JPH0412263B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to specific benzanilide derivatives and herbicides containing the benzanilide derivatives. The present inventors investigated the herbicidal activity of various compounds and discovered the unique action of a specific benzanilide derivative, leading to the completion of the present invention. That is, the first invention of the present invention is a benzanilide derivative shown below, and the second invention is a herbicide containing the benzanilide derivative as an active ingredient. general formula (In the formula, X is a hydrogen atom, a chlorine atom, a methyl group,
It represents a methoxy group, and n represents an integer of 1 to 3. ) Next, typical benzanilide derivatives according to the present invention are shown in Table 1.

【table】

【table】

【table】

[Table] The compound of the present invention combines o-chloroaniline and trifluoromethanesulfonic anhydride or trifluoromethanesulfonic acid halide with an organic basic substance such as triethylamine and pyridine, or
o-Chlortrifluoromethanesulfonanilide is synthesized by reaction in inert organic solvents such as toluene, hexane, dichloromethane, and chloroform in the presence of inorganic basic substances such as NaHCO ₃ and Na ₂ CO ₃ . , obtained o
- Reaction of chlorotrifluoromethanesulfonanilide and various substituted benzoyl chlorides in an inert organic solvent such as acetone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane in the presence of an organic basic substance such as triethylamine and pyridine. By this, various desired 2'-chloro-N-
A trifluoromethanesulfonylbenzanilide derivative can be obtained. Alternatively, by adding a basic substance such as sodium hydride or sodium ethoxide to o-chlorotrifluoromethanesulfonanilide in an inert organic solvent as described above, and then reacting with various substituted benzoyl chlorides. , various types of 2'-chloro-
N-trifluoromethanesulfonylbenzanilide derivatives can be obtained. Alternatively, an aqueous solution containing a chemical equivalent of NaOH or KOH is added to o-chlorotrifluoromethanesulfonanilide, and the water in this aqueous solution is completely evaporated to dryness.
By obtaining the sodium salt or potassium salt of o-chlorotrifluoromethanesulfonanilide and reacting it with various substituted benzoyl chlorides in an inert organic solvent such as those mentioned above, various desired 2' A -chloro-N-trifluoromethanesulfonylbenzanilide derivative can be obtained. Next, a typical synthesis example will be shown. Synthesis Example 1 (Synthesis of o-chlorotrifluoromethanesulfonanilide) 22.61 g of o-chloroaniline and 20.00 g of triethylamine were dissolved in 400 ml of dichloromethane, and while cooling this solution with ice to below 5°C, anhydrous Trifluoromethanesulfonic acid 50.00g
A homogeneous solution prepared by dissolving this in 100 ml of dichloromethane was added dropwise little by little. After the dropwise addition was completed, the reaction solution was heated and stirred under dichloromethane reflux for 3 hours to complete the reaction. After the reaction is complete,
The reaction solution was washed with 200 ml of water, then 5% NaOH
Extract with 200 ml of water 3 times, add HCl to the NaOH aqueous layer to make it neutral and acidic, extract this aqueous solution with 200 ml of dichloromethane 3 times, and dehydrate the dichloromethane layer with anhydrous magnesium sulfate.
When the solvent was recovered using a rotary evaporator, 33.7 g of o-chlorotrifluoromethanesulfonanilide, the target product, was obtained as an evaporation residue. yield
73.2%, melting point 75-77°C. Synthesis Example 2 (Synthesis of Compound No. 1 in Table 1) 0.28 g of 60% oily sodium hydride was added to 10 ml of dry dioxane, followed by 1.80 g of o-chlorotrifluoromethanesulfonanilide. After stirring this solution at room temperature for about 5 minutes, o-chlorobenzoyl chloride was added to the solution.
