JPS6210041A - Naphthoxypropionic acid derivative, production thereof and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:?The naphthoxypropionic acid derivative of formula I (X is CH or N; R<1> is H, halogen, cyano or nitro; R<2> is H, alkyl, haloalkyl, cycloalkyl, lower alkenyl or lower alkynyl). EXAMPLE:alpha-[7-(3-Chloro-5-trifluoromethyl-2-pyridyloxy)-2-naph-thox y]-propionic acid ethyl ester. USE:Useful as a herbicide having herbicidal effect against various weeds in plowed land, e.g. broad-leaved weeds such as wild buckwheat and gramineous weeds such as Deccan grass, green foxtail, etc., and exhibiting no phytotoxicity to main crops such as corn, rice, etc. PREPARATION:The compound of formula I can be produced by reacting the naphthol derivative of formula II with the halopropionic acid derivative of formula III (Y is halogen) in a solvent, in the presence of 1-1.5 equivalent of dehydrohalogenation agent, at 0-100 deg.C using a phase-transfer catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein X represents C)l or N, R is a hydrogen atom,
Represents a halogen atom, cyano group or nitro group R2
is a hydrogen atom, an alkyl group, a haloalkyl group,
Represents a cycloalkyl group, lower alkenyl group or lower alkynyl group. ] The present invention relates to a method for producing the naphthoxypropionic acid derivative (hereinafter referred to as the compound of the present invention) represented by the following formula, and a herbicide containing the same as an active ingredient.

Certain naphthoxypropionic acid derivatives, e.g.
The use of [5-(8-chloro-5-trifluoromethylpyridyl-2-oxy)-1-naphthoxy]propionic acid ethyl ester as an active ingredient in herbicides is described in JP-A-54-82477. has been done. However, these compounds cannot always be said to be sufficient as active ingredients for herbicides.

The compounds of the present invention can be used to treat various weeds that are problematic in the foliage treatment and soil treatment amount ζ of upland fields, such as American hornwort, Ebisu grass, Japanese commonweed, American golden deer, field pansies, Japanese morning glory, American morning glory, Malva morning glory, and Convolvulus. , Physalis vulgaris, Hotokenoza, Physalis spp.
The compound of the present invention has a herbicidal effect on broad-leaved weeds such as Japanese grasshopper, grasshopper, sunflower, and dogberry, as well as grass weeds such as grasshopper, grasshopper, grasshopper, oat, and oat. It does not cause any harmful effects on major crops such as wheat, rice, etc.

In addition, the compound of the present invention is effective against various weeds that are problematic in the waterlogging treatment of rice fields, such as grass weeds such as Japanese grasshopper, broad-leaved weeds such as azalea, staghorn weed, and chickweed, cyperaceae weeds such as bulrush, and cucumber. It has herbicidal efficacy and does not cause any harmful effects on rice.

In the compound of the present invention, in the general formula 1, X and R have the same meanings as above. ] A naphthol derivative represented by 1 to 1.5
Equivalent general formula % Formula %] [In the formula, Y represents a halogen atom, and R2 represents the same meaning as above. ] in an i medium, 1 to 1 halopropionic acid derivatives represented by
．． optionally in the presence of 5 equivalents of a dehydrohalogenating agent,
In the presence of a phase transfer catalyst, 0°C to 100″C, 5 minutes to lO
It can be produced by reacting for a period of time.

Moreover, the general formula [wherein R represents the same meaning as above]. A hydroxynaphthoxypropionic acid derivative represented by the following formula, and a 1 to 1.5 equivalent of the general formula c, where Z represents a halogen atom, and X and R1 have the same meanings as above. ] in a solvent, in the presence of 1 to 1.5 equivalents of a dehydrohalogenating agent, and if necessary in the presence of a phase transfer catalyst, at 50° C. to 200° C. for 1 hour to 10 hours. It can be manufactured by

In any of the above reactions, solvents include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated aromatics such as chlorobenzene. Hydrocarbons, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol,
Ethers such as dimethyl ether, esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate, nitrites such as nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N,N-diethylaniline, Tributylamine, N
- Tertiary amines such as methylmorpholine, acid amides such as formamide, N,N-dimethylformamide, N,N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, water, etc., or mixtures thereof. It will be done.

