JPS6023107B2 - α,α-dimethylphenylacetic acid anilide derivative, its production method and herbicide containing the same - Google Patents

Description

Detailed Description of the Invention The present invention is based on the general formula (where Y is a lower alkoxy group or a halogen atom (excluding a chlorine atom), x is a lower alkyl group, a lower alkoxy group, or a halogen atom, and n is 0 to 2 , and when n is 2, the individual Xs may be the same or different), a method for producing the same, and a herbicide containing the same as an active ingredient Regarding drugs.

Many phenylacetic acid anilide derivatives are already known, but no excellent herbicides have been developed.

Chemical Abstract No. 83 (1976) 6276
& describes a research report on the plant physiological damage activity of a group of phenylacetic acid anilide derivatives in which the Q-carbon atom is monosubstituted with a methyl group, that is, hydroatropaic acid anilide. Furthermore, Chemical Abstracts No. 4, Lid (19th Rat), 819, describes the production of Q.Q-dimethylphenylacetic acid anilide from isopropylphenyl acetic acid phenoxyoxime. However, to date, nothing has been reported regarding the biological activity of a 7-phenyl acetate anilide conductor in which the Q-carbon atom is di-substituted with a methyl group. The present inventors attempted to create a new herbicide by making various modifications to this family of compounds.

As a result, the Q.Q-dimethylphenylacetic acid anilide derivative has a strong herbicidal and growth-inhibiting effect on weeds that compete with it, without exhibiting any phytotoxicity in the cultivation of paddy rice fields. Although it has a slow effect, it has excellent residual effect.
It has also been found that it has various improved effects on fish, including low toxicity. The compound of formula 1 has excellent intergeneric selectivity for grasses when treated with pre-emergence flooded soil and during the growing season, and is harmless to grasses, while it is harmful to grasses, It showed excellent herbicidal and growth-inhibiting effects on cypress and other plants.

Furthermore, the compounds of the present invention exhibited remarkable effects against grass weeds, Cyperaceae weeds, etc., even when compared with the compounds used as controls in the herbicidal effect test described below. The compound of formula 1 is a Q.Q-dimethylphenyl acetic acid derivative represented by the general formula (wherein Y has the above-mentioned meaning) or its reactive derivative represented by the general formula (wherein X and n have the above-mentioned meanings). It can be produced by reacting with an aniline derivative represented by

This reaction is preferably carried out in a solvent in the presence of a suitable reaction aid.

Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as diethyl ether, tetrahydrofuran, and dioxane, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, methylene chloride, chloroform, and tetrachloride. Halogenated hydrocarbons such as carbon are used. Examples of reaction aids include phosphorus pentachloride, phosphorus trichloride, thionyl chloride, sodium hydroxide, potassium hydroxide, sodium bicarbonate,
Triethylamine, pyridine, tripropylamine, N
・N-dimethylaniline etc. are used. In the reaction, the compounds of formula 0 and formula m are used in equimolar amounts. That is advantageous. The reaction temperature is 0°C to the reflux temperature of the solvent, preferably 20 to 40°C, and the reaction is completed in 1 to 1 calm hour. The product can be isolated and purified by recrystallization, vacuum distillation, etc. Examples of solvents used for recrystallization include benzene, toluene, methyl alcohol, ethyl alcohol, chloroform, n-hexane, and ethyl acetate. Although the herbicide of the present invention may be used as a compound of formula 1 as it is, it is usually mixed with an inert solid carrier or liquid carrier, and prepared by a conventional method using an auxiliary agent as the case requires, for example, a wettable powder, an emulsion, etc. It is used in formulations.

