JPS5980661A - N-phenyltetrahydrophthalimide derivative, its preparation and herbicide containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 is lower alkoxyl, lower alkylthio, lower alkoxyl lower alkoxyl, cycloalkyloxy, halo lower lakoxyl, cyano lower alkoxyl, etc.; R2 is H, CH3 or OCH3, etc. X is Cl or Br). EXAMPLE:2-(4-Bromo-2-fluoro-5-ethoxycarbonylmethyliminophenyl)4, 5, 6, 7-tetrahydro-2H-isoindole-1,3-dione. USE:A herbicide capable of exhibiting improved herbicidal effects on broadleaf weeds by the soil treatment, gramineous weeds in upland fields or weeds in the paddy fields without giving phytotoxicity to corn, rice plant, etc. PROCESS:An aniline derivative expressed by formula II is reacted with a halocarboxylic acid ester expressed by formula III (Z is Cl or Br) in a solvent in the presence or absence of a dehydrohalogenating agent to afford the aimed compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R1 is a lower alkoxy group, a lower alkylthio group, a lower alkoxy lower alkoxy group, a cycloalkyloxy group, a cycloalkyl lower alkoxy group, a halo lower alkoxy group, or A cyano lower alkoxy group, auxiliary represents a hydrogen atom, a methyl group or a methoxy group, and X represents a chlorine atom or a bromine atom. ] The present invention relates to an N-phenyltetrahydrophthalimide derivative (hereinafter referred to as the compound of the present invention) represented by the following, a method for producing the same, and a herbicide containing the same as an active ingredient.

Certain N-phenyltetrahydrophthalimide derivatives, such as 2-(4-chloro-2-fluorophenyl)
The use of -4,5,6,7-tetrahydro-2H-isoindole-1,8-dione as an active ingredient in herbicides is described in JP-A-51-51521.

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

The compounds of the present invention can be used to treat various weeds that are problematic in foliar and soil treatments in fields, such as purslane, whiteweed, blueberry, American staghorn,
It has a herbicidal effect on broad-leaved weeds such as Japanese grasshopper, American golden deer, American morning glory, Malva morning glory, European bindweed, European morning glory, Japanese Physalis, Japanese fir, Japanese fir, Castor weed, and pigweed. The compound does not cause any harmful effects on major crops such as corn and soybeans.

・In addition, some of the compounds of the present invention can be used to control various weeds that are problematic in rice fields, such as grass weeds such as Japanese millet, broad-leaved weeds such as azalea, japonica, and chickweed, cyperaceae weeds such as cyperus cyperus, and grasses such as cyperus japonica and gourd. It has a herbicidal effect on paddy field weeds, and does not cause any harmful effects on rice.

The compounds of the present invention can be used in rice fields, fields, orchards, pastures, lawns,
It can be used as an active ingredient in forest or non-agricultural herbicides.

The compound of the present invention has the general formula [wherein, X represents the same meaning as above]. ] and 1.0 to 10 equivalents of the general formula % formula %[ ] [wherein 2 represents a chlorine atom or a bromine atom, and R1 and auxiliary represent the same meanings as above. ] in a solvent, in the presence or absence of a dehydrohalogenating agent of 0.5 to 1,0 equivalent, at 0°C to 2°C.
It can be produced by reacting at 00°C for 1.0 to 96 hours.

Solvents include ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.・Ketones such as N, isopolone, and cyclohexanone; alcohols such as methanol, ethanol, isopropanol, cyclohexanol, methyl cellosolve, diethylene glycol, and glycerin; nitrites such as acetonitrile and isobutyronitrile; , pyridine, triethylamine, N,N-diethylaniline, tributylamine, tertiary amines such as N-methylmorpholine, formamide, N,N-dimethylbormamide,
Acid amides such as acetamide, dimethyl sulfoxide,
These include sulfur compounds such as sulporan, etc., or mixtures thereof.

Dehydrohalogenation agents include organic bases such as pyridine, triethylamine, N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium Examples include alkali metal alkoxides such as ethoxides.