In any of the above reactions, dehydrohalogenation agents include organic bases such as pyridine, triethylamine, N,N-diethylaniline, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, etc. Examples include inorganic bases, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, and in any of the above reactions, phase transfer catalysts include tetrabutylammonium bromide, cetyltrimethylammonium chloride, benzyltrimethylammonium bromide, Quaternary salts such as 3-phenoxybenzyltriethylammonium bromide, dodecylbenzenediethylammonium chloride, phenyltriethylammonium iodide, dibenzo-18-
Crown ether such as Crown-6, Tris C8,6-
Examples include thioxapentyl) amine.

In any of the above reactions, the reaction solution after the completion of the reaction is subjected to normal post-treatments such as organic solvent extraction and concentration, and if necessary, purified by operations such as chromatography, distillation, and recrystallization. The desired compound of the present invention can be obtained.

Next, production examples of the compounds of the present invention will be shown.

Production Example 1 (Production of Compound 23 of the Invention) Sodium hydride (60%) 0.141N.

1.02 of 7-(8-chloro-6-trifluoromethyl-2-pyridyloxy)-2-naphthol, suspended in N-dimethylformamide 10- and at O''C under a nitrogen atmosphere.
F was added and stirred for 15 minutes. After 0.6 f of ethyl α-bromoproionate was added dropwise to this solution, stirring was continued for 2 hours at θ°C. The reaction solution was poured into water and extracted with ether. After removing the ether, the residue km was subjected to II chromatography (developing solvent: hexane: ethyl acetate; 10:1
) to give α-(7-(8-chloro-5-trifluoromethyl-2-pyridyloxy)-2-naphthoxy)
-0.98F of ethyl propionate was obtained.

nH5-Ot, 5579 Production Example 2 (Production of Compound 12 of the Invention) Ethyl a-(7-hydroxy-2-naphthoxy)-propionate 0.5
2F was dissolved in acetonitrile lO-, and to this solution were added 0.27 F of potassium carbonate and 0.45 F of 4-chloro-8-nitrobenzotrifluoride, and the mixture was heated under reflux for 5 hours. The reaction solution was poured into water and extracted with ether. After removing the ether, the residue was purified by thin layer chromatography (developing solvent: hexane:ethyl acetate = 10:l) to obtain α-(7-(2-nitro-4-trifluoromethylphenoxy)-2-naphthoxy). -0.681 of ethyl brochionate was obtained. 1.5657 Some of the compounds of the present invention that can be produced by such a production method are
Shown in the table.

Table 1 When producing the naphthoxypro-invention compound of the general formula, the raw material compound, the naphthol derivative of the general formula .7-hydroxynaphthalene in a solvent, in the presence of 1 to 8 equivalents of a dehydrohalogenating agent, and optionally in the presence of a phase transfer catalyst, at 50°C to 2°C.
It can be produced by reacting at 00°C for 1 to 10 hours.

As a solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, and isophorone. , ketones such as cyclohexanone, nitrites such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, tributylamine, and N-methylmorpholine. Examples include formamide, acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, water, etc., or mixtures thereof.

Examples of dehydrohalogenation agents include organic bases such as pyridine, triethylamine, and N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride, sodium methoxide, and sodium hydroxide. Examples include alkali metal alkoxides such as ethoxides.

As the phase transfer catalyst, quaternary salts such as tetrabutylammonium bromide, cetyltrimethylammonium chloride, benzyltrimethylammonium bromide, 8-phenoxybenzyltriethylammonium bromide, dodecylbenzyldiethyl-ammonium chloride, phenyltriethylammonium iadide,
Alternatively, crown ethers such as dibenzo-18-crown-6, tris(8,6-sioxahebutyl)amine, and the like can be mentioned.

After the reaction is complete, the reaction solution is poured into water, neutralized with acid, and subjected to conventional post-treatments such as organic solvent extraction and concentration. An example of producing a naphthol derivative is shown as a reference example.

