JPH01121279A - 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 alkyl or alkenyl or R<1> and R<2> together represent alkylene forming a ring; X and Y are H,halogen, alkyl, alkoxy, alkoxycarbonyl, nitro, amino, acylamino or trifluoromethyl; n is 0, 1 or 2, except when both R<1> and R<2> are methyl). EXAMPLE:1-(Diethylcarbamoyl)-3-(3-methyoxy-5-trifluoromethylphenylthio )-1,2,4- triazole. USE:A herbicide. PREPARATION:A triazole derivative expressed by formula II is reacted with a carbamoyl halide expressed by formula III (Z is halogen) to afford the aimed carbamoyltriazole derivative 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, Japanese Patent Application Laid-Open No. 59-89880, U.S. Patent No. 4
No. 280881 and other documents describe that certain carbamoyltriazole derivatives can be used as active ingredients of 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.

In view of this situation, the present inventors have conducted various studies and found that the carbamoyltriazole derivative represented by the following general formula CI) is an excellent product with few drawbacks as described above. The inventors have discovered that the compound has excellent herbicidal efficacy and exhibits excellent selectivity between crops and weeds, leading to the present invention.

That is, the present invention relates to the general formula CI) [wherein R1 and R2 are the same or different and represent a lower alkyl group, a lower alkenyl group, or a lower alkylene group in which R1 and R2 form a ring, and X and Y are the same or Differently, it represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, a nitro group, an amino group, an acylamino group or a trifluoromethyl group, and n represents an integer of 0.1 or 2. However, those in which R1 and R2 are both methyl groups are excluded. ] The present invention provides a carbamoyltriazole derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide containing the same as an active ingredient.

Next, the manufacturing method will be explained in detail.

The compound of the present invention has the general formula CI) [wherein X, Y and n represent the same meanings as above. ] The triazole derivative represented by the general formula [I] [in the formula
R1 and R2 have the same meanings as above, and Z represents a halogen atom. ] It can be produced by reacting with the carbamoyl halide shown below.

The reaction with is usually carried out in a solvent in the presence of a dehydrohalogenating agent, the reaction temperature range is 0 to 150°C, the reaction time is 10 minutes to 24 hours, and the reaction time is 10 minutes to 24 hours. The amount of the carbamoyl halide (1) is 1 to 1.5 equivalents, and the amount of the dehydrohalogenation agent is 1 to 5 equivalents per 1 equivalent of the 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, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, isophorone, and cyclohexanone, nitro compounds such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N,N-diethylaniline, tributylamine, and N-methylmorpholine. tertiary amines such as, acid amides such as N,N-dimethylformamide,
Sulfur compounds such as dimethyl sulfoxide and sulfolane, etc.
Or a mixture thereof.

Examples of the dehydrohalogenation agent include organic salts 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, Examples include alkali metal alkoxides such as sodium ethoxide. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as addition of water, organic solvent extraction and concentration, and, if necessary, can be purified by operations such as chromatography and recrystallization.

In addition, the compound in which n is 1 or 2 in the general formula [I] is a carbamoyltriazole represented by the general formula [I'] [wherein R1, R", X and Y do not have the same meanings as above.] It can also be produced by oxidizing a derivative.

Examples of the oxidizing agent used at this time include aromatic peracids such as metachloroperbenzoic acid, aliphatic peracids such as peracetic acid and pertrifluoroacetic acid, and hydrogen peroxide. The reaction is usually carried out in a solvent, and the solvent used varies depending on the type of oxidizing agent. For example, water, acetic acid, acetone, etc. are used for hydrogen peroxide, and halogenated carbonates such as chloroform, methylene chloride, etc. are used for aromatic peracids. Hydrogens, ethers such as diethyl ether and dioxane, and, in the case of aliphatic peracids, the corresponding carboxylic acids are usually used.

