JPS623835B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel compounds and their uses;
For details, please refer to the general formula [] (In the formula, X is a halogen atom or a trifluoromethyl group, Y is a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a lower alkoxycarbonyl group,
n is 0 or 1, Z is the formula -AR ₁ or

[Formula], A is oxygen or sulfur atom, R ₁ is β-substituted with lower alkyl group, ammonium, lower alkylammonium, di-lower alkylamino group, lower alkoxy group, lower alkylthio group, or lower alkylcarbonylamino group R ₂ represents a hydrogen atom or a lower alkyl group, and R ₃ represents a lower alkyl group, a phenyl group, a lower alkoxycarbonylmethyl group, or an amino group. However, when n is 0, the following combinations are excluded: combinations where Y is a hydrogen atom and R ₁ is a lower alkyl group, combinations where Y is a hydrogen atom, X is a trifluoromethyl group, and A is an oxygen atom, and The present invention relates to a diphenylamine derivative represented by a combination in which Y is a lower alkyl group or a lower alkenyl group, A is an oxygen atom, and R ₁ is a lower alkyl group, and a selective herbicide containing the compound as an active ingredient. The present inventors synthesized various diphenylamine derivatives and examined those suitable for the above purpose, and found that the anilinophenoxycarboxylic acid derivative represented by the general formula [] exhibits excellent selective herbicidal action. After making this discovery and conducting further biological and physical research, the present invention was completed. The compound of the present invention exhibits an extremely excellent selective herbicidal effect against weeds of the grass family, such as barnyard grass, crabgrass, oat, and sparrowweed, and has the characteristic that it is almost harmless to broad-leaved crops such as adzuki beans, soybeans, and beets. has. The compound of the present invention has almost no effect on broad-leaved crops such as radish, adzuki beans, soybeans, peas, spinach, beets, etc., even at doses that completely kill the grasshopper, a common weed, when applied to leaves. In addition, in pre-emergence soil treatment of weeds, even at a dose that completely inhibits the germination of crabgrass, there is almost no effect on the germination of broad-leaved crops, indicating that herbicides are extremely safe against chemical damage to broad-leaved crops. The range of application, such as application period, application location, and application concentration, is also extremely wide. In addition, since the compound of the present invention can be used at low concentrations, there is little concern about acute toxicity to livestock and fish, and it can be used safely. The compounds of the present invention also have analgesic, hypotensive, anti-inflammatory, and antibacterial activities, and are useful as medicines. The compound of the present invention is produced, for example, by the following reaction formula. However, Hal indicates a halogen atom,
Y' indicates the above definition of Y excluding hydrogen atoms. Next, the method for producing the compound of the present invention will be described in more detail with reference to Examples. Example 1 Ethyl 2-{4-(2-nitro-4-trifluoromethyl-N-ethoxycarbonylanilino)phenoxy}propionate (Compound 1): 2-{4-(2-nitro-4-trifluoro 2 g of methylanilino)phenoxy}propionic acid ester was dissolved in 30 ml of dimethylformamide, and 0.3 g of 50% sodium hydride was added at 0° to 5°C.
After stirring for 30 minutes, 0.7 g of ethyl chloroformate was added and the mixture was further stirred for 2 hours. The reaction solution was poured into a container and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The resulting composition was purified by silica gel column chromatography to obtain 1.6 g of the target product in the form of an oil. I got it. ⁿ²⁴ . ⁵ _D 1.5268 Example 2 2-{4-(N-ethyl-2-nitro-4-trifluoromethylanilino)phenoxy}thiolpropionic acid ethyl ester (compound 2): 2-{4-(N-ethyl- 2.5 g of thionyl chloride was added to a solution of 4 g of 2-nitro-4-trifluoromethylanilino)phenoxy}propionic acid dissolved in 50 ml of methylene chloride, and after heating and refluxing for 3 hours, excess thionyl chloride and the solvent were distilled off. and synthesized acid chloride. Dissolve this in 50 ml of benzene, stir, cool with ice water, and add 1.5 ml of pyridine.
g, and then 0.9 g of ethyl mercaptan was added dropwise. After that, the temperature was gradually returned to room temperature, and the benzene layer was taken out in water, dried, concentrated, and purified by silica gel column chromatography to obtain the target substance 2 as a red oil.
I got g. n ¹⁹ _D 1.5865 Example 3 2-{4-(N-ethyl-2-nitro-4-trifluoromethylanilino)phenoxy}propionic acid methoxyethyl ester (compound 9): 2-{4-(N-ethyl Dissolve 4 g of -2-nitro-4-trifluoromethylanilino)phenoxy}propionic acid in 40 ml of ethylene dichloride, add 1.5 ml of methyl cellosolve and 1 to 2 drops of concentrated sulfuric acid,
The mixture was heated under reflux for 3 hours while separating the produced water.
The reaction solution was poured into water, and the ethylene dichloride layer was separated, washed with a 1N aqueous caustic soda solution and then with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 4 g of the desired product as a red oil. n ²⁰ _D 1.5523 Example 4 N・N-dimethyl-2-{4-(2-nitro-4
-trifluoromethylanilino)phenoxy}
Propionic acid amide (compound 20): 2-{4-(2-nitro-4-trifluoromethylanilino)phenoxy}propionic acid chloride
A solution of 4.9g dissolved in 30ml of methylene chloride,
The mixture was gradually added dropwise at 0° C. to a mixed solution of 1.5 g of a 50% aqueous solution of N·N-dimethylamine and 50 ml of methylene chloride. After 30 minutes, the reaction solution was washed with a 10% aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, the solvent was distilled off, and purified by silica gel column chromatography to obtain 2.1 g of the desired product. mp96～
7°C Example 5 4-Methyl-4-{4-(2-nitro-4-trifluoromethylanilino)phenoxy}crotonic acid ethyl ester (compound 12): 4-(2-nitro-4-trifluoromethyl 3 g of anilinophenol was dissolved in 50 ml of methyl ethyl ketone, 2 g of ethyl 4-bromo-4-methylcrotonate and 2 g of anhydrous potassium carbonate were added, and the mixture was heated under reflux for 4 hours with stirring. After the reaction, the mixture was poured into water and extracted with chloroform to obtain 3.5 g of the target product as orange crystals. mp74-6°C Table 1 shows the structural formulas and physical constants of representative compounds of the present invention.

