JPS60243045A - Substituted phenoxyphenylacetic acid or thioacetic acid derivative and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X is O, S; R is halogen, cyano, OH, mercapto, hydrocarbyloxy, hydrocarbylthio, epoxy, acyl, acyloxy, acylthio, substituted or unsubstituted amino, alkyl or alkenyl which are substituted with heterocyclic groups]. EXAMPLE:1-Methyl-2-methoxyethyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy) phenylacetate. USE:Selective herbicide: it can do selective control of weeds in crop plants such as rice, cereal, cotton and so on with reduced application amounts by pre- or post- emergence application without damage to the crop plants and injury to mammarian animals and fishes. PREPARATION:For example, the reaction of 4-trifluoromethylphenol derivative of formula II (M is alkali metal) with a phenylacetic derivative of formula III(Y is halogen) is carried out in an inert solvent to give the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel 2-nitro-s which has selective herbicidal properties and can be suitably used as a weed control pesticide for various agricultural crops.
-(2'-Chloro-4'-trifluoromethylphenoxy)phenylacetic acid or thioacetic acid derivatives and selective herbicides containing the same as active ingredients.

Conventional technology Up to now, 4-4-carbon fibers with a carboxyl group, alkoxycarbonyl group, carboxyl-substituted alkyl group, etc. bonded to the 3-position have been developed.
It is known to use nitro-cuchloro-4'-trifluoromethyldiphenyl ether as a herbicide (Japanese Patent Publication No. 58-25<411).

However, conventional diphenyl ether herbicides
In general, those that exhibit strong herbicidal power have low selectivity;
Furthermore, those that exhibit high selectivity tend to have weak herbicidal power, making it impossible to efficiently and quickly remove only specific weeds.

By the way, in addition to strong herbicidal power and high selectivity, conventional herbicides have low toxicity to warm-blooded animals, can be commonly used throughout the entire growing season of crops, and can be used for a long time after being used sparingly. Ideally, it should have the following requirements: to decompose as quickly as possible and not contaminate the soil, but diphenyl ether-free herbicides that meet these requirements are
Not yet known.

Problems to be Solved by the Invention Under these circumstances, the present inventors have overcome the drawbacks of conventional diphenyl ether herbicides, and are harmless to cultivated crops and are effective against other herbicides that coexist with them. A novel diphenyl ether system that has selective and strong herbicidal power that allows rapid removal of unwanted plants, can be used consistently throughout the growing period of the crop, and has low toxicity to warm-blooded animals. As a result of repeated research to develop herbicides, 2-nitro-5-(2'-chloro-4'-
A novel ester of trifluoromethylphenoxy)phenylacetic acid or thioacetic acid that meets the above requirements and is useful for a wide range of broad-leaved and legume plants, such as cotton, soybean, corn, wheat, and rice, at low application rates. As a result, we have completed the present invention.

Means for solving the problem, that is, according to the present invention, the general formula (wherein, group, epoxy group,
A novel 2-nitro-5-( 2'-chloro-
This objective can be achieved by using 4'-)lifluoromethylphenoxy)phenylacetic acid or thioacetic acid derivatives as active ingredients in herbicides.

The compounds of the present invention act effectively as pre- and post-emergence herbicides on various agricultural crops at much lower application rates than conventionally known compounds with similar structures,
Moreover, it was completely unexpected that it did not cause any harm to mammals, seafood, etc.

The compound of the present invention is characterized by the R group in the general formula (1). That is, in the compounds known so far, this R is a lower alkyl group without a substituent, such as a methyl group, whereas in the compounds of the present invention, R is a straight chain or a lower alkyl group substituted with a specific substituent. It is a branched alkyl group.

The specific substituent that R has in the compound of the present invention is a halogen atom, a cyan group, and a hydroxyl group.

