JPS6314776A - Carbamoyltriazole derivative, production thereof and herbicide containing said derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A carbamoyltriazole derivative expressed by formula I (R<1> and R<2> are lower alkyl or lower alkenyl; R<1> and R<2> together form lower alkylene). EXAMPLE:1-Diethylcarbamoyl-3-(2,2-dichlorocyclopropylmethylsulfonyl)-1 ,2,4-tria zole. USE:A herbicide. PREPARATION:(i) 3-(2,2-Dichlorocyclopropylmethylsulfonyl)-1,2,4-triazole is reacted with a carbamoyl halide expressed by formula II (Y is halogen) or (ii) a triazole derivative expressed by formula III (n is 0 or 1) is reacted with an oxidizing agent to afford the aimed compound expressed by formula I.

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.

<Prior art> Until now, 1-diethyl caffreno (moyl-8-
Propylsulfonyl-1,2,4-)lyazole (Japanese Unexamined Patent Publication No. 47-2149), 1-diethylcarbamoyl-8-benzilefonyl-1,2,4-triacyazole, US Pat. No. 4,280,881 1-diethy J Recarno (Moyl-8-cyclopropylmethy J Res J Lehoni J Le-1,2,4-triazole
No. 0-100561@) etc. are known.

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

<Means for Solving the Problem> The present inventors, aware of this situation, have conducted various studies in order to develop a compound with excellent herbicidal activity, and have found 8-
It was discovered that a (2,2-dichloropropylsulfonyl)-1,2,1-triazole derivative is a compound having excellent herbicidal activity with few of the above-mentioned drawbacks, and the present invention was achieved.

That is, the present invention relates to the general formula [wherein R1 and Rsl are the same or different and represent a lower alkyl group, a lower alkenyl group, or R1 and R'A together represent an alkylene group. The present invention provides a carbamoyltriazole derivative (hereinafter referred to as the compound of the present invention) represented by the formula (hereinafter referred to as the compound of the present invention), a herbicide containing the same as an active ingredient, and a method for producing the same.

Next, the manufacturing method will be explained in detail.

The compound of the present invention has 8-(2,2-dichlorocyclopropylmethylsulfonyl)-1,2゜4-triazole and the general formula [wherein R1 and R2 are the same or different, a lower alkyl group, a lower alkenyl group] , or R1 and R1 represent an alkylene group, and Y represents a halogen atom. ] It 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, the reaction temperature ranges from θ to 150°C, the reaction time ranges from 10 minutes to 1 hour, and the reaction time ranges from 10 minutes to 1 hour. The amount is 1 to 2 equivalents of carbamoyl halide [■] and 1 to 20 equivalents of dehydrohalogenating agent per 1 equivalent of 8-(2゜2-dichlorocyclopropylmethylsulfonyl)-1,2,4-triazole. It is equivalent.

Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, etc., logenated hydrocarbons such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethylnitine, etc. Tertiary amines such as ethers, aceryls, pyridine, triethylamine, N, N-diethylaniline, tributylamine, N-methylmorpholine, etc. Examples include acid amides, dimethyl sulfoxide, sulfolane and other sulfur compounds, and mixtures thereof.

Examples of the dehydrohalogenation agent include organic bases such as pyridine, triethylamine, and N,N-diethylaniline, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride.

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.

Further, the compound of the present invention can also be produced by using the general formula 1, where R1 and R1 have the same meanings as above.

Examples of the oxidizing agent include hydrogen peroxide, aromatic peracids such as m-chloroperbenzoic acid, and aliphatic peracids such as peracetic acid and pertrifluoroacetic acid. A solvent is not necessarily used (although it is possible to use one), depending on the type of oxidizing agent. It is preferable to use hydrogenated hydrocarbons, ethers such as diethyl ether and dioxane, and fatty acids in the case of aliphatic peracids.

The reaction temperature range for this reaction is from the freezing point to the boiling point of the solvent, preferably from 0°C to 100°C, and the reaction time range is about 10 minutes to 24 hours. The amount of reagents used in the reaction is 2 to 2.5 equivalents of the oxidizing agent per 1 isodensity of the triazole derivative (li) with n==0, and n
= triazole derivative of t (1) 0 for first-class graves
．． 95 to 1.2 equivalents.

After the reaction is complete, the reaction solution is subjected to normal post-treatments such as washing with alkaline water and distilling off the solvent, or, if necessary, recrystallization,
The desired compound of the present invention can be obtained by purification by column chromatography or the like.

When producing the compound of the present invention, the starting compound t is 8-(
2,2-dichlorocyclopropylmethylsulfonyl')
-1,2,4-triazole such as 2-halomethyl-
1,1-dichlorocyclopropane and 8-mercapto-1
, 2,4-triazole in the presence of a dehydrohalogenating agent. It can be obtained by oxidation using

Further, the triazole derivative (IIl), which is another raw material compound, has the general formula [wherein n represents the same meaning as above]. ] can be obtained by reacting the triazole derivative represented by ξ with carbamoylparite (1) in the presence of a dehydrohalogenating agent.

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, solutions, etc.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 76%, preferably 1 to 65%.