【table】

[Table] The herbicide of the present invention is prepared by mixing an appropriate amount of one or more of the compounds represented by the above general formula [] with a carrier, and preparing the herbicide in the usual usage form of agricultural chemicals, such as wettable powders, emulsions, granules, etc. used in the form Examples of solid carriers include talc, bentonite, clay, diatomaceous earth, etc., and examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, dimethylformamide, and the like. If necessary, a surfactant may be added in order to obtain a uniform and stable form in these preparations. The formulation method is similar to the usual formulation method for agricultural chemicals.For example, for wettable powders, the active ingredient and solid carrier are added in appropriate amounts and a surfactant if necessary, mixed uniformly, and finely dispersed. Obtained by grinding. The active ingredient content in the hydrating agent is approximately 5-80%,
Preferably, 10 to 60% is appropriate. The emulsion is obtained by sufficiently dissolving a suitable amount of the active ingredient in the above-mentioned liquid carrier with or without the addition of a surfactant, and the active ingredient content is about 5-70%, especially 20-60%.
is preferred. In the case of granules, appropriate amounts of the active ingredient and a solid carrier, together with a surfactant if necessary,
The mixture is mixed uniformly, pulverized finely, and then made into granules with a diameter of 0.1 to 1.5 mm, preferably 0.5 to 1.0 mm, using a granulator. The amount of active ingredient in the granules is approximately 0.5 to 30%, preferably 1 to 10%. The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion.
The granules are subjected to a soil surface treatment or a soil mixing treatment before weed germination, or to a foliar spraying treatment after weed germination. When actually applying the herbicide of the present invention, 10 g or more of the active ingredient per 10 ares,
Preferably, an appropriate amount of 25 g or more is applied. The herbicide of the present invention can also be used in combination with known bactericides, insecticides, acaricides, herbicides, plant growth regulators, and the like. In particular, when used in combination with a herbicide, not only the amount of chemicals used can be reduced and labor savings can be achieved, but even higher effects can be expected due to the synergistic action of both chemicals. Known herbicides suitable for use in combination with the herbicide of the present invention include triazine herbicides such as simazine, propazine, and promethrin, carbamate herbicides such as betanal, and urea herbicides such as linyuron and tribunyl. Examples include phenoxyalkane carboxylic acid herbicides such as 2,4-PA agents, and heterocyclic herbicides such as pyrazone agents and renacil agents. Next, some examples regarding the herbicide of the present invention will be shown, but the active ingredient compounds, additives, and addition ratios are not limited to these examples and can be varied within a wide range. Example 6 Emulsion Compound 1 25 parts Dimethylformamide 47 parts Xylene 20 parts Polyoxyethylene phenyl ether 8 parts The above ingredients were mixed and dissolved to obtain an emulsion containing 25% of the active ingredient. Example 7 Wettable powder compound 12 30 parts diatomaceous earth 56 parts Higher alcohol sulfate ester 8 parts White carbon 6 parts The above are mixed uniformly and finely ground to form the active ingredients.
A 30% hydrating powder was obtained. Example 8 Granule Compound 6 3 parts bentonite 8 parts talc 85 parts polyoxyethylene alkyl phenyl sulfate 4 parts The above was mixed and ground uniformly, and the diameter was 0.5 to 0.5 in a granulator.
Granules were granulated to 1.0 mm to obtain granules containing 3% of the active ingredient. Next, test examples will be shown to demonstrate the effectiveness of the herbicide of the present invention. Test Example 1 Soil treatment test ^Two 250cm pots were filled with soil, and seeds of crabgrass, pigweed, dogberry, garland chrysanthemum, and soybean were sown and covered with soil to the extent that each seed was not visible. A chemical solution of a specified concentration prepared by diluting an emulsion of each test compound with water was added to 100%
The surface of the soil was sprayed at a rate of /10a. Three weeks later, the growth status of each weed was investigated. 0 indicates the same level of growth as without treatment, and 10 indicates withering or non-germination.
The growth status was expressed in 11 stages of ~10, and the results shown in Table 2 were obtained.