Other appropriate additives, fertilizers, agricultural chemicals such as herbicides, insecticides, fungicides, etc. may be added. Examples of solid carriers include clay, talc, kaolin, bentonite, diatom, calcium carbonate, etc., or mixtures thereof; examples of liquid carriers include benzene, xylene, kerosene, alcohol, dimethylformamide, etc., or mixtures thereof. In addition, drug dispersion, suspension, wetting, emulsification, adhesion,
Surfactants such as sodium lauryl sulfate, alkyldimethylbenzylammonium chloride, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, alkyldimethylbetaine, etc. can be used as auxiliary agents to improve properties such as adhesion. , polymer compounds such as polyvinyl alcohol, sodium alginate, etc. are used. Said formulations generally contain active ingredient in proportions by weight of 0.5 to 95%, preferably 1 to 90%.

The content of the active ingredient varies depending on the dosage form, but for example, in the case of granules and powders, it is 1 to 15%, and in the case of hydrates, it is 10%.
-80%, preferably 1-50% in the case of emulsions.
The amount of the herbicide of the present invention to be used depends on the dosage form, weather conditions, timing of use,
Although it varies depending on the soil conditions, the type of target weed, etc., the amount of active ingredient per are is usually 0.5 to 50 days, preferably 1 to 30 days.

Synthesis Example 1 (Compound No. 4) 50% of benzene, 0.50% of triethylamine, and 0.60% of m-ethylaniline were placed in a 100% four-bottle flask, and while cooling in water, Q.Q-dimethyl was added. 1.06 drops of -o-methoxyphenylacetic acid chloride were slowly added dropwise.

After the addition is complete, attach a dehydration tube to the flask and let it stand at room temperature for 3 hours. After the reaction is completed, the reaction solution is washed with water to remove triethylamine hydrochloride, the benzene layer is dried over anhydrous sodium sulfate, and the solvent is distilled off under reduced pressure. The residue was developed and purified by silica gel column chromatography (developing solvent: n-hexane/acetone = 4/1) to obtain a white solid Q.Q-dimethyl-o-methoxyphenylacetic acid-
1.35 ta of m-ethylanilide is obtained. Yield: 90.
9%, melting point 83-84 qo.

m-valued Tokusho 1 arc-1:3370 (NH), 1655 (
C=〇) Elemental analysis value: C, Niji 2302N C day N Theoretical value (%) 76.837.804.72 Actual value (%
) 76.787.824.70 Synthesis Example 2 (Compound No. 16) 50% of benzene [
, Q.Q-dimethyl-o-fluorophenyl acetic acid 0.9
1 day and 0.67 day of m-normal propylaniline were added, and while cooling in ice water and stirring, 1.03 day of dicyclohexylcarbodiimide was added dropwise.

After the addition is complete, let it stand overnight at room temperature. After the reaction is completed, the reaction solution is filtered to remove dicyclohexylcarbodiimide to which water has been added, and the furnace solution is concentrated under reduced pressure to remove the solvent.
The residue was developed on silica gel column chromatography (developing solvent: n-hexane/ethyl acetate: 8
/2) Purification and further recrystallization from n-hexane yields 1.10 ta of Q.Q-dimethyl-o-fluorophenyl acetic acid 1-m-n-propylanilide as a white solid. Yield 73.8%, melting point 61-620. IR value Shinasa 1
Skin-1: 3300 (N-H), 1660 (C = 〇) Elemental analysis value: C, C day N as phantom 22 NOF Theoretical value (%) 76.267.354.67 Actual value (%
) 76.307.324.65 Synthesis Example 3 (Compound No. 18) 50 benzene [
, 0.64 g of o-chloroaniline and 0.50 g of triethylamine were added, and 1.00 g of Q.Q-dimethyl-p-fluorophenyl acetic acid chloride was added dropwise while stirring at room temperature.

After completion of the dropwise addition, the reaction solution was left at room temperature for 3 hours. After the reaction is completed, the reaction solution is washed with water to remove triethylamine hydrochloride, the benzene layer is dried over anhydrous sodium sulfate, and the solvent is removed under reduced pressure. Column the residue with silica gel. When purified by developing with chromatography (developing solvent: n-hexane/ethyl acetate = 20/1), 1.20 ta of Q.Q-dimethyl-p-fluorophenyl acetic acid-o-chloroanilide is obtained as a colorless transparent liquid. . Yield 8
2.2%, n color 51.65441R value Obibuki-1:3
470 (NH), 1700 (C○) Elemental analysis value: C
, 6th. 5NOFCL C day N theoretical value (%) 65
．． 895.144.80 Actual value (%) 65.805.
214.82 The following compound can be obtained in the same manner as 214.82.

