JPH0784442B2 - Isoindole derivative, method for producing the same and herbicide - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel compound, a method for producing the same, and a herbicide containing the compound as an active ingredient.

[Conventional technology]

In the cultivation of agricultural and horticultural crops, many herbicides have come to be used for controlling weeds, which have required a great deal of labor. However, since it causes phytotoxicity to crops, remains in the environment, and pollutes, it is desired to develop a drug that has a lower dose and is effective, and can be used safely.

[Problems to be solved by the invention]

An object of the present invention is to industrially advantageously produce a novel isoindole derivative, and to provide a highly safe herbicide which has a wide range of selectivity between crops and weeds, is effective with a lower dose, and is effective. Is.

[Means for solving problems]

The present invention has the general formula [In the formula, X represents a halogen atom and R represents a group represented by the formula —COOR ₁ (in the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with a cyano group or a lower alkoxycarbonyl group). ) Or the formula —Y—R ₂ (wherein Y is 0 or S, R ₂ is a hydrogen atom or a cyano group, a phenoxy group, a lower alkoxy group or a group represented by the formula —COOR ₃ (wherein R ₃ is It represents a lower alkyl group which may be substituted with a cycloalkyl group or a lower alkoxycarbonyl group.)
Represents an aliphatic lower hydrocarbon group which may be substituted with. } Shows group represented by. ] The compound represented by these, its manufacturing method, and the herbicide which contains 1 type, or 2 or more types of this compound as an active ingredient.

The compound of the present invention, soil treatment under upland field conditions, in any treatment method of foliage treatment, Amaranthus chinensis, Acacia, Scutellaria,
It exhibits high herbicidal activity against various weeds such as Cyperus communis, and is less toxic to crops such as corn, wheat, soybean, and peanut. Above all, soybean exhibits high selectivity for the compound of the present invention.

It also shows high selectivity for paddy rice, and shows an excellent herbicidal action by treatment of weeds such as Nobie, Tamagami, Omodaka, etc. before and after emergence.

The compound can also be applied to control weeds in orchards, lawns, railroad ends, vacant lots and the like.

The compound of the present invention can be produced by the method shown below.

The reaction is carried out in an organic solvent or in the absence of a solvent in the presence of a condensation catalyst at 70 to 200 ° C. for 1 to several tens of hours.

Usual organic solvents such as benzene, toluene and xylene can be used as the organic solvent. As the condensation catalyst, sulfonic acids such as P-toluenesulfonic acid and tertiary amines such as dimethylaminopyridine can be used.

The compound represented by the general formula [II] can be produced, for example, according to the following reaction formula.

Further, the compound of the present invention can be produced according to the following reaction formula depending on the kind of R in the general formula [I].

When R is -COOR ₁ : (In the formula, Hal represents a halogen atom.) When R is —Y—R ₂ : Furthermore, the compound of the present invention can also be produced according to the following reaction formula.

Whichever method is used, the desired product can be obtained by carrying out usual post-treatment after completion of the reaction.

The structure of the compound of the present invention was determined by IR, NMR, MASS and the like.

[Examples] Next, the compounds of the present invention will be described in more detail with reference to Examples.

Example 1. 2- (4-Chloro-2-fluoro-5-hydroxyphenyl) -3-methylene-4,5,6,7-tetrahydroisoindol-1 (2H) -one (Compound No. 8): 4.50 g of 3-hydroxy-3-methyl-4,5,6,7-tetrahydroison benzofuran-1 (3H) -one and 4.33 g of 2-chloro-4-fluoro-5-aminophenol were suspended in 30 ml of xylene. It was P-toluenesulfonic acid
0.5 g was added, heated and azeotropically dehydrated for 20 hours.

After cooling, 30 ml of 2N NaOH aqueous solution was added to the reaction mixture, the alkali soluble matter and xylene were separated, the alkali solution was neutralized with hydrochloric acid, and the precipitated crystals were collected by filtration, dried and recrystallized with ethyl acetate to obtain 6.9 g of the desired product. Got

Yield 88% mp 205-206 ° C Example 2.2- [4-Ethoxy-2-fluoro-5- (2
-Propynyloxy) phenyl] -3-methylene-4,5,
6,7-Tetrahydroisoindole-1 (2H) -one (Compound No. 19): 2- (4-Chloro-2-fluoro-5-hydroxyphenyl) -3-methylene-4,5,6,7-tetrahydroisoindol-1 (2H) -one 1 g suspended in acetonitrile 30 ml potassium carbonate 0.47 g Added to the liquid. To this suspension, 0.41 g of propargyl bromide was added and refluxed for 1 hour.

After completion of the reaction, the solid substance was filtered off, the acetonitrile of the filtrate was distilled off under reduced pressure, the residue was dissolved in ether and washed with 1N-NaOH, the ether layer was washed with water and dried (MgSO ₄ ), and MgSO ₄ was filtered off. After separation, ether was distilled off under reduced pressure to obtain 1.07 g of the desired product.

