JPH0276846A - Cyanoacetamide derivatives and their uses - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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.

<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 and Y represents a chloro atom, a bromine atom, a trifluoromethyl group or a lower fluoroalkoxy group. However, if X represents a hydrogen atom, Y
is not a chlorine or bromine atom. ] It was 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 effects and systemic disease control effects particularly against rice blast, leading to the present invention. .

The compounds of the present invention are particularly useful for rice blast disease (Pyri cula).
riaoryzae), but there are also other plant diseases that can be controlled:
Sesame leaf blight of rice (Cochliobolus m1)
yabeanus), apple scab (Venture
ia 1naequalis), pear scab disease (Ve
nturia nashicola), oyster anthracnose (Gloeosporium kaki), cucurbit anthracnose (CCo11etotrichu lag)
enarium), kidney bean anthracnose (Col.
etotrichum lindemuthianu
m), groundnut black astringency (Mycosphaerel
la personatum) brown spot disease (Cerco
spora arachidicola), tobacco anthracnose (CCo11etotrichu taba)
cum), sugar beet brown spot (Cercospora cum), sugar beet brown spot (Cercospora cum)
beticola), etc.

Among the compounds of the present invention, those with the general formula [wherein X represents a lower alkoxy group, and Y represents a chlor atom, a bromine atom, a trifluoromethyl group, or a lower Represents a fluoroalkoxy group. ] It is a cyanoacetamide derivative shown 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 general formula [wherein X and Y represent the same meanings as above]. ] α-methylbenzylamine derivative and α-cyano-
tert-butylacetic acid or its reactive derivative,
It can be obtained by reacting in the presence of a reaction aid if necessary.

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. Examples include dicyclohexylcarbodiimide, 1-ethyl-8-(8-dimethylaminopropyl)carbodiimide hydrochloride, 1,1'-carbonyldiimide hydrochloride, and d-cyano-tert-butylacetic acid or its reactive derivative. Imidazole, 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-
Examples include methylmorpholine.

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 based on the general formula [11] per mole of d-cyano-tert-butylacetic acid or its reactive derivative.
The d-methylbenzylamine derivative represented by 1 to 1
．． 2 mol, and the reaction aid is 1 mmol to 5 mol.

In the above reaction, although a reaction solvent is not necessarily required, the reaction is carried out in the presence of a solvent within the shell.

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 filtration, extraction, concentration, etc., and subjecting it to operations such as column chromatography and recrystallization, if necessary. Note that the d-methylbenzylamine conductor represented by the general formula (II), which is one of the raw material compounds for producing the compound of the present invention, is, for example, an organic
Reactions, Vol, 5°801-880
(1949), the general formula [wherein X and Y represent the same meanings as above] is obtained. ] It can be synthesized from compounds shown in the following.

In addition, the other raw material compound d-cyano-tert-
Butylacetic acid or its reactive derivatives are, for example, J, A
m, Chem, Soc, 72.4791 (19
50) Justus Liebigs Am,
Chem, 718.101 (1968) and conventional derivatization methods, i.e. hydrolysis of carboxylic esters to give carboxylic acids (Arkiv
Kemi, 2. 821 (1950)), and the obtained carboxylic acid is converted into an acid halide to obtain a carboxylic acid halide (Tetrahedron.

85.1965 (1979)") method.

Note that the compound of the present invention has 4 atoms derived from its asymmetric carbon atom.
Stereoisomers (optical isomers) exist, and the present invention also includes these isomers and mixtures thereof.

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%.

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 hydrous silicon oxide. 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, and cottonseed oil. Examples include vegetable oils such as, dimethyl sulfoxide, acetonitrile, water, etc.

Surfactants used for emulsification, dispersion, wet spreading, 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, Examples include nonionic surfactants such as sorbitan fatty acid ester and 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. 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 0.05 to 20 (1, preferably 0.1 to 100 P) per are. When applied diluted, the application concentration is 0.0000
The content is 5 to 0.5%, preferably 1 to 0.2% O, OOO, and granules, powders, etc. are applied as they are without any dilution.

<Effects of the Invention> The compound of the present invention has an excellent effect on plant diseases caused by various plant pathogens including rice blast, and therefore can be used for various purposes as an active ingredient of a plant disease control agent.

<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.

An example of production is shown below.

Production Example 1 (Compound (8)) α-cyano-t-butyric acid is'? 0.289 (2
mmo/) was dissolved in anhydrous THF, and 1,1'-carbonyldiimidazole 0.865' (2,2 mmo7
) were added gradually. After stirring at room temperature for 1 hour, 1
-(4-trifluoromethoxyphenyl)ethyl a>
0.41'i (2 mmoA') was added. room temperature te 4
0I? After stirring H1, add ether, add 5% hydrochloric acid,
It was washed successively with saturated deuterated water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain a 0.709 viscous liquid. This was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate - 5:1) to yield 0.569 compound (8), that is, N-(1-
(4-trifluoromethoxyphenyl)ethyl]-2-
Cyano 3,3-dimethylbutanamide was obtained.

mp91-94°C 'H-NMR (CDC/8/TMS, δ (ppm)) 1
．． 06 and 1.11 (each S1 total 9H).

1.42 and 1.44 (d, J-7Hz each, 8H in total).

325 and 8.27 (each S1 combined IH).

4.65-5.25 (m, IH), 6.75
~7.85 (m, 5H).

