JPS5982360A - N-phenyltetrahydrophthalimide derivative its preparation and herbicide containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X is halogen; Y is > C=0 or group of formula II (Rs are lower alkyl or together link to form lower alkylene); Z is O or methylene]. EXAMPLE:N-[2-Fluoro-4-chloro-5-(cyclopentanon-2-yloxy)phenyl]-3, 4, 5, 6-tetrahydrophthalimide. USE:A herbicide having herbicidal efficacy against broadleaf weeds and weeds in paddy fields, etc. without phytotoxicity to beans nor rice plants. PROCESS:A compound of formula III is reacted with a compound of formula IV in a solvent, e.g. acetone or toluene, in the presence of 1-1.5 equivalents dehydrohalogenating agent, e.g. anhydrous potassium carbonate, at 5-150 deg.C for 1-10hr to give the aimed compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein X represents a halogen atom and Y represents a lower alkylene group formed by /C-O bonded to each other]. ), 2 represents an oxygen atom or a methylene group. 19.1 to the N-phenyltetrahydrophthalimide 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.

A certain divine N-7 engineering nyltetrahydrophthalimide derivative, such as N-4 dark mouth 3-(γ-butyrolactone-3-yloxy) phenyl) -3,4,! I-,,
The fact that 4-tetrahydrophthalimide can be used as an active ingredient of a scavenger is described in Kankaisho, 57-/, 9670 Publication.

However, it cannot be said that these compounds (7) are always 1tt as active ingredients of herbicides.

The compound of the present invention can be used to treat problematic foliage and soil treatments in upland fields, such as 1"II, for example, buckwheat,
Steller's knotweed, Portulaca trifoliata, Shiroza, 7. Japanese radish, Japanese radish, Shepherd's purse, American chestnut, Japanese radish, American goldfish, field pansy, Japanese red violet, American morning glory, Maruba azaroglyo, Hemlock vulgare, 4. Tokenoza, European morning glory, Japanese dogbeast, Japanese dogbeast,
F4 if (funded), Japanese millet, Japanese millet, foxtail grass, black grass, oat, oat, Seiban sorghum, old rice fat
M. J. and Kogomega spp., Cyperus spp., which has a herbicidal effect when mowed actively, and some A-Zhe 1 compounds are dice. do not have.

In addition, the compounds of the present invention can also be used as grasses of the gods, such as Japanese cabbage, etc. (The compound of the present invention has a herbicidal effect on paddy field weeds such as Cyperaceae, Cyperaceae, Cyperaceae, etc.) and does not show any harmful effects on paddy field weeds such as C. Field, one fruit tree, pasture,
The compound of the present invention can be used as an active ingredient in lawns, forests, or non-agricultural lands. N-(,:2-fluoro-g)10-j-hydroxyphenyl) 3,9. JL 6-titrahydrophthalimide and/~/. General formula of 5 and 9 [wherein, W is a chlorine atom or a bromine atom f, Zi-i*
IIM +j and -'' represent the same meaning. ] in a solvent in the presence of a dehydrohalogenating agent of /~/, , ff M m j''C~7.5'θHC1/hour~
abl can be achieved by reacting for 10 hours.

In solvents, aliphatic hydrocarbons such as hexane, heptane, monohageloin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogens such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene. Hydrocarbons, ethers such as diethyl ether, diisopropyl ether, dioxane, teF-lahydrofuran, diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, etc.
, ester gradients such as ethyl acetate, butyl acetate, diethyl carbonate, nitrides of nitroethane, nitrobenzene, acetonitrile, isobutyl nitrile, etc.
(tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine, N,N-dimethylformamide,
Acid amides such as acetamide, dimethyl sulfoxide,
Dehydrohalogenating agents include sulfur compounds such as sulfolane or mixtures thereof; Kunatori, rum, potassium carbonate, sodium hydride inorganic base,
There are alkali metal alkylene groups such as sodium methoxide and sodium ethoxide.

At the end of the reaction, the usual procedure is carried out, and the material is prepared by chromatography, distillation, and redistribution crystallization.

However, the compound has the general formula:
and Z have the same meanings as above. [In the formula, R1 represents a lower alkyl group. ] or [wherein represents a lower alkylene group. It can also be produced by reacting a hydroxy compound represented by ] in a solvent in the presence of a Lewis acid of 1.20° C. to 5θ"C/hour to /θ hour in a solvent. .

Solvents include aliphatic hydrocarbons such as hexane, butane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene! A! Halogenated hydrocarbons, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether and other ethers, methanol, ethanol, iso↓ propatool, (-butanol, octatool alcohols, ethyl acetate, butyl acetate, etc.) esters, nitrites such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, acid amides such as N,N-dimethylformamide and acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, etc. There is a mixture of

Lewis acids include organic acids such as p-toluenesulfonic acid and inorganic acids such as sulfuric acid.

After the reaction is completed, the product is subjected to post-processing such as distillation, and if necessary, it is produced by chromatography, distillation, recrystallization, etc.

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

Production Example/ (Production of Compound 2 of the Invention) N-(,2-fluoro-9-chloro-5-hydroxyphenyl)-3,'l,t, 6-titrahydrophthalimide, α-bromocyclopentanone jy1 anhydrous potassium carbonate, 2-sy diiopotassium 3. '19 was extracted with acetone and 50 at, and analyzed with silica gel chromatography (developed with ffl ethyl-n-hexane). Schiff, 7y N-(non-fluorocarbon-3-(cyclobentanon-1-yloxy)phenyl)-J,
l/l, 3. O-tetrahydrophthalimide was obtained. (
Melting point: 739~/R/'' (:N Production Example! (Production of Compound 9 of the Present Invention) 9,t, O-Tetrahydrophthalimide 311 Ethylene glycol θ, 6, p-1 Luenesulfonic acid 0.θ5y6h While removing water in θml of toluene, heat the fish for an hour. After cooling, add alcohol and ethyl acetate. It was extracted and sheathed by silica gel chromatography (developed with ethyl 4-acid and n-hexane) to obtain 1.2!
(,2,:2-ethylenedioxycyclopentyloxy)phenyl)-3,'17. j, A-tetrahydrophthalimide was obtained. (Melting point/jθ~152°C) Table 1 shows some of the compounds of the present invention that can be produced by such a production method.

Table 1 General formula When using the present invention compound as an active ingredient of a leather remover,
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 at a weight ratio of 0. /~? S%, preferably 0.3 to 0.3, is contained.

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 hydrous silicon oxide. Aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve (hr%), ketones such as acetone, cyclohexanone, and isophorone, g, 1+, vegetable oils such as soybean oil, sulphate oil, syringe oil, etc. , dimethyl sulfoxide, acetonitrile, water, etc.

Used for emulsification, dispersion, etc.
(1 Activators include alkyl sulfate salts, alkyl (
(aryl) sulfonic acid, dialkyl sulfoshophosphate, polyoxyethylene alkylaryl ether phosphate ester salt-based anionic surfactant, polyoxyethylene alkyl ethyl, polyoxyethylene alkylaryl ether, polyoxyethylene poly Oxybrobylene block copolymer, sorbitan fatty acid ester,
Examples include nonionic surfactants such as polyoxysorbitan fatty acid esters. Formulation adjuvant Niha, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PA
P (He + isopropyl phosphate), etc.

Examples of formulations are shown below. The compounds of the present invention are shown by compound numbers in Table 7. Parts indicate parts by weight.

Formulation Example: Compound i of the present invention, so@, calcium acid part of lignin sulfonate, part of lucium, part of sodium acid, and 95 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain an irrigation agent.

Formulation example! 3.76 parts of the compound of the present invention, polyoxyethylene styryl phenyl ether/liquid, 6 parts of dodecylbenzenesulfone dissolved calcium, and θ part of xylene were thoroughly mixed to form an emulsion f.
get c.

Formulation Example 3 Compound of the present invention! , 2 parts of synthetic hydrated silicon oxide/one part of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, and then granulated and dried to form granules. get.

Formulation Example: 23 parts of the compound of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water were mixed and wet-pulverized until the particle IW of the active ingredient became 3 parts micron or less. Pray for a clouding agent.

These preparations can be used as they are, or they can be spread with water, etc., and treated with foliage or soil. For soil treatment, spray the preparation on the soil surface (if necessary, mix it with the soil after spraying) or use the "J! ; Rinse with water.

Furthermore, by mixing it with other herbicides, it can be expected to increase the herbicidal efficacy. In addition, 8 test examples / Field field stem and leaf treatment test Filled with field soil in cylindrical plastic pots with a diameter of 10 tin and a depth of /θ, seeds of Japanese barnyard grass, Maruno to morning glory, radish, Japanese radish, and soybean were planted in a greenhouse at /θ. It was grown for days. The test compound, made into an emulsion according to the formulation, was boiled in water containing a spreading agent equivalent to /θ liter per area, and the D [fixed] concentration was poured into a coffin in a small ejector. After 0 spraying, the plants were grown in a greenhouse for aθ days to reduce herbicidal efficacy by 1jΔi. The results are shown in Table 30 Table 3 Test Example β Paddy Soil Treatment Test A cylindrical plastic bottle with a diameter of m and a depth of 2 tyn was filled with paddy soil.
Kikashigusa, Chickweed), Firefly seeds/~, 2
It was mixed to a depth of cr/l. Shun and Urikawa tubers were watered with river water and made into paddy fields. Bury it to a depth of 2cm, and more! Rice of a certain season was transplanted and grown in a greenhouse. Six days later (at the beginning of each weed's emergence), the test compound made into an emulsion according to Formulation Example 3 was diluted with J milliliters of water per pot, and a predetermined amount thereof was dropped onto the water surface. After dropping, the plants were grown in a greenhouse for λθ days and their herbicidal efficacy was investigated. The results are shown in Table 7.

Field test example 3 Upland soil mixing treatment test A cylindrical plastic pot with mountain diameter/θm1 depth/θ gun was filled with upland soil, and millet, oat, morning glory, Japanese radish, and soybean were diluted to zero soil. Formulation example! The test compound made into an emulsion according to Mix the parts well. After spraying! θIEI iHl Grow in a vortex chamber to increase herbicidal efficacy. Zono A+.

The results are shown in Table 9.

Group table Continuation of page 1 @ Originated by Eiki Nagano Sumitomo 4-2-1 Takashi, Takarazuka City Within Kagaku Kogyo Co., Ltd. @ Originated by Ryo Yoshida Sumitomo 4-2-1 Takashi, Takarazuka City Within Kagaku Kogyo Co., Ltd. 0 shots by Shun Hashimoto Sumitomo 4-2-1 Takashi, Takarazuka City Within Kagaku Kogyo Co., Ltd. =503-

Claims (1)

[Claims] (1) In the general formula, X represents a halogen atom 'f, and Y represents an alkyl group or a lower alkylene group bonded to each other. ) represents a methylene group spanning a ZU oxygen atom. ] N-phenyltetrahydrophthalimide derivative represented by these. (Incorporated) General formula [In the formula, X represents a halogen I compound. N indicated by 3
-(,2-Fluoroder halo j-hydroxyphenyl)-,3,ri,jI6-titrahydrophthalimide and the general formula [wherein, W is a chlorine atom or a bromine atom, and Z is an oxygen atom or a methylene group] N-phenyl represented by the general formula characterized by reacting with a halide represented by A method for producing a tetrahydrophthalimide derivative. (3) - N-phenyltetrahydro represented by the formula U [wherein, Phthalimide derivatives and the general formula % Formula % (In the formula, R1 represents a lower alkyl group.) Bo-Sini J. [In the formula, R2 represents a lower alkylene Δ-. N-phenyltetrahydro represented by the general formula % (%) [In the formula, ) is lower alkyl sphagnum moss or lower alkylene formed by adhering to each other, q has the same meaning as above.] Method for producing a phthalimide derivative. General formula [In the formula, ), Z represents an oxygen source -T, or (d represents a methylene group) A herbicide comprising an N-phenyltetrahydrophthalimide derivative as an active ingredient.