JPS6123780B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel tolyloxyphenoxypentenoic acid derivative and a herbicide containing the same. In recent years, many herbicides have been developed and put into practical use, contributing to labor savings in agricultural work. However, when these herbicides are actually used, their medicinal effects and
Since various problems have arisen in terms of safety, there is a desire for the emergence of further improved herbicides. That is, there is a strong demand for highly safe herbicides that do not affect useful crops, act effectively against harmful weeds in small doses, and do not pollute the environment. In order to meet these demands, the present inventors synthesized various compounds of tolyloxyphenoxypentenoic acid derivatives, studied their herbicidal activity, and completed the present invention. That is, an object of the present invention is to provide a novel tolyloxyphenoxypentenoic acid derivative useful as a herbicide, and a herbicide containing the same as an active ingredient. The tolyloxyphenoxypentenoic acid derivative of the present invention is This compound is a unique compound in that it exhibits herbicidal activity with excellent selectivity compared to known phenoxyphenoxy fatty acid derivatives. JP-A-52-33637 discloses that phenoxyphenoxy fatty acid derivatives are used as herbicides, and specifically exemplified compounds such as 4-[4-( 4-Trifluoromethyl-2-chlorophenoxy)phenoxy]crotonic acid ethyl ester, 4-[4-(4-trifluoromethylphenoxy)phenoxy]valeric acid ethyl ester, 4-[4-(trifluoromethyl-2) -Chlorphenoxy)phenoxy]valeryl acid ethyl ester and the like, the compounds of the present invention have a strong herbicidal activity against noxious weeds of the family Hematinaceae, such as field grass, Japanese grasshopper, and crabgrass. Moreover, the compound of the present invention is disclosed in JP-A-52-33637 and JP-A-51-12924.
Compared to 2-[4-(4-trifluoromethylphenoxy)phenoxy]propionate ethyl ester described in the specification etc., migration in soil treatment is small and activity fluctuation factors such as weather conditions and soil conditions Furthermore, it has excellent residual effect in the soil and can suppress later weeds for a long period of time.
In foliage treatment, it suppresses the recovery of incompletely dead weeds for a long period of time, and is stable against activity fluctuation factors such as rainfall, atmospheric humidity, temperature, and weed leaf age, and always shows a stable effect. The compounds of the present invention are extremely safe for useful broad-leaved crops such as radish, soybeans, peanuts, cotton, flax, beets, and sunflowers, and as mentioned above, they can be used to kill regular weeds such as field weeds. This herbicide not only has extremely excellent properties, but also can be applied at any time and in any manner, such as pre-emergence soil treatment, post-emergence soil treatment, or foliage treatment. The 4-[4-P-α,α,α-trifluorotolyloxy)phenoxy]-2-pentenoic acid ethyl ester of the present invention can be produced by the following method. That is, the compound of the present invention has 4-(P-α,
α,α-trifluorotolyloxy)phenol and 4-halogeno-2-pentenoic acid ethyl ester are used as dehydrohalogenating agents, such as alkali hydroxides such as caustic soda and caustic potash, soda carbonate,
Water, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol in the presence of an organic or inorganic base such as an alkali carbonate such as potassium carbonate or sodium bicarbonate, an alcoholate such as sodium ethylate, or a tertiary amine such as triethylamine, dimethylaniline, or pyridine. , butanol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetrachloride, dichloroethane, etc., in approximately equal molar ratios at a reaction temperature of 0°C to 150°C. A good yield can be obtained by reacting for 1 to 20 hours. Next, a synthesis example of the compound of the present invention will be given and specifically explained. Synthesis example 1 0.9 g (0.039 g) of metallic sodium in 70 ml of ethanol
mol) to form a solution of sodium ethylate, to which 8.9 g (0.035 mol) of 4-(P-α,α,α-trifluorotolyloxy)phenol was added, and then 4-bromo-2 - After adding 8.0 g (0.039 mol) of pentenoic acid ethyl ester, the mixture is allowed to react under reflux for 4 hours. The reaction mixture was extracted with toluene, and the toluene layer was washed with water, diluted hydrochloric acid, and then water, then dried over anhydrous sodium sulfate, the toluene was concentrated and distilled off, and the residue was subjected to vacuum distillation to reduce the boiling point.
