JPH0331706B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has the following features: (1) General formula () [In the formula, R is an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, or an alkenyl group having 3 to 4 carbon atoms.
represents an alkynyl group. However, it is not included when R is an isopropyl group. ] N-phenyltetrahydrophthalimide derivative represented by (2) general formula () RX () [wherein R is as described above and X represents a halogen atom. ] A halogen compound represented by and N-(4-bromo-2-fluoro-5-hydroxyphenyl)-
A method for producing an N-phenylphthalimide derivative represented by the general formula (), characterized by reacting 3,4,5,6-tetrahydrophthalimide in the presence of a base, and (3) a method for producing an N-phenylphthalimide derivative represented by the general formula (). It is a herbicide containing a compound as an active ingredient. Conventionally, it was reported in Japanese Patent Publication No. 11940-1973 that N-phenyltetrahydrophthalimide derivatives have herbicidal activity.
It is publicly known in the publication No. As a result of conducting research on tetrahydrophthalimide derivatives, the present inventors first discovered that N-(4-bromo-2-fluoro-5-isopropoxyphenyl)-3,4,
We discovered that 5,6-tetrahydrophthalimide and other compounds have excellent herbicidal efficacy at extremely low doses, and at the same time are selective for important crops such as corn.As a result of continuing research on similar compounds, we discovered that , a drug in which the group of compounds represented by the general formula () similarly has excellent herbicidal efficacy at low doses, and also exhibits herbicidal activity against weeds in important crops such as corn, cotton, soybean, and rice. The present invention was completed by discovering the excellent property that the amount has almost no effect. 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-51-
Compared to the compounds described in No. 51521 and JP-A No. 55-139305, it has significantly superior herbicidal activity, has selectivity for important crops such as cotton, soybeans, and corn, and is effective in rice fields. When used, it is less harmful to rice and has a stronger herbicidal effect than existing similar compounds, and it also has excellent herbicidal activity against Japanese millet, firefly, and urticaria, for which such compounds have not been found to have any activity. are doing. 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 the general formula () can be synthesized according to the reaction formula below. [In the formula, R and X are as described above.] ] This reaction is carried out at room temperature using a base such as potassium carbonate or sodium carbonate in a polar aprotic solvent such as dimethylformamide or dimethyl sulfoxide.
This is done by heating if necessary. The raw material compound N-(4-bromo-2-fluoro-5
-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide is a known compound 2-
It is obtained by the reaction of 5-amino-2-bromo-4-fluorophenol synthesized from bromo-4-fluorophenol and 3,4,5,6-tetrahydrophthalic anhydride. Next, the present invention will be explained in more detail with reference to Examples. Example 1 N-(4-bromo-2-fluoro-5-propargyloxyphenyl)-3,4,5,6-tetrahydrophthalimide (compound (6)) N-(4-bromo-2-fluoro-5 -hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide (1.56 g) in dimethylformamide (10 ml)
0.4 g of anhydrous potassium carbonate was added and stirred at room temperature. After stirring at around 40°C for 30 minutes, 1 g of propargyl bromide was added and stirred at 80 to 90°C for 4 hours. After cooling to room temperature, the reaction solution was poured into water and 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 to obtain 0.85 g of crystals. mp127-128℃ NMR (δppm) CDCl ₃ 1.75 (4H, m), 2.4 (4H, m), 2.6 (1H), 4.7
(1H), 6.9 (1H, d), 7.4 (1H, d) The compounds shown in Table 1 were synthesized in the same manner as in Example 1.

[Table] The compound numbers shown in Table 1 are commonly used in the following formulation examples and examples. In order to clarify the properties of the compounds of the present invention more clearly, similar compounds in Table 2 are used as comparative compounds.