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. rl 1) 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. .

Examples include dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, and J-lyoxyethylene alkylaryl ether phosphate salts. Anionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, auxiliary agents for polyoxic formulations include lignin sulfonate, alkinate, etc. , polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose),
Examples include PAP (isopropyl acid phosphate).

The compound of the present invention is usually formulated and treated with soil, foliage, or flooding before or after the emergence of weeds. Soil treatment includes soil surface treatment, soil mixing treatment, etc., and foliage treatment includes treatment from above the plant body, as well as local treatment that treats only weeds so that they do not attach to crops.

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.
0.25h2001 per are, preferably o, b
t to 9 (l), and emulsions, wettable powders, suspensions, liquid preparations, etc.
Normally, the specified amount is diluted with 1 to 10 liters of water per 1 are (if necessary, an auxiliary agent such as a spreading agent is added). Process.

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

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

First, a production example of the compound of the present invention will be shown.

Production Example 1 1-Diethylcarbamoyl-Jl-(2,2-dichloropropylmethylthio)-1,2゜4-triazole 2f was dissolved in chloroform 100-, and metachloroperbenzoic acid (content 70%)8. After adding JIF over 5 minutes while cooling with ice water, the mixture was left at room temperature for 6 hours. Washed twice with an aqueous potassium carbonate solution, dried over magnesium sulfate, and evaporated to give 1-diethylcarbamoyl-a-(g,g-dichlorocycloprobylmethylsulfonyl)-1,2,4-
) 2.14 fl of 1 azole were obtained. no 1,
5158 Production Example 2 8-(2,2-dichlorocyclopropylmethylsulfonyl)-1,2,4-triazole 1.64F was dissolved in pyridine 25-, diallylcarbamoyl chloride 1.1
1 was added, and the mixture was allowed to stand at room temperature for 8 hours, then 200% of water was added and extracted twice with 100% of methylene chloride. The methylene chloride layer was washed twice with 150 d of 1N hydrochloric acid, then once with saturated brine, dried over magnesium sulfate, and the solvent was distilled off to give 1-diallylcarbamoyl-8-(2,2-dichloro cyclopropylmethylsulfonyl)-1,2゜4-
A crude product of triazole was obtained. It was purified by column chromatography (eluent methylene chloride:acetone-80:1) to obtain 1.94f. no I-5882 Next, some of the compounds of the present invention produced by this production method are shown in Table 1.

Table 1 general formula carbamoyltriazole derivatives of Next, production examples of raw material compounds are shown as reference examples and [.

Reference Example 1 (1) Dissolve 1.62f of sodium methoxide, 8.08F of 8-mercapto-1,2,4-)riazole in 40-methanol, and dissolve 6.121f of 2-bromomethyl-1,1-dichlorocyclopropane. Additionally, it was left at room temperature overnight. After adding 200ml of water and extracting with methylene chloride, the organic layer was dried over magnesium sulfate, and the solvent was distilled off.
(2,2-dichlorocyclopropylmethylthio)-1,
5.9f of 2,4-triazole was obtained. m, p. 7
7.0°C (2) Dissolve the above 8-(2,2-dichlorocyclopropylmethylthio)-1,2,4-triazole 8f in acetic acid 15-, add 8.8 g of 80% hydrogen peroxide,
After being kept at 70°C for 2 hours, it was left at room temperature overnight. water 1
Add 00-, count the number of crystals generated, and get 8-(2,2
-dichlorocyclopropylmethylsulfonyl)-1,2
, 4-triazole 1.8N was obtained.

mspm 1 76.9°C Reference example 2 8-(2,2-dichlorocyclopropylmethylthio)-
1,2,4-)-riazole 8,6f in pyridine 25t
Ethylpropylcarbamoyl chloride 2 dissolved in aj
．． After adding 5f and leaving it at room temperature overnight, 200+d of water was added and extracted with methylene chloride. The organic layer was diluted with 1N hydrochloric acid.
After washing twice and once with saturated saline, drying with magnesium sulfate and distilling off the solvent, 1-ethylpropylcarbamoyl-8-(2,2-dichlorocyclopropylmethylthio) -1°2.4 - A crude triazole product was obtained.

It was purified by column chromatography (eluent methylene chloride:acetone=80:1) to obtain 8.51N.

nl) 1.5480 Next, a formulation example is shown. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 Compound of the present invention! , 50 parts, lignin sulfo t 1 Ω
1. 8 parts of calcium phosphate, 2 parts of sodium lauryl sulfate, and 46 parts of synthetic hydrated silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 4.10 parts of the compound of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene are thoroughly mixed to obtain an emulsion.

Formulation Example 8 2.2 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite, and 65 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 6.25 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.

Formulation Example 5 6.10 parts of the compound of the present invention, 1 part of polyoxyethylene styrylphenyl ether, and 1 part of water are mixed to obtain a liquid preparation.

