JPS5838256A - N-phenyltetrahydrophthalimide derivative, its preparation and herbicide containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:An N-tetrahydrophthalimide derivative expressed by formula I(R is 1-4C alkyl,3-4C alkenyl or 3-4C alkynyl, except when R is isopropyl). EXAMPLE:N-(4-Choloro-2-fluoro-5-propargyloxyphenyl)-3,4,5,6-tetrahydro phthalimide. USE:A herbicide having improved effects in a small amount of the chemical without the phytotoxicity to cotton, soybean, corn, etc. and improved herbicidal action on barnyard grass, bulrush and arrowhead. PROCESS:An N-(4-chloro-2-fluoro-5-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide expressed by formula II is reacted with a halide expressed by the formula RX in the presence of a base to give the compound expressed by formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the following formula:
40 alkenyl group or when the carbon number R is an inpropyl group, N-7-ethyl tetra-dolphthalite tps conductor represented by (to) general formula (]1) RX (u) [in the formula , R represents the aforementioned O and υ, and X represents a halogen atom. ] The halogen compound and N-(dark cIQ---
Fluoro-j-human diphenyl)-j, 4,
j, 4-tetrahyto-phthalimide in the presence of a base in the presence of a base, and (J) a method for producing N-phenylphthalimide derivative 014 represented by general formula (1) and (J) represented by general formula (I). It is a herbicide containing the compound as an active ingredient.

Conventional N-7 ale tetrahydrophthali! It is known from Japanese Patent Publication No. 90 that Il- and Il- derivatives have herbicidal activity.
(4t-chlorocoprooloroj-impropoxyphenyl)-3,da,5,4-tetrahydrophthalide has excellent herbicidal efficacy at an extremely low dose, and at the same time is selective for important crops such as corn. However, as a result of continuing research on similar compounds, we found that the group of compounds represented by the general formula have similarly excellent herbicidal efficacy at low doses. and corn.

The present invention was completed after discovering the excellent property that the drug has almost no effect on 0** crops such as cotton, dice, and rice at doses that exhibit herbicidal activity against weeds.

More specifically, when the compound of the present invention is used in field soil treatment and foliage treatment, existing similar compounds, such as JP-A-Shoj /-5/! ;2/issue and Tokukaisho! ; 6-1
Compared to the compounds described in Publication No. 39306, etc., it has significantly superior herbicidal activity, has selectivity for important crops such as mata, dice, and corn hay, and is effective against rice when used under water pressure. It is less harmful and exhibits a stronger herbicidal effect than existing similar compounds, and also has excellent herbicidal activity against Japanese millet, firefly, and weed, for which no activity has been found with Mukuro compounds. It can be said that the compound of the present invention has a particularly excellent property that it can be safely used on corn when used in field soil treatment and foliage treatment.

Next, the method for producing the compound of the present invention will be explained in detail. The compound represented by general formula (1) can be synthesized according to the following reaction formula.

(1) [In the formula, R and X are as defined above. ] This reaction is carried out in a polar aprotic solvent such as dimethyl*lumamide or dimethyl sulfoxide using a base such as potassium carbonate or sodium carbonate at room temperature, with heating if necessary.

The raw material compound N-(4-riQCI-,2-fluoroj-hydroxyphenyl)-Jeda,j7-tetrahydro-satalimide was synthesized from the known compound Kochloder fluorophenol and was synthesized from 4S-
Alnorcochloroderfluorophenol! , 4
1. ! ;, obtained by O reaction with tetrahydrophthal axillary anhydride (q/# Gansho 54-tei 7g No. 76).

Next, the present invention will be explained in more detail with reference to Examples.

Example/ Do(cuchloro-twofluoro-5-propargyloxyphenyl)-j, 9. j.

ni-tetrahydrophthalimide (compound 1) N-(darklow-cofluoroj-hydroxyphenyl)-j
, Q, j, j-tetrahydrophthalimide/P was dissolved in 10 dK of dimethylformamide, and anhydrous potassium carbonate O, St was added and stirred at room temperature. After stirring at around 90°C for 30 minutes, propargyl bromide/P was added and stirred for 3 hours in SO~OoC.
Extracted with ether. The ether layer was washed with water, dried over anhydrous sodium sulfate, and the concentrated residue was purified by silica gel column chromatography. crystals were obtained. mp/
j≦, Da °C Binary analysis value Actual value I) 6809H1 Chi) Example W Chess Chi) Da J Calculated value 0 to /, 1g H Da, /? Nj,?
, 2ilI Vaginal Example/The compounds shown in Table jI1 were synthesized in the same manner as in 2ilI Vaginal Example/.

/'' 7/ , -' Table 1 The compound numbers shown in Table 1 are commonly used in the following formulation examples and examples.

Furthermore, in order to clearly clarify the properties of the present compound, when actually using the compound of the present invention as a comparative compound using the similar compounds in Table 1, the active substance itself can be sprayed.
Further, any formulation form such as an aquarium, an emulsion, a granule, a fine granule, a powder, etc. can be used.

When using the compound of the present invention, it can be used as an active ingredient in an amount of about θ, θ/~j0P, although it varies depending on the formulation form, applicable crops, applicable weeds, soil conditions, etc., but is preferably used as an active ingredient. θ, /~-〇? It is.

In producing these pharmaceutical products, solid carriers include, for example, mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite), plants, etc. Examples include quality powders (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resins, polyvinyl chloride, Danzl gum, ketone resins, etc.), alumina, waxes, etc.

Examples of liquid carriers include alcohols (methyl alcohol, ethyl alcohol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, methylnaphthalene, etc.),
Chlorinated hydrogen cinnades (chloroform, carbon tetrachloride, monochlorobenzene, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (7setone, methyl ethyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol) acetate, etc.), acid 7amides (dimethylformamide, etc.), nitriles (acetonitrile, etc.), ether alcohols (ethylene glycol ethyl ether, etc.), and water.

The surfactant used for the purpose of emulsification, dispersion, spreading, etc. may be nonionic, anionic, cationic, or amphoteric.

Examples of surfactants used include polyoxyethylene alkyl ether, polyoxyethylene alkyl 7
Reel ether, polyoxyethylene fatty acid ester,
Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, oxyethylene oxypropylene polymer, polyoxyethylene alkyl phosphate ester, fatty acid salt, alkyl sulfate ester salt, alkyl sulfonate, alkylaryl sulfonate, alkyl phosphate ester salt, These include polyoxyethylene alkyl sulfate, 9th class ammonium salt, etc., but are of course not limited to these. Furthermore, for these purposes, gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol, and the like may be used as adjuvants, if necessary.

When formulating the compound of the present invention as a herbicide, the compound of the present invention is used as an active ingredient at θ,/~? Although it is possible to contain .theta., it is preferable to contain .theta., j to 10.

Examples of blending the compounds of the present invention are shown below.

The names of the compounds are indicated by the numbers in the above examples (Table 1).

Formulation Example/ Compound (1) of the present invention 0 parts by weight, 3 parts by weight of alkyl sulfate, 75 parts by weight of lignin sulfonate and 75 parts by weight of white carbon are thoroughly ground and mixed to obtain an irrigation agent.

Formulation Example: 0 parts by weight of the present compound c2), 6 parts by weight of jo% powder of polyoxyethylene alkylaryl ether, parts by weight of lignin sulfonate, and 7 parts by weight of white carbon.
Two parts by weight are thoroughly ground and mixed to obtain an irrigation agent.

Formulation Example 3 70 parts by weight of the compound of the present invention (3), emulsifier Tsurupol,!
70 parts by weight of Al:0 (registered trademark of Toho Chemical), 60 parts by weight of cyclohexanone, and 0 parts by weight of xylene are thoroughly mixed to obtain an emulsion.

Formulation Example q Compound of the present invention) 0.5 parts by weight, white carbon 0.
5 parts by weight of bentonite, 33 parts by weight of bentonite, and 6 parts by weight of clay were ground and mixed, water was added and the mixture was thoroughly kneaded, followed by granulation and drying to obtain granules.

Formulation example j 3 parts by weight of the compound (6) of the present invention, 0.0 parts by weight of isopropyl phosphate.
3 parts by weight, 66.7 parts by weight of clay, and 3 parts by weight of talc are thoroughly pulverized and mixed to obtain a powder.0 11 Right 311]HiY Neck 1■7 The compound of the present invention also aims to improve its efficacy as a herbicide. ,
It can also be used in combination with other herbicides.

In some cases, synergistic effects can be expected. Examples of this include -, dichlorophenoxyacetic acid; - methyl - dichlorophenoxyacetic acid; Noxy**, comethyl-l-chlorophenoxyacetic acid (including esters and salts)
2.4t-dichlorophenyluda'-nitrophenyl ether; J, 41. A-)
lychlorphenyl-V-nitrophenyl ether-req loader-trifluoromethylphenyl-J-ethoxy-cnido-phenyl ether; 44-dichlorophenyl-3-methoxycarbonyl-q-nitrophenyl ether and other di-7enyl ether-based defrosting agents, 1-chloro-44,6-pisethyl-aho/, J, j-triazine 11-chloro Ruder ethylamino-6-improvylamino-/.

3.
! -triazine; daramino-6-tert-butyl-3-methylthio-/.

2m-tei - Tori 1 Jin! -triazine herbicides such as J-(J,4I-dichlor7!nyl)-/,/-dimethylurea; J-CJe4t-dichlorophenyl)-7
-Medoxy/-methyneurea, /-(J,2-dimethylbenzyl)-J-p-)lylurea, /,/-dimethyl-3-(J-)lifluoromethylphenyl)urea and other urea-based herbicides , isopropyl-N-(J-chlorphenyl)carbamate; methyl-M-(J, f-dichlorophenyl)carbamate Cape carbamate herbicide, 5-(4t-chlorbesidyl)-M,M-diethylthiolcarbamate; 8-ethyl-M, M-hexamethylenethiol carbamate; 8-ethyl-N, M-diynebutylthiol carbamate, S-ethyl-M, M-
Di-Normal Propylthiol Carbamate, 8-Normal Propyl-N, N-Dinoyl Marbuq Biruthiol Carbamate Herbicide, J, Dirziclone Propionanilide; N-Methoxymethyl-96-Dinity-a- Chloracetanilide; --Chloro-', 6-dinityl-N.-(butoxymethyl)-acetanilide; Coke Chloro-'.

Acid anilide herbicides such as 6'-diethyl-N-(n-proponedethyl)-7cetanilide; N-chloroacetyl-M-(co,6-dinitylphenyl)-glycine ethyl ester; y-(-monoethyl-6-
methylphenyl)-N-(,2-methoxy-/-methyl)acetamide, j-bromo-3-sec-butyl-6-methyluracil; 3-cyclohexyl.

6-drimethylene urarel type uracil herbicide, /
/'-dimethyl-q, l-bispyridinium chloride pyridinium chlorine defrosting agent M, M-bis(phosphonomethyl)-glycine.

〇-Ethyl〇-(-Sitatroj-Methyl7enyl)
-N-Secondary-butyl carcinamide thioate,
Phosphorus-based herbicides such as S-(,2-methyl-/-piperidylcarbonylmethyl) 0.0-di-n-propyldithiowood sulfate etc. 1a, α1α-trifluoro-,2,6
-Sinitro N, M-dipropyl-p-toluidine-based toluidine herbicide, j-Taleyaributyl-3-(
4t-dichloro-5-inpropoxy-7enyl)-
/, J, 4f-oxadiazolin-noone; 3-inpropyl-/H-co, /.

J-benzothiadiazine-←)-JR-one-ka-11 dioxide, α-(β-naphthoxy)-brobionanilide, da(λ,+-dichlorobenzoyl)-/, J
-dimethynopyrazol-5-yl p-)
Shikimoto-), +-71 Nilsul-Kinyl-7, /, /-trifluoromerukino-)luidide, Darkrolow S-methylamino-λ-(3-trifluoromethylphenyl)pyridazine-J(,21)- on.

/-Methyl-J-phenyl-5-(J-1 trifluoromethylphenyl)-pyridin-4t(/H)-one, -1methyl-tei-phenylsul-trifluoromethylsulfoanilide, r-<J :q'-dichlorophenyl)
-gumethyltetrahydro-/, 2,4t-diazole-J,j-dione, darkchloride-j-methylamino-(J-trifluoromethylphenyl)pyridazin-3(JH)-one, etc. .

It is not limited to these. Furthermore, the compounds of the present invention can be used as insecticides as required.

Mixed use with insecticides, fungicides, plant growth regulators, and fertilizers is also considered chintz. In each of the Examples, the evaluation of the phytotoxicity of the cultivated material and the efficacy against weeds was performed in accordance with the criteria described below, and was expressed as an evaluation value using an integer from θ to j. Calculate the ratio of the fresh weight of the above-ground parts to the fresh weight of the plants in the forest and untreated areas.
Regarding KK, the medicinal properties and herbicidal efficacy were evaluated based on the standards shown in the table below, using numbers measured at 5 dimensions from θ. Evaluation value θ- for moth-cultured plants or/or evaluation for weeds 1'1l
Jttakeq is generally considered to have a reasonable effect of protecting cultivated plants or controlling weeds.

Only in the case of maroka and paddy rice tests, the evaluation value is calculated based on the dry weight of the title object.

Example 2 Post-germination foliage treatment efficacy comparative test direct qIk/θ(
1) A cylindrical plastic beaker with a height of 10 em was filled with field soil, and weed seeds of Japanese barnyard grass, oat, field mustard, and Japanese strawberry were sown. After covering with soil and growing in a greenhouse for 2 weeks, apply a predetermined amount of the chemical to the entire stem and leaf area from above the object using a hand sprayer. The herbicidal efficacy was investigated.

The results are shown in Table 3. The test was carried out at a ratio of 7 A fFb s and 8 spraying by preparing an emulsion and dispersing a predetermined amount in water (including the spreader). Ta.

Table 3 Example 3 Corn weeding test (stem and foliage treatment) Tate J
Pack field soil into plastic trays of 3 cm, horizontal JS cut, and height/θ equipment, and add corn, ichito, sunflowers, Ebisugusa, Malva morning glory, Wildflowers,
After sowing chickweed and foxtail grass and growing them in a greenhouse for one week, the seeds were grown in a greenhouse.
One of these trays was arranged in a frame of an, and a predetermined amount of each chemical was applied to the entire surface of the frame using a small sprayer from above the plant body. After spraying the chemicals, the plants were grown in a greenhouse for 1 week, and then the herbicidal efficacy of each plant was investigated. The results are shown in the table. Using an emulsion made according to the prescription of the treatment agent, the emulsion was emulsified in 1 liter of water with a diluted solution added to it.

In addition, the Tenshinsake KeyakiaK of the plants when treated with medicinal cutting was different, but they were at the 7- to 3-leaf stage and the plant height was - - - -.

Table 4* Atrazine e Example q Field field pre-germination soil treatment efficacy comparison test Diameter/θm
A cylindrical plastic beaker with a height of 10 m was filled with field soil and seeded with crop seeds of maize, corn, and rhubarb, and weed seeds of morning glory, corn, sorghum, and foxtail.

After soiling, a predetermined amount of the raw material was made into an emulsion, diluted with water, and treated with a hand blower.

Thereafter, they were grown in a greenhouse, and the herbicidal efficacy was observed 0 days after treatment, and the results are shown in Table 5. Upland soil was packed into plastic trays of size 1/2 cm, and sown with morning glory, Japanese ichi, Ebisugusa, Seiban sorghum, and corn.

Disperse a predetermined amount of irrigation agent in water, /are per j! The entire surface of the soil was sprayed at the same rate as above the tray using a small sprayer.

After the treatment, the plants were placed in a greenhouse for -θ days and their phytotoxicity and herbicidal efficacy were investigated.The results are shown in Table 6.

Table 6 Example 6 Flooding treatment / / ! After filling a 000 m Wagner pot with paddy soil containing various weed seeds and adding water to a depth of 41 cm, 3. S'1#: Rice seedlings and Urikawa tubers are transplanted and grown in a greenhouse for 2 days. A predetermined amount of drug formulated into an emulsion is dispersed in water, and 70% per are
Irrigation treatment was carried out in the pot at the rate of stone. After growing in the laboratory for an additional three weeks, each plant was examined for herbicidal efficacy.

Incidentally, the poles of Japanese millet, firefly, and broad-leaved weeds (e.g., Japanese azalea, azalea, and kikashigusa) were mixed into this soil.

Table 7 shows the survey results for the three cypress trees mentioned above.

Table 7 Procedural Amendment (Voluntary) Date: July 72, 1960 Director General of the Patent Office Shima 1) Tono Haruki 1, Indication of QS 1981 Patent Application No. Isgotyt Evening No. 2, Name of Invention N-7 Koniru Tetrahydrophthalimide derivatives, their production methods, and herbicides containing them as active ingredients 3
Relationship with the case of the person who made the supplementary 1st case Patent applicant address 5-1 Kitahama, Higashi-ku, Osaka-shi Akiji name (209
) Hijikata, Representative of Sumitomo Chemical Chemical Co., Ltd.
Takeshi 4 Representative Director Address: 5-15-5 Kitahama, Higashi-ku, Osaka City, Detailed explanation of the invention in the specification to be amended Copper page of the specification, Table 1, Physical property column for compound number (/θ) Add and insert the following.

rmp //j-116℃" that's all

Claims (1)

[Scope of claims]
represents an alkenyl group or a furkynyl group having 3 to 2 carbon atoms. However, if R is an isopropyl group, it is not included.
j conductor. (2) General formula [In the formula, R represents an alkyl group having 1-9 carbon atoms, an alkenyl group having 3 to 3 carbon atoms, or a furkynyl group having a Fi order number of 3 to 5. However, when R is an isopropyl group, it is not included. ] A halogen compound represented by N-(4-chloro-1-fluoro-j-hydroxyphenyl)-3,'I-,! ,
The general formula is characterized in that it is reacted with tetrahydrophthalimide in the presence of a base [wherein R is the above-mentioned and shishi]. ] A method for producing the N-phenyltetra dolphthaloid derivative shown in the following. ω) General formula [wherein R is an alkyl group having 7 to q carbon atoms, 3 to 4 carbon atoms]
t represents a fulkenyl group or a fulkynyl group having 3 to 3 carbon atoms, provided that R is an isopropyl group is not included. Characteristic herbicide. (9) The active ingredient is N-(dark fluoro-fluoroj-buqpargyloxyphenyl)-3゜G,j,j
3. The selective herbicide for corn according to claim 3, which is "t-P".