[Table] When actually using the compound of the present invention, the raw material itself can be sprayed, and hydrating powders, emulsions,
Any formulation form such as granules, fine granules, or powders can be used. When using the compound of the present invention, the active ingredient is approximately 0.01% per are, although it varies depending on the formulation form, applicable crops, applicable weeds, soil conditions, etc.
It can be used in an amount of ~50g, preferably 0.1~20g. In preparing these pharmaceutical products, solid carriers such as mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum,
calcium carbonate, apatite, etc.), vegetable powders (soybean flour, wheat flour, wood flour, tobacco flour, starch,
crystalline cellulose, etc.), polymer compounds (petroleum resin,
(polyvinyl chloride, dammargum, ketone resin, 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 hydrocarbons (chloroform, carbon tetrachloride, monochlorobenzene, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, etc.), acid amides (dimethylformamide, etc.) ), nitriles (such as acetonitrile), ether alcohols (such as ethylene glycol ethyl ether), 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 alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, oxyethylene oxypropylene polymer, polyoxy Ethylene alkyl phosphate ester, fatty acid salt,
Alkyl sulfate salts, alkyl sulfonates, alkylaryl sulfonates, alkyl phosphate salts, polyoxyethylene alkyl sulfate esters, quaternary ammonium salts, etc.
Of course, it is not limited to these.
In addition, gelatin,
Casein, sodium alginate, starch, agar, polyvinyl alcohol, etc. can be used as adjuvants. When the compound of the present invention is formulated as a herbicide, the compound of the present invention can be contained as an active ingredient in an amount of 0.1 to 95%, preferably 0.5 to 80%. Examples of blending the compounds of the present invention are shown below. In addition, the compound names are indicated by the numbers in the above-mentioned examples (Table 1). Formulation Example 1 80 parts by weight of the compound (1) of the present invention, 3 parts by weight of alkyl sulfate, 2 parts by weight of lignin sulfonate and 15 parts by weight of white carbon are thoroughly ground and mixed to obtain a wettable powder. Formulation Example 2 80 parts by weight of the compound of the present invention (2), 6 parts by weight of 50% polyoxyethylene alkylaryl ether powder, 2 parts by weight of lignin sulfonate, and 12 parts by weight of white carbon were thoroughly ground and mixed to form a wettable powder. obtain. Formulation example 3 10 parts by weight of the compound of the present invention (3), emulsifier Sorbol
10 parts by weight of 2680 (registered trademark of Toho Chemical), 60 parts by weight of cyclohexanone, and 20 parts by weight of xylene are thoroughly mixed to obtain an emulsion. Formulation example 4 0.5 parts by weight of the present compound (4), white carbon
0.5 parts by weight, 35 parts by weight of bentonite and clay
After thoroughly grinding and mixing 64 parts by weight, adding water and kneading well, the mixture is granulated and dried to obtain granules. Formulation example 5 3 parts by weight of the compound of the present invention (2), isopropyl phosphate
0.3 parts by weight, 66.7 parts by weight of clay, and 30 parts by weight of talc are thoroughly ground and mixed to obtain a powder. Furthermore, the compound of the present invention can be used in combination with other herbicides in order to improve its effectiveness as a herbicide, and in some cases, a synergistic effect can be expected. Examples include phenoxy herbicides such as 2,4-dichlorophenoxyacetic acid; 2-methyl-4-chlorophenoxybutyric acid; 2-methyl-4-chlorophenoxyacetic acid (including esters and salts);
2,4-dichlorophenyl-4'-nitrophenyl ether; 2,4,6-trichlorophenyl-