[Table] Test Example 2 Stem and Leaf Treatment Test ^Two 200cm pots were filled with soil, and seeds of crabgrass, oat, pigweed, and staghorn were sown, lightly covered with soil, and grown in a greenhouse. When the weeds grew to the 2- to 4-leaf stage, a chemical solution of a predetermined concentration prepared by diluting an emulsion of each test compound with water was sprayed on the leaves at a ratio of 100/10a. After 3 weeks, the growth status of each weed was investigated, and the growth status was expressed according to the same criteria as Test Example 1, and the results shown in Table 3 were obtained.

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, X is a halogen atom or a trifluoromethyl group, Y is a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a lower alkoxycarbonyl group,
n is 0 or 1, Z is formula -AR ₁ or [formula], A is oxygen or sulfur atom, R ₁ is lower alkyl group, ammonium, lower alkylammonium, di-lower alkylamino group, lower alkoxy group , an ethyl group β-substituted with a lower alkylthio group or a lower alkylcarbonylamino group, R ₂ is a hydrogen atom or a lower alkyl group, and R ₃ is a lower alkyl group, phenyl group, lower alkoxycarbonylmethyl group, or amino group. show. However, when n is 0, the following combinations are excluded: combinations where Y is a hydrogen atom and R ₁ is a lower alkyl group, combinations where Y is a hydrogen atom, X is a trifluoromethyl group, and A is an oxygen atom, and A combination in which Y is a lower alkyl group or a lower alkenyl group, A is an oxygen atom, and R ₁ is a lower alkyl group. ). 2 General formula (In the formula, X is a halogen atom or a trifluoromethyl group, Y is a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a lower alkoxycarbonyl group,
n is 0 or 1, Z is formula -AR ₁ or [formula], A is oxygen or sulfur atom, R ₁ is lower alkyl group, ammonium, lower alkylammonium, di-lower alkylamino group, lower alkoxy group , an ethyl group β-substituted with a lower alkylthio group or a lower alkylcarbonylamino group, R ₂ is a hydrogen atom or a lower alkyl group, and R ₃ is a lower alkyl group, phenyl group, lower alkoxycarbonylmethyl group, or amino group. show. However, when n is 0, the following combinations are excluded: combinations where Y is a hydrogen atom and R ₁ is a lower alkyl group, combinations where Y is a hydrogen atom, X is a trifluoromethyl group, and A is an oxygen atom, and A combination in which Y is a lower alkyl group or a lower alkenyl group, A is an oxygen atom, and R ₁ is a lower alkyl group. ) A selective herbicide characterized by containing a compound represented by the following as an active ingredient.