JPS6081195A - 1,2,3,4-tetrahydro-2-quinoxalinone derivative, production thereof and herbicide containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R1 is H or lower alkyl; R2 is lower alkyl; R3 is halogen or lower alkyl; X is O or S). EXAMPLE:4-( Diethoxyphosphinodithioylacetyl )-1-methyl-6-chloro-1, 2, 3, 4-tetrahydro-2-quinoxalinone. USE:A herbicide without exhibiting phytotoxicity to main crops such as corn and rice plants. PREPARATION:A 4-(halogenoacetyl)-1,2,3,4-tetrahydro-2-quinoxalinone derivative of formula II (A is halogen), e.g. 1-methyl-4-(monochloroacetyl)-6-chloro-1,2,3,4- tetrahydro-2-quinoxalinone, is reacted with a (di)thiophosphate of formula III (Y is alkali metal or ammonium radical), e.g. ammonium diethyl dithiophosphate, preferably in a solvent at 10-100 deg.C for 0.5-25hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R represents a hydrogen atom or a lower alkyl group, R2 represents a lower alkyl group, R3 represents a halogen atom or a lower alkyl group, and X represents a Represents an oxygen or sulfur atom. ] The present invention relates to a 1,2,3,4-tetrahydro-2-quinoxaline derivative (hereinafter referred to as the compound of the present invention) shown in the following, a method for producing the same, and a herbicide containing the same as an active ingredient.

The compounds of the present invention can be used to treat various weeds that are problematic in foliar and soil treatments in upland fields, such as buckwheat, purslane, chickweed, whiteweed, Japanese radish, Japanese radish, wild mustard, American hornwort, Japanese commonweed, American goldfish, and American goldenrod. Broad-leafed weeds such as morning glory, morning glory, Convolvulus, Japanese morning glory, Japanese Physalis, Japanese chamomile, Japanese barnyard grass, Japanese millet, Japanese foxtail grass, Japanese grasshopper, Sparrow fern,
Sparrow gnome, Enhaku, Japanese oat, Seiban sorghum, Shiba wheat, Umanochahiki, Gyōgishiba,
It has a herbicidal effect on weeds of the grass family, such as grass weeds, weeds of the family Asiatic family, such as dayflower, and weeds of the family Cyperaceae, such as cyperus spp. It does not cause any harmful chemical damage to major crops.

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, and cyperus, and cyperaceae such as cyperus cyperus, bulrush, cyperus japonica, and cyperus cyperus. It has a herbicidal effect on paddy field weeds such as weeds and rice fields, and does not cause any harmful effects on rice.

The compound of the present invention has the general formula [wherein R□ and R6 represent the same meanings as above, and A
represents a halogen atom. 4-(halogenoacetyl)-1,2゜3.4-tetrahydro-2-quinoxaline derivative represented by the general formula [wherein R2 is a lower alkyl group , X represents an oxygen atom or a sulfur atom, and Y represents an alkali metal atom or an ammonium radical. ] in a solvent with a thio or dithiophosphate represented by 10
It can be produced by reacting at a temperature of 100°C to 100°C for 0.5 to 25 hours.

Solvents include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated carbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene. Water X, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran,
Ethers such as diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, fatty acids such as formic acid, acetic acid, Olay 7e, methanol, ethanol, isopropanol, t-butanol, octatool, cyclo Alcohols such as hexanol, methyl cellosolve, diethylene glycol, glycerin, ethyl formate, ethyl acetate, butylacetate/L/.

Esters such as diethyl carbonate, nitrites such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, acid amides such as formamide, N,N-dimethylformamide, and acetamide, dimethyl sulfoxide, and sulporan. There are sulfur compounds such as water, etc., or mixtures thereof.

After the reaction is completed, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, chromatography,
Purify by distillation, recrystallization, etc.