A solution of 1.20 g dissolved in 10 ml of dry dioxane was added dropwise little by little at room temperature. After the dropwise addition was completed, stirring was continued for 5 hours at room temperature (18 to 20°C) to complete the reaction. Add the reaction solution to 5% hydrochloric acid water.
Pour into 150ml, extract with dichloromethane 50ml x 3 times, and dilute the dichloromethane layer with 5% Na ₂ CO ₃ 50ml x 2.
After washing twice with 50 ml of water twice, it was dehydrated with anhydrous magnesium sulfate, and then the solvent was recovered using a rotary evaporator. A small amount of n in the evaporation residue
-Hexane was added for crystallization to obtain 2.31 g of the desired product, 2,2'-dichloro-N-trifluoromethanesulfonylbenzanilide. Yield 83.7
%, and the melting point was 74-79°C. Synthesis Example 3 (Synthesis of Compound No. 2 in Table 1) 2.00 g of o-chlorotrifluoromethanesulfonanilide and 0.78 g of triethylamine were dissolved in 15 ml of acetone, and while stirring at room temperature, m-chloro was added to the solution. 1.30g of benzoyl chloride 5
A solution dissolved in ml of acetone was added dropwise little by little. After the dropwise addition was completed, stirring was continued for 7 hours at room temperature to complete the reaction. Add the reaction solution to 5% hydrochloric acid water.
Pour into 150ml, extract with dichloromethane 50ml x 3 times, and dilute the dichloromethane layer with 5% Na ₂ CO ₃ 50ml x 2.
After washing twice with 50 ml of water twice, it was dehydrated with anhydrous magnesium sulfate, and then the solvent was recovered using a rotary evaporator. A small amount of n in the evaporation residue
- When crystallized by adding hexane, the target product
2.06 g of 2',3-dichloro-N-trifluoromethanesulfonylbenzanilide was obtained. Yield 67.2
%, and the melting point was 74-78°C. Synthesis Example 4 (Synthesis of Compound No. 6 in Table 1) 1.80 g of o-chlorotrifluoromethanesulfonanilide and 0.70 g of triethylamine were dissolved in 15 ml of acetone, and p-methyl was added to the solution while stirring at room temperature. 1.07g of benzoyl chloride 10
A solution dissolved in ml of acetone was added dropwise little by little. After the dropwise addition was completed, stirring was continued for 6 hours at room temperature to complete the reaction. Add the reaction solution to 5% hydrochloric acid water.
Pour into 150ml, extract with dichloromethane 50ml x 3 times, and dilute the dichloromethane layer with 5% Na ₂ CO ₃ 50ml x 2.
After washing twice with 50 ml of water twice, it was dehydrated with anhydrous magnesium sulfate, and then the solvent was recovered using a rotary evaporator. The obtained evaporation residue was purified by silica gel column chromatography to obtain the target product, 2'-chloro-4-methyl-N.
-Trifluoromethanesulfonylbenzanilide
0.93g was obtained. The yield was 35.5%, and the melting point was 79.5-82.5°C. Synthesis Example 5 (Synthesis of Compound No. 10 in Table 1) 1.04 g of o-chlorotrifluoromethanesulfonanilide and 0.40 g of pyridine were dissolved in 10 ml of acetone, and while stirring at room temperature, 3,
10ml of 0.84g of 5-dichlorobenzoyl chloride
A solution of 100% dissolved in acetone was added dropwise little by little. After the dropwise addition was completed, stirring was continued for 7 hours at room temperature to complete the reaction. Add the reaction solution to 5% hydrochloric acid 150%
ml, extracted with dichloromethane 50ml x 3 times, and dichloromethane layer was extracted with 5% Na ₂ CO ₃ 50ml x 2.
After washing twice with 50 ml of water twice, it was dehydrated with anhydrous magnesium sulfate, and then the solvent was recovered using a rotary evaporator. A small amount of n in the evaporation residue
-Crystallize by adding hexane to obtain the desired 2′,
1.30 g of 3,5-trichloro-N-trifluoromethanesulfonylbenzanilide was obtained. Yield 75.0