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

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

Production Example 1 (Production of Compound 12 of the Invention) 2-(8-amino-4-bromo-6-fluorophenyl)-4,5,6
,7-tetrahydro-2H-isoindole-1,3-
0.85 g of dione was dissolved in 5 ml of 1.4-diokylene, 8.8 g of ethyl bromoacetate was added, and the mixture was refluxed for 6 hours. Furthermore, 0.21 g of triethylamine was added, and the mixture was refluxed for 1 hour. After cooling, water and toluene were added and extracted with toluene. The toluene layer was dried and concentrated, and the residue was purified using a silica gel column to obtain 2-(4-bromo1-2-fluoro-5-ethoxycarbonylmethyliminophenyl)-4
,5,6,7-tetrahydro-2H-isoindole-
1,3-dione 1. I got Of. nDl, 5281 Table 1 shows some of the compounds of the present invention that can be produced by such a production method.

Table 1 When producing the compound of the present invention with the general formula, the aniline derivative of the general formula [■] which is a raw material compound is prepared by the general formula [wherein X represents the same meaning as above]. ] A nitrobenzene rust conductor represented by 2.0 to 10 equivalents of iron powder is reacted in a solvent in the presence of a catalytic amount to a large excess amount of acid at 20°C to 20°C for 0.5 to 24 hours. It can be manufactured by

Solvents include alcohols such as methanol and ethanol,
Examples include tetrahydrofuran, acetic acid, water, etc.

Examples of acids include hydrochloric acid and acetic acid.

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

Next, a production example of the aniline derivative of the general formula rII] will be shown.

Production Example 2 16.2 g of 2-(4-chloro-2-fluoro-5-nitrophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione was dissolved in 200-acetic acid, 90-10 596 acetic acid water 30 parts containing 14 f iron powder
It was added dropwise at 0°C. After the addition, the mixture was refluxed for 1 hour. After cooling, chloroform was added and the mixture was separated from the furnace. r Separate the organic layer of the liquid,
The mixture was washed with saturated aqueous sodium bicarbonate, dried, and concentrated. The residue was crystallized and recrystallized from ether/petroleum ether to give 2-(8-amino-4-chloro-6-fluorophenyl)-4,5,6,
7-titrahydro2 tr-isoindole-1,8
-Dione 7.5f was obtained.

mP 144.5-146.5°C Production Example 3 In the same manner as Production Example 2, 2-(4-bromo-2-fluoro-5-ptrophenyl)-4°5.6.7-titrahydro 2H- 2 from isoindole-1,3-dione
-(8-amino-4-promo-6-fluorophenyl)
-4,b,6.7-tetrahydro-211-isoindole-L,8-dione was obtained.

+111)' 168-164.5°C When the compound of the present invention is used as an active ingredient of a herbicide, a solid carrier,
It is mixed with liquid carriers, surfactants and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, granules, powders, etc.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 01 to 9596, preferably 1 to 8096.

Solid carriers include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite,
There are fine powders or granules such as talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide, and liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, isopropanol, and ethylene chloride. Alcohols such as Recall and Cellosolve, ketones such as Athitone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile,
There is water etc.

Surfactants used for emulsification, dispersion, wet charcoal, etc. include alkyl sulfate salts, aryl (aryl)
Thoracic ionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryls, ethers, polyoxyethylene, polyoxybrobylene Examples include nonionic surfactants such as block copolymer, sorbitan fatty acid ester, and polyoxysorbitan fatty acid ester. Formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, C
Examples include MC (carboxymethyl cellulose) and FAI' (isopropyl acid phosphate).

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. 9.50 parts of the compound of the present invention, 8 parts of calcium lignin sulfonate, 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 5.10 parts of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene and 40 parts of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 3 7.2 parts of the compound of the present invention, 1 part of synthetic silicon hydroxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite, and 65 parts of kaolin and clay were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded. Granulate and dry to obtain granules.

Formulation Example 4 9.25 parts of the compound of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water were mixed and wet-pulverized until the particle size of the active ingredient became 5 microns or less to form a suspension. get a glimpse of it.

These preparations can be used as is or diluted with water, etc., and treated with foliage or soil. For soil treatment, the formulation can be applied to the soil surface (if necessary, mixed with the soil after application) or irrigated into the soil.

Furthermore, 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, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil ta improvers, and the like.

When the compound of the present invention is used as an active ingredient of a herbicide, the application rate is generally 0.01y to 100g per are;
Preferably, it is 0.1f-50g, emulsion, hydrating agent,
11 ■ Candling agent, etc., at a rate of 1 liter to 10 liters per are (if necessary, a spreading agent such as a spreading agent was added)
Apply diluted with water, and apply granules, powders, etc. as they are without diluting them in any way.

