DD256637A5 - HERBICIDAL COMPOSITION - Google Patents

Abstract

The present invention relates to a herbicidal composition containing as active ingredient a compound of general formula (I) in addition to the usual auxiliary and / or carrier substances. The invention further relates to a method for the destruction of unwanted weeds, using this herbicidal composition. The invention provides novel diphenylether herbicides which are free from the drawbacks inherent in the conventional diphenylether herbicides, which have selective and high herbicidal activity, which means complete safety for the crops and immediate destruction of all unnecessary weevils occurring there, and which can be applied continuously throughout the growing period of the crops. Formula (I)

Description

Field of application of the invention

The invention relates to a herbicidal composition containing as active ingredient 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-asubstituted acetophenone, in addition to customary excipients and / or carriers, as well as a method for the destruction of unwanted weeds, using this composition.

Characteristic of the known technical solutions

A herbicide is known which contains as an active ingredient an alkyl [2-nitro-5- (2-chloro-4-)

trifluoromethylphenoxy) phenyl] ketone compound or its oxime derivative, commonly referred to as a diphenyl ether herbicide (see, e.g., U.S. Patent Nos. 4,344,789 and 4,401,602). Another class of diphenyl ether herbicide, a herbicide containing as an effective ingredient an oxime derivative of 2-nitro-5- (2-chloro-4-trifluoromethyl-phenoxy) -phenylacetonitrile (see US Patent 4,490,167, is also well known.

However, all the known diphenylether herbicides have the disadvantage that, if they have good herbicidal activity, they have poor selectivity, and if they have good selectivity, their herbicidal activity is poor. Thus, they are all not suitable for effective and immediate control of only unwanted weed species.

The ideal herbicide would have to satisfy the following conditions in addition to the noted excellent herbicidal activity and high selectivity. The toxicity of the herbicide to warm-blooded animals should be low. The herbicide would also have to be effective in one use at any time throughout the growing time of the crops. In addition, the herbicide would have to decompose as soon as possible after use, so that the soil is not contaminated

 However, such an ideal diphenyl ether herbicide which meets the mentioned conditions is not yet known.

Object of the invention

The object of the invention is to provide a novel diphenyl ether herbicide which is free from the disadvantages inherent in the conventional diphenyl ether herbicides, which has a selective and high herbicidal activity, which means complete safety for the crops and the immediate destruction of all unnecessary weeds occurring there, and that can be applied continuously throughout the growing period of the crops.

Explanation of the essence of the invention

The invention has for its object to find a new herbicidal composition and a method for the destruction of unwanted weeds, using this composition.

The invention relates to a herbicidal composition containing as active ingredient an effective amount of a compound of general formula I _f

'Y

0. ^ J-CH ₂ -OR ¹

R ^{1 represents} a methyl group or ruT-H-A-T?

A is an oxygen atom or a sulfur atom, R ^{3 is} a hydrogen atom or a methyl group and

R ^{4 is} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms or a halogen atom-substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a carboalkoxy group having 2 to 4 carbon atoms; and

Y represents an oxygen atom or = NOR ² , wherein R ^{2 is} a hydrogen atom, an alkyl group having 1 to 3

Represents carbon atoms or j .. r ,

-GH-GR ⁰

wherein R ^{5 represents} a hydrogen atom or a methyl group,

R ⁸ and R ^{6 represent} -BR ⁷ or ^ y · "

in which represent

B is an oxygen atom or a sulfur atom,

R ^{7 is} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, a substituted or unsubstituted phenyl group, an alkyl group substituted by a halogen atom or an alkoxy group having 1 to 3 carbon atoms with 1 to 4 carbon atoms, an alkali metal, an alkaline earth metal in a proportion corresponding to the monovalent of the alkaline earth metal, an ammonium group, one substituted by an alkyl group having 1 to 4 carbon atoms

, Ammonium group, or

R ¹⁰ O

-CH-GOR ¹ '

wherein R ^{10 represents} a hydrogen atom or a methyl group, and R "represents an alkyl group having 1 to 3 carbon atoms, and R ⁸ and R ^{9 are the} same or different and each independently represents a hydrogen atom, an alkyl group having 1 to carbon atoms, an alkynyl group having 3 to 6 carbon atoms or an alkoxy group having 3 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, besides customary auxiliaries and / or carriers It has been found that a novel 5- (2-chloro-4-trifluoromethylphenoxy) -2 nitro-substituted acetophenone compound and its oxime derivatives meet the above-mentioned requirements for an improved herbicide, and that the compounds are also very effective at low dosage in a variety of broadleaf crops and Gramineae family plants such as soybeans, peanuts, corn, wheat and rice.

According to the invention, a novel 5- (2-chloro-trifluoromethylphenoxy) -2-nitro-substituted acetophenone compound and its oxime derivative having a high selectivity and a high herbicidal activity are provided. Furthermore, a method of destroying the unwanted weeds by means of the novel compound described above is provided.

The characteristic feature of the compounds according to the invention is that they have in their corresponding molecular structures

an α-substituted acetophenone or its oxime derivative, in contrast to the similar conventional compounds having in their related molecular structures an α-unsubstituted alkyl phenyl ketone such as acetophenone or propiophenone, their oxime derivative or an oxime derivative of phenylacetonitrile. Surprisingly, the introduction of a substituent in the α-position of the acetophenone component allows the compounds of the present invention to provide a pre-emergence or post-emergent herbicide which is very effective for controlling undesirable weeds at a low dosage and which provides high selectivity and high potency Compared with the conventional compounds having similar structures.

The terminology used in the following to designate the compounds according to the invention, such as, for example, 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, methyl ester) is intended to mean the syn-anti isomers and the other stereoisomers lock in. In the following, specific examples of the compound of the present invention will be mentioned.

The compounds represented by the above-mentioned formula (I) wherein Y = NOR ² include: 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime 5- (2-chloro-4-trifluoromethylphenoxy ) -2-nitro-a-methoxyacetophenone-O-methyloxime, 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O-ethyloxime, 5- (2-chloro-4-trifluoromethylphenoxy) - 2-nitro-a-methoxyacetophenone oxime-O-n-propyloxime, 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O-isopropyloxime, 5- (2-chloro-4-trifluoromethylphenoxy) - 2-nitro-a-methoxyacetophenone oxime-O- (acetic acid), sodium 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime O-acetate, potassium 5- (2-chloro-4-trifluoromethylphenoxy ) -2-nitro-α-methoxyacetophenone oxime O-acetate, calcium 5- {2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime O-acetate, magnesium 5- (2-chloro-4-trifluoromethylphenoxy ) -2-nitro-a-methoxyacetophenone oxime-O-acetate, ammonium 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyac etophenone oxime 0-acetate, methyl ammonium 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime O-acetate, dimethyl ammonium 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro α-methoxyacetophenone oxime O-acetate, 5- (12-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime O- (acetic acid, methyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2- nitro-a-methoxyacetophenone oxime-O- (acetic acid, ethyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-o: -methoxyacetophenone oxime-O- (acetic acid, n-propyl ester), 5- (2-chloro) Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, n-butyl ester) 5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, allyl ester ), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, 2-methyl-2-propenyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2- nitro-a-methoxyacetophenone oxime-0- (acetic acid, crotyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (essi g., propargyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, phenyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a -methoxyacetophenone oxime-O- (acetic acid, p-methoxyphenyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, m-chlorophenyl ester), 5- (2-methoxyacetophenone) oxime Chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, o-methylphenyl ester), '5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, 2-chloroethyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, 2-bromoethyl ester), 5- (2-chloro-4-trifluoromethylphenoxy ) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, 2,2,2-trifluoroethyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, 2 methoxy ethyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, 2-ethoxyethyl ester), 5- (2-chloro-4-) trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, 1-methyl-2-methoxyethyl ester), methyl 2 - [[[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) - a-methoxymethylbenzylidene] amino] oxy] acetoxy] acetate, ethyl 2 - [[[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a-methoxymethylbenzylidene] amino] oxy] acetoxy] acetate , n-Propyl 2 - [[[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a-methoxymethylbenzylidene] amino] oxy] acetoxy] acetate, methyl 2 - [[[[2- nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a-methoxymethylbenzylidene] amino] oxy] acetoxy] propionate, ethyl 2 - [[[[2-nitro-5- (2'-chloro-4 ' -trifluoromethylphenoxy) -a-methoxymethylbenzylidene] amino] oxy] acetoxy] propionate, n-propyl 22 - [[[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a-methoxymethylbenzylidene] amino] oxy] acetoxy] propionate, 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a; -methoxyacetophenone oxime-0-acetamide,

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, N-methylamide), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime 0- (acetic acid, N-ethyl-amide),

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, Nn-propyl-amide), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α- methoxyacetophenone oxime-O- (acetic acid, Ν, Ν-dimethylamide), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, N-methyl-N-methoxyamide), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime O- [acetic acid, N- (1,1-dimethylpropargyl) amide],

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (2-propionic acid), sodium 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α: -methoxyacetophenone oxime 0- (2-propionate), potassium 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (2-propionate),

5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-o: -methoxyacetophenone oxime-O- (2-propionic acid, methyl ester),

5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (2-propionic acid, ethyl ester),

5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone-0- (2-propionic acid, n-propyl ester),

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (2-propionic acid, allyl ester),

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (2-propionic acid, 2-methyl-2-propenyl ester),

B-ii-ChloM-trifluormethylphenoxyl ^ -nitro-a-methoxyacetopheriörrcrxi ^

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (2-propionic acid, 2-chloroethyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α- methoxyacetophenone oxime O- (2-propionic acid, 2-methoxyethyl ester), methyl 2- [2 - [[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -α-methoxymethylbenzylidene] amino] oxy] - propionyloxy] acetate, ethyl 2- [2 - [[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a: -methoxymethylbenzylidene] amino] oxy] -propionyloxy] acetate, methyl 2 - [[ [[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a-methoxymethylbenzylidene] amino] oxy] -propionyloxy] propionate, ethyl 2- [2 - [[[2-nitro-5- (2 '-chloro-4'-trifluoromethylphenoxy) -a-methoxymethylbenzyliden] amino] oxy] propionyloxy] propionate,

5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone-0- (2-propionamide)

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (2-propionic acid, N-methylamide), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-o: -methoxyacetophenone oxime-O- (2-propionic acid, Ν, Ν-dimethylamide), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α: -methoxyacetophenone oxime-O- (2-propionic acid, N-methoxyamide), 5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (thioacetic acid, S-methyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α: -methoxyacetophenone oxime -0- (thioacetic acid, S-ethyl ester),

5- (2-Chloro-4-trifluoromethylpherioxy) -2-nitro-α-methoxyacetophenone oxime-O- (thioacetic acid, S-allyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α; -methoxyacetophenone oxime -0- (2-thiopropionic acid),

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (2-thiopropionic acid, S-methyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α- methoxyacetophenone oxime-O- (2-thiopropionic acid, S-ethyl ester), methyl 2 - [[[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a: -methoxymethylbenzylidene] amino] oxy] acetylthio ] acetate, ethyl 2 - [[[[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a: -methoxymethylbenzylidene] amino] oxy] -acetylthio] acetate, methyl 2 - [[[[2 -nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a-methoxymethylbenzylidene] amino [oxy] acetylthio] propionate, ethyl 2 - [[[[2-nitro-5- (2'-chloro-4 ' -trifluoromethylphenoxy (-a-methoxymethylbenzylidenlaminoloxyl-acetylthiolpropionate, methyl 2- [2- [t- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -o; -methoxymethylbenzylidene] amino] oxy] -propionylthio] acetate , Ethyl 2- [2 - [[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -o: -methoxymethylbenzylidene] amino] oxy] -propionylthio] acetate, methyl 2- [2 - [[ [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a-methoxymeth ylbenzyliden] amino] oxy] -propionylthio] propionate,

Ethyl 2- [2 - [[[2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -a-methoxymethylbenzylidene] amino] oxy] -propionylthio] propionate.

The compounds of the above-mentioned formula (I) wherein Y is an oxygen atom include:

5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone, 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) -phenacyloxyacetic acid, methyl 2-nitro-5- (2-chloro-4 -trifluoromethylphenoxy) phenacyloxyacetate, ethyl 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, n-propyl 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, η-butyl-2-nitro- 5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, allyl 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, propargyl 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, 2 Chloroethyl 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, 2-Methoxyethyl 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, i-Methyl-2-methoxyethyl 2-nitro- 5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, methyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxyacetoxy] acetate, ethyl 2- [2-nitro-5- (2 '-chloro-4'-trifluoromethylphenoxy) phenacyloxy] acetate, methyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy ) phenacyloxyacetoxy] propionate, ethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxyacetoxy] propionate, 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionic acid, methyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, ethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, n-propyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, isopropyl 2- [2-nitro-5- (2'-chloro-4 ') trifluoromethylphenoxy) phenacyloxy] propionate, η-butyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, allyl 2- [2-nitro-5- (2'-chloro-4 '-trifluoromethylphenoxy) phenacyloxy] propionate, propargyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, 2-chloroethyl 2- [2-nitro-5- (2'-chloro 4'-trifluoromethylphenoxy) phenacyloxy] propionate, 2-methoxyethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, methyl 2- [2- [2'-nitro-5 '- (2 "-chloro-4' trifluoromethylphenoxy) phenacyloxy] propionyloxy] a cetate, ethyl 2- [2- [2'-nitro-5 '- (2 "-chloro-4" -trifluoromethylphenoxy) -phenacyloxy] -propionyloxy] -acetate, methyl 2- [2- [2-nitro-5' - ( 2 "-chloro-4" -trifluoromethylphenoxy) phenacyloxy] propionyloxy] propionate, ethyl 2- [2- [2'-nitro-5 '- (2 "-chloro-4" -trifluoromethylphenoxy) phenacyloxy] propionyloxy] propionate,

-8- ZÜÖÖ3 /

S-Methyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) prienacyloxy] thioacetate, S-ethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] thioacetate, S-AIIyI 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] thioacetate, S-propargyl 2- [2-nitro-5- (2'-chloro-4 '-trifluoromethylphenoxy) phenacyloxy] thioacetate, methyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxyacetylthio] acetate, ethyl 2- [2-nitro-5- (2'-chloro-4 '-trifluoromethylphenoxy) phenacyloxyacetylthio] acetate, methyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxyacetylthio] propionate, ethyl 2- [2-nitro-5- (2'-chloro-4 '-trifluoromethylphenoxy) phenacyloxyacetylhio] propionate, S-methyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] thiopropionate, S-ethyl 2- [2-nitro-5- (2' -chloro-4'-trifluoromethylphenoxy) phenacyloxy] thiopropionate, S-AIIyI 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] thiopropionate, S-propargyl 2- [2-nitro-5 - (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] thiopropi onat, methyl 2- [2- [2'-nitro-5 '- (2 "-chloro-4" -trifluoromethylphenoxy) phenacyloxy] propionylthio] acetate, ethyl 2- [2- [2'-nitro-5' - ( 2 "-chloro-4" -trifluoromethylphenoxy) phenacyloxy] propionylthioacetate, methyl 2- [2- [2'-nitro-5 '- (2 "-chloro-4" -trifluoromethylphenoxy) phenacyloxy] propionylthio] propionate,

Ethyl 2- [2- [2'-nitro-5 '- (2 "-chloro-4" -trifluoromethylphenoxy) phenacyloxy] propionylthio] propionate.

All of the above compounds are novel compounds that have not been previously reported in the literature. For example, they can be prepared by the methods A to D described below. Another erfihdungsgemäßer aspect is that a by the formula

Cl Ο

Ιί

C-CH ₂ -OR "

(IV)

Dargestelle compound in which R ^{1 has} the meaning defined above, is provided. In another aspect of the invention, a compound represented by the formula

01

N-O-H

(V)

represented compound in which R ^{1 has} the meaning defined above provided. Another aspect of the invention is that a by the formula

Cl

-O-R

(VII)

provided compound in which R ^{1 has} the meaning defined above, and · R ^{12 is} an alkyl group having 1 to 3 carbon atoms or

-CH-CR ⁵

5 represents, in which

R ^{6 is} a hydrogen atom or a methyl group and

R ^e -BR ⁷ or -N

represents.

in which represent

B is an oxygen atom or a sulfur atom, R ^{7 is} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a halogen atom or an alkoxy group Substituted from 1 to 3 carbon atoms

An alkyl group having 1 to 4 carbon atoms, an alkali metal, an alkaline earth metal in a proportion corresponding to the monovalent of the alkaline earth metal, an ammonium group, an ammonium group substituted with an alkyl group having 1 to 4 carbon atoms, or

R ¹⁰ O

I Il H

-Ch-C-O-R,

wherein R ^{10 represents} a hydrogen atom or a methyl group, and R ^{11 represents} an alkyl group having 1 to 3 carbon atoms, and R ⁸ and R ^{9 are the} same or different and each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkynyl group having 3 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.

All compounds (IV), (V) and (VII) are novel compounds useful as intermediates for the novel compound represented by formula (I).

The compounds (IV), (V) and (VII) can be prepared, for example, according to the method A described below.

Another aspect of the invention is that a process for the preparation of a by the formula

Cl

if-

0-R

12

C-CH ₂ -OR ^-

NO,

(La)

represented compound in which R ¹ and R ^{12 have} the meaning explained above, which provides the reaction of a by the formula

Cl

J-O-R

12

! -CH ₂ -OR ^-

(VII)

^F 3 ^C

represented compound in which R ¹ and R ^{12 have} the meaning described above, comprising a nitrating agent. Another aspect of the invention is that a process for the preparation of a by the formula

Cl

C-CH ₂ -OR-

(Ib)

NO,

Compounds of R ^{1 which have the} meaning explained above are provided, which comprises the reaction of a compound represented by the formula

Cl

F ₃ C

It

C-CH ₂ -OR-

(IV)

represented compound in which R ^{1 has} the meaning explained above, comprising a nitrating agent.

Another aspect of the invention is that a process for the preparation of a by the formula

Cl N-G-H

in H ι

C-CH ₂ -OR ^X

F ₃ C

NO,

represented compound in which R ^{1 has} the meaning explained above, which provides the reaction of a by the formula

Oil

^F 3 ^C

-CH ₂ -OR "

(Ib)

NO,

represented compound in which R ^{1 has} the meaning explained above, with hydroxylammonium chloride in the presence of an acid acceptor. In a further aspect of the invention, a process for the preparation of a compound represented by the formula

Cl

12

(La)

NOR CH ₂

NO,

represented compound in which R ¹ and R ^{12 have} the meaning explained above, provided. The process involves the reaction of a compound represented by the formula

C-CH ₂ -OR-

(Ic)

represented compound in which R ^{1 has} the meaning described above, with a represented by the formula R ¹² -Z

(Vl)

halide shown, wherein R ^{12 has} the meaning described above and Z represents a halogen atom, in the presence of an acid acceptor. As examples of the method explained above, the methods A to D will be described in detail below.

Method A Reaction Process:

Fi-O J \

U ι

C-CH ₂ -O-R ^x

(II)

(III)

Cl

" 1

C-CH ₂ -OR- ¹

(IV)

(2) (IV) +

H ₂ NOH.HCl

acid acceptor

^F 3 ^C

-0-H

(V)

(3) (V) + R ¹² Z (VI)

acid acceptor,

Cl

NOR ¹²

C-CH ₂ -OR

(VII)

(4) (VII) Nitration ^

(la) *

wherein M represents an alkali metal and Z represents a halogen atom and R ¹ and R ^{12 have} the meaning explained above. In the above-mentioned step (1), a 3-chloro-4-halobenzotrifluoride compound represented by the formula (II) is reacted with a sodium or potassium salt, preferably a potassium salt of a 3-hydroxy-substituted acetophenone compound represented by the formula (III) or its ketalen oderacetalen derivatives at a temperature of 70 ⁰ C to 160 ⁰ C, preferably at 90 ⁰ C to 140 ⁰ C, for about 1 to 8 hours to form a represented by the formula (IV) 3- (2-chloro-4 trifluoromethylphenoxy) -a-substituted acetophenone compound. The molar ratio of compound (II) to compound (III) may be greater than 1, preferably 1: 1 to 2: 1. The above-mentioned reaction may be carried out in an aprotic polar solvent such as dimethyl sulfoxide and Ν, Ν-dimethylformamide, preferably dimethylsulfoxide. In the above-mentioned step (2), the resulting compound of the formula (IV) is reacted in a conventional manner with hydroxylamine hydrochloride in the presence of an acid acceptor such as an anhydrous salt of an organic acid, e.g. For example, sodium acetate anhydride or the like, an organic salt, e.g. Sodium hydroxide, barium carbonate or the like, and an organic tertiary amine, e.g. Triethylamine, pyridine or the like to form a 3- (2-chloro-4-trifluoromethylphenoxy) -a-substituted acetophenone oxime compound represented by the formula (V). The molar ratio of the compound (IV) to hydroxylamine hydrochloride may preferably be in the range of 1: 1 to 1: 2. The reaction may be for 0.5 to 24 hours in a solvent such as alcohol, e.g. Methanol, ethanol or the like, or in a solvent mixture of an alcohol and an aromatic solvent, e.g. As ethanol and dry benzene or the like. The solvents may be used either singly or in combination. The above reaction may be carried out at a temperature generally between about 0 ^° C. and the boiling point of the single or mixed solvent, preferably at room temperature to a boiling point of the single or mixed solvent. In the above-mentioned step (3), the compound of the formula (V) may be reacted with a halide represented by the formula (VI) in the presence of an acid acceptor such as an alkoxide of an alkali metal, e.g. Sodium methylate and a metal hydride, eg, sodium hydride, to form an oxime derivative of 3- (2-chloro-4-trifluoromethylphenoxy) -a-substituted acetophenone represented by the formula (VII). The molar ratio of compound (V) to compound (Vl) is preferably in the range of 1: 1 to 1: 2. The reaction may be carried out in a suitable solvent selected from an alkanolic solvent such as methanol and ethanol

Ether solvents such as ether or tetrahydrofuran, an aprotic polar solvent such as Ν, Ν-dimethylformamide and Ν, Ν-dimethylacetamide and an aromatic solvent such as benzene is selected. The solvents may be used either singly or in combination. The reaction can be performed at a temperature up to about 15O ⁰ C, generally between about -10 ° C - preferably between 0 ⁰ C to about 100 ⁰ C, is located. In the above-mentioned step (4), the compound of the formula (VII) is reacted with a conventional nitrating agent such as potassium nitrate in concentrated sulfuric acid, an acid mixture of sulfuric acid and nitric acid and the like to form a compound represented by the formula (Ia). The molar ratio of compound (VII) to the nitrating agent may preferably be between 1: 1 to 1: 1.5. The nitration may be at a temperature which is generally between -20 ⁰ C and 8O ⁰ C, preferably between -10 ⁰ C to about 50 ⁰ C, are carried out for about 0.5 to 6 hours. If desired, nitration may be carried out in an inert organic solvent such as 1,2-dichloroethane and other chlorohydrocarbons.

Method B reaction process:

C-CH ₂ -OR ¹ + R ¹² -O-r

(IV)

(X)

acid acceptor *

Cl

^F 3 ^C

NOR ¹² C-CH ₂ -O-R ^:

NO,

(2) (VII) nitration.

JfXX

NO,

(La)

wherein R ¹ and R ^{12 have} the meaning defined above and η is an integer 1 or 2. ^!

In the above-mentioned step (1), a 3- (2-chloro-4-trifluoromethylphenoxy) -o: -substituted acetophenone compound represented by the formula (IV) is reacted in a known manner with a hydrochloride of a hydroxylamine derivative represented by the formula (X) in the presence an acid acceptor such as an anhydrous salt of an organic acid, e.g. For example, sodium acetate anhydride, an inorganic salt, eg. For example, sodium hydroxide and barium carbonate and an organic tertiary amine, eg. For example, triethylamine and pyridine to form an oxime derivative of the represented by the formula (VII) represented 3- (2-chloro-4-trifluoromethylphenoxy) -a-substituted acetophenone. The molar ratio of compound (IV) to compound (X) is preferably between 1: 1 to 1: 2. The reaction may be carried out in an organic solvent such as an alcohol, e.g. Anhydrous ethanol, and a mixed solvent of an alcohol and an aromatic solvent, e.g. As anhydrous ethanol and dry benzene done. The solvents may be used either singly or in combination. The reaction may be carried out at the same temperature as described for step (2) of process A for about 0.5 to 24 hours.

In the above-mentioned step (2), the nitration reaction is carried out in substantially the same manner as described for the step (4) of Process A, whereby a compound of the formula (Ia) of the present invention is obtained.

Method C reaction process:

(IV)

Nitration y

Cl

^F 3 ^C

-CH ₂ -O-R '

(Ib)

(2) (Ib) + H ₂ NOH-HCl Cl

aäureakzeptorv

F ₃ C

(Lc)

N-O-H

NO,

(3) (IC) ₊ R ¹² Z (VI)

acid acceptor

^F 3 ^C

Cl

(La)

NOR ¹² C-CH ₂ -OR

NO,

wherein R ¹ , R ¹² and Z have the meaning defined above.

In the above-mentioned step (1), a 3- (2-chloro-4-trifluoromethylphenoxy) -a-substituted acetophenone compound represented by the formula (IV) is synthesized in substantially the same manner as in the step (4) of Process A described nitrated to

to win the compound of formula (Ib) according to the invention.

Subsequently, the compound of formula (I b) obtained in step (2) is reacted with hydroxylamine hydrochloride in the presence of an acid acceptor to form an oxime represented by formula (I c) of the invention. This reaction can be carried out in substantially the same manner as described in Step (2) of Method A, except that the molar ratio of compound (Ib) to hydroxylamine hydrochloride is preferably between 1: 1 and 1: 1.5

can lie.

Further, the recovered oxime of formula (Ic) in step (3) is reacted with a halide represented by formula (VI) in the presence of an acid acceptor in substantially the same manner as described in step (3) of method A. to obtain a compound of the invention represented by the formula (la).

Method D Reaction Process:

Cl 0

0 ^^ ^ .C-CH ₂ -OR ¹ + R ¹² -O-NH ₂ .- | hc1

(X)

Cl NOR ¹²

I-CH ₀ -OR-

Saureakzeptor

³ (la)

wherein R ¹ , R ¹² and η have the meaning defined above.

In this method, ¹ Si represented by the formula (Ib) is used. substituted acetophenone derivative with a hydrochloride of a hydroxylamine derivative represented by formula (X) to form a compound of formula (Ia) of the invention. The reaction is carried out in the presence of an acid acceptor such as an anhydrous salt of an organic acid, e.g. For example, sodium acetate anhydride, an inorganic salt such. For example, sodium hydroxide and barium carbonate, and an organic tertiary amine, for. For example, triethylamine and pyridine. A preferred molar ratio of compound (I b) to compound (X) may be between 1: 1 and 1: 5, and the reaction time may be 0.5 to 24 hours. The reaction may be carried out in an organic solvent such as an alcohol, eg, anhydrous ethanol, and a mixed solvent of an alcoholic and an aromatic solvent, eg, anhydrous ethanol and dry benzene. The solvents may be used either singly or in combination. The reaction may be carried out at a temperature as described in step (2) of method A.

The above methods A to D illustrate the preferred methods of the invention. They do not constitute a limitation of the present invention. The compounds of the invention can be obtained by various processes which are modifications of conventionally known processes for the preparation of similar compounds. In still another aspect of the present invention, there is provided a herbicidal composition comprising, as an effective ingredient, a herbicidally effective amount of one represented by the following formula

Cl γ

O ^ ₉ . C-CH ₀ -OR ¹

containing compound wherein R ¹ and Y have the meaning defined above.

The term "herbicidally effective amount" as used herein is intended to mean an amount necessary for effective control under environmental conditions, that is, the weeds are severely damaged so that they can not recover from the application of the compound or they are killed, the crops do not cause any significant damage

experience.

The herbicidal activity of the compound (I) of the present invention will be illustrated below with respect to the prevention and elimination of weeds growing on plowed fields. The compound (I) according to the invention can be used effectively in plowed fields both in pre-emergence and in postemergence treatments over a relatively long period of time and has an extraordinarily high herbicidal activity even at astonishingly low doses. The compound (I) of the present invention has excellent herbicidal activity against dangerous weeds growing on plowed fields such as weeds of the family Granmineae, e.g. Cough, yellowfin, millet and the like; broadleaf weeds, e.g. B. Common Goosefoot, Peacockweed, Wooly Honeygrass, Greater Burdock, hemp sesbania, Amaranth, Morning Glory, teaw'eed (sida spinosa?), Sickle Pod, Common Datura, Black Nightshade, Winds, Common Chickweed, Common Purslane, and the like, as well as various other weeds. Of these, especially in the soybean fields dangerous weeds Wooly honey grass, Norway lace, common datura, winds, hemp sesbania and teaweed by the compound (I) according to the invention in an astonishingly low dosage effective

fought.

Thus, the characteristic feature of the compound (I) of the present invention is that the compound exhibits excellent herbicidal activity in both pre-emergence and postemergence applications and also excellent selectivity not only in broadleaf crops such as soybean, peanut plants and the like, but

also in the family Gramineae belonging crops such as corn, wheat, rice and the like.

Moreover, the compound of the present invention is not only remarkable for weeds on plowed fields

high herbicidal activity but also on weeds on rice fields. _ /,

That is, the compound (I) of the present invention has a high herbicidal activity even at a low dose in a variety of weeds on paddy fields, for example, the weeds belonging to the family Gramineae, such as millet and the like; in broadleaf weeds growing on paddy fields, such as monochoria, toothcup (rotala ramosior?), dandruff, false pimpernel, and the like; in perennial weeds on paddy fields such as arrowhead, sedge and the like. The compound (I) of the present invention has no significant phytotoxicity to rice plants when used in such a herbicidally effective amount that the weeds are effectively destroyed. From the foregoing, it will be understood that the compound (I) of the present invention can be used for selectively destroying weeds growing between soybean, peanut, corn, wheat, barley, rice and the like both in the preliminary treatment and in the post-treatment. Because of its broad applicability and excellent herbicidal activity, the compound of the invention is also useful as an effective herbicide for a pasture, an orchard, a meadow and for fallow land.

For practical use, the compound of the present invention may be used as a herbicide as such or may be processed into various preparations such as wettable powder, emulsifiable concentrate, granules, dusts and the like.

As the solid carrier for the formulation of the present compound to the various preparations described above, mineral powders (e.g., kaolin, bentonite, clay, montmorillonite, talc, diatomite, mica, vermiculite, gypsum, calcium carbonate, apatite, and the like), plant powders (e.g. , Soybean meal, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose and the like), high polymer compounds (e.g., petroleum resin, polyvinyl chloride, ketone resin and the like), and further alumina and waxes. As the liquid carrier, for example, alcohols (methanol, ethanol, butanol, ethylene glycol, benzyl alcohol and the like), aromatic hydrocarbons (such as toluene, benzene, xylene and the like), chlorinated hydrocarbons (chloroform, carbon tetrachloride, monochlorobenzene and the like). Ether (dioxane, tetrahydrofuran and the like). Ketones (acetone, methyl ethyl ketone, cyclohexanone and the like). Esters (ethyl acetate, butyl acetate and the like), acid amides (Ν, Ν-dimethylacetamide and the like), nitriles (acetonitrile and the like), ether alcohols (ethylene glycol ethyl ether and the like) and water. As the surfactant used as the emulsifier, dispersant, wetting agent, etc. for the present compound (I), there may be mentioned nonionic, anionic, cationic and amphoteric substances. Specific examples of surfactants which can be used for the present invention are polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, oxyethylene polymer, oxypropylene polymer, polyoxyethylene alkyl phosphate, fatty acid salt, alkylsulfate salt, alkylsulfonate salt, alkylarylsulfonate salt, alkylphosphate salt, polyoxyethylene alkylsulfate, quaternary ammonium salt and oxyalkylamine. Further, as needed, gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol and the like can be used as an auxiliary aid for the present invention.

The content of the compound (I) of the present invention in the herbicidal composition may vary depending on the kind and purpose for which the composition is intended, but it is generally between 0.05 to 95 mass%, preferably about 5 to 75 Ma .-% based on the total mass of the composition.

Moreover, in order to improve the herbicidal activity, the compound (I) of the present invention may be mixed with other herbicidally active ingredients, and in some cases, a synergistic effect is expected. For example, the following ingredients may be mixed with the compound (I) of the present invention.

(A) Phenoxy type herbicide

2,4-dichlorophenoxyacetic acid; 2-methyl-4-chlorophenoxy acetic acid; Butyl 2- [4- (5-trifluoromethyl-2-

pyridyloxy) phenoxy] propionate (including its esters and salts); Ethyl 2- [4- (6-chloro-2-quinoxalinyloxy) phenoxy] propionate; Etc.

(B) Diphenyl ether type herbicide

2,4,6-Trichlorphenyr4'-nitrophenyl ether; 2,4-dichlorophenyl 4'-nitro-3'-methoxyphenyl ether; 2,4-dichlorophenyl 3'-methoxycarbonyl-1'-nitrophenyl ether; 2-chloro-4-trifluoromethylphenyl 3'-ethoxy-4'-nitrophenyl ether; Sodium 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate; 5- (2-chloro-4-trifluoromethylphenoxy) -N-methylsulfonyl-2-nitro-benzamide; Ethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) benzoyloxy] propionate; 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitroacetophenone oxime-O- (acetic acid, methyl ester); Etc.

(C) Triazine type herbicide

2-chloro-4,6-bis-ethylamino-1,3,5-triazine, '2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine; 2-methylthio-4,6-bis-ethylamino-1,3,5-triazine; 4-amino-6-tert-butyl-3-rnethylthio-1,2,4-triazin-5 (4H) -one; Etc.

(D) Herbicide of the urea type

3- (3,4-dichlorophenyl) -1,1-dimethylurea; 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea; 3- (5,8, S-trifluoro-m-tolyl) -1,1-dimethylurea; 3- [4- (4-Methylphenethyloxy) phenyl] -1-methoxy-1-methylurea; 3- (5-t-butyl-3,4-thiadiazol-2-yl) - 4-hydroxy-1-methyl-2-imidazolidone; Etc.

(E) carbamate type herbicide

Isopropyl N- (3-chlorophenyl) carbamate; Methyl N- (3,4-dichlorophenyl) carbamate; 4-chloro-2-butynyl N-β-chlorophenylcarbamate; Etc.

(F) thiocarbamate type herbicide

S-ethyl Ν, Ν-hexamethylenethiolcarbamate; S- (4-chlorobenzyl) Ν, Ν-diethylthiolcarbamate; S-ethyl dipropylthiolcarbamate; Etc.

(G) anilide type herbicide

3 ', 4'-dichloropropionanilide; N-methoxymethyl ^ '^' - diethyl ^ -chloroacetanilide; 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) acetanilide;

2-chloro-2 ', 6'-diethyl-N- (propoxyethyl) acetanilide; 8- (2-naphthoxy) -propionanilide; Etc.

(H) herbicide of the uracil type ö-bromo-S-sec-butyl-e-methyluracil; S-cyclohexyl-ö ^ -trimethylenuracil; Etc.

(I) dipyridinium salt type herbicide IJ'-dimethyl ^^ '- dipyridinium dichloride; 1, V-ethylene-2,2'-dipyridiniumdibromid; Etc.

(J) Phosphorus herbicide

N- (phosphonomethyl) glycine; 0-ethyl, 0- (2-nitro-5-methylphenyl) N-sec-butylphosphoramidothioate; 0-methyl, 0- (2-nitro-4-methylphenyl) N-isopropylphosphoramidothioate; S- (2-methyl-1,1'-piperidylcarbonylmethoxy-O-di-n-propyl dithiophosphate;

(2-amino-4-methylphosphinobutyryl) alanylalaninmononatriumsalz; Etc.

(K) Toluidine-type herbicide

^, ^ "^ Trifluoro ^^ - dinitro-N, N-dipropyl-p-toluidine; N-f-cyclopropylmethyl-1-trifluoro-1-nitro-N-propyl-p-toluidine;

(L) Other herbicides

5-t-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2-one; 3-isopropyl-1H- ^ i ^ -benzothiaziadinTäfäHi-on 2,2-dioxide; 2- (a-naphthoxy) -N, N-diethylpropionamide; S-amino ^ ö-dichloro-benzoic acid; 4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazole-5-YIp-toluenesulfonate; 2-chloro-N - benzenesulfonamide [(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl]; Methyl 2 - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonylaminosulfonylmethyl benzoate; N- (1-methyl-1-phenylethyl) -2-bromo-3,3-dimethylbutanamide; 2- [1-N-Allyloxyamino) butylidene] -4-methoxycarbonyl-5,5-dimethylcyclohexane-1,3-dione sodium salt; 2- [1- (ethoxyimino) butyl] -5- (2 ^ ethylthiopropyl) -3-hydroxy-2-cyclohexen-1-one; exo-1-methyl-4- (1-methylethyl) -2 - [(2-

methylphenyl) methoxy] -7-oxabicyclo [2.2.1] heptane; Ethyl 2 - [[[[[4-chloro-6-methoxy-pyrimidine-2-

yl] amino] carbonyl] amino] sulfonyl] benzoate; 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid; Methyl 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazole] -ylJ-S-quinolinecarboxylate; 2- (2-chlorophenyl) methyl-4,4-dimethyl-3-

isoxazolidinone; Etc.

The above-mentioned herbicides have been mentioned only as examples, they do not limit the scope of the herbicides which can be used together with the compound (I) according to the invention. The herbicide according to the invention

may also be used in conjunction with insecticides, such as pyrethroid-type insecticides, fungicides,

Plant growth regulators, microbial agricultural chemicals and fertilizers.

The above-mentioned other ingredients may be combined with the compound (I) of the present invention for producing a herbicidal composition in an amount of about 5 to 95% by mass based on the total mass of the active ingredients in the

herbicidal composition, to be mixed.

According to another aspect of the invention, there is provided a method of destroying unwanted weirs,

in which a herbicidally effective amount of a compound of formula

wherein Y and R ¹ are as defined above, to which weeds are applied, said compound per se or in the form of a herbicidal composition comprising the compound (I) as an effective ingredient and an agriculturally acceptable carrier as defined above contains, is present. The term "apply to the weeds" as used herein means any method of contacting the weeds, either as a preliminary method (before the weeds emerge from the soil) and / or postemergence (after the weeds have emerged from the soil ), such as the application of granules from the compound to the soil prior to emergence or spraying of a solution of the compound or compounds of formula (I), or by any other method known to those skilled in the art, by which the weeds before or after emergence , or both before and after emergence, but preferably after emergence, come into contact with one or more of the compounds of the formula (I) of the invention described hereinbelow The dosage of the compounds (I) of the invention may range from 0.5 to 150 g / 1 Oa, preferably at 1 to 70g / 1 Oa.

The method described above is useful for the effective and selective control of undesired weeds in a lower dosage of the compounds of the invention than that of the conventional diphenyl ether type herbicides. The selective herbicidal activity is particularly high when the compounds (I) according to the invention are applied to the unwanted weeds between soybean plants. Furthermore, the method described above continues to be useful throughout the growing period of crops, including broadleaf plants such as soybean and peanut plants, as well as Gramineae family crops such as corn, wheat, barley and rice. In the application examples described later, in which the active compound is used in the form of a herbicidal composition, the dosage of the composition is determined by means of the unit "a.i. g / 10a ", which means" g / 1 Oa "with respect to the amount of the active ingredient".

embodiment

The present invention is explained in more detail below by examples of the preparation of the compounds according to the invention and by application examples for the formulations and the effectiveness of the compounds according to the invention as a herbicide. These examples in no way limit the scope of the present invention.

example 1

Preparation of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-o: methoxy-acetophenone: Compound No. 51 a) 63 g of 3-chloro-4-fluorobenzotrifluoride and 61 g of S'-hydroxy-1-methoxy Acetophenone potassium salt was added to 200 ml of dimethylsulfoxide. Subsequently, the reaction was carried out at 100 ^° C. for 3 hours. After completion of the reaction, the liquid reaction mixture was poured into ice-water, and then the reaction product was extracted with ether. The ether layer was washed with water and dried over anhydrous sodium sulfate, then the ether was removed under reduced pressure with evaporation. The obtained residue was subjected to vacuum-distraction to obtain a fraction at 16O ⁰ C to 170 ° C under 2.5 mm Hg. The thus-obtained fraction was allowed to stand to recover 85 g of a white crystalline substance of 3- (2-chloro-4-trifluoromethyl-phenoxy) -o; -methoxyacetophenone having a melting point of 104.5 ° C to 106 ° C. The following NMR spectral data of this compound were determined.

¹ H-NMR spectral data [CDCl ₃ , δ (ppm)]: 3.43 (2.3H), 4.58 (s, 2H), 6.84-7.70 (m, 7H)

b) 3.4 g of the compound 3- (2-chloro-4-trifluoromethylphenoxy) -o: -methoxyacetophenone obtained in step a) were added to a mixture of 20 ml of dichloromethane and 10 ml of concentrated sulfuric acid which had been cooled to below 5 ° C was, given. Subsequently, 1 g of potassium nitrate was added gradually within 10 minutes. After completion of the addition, the reaction was allowed to continue at below 5 ° C for 30 minutes. Then, the reaction mixture was poured into ice water, to which 50 ml of dichloromethane was added. The dichloromethane layer was separated by extraction, washed with a saturated aqueous sodium chloride solution and with water, dried over anhydrous sodium sulfate, and then the dichloromethane was removed by evaporation under reduced pressure to obtain the crude product. The crude product thus obtained was purified by silica gel column chromatography. 2.3 g of a light brown crystalline substance 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone having a melting point of 95 ⁰ C to 96 ° C were recovered.

Example 2

Preparation of syn- and anti-isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime: Compound No. 1 and Compound No. 2

3.9 g of Compound 5- (2-chloro-4-trifluoromethylphenoxy) -2-a-methoxyacetophenone (Compound No. 51) prepared in Example 1 was dissolved in a mixture of 20 ml of anhydrous ethanol and 20 ml of dry benzene. To the resulting solution were added 1.4 g of anhydrous sodium acetate and 1.2 g of hydroxylamine hydrochloride. The mixture was heated at reflux for 8 hours and then cooled, then the reaction product was extracted by adding water and ether. The organic layer was washed with water and dried over anhydrous sodium sulfate, then ether and benzene were removed by evaporation under reduced pressure to obtain syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2 -nitro-o; -methoxyacetophenone oxime existing reaction product. The product thus obtained was subjected to separation and purification by silica gel column chromatography. In this case, 1.8 g of light brown crystals of the syn-isomer of the oxime with a melting point of 123 ° C to 125 ⁰ C (Compound Nr. 1) and 1.4 g of a pale yellow viscous oily substance of the anti-isomer of the oxime with a refractive index r \ o ° of 1.5278 (compound no.2) won.

Example 3

Preparation of syn- and anti-isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime O- (acetic acid, methyl ester): Compound No.9

a) 3.4 g of the prepared in the same manner as in step a) of Example 1 3- (2-chloro-4-trifluoromethylphenpxy) -amethoxyacetophenons were dissolved in 20 ml of ethanol, then 1 g of anhydrous sodium acetate and 0.8 g Added hydroxylamine hydrochloride. Thereafter, the reaction was allowed to continue overnight at room temperature. After completion of the reaction, water and ether were added to extract the reaction product. The organic layer was washed with water and dried over anhydrous sodium sulfate, followed by removal of the ether by evaporation under reduced pressure. 3.5g of a light yellow gummy substance consisting of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -a-methoxyacetophenone oxime were recovered. The following NMR spectral data of this compound were determined.

'H NMR Spectral Data [CDCl ₃ , δ (ppm)] 3.32 (s, 3H), 4.58 (s, 2H), 6.85-7.67 (m, 7H), 8 , 58 (s, 1H)

b) 3.5 g of the syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -amethoxyacetophenone oxime obtained in step a) above were dissolved in 20 ml of dry benzene. To the resulting solution, 0.5 g of potassium hydride (in the form of an oil suspension in a concentration of about 60% by mass) was added. The resulting mixture was stirred at room temperature for about 30 minutes until no more hydrogen gas was formed. Subsequently, the mixture was cooled to 5 to 10 ⁰ C and 1.8 g of methyl bromoacetate were added. The mixture was then stirred at 5 to 10 ⁰ C for 1 hour and further at room temperature overnight. After completion of the reaction, the reaction mixture was poured into ice-water, and ether was added to extract the reaction product. The organic layer was washed with water, then ether and benzene were removed by evaporation under reduced pressure to recover a crude product. The crude product thus obtained was purified by silica gel column chromatography. There were obtained 3.2 g of a light yellow gummy substance consisting of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -a: - methoxyacetophenone oxime-O- (acetic acid, methyl ester).

c) 3.5 g of the syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -ametoxyacetophenone oxime O- (acetic acid, methyl ester) obtained in step b) above were dissolved in 30 ml of dichloromethane and the solution became cooled to about 0 ⁰ C. To the resulting solution was cooled to about 0 ⁰ C and from 8.6 g of concentrated sulfuric acid and 0.8 g of nitric acid (d: 1.42) existing acid mixture dropwise added within 15 minutes. After completion of the dropwise addition, the reaction was allowed even at 0 ⁰ C for 30 minutes to 5 ° C and further continue at room temperature for 1 hour. After completion of the reaction, the reaction mixture was poured into ice-water and then extracted with dichloromethane. The dichloromethane layer containing the reaction product was washed with water and dried over anhydrous sodium sulfate, then the dichloromethane was removed by evaporation under reduced pressure to recover a crude product. The crude product thus obtained was purified by silica gel column chromatography. There were obtained 2.6 g of a white gummy substance consisting of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, methyl ester). The substance was allowed to stand at room temperature to obtain a white solid having a melting point of 55 ° C to 57 ⁰ C.

Example 4

Preparation of syn- and anti-isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, methyl ester): Compound No.9

a) 68.9 g of the compound 3- (2-chloro-4-trifluoromethylphenoxy) -a-methoxyacetophenone prepared in the same manner as in step a) of Example 1 were dissolved in 600 ml of methanol. To the resulting solution were 16.4g

anhydrous sodium acetate and 43.7g carboxymethoxylamine hydrochloride, then refluxing

2,

heated for an hour. After completion of the reaction, the reaction mixture was cooled, the inorganic salt was filtered off, and from the filtrate, most of the methanol was removed by evaporation under reduced pressure. Subsequently, water and dichloromethane were added for extraction. The dichloromethane layer was separated, washed with water and dried over anhydrous sodium sulfate, then the dichloromethane was removed by evaporation under reduced pressure. There were obtained 79.3g light yellow crystals of 3- (2-chloro-4-trifluoromethylphenoxy) -amethoxyacetophenonoxime O- (acetic acid) having a melting point of 88 ° C to 89 ⁰ C. The following NMR spectral data of the compound were determined:

'H-NMR Spectral Data [CDCl ₃ , δ (ppm)] 3.33 (s, 3H), 4.59 (s, 2H), 4.71 (s, 2H), 6.77-7 , 64 (m, 7H), 10.88 (s, 1H)

b) 62.6 g of the compound obtained in step a) above 3- (2-chloro-4-trifluoromethylphenoxy) -a-methoxyacetophenonoxim-O- (acetic acid) were cooled to below 5 ⁰ C and from 300 ml of dichloromethane and 150 ml of concentrated sulfuric acid mixture, which was then added gradually 15.2 g of potassium nitrate. The reaction was allowed to continue for 1 hour at below 5 ° C and the liquid reaction mixture was poured into ice-water. Subsequently, 500 ml of dichloromethane were added for extraction. The dichloromethane layer was separated, washed with a saturated aqueous sodium chloride solution and with water, and dried over anhydrous sodium sulfate. Dichloromethane was then removed by evaporation under reduced pressure to yield a crude product. The crude product thus obtained was purified by silica gel column chromatography and 45 g of white crystals consisting of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid) (Compound 7) with a melting point of 100 ^c C to 102 ° C, were recovered.

The following spectral data of this compound were determined:

¹ H-NMR spectral data [CDCl ₃ , δ (ppm)] 3.18 and 3.35 (s, 3H), 4.29 and 4.70 (s, 2H), 4.55 (s, 2H), 6.91-8.18 (m, 6H), 10.15 (s, 1H)

c) 4.6 g of the syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-amethoxyacetophenone oxime O- (acetic acid) obtained in step b) above were dissolved in 100 ml of methanol and then added a catalytic amount of p-toluenesulfonic acid. The resulting solution was refluxed for 5 hours. After completion of the reaction, the methanol was distilled off under reduced pressure. The residue was dissolved in ethyl acetate, and the ethyl acetate layer was washed with water and dried over anhydrous sodium sulfate, followed by removal of the ethyl acetate by evaporation under reduced pressure. There was recovered 4.8 g of a white gummy substance consisting of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, methyl ester). The thus-obtained substance was allowed to stand at room temperature in the same manner as in Example 3 to recover white crystals having a melting point of 45 ^° C. to 56 ^° C.

Example 5

Preparation of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, phenyl ester): Compound No. 18

a) 13.9 g of the syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime obtained in substantially the same manner as in step b) of Example 4 - (acetic acid) were dissolved in 100ml benzene. Then, 7.1 g of thionyl chloride was added and the resulting reaction mixture was refluxed for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and 14.2 g of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetyl chloride) were recovered.

b) 0.9 g of phenol were dissolved in 20 ml of dry benzene. Subsequently, 0.5 g of sodium hydride (in the form of an oily suspension in a concentration of about 60% by mass) was added, and the resultant mixture was stirred at room temperature for about 30 minutes until no hydrogen gas was formed. Thereafter, the mixture was cooled to 5 ° C to 10 ° C. To the resulting solution was added 4.8 g of the syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxyl-nitro-α-methoxyacetophenone oxime-O-facetyl chloride) obtained in step a) above. The reaction was allowed to continue overnight at room temperature. After completion of the reaction, cold water and ether were added to extract a reaction product. The separated ether layer was washed with water and dried over anhydrous sodium sulfate. Then, the ether was distilled off under reduced pressure and a crude product was recovered. The crude product thus obtained was purified by silica gel column chromatography to obtain 3.5 g of a pale yellow oily substance of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-x-methoxyacetophenone oxime-O- (acetic acid). phenylester) with a refractive index Πρ ⁰ of 1.5539.

Examples,

Preparation of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy-2-nitro-a: -pethoxyacetophenone oxime-O- (acetic acid, ethyl ester): Compound No. 10

1.9 g of compound 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone (Compound No. 51) prepared in substantially the same manner as in Example 1 were dissolved in a mixture of 20 ml of anhydrous Ethanol and 20 ml of dry benzene, then 0.6 g of anhydrous sodium acetate and 1.2 g of 0-ethoxycarbonylmethylhydroxylamine hydrochloride were added. Thereafter, the mixture was refluxed for 8 hours and finally cooled. Then, water and ether were added to extract a reaction product. The organic layer was washed with water and dried over sodium sulfate anhydride. Ether and benzene were distilled off under reduced pressure and a crude product was recovered. This crude product was purified by silica gel chromatography. 2.1 g of a light orange viscous oily substance (Compound No. 10) were obtained, which consist of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-o; -methoxyacetophenone oxime. 0- (acetic acid, ethyl ester) with a refractive index no ° of 1.5276.