%, and the melting point was 116.5-120°C. Synthesis Example 6 (Synthesis of Compound No. 13 in Table 1) 1.13 g of sodium salt of o-chlorotrifluoromethanesulfonanilide was dispersed in 10 ml of methyl isobutyl ketone, and in this dispersion, while stirring at room temperature, A solution of 0.80 g of 2,6-dimethoxybenzoyl chloride dissolved in 10 ml of methyl isobutyl ketone was added dropwise little by little. After the dropwise addition was completed, stirring was continued for 5 hours at room temperature to complete the reaction. Add 150 ml of dichloromethane to the reaction solution, and add 50 ml of 5% Na ₂ CO ₃ twice to this solution.
It was washed with 50 ml of water twice, dehydrated with anhydrous sodium sulfate, and then the solvent was recovered using a rotary evaporator. As the evaporation residue, the desired 2′−
1.44 g of chloro-2,6-dimethoxy-N-trifluoromethanesulfonylbenzanilide was obtained.
The yield was 84.8%, and the melting point was 135-138.5°C. Synthesis Example 7 (Synthesis of Compound No. 17 in Table 1) 1.80 g of o-chlorotrifluoromethanesulfonanilide and 0.70 g of triethylamine were dissolved in 10 ml of acetone, and while stirring at room temperature, 2,5- Dichlorobenzoyl chloride 1.45
A solution prepared by dissolving G in 10 ml of acetone was added dropwise little by little. After the dropwise addition was completed, stirring was continued for 7 hours at room temperature to complete the reaction. The reaction solution was poured into 150 ml of 5% hydrochloric acid water, extracted with 50 ml of dichloromethane 3 times, and the dichloromethane layer was extracted with 50 ml of 5% Na ₂ CO ₃
After washing twice with 50 ml of water and twice with 50 ml of water, it was dehydrated with anhydrous sodium sulfate, and the solvent was recovered using a rotary evaporator. The obtained evaporation residue was purified by silica gel column chromatography to obtain the desired 2,2',5-trichloro-N-trifluoromethanesulfonylbenzanilide 1.82
I got g. The yield was 60.7%, and the melting point was 104-106.5°C. Depending on the purpose of use, the compound of the present invention can be dissolved in an appropriate liquid carrier (e.g., an organic solvent, etc.) or mixed with an appropriate solid carrier (e.g., a filler, etc.). By adding various auxiliary agents (e.g. emulsifiers, stabilizers, dispersants, etc.) as appropriate, it can be used in formulations in various forms used in general agricultural chemicals, such as emulsions, wettable powders, and granules. can do. The compound of the present invention can be used in combination with one or more other herbicides, pesticides such as insecticides, fungicides, and plant growth regulators, and can also be used in mixed preparations with these. The content of the active ingredient of the compound of the present invention is
10-70%, 40-80% for wettable powders, 1-10 for granules
% (both weight %) is desirable. The amount of the compound of the present invention used is 25 to 500% of the active ingredient.
g/10a, preferably 100-200g/10a
It is. At this dose, there is no chemical damage even to directly sown rice, and it is possible to control all weeds from annual to perennial.It has a particularly high herbicidal effect on weeds of the Cyperaceae family, namely Cyperaceae and Cyperus japonica, and has an active ingredient of 50%.
Control is possible even at less than g/10a. The present invention will be explained below with reference to Examples and Test Examples. "Parts" in the examples represent "parts by weight." In addition, the active ingredient compounds are indicated by the compound numbers of the synthesis examples. Example 1 (Emulsion) A test compound was dissolved in a mixed solvent of xylene, isophorone, and cyclohexanone, and an emulsifier was added thereto and mixed and dissolved to obtain a 25% emulsion of the present invention. When using this emulsion, it was diluted with water to a predetermined concentration suitable for the sample to prepare a dispersion. Compound No. 1 Compound 25 parts xylene 20 parts isophorone 20 parts cyclohexanone 25 parts Emulsifier (Solpol 800A Toho Chemical Co., Ltd. trademark)
