JPS59155358A - 4,5,6,7-tetrahydro-2h-isoindole-1,3-dione derivative, its preparation and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:4,5,6,7-Tetrahydro-2H-isoindole-1,3-dione derivative of formula I (R1 and R2 are H or methyl; R3 is lower alkyl). EXAMPLE:2-[4-Chloro-2-fluoro-5-(2-ethoxycarbonylvinylene)phenyl]-4,5,6 ,7-tetrahydro-2H-isoindole-1,3-dione. USE:A herbicide exhibiting little phytotoxicity to rice plant. PREPARATION:The objective compound of formula I can be prepared by reacting the aniline derivative of formula II with 3,4,5,6-tetrahydrophthalic anhydride in a solvent at 80 deg.C- the boiling point of the solvent for 1-24hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R1 and R2 are the same or different and represent a hydrogen atom or a methyl group, and phantom represents a lower alkyl group. ] 4,5,6,7-tetrahydro-2H-isoindole-1,3-dione derivative (hereinafter referred to as the compound of the present invention) shown by the formula (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. It is.

Certain tetrahydro-2H-isoindole-1,3
-dione derivatives, for example 2-(4-chlorophenyl)
-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione, 2-(2-fluoro-4-chloro-5-carboxyphenyl)-4,5,6,7-tetrahydro-2H - Isoindole-1,3-dione is used as an active ingredient in herbicides, respectively.
It is described in 8-11940 and JP-A-57-112871.

However, these compounds cannot always be said to be sufficient as active ingredients for herbicides.

The compounds of the present invention can be used to treat various weeds that are problematic in foliage and soil treatments in fields, such as freckle, snail knotweed, purslane, whiteweed, blueberry, American blackberry, yellowweed, common grass, common grass, common grass, field grass, etc. Pansies, Yaemugura, American morning glories, Maruba morning glories, Convolvulus,
Broad-leafed weeds such as Prunus japonicus, Hotokenoza, Prunus japonicus, Prunus japonicum, Prunus fulva, Prunus elegans, Onamo epsilon, sunflower, Prunus japonicus, corn marigold, grass family weeds such as barnyard grass, Japanese millet, foxtail grass, blackberry, etc., and weeds of the Asiatic family such as dayflower, Some of the compounds of the present invention have a herbicidal effect against weeds of the family Cyperaceae, such as Cyperus japonica, and do not cause any problematic phytotoxicity to major crops such as corn, wheat, rice, and diver.

In addition, the compound of the present invention can be applied to various weeds that are problematic in the flooding treatment of rice fields, such as grass weeds such as Japanese millet grass,
It has a herbicidal effect on broad-leaved weeds such as azalea, Japanese chickweed, and Japanese chickweed, Cyperaceae weeds such as Japanese cypress, Japanese cypress, Japanese cypress, and paddy field weeds such as Japanese cypress and Japanese chickweed. Does not show drug damage.

The compound of the present invention has the general formula: [wherein R1, R2 and R8 have the same meanings as above. ] The aniline derivative represented by and 8.4,5.6-titrahydrophthalic anhydride in a solvent at 80°C to the boiling point of the solvent,
It can be produced by reacting for 1 to 24 hours.

The amount of the reagent used in the reaction is 1.0 to 1.05 equivalents of 8,4,5.6-titrahydrophthalic anhydride per equivalent of aniline derivative [■].

Solvents include aliphatic hydrocarbons such as hexane, heptane, and ligroin; aromatic hydrocarbons such as benzene, tonolenine, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene; 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, fatty acids such as formic acid, acetic acid, and oleic acid, retanol, isopropanol, [-butanol,
Alcohols such as octatool, cyclohexanol, methyl cellosolve, diethylene gelcol, glycerin, esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate, nitrations such as nitroethane and nitrobenzene, acetonitrile, isobutyronitrile, etc. nitriles, tertiary amines such as pyridine, triethylamine, N,N-jethylaniline, tributylamine, N-methylmorpholine, formamide, N.

Examples include acid amides such as N-dimethylformamide and acetamide, sulfur compounds such as dimethyl sulfoxide and sulporan, water, and mixtures thereof.

After the reaction is completed, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, distillation, recrystallization, etc.

Or the general formula % formula % [wherein R1 and R2 represent the same meanings as above]. ] A carboxylic acid represented by the general formula % formula % [ [wherein auxiliary represents the same meaning as above. It can be produced by reacting the alcohol represented by the formula (IV') with a catalytic amount of a deoxidizing agent in the presence or absence of a solvent at the boiling point of the solvent or alcohol (IV').

The amount of alcohol ['l] to be subjected to this reaction is 1.0 to large excess equivalent relative to 1 equivalent of carboxylic acid [■],
Examples of the solvent include aromatic hydrocarbons such as toluene and benzene, and examples of the deoxidizing agent include concentrated sulfuric acid, alkylsulfonic acid, and arylsulfonic acid.