Reference Example 1 1.92 f° of 2,7-hydroxynaphthalene was dissolved in 20-dimethyl sulfoxide, and 0.92 f of potassium carbonate and 2,17 f of 2,8-dichloro-5-trifluoromethylpyridine were added to this solution. Approximately 140℃ for 4 hours
and stirred. The reaction solution was poured into water, neutralized with dilute hydrochloric acid, and then extracted with ethyl acetate. After removing ethyl acetate, the residue was subjected to silica gel column chromatography (
Separation was performed using a developing solvent (hexane:ethyl acetate=8:1) to obtain 1.77 units of 7-(8-chloro-5-trifluoromethyl-2-pyridyloxy)-2-naphthol. m, 9.204-205°C Reference Example 2 1.92 g of 2.7-hydroxynaphthalene was dissolved in 20-dimethyl sulfoxide, and 0% of water was added to this solution.
．． 791 and 1.81f of 2-chloro-5-trifluoromethylpyridine were added, and the mixture was stirred for 5 hours while maintaining the temperature at about 180°C.

The reaction solution was poured into water, neutralized with dilute hydrochloric acid, and then extracted with ethyl acetate. After removing ethyl acetate, the residue was separated by silica gel column chromatography (developing solvent: hexane:ethyl acetate = 8:1), and 7-(
5-trifluoromethyl-2-pyridyloxy)-2-
Naphthol 1.41F was obtained. m, 9.166-156
°C When using the compound of the present invention as an active ingredient of a herbicide,
It is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, granules, etc.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.01 to 8096%, preferably 0.1 to 50%.

Examples of solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut 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, vegetable oils such as soybean oil and cottonseed oil, and dimethyl sulfoxide. , acetonitrile, water, etc.

Surfactants used for emulsification, dispersion, wetting layers, etc. include anionic surfactants such as alkyl sulfate salts, alkylaryl sulfonates, dialkyl sulfosuccinates, and polyoxyethylene alkylaryl ether phosphate salts. agent, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. As formulation aids, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PA
Examples include P (isopropyl acid phosphate).

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Part indicates Mfi1 part.

Formulation Example 1 22.50 parts of the compound of the present invention, 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 28.10 parts of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 80 parts of xylene and 40 parts of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 8 9.2 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite, and 66 parts of kaolin clay were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded. The granules are dried to obtain granules.

Formulation Example 4 22.25 parts of the compound of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 8 parts of CMC, and 69 parts of water are mixed and wet-pulverized until the particle size becomes 5 microns or less to obtain a suspension.

The compound of the present invention thus formulated is treated with soil, foliage, or flooding before or after the emergence of weeds. Soil treatment includes soil surface treatment, soil mixing treatment, etc. For foliage treatment, in addition to treatment from above the plant body,
There are local treatments that treat only weeds so that they do not attach to crops.

Furthermore, by mixing it with other herbicides, it can be expected to increase the herbicidal efficacy. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners, and the like.

The compound of the present invention can be used in rice fields, fields, orchards, pastures,
It can be used as an active ingredient in herbicides for lawns, forests, non-agricultural lands, etc.

When the compound of the present invention is used as an active ingredient of a herbicide, the amount to be treated will vary depending on weather conditions, formulation form, treatment time, method, location, target weeds, target crops, etc., but usually 1.
0.08g to 2ooy1 per are, preferably O,
lf to 100 f, and emulsions, wettable powders, suspension agents, etc. are usually mixed with 1 liter to 10 liters of water per 1 are (if necessary, auxiliary agents such as spreading agents are added). Granules and the like are usually treated as they are without any dilution.

In addition to the above-mentioned surfactants, the spreading agent may include polyoxyethylene resin acid (ester), liquen sulfonate,
Examples include abietate, dinaphthylmethane disulfonate, and paraffin.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients of herbicides. In addition, the compound of the present invention has j11
The compound number shown in the table is the compound used for comparison.
Indicated by compound symbol in the table.

Table 2 In addition, the herbicidal efficacy was determined by visually observing the degree of inhibition of budding and growth of the test plants during the survey, and was evaluated as "O" if there was no or almost no difference from the case where the compound was not tested. If the plant is withered or its growth is completely inhibited, it is evaluated as "5", and evaluated on a scale of θ to 5, 0.1.2.
8.4.5.

