JPS61140546A - Novel alpha-methoxyacetophenone derivative and herbicide comprising same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I {X is 0, or =N-O-R<1> [R<1> is H, lower alkyl, lower alkyl which is replaced with halogen, cyano, etc., group shown by the formula II (R2 is H, or methyl; R3 is H, lower alkyl, alkali metal, etc.), etc.}. EXAMPLE:5-( 2'-Chloro-4'-trifluoromethylphenoxy )-2-nitro-alpha-met-ho-xyacetophe none. USE:A herbicide. Having highly herbicidal action especially on gramineous weeds, broad-leaved weeds, etc. in paddy fields, showing high selectivity. PREPARATION:3-(2'-Chloro-4'-trifluoromethylphenoxy)-alpha-methoxyacet- op-henone shown by the formula III is reacted with a nitrating agent such as potassium nitrate, mixed sulfurica cid/nitric acid, etc. in conc. sulfuric acid at -20-100 deg.C optionally in an inert solvent, to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention has a novel 5-(2'-chloro-4 /h trifluoromethylphenoxy)-2
-nitro-α-methoxyacetophenone and 5-(2'
-Chloro-41-trifluoromethylphenoxy)-2
-Nitro-α-methoxyacetophenone oxime derivatives and selective herbicides containing the same as active ingredients.

BACKGROUND OF THE INVENTION It has been known to use alkyl[2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy]phenyl]ketones and their oxime derivatives as herbicides (JP-A No. Publication No. 56-32432).

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, conventional herbicides have not only strong herbicidal power and high selectivity, but also low toxicity to warm-blooded animals, can be commonly used throughout the entire growing season of crops, and are completely recyclable after use. Ideally, it should also have the requirements of decomposing as quickly as possible and not contaminating soil II, but diphenyl ether herbicides that meet these requirements are
'1 is not 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, to be harmless to cultivated crops, and to eliminate other herbicides that coexist with them. A novel diphenyl ether-based herbicide that has selective and strong herbicidal power that can quickly eliminate unnecessary plants, can be used consistently throughout the growing period of the crop, and has low toxicity to mixed-breed animals. The aim is to provide agents for

Means for Solving the Problems As a result of extensive research, the present inventors found that 5-(2'-chloro-4'-)IJfluoromethylphenoxy)-2-
Nitro-alpha-methoxyacetophenone and its oxime derivatives are suitable for the above-mentioned purposes and can be applied to soybeans, cotton, corn and wheat at low application rates.

It has been found that the present invention is useful for a wide range of broad-leaved and perennial crops such as rice, and based on this knowledge, the present invention has been accomplished.

That is, according to the present invention, the general formula % formula % (wherein X is an oxygen atom or a substituent represented by 5ti-o-R+, R1 is a hydrogen atom: linear or branched lower alkyl Group: )・Rogen atom, linear or branched lower alkyl group substituted with a cyano group or alkoxy group; lower alkenyl group; lower alkynyl group or group represented by 1 I+ 10H-0-0-0-R5 R2 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a lower alkyl group,
A novel 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro- By using α-methoxyacetophenone and 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime derivatives as active ingredients of herbicides.

That purpose can be achieved.

The compound of the present invention acts effectively as a pre-emergence and post-emergence herbicide on various agricultural crops than conventionally known compounds with a similar structure at a low spray dose, and also acts on mammals as a herbicide. It was completely unexpected that it did not cause any harm to seafood etc.

Furthermore, the compound of the present invention is characterized in that it is α-methoxyacetophenone and its oxime derivative, whereas the compounds known so far are alkyl phenyl ketones and their oxime derivatives such as acetophenone and flobiophenone. . It is a surprising fact that the compound of the present invention exhibits excellent selectivity for various agricultural crops by introducing a methoxy group into the α-position of the carbonyl group.

Specific examples of the compound of the present invention represented by the general formula [1] are 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-5-(2'-1'rolow4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime.

5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone-〇-methyloxime, 5-(2'-chloro-4'-trifluoromethylphenoxy)-2- Nitro-α-methoxyacetophenone-〇-ethyloxime, 5-(2′-10-4′-)17fluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-〇-n-7′-robyroxime.