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 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

(!!1) In addition, the herbicidal efficacy of rOJ is determined by visually observing the degree of budding and growth inhibition of the test plants during by-products, and determining that there is no or almost no difference in the herbicidal efficacy from when no chemical fertilizers are provided. If the test plant dies or its growth is completely inhibited, r4=! J2.8.4.5z;L;1=1''
Indicated by

Test Example 1 Upland Soil Treatment Test A cylindrical plastic pot with a diameter of 1 Oc II 11 and a depth of 10 cm was filled with upland soil, sown with Japanese barnyard grass, Japanese barnyard grass, and lily, and covered with soil. The test compound was made into an emulsion according to Formulation Example 2,
A predetermined amount of the solution was diluted with water equivalent to 10 liters per are and 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 8.

@Table 8 Test Example 2 Field Soil Treatment Test A cylindrical plasti and kubot with a diameter of 10 am and a depth of 10 a+ were filled with field soil, and barnyard grass and 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, a predetermined amount of the emulsion was diluted with water containing a spreading agent equivalent to bto liters per are, and the foliage of the plant was treated with 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.

II Table 4 Test Example 8 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 81 m and a depth of 12 m was filled with paddy soil, and seeds of Japanese millet and bulrush were mixed to a depth of 1 to 2 seeds.

After being flooded into paddy fields, they were grown in a greenhouse. After 6 days (at the beginning of the development of each violet), make an emulsion of the test compound according to Formulation Example 2, dilute the specified amount with 5 liters of water,
Treated on 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 5.

□, \、 \、 \、 ゝ＼、 \81, □゛.

1. \, "\ @ Table 6 Test Example 4 Paddy field flooding treatment test 175000a Paddy soil was tied in a Wagner pot, and seeds of Japanese millet, broad-leaved weeds (Azeena, Kikashigusa, Chickweed), bulrush seeds, and overwintering stems of Pinus japonicum were added to one or two countries. After flooding to create a paddy field, Urikawa tubers were buried at a depth of 1 to 21, and rice at the 8-leaf stage was transplanted and grown in a greenhouse. 4 days later ( At the beginning of the budding period 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 10 milliliters of water, and the water was treated at a depth of 4 Iljl. After treatment, the emulsion was grown indoors for 20 days. The herbicidal efficacy was investigated.The results are shown in Table 6.For two days from the day after the treatment, 8α
The amount of water leaked was equivalent to the depth of water.

Table 6 <Effects of the Invention> As explained above, the compound of the present invention is effective against various weeds that are a problem in foliage treatment and soil treatment in fields, such as freckle currant, snail knotweed, purslane, chickweed, white locust, blue radish, daikon radish, Noharagarashi, shepherd's purse,
American golden deer, American golden deer,
Broad-leaved weeds such as field pansies, morning glories, morning glories, Convolvulus, Convolvulus, Phyllanthus vulgaris, Hotokenoza, White-bellied four-legged morning glories, Japanese Physalis, Japanese Physalis, Japanese chamomile, corn marigolds, barnyard grass, Japanese millet, Japanese foxtail grass, black-leaved weeds,
It has a herbicidal effect on weeds of the Poaceae family, such as sycamore, oat, oat, Seiban sorghum, and sorghum, as well as weeds of the Cyperaceae family, such as Asiatic dayflower, and Cyperaceae, such as Cyperus japonica and Porites, and moreover, the present invention The compound does not cause any harmful effects on major crops such as corn, rice, soybean, cotton, and sugar beet.

In addition, the compound of the present invention can be applied to various weeds that are problematic in the flooding treatment of paddy fields, such as grasses such as Japanese grasshopper, azalea, commonweed, [broad-leafed weeds such as Japanese chickweed, Japanese cypress, Japanese cypress, Japanese cypress, Japanese cypress, and Japanese cypress]. Cyperus cyperus and others do not cause any harmful effects on rice.

Furthermore, the compound of the present invention can be used as a herbicide in rice fields, fields, orchards, pastures, lawns, forests, non-agricultural lands, etc., and can also be used in combination with other herbicides to kill weeds. It can be expected to increase efficacy. Furthermore, it can also be used in combination with insecticides, acaricides, nematicides, fungicides, plant P1 regulators, fertilizers, soil conditioners, etc.

/′ ・′−・／／ I-juku/・ ／・′□″′ (80 complete)

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are the same or different,
Lower alkyl group, lower alkenyl group, or R^1 and R
^2 represents an alkylene group. ] A carbamoyltriazole derivative represented by (2) 3-(2,2-dichlorocyclopropylmethylsulfonyl)-1,2,4-triazole and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 and R^ 2 are the same or different;
Lower alkyl group, lower alkenyl group, or R^1 and R
^2 represents an alkylene group, and Y represents a halogen atom. ) There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 represent 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. ▼ (2) [In the formula, R^1 and R^2 are the same or different,
Lower alkyl group, lower alkenyl group, or R^1 and R
^2 represents an alkylene group, and n represents 0 or 1. [In the formula, R^1 and R^2 have the same meanings as above. ] A method for producing a carbamoyltriazole derivative shown in the following. (4) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) [In the formula, R^1 and R^2 are the same or different,
A lower alkyl group, a lower alkenyl group, and R^1 and R^2 represent an alkylene group. ] A herbicide characterized by containing a carbamoyltriazole derivative as an active ingredient.