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

Production Example 1 (Production of Compound 4 of the Present Invention) 0.32 of 1-methyl-4-(monochloroacetyl)-
6-chloro-1,2,3,4-tetrahydro-2-quinoxaline was dissolved in 504 acetone, and 0.2
59 diethyldithiophosphate ammonium salt was added at once and stirred at room temperature for 12 hours. The reaction solution was poured into 1001 nl of toluene, washed with water, dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure.
0.539 yellowish brown crystals were obtained. This was carried out using column chromatography packed with silica gel (eluent: I.luene/
Purified by ethyl acetate), melting point 114 at 0.43 F.
．． 4-(diei-xyphosphinodithiolacetyl)-1-methyl-6-chloro-1°2.3.4- at 2°C
Yellow-white needle-shaped crystals of tetrahydro-2-cynokine 1 were obtained. (Yield: 93 cm) Some of the compounds of the present invention that can be produced by such a production method are shown in Table 1.

Table 1 When producing the compounds of the present invention, the raw material compound 4-(
halogenacetyl)-1,2,3゜4-tetrahydro-
The 2-quinoxaline derivative (II) is 1 or 2 represented by the general formula [wherein 1 represents a hydrogen atom or a lower alkyl group, and R3 represents a halogen atom or a lower alkyl group]. , 3.4-tetrahydro-2-quinoxalinone derivative and the general formula % formula %) [In the formula, A represents a halogen atom], and Z represents a chlorine atom or a bromine atom. ] It can be produced by reacting a monohaloacetyl halide represented by the following in a solvent in the presence of an organic base at 0° C. to 50° C. for 2 hours to 6 hours.

The amount of reagents used in this reaction is 1,2,3°4-teI
・Monohaloacetyl halide (V) is 1 to 1.5 per equivalent of Rahydro-2-quinoxaline derivative [■]
equivalent, the organic base is 1 to 1.5 equivalents.

Solvents include chloroform, dichloromethane, dichloroethane, and other non-rogenated hydrocarbons, and benzene, toluene, xylene, and the like.

After the reaction is complete, wash the reaction solution with hydrochloric acid, sodium bicarbonate, water, etc.
Conventional post-treatments such as drying and concentration of the organic layer are performed, and if necessary, information is clarified by chromatography, distillation, recrystallization, etc.

Next, this 4-(halogenoacetyl)-1,2゜3.4-
An example of producing a tetrahydro-2-quinoxaline derivative [■] is shown below.

Production Example 2 1.22F 1-methyl-6-chloro-1,2°3.4
-Tetrahydro-2-quinoxaline was dissolved in 50 ml of chloroform, and 1.051' of monochloroacetyl chloride was added at once. Next, 0.949 g of triethylamine was added dropwise while stirring at 0 to 50°C, and after the dropwise addition was completed, the mixture was stirred at room temperature for 3 hours. The reaction solution was washed with 1N hydrochloric acid, saturated aqueous sodium bicarbonate, and water, and dried over anhydrous magnesium sulfate.

The organic layer was condensed under reduced pressure by 4°3 to obtain 2°2 yellowish brown crystals. This was purified by column chromatography packed with silica gel (eluent: toluene/ethyl acetate).
1-Methyl-4-monochloroacetyl-6-chloro-1,2,3° at 112° C. When the compound of the present invention is used as an active ingredient of a herbicide, a solid carrier is commonly used. , mixed with 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 0.1 to 90%, preferably 0.2 to 80%.

Solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calanite, 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, soybean oil, cottonseed oil, etc. vegetable oil, dimethyl sulfoxide, acetonitrile, water, etc.

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

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

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Parts indicate parts by weight.

Formulation Example 1 20.50 parts of the compound of the present invention, 3 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 14.2 parts of the compound of the present invention, 14s of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene, and 48 parts of isophorone.
Mix well to obtain an emulsion.

Formulation Example 3 4.2 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 30 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 11.25 parts of the compound of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 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., 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.

By mixing it with other herbicides, we can expect to increase its 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 a house grass 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, its application varies depending on weather conditions, formulation form, application time, moth method, location, target weeds, target crops, etc., but usually 1.
0.5P~2002 per are, preferably 17~
100y, and emulsions, wetting agents, suspending agents, etc. are usually used in a specified amount of 1 liter to 10 liters per 1 area (
If necessary, the preparation is diluted with water (to which an adjuvant such as a spreading agent is added), and granules and the like are usually processed as they are without any dilution.

In addition to the above-mentioned surfactants, the spreading agent includes polyoxyethylene W fat rl! (ester), lignin sulfonate, abietate, dinaphthylmethane disulfonate, paraffin, etc.

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.

Table 2 In addition, herbicidal efficacy is determined by visually observing the degree of budding and growth inhibition of the test plants during the survey, and ``0'' indicates that there is no or almost no difference from the case where no compound is used. The plant is rated on a scale of 0 to 5, with a score of 5 indicating that the plant has died or its growth has been completely inhibited.
．． 3.4.5.

Test Example 1 Upland Soil IJIJ Mixing Treatment Test Upland soil was packed into a cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm, and barnyard grass, oats, blackberry grass, and wild foxtail were sown.
T. 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 soil surface was treated with a small sprayer. Mixed. 20 days after treatment
The plants were grown in a greenhouse for 1 day and their herbicidal efficacy was measured.

The results are shown in Table 3.

Table 3 Test Example 2 Upland Stem and Leaves Treatment Test A cylindrical plastic pot with a diameter of 100 mm and a depth of 10 on was filled with upland soil, and millet, oat, 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 specified salt was added to 1
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 4.

Table 4 Test Example 3 Paddy field flooding treatment/test A cylindrical plastic pot with a diameter of 8 cm and a depth of 12 cIII is filled with paddy soil, and 1 to 2 seeds of Japanese millet, broad-leaved weeds (Azaena, Kikashigusa, Chickweed), and firefly are added to the pot.
It was mixed to a depth of cII+. After flooding the rice field to create a paddy field, two-leaf stage rice was transplanted and grown in a greenhouse. After 6 days (early stage of each weed's emergence), make the test compound into an emulsion according to Formulation Example 2, dilute the specified salt with 5 milliliters of water,
Treated on the water surface. After treatment, the plants were grown in a greenhouse for 20 E1.
The herbicidal efficacy was investigated. The results are shown in Table 5.

Table 5 Test Example 4 Upland soil treatment test area 1 area 33 x 23 cm2, depth 11G vat was filled with upland soil, and corn, soybean, cotton, sorghum, Seiban sorghum, foxtail grass, golden millet, and green millet were sown. Covered with soil to a thickness of ~20 mm. The test compound was made into an emulsion according to Formulation Example 2, and the predetermined amount was added per 1 are! It was diluted with 0 liters of water 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 6.

Trial example 5 Paddy field flooding treatment test 1/5000a Fill a Wagnerbot with paddy soil, and add 1 to 2 seeds of Japanese millet, broad-leaved weeds (Azeena, Kikashigusa, Chickweed), bulrush seeds, and wintering petals
Mixed to a depth of cm. After being flooded and turned into a paddy field,
Rice plants at the three-leaf stage were transplanted and grown in a greenhouse. After 5 days (early stage of germination of Japanese millet), the test compound was made into an emulsion according to Lung Lateral 2, and the prescribed amount was diluted with 10 milliliters of water and treated with water (mouth 1, the water depth was 4 cI + 1). .

After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated.

The results are shown in Table 17. In addition, for two days from the day after the treatment, star Ω water was applied at a water depth of 3 on per day.

C11J7 Table Test Example 6 Field soil treatment trial area 33 x 230112. The seeds were sown in an 11-deep vat and covered with soil to a thickness of 1 to 2 cm. The 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. 28 days after processing in the greenhouse Procedural amendment (voluntary) March 26, 1939 1, Indication of the case 1981 Mochi J'"Publication No. 1905451'; 2 Title of the invention 1, 2.8.4- Te) Rahydro-2-quinoxaline derivative, its simple manufacturing method, and herbicide 3 containing it as an active ingredient Relationship with the proposed case to be amended Patent applicant address Osaka 111!, I!-ku Kitahama 5-J-[115 Address name (209) Sumitomo Chemical Industries Co., Ltd. Representative Sat
Takeshi 4, Agent Address: 5-5 Kitahama 5-1:15, Kozuka-ku, Osaka, Detailed Description of the Invention in the Specification Subject to Amendment 5 6, Contents of the Amendment (1) Table 1, Page 10 of the Specification Compound number 19 2 in
Correct "〃" to J n-0311, J ni.

(2) Correct "〃" to 1-c2n, 1 for 1L2 of the same compound number 2o.

Above procedure 1 city IE >5. (Spontaneous) February 73, 1939 1, Indication of the incident 1981 Patent lx', i! No. 190545 2, Title of the invention 1.2,3.4-tetrahydro-2-quinoxaline derivative, its production method and herbicide containing it as an active ingredient 3
, Relationship with the case of the person making the amendment
9) Sumitomo Chemical Co., Ltd. Representative: Takeshi Hijikata 4, Agent address: Kita t!, Kozuka-ku, Osaka! (5-chome, 15-5, subject of correction: 11, 11, Tsukasa 6, detailed explanation of the invention of Akira 111J, page 7, lines 13 to 14, "Hydroxic acid , fatty acid deposits such as acetic acid and oleic acid," are removed.

(2) Correct “acetamide” in the 2nd and 3rd lines of the 81st subsection of the Meiji 91 to read [N, NF” methylacetamide.

(8) Mingsang 1st Book, page 8, lines 12 to 14 rl-
Methyl-4-(monochloroacetyl)-6-chloro-
1,2,8,4-tetrahydro-2-quinoxaline
"l-methyl-4-chloroacetyl-6-chloro-1
, 2゜3.4-tetrahydro-2-quinoxaline.''

(4) In Table 1 on pages 10 and 11 of the specification, the "compound number" and the adjacent rRJ, which is written as "R3", are corrected as "R3".
do.

(5) r CzHa J in the "Compound No. 8" row of Table 1 on page 10 of the specification is corrected to r C2[(6J).

(6) Specification No. 13 @ between lines 5 and 6 [Organic bases include pyridine, triethylamine, N,N-diethylaniline, tributylamine, etc. ] Insert.

(7) [l-Methyl-4-monochloroacetyl-6-chloro-1,2,3
, 4-tetrahydro-2-quinoxaline] to ``l-methyl-4-chloroacetyl-6-chloro-1,2,3,
4-Tetrahydro-2-quinoxaline".

(8) Correct the formula section in Table 2 Chemistry 41 of Specification No. 19tT.

that's all

Claims (3)

[Claims] (1) General formula [In the formula, k represents a hydrogen atom or a lower alkyl group, R2 represents a lower alkyl group, R and s represent a halogen atom or a lower alkyl group, and X represents an oxygen atom or a sulfur atom. represents. ] A 1,2,3,4-tetrahydro-2-quinoxaline derivative represented by the following. (2) General formula [wherein R represents a hydrogen atom or a lower alkyl group, R3 represents a halogen atom or a lower alkyl group, and A represents a halogen atom. ] 4-(halogenoacetyl)-3゜2.3.4 represented by
-Tetrahydro-2-quinoxaline derivatives and the general formula (%) [In the formula, R2 represents a lower alkyl group, X represents an oxygen atom or a sulfur atom, and Y represents an alkali metal atom or an ammonium group. [In the formula, R□, R2, R3 and x have the same meanings as above. ] A method for producing a 1,2.3.4-tetrahydro-2-quinoxaline derivative represented by the following. (3) General formula [wherein R□ represents a hydrogen atom or a lower alkyl group, 1 (2 represents a lower alkyl group, R3 represents a halogen atom or a lower alkyl group, and X represents an oxygen atom or a sulfur atom] A herbicide comprising a 1,2,3,4-tetrahydro-2-quinoxaline derivative represented by the following as an active ingredient.