JPS6216451A - Novel acetophenone derivative containing substituent group at alpha-position and herbicide containing same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is group shown by the formula II; R<1> is H or methyl; m is 1-3; R<2> is OR<3>, SR<4>, etc.; R<3> is lower alkenyl, lower alkynyl, lower alkyl which may be replaced with halogen, cyano, etc.; R<4> is H, lower alkyl, lower alkenyl, etc.). EXAMPLE:Allyl 2-nitro-5-( 2'-chloro-4'-trifluoromethylphenoxy )phenacyloxyacetate. USE:A herbicide acting effectively on various crops with a small amount of application as a herbicide before or after germination, not providing mammals and fishes and shellfishes with damage. PREPARATION:A compound shown by the formula III is reacted with a nitrating agent such as potassium nitrate, sulfuric acid-nitric acid mixture, etc., in conc. sulfuric acid to give a compound shown by the formula I. The reaction is car ried out optionally in an inert organic solvent (e.g., 1,2-dichloroethane) at about -20 deg.C-100 deg.C.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a novel 5-(2'-chloro- The present invention relates to a 4'-trifluoromethylphenoxy-2-nitro-α-substituted acetophenone derivative and a selective herbicide containing the same as an active ingredient.

(Prior Art) Until now, it has not been known to use alkyl[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenyl koketones and their oxime derivatives as herbicides. (Unexamined Japanese Patent Publication No. 56-32432)
.

However, conventional diphenyl ether herbicides
In general, those that exhibit strong herbicidal power tend to have low selectivity, and those that exhibit high selectivity tend to have weak herbicidal power. I couldn't.

In addition to the strong herbicidal power and high selectivity of conventional herbicides, they also have low toxicity to warm-blooded animals.
Ideally, it should be able to be used commonly throughout the entire growing season of crops, and be able to decompose as quickly as possible after use without contaminating the soil.
A diphenyl ether herbicide that meets these requirements is not yet known.

(Problems to be Solved by the Invention) Under these circumstances, the purpose of the present invention is to overcome the drawbacks of conventional diphenyl ether herbicides, and to produce a herbicide that is harmless to cultivated crops and does not coexist with them. A novel diphenyl ether system that has selective and strong herbicidal power that can quickly eliminate other unwanted plants, can be used consistently throughout the growing period of the crop, and has low toxicity to warm-blooded animals. The aim is to provide herbicides.

(Means for Solving the Problems) As a result of extensive research, the present inventors found that 5-(2'-chloro-4'-)! jFluoromethylphenoky/)-2
It has been found that -ditoro α-substituted acetophenone derivatives are suitable for the above-mentioned purpose and are useful for a wide range of broad-leaved and carnivorous plants such as soybean, cotton, corn, wheat, and rice at low application rates. The present invention was made based on this knowledge.

That is, according to the present invention, alkenyl group in general formula (I): lower alkynyl group The lower a substituted with a dihalogen atom, cyano group, or alkoxy group is a hydrogen atom, a lower alkyl group, or a lower alkenyl group.

Group 111 is a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group, R'Fi lower alkenyl group: a lower alkynyl group: a lower alkyl group substituted with a cyano group or an alkoxy group, and 11
1 represents a hydrogen atom; 7'C represents a methyl group; %R' represents a lower alkyl group; RIG and RO represent a lower alkyl group; ] 5 −(
2'-chloro-4'-trifluoromethylphenoxy)
This objective can be achieved by using -2-nitro α-substituted acetophenone derivatives as active ingredients of herbicides.

The compounds of the present invention act more effectively as pre- and post-emergence herbicides on various agricultural crops than conventionally known compounds with similar structures at low dosages;
It was completely unexpected that it would cause harm to mammals, seafood, etc.

Furthermore, the compound of the present invention is an α-substituted acetophenone oxime derivative, whereas the compounds known so far are alkyl phenyl ketone and hisso oxime derivatives such as acetophenone and gropiofenone. be. It is a surprising fact that the compounds of the present invention exhibit excellent selectivity for various agricultural crops by introducing a substituent into the α-position of the carbonyl group.

Specific examples of the compound of the present invention represented by the general formula (I) are as follows.

Allyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyacetate 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyacetic acid 2 -butenyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy) phenacyloxyacetic acid propargyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy) 7-enacyloxyacetic acid Chloromethyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacylacetate 2-chloroethyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phena Siloxy 6-acid 2゜2.2
-Trifluoroethyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyacetate cyanmethyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy) 2-Cyanethyl phenacyloxyacetate 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy) 2-methoxyethyl phenacyloxyacetate 2-nitro-5-(2'-chloro-41- Trifluoromethylphenoxy) phenacyloxyacetic acid 1-methyl-
2-methoxyethyl 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy] phenacyloxyacetyl]
Methyl acetate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyacetyl]
Ethyl acetate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyacetyl]
Methyl propionate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyacetyl]
Ethyl propionate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]allyl propionate 2-[2-nitro-5-(2'-chloro-4') -trifluoromethylphenoxy)phenacyloxy]crotyl propionate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propargyl propionate 2-[2-nitro- Chloromethyl 2-[2-nitro-5-('2'-chloro-4'-trifluoromethylphenoxy)phenacyl 5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionate 2-chloroethyloxy]propionate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionate 2-[2- Nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]cyanomethyl propionate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phena siloxy]2-cyanoethyl propionate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy]phenacyloxy]2-methoxyethyl propionate 2-[2-nitro-5- 1-Methyl-2-methoxyethyl 2- (2-[:
2'-nitro57- (2#-chloro-4#-trifluoromethylphenoxy)phenacyloxyfupropionyl) methyl acetate 2- (2-(2'-nitro5'-(2"-chloro-
4"-trifluoromethylphenoxy)phenacyloxyfupropionyl)ethyl acetate 2- (2-(2'-nitros/ -(2JF-chloro-4"-trifluoromethylphenoxy)phenacyloxyfupropionyl)propion Methyl acid 2-[2
-[2'-nitro5'-(2"-chloro-4"-)!
J Fluoromethylphenoxy)phenacyloxyfupropionyl)ethyl propionate 3-[2-nitro-5-
Allyl (2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionic acid 5-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy]phenacyloxy]propionic acid Propargyl 3-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionate 2-methoxyethyl 5-[2-nitro-5-(2'-chloro-4 '-Trifluoromethylphenoxy) phenacyloxylapropionate cyanomethyl 2-(3-(2'-nitro5'-(2"-chloro-4
″-trifluoromethylphenoxy) phenacyloxyfupropionyl) ethyl acetate 2- (3-(2′-nitro5′-(2″-chloro-
4"-Trifluoromethylphenoxy)phenacyloxyfupropionyl)methyl propionate 4-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy]phenacyloxy]allyl butyrate 4-[2 -nitro-5-(2'-chloro-4'-trifluoromethylphenoxy]phenacyloxy]propargyl butyrate 4-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyl Oxy]butyric acid 2-
Methoxyethyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxythioacetate 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy S-methyl thioacetate 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy) phenacyloxythioacetate S-ethyl 2-nitro-5-(2'-chloro-4'-trifluoro methylphenoxy) phenacyloxythioacetic acid 5-n-
Propyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxythioacetate Allyl 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy Propargyl thioacetate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy]phenacyloxyacetylthio]methyl acetate 2-[2-nitro-5-(2'-chloro-4 '-Trifluoromethylphenoxy) phenacyloxyacetylthio]ethyl acetate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy]phenacyloxyacetylthio]methyl propionate 2-[ Ethyl 2-nitro-5-(2'-trifluoromethylphenoxy]phenacyloxyacetylthio]propionate 2-[2-nitro-5-(2'-chloro-4'-trifluoro methylphenoxy)7enacyloxy]thiopropionic acid 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxycothiopropionate S-methyl 2-[2-nitro-5- (2'-Chloro-4'-trifluoromethylphenoxy) phenacyloxycothiopropionate S-ethyl 2-[2-nitro-5-(2'-kuturo-4'-trifluoromethylphenoxy] phenacyloxy]thio Propion fil 3-n-propyl.