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

Production Example 1 (Production of Compound 1 of the Invention) 3-amino-6-chloro-4-fluoro-cinnamate ethyl ester 0.24 f, 3,4°5.6-titrahydrophthalic anhydride 0.16 f was heated to reflux with 5TrLt acetic acid for 1.5 hours.

After cooling, water and toluene were added and extracted with toluene. The toluene layer was washed with saturated sodium bicarbonate solution, dried, and concentrated. The residue was crystallized from methanol, recrystallized from ethanol,
2-[4-chloro-2-fluoro-5-(2-ethoxycarbonylvinylene)phenyl]-4,5,6,7-tetrahydro-2H-isoindole-1,8-dione 0
．． 15! I got it.

m-p・129-130°C Production Example 2 (Production of Compound 3 of the Invention) 2-[4-chloro-2-fluoro-5-(2-carboxy-1-methylvinylene)phenyl]-4.5,6 .7
-Titrahydro 2H-isoindole-1,8-dione 11, methanol 20ml. The mixture was heated under reflux for 3 hours with several drops of concentrated sulfuric acid. Methanol was distilled off under reduced pressure, and water was added to the residue.
Toluene was added and extracted. The toluene layer was washed with water and saturated sodium bicarbonate solution, dried and concentrated, and the residue was purified using a silica gel column to give 2-[4-chloro-2-fluoro-5-(2-
methoxycarbonyl-1-methylvinylene)phenyl]
-4.5.6.7-titrahydro-2H-isoindole-1,8-dione 0.6121.5 was obtained. It is shown in Table 1.

When producing the compound of the present invention with the general formula shown in Table 1, the raw materials aniline derivative [nl and carboxylic acid [m] can be produced by the following route.

2R1 (v) (VI) [In the formula, R1 and R2 represent the same meanings as above, and in the case of a hydrogen atom or a lower alkyl route, 4-lower alkyl is used, and the ketone (v) is Appropriate wit
With reagents such as ig reagent or alkyl malonate,
After producing carboxylic acid p, (■'), it is nitrated with a mixed acid of nitric acid and chloric acid to obtain nitrobenzene (■), and then the nitro group is selectively reduced using iron in acetic acid,
Aniline derivative (■) (However, R4-lower alkyl group)
can be obtained when R4=hydrogen atom, and in the same manner as above, an aniline derivative (VmM, where R
4-hydrogen atom), and further react with 8,4,5.6-ketonehydrophthalic anhydride in the presence of a solvent such as acetic acid, water, toluene, etc. to obtain carboxylic acid (III). I can do it.

Next, a production example of the aniline derivative [■] will be shown.

Production Example 3 Dissolve 5 g of 2-chloro-4-fluoro-benzaldehyde in 5rnt of benzene, 7.1 g of triethylphosphonoacetate, and 1.6 g of sulfur hydride (50%).
was added dropwise to a benzene solution of the Wittig reagent prepared from 15 ml of benzene at 10 to 20°C. Another 20~
After stirring at 80° C. for 3 hours, water was added and the benzene layer was separated, dried and concentrated to obtain 7 g of crude ethyl 2-chloro-4-fluorocinnamate. Dissolve this in 5ml of concentrated sulfuric acid,
A mixed acid of 2.5 Il of fuming nitric acid and 2 rrLt of concentrated sulfuric acid was added dropwise at room temperature, and the mixture was stirred at 20 to 30°C for 1 hour. After pouring into water, the mixture was extracted with ether, washed with water, dried, and concentrated. The residue was purified using a silica gel column to obtain 0.6 g of ethyl 2-chloro-4-fluoro-5-nitro-cinnamate. (m-
(p・105 to 105.5°C) This was further dissolved in 5 ml of acetic acid and added dropwise under reflux to a system containing 0.6 g of iron powder and 10 ml of 5% aqueous acetic acid. After the dropwise addition, the mixture was refluxed for 80 minutes, left to cool, and chloroform was added for extraction. The chloroform layer was washed with water and saturated soap water, dried, and diluted with 11 [L, 0.2 ethyl 3-amino-4-fluoro-6-chloro-cinnamate.
I got 89.

(m-p・127-127.5°C) 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 0.05 to 95%, preferably 0.1 to 80%.

Solid carriers include fine powders or granules such as kaolin clay, cottonwood clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide; Supports include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, Examples include acetonitrile and water.

Surfactants used for emulsification, dispersion, wetting, 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, holoxyethylene alkylaryl ether,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, C
Examples include MC (carboxymethyl cellulose) and PAP (isopropyl acid phosphate).

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 1.50 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 4.10 parts of the compound of the present invention, 14 parts of polyoxyethicine styryl phenyl ether, 6 parts of calcium F-decylbensene sulfonate, and 70 parts of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 3 3.2 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 1.25 parts of the compound of the present invention, 8 parts of POIJ oxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water were mixed and wet-pulverized until the particle size became 5 microns or less to obtain a suspension.