4'-nitrophenyl ether; 2-chloro-4-
Trifluoromethylphenyl-3'-ethoxy-
Diphenyl such as 4'-nitrophenyl ether; 2,4-dichlorophenyl-4'-nitro-3'-methoxyphenyl ether; 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitrophenyl ether Ether herbicide, 2-chloro-4,
6-bisethylamino-1,3,5-triazine; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine; 2-methylthio-4,6-bisethylamino-1, 3,
5-triazine; 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine;
Triazine herbicides such as 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-one, 3-(3,4-dichlorophenyl)-1,1-dimethylurea; 3 -(3,4
-dichlorophenyl)-1-methoxy-1-methylurea, 1-(2,2-dimethylbenzyl)-3
-p-tolylurea, 1,1-dimethyl-3-
Urea herbicides such as (3-trifluoromethylphenyl)urea, isopropyl-N-(3-chlorophenyl)carbamate; methyl-N-(3,4
Carbamate herbicides such as -dichlorophenyl)carbamate, S-(4-chlorobenzyl)-N,
N-diethylthiol carbamate; S-ethyl-N,N-hexamethylenethiol carbamate; S-ethyl-N,N-diisobutylthiol carbamate, S-ethyl-N,N-dinormalpropylthiol carbamate, S-normalpropyl- Thiol carbamate herbicides such as N,N-di-normalpropylthiol carbamate,
3,4-dichloropropionanilide; N-methoxymethyl-2,6-diethyl-α-chloroacetanilide; 2-chloro-2',6'-diethyl-N
-(Butoxymethyl)-acetanilide; 2-chloro-2',6'-diethyl-N-(n-propoxyethyl)-acetanilide; N-chloroacetyl-
Acid anilide herbicides such as N-(2,6-diethylphenyl)-glycine ethyl ester, 2-chloro-N-(2-ethyl-6-methylphenyl)-N-
(2-methoxy-1-methyl)acetamide, 5
-bromo-3-sec-butyl-6-methyluracil; uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil, 1,1'-
Pyridinium chlorine herbicides such as dimethyl-4,4-bispyridinium chloride, N,N-bis(phosphonomethyl)-glycine, O-ethyl-O-
(2-nitro-5-methylphenyl)-N-secondary-butylphosphoroamidothioate, S-
(2-methyl-1-piperidylcarbonylmethyl)
Phosphorus herbicides such as O,O-di-n-propyldithiophosphate, α,α,α-trifluoro-
Toluidine herbicides such as 2,6-dinitro-N,N-dipropyl-p-toluidine, 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4 -Oxadiazolin-2-one; 3-isopropyl-1H-2,
1,3-Benzothiadiazin-(4)-3H-one-
2,2-dioxide, α-(β-naphthoxy)-propionanilide, 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazole-5-
p-toluenesulfonate, 4'-phenylsulfonyl-1,1,1-trifluorosulfono-O-toluidide, 4-chloro-5-methylamino-2-(3-trifluoromethylphenyl)
Pyridazin-3(2H)-one, 1-methyl-3-
Phenyl-5-(3-trifluoromethylphenyl)pyridin-4(1H)-one, 2-methyl-4
-Phenylsulfonyltrifluoromethylsulfoanilide, 2-(3',4'-dichlorophenyl)-
4-methyltetrahydro-1,2,4-oxadiazole-3,5-dione, 4-chloro-5-methylamino-2-(3-trifluoromethylphenyl)pyridazin-3(2H)-one, etc. Examples include, but are not limited to. Furthermore, the compound of the present invention can be used in combination with insecticides, nematicides, fungicides, plant growth regulators, fertilizers, etc., if necessary. Next, the present invention will be explained in more detail by giving examples as herbicides. In each of the following examples as herbicides, evaluations of phytotoxicity to cultivated plants and efficacy against weeds were all in accordance with the criteria described below. , expressed as an evaluation value using an integer from 0 to 5. At the time of the survey, the fresh weight of the above-ground parts of the plants that remained withered was measured, and the ratio (%) when compared with the fresh weight of the plants in the untreated area was calculated. Cultivated plants and weeds were evaluated for chemical damage and herbicidal efficacy using numbers from 0 to 5 based on the criteria shown in the table below. An evaluation value of 0 or 1 for cultivated plants or an evaluation value of 5 or 4 for weeds is generally considered to be an appropriate cultivated plant protection effect or weed control effect. In addition, only in the case of rice trials, evaluation values are calculated based on the dry weight of the plants.