10 parts Example 2 (emulsion) Compound No. 1 of the present invention was dissolved in xylene, an emulsifier was added thereto, and the mixture was stirred and dissolved to obtain a 20% emulsion. Compound No. 1 20 parts xylene 70 parts Emulsifier Solpol 800A 10 parts Example 3 (emulsion) Add a mixed solvent of xylene and cyclohexanone to compound No. 15 of the present invention and dissolve, then add the emulsifier and dissolve with stirring. , a 20% emulsion was obtained. Compound No. 15 20 parts xylene 40 parts cyclohexanone 30 parts Emulsifier Solpol 800A 10 parts Example 4 (wettable powder) The test compound was ground, and kaolin clay, talc, and a dispersant were added as carriers and mixed and ground to form the present invention.
A 50% hydrating powder was obtained. Compound No. 10 50 parts kaolin clay 25 parts talc 20 parts polyoxyethylene alkylaryl ether sulfate ammonium salt 4 parts dioctyl sodium sulfosuccinate 1 part Example 5 (hydrating agent) Compound No. 12 of the present invention with an inorganic carrier was added and pulverized using a crusher, then a dispersant was added and mixed well to obtain a 20% hydrating powder. Compound No. 12 20 parts Kaolin clay 70 parts White carbon 4 parts Solpol 5039 4 parts Solpol 5050 2 parts Example 6 (hydrating agent) Add an inorganic carrier to the compound No. 13 of the present invention, crush it with a grinder, and then disperse. and mixed well to obtain a 40% hydrating powder. Compound No. 13 40 parts Kaolin clay 50 parts White carbon 4 parts Solpol 5039 4 parts Solpol 5050 2 parts Example 7 (granules) After finely pulverizing the test compound, talc, bentonite, or a dispersant may be added as a carrier. mix,
Granulation was performed using a granulator to obtain a 5% granule of the present invention. Compound No. 13 5 parts bentonite 30 parts kaolin clay 20 parts talc 40 parts polyoxyethylene alkyl phenol ether sodium sulfate 2 parts polyoxyethylene lauryl ether 3 parts Example 8 (granules) Compound No. 10 of the present invention contains inorganic After adding a carrier and pulverizing with a ball mill, a surfactant and water were added, and the mixture was kneaded uniformly with a kneader, granulated using a granulator, and dried to obtain 5% granules. Compound No. 10 5 parts Bentonite 50 parts Talc 30 parts White carbon 5 parts Sodium tripolyphosphate 5 parts Sodium ligninsulfonate 3 parts Rapizol B-80 2 parts (Nippon Oil & Fats Co., Ltd. trademark) Example 9 (Granules) The present invention Add a small amount of surfactant and inorganic carrier to Compound No. 8, mix and stir, then add the inorganic carrier and repeat the stirring several times. When it becomes a uniform powder, add water and mix it uniformly with a kneader. The mixture was kneaded, made into granules using a granulator, and dried to obtain 5% granules. Compound No. 8 5 parts Bentonite 40 parts Kaolin clay 46 parts Sodium tripolyphosphate 5 parts Toxanone GR-30 4 parts (trademark of Sanyo Chemical Industries, Ltd.) Next, the present invention will be specifically explained using test examples. Test Example 1 ^A 150 cm square pot was filled with paddy soil, and major weeds such as Japanese grasshopper, Japanese grasshopper, and bulrush were sown, and tubers of Japanese grasshopper and Japanese cypress were embedded. Paddy rice seedlings (cultivar Koshihikari, 2nd to 3rd leaf stage) that had been raised in advance were transplanted, submerged in 3 cm of water, and treated with a diluted solution of the test chemical at a predetermined concentration 3 days after transplanting the rice. The herbicidal effect and chemical damage to paddy rice were observed and investigated 30 days after treatment. The evaluation criteria for herbicidal effectiveness are as follows. In addition, chemical damage was determined by observing the damage symptoms that appeared on the stems and leaves of the rice plants and their growth status, and using the following evaluation criteria. The results are shown in Table 2. [Herbicidal effect] [Drug damage] 5 100% control 5 Death 4 80% 4 Major damage 3 60% 3 Medium damage 2 40% 2 Minor damage 1 20% 1 Slight damage 0 Same as no treatment 0 Harmless The evaluation criteria for Test Example 2 and below are also the same.