Treat water. 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.

Furthermore, 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 herbicides for lawns, forests, non-agricultural lands, etc.

When using the compound of the present invention as an active ingredient of a herbicide, the application amount varies depending on weather conditions, formulation form, application time, method, location, target weeds, target crops, etc., but is usually 0.05g to 20g per are. , preferably 0.1g
~10fI, and emulsions, wettable powders, suspensions, etc. are diluted with water (adding spreading aids such as spreading agents, if necessary) at a rate of 1 liter to 10 liters per are. Apply the granules as they are without diluting them in any way.

In addition to the above-mentioned surfactants, the spreading agent includes polyoxyethylene mFJWe<ester), lignin sulfonate,
Examples include ahietate, dinaphthylmethane disulfonate, and paraffin.

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, the herbicidal efficacy was determined by visually observing the degree of budding and growth inhibition of the test plants at the time of the survey, and rOJ was defined as the one with no or almost no effect on the test plants. A score of 5 indicates that the plant has withered or its growth is completely inhibited, and is evaluated in 6 stages from θ to 5: 0, 1, 2.
3.4.5.

Test Example 1 Upland Soil Mixing Treatment Test A cylindrical plastic hotpot with a diameter of 10 crn and a depth of 1 ocIn was filled with upland soil, and sown with Japanese barnyard grass, Japanese amberjack, Japanese morning glory, and Japanese crocodile, and covered with soil. The test compound was made into a hydrating powder according to Formulation Example 1, a predetermined amount of it was diluted with water, and the mixture was sprayed on the soil surface using a small sprayer at a rate of 10 liters per are, and then sprayed at a depth of up to 4 crn. The soil surface layer was thoroughly mixed. After spraying, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 3.

Table 3 Test Example 2 Field soil stem leaf treatment test diameter 10c! Filled with field soil in a cylindrical plasti pot with a depth of 10 crn, Japanese barnyard grass, Japanese amberjack, Japanese morning glory, and Japanese crocodile were sown and grown in a greenhouse for 10 days.
Thereafter, make an emulsion of the test compound according to Formulation Example 2 & above, dilute a predetermined amount with water containing a spreading agent, and spray from the sides of the plant with a small sprayer at a rate of 10 liters per arj. Sprayed on foliage. After spraying, 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 ctn and a depth of 12 cm is filled with paddy soil, and seeds of Japanese millet and broad-leaved weeds (Azaena, Azalea, Chickweed) are placed at a depth of 1 to 2 cm. mixed into. After flooding to create a paddy field condition, tubers of Urikawa were buried at a depth of 1 to 2 cr++ (7), and then rice at the two-leaf stage was transplanted and grown in a greenhouse. Six days later (at the beginning of each weed's emergence), the test compound was made into granules according to Formulation Example 3, a predetermined amount of which was diluted with water, and dropped onto the water surface at a rate of 5 milliliters per pot. After dropping, 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 Test Example 4 Field soil stem and leaf treatment test A vat with an area of 88 x 2 B, ffl, and a depth of 11 ctn was filled with field soil, and the field soil was filled with field soil, and the soil was applied to a vat with an area of 88 x 2 B, ffl, and a depth of 11 ctn. Dogwood, wheat, soybeans, and corn were sown and grown for 18 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, diluted with water containing a spreading agent, and
The mixture was sprayed uniformly over the entire dry part of the stem from above using a small sprayer at a rate of 5 liters per area. At this time, the growth of each plant varies depending on the grass species, but at the 1-4 leaf stage,
The plant height was 2 to 12 cIn. The herbicidal efficacy was investigated 20 days after spraying.

The results are shown in Table 6. Note that this test was conducted in a greenhouse throughout the entire period.

Claims (4)

[Claims] (1) General formula [In the formula, auxiliary and R2 are the same or different and represent a hydrogen atom or a methyl group, and 1 represents a lower alkyl group. ] A 4,5,6,7-tetrahydro-2H-isoindole-1,3-dione derivative represented by the following. (2) General formula [wherein kl and R2 are the same or different and represent a hydrogen atom or a methyl group, and R8 represents a lower alkyl group. [In the formula, R1, R2 and R8 have the same meanings as above. ] (3) General formula ■ζIR2 [In the formula, P, 1 and 2 are the same or different and represent a hydrogen atom or a methyl group. ] is a carboxylic acid represented by the general formula [wherein auxiliary represents a lower alkyl group]. [In the formula, R1, R2 and R8 have the same meanings as above. ] A method for producing a 4,5,6.7-tetrahydro-2H-isoindole-1,3-dione derivative shown in the following. (4) General Formula) [In the formula, Kawa and Toshi are the same or different and represent a hydrogen atom or a methyl group, and R3 represents a lower alkyl group. ] 4, 5.6.7-tetrahydro-2EI-
A herbicide characterized by containing an isoindole-1,3-dione derivative as an active ingredient. 1