At 173°C/0.01mmHg, pale yellow wither liquid with ^n20D _1.5175
Obtain 10.8 g (yield 81.5%). Synthesis Example 2 25.4 g (0.1 mol) of 4-(P-α, α, α-trifluorotolyloxy)phenol was dissolved in 100 ml of dimethylformamide, and 19.3 g (0.14 mol) of sodium carbonate and 4-bromo -2-
Add 24.8 g (0.12 mol) of pentenoic acid ethyl ester and react at 100° C. for 4 hours with stirring. The reaction mixture is poured into water and then extracted with dichloromethane. The dichloromethane layer was washed with water, diluted hydrochloric acid, and then water, then dried over anhydrous sodium sulfate, the dichloromethane was concentrated and distilled off, and the residue was subjected to vacuum distillation to give a pale yellow color with a boiling point of 173° _C /0.01mmHg and ^n20D of 1.5175. 324 g (85.2% yield) of viscous liquid are obtained. As mentioned above, the compound of the present invention synthesized in this manner has extremely strong herbicidal activity and is highly safe for many crops, but
Of course, the compound of the present invention can be used in a wide variety of applications, such as soil treatment or foliage treatment, such as upland, paddy fields, orchards, mountain forests, and non-agricultural land, by appropriately selecting the application method, amount, etc. The application amount of the compound of the present invention cannot be determined unconditionally due to differences in weather conditions, soil conditions, formulation form, application timing, application method, type of cultivated crops or target weeds, etc., but in general, in the case of soil treatment, it is effective per hectare. The amount of ingredients is 0.01 to 10 kg, preferably 0.1 to 5 kg,
The most desirable amount is 0.5 to 3 kg, and when controlling weeds by foliar treatment, it is 10 to 10,000 ppm, preferably 100 to 5,000 ppm, and more preferably 250 to 300 ppm.
Dilute to 3000ppm and process. When using the compound of the present invention as a herbicide, the obtained raw material itself may be treated, but it may be processed in any of the following formulations such as granules, wettable powders, powders, emulsions, fine granules, flowable suspensions, etc. If it is processed and used, even better results can be obtained. To produce herbicides in these formulations, the compound of the present invention is mixed with a solid carrier such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, permiculite, slaked lime, ammonium sulfate, or urea, alcohol, dioxane, or acetone. , cyclohexane,
Liquid carriers such as methylnaphthalene and dimethylformamide, emulsifiers and dispersants such as alkyl sulfates, alkyl sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene sorbitan monoalkylate, carboxymethyl cellulose , gum arabic, and other adjuvants as appropriate and uniformly mixed, dissolved, or formulated. Further, if desired, the compound of the present invention can be used in combination with other herbicides and the like. For example, carboxylic acids include 2,3,6-trichlorobenzoic acid and its salts, 2,3,5,6-tetrachlorobenzoic acid and its salts, 2-methoxy-3,
5,6-trichlorobenzoic acid and its salts, 2-methoxy-3,6-dichlorobenzoic acid and its salts,
2-Methyl-3,6-dichlorobenzoic acid and its salts, 2,3-dichloro-6-methylbenzoic acid and its salts, 2,4-dichlorophenoxyacetic acid, its salts and esters, 2,4,5 -Trichlorophenoxyacetic acid, its salts and esters, 2-methyl-4
- chlorophenoxyacetic acid, its salts and esters,
2-(2,4,5-trichlorophenoxy)propionic acid, its salts and esters, 2-(2,4-