Production Example 2 (Compound (7)) In a solution of 0.429 CBmmol of α-cyano-t-butylacetic acid dissolved in 5 rnl of anhydrous tetrahydrofuran,
1.1'-carbonyldiimidazole 0.58 F(3
,5mmo! ) was added little by little and stirred at room temperature for 1 hour. 0.569 (8 mmo/) of 1-(4-chloro-2-methoxyphenyl)ethylamine was added dropwise to this solution, 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 (elution solvent: hexane:
Purified by ethyl acetate-2=1) and purified with 0.88 P of N
-(1-(4-chloro-2-methoxyphenyl)ethyl]-2-cyano8.8-dimethyl-butanamide was obtained.

mp 144-147°C'H-NMR (CDCls/TMS, δ(ppm))
1.08 and 1.16 (each S9 total 9H)
.

1.45 (d, J-7Hz, 8H).

3.05 and 8.09 (each S9 together with IH)
.

8.85 (S, 8H), 4.85-5.4 (
m, IH).

6.7-7.4 (m, 4H) Mass spectrum (m/e, 70eV) 308 (M), 293,251,184,169° Compounds of the present invention that can be produced by such a production method are shown in Table 1. show.

Compounds Shown in Table 1 Next, an example of the production of an α-methylbenzylamine derivative shown by the general formula (■) will be shown.

Reference production example 1 1) -(1,1,2,2-tetrafluoroethoxy)aceto7/ :/ 9.449 (40mmo/)
, formamide (160mm0/)% and 90%
Heating a mixture of formic acid 1- at 180-190°C for 5 hours,
Cooled. The resulting crystals were filtered and washed successively with cold water and cold hexane. The obtained crystals (10,75') were suspended in 20°C of ethanol, 20°C of 6N hydrochloric acid was added, and the mixture was heated at 50°C.
It was heated for 1 hour. The mixture was cooled with water, water was added, and the mixture was extracted twice with methylene chloride. 15. 40% caustic soda aqueous solution while cooling the aqueous layer on ice. After making the mixture alkaline with , I/, it was extracted twice with ether.

After drying over anhydrous magnesium sulfate and concentrating, 1-(4-(1°1.
2.2-tetrafluoroethoxy)phenyl]ethylamine 5.97F (68%) was obtained.

Reference production example 2 4-chloro-2-methoxyacetophenone 7.48S'
(40,8 mmo/ ), formamide 7,48
A mixture of F (161.2 mmol) and 90% formic acid 1- was heated at 180-190°C for 6 hours and cooled. Water was added, extracted with chloroform, and then concentrated.

The obtained oily residue (9,871 i) was added with 4 rnl of concentrated hydrochloric acid and heated at 100°C for 1 hour. After cooling with water, water was added,
Extracted twice with chloroform. The aqueous layer was made alkaline with an aqueous solution of caustic soda while cooling with water, and then extracted twice with ether. After drying over anhydrous magnesium sulfate and concentrating, 5.249 (7
0%) was obtained.

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

Examples of formulations of the compound shown below are shown below. 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 αυ of the present invention, 8 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed to form a hydrating agent for each of the compounds of the present invention. obtain.

Formulation Example 2 25 parts each of the compounds (1) to αυ of the present invention, polyoxyethylene sorbitan monooleate ai, CfviCa part 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 the invention compound anastomoses is obtained.

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

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

Formulation Example 5 2 parts each of the compounds (1) to αυ of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite, and 65 parts of kaolin clay were thoroughly ground and mixed, and water was added and kneaded well. Thereafter, granulation and drying are performed 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 2.

Table 2 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, the rating is ``5''; If about 10 copies are accepted, r4J, 80. If around 50% of copies are recognized, I'll give a rating of ``2'', and if around 70 copies are accepted, a rating of ``1'' will be given.
'', and 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, and each is indicated as 5.4.8.2.1.0.

Test Example 1 Rice blast control test (preventive effect) A plastic pot was filled with sandy loam, rice (Kinki No. 83) was sown, and the pot was 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 sprayed with an air-dried spore suspension of the blast fungus and 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 8.

Table 3 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 injected into the soil of rice seedlings. After warming, they were grown in a greenhouse for 7 days, and then sprayed and inoculated with a spore suspension of the blast fungus. After inoculation, the plants were kept in a dark and humid room at 28°C for 4 days, and then their pesticidal efficacy was investigated. The results are shown in Table 4.

Claims (5)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, Represents a fluoroalkoxy group. However, if X represents a hydrogen atom, Y
is not a chlorine or bromine atom. ] A cyanoacetamide derivative represented by. (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X' represents a lower alkoxy group, and Y represents a chloro atom, a bromine atom, a trifluoromethyl group, or a lower fluoroalkoxy group. ] A cyanoacetamide derivative represented by (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Represents a fluoroalkoxy group. However, if X represents a hydrogen atom, Y
is not a chlorine or bromine atom. ] The method for producing a cyanoacetamide derivative according to item 1, which comprises reacting the α-methylbenzylamine derivative represented by the formula with α-cyano-tert-butylacetic acid or a reactive derivative thereof. (4) A plant disease control agent containing the cyanoacetamide derivative described in item 1 as an active ingredient. (5) A rice blast control agent containing the cyanoacetamide derivative described in item 1 as an active ingredient.