JPS63208564A - Organic sulfur compound, its production and herbicide containing said compound as active - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is oxoalkyl, oxocycloalkyl, alkoxycarbonyl, benzoyl-lower alkyl or cyano-lower alkyl; X is H or Cl; n is 1 or 2). EXAMPLE:2-(3-Oxo)butyl 2,6-dichlorobenzyl sulfoxide. USE:A herbicide having excellent herbicidal effect and exhibiting excellent selectivity between crops and weeds. It is useful especially against broad-leaved weeds in plowed field, e.g. wild buckwheat, common purslane, Indian mallow, etc., and is free from phytotoxicity to crops such as corn, wheat, cotton, beet, etc. PREPARATION:The compound of formula I can be produced by oxidizing a benzyl sulfide compound of formula II with a oxidizing agent (e.g. m- chloroperbenzoic acid) in a solvent (e.g. chloroform) at 0-150 deg.C for 0.5-16hr.

Description

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

<Prior Art> Until now, JP-A-51-46106 has described the use of 8-(2°6-dichlorobenzyl)thiol carbamate and the like as an active ingredient 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 made various studies and found that the organic sulfur compound represented by the following general formula [11] is an excellent compound with few drawbacks as described above. We have discovered that this is a compound that has 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 [I] [wherein R represents an oxoalkyl group, oxocycloalkyl group, alkoxycarbonyl group, benzoyl lower alkyl group or cyano lower alkyl group, and X represents a hydrogen atom or a chlorine atom] , n represents an integer of 1 or 2. ] The present invention relates to an organic sulfur compound represented by (hereinafter referred to as the compound of the present invention), a method for producing the compound, and a herbicide containing the compound as an active ingredient.

The compound of the present invention has the general formula [wherein R and X represent the same meanings as above]. ] It can be produced by oxidizing the benzyl sulfide compound shown below.

This reaction usually uses peracids such as m-chloroperbenzoic acid and peracetic acid, hydrogen peroxide, oxygen, oxidizing agents such as chromic acid, potassium permanganate, and sodium metaperiodate, and the reaction temperature is 0 to 0. Generally, the temperature is 150°C and the reaction time is in the range of 0.5 to 16 hours.

The amount of reagents used in the reaction is the benzyl sulfide compound Q.
The amount of the oxidizing agent is usually 1 to 2.5 equivalents based on the IQI. Examples of the solvent used in the reaction include hexane,
Aliphatic hydrocarbons such as heptane, ligroin, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene, diethyl ether, Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, fatty acids such as formic acid, acetic acid, oleic acid, methanol, ethyl alcohol, isopropanol, t -Alcohols such as butanol, octatool, cyclohexanol, methyl cellosolve, diethylene glycol, glycerin, water, etc., or mixtures thereof can be mentioned. After completion of the reaction, the reaction solution is subjected to usual post-treatments such as extraction with all solvents and concentration, and if necessary, purified by operations such as chromatography, distillation, and recrystallization to obtain the desired compound of the present invention. be able to.

When producing the compound of the present invention, a benzyl sulfide compound represented by the formula, which is a raw material compound, is prepared using the general formula [wherein, X represents the same meaning as above]. A thiol compound represented by the general formula -YIXvl [wherein R represents the same meaning as above, and Y represents a halogen atom. ] It can be produced by reacting with a halogen compound shown in (Production method A).

In addition, the benzyl sulfide compound represented by the formula ', which is a raw material compound, is represented by the general formula (2) [wherein, X and Y represent the same meanings as above. ] A halogen compound represented by the general formula (I)-8H [wherein R represents the same meaning as above]. ] (Production method B).