dichlorophenoxy)butyric acid, its salts and esters, 4-(2-methyl-4-chlorophenoxy)
Butyric acid, its salts and esters, 2,3,6-trichlorophenylacetic acid and its salts, 3,6-endoxohexahydrophthalic acid, dimethyl 2,3,5,6-tetrachloroterephthalate, trichloroacetic acid and its salts Carbamic acids include N,N-di(n-propyl)thiolcarbamate S-ethyl, N,N
-di(n-propyl)thiolcarbamate S-
Propyl, N-ethyl-N-(n-butyl)thiol S-ethyl, N-ethyl-N-
(n-butyl)thiolcarbamate S-propyl, N,N-diethyldithiocarbamate S-
(2-chlorallyl), N-methyldithiocarbamate, S-ethyl hexahydro-IH-azepine-1-carbothioate, S-(4-chlorobenzyl) N,N-diethylthiolcarbamate, N,
N-di(sec-butyl)thiolcarbamate S
-benzyl, isopropyl N-phenylcarbamate, isopropyl N-(m-chlorophenyl)carbamate, 4-chloro-2-butyl N-(m-chlorophenyl)carbamate, N-(3,4
methyl -dichlorophenyl)carbamate, methyl sulfanilylcarbamate, etc., phenols include 4,6-dinitro-o-(sec-butyl)phenol and its salts, pentachlorophenol and its salts, etc., and urea As 3-(3,
4-Dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-
(3,4-dichlorophenyl)-3-methoxy-
1,1.Dimethylurea, 3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea, 3
-(3,4-dichlorophenyl)-1-(n-butyl)-1-methylurea, 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, 3-
(4-chlorophenyl)-1-methoxy-1-methylurea, 3-(3,4-dichlorophenyl)-1,
1,3-trimethylurea, 3-(3,4-dichlorophenyl)-1,1-diethylurea, 1-(2-
methylcyclohexyl)-3-phenylurea, 1
-[5-(t-butyl)-1,3,4-thiadiazol-2-yl]-1,3-dimethylurea, 3-
(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea, 1,3-bis(2,2,2- Trichlor-1-hydroxyethyl)urea, etc., and triazines include 2-chloro-4,6-bis(ethylamino)-S-triazine, 2-chloro-4-ethylamino-6-isopropylamino-S- Triazine, 2-chloro-4,6-bis(methoxypropylamino)-S
-triazine, 2-methoxy-4,6-bis(isopropylamino)-S-triazine, 2-methylthio-4,6-bis(isopropylamino)-
S-triazine, 2-methylthio-4,6-bis(ethylamino)-S-triazine, 2-methylthio-4-ethylamino-6-inpropylamino-S-triazine, 2-chloro-4,6-bis (isopropylamino)-S-triazine, 2-methoxy-4,6-bis(ethylamino)-S-triazine, 2-methoxy-4-ethylamino-6
-isopropylamino-S-triazine, 2-methylthio-4-(2-methoxyethylamino)-6
-isopropylamino-S-triazine, 2-
(4-chloro-6-ethylamino-S-triazin-2-yl)amino-2-methylpropionitrile, 4-amino-6-(t-butyl)-3-methylthio-1,2,4-triazine -5(4H)-one, 3-cyclohexyl-6-dimethylamino-
1-Methyl-S-triazine-2,4-(1H,
3H)-dione etc., but as an ether derivative, 2,
4-dichloro-4'-nitrodiphenyl ether,
2,4,6-trichloro-4'-nitrodiphenyl ether, 2,4-dichloro-6-fluoro-
4'-Nitrodiphenyl ether, 3-methyl-
4'-Nitrodiphenyl ether, 3,5-dimethyl-4'-nitrodiphenyl ether, 2,4'-dinitro-4-trifluoromethyldiphenyl ether, 2,4-dichloro-3'-methoxy-4 '-Nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-4'-nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-3'-
Ethoxy-4'-nitrodiphenyl ether, 2-
Chlor-4-trifluoromethyl-3'-carbetoxy-4'-nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-3'-(1carbetoxy)ethoxy-4'-nitrodiphenyl ether, etc. The anilides include N-(3,4-dichlorophenyl)propionamide, N-(3,4-
dichlorophenyl) methacrylamide, N-(3
-chloro-4-methylphenyl)-2-methylpentanamide, N-(3,4-dichlorophenyl)trimethylacetamide, N-(3,4-dichlorophenyl)-α,α-dimethylvaleramide, N-isopropyl-N- Phenylchloroacetamide, N-n-butoxymethyl-N-(2,
6-diethylphenyl) chloroacetamide, N
-Methoxymethyl-N-(2,6-diethylphenyl)chloroacetamide, etc., and as uracils, 5-bromo-3-(sec-butyl)-6-methyluracil, 5-bromo-3-cyclohexyl-
1,6-dimethyluracil, 3-cyclohexyl-5,6-trimethyleneuracil, 5-bromo-