Test Example 1 Upland Stem and Leaves Treatment Test A cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cfR was filled with upland soil, and barnyard grass, oats, radish, and Japanese radish were sown and grown in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and the predetermined liter of the emulsion was
The mixture was diluted with water containing a spreading agent equivalent to 10 liters per area, and treated with a small sprayer from above the plant. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 8.

Table 8 Test Example 2 Upland soil treatment test area 88x28c! Field soil was packed into a vat with an A1 depth of 11 IM, and corn, morning glory, Japanese yam, Japanese grass, Japanese millet, Seiban sorghum, and foxglove were sown, and the soil was covered with soil to a thickness of 1 to 2 cIt1. Formulation example 2
The test compound was made into an emulsion according to the method described above, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the mixture was applied to the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 4.

Table 4 Test Example 8 Field soil stem and leaf treatment test A vat with an area of 88 x 28 d and a depth of 11 crR was filled with field soil, and sowed with Marpa morning glory, Japanese fir tree, Japanese grass, Japanese grass, maize, wheat, Japanese millet, and rice.
It was grown for 18 days.

Thereafter, make an emulsion of the test compound according to Formulation Example 2, dilute the specified amount with water equivalent to 5 liters per are containing a spreading agent, and apply it uniformly over the entire stem and leaf area from the top of the plant using a small sprayer. Processed. At this time, the growth conditions of weeds and crops vary depending on the grass species, but the 1-4 leaf stage and the plant height are 2-12 cm.
It was 3. The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 5.

Note that this test was conducted in a greenhouse throughout the entire period.

Table 6 Test Example 4 Upland Stem and Leaves Treatment Test Area: 118 x 28 d, depth 11 vats were filled with upland soil and sown with wheat, morning glory, Japanese commonweed, Japanese millet, and foxtail grass, and grown for 18 days. Thereafter, a predetermined amount of the test compound made into an emulsion according to Formulation Example 2 was diluted with water equivalent to 5 liters per are containing a spreading agent, and the mixture was uniformly applied from the top of the plant to the entire stem and leaf area using a small sprayer. did. At this time, the growth conditions of weeds and crops varied depending on the grass species, but they were in the 1-4 leaf stage and the plant height was 2-12 cIt1.

The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 6. This test was conducted in a greenhouse throughout the entire period.

Table 6 Test Example 5 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8 cm and a depth of 12 tM was filled with paddy soil, and 1 to 2 seeds of Japanese millet, broad-leaved weeds (Azaena, Kikashigusa, Chickweed), and firefly were added to the pot.
It was mixed to a depth of cm. After being flooded and turned into a paddy field,
Urikawa tubers were buried at a depth of 1 to 2 cW1, and then rice at the second vegetable stage was transplanted and grown in a greenhouse. Six days later (at the beginning of each weed's emergence), the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with 5 milliliters of water, and the emulsion was applied to the water surface. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 7.

Table 7

Claims (1)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X represents CH or N, and R^1 represents a hydrogen atom, a halogen atom, a cyano group, or a nitro group. , R^2 represents a hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a lower alkenyl group or a lower alkynyl group. ] A naphthoxypropionic acid derivative represented by (2) General formula▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents CH or N, and R^1 represents a hydrogen atom, a halogen atom, a cyano group, or a nitro group. ] There are naphthol derivatives represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc. group or lower alkynyl group. [In the formula, X, R^1 and R^2 have the same meanings as above. ] A method for producing a naphthoxypropionic acid derivative. (8) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^2 represents a hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a lower alkenyl group, or a lower alkynyl group. ] There are hydroxynaphthoxypropionic acid derivatives represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents CH or N, Z represents a halogen atom, R^1 represents a hydrogen atom, Represents a halogen atom, cyano group or nitro group. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting with a halide represented by ▼ [In the formula, X, R^1 and R^2 represent the same meanings as above. ] A method for producing a naphthoxypropionic acid derivative. (4) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X represents CH or N, R^1 represents a hydrogen atom, a halogen atom, a cyano group, or a nitro group, and R^2 represents hydrogen Represents an atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a lower alkenyl group or a lower alkynyl group. ] A herbicide characterized by containing a naphthoxypropionic acid derivative represented by the following as an active ingredient.