For both production methods A and B, the reaction is usually carried out without a solvent or in a solvent in the presence of a dehydrohalogenating agent, with a standard reaction temperature range of 0 to 150°C and a reaction time of 0.5 to 24 hours. be. As a reaction solvent, hexane, heptane,
Aliphatic hydrocarbons such as ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene, diethyl ether and diisopropyl ether , dioxane,
Ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone, methanol, ethanol, isopropanol, t-butanol, octatool, cyclohexanol, methyl cellosolve, diethylene glycol,
Alcohols such as glycerin, esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate, nitrates such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N,N-diethyl Examples include tertiary amines such as aniline, tributylamine and N-methylmorpholine, acid amides such as formamide, N,N-dimethylformamide and acetamide, 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 hydroxide, sodium methoxide, and sodium hydroxide. Examples include alkali metal alkoxides such as ethoxides.

After the reaction is complete, the reaction solution is subjected to conventional treatments such as organic solvent extraction and concentration, and if necessary, chromatography, distillation,
By purifying by operations such as recrystallization, the desired thiol compound represented by the general formula can be obtained.

The compound of the present invention has good herbicidal efficacy and
Shows excellent selectivity among weeds. That is, the compound of the present invention can be used to eliminate various weeds that are problematic in soil treatment in fields, such as buckwheat, snail knotweed, purslane, chickweed,
The compound of the present invention has a herbicidal effect on broad-leaved weeds such as whiteweed, Japanese radish, Japanese radish, Japanese radish, shepherd's purse, American hornwort, Ebisu grass, Japanese radish, American morning glory, Common morning glory, Japanese Physalis, and Japanese fir tree. It does not cause any harmful chemical damage to major crops such as cotton, sugar beet, etc.

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 1 to 904%, preferably 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, walnut powder, urea, ammonium sulfate, and synthetic hydrated silicon. 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 attack, 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 ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. .

As formulation aids, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, C! M
Examples include O (carboxymethyl cellulose) and PAP (isopropyl acid phosphate).

The compound of the present invention is usually formulated and treated in soil before the emergence of weeds. Soil treatment includes soil surface treatment, soil mixing treatment, etc.

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

The compound of the present invention can be used as an active ingredient of a herbicide for paddy fields, fields, orchards, pastures, lawns, forests, or non-agricultural lands.

When the compound of the present invention is used as an active ingredient of a herbicide, the treatment kk depends on weather conditions, formulation form, treatment time, method,
Although it varies depending on the location, target weeds, target crops, etc., it is usually 12 to 200 f per are, preferably 22 to 200 f.
Emulsions, wettable powders, suspensions, etc. are usually processed by diluting the specified mackerel with 1 liter to 10 liters of water per 1 area, while granules, etc. are usually processed as they are without any dilution. Process.

<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 (Production of compound (1) of the present invention) 2-'(8-
2t of oxo)butyl 2,6-dichlorobenzyl sulfide was dissolved in 1GOrH of chloroform, and 2.9f of m-chloroperbenzoic acid (purity near 0%) was added little by little under water cooling. After stirring at room temperature for 6 hours, the reaction solution was washed successively with water, a saturated aqueous sodium bicarbonate solution, and water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give 2= (
8-oxo)butyl 2,6-dichlorobenzyl sulfoxide 2.1f was obtained.

Production Example 2 (Production of Compound (2) of the Present Invention) 2- (8-oxo)butyl 2.6-dichlorobenzyl sulfone 2.22 was obtained.

Table 1 shows some of the compounds of the present invention produced according to the above production examples.

Table 1 Next, an example of manufacturing a benzyl sulfide compound, which is a raw material compound, is shown as a reference example.

Reference example 1 2.6-cyclobenzylmerkabutane 1.9 furnace 50
Dissolved in 1 nJ of tetrahydrofuran and diluted to 28% at room temperature.
Sodium methoxide methanol solution2. O2 was added. 1.1 f of 8-chloro-2-butanone was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 6 hours. The reaction solution was poured into 200 mJ of water and extracted with ether. The ether layer was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and 2-(
2.62 of 3-oxo)butyl 2,6-dichlorobenzyl sulfide was obtained.