Table 1 Formulation Example 1 (Granules) Compound of the Invention (No. 4) 5 parts Sodium dodecylbenzenesulfonate 2 parts Sodium lauryl sulfate 1 part Talc -
2 Foundation Pentonite
Mix 72 parts of the above ingredients, add an appropriate amount of water, knead, granulate through a granulator, dry,
Rectify to obtain granules.

Formulation Example 2 (Granules) Pentonite 2 parts Clay 76 parts Sodium ligninsulfonate 3 parts Sodium alkylbenzene sulfonate 1 part The above ingredients were mixed and kneaded with water, then granulated through a granulator, dried, and adjusted. Grind to make granules.

Granules are obtained by impregnating 95 parts of the granules with 5 parts of the compound of the present invention (No. 13). If the compound of the present invention is in solid form, it is dissolved in an appropriate amount of an organic solvent and impregnated. Formulation Example 3 (Emulsion) Compound of the present invention (No. 16) 3 parts polyoxyethylene alkylaryl ether 1 part xylene 6 parts The above components are mixed and dissolved to obtain an emulsion.

Formulation example 4 (hydrating powder) Compound of the present invention (N0.19) 5 parts polyvinyl alcohol 2 parts sodium dodecylbenzenesulfonate 3 parts diatom
45 parts of the above ingredients are mixed and ground to obtain a wettable powder.

Test example Fill a pot of 11/5000 are with paddy soil, transplant paddy rice at the 2-leaf stage, sow Nobye, Tamagalli and Hotaru seeds, plant Mizugalli tubers, and flood to a depth of 3 skins. did.

Three days after weed germination, a predetermined amount of the hydrating powder prepared according to Formulation Example 4 was used to treat flooded soil. After chemical treatment 3
The degree of chemical damage and herbicidal efficacy of the paddy rice and each weed was observed every week. The results are shown in Table 2. In addition to the compounds of the present invention, the following compounds were used for comparison in the test. The criteria for the degree of chemical damage to rice were as follows.

-: Harmless +: Slight harm ±: Value should be small -: Moderate harm: Table 2 Table 2 Test example 2 Fill a 1/5000 are pot with Mizutashijo so that the water depth is 1 skin. It was flooded.

On the second day after flooding, the soil was irrigated using the hydrating powder prepared according to Formulation Example 4 in an amount equivalent to 20 days/a (active ingredient).
Nopye seeds were sown at 5-day intervals after the treatment, and three weeks after sowing, the nopye seeds were pulled out and the dry weight of the aboveground parts was investigated.
The results are shown in Table 3. In addition to the compounds of the present invention, the following compounds were used for comparison in the test. Table 3

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Y is a lower alkoxy group or a halogen atom (excluding a chlorine atom), , n represents an integer of 0 to 2, and when n is 2, the individual Xs may be the same or different). 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y has the meaning below) α・α−
Dimethylphenylacetic acid derivative or its reactive derivative,
General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula ▲ characterized by reacting with the aniline derivative represented by (in the formula, X and n have the meanings given below)
There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Y is a lower alkoxy group or a halogen atom (excluding a chlorine atom), X is a lower alkyl group, a lower alkoxy group, or a halogen atom, and n is an integer from 0 to 2. , when n is 2, the individual Xs may be the same or different). 3 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Y is a lower alkoxy group or a halogen atom (excluding a chlorine atom), X is a lower alkyl group, a lower alkoxy group, or a halogen atom, n is 0 to 2 , and when n is 2, the individual Xs may be the same or different). .