5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone-〇 -iso-furobyloxime, 5-(2'-chloro-4'-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone-〇-n-butyloxime, 5-(2'-chloro-47-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-〇-1so-butyloxime, 5 -(2'-chloro-4/
-trifluoromethylphenoxy)-2-nitroα
-Methoxyacetophene/7-O-(2-chloroether)
Oxime, 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-〇-(2-bromoethyl)oxime.

5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone-
0-(a-chloropropyl)oxime.

5-(2'-chloro-4'-trifluoromethylphene/
*C)-2-nitro α-methoxyacetophenone-
o-(2-chloropropyl)oxime, 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-o-(3-bromopropyl)oxime.

5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-o
-(2-fluoroethyl)oxime, 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro alpha-methoxy, diacetophenone-o-(3-fluoropropyl)oxime.

5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone-o
-(2-methoxyethyl)oxime.

5-(2'-chloro-4'-) 17fluoromethylphenoxy)-2-nitro α-methoxyacetophenone-〇-(2-ethoxyethyl)oxime, 5-(2'
-Chloro-41-trifluoromethylphenoxy)-2
-Nitro-α-methoxyacetophenone-o-(3-methoxyethyl)oxime.

5-(2'-1'Rolow 4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-
o-(1-methyl-2-methoxyethyl)oxime.

5-(2'-chloro-4'-trifluoromethylphenox7)-2-nitro-α-methoxyacetophenone-〇-(1-methyl-2-ethoxyethyl)oxime, 5-(2'-chloro-4 '-)! J Fluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-
o-(2-methoxypropyl)oxime, 5-(2'-
10row 4'-)lifluoromethylphenoxy)-2-
Nitro-α-methoxyacetophenone-o-(2-ethoxyethyl)oxime, 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-〇-(1-methyl- 3-methoxypropyl) oxime.

5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-
0-(1-methyl-2-methoxypropyl)oxime.

5-(2′-chloro-4′-toIJfluoromethylphenoxy)-2-nitro α-methoxyacetophenone-〇-cyanmethyloxime.

5-(2'-chloro-4'-)IJfluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-
〇-(2-cyanoethyl)oxime, 5-(2'-10
Low 4'-)! J Fluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-〇-(a-cyanopropyl)oxime, 5-(2'-10rho 47 l
, trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone-〇-allyloxime.

5-(2'-chloro-47), 5-(2'-10-4
'-trifluoromethylphenoxy)-2-nitro-α
-methoxyacetophenone-〇-(2-methyl-2-propenyl)oxime, 5-(2'-chloro-4/ )-lifluoromethylphenoxy)-2-nitroα-methoxyacetophenone-〇-7' lobargyl Oxime, 5-(2'-/colo-
4'-IJfluoromethylphenoxy)-2-nitro-α-methoxyacetophenone-o-(2-butenyl)oxime.

5-(2'-chloro-4'-)fluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime-〇-acetic acid, 5-(2'-chloro-4'-fluoromethylphenoxy)- 2-nitroα-methoxyacetophenone oxime-〇-sodium acetate, 5-(2'-chloro-
47-trifluoromethylphenoxy)-2-nitro-
α-methoxyacetophenone oxime-〇-potassium acetate, 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime-〇-calcium acetate.

5-(2'-chloro-4'-fluoromethylphenoxy)-2-nitroα-methoxyacetophenone oxime-〇-4E acid magnesium, 5-(2'-chloro-4'-)lifluoromethylphenoxy )-2-nitro-α-methoxyacetophenone oxime-o-ammonium acetate, 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-2) rho-α-methoxyacetophenone oxime-o-methylammonium acetate .

5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime-〇-dimethylammonium acetate, 5-(2'-chloro-4'-trifluoromethylphenoxy)- 2-Nitro-α-methoxyacetophenone oxime-〇-(acetic acid, methyl ester).