S-allyl 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxycothiopropionate 2-[2-nitro-5-(2'-chloro-4'- S-propargyl trifluoromethylphenoxy)phenacyloxycothiopropionate 2-(2-(2'-nitro5'-(2"-chloro-
4“-trifluoromethylphenoxy)phenacyloxy]globionylteo)methyl acetate 2- (2-(2'
-nitro5/ -(2N-riacr-4#-)lifluoromethylphenoxy)phenacyloxyphpropionylthio)ethyl acetate 2- (2-[2'-nitro57
- Methyl (2N-chloro-4'-trifluoromethylphenoxy)7enacyloxy]propionylthio)propionate 2-(2-(2'-nitros/ -(2#
-Chloro-4'-trifluoromethylphenoxy)phenacyloxyfupropionylthio)propionic acid ether 3-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxycothiopropionic acid S-Methyl 3-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxycothiopropionate S-allyl 2-(5-(2'-nitro-5'-( 2“-chloro-4
“-trifluoromethylphenoxy)phenacyloxy]glopionylthio)ethyl acetate 4-[2-nitro-5
-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxycothiobutyrate S-methyl 2- (4-[2'-nitro-5'-(2"-chloro-
4'-)! J Fluoromethylphenoxy)phenacyloxyfupropionylthio)ethyl acetate N-allyl-2-
Nitro-5-(2'-chloro-4/-trifluoromethylphenoxy)phenacyloxyacetamide N-propargyl-2-nitro-5-(2'-chloro-4'-1Jfluoromethylphenoxy)phena Siloxyacetamide N-(2-methoxyethyl)-2-nitro-5(2/-
Chloro-4'-)! J Fluoromethylphenoxy) phenacyloxyacetic acid amide N-(2-ri-aloethyl)-2-nitro5-(2'-
Chloro-4'-) 1) Fluoromethylphenoxy) phenacyloxyacetic acid amide N-cyanomethyl-2-nitro5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxyacetic acid amide 2- [2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyacetylamino]methyl acetate 2-[2-nitro-5-(2'-chloro-4'-trifluoromethyl phenoxy) 7-enacyloxyacetylamino]methyl propionate N-methyl-N-allyl-2-nitro-5-(2'-chloroo-4'-trifluoromethylphenoxy) phenacyloxyacetic acid amide N- Allyl-2-[2-nitro-5-(2'-chloro-
4'-)'J fluoromethylphenoxy) phenacyloxy]propionic acid amide N-propargyl-2-[2-nitro-5-(2'-chloro-4'-1J fluoromethylphenoxy) phenacyloxyfupropionic acid Amide N-(2-methoxyethyl)-2-(2-nido-5-(2'-chloro-4'-
Trifluoromethylphenoxy)phenacyloxy]propionic acid amide N-(2-ethoxyethyl)-2-[:2-nitro-5
-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionic acid amide N-(2-chloroethyl)-2-[2-nitro-5-(
2'-chloro-4'-trifluoromethylphenoxy)
phenacyloxy]propionic acid amide N-cyanomethyl-2-[2-nitro-5-(2/-chloro-47-)! J Fluoromethylphenoxy) phenacyloxyfupropionic acid amide N-(2-cyano1-tyl)-2-(2-nitro-5-(2'-chloro-4'-
trifluoromethylphenoxy) phenacyloxyfupropionic acid amide 2-(2-(2'-nitro-5'-(2"-chloro-4
“-trifluoromethylphenoxy)phenacyloxy]propionylamino)methyl acetate 2- (2-(2'
-nitro-s/(211-chloro-41-trifluoromethylphenoxy)phenacyloxyfuproonylamino)ethyl acetate 2- (2-[: 2'-nitro-5'-(2"-chloro-4" -trifluoromethylphenoxy)phenacyloxy]propionylamino)methyl propionate 2- (2-(2'-nitro5'-(2"-chloro-
4“-Trifluoromethylphenoxy)phenacyloxy]propionylamino)ethyl propionate N-methyl-N-allyl-2-[2-nitro-5-(2
'-/-low 4'-)! jfluoromethylphenoxy)
Phenacyloxyfupropionic acid amide N,N-diallyl-2-[2-nitro-5-(2'-chloro-47-)
(lifluoromethylphenoxy) phenacyloxyfupropionic acid amide N-methyl-N-propargyl-2-[2-nitro-5
-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionic acid amide N-allyl-3-[2-nitro-5-(2'-chloro-
4'-Trifluoromethylphenoxy) phenacyloxyfupropionic acid amide N-propargyl-3-[2-nitro-5-(2'-chloro-4'-)9fluoromethylphenoxy) phenacyloxyfupropionic acid Acid amide N-cyanomethyl-5-
[2-Nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyfupropionic acid amide 2-('5- (2'-nitro-5'-(2"-
Chloro-4#-trifluoromethylphenoxy) phenacyloxy] propionylamino) methyl acetate N-allyl-4-[2-nitro-5-(2'-chloro-4'-)
'J Fluoromethylphenoxy)zena〃Kanokishi〃butyric acid amide N-(2-methoxyethyl)-4-(2-nitro-5-
(2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy]butyric acid amide N-cyanomethyl-4
-[2-nitro-5-(,2/ -chloro-4'-1)
fluoromethylphenoxy)7enacyloxy]butyric acid amide 2-(4-(2'-nitro-s/ -<2#-chloro-4#++)lifluoromethylphenoxy)phenacyloxycobutyrylamino)acetic acid Methyl These compounds are all new compounds that have not been described in any literature, and can be produced, for example, according to Methods A to C shown below.