A hydrocarbyloxy group, a hydrocarbylthio group, an epoxy group, an acyl group, an acyloxy group, an acylthio group, a substituted or unsubstituted amine group, or a heterocyclic group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Also,
A hydrocarbyloxy group is a hydroxyl group in which the hydrogen atom is substituted with a hydrocarbon group, that is, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an alkynyl group, and when an aromatic ring is present in this group, may further have a substituent. Examples of the hydrocarbyloxy group include a methoxy group, an ethoxy group, an allyloxy group, a propynyloxy group, a benzyloxy group, and a p-methylbenzyloxy group. Next, a hydrocarbylthio group is a group in which a sulfur atom is substituted for the oxygen atom of a hydrocarbyloxy group.
Examples include methylthio group, ethylthio group, allylthio group, and benzylthio group. The above acyl group, acyloxy group, and acylthio group may be either aliphatic or aromatic, and may be further substituted. Examples of such groups include acetyl, glopionyl, benzoyl, acetyloxy, butyroyloxy,
Examples include acetylthio group. Further, the substituted amine group may be mono-substituted or di-substituted, and includes, for example, a monomethylamine group, a dimethylamino group, a monomethylamine group, a diethylamino group, a /thylethylamino group, and a methylmethoxyamino group.

Next, the above-mentioned heterocyclic group may be completely unsaturated, or may be partially or completely saturated.

Examples of such substances include thiophene, furan,
Mention may be made of groups derived from virol, pyridine, quinoline, piperazine, imidazole or hydrides thereof.