5-(2'-chloro-4'-)lifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime-〇-(acetic acid, ethyl ester), 5-(2'
-chloro-4'-toIJfluoromethylphenoxy)-
2-nitro α-methoxyacetophenone oxime-〇 -C acetic acid, n-7”lopyl ester), 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone oxime-o -C acetic acid, 1so-7'robyl ester), 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone oxime-〇-(acetic acid, n-butyl ester) , 5-(2'-chloro-4'-)!jfluoromethylphenoxy)-2-nitro α-methoxyacetophenone oxime-〇-(2-7'ropionic acid).

5-(2'-Chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone oxime-o-(2-sodium propionate).

5-(2'-chloro-4'-)! J fluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime-〇-(2-potassium propionate, rum), 5-(2'-chloro-4'-toIJ fluoromethylphenoxy)-2-nitro- α-Methoxyacetophenone oxime-〇-(2-7'calcium ropionate).

5-(2'-chloro-4'-)lifluoromethylphenoxy)-2-nitroα-methoxyacetophenone oxime-〇-(2-propionate ammonium), 5-(2'-chloro-4'-trifluoromethylphenoxy) fluoromethylphenoxy)-2-nitro α-methoxyacetophenone oxime-〇-(2-furopionic acid, methyl ester) + 5- (2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α- Methoxyacetophenone oxime-〇-(2-propionic acid, ethyl ester).

5-(2'-Chloro-4'-) 1.1 Fluoromethylphenoxy)-2-nitro alpha-methoxyacetophenone oxime-o-(2-7'' robionic acid, n-propyl ester).

5-(2'-chloro-4'-toIJfluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime-o-(2-7'ropionic acid, -butyl ester), 5-(2'- Chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone oxime-o-(2-7'ropionic acid, is.

-propyl ester).

and so on.

All of these compounds are new compounds that have not been described in any literature and can be produced, for example, according to Methods A to E shown below.

(1) Method A○ [■] That is, 1a-(2'-chloro-
4'-Trifluoromethylphenoxy)-α-methoxyacetophenone was soaked in sulfuric acid with potassium nitrate.

The compound of the present invention [1a,:] can be obtained by nitration with a mixed sulfuric acid/nitric acid or a similar nitrating agent. The reaction temperature in the nitration reaction is generally from about -20°C to about 100°C, preferably from about -10°C to about 50°C, and an inert organic solvent, such as 1. This can be done in the presence of 2-dichloroethane or other chlorinated hydrocarbons.

(2) Method B (Ia][:[[l] cH2-o-cn5 (2 in the formula is a halogen atom) This method is preferably carried out under anhydrous conditions, that is, [I
s -(2'-chloro-47-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone represented by a] and a hydrohalide salt of a hydroxyamine represented by the formula An alcohol such as anhydrous ethanol in the presence of an acid binder such as an anhydrous organic acid salt such as sodium acetate or an organic tertiary amine such as triethylamine.

The compound 5 of the present invention represented by formula 1 [1b] is obtained by carrying out a dehydration reaction according to a conventional method in a single or mixed organic solvent such as a mixed solvent of an alcohol such as anhydrous ethanol and dry benzene and an aromatic solvent. -(2'-chloro-4'
-trifluoromethylphenoquine)-2-nitro-α-
Methoxyacetophenone oxime is obtained. The reaction temperature in the oxime formation reaction is generally from about 0°C to about 0°C.
The boiling point range of the solvent or mixed solvent is preferably from room temperature to the boiling point of the single solvent or mixed solvent.

(3) Method C CH2-0-OH5 [Ib] [■] (R1 and 2 in the formula have the same meanings as above) That is, the α-methoxyacetophenone oxime derivative represented by the formula (Ib) and the formula [IV ) with a halogeno compound represented by formula [1c] in the presence of an alkali metal alcoholade such as sodium methylate or an acid binder such as sodium hydride, the compound of the present invention represented by formula [1c] can be obtained. . Solvents used here include, for example, alkanol solvents such as methanol and ethanol, ether solvents such as diethyl ether and tetrahydro7rane, and aprotic solvents such as N,N-dimethylformamide and N,N-dimethylacetamide. These are polar solvents and aromatic solvents such as benzene, and they can be used alone or in a mixture of two or more. The reaction temperature generally ranges from about -10°C to about 150°C, preferably from about θ°C to about 100°C.