Yield 95% mp 125-126 ° C Example 3.2 2- [4-chloro-2-fluoro-5- (1-
Methoxycarbonylethylthio) phenyl] -3-methylene-4,5,6,7-tetrahydroisoindole-1 (2
H) -one (Compound No. 23): 3-Hydroxy-3-methyl-4,5,6,7-tetrahydroisobenzofuran-1 (3H) -one 1 g and 4-chloro-2
1.57 g of -fluoro-5- (1-methoxycarbonylethylthio) aniline was mixed, 0.3 g of P-toluenesulfonic acid was added thereto, and the mixture was reacted at 130 ° C for 2 hours. After cooling, the reaction mixture is purified by column chromatography,
20 g of the desired product was obtained as a pale yellow oily substance. Yield 85%
▲ n ²⁰ _D ▼ 1.5880 Reference Example. Synthesis of 3-hydroxy-3-methyl-4,5,6,7-tetrahydroisobenzofuran 1- (3H): 10 g of 3,4,5,6-tetrahydrophthalic anhydride was added to 10 g of pyridine.
Dissolve it in ml and add 10.3 g of malonic acid to it at room temperature.
The reaction was carried out at 0 to 70 ° C for 24 hours. After completion of the reaction, the reaction mixture was poured into ice water containing pyridine and an equimolar amount of hydrochloric acid, and the precipitated crystals were collected by filtration. The mother liquor was extracted with chloroform, washed with water, dried and then the chloroform was distilled off. The residue was combined with the above-mentioned crystals and recrystallized from toluene.

Yield 8.90 g Yield 80% m.p. 110-111 ° C Table 1 shows typical examples of the compound of the present invention.

[Means for Solving Problems-Herbicides] The herbicides of the present invention contain one or more compounds represented by the general formula [I] as an active ingredient and have a form similar to that of usual pesticides. . That is, the active ingredient compound is generally used in the form of a wettable powder, an emulsion, a granule, an aqueous solvent, a flowable agent, etc. by mixing an appropriate amount with a carrier. Examples of the solid carrier include talc, white carbon, bentonite, clay, diatomaceous earth, and the like, and examples of the liquid carrier include water, alcohol, benzene, xylene, kerosene, mineral oil, synchrohexane, cyclohexanone, dimethylformamide, and the like. Surfactants can also be added if necessary to obtain a uniform and stable form in these formulations.

The concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the above-mentioned preparation. For example, 5 to 70%, preferably 10 to 30% for wettable powder and 3 to 3 for emulsion. 70%, preferably 5 to 20%: in granules
Concentrations of 0.01-30%, preferably 0.05-10% are used.

The wettable powder and emulsion thus obtained are diluted with water to a predetermined concentration to give a suspension or emulsion, and the granules are sprayed or mixed into the soil before or after germination of weeds. It is processed. In actual application of the herbicide of the present invention, an appropriate amount of 1 g or more of the active ingredient is applied per 10 ares.

Further, the herbicide of the present invention is a known fungicide, insecticide, acaricide,
It can also be used as a mixture with a herbicide, a plant growth regulator or the like. In particular, when used in combination with a herbicide, not only can the amount of drug used be reduced and labor can be saved, but a higher effect due to the synergistic action of the mixed drug can be expected. In that case, a combination with a plurality of known herbicides is also possible. Suitable agents to be used in combination with the herbicide of the present invention include bench carb, molynate, MY-93 [S- (2,2-dimethylbenzyl) 1-piperidine carbothioate] and other carbamate herbicides, thiocarbamate herbicides. Agents, acid amide herbicides such as butachlor and pretilachlor, diphenyl ether herbicides such as clomethoxynil and bifenox, pyrazole herbicides such as pyrazolate and pyrazoxifene, chlorsulfuron, sulfometuron-
Sulfonylurea herbicides such as methyl, phenoxyalkanecarboxylic acid herbicides such as MCP and MCPB, phenoxyphenoxypropionic acid herbicides such as diclofop-methyl, pyridyloxyphenoxypropionic acid herbicides such as fluazifop-butyl, and others. As piperophos, dimuron, bentazone, oxadiazone, NTN-801 (2
-Benzothiazol-2-yloxy-N-methylacetanilide), naproanilide, HW-52 (4-ethoxymethoxybenz-2 ', 3'-dichloroanilide), KN
W-242 [1- (3-methylphenyl) -5-phenyl-1
H-1,2,4-triazole-3-carboxamide], S-
Examples thereof include cyclohexanedione-based herbicides such as 47 [N-2,2-dimethylbenzyl) -d-bromota-sharyl-butylacetamide, setoxydim, and alloxydim-sodium. It is also possible to add vegetable oils and oil concentrates to these combinations.

[Example-herbicide]

Next, some formulation examples of the herbicide of the present invention will be shown, but the active ingredient compounds, additives and addition ratios can be changed within a wide range without being limited to these examples.

Example 4 Wettable powder Compound 1 of the present invention 20 parts White carbon 20 parts Diatomaceous earth 52 parts Sodium alkyl sulfate 8 parts The above components were uniformly mixed and finely pulverized to obtain a wettable powder containing 20% of the active ingredient.

