphenyl)ethyl-2-cyanoacetamide.

mp 190-198°C IH-NMR (CDC4a/DMSO-ds, δ
(ppm)) 1.80 (d%J=7H2,8H), 8.
66 (8,2H), 8.85 (8,8H), 4.9~
5.4 (m, IH), 6.85-7.4 (m, 8
H"), 8.4 to 8.8 (Md5I H) Next, formulation examples are shown. The compounds of the present invention are indicated by the compound numbers in Table 2. Parts represent parts by weight.

Formulation Example 1 50 parts each of the compounds (1) to (22) of the present invention, 2 parts of calcium lignin sulfonate, 2 parts of sulium lauryl sulfate, and 46 parts of synthetic hydrous silicon oxide were pulverized and mixed to prepare a pot for the compound of the present invention. Use a hydrating agent.

Formulation Example 2 25 parts each of the compounds (1) to (22) of the present invention, 8 parts of poly(quaternary diethylene sorbitan monooleate), 8 parts of CMC, and 69 parts of water were mixed until the particle size of effective depletion was 5 microns or less. A suspension of the compound of the present invention is obtained by wet grinding.

Formulation Example 8 2 parts each of the compounds (1) to (22) of the present invention, 88 parts of kaolin 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 (22) of the present invention, 14 parts of poly(quaternary diethylene styrylphenyl ether), 6 parts of calcium dodecylbenzenesulfonate, and 60 parts of xylene
The components are thoroughly mixed to obtain an emulsion containing the compound of the present invention.

Formulation Example 5 2 parts each of the compounds (1) to (22) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, and water is added. After kneading, the mixture is granulated and dried to obtain granules containing the 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 4.

In addition, the control efficacy is determined by visually observing the disease 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, it is rated ``5'' and 1096. r4j if approximately 80 copies are accepted, r8 if approximately 50 copies are accepted, 2 if approximately 50 copies are accepted, rlJ if approximately 70 copies are accepted.
, if there is no difference from the disease onset state when no compound is tested, it is evaluated as "0" and evaluated on a 6-level scale,
5.4.8.2.1.0 respectively.

Test Example 1 Rice blast control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) 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 are sprayed with a spore suspension of the blast fungus, which is air-dried.
Inoculated. After inoculation, the plants were grown for 4 days at 28° C. in the dark and humid, and the control efficacy was investigated. The results are shown in Table 5.

Table 5 Test Example 2 Rice blast control test (osmotic transfer effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 14 days. A test drug prepared as an emulsion according to Formulation Example 4 was diluted with water and a predetermined amount of the drug was sprinkled onto the soil of rice seedlings. 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 inoculation, the seeds were weighed at 28° C. in the dark and humid for 4 days, and then the control efficacy was investigated. The results are shown in Table #I6.

Table 1 Test Example 8 Phytotoxicity test on rice A plastic pot was filled with sandy loam, rice (Kinki No. 88) was sown, and grown in a greenhouse for 14 days. A test drug prepared as an emulsion according to Formulation Example 4 was diluted with water and a predetermined amount of the drug was sprinkled onto the soil of rice seedlings. After irrigation, the plants were grown in a greenhouse for 7 days. After weighing for 4 days at 28° C. in the dark and high humidity, the degree of chemical damage was investigated.

The results are shown in Table 7.

The degree of phytotoxicity is determined by visually observing the state of phytotoxicity of the test plants during the survey.If no phytotoxicity is observed, it is marked as "-", if it is very slightly observed, it is "±", if it is weakly observed, it is marked as "+", and if it is strongly observed. If it is recognized, it is evaluated as "廿" and evaluated on a four-level scale, which is indicated by -, shi, +, and 廿, respectively.

Claims (6)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is a secondary alkyl group having 3 to 6 carbon atoms, a secondary or tertiary alkenyl group having 4 to 6 carbon atoms, Alternatively, it represents a secondary or tertiary alkynyl group having 4 to 6 carbon atoms. X, Y and Z are the same or different and represent a hydrogen atom, a chloro atom, a bromine atom, a methyl group, an ethyl group, a lower alkoxy group, a trifluoromethyl group or a lower fluoroalkoxy group. However, when X and Y are the same or different and represent a hydrogen atom or a chloro atom,
Z is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group,
Not a trifluoromethyl group or lower fluoroalkoxy group. ] A cyanoacetamide derivative represented by. (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X' represents a lower alkoxy group, and Z' represents a chloro atom, a bromine atom, a lower alkoxy group, or a trifluoromethyl group. ] A cyanoacetamide derivative represented by. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc.
Represents a lower alkoxy group, trifluoromethyl group or lower fluoroalkoxy group. However, X and Y are
When Z is the same or different and represents a hydrogen atom or a chloro atom, Z is not a hydrogen atom, a chloro atom, a bromine atom, a methyl group, a trifluoromethyl group or a lower fluoroalkoxy group. ] α-methylbenzylamine derivatives shown by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a secondary alkyl group having 3 to 6 carbon atoms, 2 It represents a class or tertiary alkenyl group, or a secondary or tertiary alkynyl group having 4 to 6 carbon atoms. 2. The method for producing a cyanoacetamide derivative according to item 1, which comprises reacting with an α-substituted cyanoacetic acid or a reactive derivative thereof. (4) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Or represents a lower fluoroalkoxy group. However, when X and Y are the same or different and represent a hydrogen atom or a chloro atom,
Z is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group,
Not a trifluoromethyl group or lower fluoroalkoxy group. ] A cyanoacetamide derivative represented by the general formula R'-L [wherein R' is a secondary alkyl group having 3 to 6 carbon atoms, a secondary alkenyl group having 4 to 6 carbon atoms, or Carbon number 4
~6 secondary alkynyl groups, and L represents a leaving group such as a chloro atom, a bromo atom, an iodo atom, or a methanesulfonyloxy group or a p-toluenesulfonyloxy group. ] It is characterized by reacting with the compound shown by these. 2. A method for producing a cyanoacetamide derivative according to item 1. (5) A plant disease control agent containing the cyanoacetamide derivative described in item 1 as an active ingredient. (6) A rice blast control agent containing the cyanoacetamide derivative described in item 1 as an active ingredient.