Reference Example 2 Methyl thioglycolate 1.1F was dissolved in 50 mJ of tetrahydrofuran, and the solution was heated to 28% at room temperature. ! Monosodium methoxide methanol solution2. Added Of. Reaction solution 6ζ
20 mj of a solution of 2.62 2.6-cyclobenzyl bromide in tetrahydrofuran was added dropwise at room temperature. 6 at room temperature
After stirring for an hour, the reaction solution was poured into 200 mj of water and extracted with ether. The ether layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain methoxycarbonylmethyl 2,6-dichlorobenzyl sulfide 26.
I got 8f.

Table 2 shows some benzyl sulfide compound circles produced according to the above reference example.

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

Formulation Example 1 50 parts each of the compounds (1) to (12) of the present invention, 8 parts of calcium lignosulfonate, 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 (12) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 7 parts of cyclohexanone
Mix 0 parts thoroughly to obtain an emulsion.

Formulation Example 8 2 parts of the compound of the present invention (9), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite, and 65 parts of kaolin clay were thoroughly ground and mixed, and water was added and kneaded thoroughly. Granulate and dry to obtain granules.

Formulation Example 4 25 parts of the compound of the present invention (12), 3 parts of polyoxyethylene sorbitan monooleate, ", C" 08917
5. Mix 69 parts of water and wet grind until the particle size is 5 microns 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 1, and the compounds used for comparison are indicated by the compound symbols in Table 3.

Table 8 CA=Chemical Abstract
bs'tracts) Also, the evaluation of herbicidal efficacy and phytotoxicity was carried out using G (test plants (weeds and crops) at the time of the survey, where there was no or almost no difference in the budding and growth conditions compared to untreated plants). 0.1.2.8.4. The test plant is classified into 1'1 stage from 0 to 10, with "1O" indicating that the test plant is completely dead or that its sprouting or growth is completely suppressed.0.1.2.8.4. 5.6.7.8.9.10.

Test Example 1 Upland Soil Surface Treatment Test A cylindrical plastic pot with a diameter of 10 holes and a depth of 10 holes was filled with upland soil, and Fluva morning glory and Ichibi were sown in the dishes 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.

Calculation and q friend test example 2 Upland soil treatment test Pack field soil into a vat with an area of 88 x 28 d and a depth of 113 d, and sow cotton, sugar beet, corn, wheat, Japanese morning glory, Japanese fir tree, Japanese velvet, Ebisugusa, and Japanese wildflower with a concentration of 1 to 2 crR. Covered with soil to a thickness. 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 5.

Table 5 <Effects of the Invention> The compounds of the present invention have similar herbicidal efficacy against various weeds that are a problem in soil layer treatment of dry land, and exhibit excellent selectivity between major crops and weeds. Therefore, it can be used for various purposes as an active ingredient in herbicides.

Claims (3)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents an oxoalkyl group, oxocycloalkyl group, alkoxycarbonyl group, benzoyl lower alkyl group or cyano lower alkyl group, and X is a hydrogen atom. or represents a chlorine atom, and n represents an integer of 1 or 2. ] An organic sulfur compound represented by (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents an oxoalkyl group, oxocycloalkyl group, alkoxycarbonyl group, benzoyl lower alkyl group, or cyano lower alkyl group, and X is a hydrogen atom. Or represents a chlorine atom. ] A general formula characterized by oxidizing a benzyl sulfide compound represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R and X represent the same meanings as above, and n is an integer of 1 or 2. represent. ] A method for producing an organic sulfur compound shown in (3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents an oxoalkyl group, oxocycloalkyl group, alkoxycarbonyl group, benzoyl lower alkyl group, or cyano lower alkyl group, and X is a hydrogen atom. or represents a chlorine atom, and n represents 1 or 2. ] A herbicide characterized by containing an organic sulfur compound represented by the following as an active ingredient.