Example 5 Emulsion Compound of the present invention 23 20 parts Xylene 55 parts Dimethylformamide 15 parts Polyoxyethylene phenyl ether 10 parts The above components were mixed and dissolved to obtain an emulsion containing 20% of the active ingredient.

Example 6 Wettable powder Compound 19 of the present invention 5 parts Talc 40 parts Clay 38 parts Bentonite 10 parts Sodium alkyl sulfate 7 parts The above components are uniformly mixed and finely pulverized, and then granulated into particles having a diameter of 0.5 to 1.0 mm. A granule containing 5% of the active ingredient was obtained.

〔The invention's effect〕

 Next, test examples relating to the effect of the herbicide of the present invention will be shown.

Test Example 1 A pad of 150 cm ² was filled with paddy soil, seeds of Nobie, Tamagayatsu, Omodaka and Firefly were sown, and pine by transplanting seedlings, lightly soiled, and rice at 2 to 3 leaf stage (variety: Nipponbare) 1 Strains (2) were transplanted. The next day, maintaining a water depth of 2 to 3 cm, granules of each compound were treated in a predetermined dose and grown in a greenhouse. Three weeks after the treatment with the folic agent, the growth conditions of rice and each weed were investigated according to the following criteria, and the results shown in Table 2 were obtained.

Survey criteria Weeding rate Index 0% 0 20-29% 2 40-49% 4 60-69% 6 80-89% 8 100% 10 Also, the numbers 1,3,5,7,9 are 0 and 2, respectively. 2 and 4 and 6 and 6
And values between 8 and 8 and 10 are shown.

Test Example 2 A 250 cm ² pot was filled with soil, and the surface layer of velvetleaf, azalea,
Seeds of Amaranthus, purslane, and soybean were sown, and the soil was covered so that the seeds could not be seen. Immediately, an emulsion of each test compound was diluted with water and adjusted to a predetermined concentration, and a chemical solution of 100 l / 10a was sprayed on the soil surface with a small sprayer and grown in a greenhouse. Water was sprinkled every day so that the soil surface became moist. Three weeks after the chemical application, the growth condition of each weed was investigated according to the same criteria as in Test Example 1, and the results are shown in Table 3.

Test Example 3 A 200 cm ² pot was filled with soil, and various larvae of crabgrass, cyperaceae, scabbard, and Aedes persica were sown on the surface, lightly covered with soil, and grown in a greenhouse. When each weed grew to a plant height of 3 to 15 cm, a chemical solution prepared by diluting an emulsion of each test compound with water was sprayed on the foliage of the weed with a small sprayer at a ratio of 100 l / 10a. After 3 weeks, the growth condition of weeds was investigated by the same criteria as in Test Example 1, and the results are shown in Table 4.

Claims (3)

[Claims] 1. A general formula [In the formula, X represents a halogen atom and R represents a group represented by the formula —COOR ₁ (in the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with a cyano group or a lower alkoxycarbonyl group). ) Or the formula —Y—R ₂ {wherein Y is O or S, R ₂ is a hydrogen atom or a cyano group, a phenoxy group, a lower alkoxy group or a group represented by the formula —COOR ₃ (wherein R ₃ is It represents a lower alkyl group which may be substituted with a cycloalkyl group or a lower alkoxycarbonyl group.)
Represents an aliphatic lower hydrocarbon group which may be substituted with. } Shows group represented by. ] The compound represented by these. 2. A formula Represented by -3-hydroxy-3-methyl-4,5,6,7-
Tetrahydroisobenzofuran-1 (3H) -one and general formula [Wherein, X represents a halogen atom, R represents a group represented by the formula -COOR ₁ (in the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with a cyano group or a lower alkoxycarbonyl group). .) or wherein -Y-R ₂ {wherein, Y is O or S
R ₂ is a hydrogen atom or a cyano group, a phenoxy group, a lower alkoxy group or a group represented by the formula —COOR ₃ (wherein R ₃
Represents a lower alkyl group which may be substituted with a cycloalkyl group or a lower alkoxycarbonyl group. ) Represents an aliphatic lower hydrocarbon group which may be substituted with). } Shows the group represented by. ] A general formula characterized by being reacted with a compound represented by (In the formula, X and R have the same meanings as described above.) A method for producing a compound represented by the formula. 3. General formula [Wherein, X represents a halogen atom, R represents a group represented by the formula -COOR ₁ (in the formula, R ₁ represents a hydrogen atom or a lower alkyl group which may be substituted with a cyano group or a lower alkoxycarbonyl group). .) or wherein -Y-R ₂ {wherein, Y is O or S
R ₂ is a hydrogen atom or a cyano group, a phenoxy group, a lower alkoxy group or a group represented by the formula —COOR ₃ (wherein R 2
₃ represents a lower alkyl group which may be substituted with a cycloalkyl group or a lower alkoxycarbonyl group. ) Represents an aliphatic lower hydrocarbon group which may be substituted with). } Shows the group represented by. ] The herbicide which contains 1 type, or 2 or more types of the compound represented by these as an active ingredient.