【table】

【table】

[Table] As shown in the above results, the compound of the present invention has an active ingredient of 500 g against annual weeds such as Japanese field weeds and Japanese grasshoppers, as well as perennial weeds that are currently considered difficult to control, such as Cyperaceae's Cyperaceae, Cyperaceae's Cyperaceae, and Omodakaceae's Prickly Pear. /10a provides complete control. Furthermore, there is no chemical damage to transplanted paddy rice. On the other hand, although the control compound has a high herbicidal effect, it also has very strong phytotoxicity and has no selectivity between rice and weeds. Test Example ² Paddy soil was filled in a 400 cm square pot, and pre-raised paddy rice seedlings (variety: Koshihikari 2nd to 3rd leaf stage) were transplanted, and the rice was then flooded with 3 cm of water and a predetermined concentration diluted solution of the test chemical was added to the paddy rice transplant 3. Processed after 1 day. Thirty days after treatment, chemical damage to paddy rice was investigated by observation. The results are shown in Table 3. The numerical values in Table 3 indicate drug damage.

【table】

[Table] As shown in the above results, the compound of the present invention had high selectivity to paddy rice and was useful as a paddy herbicide. On the other hand, the control compound has no selectivity and has no utility as a paddy herbicide. Test Example 3 ^A 400cm square pot was filled with paddy soil, and major weeds such as Japanese grasshopper, Japanese cypress, and bulrush were sown, and tubers of Japanese grasshopper and Japanese cypress were embedded. Also,
Embed fir (variety: Koshihikari 20 grains) coated with calcium peroxide to a depth of 1 cm.
Three days after seeding, the cells were flooded with water and treated with a diluted solution of the test chemical at a predetermined concentration. Thirty days after treatment, the phytotoxic effects and herbicidal effects on directly sown rice were investigated by observation. The results are shown in Table 4.

【table】

[Table] As shown in the above results, the compound of the present invention has a sufficient herbicidal effect even when the dose is reduced, and is particularly effective against firefly and Cyperus japonica belonging to the Cyperaceae family. Furthermore, no chemical damage was observed even in directly seeded rice, making it an extremely safe drug. On the other hand, the control compound has very strong drug toxicity and no selectivity is observed. Therefore, it can be seen that the herbicide containing the compound of the present invention as an active ingredient can be applied to direct sowing cultivation in flooded soil, and is extremely safe and highly selective. Test Example 4 Paddy soil was filled in a ^400cm square pot, and major weeds such as Japanese grasshopper, Japanese grasshopper, and bulrush were sown, and tubers of Japanese grasshopper and Japanese cypress were embedded. Also,
Embed fir (variety: Koshihikari 20 grains) coated with calcium peroxide to a depth of 1 cm.
15 days after seeding, the cells were flooded with a diluted solution of the test drug at a predetermined concentration. Thirty days after treatment, the chemical damage to paddy rice and herbicidal effect were investigated by observation. The results are shown in Table 5. The leaf stages of paddy rice and weeds at the time of treatment were 1.5 leaf stage for paddy rice, 2.0 leaf stage for Japanese wild grass, 3.0 leaf stage for Konagi, 2.0 leaf stage for Firefly, 2.5 leaf stage for Cyperus japonica, and 3.0 leaf stage for Urikawa.

【table】

[Table] As shown in the above results, the herbicide containing the compound of the present invention as an active ingredient has a herbicidal effect close to that of initial treatment even when applied during the weed growth period, can kill a wide range of weed species, and has a long suitable treatment period. It can be seen that there is no chemical damage to paddy rice, and it is extremely safe and highly selective. On the other hand, although the control compound has a herbicidal effect, it is extremely harmful to paddy rice and has no selectivity at all.

Claims (1)

[Claims] 1. General formula (In the formula, X is a hydrogen atom, a chlorine atom, a methyl group,
It represents a methoxy group, and n represents an integer of 1 to 3. )
A benzanilide derivative represented by 2 General formula (In the formula, X is a hydrogen atom, a chlorine atom, a methyl group,
It represents a methoxy group, and n represents an integer of 1 to 3. )
A herbicide containing a benzanilide derivative represented by: