JPH0348898B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to specific benzoic acid amide derivatives and herbicides containing the same. The present inventors focused on benzoic acid compounds and investigated their herbicidal activity, and discovered the unique action of a specific α-methylbenzyloxybenzoic acid amide derivative, leading to the completion of the present invention. . The first invention of the present invention is the general formula [] [However, in the formula, X represents a hydrogen atom, a chlorine atom, or a methyl group. R ₁ and R ₂ represent a hydrogen atom, a lower alkyl group, an allyl group, a propargyl group, a methoxy group or a methoxyethyl group. However, R ₁ and R ₂ do not both represent a hydrogen atom. Also
R ₁ and R ₂ may form a 1-pyrrolidinyl group, a piperidino group, a hexamethyleneimino group or a 2-methylpiperidino group together with the nitrogen atom in the formula. ] It is a 3-(α-methylbenzyloxy)benzoic acid amide derivative represented by: The second invention is a herbicide containing the compound. Next, typical 3-(α-methylbenzyloxy)benzoic acid amide derivatives according to the present invention are shown.

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[Table] The compounds of the present invention can be synthesized by various methods shown below. () General formula [However, in the formula, X is as defined above.
Y represents a halogen atom. ] α-Methylbenzyl halides represented by and the general formula [However, in the formula, R ₁ and R ₂ are as defined above. ] is reacted with a metahydroxybenzoic acid amide derivative represented by: That is, α-methylbenzyl halides [] and metahydroxybenzoic acid amide derivatives [] are reacted by heating in the presence of a dehydrohalogenating agent without a solvent or in an inert organic solvent. Suitable inert solvents include toluene, xylene, dimethylformamide, dimethylsulfoxide, diglyme, etc., or mixtures thereof. As the dehydrohalogenating agent, sodium carbonate, potassium carbonate, etc. are preferably used. The reaction temperature and reaction time vary mainly depending on the type of reagent used, but generally 50°C to reflux temperature and 1 to 10 hours are suitable. After the reaction is completed, the target compound can be obtained from the reaction mixture according to a conventional method. () General formula [However, in the formula, X is as defined above. ] 3-(α-methylbenzyloxy) represented by
Benzoic acid or its reactive derivatives and general formula [However, in the formula, R and R are as defined above. ] is reacted with the amine represented by The reactive derivatives mentioned here include acid halides,
Examples include acid anhydrides and esters. This reaction is carried out without a solvent or in an inert organic solvent. Among the free acids and reactive derivatives, acid chlorides are commonly used and carried out in the presence of a dehydrochlorinating agent. The acid chloride used is synthesized from the free acid and thionyl chloride or phosgene. Suitable inert organic solvents include toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, dichloromethane, carbon tetrachloride, ethyl acetate, etc., or mixtures thereof. Further, as the dehydrochlorination agent, it is appropriate to use, for example, triethylamine, sodium hydrogen carbonate, sodium carbonate, and the like. Since the reaction is generally exothermic, it is usually carried out under cooling. The reaction time varies mainly depending on the reaction temperature and the compound used, but is about instantaneous to several hours. After the reaction is completed, the target compound can be obtained from the reaction mixture according to a conventional method. Next, representative examples of synthesis will be shown. Synthesis example 1 N-methyl-3-(α-methylbenzyloxy)
Benzoic acid amide N-methyl-3-hydroxybenzoic acid amide
5.0 g of α-methylbenzyl bromide and 5.4 g of potassium carbonate were dissolved in 30 ml of dimethylformamide and stirred at 70°C for 6 hours. After the reaction is complete,
The reaction mixture was poured into 300 ml of water, and the precipitated crystals were filtered and dried to obtain 7.6 g of crude crystals, which were recrystallized from a mixed solvent of toluene and hexane.
N-methyl-3-(α-methylbenzyloxy)
4.8 g of benzoic acid amide was obtained. Melting point 118~120℃
Yield 63% (based on α-methylbenzyl bromide) Elemental analysis value C ₁₆ H ₁₇ NO ₂ Calculated value: C75.29 H6.67 N5.49 Experimental value: C75.02 H6.81 N5.38 IR (Nujol method) , cm ^-1 ) 3290 1620 1540 1305 Synthesis example 2 N,N-diethyl-3-{1-(4-methylphenyl)ethoxy}benzoic acid amide 3-{1-(4-methylphenyl)ethoxy}benzoic acid chloride 5.5 g While cooling and stirring in a water bath, 5 ml of diethylamine was added dropwise to the tetrahydrofuran solution, and after the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. After the reaction was completed, the reaction solution was poured into 200 ml of water, and the liberated oil was extracted with ethyl acetate.
After dehydrating the ethyl acetate layer with magnesium sulfate, the solvent was distilled off to give an oily N,N-diethyl-3-{1-
6.1 g of (4-methylphenyl)ethoxy}benzoic acid amide was obtained. n ³¹ _D 1.5485 IR (rock salt sandwich, cm ^-1 ) 1620 1575 1435 1290 Synthesis example 3 1-[3-{1-(4-chlorophenyl)ethoxy}benzoyl]biperidine 3-{1-(4-chlorophenyl)ethoxy }To a solution of 10.3 g of benzoyl chloride in tetrahydrofuran, piperidine 9 was added while stirring while cooling in an ice bath.
ml was added dropwise, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. After the reaction is complete, pour the reaction solution into 500ml of water.
The precipitated crystals were filtered and dried to obtain 11.8 g of crude crystals. This was recrystallized from methanol and 1-[3
9.0 g of -{1-(4-chlorophenyl)ethoxy}benzoyl]biperidine was obtained. Melting point 93~95℃
Yield 75% (carboxylic acid chloride basis) Elemental analysis value C ₂₀ H ₂₂ ClNO ₂ Calculated value: C69.87 H6.40 N4.08 Experimental value: C70.02 H6.67 N3.92 IR (Nujol method, cm ^{- 1} ) 1615 1440 1230 1015 The herbicide of the present invention is prepared by mixing the compound represented by the general formula [] with various carriers as an active ingredient,
It can be obtained by formulating into the form of wettable powders, emulsions, powders, granules, etc. Among the carriers, a commonly used organic solvent is used as the liquid carrier, and a commonly used fine mineral powder is used as the solid carrier. Further, during preparation of the formulation, a surfactant is added to impart emulsifying properties, dispersibility, spreading properties, and the like. Furthermore, other agricultural chemicals such as fertilizers, herbicides, insecticides, and fungicides can also be used in combination. For use as a herbicide, the active ingredient compound is applied in sufficient amounts to achieve the desired herbicidal action.
The amount of application is within the range of 1 to 2000g/10a of active ingredient, but usually 1 to 1000g/10a.
10a, preferably 100 to 500 g/10a, and is used in the form of a wettable powder, emulsion, powder, granule, etc. containing 0.1 to 50% of the active ingredient. To form an emulsion, the active ingredient is dissolved in an agriculturally acceptable organic solvent and a solvent-soluble emulsifier is added.
Suitable solvents are generally immiscible with water and include
Hydrocarbons, chlorinated hydrocarbons, ketones, esters,
Organic solvents such as alcohols and amides. Useful solvents may include toluene, xylene, naphtha, perchlorethylene, cyclohexanone, isophorone and dimethylformamide or mixtures thereof. Particularly suitable solvents are aromatic hydrocarbons and ketones, although mixtures of solvents are commonly used. The surfactant used as an emulsifier is approximately
It accounts for 0.5 to 20 parts by weight and may be anionic, cationic, or nonionic. Anionic surfactants include alcohol sulfates or sulfonates, alkylaryl sulfonates or sulfosuccinates, such as calcium dodecylbenzenesulfonate or sodium dioctylsulfosuccinate. Cationic surfactants include fatty alkyl amine salts and fatty acid alkyl quaternary salts, such as laurylamine hydrochloride or lauryldimethylbenzine ammonium chloride. Nonionic emulsifiers that can be used include alkylphenols, fatty alcohols, mercaptans or ethylene oxide adducts of fatty acids, such as polyethylene glycol esters of stearic acid or polyethylene glycol ethers of palmityl alcohol or octylphenol. The concentration of active ingredient is between 5 and 80 parts by weight, especially
A suitable range is 10 to 30 parts by weight. Wettable powders are prepared by adding the active ingredient to an inert finely divided solid carrier and a surfactant. Active ingredients range from 5 to 50
Within the range of parts by weight, and the surfactant is from 0.5 to
It is typically present in amounts of 20 parts by weight. Solid carriers commonly used for formulating the active ingredients are naturally occurring clays, silicates and silicas, limes and carbonates and organic carriers. Typical examples of these are kaolin, Siegrite, Fuller's earth,
Talc, diatomaceous earth, magnesium lime, dolomite and walnut flour. Commonly used emulsifiers and wetting agents are polyoxyethylenated alkylphenols, fatty alcohols, fatty acids and alkylamines, alkylarylsulfonates and alkylsulfosuccinates, and the like. Spreading agents include materials such as glycerin mannitus laurate and conjugates of oleic acid and polyglycene modified with phthalic anhydride. As the dispersant, a sodium salt of a copolymer of maleic anhydride and olefin, such as diisobutylene, sodium ligninsulfonate, and sodium formaldehyde-naphthalenesulfonate are used. Powders are prepared by combining the active ingredient with inert carriers customary for the manufacture of powders, such as talc, finely divided clay, diatomaceous earth, magnesium carbonate or wheat flour. Concentrated powders are commonly prepared in which the active ingredient is present in the range of 10 to 80 parts by weight, but for application as a herbicide, further solids are added to dilute to about 1 to 20 parts by weight. Granules are made by incorporating the active ingredient into agriculturally acceptable carriers, such as bentonite, kaolin clay, eidolon or talc. Such granules contain 1 to 50 parts by weight of the active ingredient. The herbicide of the present invention can be applied to a variety of harmful weeds, including typical harmful grasses such as field grass, Japanese cypress, and chickweed, which are known to be harmful to rice fields, and representative harmful grasses, such as Japanese grasshopper and Japanese chickweed, which are known to be harmful to upland fields. Shows herbicidal activity against. Furthermore, no chemical damage to rice or soybeans is observed. Next, the herbicide of the present invention will be explained using formulation examples and test examples. Specific examples for the preparation of the agent of the present invention are shown below. Note that "parts" means "parts by weight." Example 1 (Emulsion) Compound No. 9 25 parts Xylene 35 parts Cyclohexanone 30 parts Solpol 800A 10 parts (trademark of Toho Chemical Co., Ltd.) were uniformly mixed and dissolved to obtain an emulsion of the present invention. Example 2 (Wettable powder) Compound No. 1 50 parts Kaolin clay 45 parts Solpol 5039 5 parts were mixed and ground to obtain a wettable powder of the present invention. Example 3 (Powder) 5 parts of Compound No.-34 and 95 parts of kaolin clay were mixed and ground to obtain a powder of the present invention. Example 4 (Granules) Compound No.-12 5 parts Bentonite 45 parts Talc 45 parts Sodium ligninsulfonate 5 parts were uniformly mixed and ground, water was added, kneaded, and granulated and dried to obtain granules of the present invention. . Next, the usefulness of the compounds according to the present invention will be specifically explained in the following test examples. Test Example 1 (Paddy soil treatment) Paddy soil was filled in a pot with a diameter of 11.5 cm and a depth of 10 cm, and after adding paddy soil containing various paddy weeds to the surface layer, fertilization was applied, plowing was done, and the water was flooded to 3 cm. : Nihonbare, leaf age 2.5 leaf stage) Two plants were transplanted.
On the fourth day after transplanting the paddy rice, a predetermined amount of the diluted solution of the present invention agent with water was dropped into the water using a pipette. The investigation was carried out by observing the herbicidal effect and the presence or absence of chemical damage to paddy rice on the 20th day after chemical treatment. The results are shown in Table 2. The evaluation in the table is based on the following criteria. Herbicidal effect index Herbicidal damage index 5: Complete herbicidal effect -: Harmless 4: 80-90% herbicidal effect ±: Slightly harmful 3: Herbicidal effect of 60-79%: Minor damage 2: Herbicidal effect of 40-59%: Large Harm 1: Weeding effect of 20-39%: Severe damage 0: Weeding effect of 20% or less The seeds were sown and the soil was covered with 2 cm of field soil mixed with seeds of crabgrass and blueberry, and then watered evenly. On the day after sowing, a predetermined amount of a solution of the present invention agent diluted with water was applied uniformly to the soil surface. The investigation was carried out by observing the chemical damage to soybeans and the herbicidal effect on various weeds on the 20th day after chemical treatment. The results are shown in Table 2. The evaluations in the table were conducted according to the standards of Test Example 1.

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Claims (1)

[Claims] 1. General formula [However, in the formula, X represents a hydrogen atom, a chlorine atom, or a methyl group. R ₁ and R ₂ represent a hydrogen atom, a lower alkyl group, an allyl group, a propargyl group, a methoxy group or a methoxyethyl group. However, R ₁ and R ₂ do not both represent a hydrogen atom. Further, R ₁ and R may form a 1-pyrrolidinyl group, a piperidino group, a hexamethyleneimino group, or a 2-methylpiperidino group together with the nitrogen atom in the formula. ] A 3-(α-methylbenzyloxy)benzoic acid amide derivative represented by: 2 General formula [However, in the formula, X represents a hydrogen atom, a chlorine atom, or a methyl group. R ₁ and R ₂ represent a hydrogen atom, a lower alkyl group, an allyl group, a propargyl group, a methoxy group or a methoxyethyl group. However, R ₁ and R ₂ never represent a hydrogen atom. Also R ₁
and R ₂ may form a 1-pyrrolidinyl group, a piperidino group, a hexamethyleneimino group or a 2-methylpiperidino group together with the nitrogen atom in the formula. A herbicide containing a 3-(α-methylbenzyloxy)benzoic acid amide derivative represented by the following.