(4) Method D cu2-o-aH3 [Ia] [■] ICI (R1 and 2 in the formula have the same meanings as above) This method is preferably carried out under anhydrous conditions. That is, the α-methoxyacetophenone derivative represented by the formula [■a] and the formula [■]
In the presence of an acid binder such as an anhydrous organic acid salt such as anhydrous sodium acetate or an organic tertiary amine such as triethylamine, an alcohol such as anhydrous ethanol, By carrying out a dehydration reaction according to a conventional method in a single or mixed organic solvent such as a mixed solvent of an alcohol such as anhydrous ethanol and dry benzene and an aromatic solvent.

A compound of the present invention represented by the formula [IC] is obtained. The reaction temperature in the oxime formation reaction is as described in Method B.

(5) Method E [■] [■] CH2-0-CH3 CnH2-0-CH5 (R1 and 2 in the formula have the same meanings as above) The first stage reaction of this method is carried out under anhydrous conditions. is preferred. That is, by reacting the α-methoxyacetophenone derivative represented by the formula [ll] with the hydrohalide salt of the hydroxylamine derivative represented by the formula [■] in the same manner as in Method D, the product represented by the formula [■] can be obtained. An α-methoxyacetophenone oxime-〇-substituted product is obtained. Next, by nitrating the compound represented by the formula [■], the compound of the present invention [
The zero nitration reaction giving IC) can be carried out with potassium nitrate, mixed sulfuric acid/nitric acid and similar nitration agents in sulfuric acid. The reaction temperature in the nitration reaction is generally from about -20°C to about 80°C, preferably from about -10°C to about 50°C. - Can be carried out in the presence of dichloroethane or other chlorinated hydrocarbons.

The method for producing the compound of the present invention is not limited to these Methods E to E, and can be produced by any number of methods by modifying conventionally known methods for producing similar compounds.

Next, the herbicidal action of one 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 applied to weeds of the grass family, such as poisonous grass weeds, foxtail grass, and Japanese grasshopper, which are harmful to upland fields, especially pigweed, Japanese knotweed, Japanese grasshopper, Japanese snail, American hornwort, blackberry grass, and Japanese grasshopper.

It exhibits extremely strong herbicidal activity against broad-leaved weeds such as chickweed and purslane, as well as various other weeds, in both pre-emergence soil treatment and post-emergence foliage treatment at surprisingly low doses. The compound of the present invention is characterized by the above-mentioned strong herbicidal activity and is effective against broad-leaved crops such as soybeans and cotton, as well as corn.

It also has extremely excellent selectivity in pre-emergence and post-emergence treatments for legume crops such as wheat and rice. The general usage amount of the compound of the present invention is as follows:
0.5 to 100 per 10 are? and preferably 1
Shows excellent herbicidal effects at dosages of ~502. The most outstanding feature of the compounds of the present invention is their selectivity to soybeans. For example, a 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitroacetophenone oxime derivative (% Kaisho s 6-3
2432), the dosage required to obtain a satisfactory herbicidal effect is 1 to 302 per 10 ares, which is almost the same for both, but the compound of the present invention is 10 times safer for soybeans. More than that. Also.

2-nitro-5- which is said to have selectivity for soybeans
The amount of sodium (2'-chloro-47-trifluoromethylphenoxy)benzoate used is 20 to 100 am.
501, it can be seen that the compounds of the present invention have much stronger herbicidal activity and superior selectivity than conventional known compounds.

Furthermore, the compounds of the present invention have extremely strong herbicidal activity against paddy field weeds other than upland weeds.

In other words, the compound of the present invention can be used in low doses against broad-leaved weeds that grow in paddy fields, such as the harmful grass weeds such as grassweeds such as Japanese grass grass, grasshopper, and other broad-leaved weeds that grow in paddy fields, such as paddy fields, as well as perennial weeds such as prickly pear and Japanese cypress. Shows strong herbicidal activity. On the other hand, the effective dosage of the compound of the present invention against weeds. The chemical damage to paddy rice is extremely slight and almost unnoticeable.

Therefore, one compound of the present invention is used for the purpose of selectively weeding weeds in agricultural crops such as soybean, cotton, corn, wheat, barley, and rice. and these can be applied both pre- and post-emergent to weeds. 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 active substance itself can be sprayed, and any formulation form such as an aqueous solution, emulsion, granule, or powder can be used.

In the preparation of these formulations, solid carriers include, for example, mineral powders (casulin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, ceracola).

calcium carbonate, phosphorous lime, etc.), vegetable powders (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resins, etc.).

polyvinyl chloride, ketone resin, etc.), as well as alumina,
Wax etc. can be used.

Examples of liquid carriers include alcohols (methanol, ethanol, butanol, ethylene glycol, benzyl alcohol fX, etc.) and 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 (such as acetonitrile), ether alcohols (such as ethylene glycol ethyl ether), or water.

As the surfactant used for the purpose of emulsification 1 dispersion, diffusion, etc., any of nonionic, anionic, cationic, and amphoteric ionic surfactants can be used. Examples of surfactants that can be used in the present invention are:
Polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene rubitan fatty acid ester, oxyethylene polymer-oxypropylene polymer, polyoxyethylene alkyl phosphate ester, fatty acid salt , alkyl sulfate ester W, furkyl sulfonate, alkylaryl sulfonate, alkyl phosphate ester salt, phoroxyshetylene alkyl sulfate ester, quaternary ammonium salt,
Oxyalkylamines and the like. In addition, 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 efficacy as a herbicide, and in some cases, a synergistic effect can be expected. For example, the components listed in the first paragraph may be used.

(A) Phenoxy herbicide 2.4-dichlorophenoxyacetic acid: 2-methyl-4-chlorophenoxyacetic acid; phthyl-2-[4-(5-1-!
jFluoromethyl-2-pyridyloxy)phenoxy]
Propionate (including its respective esters and salts);
Ethyl-2-[4-(6-chloro-2-quinoxalinyloxy)phenoxy]propionate and the like.

(B) Diphenyl ether herbicide 2.4-dichlorophenyl-4'-nitrophenyl ether: 2.4
+6-)! J Chlorphenyl-4'-nitrophenyl ether; 2,4-dichlorophenyl-4'-ditrophenyl 3'-methoxyphenyl ether; 2,4-dichlorophenyl-3'-methoxycarbonyl/l/- 4'-nitrophenyl ether: 2-1oo-4-trifluoromethylphenyl-3'-ethoxy-4'-nitrophenyl ether: s-[2-chloro-4-()lifluoromethyl)phenoxycou2 - Nitrobenzoic acid sodium salt, etc.

(C) Triazine herbicide 2-chloro-4,6-pisethylamino-1.3.5-
Triazine: 2-chloro-4-ethelamino-6-improbylamino-1,3,5-triazine: 2-methylthio-4,6-pisethylamino-1,3°5-triazine, etc.

(D) Urea herbicide 3-(3,4-dichlorophenyl)-1,1-dimethylurea; 3-(3,4-dichlorophenyl)-1
-Methoxy-1-methylurea: 3-(α,α,α-trifluoro-m-tolyl)-1,1-dimethylurea;
3-[4-(4-methylphenethyloxy)phenyl-1-methoxy-1-methylurea; a-(S-t-butyl-3,4-thiadiazol-2-yl)-4-hydroxy-1-meth Ru2-imidazolitone, etc.

(Gen. Carbamate herbicide Isopropyl-N-(3-chlorophenyl)carbamate; Methyl-N-(3,4-dichlorophenyl)carbamate: 4-chloro-2-butynyl-N-(a-10ruphenyl)carbamate Nat.

(F) Thiol carbamate herbicide B -x Chil-N,N-hexamethylenethiol carbamate: 5
-(4-chlorobenzyl) -N,N-diethylthiol carbamate: S-etheldiprobyl thiol carbamate, etc.

(G) Anilide herbicide 3.4-dichloropropionanilide: N-methoxymethyl-2/, 6/-diethyl-2-chloroacetanilide; 2-chloro-2',6'-diethyl-N-(butoxy methyl)-acetanilide; 2-chloro-2',6
'-Diethyl-N-(propoxyethyl)-acetanilide; α-(2-naphthoxy)propionanilide, etc.

(→Uracil herbicide 5-bromo-3-sec-butyl-6-methyluracil; 3-cyclohexyl-5,6-)1.1 methyleneuracil, etc.

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

(J) Phosphorus herbicide N-(phosphonomethyl)glycine; 0-ethyl-o-(
2-nitro-5-methylphenyl)-N-8ec-butylphosphoroamidothioate; 〇-methyl-o-(2-
Nitro-4-methylphenyl)-N-inpropyl phosphoroamide thioate: S-, (2-methylphenyl 1,1
-hyhericylcarbonylmethyl) -0,0-di-n-
Propyldithiophosphate; (2-amino-4-methylphosphino-butyryl)-alanylalanine monosodium salt, etc.

(3) Toluidine herbicide α, α, α-trifluoro 2,6-sinitro N, N
-dipropyl-p-)luidine: N-(cyclopropylmethyl)-α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine, etc.

(odor) Other herbicides 5-tert-butyl-3-(2,4-dichloro-5-impropoxyphenyl) -1,3,4-oxadiazolin-2-one; 3-inpropyl-2,1 , 3-benzothiadiazinone-4,2,2-dioxide; 2-(α-
naphthoxy)-N,N-diethylpropionamide; 3
-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-triazin-2-yl)aminocarbonyl]benzenesulfonamide; 2-[(4,6-cymethoxypyrimidine-2-
yl)aminecarbonylaminosulfonylmethyl]benzoic acid methyl ester: N-(1-methyl-1-phenylethyl)-2-promo a, 3-dimethylbutanamide: 2-[1-(N-allyloxyamino)phthylidene ]-4-methoxycarbonyl-5゜5-dimethylcyclohexane-1,3-dione sodium salt; 2-[1
-(ethoxyimino)butyl]-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexane-1
-Onnato.

The above herbicides are merely examples, and other herbicides that can be used in combination with one 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 for soybeans, and is effective even during the plant growth period. Since it can be used in the same manner across all species and has low toxicity, it is suitably used as a herbicide for broad-leaved and gristaceous crops 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 the herbicide in an amount of 1 to 50 r (i active ingredient) per 10 are.

Example Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Preparation of 5-(2'-chloro-4'-)IJfluoromethylphenoxy)-2-nitroα-methoxyacetophenone (compound 1) 3-42'-chloro0-4'-1-lifluoro methylphenoxy)-α-methoxyacetophenone 3.42,
After adding it to a mixed solution of 201 nl of dichloromethane and 10 ml of concentrated sulfuric acid cooled to below 5°C, 1 ml of potassium nitrate was added.
1 was added little by little over a period of 10 minutes.

After the addition was completed, the reaction was carried out at 5° C. or lower for 30 minutes. After the reaction, 1 reaction solution was poured into ice water, and dichloromethane 5
After adding 0-, an extraction operation was performed to separate the dichloromethane layer, which was washed with saturated brine and water, and dried over anhydrous sodium sulfate. After drying, dichloromethane was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography.
'-Chloro-4'-trifluoromethylphenoxy)-
2.3 tons of light brown crystals of 2-nitro α-methoxyacetophenone were obtained.

Example 2 Preparation of syn and anti isomers (compound 2 and compound 3) of 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone oxime 5-(2'- Chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophyl
．． 9tk absolute ethanol 20- and dry benzene 20-
Add acetic anhydride to a solution of IJum 1.4? and 1.21 liters of hydroxylamine hydrochloride were added. The reaction mixture was heated under reflux for 8 hours, cooled, and water and ether were added to extract the reaction product. The organic layer was washed with water, dried over anhydrous sodium sulfate, and then ether and benzene were distilled off under reduced pressure to give 5-(2'-,!70ro4'-fluoromethylphenoxy)-2-nitro-α- A crude product consisting of syn and anti isomers of methoxyacetophenone oxime was obtained. As a result of separation and purification by silica gel column chromatography, the melting point was 123-125.
Pale brown crystals of the syn isomer (compound 2) of 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime (compound 2) at 1.81 and refractive index n: ' 1.5278 anti
Light yellow glaze butterfly oil of isomer (compound 3) 1.42
I got it.

Example 3 Syn and a of 5-(2'-10-4'-)lifluoromethylphenoxy)-2-nitro α-methoxyacetophenone oxime-〇-(vinegar rlL ethyl ester)
Preparation of nti isomer (compound 17) 5-(2'-rioo
-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone 1.95'i anhydrous ethaneol 20- and dry benzene 0.69 rnt and 0-ethoxycarbonylmethyl 1.21 liters of hydroxylamine hydrochloride was added. The reaction mixture was heated under reflux for 8 hours, cooled, and water and ether were added to extract the reaction product. The organic layer was washed with water and diluted with anhydrous nitric acid. After drying over IJum, ether and benzene were distilled off under reduced pressure to give 5-(2'-chloro-4'-1
-IJfluoromethylphenoxy)-2-nitro-α-
A crude product consisting of syn and anti isomers of methoxyacetophenone oxime-〇-(acetic acid, ethyl ester) was obtained. As a result of purification by silica gel column chromatography, 5 has a refractive index n2' of 1.5276.
-(2'-Chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime -(acetic acid).

Pale orange viscous oil consisting of syn and anti isomers of ethyl ester (compound 17) 2.1 f
I got it.

Example 4 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro α-methoxyacetophenone-
Preparation of syn and anti isomers of 〇-methyloxime (compound 4)a) 3.42 of 3-(2'-chloro-47-trifluoromethylphenoxy)-α-methoxyacetophenone was mixed with 20-g of absolute ethanol and dry benzene. 1 part of anhydrous sodium acetate and 11 parts of 0-methylhydroxylamine hydrochloride were added to the solution dissolved in 20-. The reaction mixture was
The reaction was carried out at ~50°C for 3 hours. After the reaction was completed, water and ether were added to extract the reaction product, washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a-(2'-
Chloro0-4'-1 fluoromethylphenoxy)-α-
3.61 of a pale yellow oil of metquinacetophenone-0-methyloxime was obtained.

b) 3-(2'-chloro-4'-trifluoromethylphenoxy)-α-methoxyacetophenone obtained in a)
〇-Methyl oxime 3.6 f'lid, dichloromethane 30- and concentrated sulfuric acid 10Wd cooled to below 5°C! , and then 1 ton of potassium nitrate was added little by little over 10 minutes. After the addition is complete, heat at 5°C or below.
The reaction was allowed to proceed for 0 minutes. After completion of the reaction, the reaction mixture was poured into ice water, and 50 g of dichloromethane was further added thereto, followed by extraction operation to separate the dichloromethane layer, washed with saturated brine and water, and dried over anhydrous sodium sulfate. After drying, dichloromethane was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography. Pale yellow glazed butterfly oil consisting of the syn and anti isomers of (fluoromethylphenoxy)-2-nitro α-methoxyacetophenone-O-methyloxime (Compound 4)2. Ill'i got it.

When this pale yellow oil is dissolved in methanol, the melting point is 81-8.
Pale yellow crystals at 2°C were obtained.

Example 5 Table 1 shows the structures, physical properties, single element analysis values, and IH-NMR analysis data of the compounds of the present invention produced in the same manner as in each of the above Examples. Needless to say, it is not limited. Note that 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 are 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 10 parts by weight of talc were thoroughly ground and mixed to make an irrigation agent.

Formulation 2 (emulsion) 5 parts by weight of the compound of the present invention, 10 parts by weight of Tsurupol 3005
Parts by weight and 40 parts by weight of xylene are thoroughly mixed to form 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, the mixture is granulated and dried to form granules.

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

Usage Example 1 A pot filled with field soil of 1/2500 are was prepared in a greenhouse. Soybeans per pot.

I sowed corn, crabgrass, Japanese knotweed, and Japanese knotweed.

Pre-emergence treatment is 25 per 10 ares 24 hours after sowing.
2 was applied. On the other hand, post-emergence treatment.