3-isopropyl-6-methyluracil, 3-
(t-butyl)-5-chloro-6-methyluracil, etc. Nitriles include 2,6-dichlorobenzonitrile, diphenylacetonitrile, 3,5
-dibromo-4-hydroxybenzonitrile,
3,5-diiodo-4-hydroxybenzonitrile and others include 2-chloro-N,N-diallylacetamide, N-(1,1-dimethyl-
2-propyl)-3,5-dichlorobenzamide, maleic hydrazide, 3-amino-1,
2,4-triazole, monosodium methane arsonate, disodium methane arsonate, N,
N-dimethyl-α,α-diphenylacetamide, N,N-di(n-propyl)-2,6-dinitro-4-trifluoromethylaniline, N,N
-di(n-propyl)-2,6-dinitro-4-
Methylaniline, N,N-di(n-propyl)-
2,6-dinitro-4-methylsulfonylaniline, O-(2,4-dichlorophenyl)-O-methyl-isopropylphosphoramide thioate, 4
-amino-3,5,6-trichloropicolinic acid,
2,3-dichloro-1,4-naphthoquinone, dimethoxythiocarbonyl disulfide, 3-isopropyl-1H-2,1,3-benzothiadiazine. (4) 3H-one-2,2-dioxide, 6,
7-dihydrodipyridol [1,2-a:2':
1'-c] pyrazinium salt, 1,1'-dimethyl-
4,4'-bipyridinium salt, 3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H
-1,3,5-thiadiazine, 1,2-dimethyl-3,5-diphenylpyrazolium methylsulfate, N-sec-butyl-2,6-dinitro-
3,4-xylidine, N-(sec-butyl)-4-
(t-butyl)-2,6-dinitroaniline,
^N3 , ^N3 -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine, 1,1,1-trifluoro-(4'-phenylsulfonyl)methanesulfono-O-toluidine,
2-(1-naphthoxy)-N,N-diethylpropionamide, 2-(t-butyl)-4-(2,4-
dichloro-5-isoproboxyphenyl)-1,
3,4-oxadiazolin-5-one, 4-chloro-5-methylamino-2-(α,α,α-trifluoro-m-tolyl)-3(2H)-pyridazinone, N-cyclopropylmethyl- α,α,α-trifluoro-2,6-dinitro-N-propyl-
Examples include p-toluidine and N-phosphonomethylglycine. When using a mixture of the compound of the present invention and the above-mentioned herbicide, it goes without saying that the mixing ratio and the amount of the herbicide used will vary depending on the selectivity and efficacy of the crop to be treated and the desired weed control. Next, blending examples will be described, but it goes without saying that the types and blending ratios of additives are not limited to these, and can be varied within a wide range. However, the numbers are shown in weight percentages. Formulation Example 1 Wettable powder The compound of the present invention 30%, higher alcohol sulfate ester sodium salt 5%, clay 65% or more are mixed and pulverized uniformly to prepare a wettable powder. Formulation Example 2 Emulsion Compound of the present invention 25% Polyoxyethylene alkylaryl ether 10% Calcium dinaphthylmethane disulfonate 5% Xylene 60% or more are uniformly dissolved to form an emulsion. Formulation Example 3 Granules Compound of the present invention 3% Bentonite 40% Clay 50% Sodium ligninsulfonate 7% or more are uniformly mixed and pulverized, water is added, kneaded, and then granulated and dried to obtain granules. Formulation Example 4 Powder 2% of the compound of the present invention and 98% or more of clay are uniformly mixed and pulverized to form a powder. Next, the herbicidal activity of the compounds of the present invention will be specifically explained with reference to test examples. Test Example 1 Test against crops and upland weeds by ^pre -germination soil treatment Seeds of rice, corn, wheat, soybean, cotton, radish, wild field, crabgrass, sparrow gnome, jonson grass, and pigweed were placed per container in polyethylene containers with an area of 2000 cm2. 25 grains each
The seeds were sown at a depth of 0.5 cm, and the emulsions prepared according to Formulation Example 2 were mixed with active ingredient amounts of 0.5, 0.25, 0.125, and 0.062.
