JPH01102070A - Carbamoyltriazole derivative, its production, and herbicide containing the same as an active ingredient - Google Patents

Abstract

NEW MATERIAL:A carbamoyltrizole derivative of formula I (R1, R2 are lower alkyl; n is 0, 1, 2; m is 1, 2). EXAMPLE:1-(Diethylcarbamoyl)-8-(4-trifluorobenzylthio)-1,2,4-triazole. USE:It is used as a herbicide. It manifests excellent herbicidal effects against weeds which cause troubles in soil treatment in fields, foliage treatment and flooded paddy treatment and shows high selectivity between main crops and weeds. It causes no chemical injure to rice plant, corn and wheat. PREPARATION:The reaction of a triazole derivative of formula II with a carbamoyl halide of formula III (X is halogen) is carried out in a solvent in the presence of a dehydrohalogenation agent at 0-150 deg.C to give the compound of formula I. The amount of the compound of formula III is 1-1.5 equivalent to 1 equivalent of the compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel carbamoyltriazole derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

<Conventional technology> Until now, US patent! Specification No. 4280881, Japanese Unexamined Patent Publication No. 1973
No. 9-89880 and other publications describe the use of carbamoyltriazole derivatives as active ingredients in herbicides.

<Problems to be Solved by the Invention> However, these compounds are not necessarily satisfactory because their herbicidal efficacy is insufficient or their selectivity between crops and weeds is poor.

<Means for Solving the Problems> In view of the current situation, the present inventors have made extensive studies and found that a carbamoyltriazole derivative represented by the following general formula (i) has the above-mentioned drawbacks. Less, better #c
1! We have discovered that this compound is effective and exhibits excellent selectivity between crops and weeds, leading to the present invention.

That is, the present invention is based on the general formula [wherein R1 and R are lower alkyl groups, n is 0,1
or an integer of 2; m represents an integer of 1 or 2; ] A carbamoyltriazole derivative (hereinafter referred to as the compound of the present invention) represented by the following, a method for producing the same, and a herbicide containing the same as an active ingredient are provided.

Next, the manufacturing method will be explained in detail.

The compound of the present invention has the general formula [wherein n and m have the same meanings as above. ] A triazole conductor represented by the general formula [wherein, X is a halogen atom, and R1 and R2 have the same meanings as in Off notation. ] ξ can be produced by reacting with the carbamoyl halide shown below.

This reaction is usually carried out in a solvent in the presence of a dehydrohalogenating agent, with a reaction temperature range of 0 to 150°C and a reaction time range of 10 minutes to 24 hours. The amount of carbamoylparite Ml(1) is 1 to 1.6 equivalents and the dehydrohalogenation agent is 1 to 6 equivalents per equivalent of triazole derivative [I].

As a solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, 'dichlorobenzene, diethyl ether,
Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and diethylene glycol dimethyl ether; ketones such as acetone, methylmorpholine, methyl isobutyl ketone, isophorone, and cyclohexanone; nitro compounds such as nitroethane and nitrobenzene; nitrites such as acetonitrile and isobutyronitrile; Tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine, acid amides such as N,N-dimethylformamide,
- Sulfur compounds such as dimethyl sulfoxide and sulfolane, or mixtures thereof.

! Examples of halogenated ice hydrogen agents include organic bases such as pyridine, triethylamine, N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride, and sodium methoxide. , alkali metal alkoxides such as sodium ethoxide, and the like.

After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by chromatography, recrystallization, etc. to obtain the desired compound of the present invention. can.

Further, the compound of the present invention in which n is 1 or 2 in the general formula (1) is represented by the general formula (wherein R1, island and m have the same meanings as above).

] It can also be produced by oxidizing the compound of the present invention represented by the following using an oxidizing agent.

Examples of the oxidizing agent include hydrogen peroxide, aromatic peracids such as metachloroperbenzoic acid, and aliphatic peracids such as peracetic acid and pertrifluoroacetic acid. A solvent does not necessarily need to be used, but if it is used, it depends on the type of oxidizing agent. For example, for hydrogen peroxide, water, glacial acetic acid, acetone, etc. are used; for aromatic peracids, halogenated hydrocarbons such as chloroform, methylene chloride, etc. Ethers such as, diethyl ether, and dioxane are preferred. In the case of aliphatic peracids, it is preferable to use the oxidizing agent itself in excess.

The reaction temperature range is 0 to 100°C, and the reaction time range is 10
The reaction time is from 1 to 24 hours, and the amount of the reagent used in the reaction is 1 to 8 equivalents of the oxidizing agent per 1 equivalent of carbamoyltriazole derivative (1').

After completion of the reaction, the reaction solution can be subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by operations such as chromatography and recrystallization to obtain the desired compound of the present invention. .

Examples of the compounds of the present invention include the following compounds.