For soybeans, 10 tons/10 ares were applied at the 2- to 3-leaf stage, for corn, at the 3-4 leaf stage, and for weeds, at the 2-2.5 leaf stage. Spraying method is emulsion of specified concentration (formulation 2)
was diluted in 1 oz of water and applied with a glass sprayer. The degree of weed control ability was observed 14 days after chemical treatment, and the degree of chemical damage to the crops was observed 30 days after treatment. The results are shown in Table 2 below. The values in the table are based on the following criteria.

5: Complete inhibition 4: 80% inhibition 3 60% inhibition 2: 40% inhibition, 20% inhibition 0, no effect Usage example 2 The magnitude of activity between syn and anti isomers of oxime derivatives We conducted a test to find out the difference.

A pot with a size of 1/2500 are filled with field soil was prepared in a greenhouse. Soybeans per pot.

We grew corn, crabgrass, goldenrod, pigweed, and Japanese knotweed. For soybeans, the foliage treatment was performed at the 2- to 3-leaf stage, for corn at the 3- to 4-leaf stage, and for weeds at the 2- to 2.5-leaf stage. Spraying method is emulsion of specified concentration (formulation-2)
was diluted with 10 tons of water per area and applied with a glass sprayer. After drug treatment.

The degree of weed control ability was observed on the 14th day, 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.

Table 3 Usage example 3 Set up a 1d plot in the field and grow soybeans as a crop.

Corn seeds are used as a weed.

Golden millet, pigweed, giant knotweed, ichi, American hornwort, mulva morning glory, golden millet.

Chickweed seeds were sown and grown. Soybeans are at the 2nd to 3rd leaf stage, corn is at the 3rd to 4th leaf stage, and weeds are at the 3rd to 5th leaf stage.
Stems and leaves were treated during the leaf stage. The spraying method was to dilute an emulsion (formulation 2) with a predetermined concentration in 10 tons of water per area and use a sprayer. After drug treatment.

The degree of weed control ability was observed monthly on the 14th, and the degree of chemical damage to the crops was observed on the 30th. The results are shown in Table 4. Note that the criteria in the table are the same as in Use Example 1.

Usage Example 4 A pot filled with paddy soil of 1/5000 are was prepared in a greenhouse. Seeds of barnyard grass and Japanese grass, the annual broad-leaved weed Kikashigusa, azalea, and the perennial weed bulrush were mixed with dry paddy soil and mixed into the surface layer □. In addition, tubers of perennial weeds such as Prunus spp.

For rice, three-leaf stage seedlings were transplanted into the soil surface layer 2 to 3 cIn.

For the chemical treatment, a liquid prepared by diluting an emulsion (prescription 2) of a predetermined concentration with water was dropped with a pipette at the 0.5 to 1 leaf stage of barnyard grass. At 21 days after the chemical spraying, the degree of chemical damage to rice and weed control ability was observed. The results are shown in Table 5.

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

CR2

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is an oxygen atom or a substituent represented by =N-O-R^1, and R^1 is hydrogen Atom; Straight-chain or branched lower alkyl group; Straight-chain or branched lower alkyl group substituted with a halogen atom, cyano group, or alkoxy group; Lower alkenyl group; Lower alkynyl group or ▲ Numerical formula, chemical formula , tables etc. are the groups shown by ▼, where R^2 is a hydrogen atom or a methyl group, R^3 is a hydrogen atom, a lower alkyl group, an alkali metal, an alkaline earth metal equivalent to one valence,
ammonium group or alkyl-substituted ammonium group) and 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone and 5-(2'-chloro -4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime derivative. 2 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (X in the formula is an oxygen atom or a substituent represented by =N-O-R^1, and R^1 is a hydrogen atom; linear or Branched lower alkyl group; linear or branched lower alkyl group substituted with a halogen atom, cyano group or alkoxy group; lower alkenyl group; lower alkynyl group or ▲Mathematical formula, chemical formula, table, etc. is a group represented by, R^2 is a hydrogen atom or a methyl group, R^3 is a hydrogen atom, a lower alkyl group, an alkali metal, an alkaline earth metal equivalent to one valence,
ammonium group or alkyl-substituted ammonium group) and 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone and 5-(2'-chloro A selective herbicide containing a -4'-trifluoromethylphenoxy)-2-nitro-α-methoxyacetophenone oxime derivative as an active ingredient.