(1) Method A (in the formula, R has the same meaning as above), that is, 5-(2'-chloro-4'
The compound (I) of the present invention can be obtained by nitrating a -trifluoromethylphenoxy)-α-substituted acetophenone with a nitrating agent such as potassium nitrate or a sulfuric acid-nitric acid mixture in concentrated sulfuric acid. The reaction temperature in the nitration reaction is generally in the range of about -20C to about 100Gb, preferably about -10C to about 50C, and if necessary an inert organic solvent, such as 1.2-Gb, is used.
It can be carried out in the presence of dichloroethane or other chlorinated hydrocarbons. Furthermore, the general formula (to) used in the main floor
The compound represented by and the compound whose dicarbonyl group is protected by, for example, acetal f or ketalization are equivalent individuals, and no matter which derivative is used, the nitration reaction can be carried out in exactly the same way. It goes without saying that the compound (I) of the present invention can be obtained by performing the following steps.

(2) Method B (LID (IV)
) (Ia) (in the formula, % R1, R" and m have the same meanings as above), that is, 9, a carboxylic acid derivative represented by the formula (IID) and an alcohol derivative represented by the formula (IV) are mixed with concentrated sulfuric acid or p -) The compound of the present invention represented by formula (Ia) is obtained by dehydration using toluenesulfonic acid as a catalyst in an inert organic solvent such as benzene or toluene according to a conventional method (3) Method C ( 11[) (Ib) (In the formula, 2 represents a)-logen atom, and ul, Rt and m have the same meanings as above) That is, the carboxylic acid derivative and inorganic-logenide represented by the formula (11D) By reacting in the presence of a solvent or in the absence of 7'Cu, an acid halide represented by formula (V) can be obtained.The inorganic halides used here include, for example, thionyl chloride, phosphoryl chloride, , phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, etc.Furthermore, for example, zinc chloride, pyrrolidine, iodine, triethylamine, etc. can be used in combination with thionyl chloride as a catalyst.Next, in formula 1 (V) The indicated acid halide and formula (
By reacting an alcohol derivative, thiol derivative or amine derivative represented by VD in the presence of an acid binder in the presence or absence of a solvent, the formula
The compound of the present invention represented by b) is obtained. Solvents used here include water, ethereal solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as chloroform and dichloromethane, aromatic solvents such as benzene and toluene, and N,N-dimethylformamide. Aprotic polar solvents and the like can be used alone or in combination of two or more thereof.

Yes, acid binders include tertiary amines such as triethylamine and pyridine, alkali metal alcoholides such as sodium methoxide and sodium ethylate, and alkali metals such as sodium bicarbonate and potassium carbonate. Bicarbonates and carbonates can be used. The reaction temperature generally ranges from about -20C to about 150C, preferably from about -5C to about 80C. Sara K
, a phase transfer catalyst such as triethylbenzylammonium halide may also be used.

(4) D method (VID (■) (Ia
) (In the formula, M represents an alkali metal, R", R",
(m and 2 have the same meanings as above) That is, by reacting an alkali metal salt of a carboxylic acid represented by formula (vIL) and a halide represented by formula (VID) according to a conventional method, formula (Ia ) is obtained.The alkali metal salt represented by 2〇'ID is an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, or an alkali metal hydroxide such as sodium methylate or sodium ethylate. It is easily obtained by the reaction of an alkali metal alcoholade, an alkali metal carbonate such as potassium carbonate, etc. with a free acid, and the alkali metal salt can be prepared with the formula (
It can be subjected to a reaction with a halide represented by ν behavior. The solvents used include water, 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
- Aprotic polar solvents such as dimethylformamide can be used alone or in combination. The reaction temperature is generally about -10C to about 180C,
Preferably a range from room temperature to about 1200 ℃ is used.

The method for producing the compound of the present invention is not limited to these Methods A to D, and can be prepared by various methods by modifying conventionally known methods for producing similar compounds.

Next, the herbicidal action of the compounds of the present invention will be explained using weed control in fields as an example.

The compound of the present invention can be used to apply the compounds of the grass family, which are harmful weeds in upland fields, such as grasshopper, foxtail grass, and common grass, especially broad-leaved weeds such as pigweed, Japanese knotweed, Japanese knotweed, Japanese knotweed, Japanese blackberry, Japanese blackberry, Japanese commonweed, common morning glory, chickweed, purslane, and others. For various weeds in both pre-emergence soil treatment and post-emergence foliage treatment,
It exhibits extremely strong herbicidal activity at extremely low doses. The characteristics of the compound of the present invention are the above-mentioned strong herbicidal activity and broad-leaved plants such as soybeans and cotton, as well as corn, wheat, etc.
It also has extremely excellent selectivity in pre-emergence and post-emergence treatments for plants of the Carotid family, such as rice. The general usage amount of the compound of the present invention is 10
R 7' (5o, s ~ 150?), and preferably exhibits an excellent herbicidal effect at a dosage of 1 to 50?. , 5-(2'
-Chloro-4'-)! jfluoromethylphenoxy)-
2-Nitroacetophenone oxime derivative (Unexamined Japanese Patent Publication No. 1983
52452), the dose required to obtain a satisfactory herbicidal effect is 1 to 3 per 10 ares.
0f and the two are almost equivalent, but the compound of the present invention is significantly superior in safety to soybeans. In addition, 2-nitro-5-(2'-chloro-
Considering the fact that the amount of sodium 4'-trifluoromethylphenoxybenzoate used is 20~Sat'''C per 10 ares, the compound of the present invention has much stronger herbicidal activity and superiority than conventionally known compounds. It can be seen that it has a high selectivity.

Furthermore, one compound of the present invention has extremely strong herbicidal activity against paddy field weeds other than upland weeds. That is,
The compounds of the present invention are effective at low doses against broad-leaved weeds that grow in rice fields, such as persistent grass weeds such as Japanese grass grass, Japanese grass weed, Japanese grass weed, water chickweed, and azalea, as well as perennial weeds such as staghorn weed and water cypress. Shows herbicidal activity.

On the other hand, the phytotoxicity of the compound of the present invention to paddy rice at an effective dose applied to weeds is extremely slight and hardly observed.

Therefore, the compounds of the present invention can be used for the purpose of selectively weeding weeds in agricultural crops such as soybeans, cotton, corn, wheat, barley, and rice, and they Applicable to both. Further, the compound of the present invention can 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.

When actually using the compound of the present invention, the raw material itself can be dispersed, and any formulation form such as a wettable powder, emulsion, granule, or powder can be used.

In the preparation of these formulations, solid carriers include, for example, mineral powders (kaolin, bentonite, clay, montmorillonite, Merck, diatomaceous earth, mica,
vermiculite, ceracola, calcium carbonate, phosphorous lime, etc.), vegetable powders (soybean flour, wheat flour, wood flour, tobacco flour, starch, 'crystalline sululose, etc.), polymer compounds (petroleum resins, polyvinyl chloride, ketone resins, etc.) Furthermore, alumina, waxes, etc. can be used.

Examples of liquid carriers include alcohols (methanol, ethanol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic IF group hydrocarbons (toluene, benzene, xylene, etc.), and 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 ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and oxyethylene polymer. , oxypropylene polymer, polyoxyethylene alkyl phosphate, fatty acid salt, alkyl sulfate salt, alkyl sulfonate, alkylaryl sulfonate, alkyl phosphate salt, polyoxyethylene alkyl sulfate, quaternary ammonium salt , oxyalkylamines, etc. Also, if necessary.

Gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol, etc. can be used as adjuvants.

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

(4) Phenoxy herbicide 2.4-dichlorophenoxyacetic acid = 2-methyl-4-chlorophenoxyacetic acid nia'thyl-2-(4-(5-)lifluoromethyl-2-pyridyloxy)phenoxy]propionate (Including respective esters and salts): Ethyl-2-(4-(6-chloro-2-quinoxalinyloxy)phenoxy)gropionate, etc.

(B) Diphenyl ether herbicide 2.4-dichlorophenyl-4'-nitrophenyl ether: 2,4
．． 6-Dolichlorophenylated 4'-nitrophenyl ether: 2.4-dichlorphenylated 4'-2) 0-3
'-Me) Phenyl ether: 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-di)lobenzoic acid sodium salt and the like.

(C) Triazine herbicide 2-chloro-4,6-pisethylamino-1,5°5-
Triazine di-2-chloro-4-ethylamino-6-itubrobylamino-1,3.5-) riazine = 2-methylthio-4,6-bisethylamino-1°3.5-) riazine, and the like.

) Urea herbicide 3-(3,4-dichlorophenyl)-1,1-dimethylurea: 3-(5,4-dichlorophenyl)-1-methoxy-1-methylurea = 3-(α, α,α-trifluoro m-)dyl)-1,1-dimethylurea: 3-(
4-(4-methylphenethyloxy)phenyl]-1-
Methoxy-1-methylurea: 3-(5-t-butyl-
3°4-thiadiazol-2-yl)-4-71 idroxy-1-methyl-2-imidazolitone, etc.

(g) Carbamate herbicide Isopropyl-N-(5-chlorophenyl)carbamate: Methyl-N-(3,4-dichlorophenyl)carbamate = 4-chloro-2-butynyl-N-(3-chlorophenyl)carbamate Nado.

(g) Thiol carbamate herbicide S-ethyl-N
, N-hexamethylenethiol carbamate di 19-(
4-chlorobenzyl)-N.

N-diethylthiol carbamate: S-ethyldipropylthiol carbamate, etc.

(6) Anilide herbicide 3.4-Dichloropropionanilide 2N-methoxymethyl-2/, 61-diethyl-2-chloroacetanilide = 2-chloro-27, 61-diethyl-N-(butoxymethyl)- Acetanilide: 2-chloro-2',
6'-diethyl-N-(propoxyethyl)-acetanilide: α-(2-naphthoxy)propionanilide, etc.

(6) Uracil herbicide 5-bromo-5-see-butyl-6-methyluracil: 3-cyclohexyl-5,6-drimethyleneuracil, etc.

CI) Dipyridinium salt herbicides 1.1'-dimethyl-4,4'-dipyridinium dichloride: 1,1'-ethylene-2,2'-dipyridinium dibromide, etc.

(J) Phosphorus herbicide N-(phosphonomethyl)glycine:〇-ethyl-Q-(
2-Nitro-5-methylphenyl)-N-5ee-butylphosphoramidothioate 20-methyl-〇-(2-
Nitro-4-methylphenyl)-N-(sobropylphosphoroamidethioate 25-(2-methyl-1,1'-
piperidylcarbonylmethyl)-0,0-di-n-propyldithiophosphate: (2-amino-4-methylphosphinonibutyryl)-7 ranylalanine monosodium salt, and the like.

(Transformation) Toluidine herbicide α, α, α-trifluoro 2,6-sinitro N, N
-dipropyl-p-)luidine diN-(cyclopropylmethyl)-α,α,α-trifluoro2,6-dinitro-N-propyl-p-toluidine, etc. (Q Other herbicides 5-t-butyl- 5-<2.4-dichloro-5-impropoxyphenyl) -1,3,4-oxadiazolin-2-one = 3-isopropyl-2,1,5-benzothiadiazinone-4,2,2 −dioxide=2−(α−
(7toxy) -N,N-diethylpropion ymide:
, 3-amino-2,5-dichlorobenzoic acid: 4- (
2,4-dichlorobenzoyl)-1,3-dimethylhyrazol-5-yl-p-toluenesulfonate: 2-
Chloro-N-[(4-methoxy-6-methyl-1,5,
5-)Ryazin-2-yl)aminocarbonyl]benzenesulfonamide: 2-((4,6-cymethoxypyrimidin-2-yl)aminocarbonylaminosulfonylmethyl]benzoic acid methyl ester: N-(1-methyl -1
-phenylethyl)-2-promo5.5-dimethylbutanamide: 2-(1-(N-acryloxyamino)butylidene]-4-methoxycarbonyl-S, S
-dimethylcyclohexane-1,3-dione sodium salt: 2-(1-(ethoxyimino)butyl)-5-(2
-ethylthiopropyl)-3-hydroxy-2-cyclohexan-1-one, etc.

The above herbicides are merely examples, and 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.

(Effects of the Invention) As described above, the compound of the present invention not only exhibits a strong herbicidal effect at a lower usage amount than conventional diphenyl ether herbicides, but also has selectivity particularly for soybeans, and also improves plant growth. Since it can be used in the same manner over the entire period and has low toxicity, it is suitably used as a herbicide for broad-leaved and gristaceous plants such as soybean, cotton, corn, wheat, barley, and rice.

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 to 50 f (active ingredient) per 10 ares.

(Example) Next, the present invention will be explained in more detail by way of examples.

Example 1 Preparation of 2-methoxyethyl 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionate 2-(3-(2'-chloro-4 1.4f of 2-methoxymethyl ′-trifluoromethylphenoxy)phenacyloxy]propionate
．． Dissolved in 10 d of 2-dichloroethane and poured into 5 d of concentrated sulfuric acid cooled to OC. After adding 0.3 f of potassium nitrate while keeping the reaction temperature below 5C, the reaction was further continued for 1 hour. After the reaction was completed, the reaction mixture was poured into ice water, and dichloromethane was further added to extract the reaction product. As usual, the organic layer is treated with water, followed by bicarbonate) IJ
After washing with an um solution and further water, and drying, the solvent was removed under reduced pressure to obtain a crude product. As a result of purification by silica gel column chromatography, 2-methoxy 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionic acid had a refractive index of 1.5231. 0.7f of ethyl yellow oil was obtained.

Example 2 2-[2-2) a-5-(2'-black c1-41-
Production of glopargyl trifluoromethylphenoxy)phenacyloxy]propionate 1.59 of 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy]7enacyloxy)propionic acid was dissolved in benzene at 20 dK. Subsequently, 0.62% of glopargyl alcohol and a catalytic amount of p-toluenesulfonic acid were added, and the mixture was heated under reflux for 3 hours.After the reaction was completed, water and ether were added to carry out an extraction operation, and the organic layer was separated. Next, ether and benzene were distilled off under 1 reduced pressure, and the resulting crude product was subjected to silica gel thin layer chromatography (developing solvent: n-hexane: ethyl acetate 2:1 v/
) As a result of preparative purification, the refractive index was no '1-53.
2-[2-nitro-5-(2'-chloro-
Pale oily substance of propargyl 4'-trifluoromethylphenoxy)phenacyloxy]propionate 0.
I got 72.

Example 3 Preparation of N-allyl-2-[2-nitro-5-, (2'-chloro-4'-)lifluoromethylphenoxy)7enacyloxy]propionic acid amide (a) 2-(2-nitro-5-) 1.31 g of 5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxyfupropionic acid was dissolved in 20 g of benzene, 1 g of thionyl chloride was added, and the mixture was heated under reflux for 8 hours. After the reaction was completed, the solvent was removed under reduced pressure to obtain 2-[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)phenacyloxy]propionic acid chloride 1.41. .

(b) After dissolving in 0.42 t of allylamine and 70.6 t of triethylamine, (a)
2-[2-nitro-5-(2'-chloro-4'-
A benzene solution containing 1.41 parts of trifluoromethylphenoxy)7enacyloxy]propionic acid chloride (5-5) was added dropwise at room temperature, and the mixture was allowed to react overnight at room temperature.

After the reaction was completed, water and ether were added, extraction was performed in a conventional manner, and the organic layer was separated. After washing the organic layer with water, ether and benzene were distilled off under reduced pressure, and the resulting crude product was subjected to silica gel thin layer chromatography (developing solvent n
-hexane:ethyl acetate 2:1'v/v) and preparative purification revealed that N-allyl-2-[2-nitro-5-(2'-chloro-4'- A pale red oil-released *Vtlt of trifluoromethylphenoxy)7enacyloxy]propionic acid amide was obtained.

Example 4 Tables 1 and 2 illustrate the structures, physical properties, elemental analysis values, and H-NMR analysis data of the compounds of the present invention produced in the same manner as in the above examples. It goes without saying that the compounds are not limited to these compounds.The compound numbers in the table are commonly used in the examples of this specification.

Application example Next, typical formulation examples of the compounds of the present invention will be shown.

Prescription 1 (Irrigation agent) 25 parts by weight of the compound of the present invention, 5 parts by weight of Tsurupol 5039 (manufactured by Toho Chemical Industry Co., Ltd., trade name), and 1 part by weight of talc.
A wettable powder is obtained by thoroughly grinding and mixing 0 parts by weight.

Prescription 2 (Emulsion) 5 parts by weight of the compound of the present invention, 10 parts by weight of Tsurpol 5005X (manufactured by Toho Chemical Industry Co., Ltd.), 45 parts by weight of n-damenol and 40 parts by weight of xylene are thoroughly mixed to prepare an emulsion.

Formulation 3 (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,
Granulate and dry to make granules.

Prescription 4 (Powder) 1 part by weight of the compound of the present invention and 99 parts by weight of clay are thoroughly mixed to prepare a powder.

Usage Example 1 A pot with a size of 1/2500 are filled with field soil was prepared in a greenhouse. Seeds of large maize, crabgrass, Japanese radish, pigweed, and Japanese knotweed were sown in each pot.

Pre-germination treatment is done 24 hours after sowing with 107-Rushi25? was applied. On the other hand, post-emergence treated soybeans are treated at the 2nd to 5th leaf stage, corn at the 34th leaf stage, and weed Fi2 to 2.
The test was carried out by applying 109 per 10 ares at the 5th leaf stage. The spraying method was to dilute the emulsion (Formula 2) of the designated garden in 10 tons of water and use a glass sprayer. The degree of weed control ability was observed on the first day after the leaf agent treatment, and the degree of chemical damage to the plants was observed on the 30th day. The results are shown in Table 3. The numbers in the table are
Based on the following criteria:

5: Complete suppression 4: 80% suppression 5: 60% suppression 2: 40% suppression Control: 20% suppression 0: No effect Usage example 2 Bot HC paddy soil of 1/5000 are in a greenhouse I prepared something packed. Seeds of Japanese barnyard grass, Japanese grasshopper, annual broad-leaved weeds, and azaleas, and perennial weeds, bulrushes, were mixed with dry paddy soil and mixed into the surface layer. In addition, as perennial weeds, tubers of Japanese cypress and Japanese cypress were transplanted.

For rice, seedlings at the 5-leaf stage were transplanted to the 2nd to 5th layer of the soil surface.

For chemical treatment, a predetermined once-diluted emulsion (prescription 2) diluted with water was dropped with a pipette at the 0.5 to 1 leaf stage of barnyard grass. On the 21st day after the chemical spraying, the degree of chemical damage to rice and weed control ability was observed. The results are shown in Table 4.

Note that the criteria in the table are the same as in Use Example 1.

(Note 1) Comparative drug 1: (Note 2) Comparative drug 2: CH.

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R represents the group shown by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1 is a hydrogen atom Or methyl group, m is 1, 2 or 3, R^2 is OR^3, SR^4 or ▲ Numerical formula, chemical formula, table, etc. ▼, R^3 is lower alkenyl group: lower alkynyl group: halogen atom, A lower alkyl group substituted with a cyano group or an alkoxy group, or a group represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc., R^4 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a ▲ mathematical formula, There are chemical formulas, tables, etc. Groups shown by ▼, R^5 is a hydrogen atom, lower alkyl group, lower alkenyl group, or lower alkynyl group, R^6 is a lower alkenyl group: lower alkynyl group: halogen atom, cyano group, or alkoxy Lower alkyl group substituted with group or ▲
There are mathematical formulas, chemical formulas, tables, etc. The group shown by ▼, R^7, R^9 and R^1^1 are hydrogen atoms or methyl groups, R^8, R^1^0 and R^1^2 are Represents a lower alkyl group. ] 5-(2'-chloro-4
'-trifluoromethylphenoxy)-2-nitro-α
-Substituted acetophenone derivatives. (2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents the group shown by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1 is a hydrogen atom Or methyl group, m is 1, 2 or 3, R^2 is OR^3, SR^4 or ▲ Numerical formula, chemical formula, table, etc. ▼, R^3 is lower alkenyl group: lower alkynyl group: halogen atom, A lower alkyl group substituted with a cyano group or an alkoxy group, or a group represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc., R^4 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a ▲ mathematical formula, There are chemical formulas, tables, etc. Groups shown by ▼, R^5 is a hydrogen atom, lower alkyl group, lower alkenyl group, or lower alkynyl group, R^6 is a lower alkenyl group: lower alkynyl group: halogen atom, cyano group, or alkoxy Lower alkyl group substituted with group or ▲
There are mathematical formulas, chemical formulas, tables, etc. The group shown by ▼, R^7, R^9, and R^1^1 are hydrogen atoms or methyl groups, R^8, R^1^0, and R^1^2 represents a lower alkyl group. ] 5-(2'-chloro-
4'-trifluoromethylphenoxy)-2-nitro-
A selective herbicide containing an α-substituted acetophenone derivative as an active ingredient.