Table 1 General formula % Formula % When producing the compound of the present invention, the triazole derivative represented by the general formula (1), which is a raw material compound, has the general formula [wherein, Y is a halogen atom, and in has the same meaning as above] represent. ] Substituted benzyl halide represented by the formula and 8- represented by the formula
It can be produced by reacting mercapto-1,2,4-triazole in the presence of a dehydrohalogenating agent.

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.

After the reaction is completed, the reaction solution j is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by chromatography, recrystallization, etc. to obtain the desired triazole derivative CI). Can be done.

The compounds of the present invention have excellent herbicidal efficacy and exhibit excellent selectivity between crops and weeds. That is, the compound of the present invention is
Various weeds that are problematic in the treatment of foliage and soil in upland fields, such as sopaca vulgaris, Japanese knotweed, purslane, chickweed, white radish, blue radish, Japanese radish, Japanese radish, shepherd's purse, American hornwort, Japanese commonweed, American goldenrod, field pansy, American Broad-leafed weeds such as morning glory, morning glory, Convolvulus, Japanese staghorn, Hotokenoza, White-breasted morning glory, Japanese Physalis, Japanese violet, Japanese chamomile, corn marigold, barnyard grass, Japanese millet, foxtail grass, black grass, Japanese sycamore, Japanese oat, oat, oat , has a herbicidal effect against weeds of the grass family such as Seiban sorghum, barley, horseweed, and grasshopper, as well as weeds of the family Cyperaceae such as dayflower, and weeds of the family Cyperaceae such as cyperus japonica and Japanese cyperus.
Moreover, the compound of the present invention can be used in corn, wheat, rice,
It does not cause any harmful chemical damage to major crops such as soybean, cotton, and sugar beet.

In addition, the compound of the present invention can be applied to 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, japonica japonica, and chickweed; It has a herbicidal effect against weeds of the Cyperaceae family, Cyperaceae, Cyperaceae, etc., and does not cause any harmful effects on rice.

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, and the like.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 90%, preferably 0.2 to 80%.

Examples of solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, chloride shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Examples of 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 vegetable oils such as soybean oil and cottonseed oil. dimethyl sulfoxide, N,
Examples include N-dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wet layer, etc. include anionic surfactants such as alkyl sulfate salts, alginates, polyoxyethylene alkylaryl ether phosphate salts, Examples include nonionic surfactants such as ether, polyoxyethylene alkylaryl ether, I-lyoxyethylene polyoxypropylene block co-I remer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.

Other formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), and the like.

The compound of the present invention is usually formulated and used for soil treatment, foliage treatment, or treatment from above the weeds before or after the emergence of weeds, as well as local treatment for treating only weeds so that they do not attach to crops.

Further, 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 lawns, forests or non-agricultural lands. 0. 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.
0.2g to 200g per are, preferably 0.2g to 200g1.
5g to 100g, and emulsions, wettable powders, gluing agents, etc. are usually diluted with 1 liter to 10 liters of water per 1 area (if necessary, auxiliary agents such as spreading agents are added). Granules, etc. are usually processed without any dilution (processed as is).

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

<Effects of the Invention> The compound of the present invention has excellent herbicidal efficacy against various weeds that are problematic in soil treatment and foliage treatment of upland fields, as well as in flooding treatment of paddy fields, and has excellent weed control properties between major crops and weeds. Since it exhibits selectivity, it can be used as an active ingredient in herbicides for various purposes.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to production examples, reference examples, formulation examples, and test examples, but the present invention is not limited to these examples.

Production Example 1 (Production of Compound (1) of the Present Invention) 8-(4-)Lifluoromethylbenzylthio)-1,2,4-triazole s, rxy was dissolved in 80% of pyridine, and 2.8% of diethylcarbamoyl chloride was added. was added and stirred at room temperature for 12 hours. Pyridine was removed under reduced pressure, and ethyl acetate was added to the residue, which was washed once with 1N hydrochloric acid and further washed eight times with saturated brine. After drying over anhydrous magnesium sulfate and distilling off the solvent, 1-(diethylcarbamoyl')-8-(
4-trifluoromethylbenzylthio)-1゜2.4-
) Riazole 8.89F was obtained.

Yield 75.8% n, 1.5197 Production Example 2 (Production of Compound (2) of the Present Invention) 1-(Diethylcarbamoyl)-8-(4-trifluoromethylbenzylthio)-1°2.4-triazole 1.07F was dissolved in 100 ml of chloroform, and metachloroperbenzoic acid (content 70%>0.74f dissolved in 20 d of chloroform) was added dropwise at 0 to 6°C.
After stirring for a minute, the mixture was washed eight times with a 20% aqueous potassium carbonate solution and twice with saturated brine. It was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 1.07f of 1-(diethylcarbamoyl)-8-(4-)lifluoromethylbenzylsulfinyl)-1,2,4-)riazole.
-Yield 95.6% Production Example 8 (Production of Compound (8) of the Present Invention) 1-(diethylcarbamoyl)-8-(4-trifluoromethylbenzylthio)-1゜2.4-triazole 1.07N was dissolved in 100 ml of chloroform, 2.00 f of metachlorobenzoic acid (70% content) was added, and the mixture was stirred at room temperature for 12 hours.The mixture was washed eight times with a 20% aqueous potassium carbonate solution and then twice with saturated brine. It was dried over anhydrous magnesium sulfate and the solvent was distilled off to obtain 1.06f of 1-(diethylcarbamoyl)-8-(4-)lifluoromethylbenzylsulfonyl)-1,2,4-triazole.

Yield 98.8% m9 94.5-95.6°C Table 2 shows the amount of the compound of the present invention produced according to this production method.

Table 2 General formula % Formula % Next, a production example of the triazole derivative (1) which is a raw material compound is shown as a reference example.

Reference Example 1 (Production of raw material compound (a)) Dissolve 1.82N of potassium hydroxide (content 86%) in 60s/methanol, add 2.02f of 8-mercapto 1,2,4-triazole, and stir at room temperature for 80% Stir for a minute.

4.781 ml of 4-trifluoromethylbenzyl bromide was dissolved in 20 sl of methanol and added. Ethyl acid was added at room temperature for 80 minutes, washed twice with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to give 8-(4-).
fluoromethylbenzylthio)”-1=2*4
-) Riazole 4.78f yield 92.8% m911
Table 8 shows some of the triazole derivatives (1) that can be produced in this manner.

Table 8 Triazole derivatives of the general formula. Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 2. Parts are parts by weight.

Formulation Example 1 50 parts of the compound (2) of the present invention, 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 46 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 10 parts each of the compounds (1) to (5) of the present invention, 14 parts of polyoxyethylene styrylphenyl 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 2 parts of the present compound (6), 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, and water was added and kneaded thoroughly. , granulation and drying to obtain granules.

Formulation Example 4 25 parts of the compound (8) 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 6 tons or less to obtain a suspension.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients of herbicides. The compounds of the present invention are indicated by the compound numbers in Table 2, and the compounds used for comparison are indicated by the compound symbols in Table 4.

Table 4 In addition, for evaluation of herbicidal efficacy and chemical damage, the conditions of budding and growth of the test plants (weeds and crops) at the time of the survey were determined to be "no or almost no difference" compared to untreated plants.
0", and those in which the test plant is completely dead or whose budding or growth is completely suppressed are designated as [101], and O to 1
Classified into 11 stages of 0, 0.1.2.8.4.6.6.
7.8.9.1G.

Test Example 1 Field Soil Surface Treatment Test Cylindrical plastic l with diameter IQal and depth 10a11
Fill the pot with field soil, sow barnyard grass, and cover with soil. The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion 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 6.

Table 6 Test Example 2 Upland Stem and Leaves Treatment Test A cylindrical plastic pot with a diameter of 10 cm and a depth of 103 cm was filled with upland soil, and barnyard grass was sown and grown for 10 days in a greenhouse. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water containing a spreading agent equivalent to 10 liters per are, and the foliage was treated from above the plant 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 6.

Table 6 Test Example 8 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 83 mm and a depth of 123 mm was filled with paddy soil, and seeds of Japanese millet were mixed in at a depth of 1 to 2 α. After flooding the rice field to create a paddy field, two-leaf stage rice was transplanted and grown in a greenhouse. After 6 days (at the beginning of the generation of Japanese millet), the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with 5 liters 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 Test Example 4 Paddy field flooding treatment test 115,000 m Wagner pots were filled with paddy soil, and were planted with Japanese millet and broad-leaved weeds (Azaena, Kikashigusa, and Chickweed).
, the seeds of firefly were mixed in to a depth of 1 to 2 cm. After flooding the rice field to create a paddy field, rice at the 8-leaf stage was transplanted and grown in a greenhouse. After 4 days, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was diluted with 10 tons of water and applied to the water surface to a depth of 43 cm. After treatment, the plants were grown in a greenhouse for 20 days, and their herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 8. Note that for two days from the day after the treatment, water leaked in an amount equivalent to a water depth of 8 cII per day.

Table 8

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are lower alkyl groups, n is 0
, an integer of 1 or 2, and m represents an integer of 1 or 2. ] A carbamoyltriazole derivative represented by (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, n represents an integer of 0, 1 or 2, and m represents an integer of 1 or 2. ] There are triazole derivatives represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are lower alkyl groups, and X represents a halogen atom. [In the formula, R_1, R_2, n and m have the same meanings as above. ] A method for producing a carbamoyltriazole derivative shown in the following. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are lower alkyl groups, m is 1
or represents an integer of 2. ] A general formula characterized by oxidizing a carbamoyltriazole derivative represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, n is an integer of 1 or 2, R_1, R_2 and m have the same meaning as above. represent. ] A method for producing a carbamoyltriazole derivative shown in the following. (4) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are lower alkyl groups, n is 0
, an integer of 1 or 2, and m represents an integer of 1 or 2. ] A herbicide characterized by containing a carbamoyltriazole derivative represented by the following as an active ingredient.