Next, specific examples of the compound of the present invention represented by the general formula (1) include, for example, 2-nitro-5-(2''chloro-4'
-)Lifluoromethylphenoxy)phenylacetic acid 2-1
0 loethyl, 2-nitro-5-(2'-chloro-4'-
trifluoromethylphenoxy)phenylacetic acid cyanmethyl ester, 2-nitro-5-(2'-chloro-4'
-trifluoromethylphenoxy)phenylacetic acid 2-hydroxyethyl ester, 2-nitro-5-(2'-chloro-41-trifluoromethylphenoxy)phenylthioacetic acid 5-2-chloroethyl ester, 2-nitro-
5-(2'-chloro-4'-11fluoromethylphenoxy)phenylthio Il[5-1-methyl-2-hydroxyethyl ester, 2-'nitro 5-(2'-chloro-4'-)ly 2-(4-methoxybenzyloxy)ethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid2. +-Epoxypropyl ester, 2-nitro-5-(2'-chloro-4
'-trifluoromethylphenoxy)phenylacetic acid methylcarbonylmethyl ester, 2-nitro-s-(2
'-chloroo-4'-)trifluoromethylphenoxy)phenylacetic acid 5-2-methylcarbonylethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-phenylcarbonylethyl ester, 2-nitro-5-(2'-
Chloro-4'-) IJ fluoromethylphenoxy)phenylacetic acid 2-acetoxyethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)pheny/I/acetic acid 2-benzoyloxyethyl ester , 2-nitro-5-(2'-chloro-4'-
Trifluoromethylenoxy]phenylacetic acid 2- (
N,N-dimethylamine]ethyl ester, 2-nitro-5-(2'-chloroalhlyfluoromethylphenoxy)phenylacetic acid 2-(N-methyl-N-methoxyamino)ethyl ester, 2-nitro-5 -(,2'-chloro-4'-trifluoromethylphenoxyraphenylacetic acid 1-methoxyethyl ester, 2-nitro-5-(
21-chloro-4'-trifluoromethylphenoxy)
Phenylacetic acid 1-methyl 2-methylcarbonyloxyethyl ester, 2-nitro-5-(2'-chloro-4'
-trifluoromethylphene/+shi]phenylacetic acid 3-chloro-2-propenyl ester, 2-nitro-5-(2
'-chloro-4'-trifluoromethylphenoxy]phenylacetic acid N-methyl-4-piperidylmethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2- Tetrahydropyranyl methyl ester, 2-nitro-s-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid furfuryl ester, 2-nitro-5-('2'-
chloro4”-) +7 fluoromethylphenoxy) phenyl 1n2-(2-chenyl)ethyl ester, 2-
Nitro-s-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 6-(3-pyridylcopropyl ester, 2-nitro-5-(2'-chloro-4
'-Trifluoromethylphenoxy)phenylacetic acid benzyl ester, 2-nitro-5-(2',6'-dichloro-4'-trifluoromethylphenoxy)phenylacetic acid 4-methylbenzyl ester, 2-nitro-5-( 2
'-Chloro-4'-trifluoromethylphenoxy]phenylIt acid 2-)lifluoroacetoxyethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-(2 -chlorobenzoyloxy)ethyl ester, 2-nitro-s
-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-bromomethylcarbonylethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-( -6-
medoxyphenylcarbonyl)ethyl ester, 2-nitro-5-(2'-chloro-47-trifluoromethylphenoxy)phenylacetic acid 2-acetylthioethyl ester, 2-nitro-5-(2'-chloro-4 '-Trifluoromethylphenoxy)phenylacetic acid 2-pensoylthioethyl ester, 2-nitro-5-(2'-chloro-4'-)')fluoromethylphenoxy)phenyl (1+[2-methoxyethyl ester, 2 -nitro-s
-(2'-chloro-4'-trifluoromethylphenoxy)phenyl [1J22-ethoxyethyl ester,
2-nitro-5-(2'-10rho4'-trifluoromethylphenoxy)phenyl W+[2-(1-methylethoxy)ethyl ester, 2-nitro-s-(2'-
Chloro-4'-trifluoromethylphenoxy)phenyl? '+ acid 2 (2-propenyloxy) ethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy) phenyl acetic acid 2-(2-propenyloxy) ethyl ester, 2-nitro- 5-(2'
-Chloro-4'-)lifluoromethylphenoxy)phenylacetic acid 2-phenylmethoxyethyl ester, 2-
Nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 6-methoxyethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 6- Ethoxyglobyl ester, 2-nitro-5-(2'-chloro-4'
-trifluoromethylphenoxy)phenylacetic acid 3-(
1-methylethoxy)furoyl ester, 2-nitro-
s -(2'-chloro-4'-trifluoromethylphenoxy)phenyl Ir acid 3-(2-propenyloxy)
Propyl ester, 2-nitro-5, (2”l flow 4
'-) ') Fluoromethylphenoxy) phenylacetic acid 1-1 thyl-2-methoxyethyl ester, 2-nitro-s -(2'-chloro-4'-trifluoromethylphenoxyraphenylacetic acid 2-ethoxy-1- Methyl ethyl ester, 2-nitro-5-(2'-chloro-4'-
trifluoromethylphenoxy)phenylacetic acid 1-methyl-2-(1-methylethoxy)ethyl ester, 2
--1-1-0-5'-(2',-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 1-methyl-2-(2-propenyloxy)ethyl ester, 2-
nitro-5-(2'-chloro-41)lifluoromethylphenoxy)phenylacetic acid methylthiomethyl ester,
2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid ethylthiomethyl ester, 2. -nitro-5- (2'-chloro-47-trifluoromethylphenoxyraphenylacetic acid 1-methylethylthiomethyl ester, 2-nitro-5-(2'-
Chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-propenylthiomethyl ester, 2-nitro-5-(2'-10-4'-trifluoromethylphenoxy)phenylacetic acid 2-propynylthiomethyl ester, 2- Nido-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-methylthioethyl ester, 2-nitro-5-(2'-chloro-4'
-trifluoromethylphenoxy)phenylacetic acid 2-ethylthioethyl ester, 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-(2-propenylthio]ethyl ester, 2-
Nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-(2-propynylthio)ethyl ester 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy) Phenylacetic acid S-methoxymethyl ester, 2-nitro-s-(2
'-Chloro 4/)lifluoromethylphenoxy) phenyldithioacetic acid s-ethoxymethyl ester, 2-nido-5-(2'?Roreau 4/)lifluoromethylphenoxy]phenylthioacetic acid s-2-methoxyethyl ester, 2-nitro-s (2/-chloro-4'-)lifluoromethylphenoxy)phenyldithioacetic acid-2
-Ethoxyethylvarnish 7/2-nitro-5- (
2'-chloro-4'-tri7fluoromethylphenoxy)
Phenylthioacetic acid B-2-(2-flobenyloxy)ethyl ester, 2-nitro-s-(2'-chloro-4'-MJ fluoromethylphenoxypropyl ester, 2-=)rho-s-(2'-1).

Low 4'-)! J Fluoromethylphenoxy] phenylthioacetic acid S-1-methyl-2-methoxyethyl ester, 2-nitro-s (2/-chloro-4'-trifluoromethylphenoxy) phenylthioacetic acid EI -
Examples include 2-methylthioethyl ester.

These compounds are all new compounds that have not been published in any literature, and can be produced, for example, according to Methods A to E shown below.

[Method A]

<B) (Ill) (IV) (I') (R in the formula has the same meaning as above) That is, 6-(:4'-t1) represented by the formula (It)
Alcohol-toluenesulfonic acid, etc. represented by the formula Gl[) is catalyzed and dehydrated by a conventional method (2) in an inert organic solvent such as benzene or toluene. A 3-(4'-trifluoromethylphenoxy)phenylacetate derivative of formula (IV) is obtained.Subsequently, acetyl nitrate, potassium nitrate in sulfuric acid, mixed sulfuric acid/nitric acid, nitronium tetrafluoro The compound of the present invention can be obtained by nitration with a similar nitrating agent (2).The reaction temperature in the nitroich reaction is generally (- is about -2
0°C to about ioo°C, preferably about -10°C to about 50°C
C. and optionally in the presence of an inert organic solvent such as 12-dichloroethane or other chlorinated hydrocarbon.

[Method B]

(II) (,]II') (having the same meaning as R in the formula or as above), that is, 3-(4'-) represented by the formula (Il)! The compound of the present invention can be obtained by obtaining the j-fluoromethylphenoxy)phenylacetic acid derivative and the intermediate represented by the formula, and then nitrating it in the same manner as the hexamethoxymethod. The dehydrating agent used here may be a reactive type dehydrating agent that performs dehydration through a chemical reaction, or an adsorption type dehydrating agent that performs physical dehydration.

As the reactive dehydrating agent, for example, N,N'-dicyclohexylcarbodiimide (DOO) or a mixture of silicon tetrachloride and pyridine can be used. Further, as the adsorption type dehydrating agent, for example, Molecular Sheep 5A or the like can be used in a non-aqueous solvent system.

[C method]

(IV') (I) 3-(4'-t!jfluoromethylphenoxy)phenyl represented by formula (V) Acetate halide derivatives and formula (■′
] by reacting the compound represented by the formula (■
After obtaining the intermediate represented by , the compound of the present invention can be obtained by nitration in the same manner as in Method A. Solvents used here include, for example, ether solvents such as diethyl ether and tetrahydrofuran, aromatic solvents such as toluene, halogenated hydrocarbons such as chloroform, N,N-dimethylformamide and dimethyl sulfoxide. Aprotic polar solvents and the like can be used alone or in combination of two or more thereof, and in some cases, water can also be used as a solvent.

Acid binders include, for example, tertiary amines such as triethylamine and pyridine, alkali metal alcoholides such as sodium methylate and sodium ethylate, alkali metal carbonates and bicarbonates such as potassium carbonate and sodium bicarbonate. Carbonates can be used. Alkali metal hydroxides such as potassium hydroxide and sodium hydroxide can also be used as acid binders in combination with water solvents.

[Method D].

]1 (Vl) (Vi) O 111 (■ (I) (M in the formula is an alkali metal, R, X and Y have the same meanings as above) Substituted phenylacetic acid and substituted Formula 9 (■
After obtaining the intermediate represented by '], it can be obtained using Method A. The alkali metal salt represented by formula 1 (Vl) is an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkali metal alcoholade such as sodium methylate or sodium ethylate, or an alkali metal salt such as potassium carbonate. It is easily obtained by the reaction of a metal carbonate, etc. with a free acid, and the alkali metal salt can be obtained by reaction with a halogenide represented by the formula (VH) after or without isolation. can be provided. Solvents that can be used include ether solvents such as tetrahydrofuran and 1,4-dioxane, carbonyl solvents such as acetone and ethyl methyl ketone, aromatic solvents such as benzene and toluene, N,N-dimethylformamide, etc. Aprotic polar solvents such as dimethyl sulfoxide can be used alone or in combination.

[Law 8].

1 0H2-0-X-ROJ OH, -0-X-R-μ A
-, (' bar- (wherein R, The compound of the present invention can be obtained by reacting the compound with a phenylacetic acid derivative.This reaction is generally carried out at 0°C to 25°C.
It can be carried out at a temperature of 0°C, preferably between about 60°C and 180°C. This reaction can also be carried out using a suitable solvent, such as sulfolane, dimethyl sulfoxide, N,
It can be carried out in N-dimethylformamide, hexamethylphosphorustriamide or other inert organic solvents.

In addition, in the He method or D method, nitration is performed in the final step, but first the formula (■ with (■)) or (
After nitration of the raw material compound represented by VI), predetermined esterification and other reactions can also be carried out.

Next, the herbicidal action of the compounds of the present invention will be explained using an example of weed control in paddy rice. The compounds of the present invention can be applied over a wide period of time from before to after transplanting paddy rice, and are particularly capable of powerfully and rapidly killing barnyard grass, a highly damaging grass weed in paddy fields. on the other hand,
At the effective dose of the compound of the present invention applied to weeds, almost no phytotoxicity is observed in paddy rice. Furthermore, the compound of the present invention also exhibits strong herbicidal activity against broad-leaved weeds that grow in paddy fields, such as Prunus elegans, Kikashigusa, water chickweed, and azalea, making it possible to obtain a satisfactory herbicidal effect with an unprecedentedly low dose. . The compound of the present invention is generally used in an amount of 0.5 to 100 g/10a, particularly preferably 1.5 to 50 g/10a, which exhibits excellent herbicidal effects. This dose is the same as that of 2,4.6 F')chloro-1-(4'-nitronenoxy)benzene, 2,4-dichloro-1-(s'-
Methoxy-4'-nitrophenoxy)benzene, 2-nitro-5-(2'.

Compared to the effective dose of 200 to 2 soy/1 oa of 4'-cyclolonenoxy]benzoic acid methyl ester, the compound of the present invention has a surprisingly low value of 6D, and has far more powerful herbicidal activity than conventional known compounds. It can be seen that it has

Furthermore, the compounds of the present invention have extremely strong herbicidal activity against upland weeds other than paddy field weeds. That is,
The compounds of the present invention are used, for example, in broad-leaved weeds such as Japanese knotweed, Japanese knotweed, Japanese knotweed, chickweed, and bindweed;

It exhibits strong herbicidal activity against various weeds such as Poaceae weeds such as Sparrow grass at low doses. The compound of the present invention has a high degree of selectivity in pre- and post-emergence treatments not only for broad-leaved crops such as soybeans and cotton, but also for legume crops such as rice, corn, and wheat. It is that you are. The compound of the present invention can also be used as a herbicide for pastures, orchards, lawns, and non-agricultural lands by taking advantage of its wide herbicidal range and strong herbicidal power.

A known compound [2-nitro-s-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid methyl ester] which has a similar structure to the compound of the present invention does not show loading selectivity between rice and barnyard grass. There is a drawback. In contrast, the compound of the present invention is different from conventional diphenyl ether herbicides in that it has outstanding activity and extremely excellent loading selectivity for grasses, making it an extremely powerful and useful herbicide. can.

Therefore, the compounds of the present invention can be used in rice and cereals, e.g.
It can be used to selectively weed weeds in barley, wheat, and even corn, soybeans, and cotton.
And these can be applied both pre- and post-emergence of weeds.

The compounds of the invention can be used in a wide range of application rates, for example from 0.5 to io in 10 ares.

g, preferably from 1.5 to 50.9 g.

When actually using the compound of the present invention, the active substance itself can be sprayed, and any formulation form such as an aqueous solution, emulsion, granule, or powder can be used.

In preparing these pharmaceutical products, solid carriers include, for example, mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, ceracola, calcium carbonate, phosphoric lime, etc.), vegetable powders, etc. quality powders (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resins, polyvinyl chloride, ketone resins, etc.), and
Alumina, waxes, etc. can be used.

Examples of liquid carriers include alcohols (methanol, ethanol, butanol, ethylene glycol,
benzyl alcohol), aromatic hydrocarbons (toluene, benzene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, monochlorobenzene, etc.),
Ethers (dioxane, tetrahydrofuran, etc.),
Ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), acid amides (N,N-dimethylacetamide, etc.), nitriles (acetonitrile, etc.), ether alcohols (ethylene glycol ethyl [ether, etc.] or water, etc. can be used.

As the surfactant used for the purpose of emulsification, dispersion, diffusion, etc., any of nonionic, anionic, cationic and amphoteric surfactants can be used. Examples of surfactants that can be used in the present invention include polyoxyethylene alkyl erthyl, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, oxyethylene Polymer ~, oxypropylene polymer, polyoxyethylene alkyl phosphate, fatty acid salt, alkyl sulfate, alkyl sulfonate, alkylaryl sulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate, quaternary Examples include ammonium salts and oxyalkylamines, but needless to say, they are not limited to these. Moreover, gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol, etc. can be used as adjuvants, if necessary.

Furthermore, the compound of the present invention can be used in combination with other herbicides to improve its effectiveness as a herbicide, and in some cases, a synergistic effect can be expected. For example, the following components can be used together.

(A) Phenoxy herbicide 2.4-dichlorophenoxyacetic acid; 2-methyl-4-chlorophenoxyacetic acid; butyl-2-(4-(5-)lifluoromethyl-2-pyridyloxy]phenoxy]gropionate ( (including respective esters and salts); ethyl-2-(4-(6-chloro-2-quinoxalinyloxy)phenoxy)globionate, etc.

(B) Diphenyl ether herbicide 2,4-dichlorophenyl-4'-nitrophenyl ether, 2,4.6-)dichlorophenyl-4'nitrophenyl ether; 2,4-dichlorophenyl-4
'-Nitrow 3'-methoxyphenyl ether; 2.4
-dichlorophenyl-3'-methoxycarbonyl-4'
-Nitrophenyl ether i2-chloro-4-)lifluoromethylphenyl-3'-ethoxy-4'-nitronenyl enithel; 5-(2-ri.

Ru-4-()lifluoromethyl)phenoxycou-2-nitrobenzoic acid sodium salt, etc.

(C) Triazine herbicide 2-chloro-4,6-pisethylamino-1,3.5-
Triazine; 2-chloro-4-ethylamino-6-ingrobylamino-1,3,5-)riazine; 2-methylthio-4,6-pisethylamino-1,6°5-triazine, etc.

(D) Urea herbicide 3-(3,4-dichlorophenyl)-1,1-dimethylurea 13-(5,4-dichlorophenyl]-1-methoxy-1-methylurea; 6-(α, α, α-trifluoro m-)lyl)-1,1-dimethylurea; s-
[4(4-Me-tylphenethyloxy)phenylter 1
-methoxy-1-methylurea;' (s-t-butyl-5,4-thiadiazol-2-yl)-4-hydroxy-1-methyl-2-imidazolitone, etc.

(Uniform carbamate herbicide isopropyl-N-(3-chlorenyl)carbamate; methyl-N-(3,4-'dichlorphenyl)carbamate;4-chloro-2-butynyl-N-('3-chlorphenyl) Carbamate nato.

(g) Thiol carbamate herbicide S-ethyl-N, N-hexamethylenethiol carbamate 1S-(4-chlorobenzyl)-N, N-diethylthiol carbamate) iS-ethyldipropylthiol carbamate, etc.

(G) Anilide herbicide 6.4-dichloropropionanilide; N-methoxymethyl-2', 6'-diethyl-2-chloroacetanilide; 2-chloro-2/, 6J-diethyl-N-(butoxymethyl )-acetanilide; 2-chloro-2”,
6'-diethyl-N-(progoxyethyl)-acetanilide; α-(2-nandoxy)propionanilide, and the like.

(b) Uracil herbicides such as 5-bromo-3-sθC-butyl-6-methyluracil; 3-cyclohexyl-5,6-)rimethyleneu2cil;

(Engineering) Dipyridinium salt herbicide 1.1'-dimethyl-4,4'-dipyridinium dichloride; 1. i'-ethylene-2,2'-dipyridinium dibromide and the like.

+J) Phosphorus herbicide N-(phosphonomethyl)glycine;〇-ethyl〇-(
2-Nitro-5-methylphenyl)-N-5ec-butylphosphoramidothioate;
s -(2-methyl-1,1-nitro-4-methylphenyl)-N-isopropylphosphoroamidothioate
(2-amino-4-methylphosphino-butyryl)-alanylalanine monosodium salt, etc.

(5) Toluidine herbicide α,α,α-trifluoro-2,6-sinitro-N.

N-dipropyl-p-)luidine; N-(cyclopropylmethyl]-α,α,α-trifluoro-2I6-sinitro N-propyl-I)-)luidine, and the like.

(L) Other herbicides 5-t-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazoline-
2-one; 3-improvil-2,1,3-benzothiadiazinone-4,2,2-dioxide; 2-(α-naphthoxy)-N,N-diethylpropionamide; 6-
Amino-2,5-dichlorobenzoic acid; 4 (2,4-dichlorobenzoyl)-1,3-dimethylpyrazole-
5-yl-p-)luenesulfonate; 2-chloro-N
-((4-methoxy-6-methyl-1,3',5-)riazin-2-yl)aminocarbonyl]benzenesulfonamide; 2-((4,6-cymethoxypyrimidin-2-yl)aminocarbonyl Aminosulfonylmethyl]
Benzoic acid methyl ester; N-(i-methyl-1-phenylethyl)-2-7'romo5.3-dimethylp,tanamide; 2-(1-(N-allyloxyamino)butylidene 4-methoxycarbonyl-5゜5-dimethylcyclohexane-1,3-dione sodium salt; 2-(
1-(ethoxyimino)butyl]-5-(2-ethylthiopropyl)-6-hydroxy-2-cyclohexane-
1-Onnato.

The above herbicides are merely examples, and it goes without saying that other herbicides that can be used in combination with the compound of the present invention are not limited to these. The herbicide of the present invention can also be used in combination with pyrethroid insecticides, other insecticides, fungicides, plant regulators, microbial pesticides, and fertilizers.

EXAMPLES Next, the method for producing the compounds of the present invention will be explained in more detail with reference to Examples.

Example 1 Preparation of 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxyraphenyl acetic acid 2-methoxyethyl ester a) 3-(2'-chloro-4'-trifluoromethylphenoxyla Phenyl in 3.3F, 2-methoxyethanol 1.51 was dissolved in 5 oul of benzene, and p
-) After adding 0.5.9 g of luenesulfonic acid, the mixture was heated under reflux for 6 hours. After the reaction was completed, 50 ml of ether was added, washed with water in the usual manner, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 3i-(2'-chloro-47)lifluoromethylphenoxy)phenylacetic acid. 3.9y of 2-methoxyethyl ester was obtained.

b) 6.9 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-methoxyethyl ester obtained in a) was added to 35 g of acetic anhydride, and the mixture was heated to below 10°C in a water bath while stirring. Cooled. Subsequently, 2.9 g of copper nitrate was gradually added over 5 minutes. After the addition was completed, the reaction was completed at 10° C. or lower for 1 hour and then at room temperature for 5 hours. The reaction solution was placed on ice, 200@l of ether was added, and the reaction solution was neutralized with an aqueous sodium hydroxide solution. After further acidifying with hydrochloric acid, the ether extract layer was separated, washed with water and dried over anhydrous sodium sulfate, and the ether was distilled off under reduced pressure. The resulting crude crystals were recrystallized from a mixed solvent of ethyl acetate/n-hexane. ,
2-nitros-(2') with melting point 71.9-72.5°C
3 g of white crystals of -chloro-4'-trifluoromethylphenoxy)phenylacetic acid 2-methoxyethyl ester were obtained.

Example 2 Preparation of 2-nitro-5-(2'-chloro-47-trifluoromethylphenoxy)phenylacetic acid 1-methyl-2-methoxyethyl ester 2-chloro-4-trifluoromethylphenol 2I was dissolved in dimethyl sulfoxide ( DMSO), 1.6 g of anhydrous potassium carbonate was added thereto, and the mixture was stirred at room temperature for 1 hour. followed by 6-fluoro-6-nitrophenylacetic acid 1-methyl-2-meth)-1-diethyl ester 2
．． 7 g was added, stirred at room temperature for 30 minutes, and then reacted at 70°C for 2 hours. After the reaction was completed, 50 ml of water was added to the reaction solution, and the mixture was extracted twice with 30 ml of ether. The ether layer was washed with water, dried over anhydrous sodium sulfate, the ether was distilled off under reduced pressure, and the resulting crude crystals were recrystallized from a mixed solvent of ethyl acetate/n-hexane, with a melting point of 78.9 to 79.6. White solid of 2-nitros-(2'-chloro-4'-trifluoromethylphenoxy)phenylacetic acid 1-methyl-2-methoxyethyl ester at 3. I got sg.

Example 3 In the same manner as in Example 1, the first
Compounds having the substituents shown in the table were prepared.

Table 1 shows these physical property values and analysis results.

1 Next, a formulation example when the compound of the present invention is used as a herbicide and its herbicidal effect will be shown as an application example.

Application Example Prescription Example 1 (Irrigation agent) 25 parts by weight of the compound of the present invention, 95 parts by weight of Tsurupol 5039 (manufactured by Toho Chemical Industry Co., Ltd., trade name), and 70 parts by weight of talc.
The parts by weight are thoroughly ground and mixed to make an irrigation agent.

Formulation Example 2 (Emulsion) An emulsion is prepared by thoroughly mixing 5 parts by weight of the compound of the present invention, 10 parts by weight of Tsurupol 5005X (manufactured by Toho Chemical Industry Co., Ltd.), 45 parts by weight of n-butanol, and 40 parts by weight of xylene.

Formulation Example 6 (Granules) 1 part by weight of the compound of the present invention, 45 parts by weight of bentonite, 44 parts by weight of clay, 5 parts by weight of sodium ligninsulfonate and 5 parts by weight of sodium dodecylbenzenesulfonate are thoroughly ground and mixed, and water may be added. After kneading, the mixture is granulated and dried to form granules.

Formulation Example 4 (Powder) 1 part by weight of the compound of the present invention and 99 parts by weight of clay are thoroughly ground and mixed to form granules.

The amount of the herbicide of the present invention to be used varies depending on the method of use, place of use, and type of target weed, but it is usually sufficient to use an amount of 1.5 to 50 g (active ingredient) per 10 ares.

Usage Example 1 A 1/5000 R pot filled with paddy soil was prepared in a greenhouse. For rice, seedlings at the 3-leaf stage are placed in the soil surface layer 2~Sa.
Transplanted to n. In addition, a method was used in which the seeds of Japanese barnyard grass, Japanese grasshopper, and annual broad-leaved weed seeds were mixed with dry paddy soil and mixed into the surface layer. Furthermore, as a perennial weed,
The 6-drug treatment with sowing firefly seeds resulted in barnyard grass 0.5 to 0.5%.
At the 1.0 leaf stage, a predetermined concentration of emulsion (formulation method 2) was dropped with a pipette. 21 days after the chemical application, the degree of chemical damage to rice and weed control ability was observed. The results are shown in the second column.

The values in the table are based on the following criteria.

5: Complete suppression 4: 80% suppression 3: 60% suppression 2: 40% suppression 12 20% suppression 0: No effect A 1 are pot filled with upland soil was prepared. Seeds of soybean, corn, crabgrass, Japanese knotweed, and Japanese knotweed were sown in each pot.

Pre-germination treatment was carried out 24 hours after sowing with 10 are per kg) 60
g was applied. On the other hand, post-emergence treatment.

For soybeans, 30 g per 10 als was applied at the 2nd to 6th leaf stage, for corn at the 6th to 4th leaf stage, and for weeds at the 2nd to 2nd and 5th leaf stage. The spraying method is as follows:
) was diluted with R*)*s7 water and applied with a glass sprayer. The degree of weed control ability was observed on the 14th day after chemical treatment, and the degree of chemical damage to the crops was observed on the 30th day. The results are shown in Table 3. Note that the criteria in the table are the same as in Use Example 1.

Procedural amendment dated June 19, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 1110062 of 1982, Title of the invention Substituted phenoxyphenylacetic acid or thioacetic acid derivatives and their use as active ingredients Relationship between herbicide 3 and the amended case Patent applicant representative Teru Miyazaki 4, agent Kawa Shimitsu Kuninobu Building 8th floor 5, 2-2-2 Shinbashi, Minato-ku, Tokyo
, Date of amendment order Initiation 6, Number of inventions increased by amendment 0 7, Subject of amendment Detailed explanation of the invention in the specification k, 8, Contents of amendment (1) Line 37 of the specification, page S] [...shown in Table 1] ] After that, add the following text on a new line.

Claims (1)

[Scope of Claims] 1 General formula 0 (in the formula, X is an oxygen atom or a sulfur atom, R is a halogen atom, a cyan group, a hydroxyl group, a mercapto group, a hydrocarbyloxy group, a hydrocarbylthio group, an epoxy group,
2-nitro-5-(2′ -Chloro-4'-
trifluoromethylphenoxy)phenylacetic acid or thioacetic acid derivatives. 2 General formula (in the formula, X is an oxygen atom or a sulfur atom, R is) ・Rogen atom, cyano group, hydroxyl group, mercapto group, hydrocarbyloxy group, hydrocarbylthio group, epoxy group, acyl group, acyloxy group, acylthio group 2-nitro-5-(2'-chloro-4'-
A herbicide containing a trifluoromethylphenoxy) phenyl acetic acid or thioacetic acid derivative as an active ingredient.