JPS59225154A - Benzoic acid amide derivative and herbicide containing it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (X is H, methyl, Cl, methoxy, nitro, etc.; n is 1-3; R1 and R2 are H, lower alkyl, aryl, 2-methoxyethyl, with the proviso that R1 and R2 are not H at the same time). EXAMPLE:N,N-Dimethyl-3-{2-(3-trifluorophenoxy)ethoxy}benzoic acid amide. USE:A herbicide. Showing herbicidal activity against various kinds of harmful weeds including strong weeds in paddy fields (e.g., Echinochloa crus-galli Beauv. var. praticola Ohwi., umbrella plant, long stemmed water-wort, etc.) and strong weeds in plowed fields (e.g., Amaranthus viridis L., large crab-grass, etc.). Having no phytotoxicity to rice plant and soybean. PREPARATION:A 2-phenoxyethyl halide shown by the formula II (Y is halogen) is reacted with a metahydroxybenzoic acid amide derivative shown by the formula III in the absence of a solvent or in an inert organic solvent such as toluene, xylene, etc. in the presence of a dehydrohalogenating agent such as Na2CO3, etc. under heating, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to certain benzoic acid 1-mide derivatives and herbicides containing the same.

The present inventors focused on benzoic acid compounds and investigated their herbicidal activity, and discovered a unique action of a specific benzoic acid amide derivative, leading to the completion of the present invention.

The first invention of the present invention is represented by the general formula CI) [wherein X represents a hydrogen atom, a methyl group, a chlorine atom, a methoxy group, a nitro group, or a trifluoromethyl group.

n represents an integer from 1 to 3, and when n is 2 or 3,
may be the same or different from each other. Horse and R2 represent a hydrogen atom, a lower alkyl group, an allyl group, or a 2-methoxyethyl group.

However, R1 and R2 do not both represent hydrogen atoms. Further, R1 and R2 may form a busy biaridinyl group, a piperidino group, a hexamethyleneimino group or a methyl-substituted piperidino group with the nitrogen atom in the formula. ] It is a benzoic acid amide derivative represented by. The second invention is a herbicide containing the compound.

Next, typical benzoic acid amide derivatives according to the present invention are shown.

The compounds of the present invention shown in Table 1 can be synthesized by various methods shown below.

(1) General formula [However, X in the formula is as defined above. Y represents a halogen atom. ] 2-phenoxyethyl halides represented by the general formula [However, R1 and R2 in the formula are as defined in the above-mentioned foot gland. ] is reacted with a metahydroxybenzoic acid amide derivative represented by

That is, 2-phenoxyethylhala (do 11 (II)
and the metahydroxybenzoic acid amide derivative [1] are reacted by heating in the absence of a solvent or in an inert organic solvent in the presence of a dehalogenating and hydrogenating agent. Suitable inert organic solvents include toluene, xylene, dimethylformamide, methyl isobutyl ketone, dimethyl sulfoxide, 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 compound used, but generally 80° C. to reflux temperature and 5 to 40 hours are suitable. After the reaction is completed, the target compound can be obtained from the reaction mixture according to a conventional method.

(11) General formula [However, X in the formula is as defined above. ] 3-(2-phenoxyethoxy)benzoic acid or its reactive derivative represented by the general formula % formula % ( ) [However, RI and R2 in the formula are as defined above. ] is reacted with the amine represented by

The reactive derivatives mentioned here include acid halides, acid anhydrides, esters, and the like.

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. As the dehydrochlorination agent, for example, triethylamine, sodium bicarbonate, sodium carbonate, etc. are suitable.

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 amount of compounds used, but it ranges from instantaneous to several hours. After completion of the reaction, the target compound can be obtained from the reaction mixture in a conventional manner.

Next, a typical synthesis example will be shown.

Synthesis Example I N,N-dimethyl-5-(2-(3-trifluorophenoxy)ethoxy)benzoic acid amide N,N-dimethyl-3-hydroxybenzoic acid amide4.
9f, 2-(3-)lifluoromethylphenoxy)ethyl bromide a1f, potassium carbonate 5,4 F'4t
Dissolve 30dK in dimethylformamide and heat at 110℃ for 2
Stirred for 3 hours. After the reaction was completed, the reaction mixture was poured into 300-g water, and the precipitated crystals were filtered off and dried to give crude crystals.
．． I got 8 f. This was recrystallized from a mixed solvent of toluene and hexane, and N,N-dimethyl-5-(2-(3-
) Lifluorophenoxy) Ethoxy) Benzoic acid amide a
Obtained 2F. Melting point 78-80℃ Yield 77% (bromide basis) Elemental analysis value Calculated value as Cl8H18F3NO3: C
61,19R5,10N3.97 Experimental value: C60,9
7H5,02N A78I R (Nujol method cm-
) 1620 1447 1343 1527 Synthesis Example 2 N-ethyl-3-(2-(5-methylphenoxy)
Ethoxy) benzoic acid amide 5-(2-(s-methylphenoxy) ethoxy) Benzoic acid chloride 2.9 f of dioxane solution was cooled in a water bath while stirring, 3 d of 70% ethylamine aqueous solution was added dropwise, and after the dropwise addition was completed, room temperature was reached. The mixture was stirred for 1 hour. After the reaction was completed, the reaction solution was poured into 200 ml of water, and the precipitated crystals were filtered off and dried to obtain 2.9 f of crude crystals. This was recrystallized from ethanol and N-ethyl-
5-(2-(5-methylphenoxy)ethoxy)benzoic acid amide 2, Of was obtained. Threat point: 149-151°C Yield: 67% (carboxylic acid chloride basis) Elemental analysis value: Calculated value as C, 8H2, No. 3: C7
2,24H7,02N 4.68 Experimental value: C72,11
H6,95N4.56I R (Nujo J method t'm-
) 5220 1640 1590 1547 Synthesis Example 5 N,N-dimethyl-! 1-(2-(3-chlorophenoxy)ethoxy)benzoic acid yiM3-(2-(!l
-chlorophenoxy)ethoxy)benzoic acid chloride z
A 50% dimethylamine aqueous solution 7 was added dropwise to the tetrahydrofuran solution of 8 while stirring while cooling in a water bath, 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 40 ml of water, and the precipitated crystals were separated by filtration and dried to obtain 7.7 f of crude crystals. This was recrystallized from a mixed solvent of toluene and hexane to obtain N,N-dimethyl-3
-(2-(ro-chlorophenoxy)ethoxy)benzoic acid amide 5.81 was obtained. Melting point 69-71℃ Yield 73% (
Carboxylic acid chloride basis) elemental analysis value C*tHIs
Calculated value as C1NO3: C65,B5 H5,6
5N 4.5B Experimental value: C6A76 H5,77N
4.24 The herbicide of the present invention can be obtained by mixing the compound represented by the general formula (1) as an active ingredient with various carriers and formulating it in the form of a wettable powder, emulsion, powder, granule, etc. It will be done. 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. It is also possible to use a mixture of other agricultural chemicals such as sardines, fertilizers, herbicides, insecticides, and fungicides.

For use as a herbicide, the active ingredient compound is applied in sufficient amounts to achieve the desired herbicidal action.

Its application rate is from 1 to 2000 f/10 of active ingredient
It is applied within the range of a, but usually 1 to 1000
F/10-+.

It is preferably used in the form of a wettable powder, emulsion, powder, or granule containing 0.1 to 50% of the active ingredient, preferably 100 to 500 F/10a.

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 are organic solvents such as hydrocarbons, chlorinated hydrocarbons, ketones, esters, 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 accounts for about 0.5 to 20 parts by weight of the emulsion and may be anionic or cationic.
Alternatively, it may be nonionic.

Anionic surfactants are alcohol sulfates or sulfonates, alkylaryl sulfonates or sulfosuccinates, such as calcium dodecylbenzenesulfonate or sodium dioctylsulfosuccinate.

Cationic surfactants include aliphatic alkyl amine salts and fatty acid monolkyl quaternary salts, such as laurylamine hydrochloride or lauryldimethylbenzylammonium chloride.

Non-ionic emulsifiers that can be used include ethylene oxide adducts of alkylphenols, fatty alcohols, mercaptans or fatty acids, such as polyethylene glycol esters of stear'-, lJ acid or polyethylene glycol ethers of valmityl alcohol or octylphenol. can.

The concentration of the active ingredient is suitably in the range of 5 to 80 parts by weight, particularly 10 to 30 parts by weight.

Irrigation agents are made by adding the active ingredient to an inert finely divided solid carrier and a surfactant. The active ingredient is usually present in the range of 5 to 50 parts by weight and the surfactant in 0.5 to 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,
These are gicrite, 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 dialkylsulfosuccinates, and the like.

Spreading agents include materials such as glycerin mannitlaurate and conjugates of oleic acid and polyglycerin modified with phthalic anhydride.

Dispersants include sodium salts of copolymers of maleic anhydride and olefins, such as diisobutylene, sodium ligninsulfonate, and sodium formaldehyde-naphthalenesulfonate.

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 with the active ingredient present in the range of 10 to 80 parts by weight are commonly prepared, but for application as herbicides, further solids are added to dilute to about 1 to 20 parts by weight.

Granules are prepared by incorporating the active ingredient into a commercially acceptable carrier, such as bentonite, kaolin clay, diatomaceous earth or talc). Such granules contain between 1 and 750 parts by weight of the active ingredient.

The herbicide of the present invention can be applied to various harmful weeds, including typical harmful grasses such as Japanese 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 fields. Shows herbicidal activity against. Furthermore, no chemical damage to rice or soybeans is observed.

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 number-4925 parts Xylene 35 parts Cyclohexanone 30 parts Tsurupol 800A 10 copies (Toho Chemical Trademark) were uniformly mixed and dissolved to obtain an emulsion of the present invention.

Example 2 (Irrigation agent) Compound number - 5750 parts Kaolin clay 45 parts Crane pole 5059 5 parts were mixed and ground to obtain a wettable powder of the present invention.

Example 3 (powder) Compound number - 355 parts Kaolin clay 95 parts The mixture was mixed and ground to obtain the powder of the present invention.

Example 4 (Granules) Compound number - 195 parts Bentonite 45 parts Talc 45s 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 packed into a pot with a diameter of 11.5 tyR and a depth of 10 holes, and after adding paddy soil containing various paddy weeds to the surface layer, fertilization was applied, plowing was done, and water was added to the pot. Two paddy rice seedlings (variety Ninihonbare, leaf age 2.5) were transplanted. After transplanting paddy rice 4
On the second day, a predetermined amount of the diluted solution of the present invention agent was dropped into water in a jar.

The investigation was carried out by observing the herbicidal effect and the presence or absence of chemical damage to Mizuhori 200 days after chemical treatment. The results are shown in Table 2. The evaluation in the table is based on the following criteria.

Herbicidal effect index: Phytotoxicity index 5: Complete herbicidal effect -2: Harmless 4: 80-90% herbicidal effect 3: Weeding effect of 60-79%
Small book 2: 40-59% weeding effect ■: Major damage 1:20
Weeding effect of ~39% Book: Afterword 0: Weeding effect of 20% or less The seeds were sown and a predetermined amount of the diluted solution of 2a covered with water was applied uniformly to the soil surface on the ground surface of the field where the seeds of crabgrass and 1 obi were mixed. The investigation was conducted by observing chemical damage to soybeans and herbicidal effects on various weeds 200 days after chemical treatment.

The results are shown in Table 2. The evaluation in the table was performed according to the standards of Test Example 1.

Table 2 Continuation of page 1 0 shots: Takeo Nariki 6-2-30 Oji, Kita-ku, Tokyo Hodogaya Chemical Industry Co., Ltd. Central Research Institute Inside the salient point 0 shots Akira Yasuya Sakuraba 6-2-30 Oji, Kita-ku, Tokyo Hodogaya Chemical Industry Co., Ltd. Central Research Institute Inside the laboratory

Claims (1)

[Claims] 1. General formula [However, in the formula, X is a hydrogen atom, a methyl group, a chlorine atom,
Represents a methoxy group, nitro group, or trifluoromethyl group. n represents an integer of 1 to 3, and when n is 2 or 3, X may be the same or different from each other. R1 and R
2 represents a hydrogen atom, a lower alkyl group, an allyl group, or a 2-methoxyethyl group. However, R1 and R2 do not both represent hydrogen atoms. Further, R and R2 may form a pyrrolidinyl group, a piperidino group, a hexamethyleneimino group, or a methyl-substituted piperidino group together with the nitrogen atom in the formula. ] A benzoic acid amide derivative represented by 2. General formula [However, X in the formula represents a hydrogen atom, a methyl group, a chlorine atom, a methoxy group, a nitro group, or a trifluoromethyl group. n represents an integer from 1 to 5, and when n is 2 or 3,
may be the same or different from each other. R1 and R2
represents a hydrogen atom, a lower alkyl group, an allyl group, or a 2-methoxyethyl group. However, R1 and R2 do not both represent hydrogen atoms. Further, R1 and R2 may form a pyrrolidinyl group, a piperidino group, a hexamethyleneimino group or a methyl-substituted piperidino group together with the nitrogen atom in the formula. A herbicide containing a benzoic acid amide derivative represented by ].