The reaction temperature range is usually 0 to 100°C, the reaction time is usually 10 minutes to 24 hours, and the amount of reagent used in the reaction is usually 1 equivalent of carbamoyltriazole derivative CI'). 1 to 5 equivalents, but general formula C
In the production of the product indicated by n=1 in I),
Usually carried out at 0°C to room temperature using 0.9 to 1.2 equivalents of oxidizing agent, n = 2, and in the production of the indicated product,
It is usually carried out at room temperature to 100°C using 2 to 5 equivalents of an oxidizing agent.

After the reaction is completed, water is added and conventional post-treatments such as organic solvent extraction and concentration are performed to obtain the target compound. In addition, operations such as chromatography and recrystallization are performed as necessary.

When producing the compound of the present invention, triazole derivatives represented by the general formula CI), which are starting compounds, where n is 1 or 2 can be prepared by oxidizing those where n is 0 according to the above method. Manufactured.

Furthermore, among the triazole derivatives represented by the general formula (II), those in which n is 0 have the general formula IJ) [wherein, X and Y represent the same meanings as above, W is a halogen atom, H3
Represents O4, No, or ClO4. ] A diazonium salt represented by the general formula CD [where M represents an alkali metal]. ] It can be produced by reacting with the compound shown below.

Further, some triazole derivatives represented by the general formula (1) where n=0 have the general formula [■] [where x' and Y' are the same or different, a hydrogen atom, a halogen atom,
It represents a nitro group or a trifluoromethyl group, and ■ represents a halogen atom. However, cases in which x' and Y' are both hydrogen atoms are excluded. ] The compound shown and 8-mercapto-LH-1゜2.4
-) It can also be produced by reacting with lyazole in the presence of a base.

Examples of the base used include sodium hydroxide,
Examples include potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, and sodium ethoxide.

Further, a catalytic amount of a copper compound or the like may be added when carrying out the reaction.

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 freckles, Japanese knotweed, purslane, chickweed, white radish, Japanese radish, daikon radish, shepherd's purse, shepherd's purse, American hornwort, field pansy, American goldenrod, field pansy, American Broad-leaved weeds such as morning glory, morning glory, European bindweed, Japanese oatweed, white-breasted morning glory, Japanese oat, Japanese oat, corn marigold, etc., barnyard grass, Japanese millet, foxtail grass, black-seed grass, sycamore, Japanese sorghum, oat, oat, Seiban sorghum , The compound of the present invention has a herbicidal effect on weeds of the grass family, such as grasshopper, grasshopper, and cypress, as well as weeds of the cyperaceae family, such as dayflower, and cypressweeds, such as cyperus spp. It does not cause any harmful effects on 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, commonweed, and chickweed, and cypress weeds such as cypress It has a herbicidal effect on weeds of the same family, such as Physcomitrella sinensis and Prunus elegans, and does not cause any problematic phytotoxicity to 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, Kulu main 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, and water.

Surfactants used for emulsification, dispersion, wetting layers, etc. include alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphate salts, etc. Nonionic surfactants such as anionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. .

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 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.

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.

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.
0.2f to 200 f1 preferably 0.5 per are
f to 10 (1'), and emulsions, wetting agents, suspending agents, etc. are usually used in a specified amount of 1 liter to 10 liters per are (if necessary, auxiliary agents such as spreading agents are added). ) It is treated by diluting it with water, and granules etc. are usually treated as they are without any dilution.

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

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

Production Example 1 2.44N of 8-(8-methoxy-5-trifluoromethylphenylthio)-1,2,4-triazole was dissolved in 20+l of pyridine, 1.45 full of diethylcarbamoyl chloride was added, and the mixture was stirred at room temperature for 12 hours. next,
Pyridine was distilled off under reduced pressure, ethyl acetate was added to the residue,
It was washed eight times with 1N hydrochloric acid and then with saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to give 1-(diethylcarbamoyl)-8-(8-methoxy-
5-trifluoromethylphenylthio)-1,2,4-
Triazole 8.40f was obtained.

n, 1.5215 Production Example 2 1-Diethylcarbamoyl-8-(2-methylphenylthio)-1,2,4-)riazole 1.4TI was dissolved in 120 yxl of chloroform, and metachloroperbenzoic acid (content 70%) was dissolved. 1.25f in chloroform 20te
The solution was added dropwise at 0 to 5°C. After stirring at 0 to 5°C for 1 hour, the mixture was washed eight times with a 20% aqueous potassium carbonate solution, and then twice with saturated brine.

After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 1-diethylcarbamoyl-8-(2-methylphenylsulfinyl)-1.2.4-triazole 1.2
I got Of.

nD 1.5688 Production Example 8 1-diethylcarbamoyl-8-(8-chlorophenylthio)-1,2,4-triazole 1.09f was dissolved in 120 yl of chloroform, and metachloroperbenzoic acid (R content 70%) 2, 16 f was added and stirred at room temperature for 12 hours.

It was washed eight times with a 20% aqueous potassium carbonate solution, and then twice with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from a mixed solvent of benzene and hexane to give 1-diethylcarbamoyl-8-(8-chlorophenylsulfonyl)-1,2,4.
-0.98 g of triazole was obtained.

Melting point: 118.0-120.0°C Next, Table 1 shows some of the compounds of the present invention produced according to the above method.

Next, a production example of the triazole derivative (1), which is a raw material compound, will be shown as a reference example.

Reference example 1 8-trifluoromethylaniline 14.5Of water 15
0 ml and 20.4 s/concentrated hydrochloric acid were added. 0~5℃
Add 6.90f of sodium nitrite to 20g of water while stirring with
The solution dissolved in / was added, and stirring was continued for an additional 20 minutes.

After neutralization with 26% aqueous sodium hydroxide solution, potassium hydroxide 7,92F and 8-mercapto-IH-1,2,4-) lyazole 12.12% in methanol 50 resistant.
A solution containing F was added dropwise. Stirred at 0-5°C for 2 hours and then at room temperature for 1 hour.

The reaction solution was saturated with sodium chloride and extracted with ethyl acetate.

The ethyl acetate layer was washed twice with saturated brine and dried over anhydrous magnesium sulfate.

The residue obtained by distilling off the solvent under reduced pressure was treated with column chromatography to obtain 15.80f of 8-(8-)lifluoromethylphenylthio)-1,2,4-triazole.

Melting point 71.0-72.5°C Reference example 2 2.00f of sodium hydride (content 60%) was dissolved in N,N-
Suspend in 100 ml of dimethylformamide and add 8-mercapto-IH-1,2°4-triazole 5.05F.
was added and stirred at room temperature for 80 minutes. 14.65F of 8.5-bis(trifluoromethyl)bromobenzene and a catalytic amount of cuprous chloride were added, and the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After cooling, the solvent was distilled off under reduced pressure, ethyl acetate was added, and the mixture was washed twice with saturated brine. The crystals obtained by drying over anhydrous magnesium sulfate and distilling off the solvent under reduced pressure were mixed with benzene,
After washing with a hexane mixed solvent and drying under reduced pressure, 8-(
8,5-bis(trifluoromethyl)phenylthio)-
1,2,4-) Riazole 6.00f was obtained.

Melting point: 110.5-111.0°C Triazole derivative (
Some of 1) are shown in Table 2.

Table 2 shows formulation examples. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 50 parts of the compound of the present invention, 8 parts of calcium lignosulfonate, 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 10 parts each of the compounds (1) to (62) 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 compound of the present invention (88), 1 part of synthetic hydrous silicon oxide,
2 parts calcium lignin sulfonate, 80 parts bentonite
1 part and 65 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, and then granulated and dried to obtain granules.

Formulation Example 4 25 parts of the compound of the present invention (20), 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.