In addition to the above-mentioned surfactants, spreading agents include polyoxyethylene resin acids (esters), lignin sulfonate, abietate, dinaphthylmethane disulfonate, paraffin, and the like.

Next, test examples will show 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 shows the chemical damage to crops and the herbicidal efficacy against 'a' (8 grasses). (The ratio (96) to the case of no trial is 1t-j'?:L, 3rd
Evaluate according to the classification in the table, mulberry 7v and weeding power O
It is indicated by a numerical value from to 5.

Table 8 Test Example 1 Upland straw treatment test A vat with an area of 88 x 28 crtt” and a depth of 11 m was filled with upland soil,
Physalis albicans, Physcomitrella sinensis, and C. japonica were sown and allowed to withstand acid for 1" and 8 days.

Thereafter, the emulsion of the test compound was diluted with 10 liters of water containing a spreading agent per are, and a predetermined amount of the diluted solution was uniformly sprayed from above the plant over the entire foliage area using a small sprayer. At this time, the growth of each plant differs depending on the grass species, but
At the four-leaf stage, the plant height was 2 to 12 crn. The herbicidal efficacy was investigated 20 days after spraying. The results are shown in Table 4. This test was conducted in a greenhouse throughout the entire period.

Table 4 Continued from Table 4 Test Example 2 Upland Soil Mixture Treatment Test A cylindrical plus deck pot with a diameter of 10 mm and a depth of 1 ocIn was filled with upland soil, and soybean, cotton, morning glory,
Ichibi was sown and covered with soil.

The test compound made into an emulsion was heated at 10° per are,
After diluting the solution with an appropriate amount of water and spraying a predetermined amount on the soil surface with a small sprayer, the surface layer of the soil was thoroughly mixed to a depth of 4 cm. After spraying, 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 3 Paddy field gutter treatment test Paddy field gutter was packed into a cylindrical plastic pot with a diameter of 8 cm,
1-2 cm of seeds of Azena, Kikashigusa, Chickweed)
It was mixed to a depth of . After flooding to form a paddy field of 1 yen, tubers of Urikawa were buried at a depth of 1 to 2 t:m, and then 2 t:m deep.
Rice plants at the leaf stage were transplanted and grown in a greenhouse. After 6 days (at the beginning of the development of each shiitake mushroom), the test compound was made into an emulsion and diluted with 5 milliliters of water per bottle, and the predetermined area was dropped on the water surface. After the drop, the mushrooms were grown in a greenhouse for 20 days. , tattooed herbicidal efficacy.

The results are shown in Table 6. Table 6

Claims (1)

[Claims] (1) General formula [wherein, river is a lower alkoxy group, a lower alkylthio group,
A lower alkoxy lower alkoxy group, a cycloalkyloxy group, a cycloalkyl lower alkoxy group, a halo lower alkoxy group or a cyano lower alkoxy group, R2 represents a hydrogen atom, a methyl group or a methoxy group, and X represents a chlorine atom or a bromine atom. ] N-phenyltetrahydrophthalimide derivative represented by these. (2) General formula (wherein, X represents a chlorine atom or a bromine atom).
] Aniline derivatives represented by the general formula % Formula % [In the formula, R1 is a lower alkoxy group, a lower alkylthio group, a lower alkoxy lower alkoxy group, a cycloalkyloxy group, a cycloalkyl lower alkoxy group, a halo lower alkyl: Joxy group or a cyano lower alkoxy group, k2 represents a hydrogen atom, a methyl group or a methoxy group, and Z represents a chlorine atom or a bromine atom. ] N-phenyltetrahydrophthal-imide represented by general formulas 1 and 2 [wherein R1, :R2 and X represent the same meanings as above] Method for producing derivatives. (8) General formula [In the formula, Kawa is a lower alkoxy group, lower alkyl lower alkoxy group, halo lower alkoxy group or cyano lower penta-alkoxy group, auxiliary is a hydrogen atom, methyl group or methoxy group, and X is a chlorine atom or Represents a bromine atom. A herbicide comprising an N-phenyltetrahydrophthalimide derivative represented by the following as an active ingredient.