It was diluted with water to give kg/ha and 20 ml per container was uniformly sprayed on the soil surface. 20 days after spraying, the herbicidal effect and chemical damage to crops were investigated. The results were expressed as follows.

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[Table] Test Example ² Test against crops and upland weeds by treating foliage at the early stage of germination Rice, corn, wheat, soybean, cotton, radish, field weed, blackberry, sparrow gnome, jonsongrass, and pigweed were placed in polyethylene containers with an area of 2000 cm2. 25 seeds were sown per container, and after sowing, when the test plants reached 2 to 4 leaves, an emulsion prepared according to Formulation Example 2 was added with the amount of active ingredient.
It was diluted with water to 125, 62.5, and 31.25 ppm, and 20 ml per container was sprayed on test plants. 20 days after spraying, the herbicidal effect and chemical damage to crops were investigated. The results were expressed as follows.

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[Table] Test Example 3 Test against crops and upland weeds by ^pre -germination soil treatment Seeds of Japanese wildflower, crabgrass, Japanese radish grass, rice, corn, wheat, soybean, cotton, radish, and pigweed were placed in polyethylene containers with an area of 2000 cm2. 25 seeds per seed were sown at a depth of 0.5 cm, and the moisture content of the surface soil was set at 8-10. For herbicide treatment, an emulsion prepared according to Formulation Example 2 was diluted with water to give an active ingredient amount of 0.4, 0.2, 0.1, or 0.05 kg/ha, and 20 ml per container was uniformly sprayed on the soil surface. 20 days after spraying, the herbicidal effect and chemical damage to crops were investigated. The results were expressed as follows.

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[Table] Test Example 4 Test against crops and field weeds by foliage treatment 25 seeds each of Japanese wildflower, crabgrass, japonica grass, corn, wheat, soybean, cotton, radish, and pigweed were placed in polyethylene containers with an area of ²⁰⁰⁰ cm 3 . After sowing, the test plants
1.5~ When reaching the 3 leaf stage, reduce the surface soil moisture by 8~
An emulsion prepared according to Formulation Example 2 with a concentration of 10% was diluted with water to give an active ingredient amount of 200, 100, 50, 25, and 12.5 ppm, and 20 ml per container was sprayed on test plants. 25 days after spraying, the herbicidal effect and chemical damage to crops were investigated. The results were expressed as follows.

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[Table] Test Example 5 Rain Resistance Test 30 seeds of Japanese millet were sown per container in polyethylene containers with an area of ¹⁰⁰⁰ cm2, and 4.5
When the plant reached the ~5 leaf stage, an emulsion prepared according to Formulation Example 2 was diluted with water to give an active ingredient amount of 500 and 250 ppm, and 10 ml per container was sprayed on the test plants. After spraying, artificial rainfall was applied for 15 minutes at a rate of 20 mm per hour at 1/4, 1/2, 1, 3, 6, and 12 hours. The herbicidal effect was investigated 20 days after treatment. The results were expressed as follows.

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[Table] Test Example 6 Residual Effect Test in Soil A polyethylene container with an area of 2000 cm ² was filled with upland soil (Kikugawa Town), and the emulsion prepared according to Formulation Example 2 was mixed with an active ingredient amount of 0.8 and 0.4 kg. The solution was diluted with water to a volume of /ha and 20 ml per container was uniformly sprayed onto the soil surface. After the treatment, the seeds of the test plants were sown every week. On the 20th day after sowing, the degree of suppression of wild fleas was investigated to determine the residual effect of each drug. The results were expressed as follows.

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Claims (1)

[Claims] 1 formula Tolyloxyphenoxypentenoic acid derivative represented by 2 formulas A herbicide characterized by containing a tolyloxyphenoxypentenoic acid derivative represented by as an active ingredient.