【table】

[Table] Example 2 Comparative test on post-germination foliage treatment efficacy A cylindrical plastic beaker with a diameter of 10 cm and a height of 10 cm was filled with field soil, and weed seeds of Japanese barnyard grass, oat, wild mustard, and Japanese grass were sown. After covering with soil,
After growing in a greenhouse for two weeks, a predetermined amount of the chemical was applied to the entire stem and leaves from the top of the plant using a hand sprayer. After the chemical treatment, each plant was grown in a greenhouse for another three weeks, and then the herbicidal efficacy of each plant was investigated. The results are shown in Table 3. The processing agent was formulated into an emulsion, a predetermined amount was dispersed in water (including a spreading agent), and the test was conducted at a rate of 5 sprays per are.

[Table] Example 3 Corn weed control test (stem and foliage treatment) Field soil was packed into plastic trays measuring 35 cm in height, 25 cm in width, and 10 cm in height, and corn, Japanese croaker, sunflower, Ebisu grass, Malva morning glory, Wild mustard, Chickweed, and Wildflower were sown. After growing in a greenhouse for two weeks, compare two of these trays in a frame of 50 cm in length, 100 cm in width, and 40 cm in height, and spray a predetermined amount of each chemical over the entire frame with a small sprayer from above the plants. The stems and leaves were treated. After being grown in a greenhouse for an additional three weeks after spraying the chemicals, each plant was examined for chemical damage or herbicidal efficacy. The result is the fourth
Shown in the table. The processing agent used was an emulsion made according to the recipe in Formulation Example 3, and 25ml of water with a spreading agent added.
An emulsified product was tested. The size of plants when treated with chemicals varies depending on the species, but approximately 1 to 1 true leaf
The plant height was 2 to 20 cm at the three-leaf stage.

[Table] Example 4 Pre-emergence soil treatment efficacy comparison test for upland fields A cylindrical plastic beaker with a diameter of 10 cm and a height of 10 cm was filled with upland soil, and crop seeds of corn, cotton, and soybean and weed seeds of morning glory, Japanese yam, Seiban sorghum, and foxtail were added. was sown. After covering with soil, a predetermined amount of the raw material was made into an emulsion, diluted with water, and the soil was treated with a hand sprayer. Thereafter, the plants were grown in a greenhouse, and the herbicidal efficacy was observed on the 20th day after treatment. The results are shown in Table 5.

【table】

[Table] Example 5 Pre-germination soil treatment test A plastic tray measuring 35 cm in length, 25 cm in width, and 15 cm in height was filled with field soil and sown with morning glory, Japanese yam, Ebisugusa, Seiban sorghum, and corn. A predetermined amount of the hydrating agent was dispersed in water, and the entire surface of the soil was sprayed from above the tray using a small sprayer at a rate of 5 sprays per are. After treatment, the plants were placed in a greenhouse for 20 days and their phytotoxicity and herbicidal efficacy were investigated. The results are shown in Table 6.

[Table] Example 6 Flooding Treatment Fill a 1/5000a Wagner pot with paddy soil containing various weed seeds, add water to a depth of 4 cm, and then transplant rice seedlings at the 3.5 leaf stage and Urikawa tubers. and grow in a greenhouse for 2 days. A predetermined amount of the drug formulated into an emulsion was dispersed in water and irrigated into the pot at a rate of 10 per are. After growing in the greenhouse for an additional three weeks, the herbicidal efficacy of each plant was investigated. The soil was mixed with seeds of Japanese millet, firefly, and broad-leaved weeds (Japanese aspen, Japanese azalea, Kikashigusa, etc.). Table 7 shows the results of the above three types of investigations.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, or an alkynyl group having 3 to 4 carbon atoms. However, it is not included when R is an isopropyl group. ] N-phenyltetrahydrophthalimide derivative 2 represented by the general formula RX [wherein, X represents a halogen atom]. R represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, or an alkynyl group having 3 to 4 carbon atoms. However, it is not included when R is an isopropyl group. ] A halogen compound represented by and N-(4-bromo-
2-fluoro-5-hydroxyphenyl)-3,
General formula characterized by reacting 4,5,6-tetrahydrophthalimide in the presence of a base [In the formula, R is as described above. ] Production method 3 of N-phenyltetrahydrophthalimide derivative represented by general formula [In the formula, R represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, or an alkynyl group having 3 to 4 carbon atoms. However, it is not included when R is an isopropyl group. ] A herbicide characterized by containing an N-phenyltetrahydrophthalimide derivative as an active ingredient. 4 The active ingredient is N-(4-bromo-2-fluoro-5-propargyloxyphenyl)-3,4,
The selective herbicide for corn according to claim 3, which is 5,6-tetrahydrophthalimide.