Next, test examples will demonstrate that the compounds of the present invention are useful as active ingredients in herbicides27). 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 8.

Table 8 - Evaluation of herbicidal efficacy and phytotoxicity is based on whether the germination and growth conditions of the test plants (weeds and crops) at the time of the survey are completely or almost different from those of untreated plants.
If the test plant is completely dead or its budding or growth is completely suppressed, it is set as "101," and θ
Classified into 11 stages of ~100.1.2.8.4.5.6
．． 7.8.9.10.

Test Example 1 Upland Soil Surface Treatment Test A cylindrical plastic pot with a diameter of 103 mm and a depth of 10 α was filled with upland soil, sown with barnyard grass, and covered 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 4.

Table 4 Test Example 2 Upland Stem and Leaf Treatment Test A cylindrical plastic pot with a diameter of 103 mm and a depth of 11'W was filled with upland soil, and barnyard grass was 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 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 5 Test Example 8 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8 cIII and a depth of 121 m was filled with paddy soil, and seeds of Japanese millet were mixed in at a depth of 1 to 23 m. After being flooded into paddy fields, they were grown in a greenhouse. Formulation Example 2 after 6 days (in the early stage of the outbreak of Japanese millet)
The test compound was made into an emulsion according to the method described above, and a predetermined amount of the emulsion was diluted with 5 milliliters of water and 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 6.

Table 6 Test Example 4 Paddy field flooding treatment test 115000a Wagner pots were filled with paddy soil and treated with Japanese millet and broad-leaved weeds (Azaena, Kikashigusa, Chickweed)
, the seeds of firefly were mixed in at a depth of 1 to 21. 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 IOE liter of water and applied to the water surface to a water depth of 4c11. 20 days after treatment
The plants were grown in a greenhouse for one day and their herbicidal efficacy and phytotoxicity were investigated.

The results are shown in Table 7. Note that for two days from the day after the treatment, water leaked in an amount equivalent to a water depth of 8 cIM per day.

Table 7 <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 rice fields, and 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 rice fields. Since it exhibits excellent selectivity for herbicides, it can be used in a variety of applications as an active ingredient in herbicides.

(89 completed)

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 and R^2 are the same or different, and are lower alkyl group, lower alkenyl group, or R^1 Represents a lower alkylene group forming a ring with R^2, X and Y are the same or different, hydrogen atom, halogen atom, lower alkyl group, lower alkoxy group, lower alkoxycarbonyl group, nitro group, amino group, acylamino group or represents a trifluoromethyl group, n is 0, 1
or represents an integer of 2. However, those in which R^1 and R^2 are both methyl groups are excluded. ] A carbamoyltriazole derivative represented by (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X and Y are the same or different, hydrogen atom,
It represents a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, a nitro group, an amino group, an acylamino group or a trifluoromethyl group, and n represents 0, 1 or 2. ] There are triazole derivatives represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc. 2
represents a lower alkylene group forming a ring, and Z represents a halogen atom. However, those in which R^1 and R^2 are both methyl groups are excluded. ] A general formula characterized by reacting with a carbamoyl halide represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2, X, Y and n have the same meanings as above. represent. ] A method for producing a carbamoyltriazole derivative shown in the following. (8) General formula ▲ Numerical formula, chemical formula, table, 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 a lower alkylene group forming a ring with Represents a methyl group. However, those in which R^1 and R^2 are both methyl groups are excluded. ] A general formula characterized by oxidizing a carbamoyltriazole derivative represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2, X and Y represent the same meanings as above, n represents 1 or 2. ] A method for producing a carbamoyltriazole derivative. (4) General formula ▲ Numerical formula, chemical formula, table, 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 a lower alkylene group forming a ring with It represents a methyl group, and n represents an integer of 0, 1 or 2. However, those in which R^1 and R^2 are both methyl groups are excluded. ] A herbicide characterized by containing a carbamoyltriazole derivative represented by the following as an active ingredient.