Example 7

Preparation of ethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate: Compound No. 57

a) 3.7 g of 2- [3- (2'-chloro-4'-trifluoromethylphenoxy) phenyl] -1,3-dioxolane-2-methanol were dissolved in 20 ml of dry N, N-dimethylacetamide and then 0.48 g of sodium hydride (in the form of an oily suspension in a concentration of about 60% by mass) at room temperature. The mixture was heated to 40 ° C to 50 ⁰ C and stirred until no more hydrogen gas was formed. Subsequently, the mixture was cooled to about 0 ⁰ C and 2.2 g of ethyl 2-bromopropionate were added dropwise to the mixture. After completion of the dropwise addition, the mixture was stirred for one hour at room temperature until the reaction was completed. Then, the reaction mixture was poured into ice water and then extracted twice with 30 ml each of ether. The organic layer was separated, washed and dried in a conventional manner.

Thereafter, the ether was distilled off under reduced pressure to obtain a crude product. The crude product thus obtained was purified by silica gel column chromatography to give 4 g of a colorless oily substance of 2- [3- (2'-chloro-4'-trifluoromethylphenoxy) phenyl] -2- (1-ethoxycarbonylethoxy) methyl-1,3-dioxolane ,

b) 4 g of the compound obtained in step a) above 2- [3- (2'-chloro-4'-trifluoromethylphenoxy) phenyl] -2- (1-ethoxycarbonylethoxy) methyl-1,3-dioxolane were dissolved in 20 ml of 1.2 dichloroethane, and the solution was then poured in 10 ml of concentrated sulfuric acid which had been cooled to 0 ⁰ C. To the solution was added dropwise a cooled mixture of 4 g of concentrated sulfuric acid and 2 g of nitric acid (specific gravity: 1.42), keeping the temperature of the solution below 5 ^° C. Subsequently, the reaction was allowed to continue for 1.5 hours while maintaining this temperature. After completion of the reaction, the reaction mixture was poured into ice water, and the reaction product was recovered by extraction with 50 ml of 1,2-dichloroethane. The organic layer was separated in a conventional manner, washed with water and then dried with aqueous sodium bicarbonate solution and further with water. Thereafter, 1,2-dichloroethane was distilled off under reduced pressure and a crude product was recovered. This crude product was purified by silica gel column chromatography to obtain 2.4 g of a yellow oily substance of ethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] -propionate having a refractive index nj) ¹ ' ⁵ from 1.5300.

Example 8

Preparation of syn- and anti-isomers 5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid, N-methyl-N-methoxyamide): Compound No.45

To 10 ml of Ν, Ν-dimethylacetamide were added 0.2 g of Ν, Ο-dimethylhydroxylamine hydrochloride and 0.21 g of triethylamine. 3 ml of a solution of Ν, Ν-dimethylacetamide, 1 g of the syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2, obtained in stage a) of example 5, were added dropwise to this solution at room temperature nitro-amethoxyacetophenone oxime-O-facetyl chloride). The reaction was allowed to continue for 3 hours. After completion of the reaction, the reaction product was extracted with water and ether in a conventional manner. The ether layer was separated, washed with water and dried over anhydrous sodium sulfate. Thereafter, the ether was distilled off under reduced pressure and a crude product was recovered. This crude product was purified by silica gel chromatography and 0.7 g of light yellow crystals were obtained, which consist of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a: -methoxyacetophenone oxime-O- (acetic acid, N-methyl-N-methoxyamide) having a melting point of 85 ° C to 88 ° C passed.

Example 9

Preparation of syn- and anti-isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime O- (acetic acid, ethyl ester): Compound No. 10 »

0.8 g of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α: -methoxyacetophenone oxime prepared in substantially the same manner as in Example 2 were dissolved in a mixture of 10 ml dry benzene and 10ml dry Ν, Ν-dimethylacetamide dissolved. To the solution was added 0.1 g of sodium hydride (in the form of an oily suspension in a concentration of about 60% by mass). The mixture was stirred therein at room temperature for 30 minutes until no more hydrogen gas was formed. Subsequently, the mixture was cooled to 5 to 10 ⁰ C and 0.4 g of ethyl bromoacetate were added. Thereafter, the mixture was stirred at 5 to 10 ⁰ C for one hour and further at room temperature overnight. After completion of the reaction, the reaction mixture was poured into ice-water, and thereafter ether was added to extract the reaction product. The organic layer was washed with water, and ether and benzene were distilled off under reduced pressure to obtain a Rob product. The crude product thus obtained was purified by silica gel column chromatography to obtain 0.68 g of a light orange viscous oily substance (Compound No. 10) consisting of syn and anti isomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2- nitro-amethoxyacetophenone oxime-O- (acetic acid, ethyl ester).

Example 10

Various compounds of the invention were prepared in substantially the same manner as in the examples discussed above. The structures, physical properties and NMR data of these compounds are listed in Tables 1 and 2 together with the data of the compounds prepared according to Examples 1 to 9. However, the scope of the present invention should not be limited to these compounds.

Table 1

N-O-R

C-CH ₂ -OR "

Connection no. R ¹ R ² Physical Properties H-NMR spectral data (<f " 5 -CDCl ₃ ) 1 2 3. 4 (DHSO), 3.12 (s, 3H 6.98 -> / 3.08 (m, 6H), 1 -CH ₃ -H (syn) Melting point ⁽⁰ G) 123-V125 2.53 2H). (UMSO), 3.31 (s, 3H 6.93 ~ 3.13 (m, 6H), ). ' 4.40 (s, 11.39 (s, IH) 2 -CH ₃ -H (anti) "30 ⁿ D 1,5273 2.53 2H), and 3.37 (s, 3H), 3,311), 4,30 and 4,43 (s • ^ 8,16 (m, 6H) ), 4.25 (s, 11.03 (s, IH) 3 -CH ₃ -CH ₃ Melting point ( ⁰ C) 31 ^ 82 3:18 (pp. 6,89 , 79 and 3, 97, 2H)

-CH

-C ₂ H ₅

1.5255

1.16 and 1.25 (t, 3H), 3.09 and 3 (s, 3H), 3.93 and 4.10 (q, 2H),

4.17 and 4.36 (s, 2H), 6.72 ^ 7.97 (m, 6H)

-CH-

-C ₃ H ₇ (n)

30 ⁿ D 1.5279

0.75 and 0.92 (t, 3H), 1.20 ^ 1.83 (m, 2H) ₁ 3.09 and 3.29 (s, 3H), '3.87 and 4.03 (t, 2H), 4.21 and 4.36 (s, 2H), 6.74~8.03 (in, 6H)

N) UI O)

-CH

1.5279

1.07 and 1.26 (d, 6H), 3.09 and 3.32 (s, 3H), 4.20 and 4.34 (s _t 2H), 3.88 ~ 4.52 (m, IH ), 6.68 ^ 7.99 (m, 6H)

CH ₃ -CH ₂ COOH

melting point

( ⁰ C) 100 ^ 102

3.18 and 3.35 (s, 3H), 4.29 and 4.70 (s, 2H), 4.55 (s, 2H), 6.91~8.18 (m, 6H), 10, 15 (s, IH)

CH ₃ -CH ₂ COONa

Melting point O

95 ^ 105 (decomposes)

3.12 and 3.29 (s, 3H), 4.13 and 4.46 (s, 2H), 4.26 (s, 2H), 7.03 x 8.29 (m, 6H)

-CH ₃ -CH ₂ COUCH ₃ melting point ( ⁰ C)

55 ^ 57

3.17 and 3.32 (s, 3H), 3.67 and 3.72 (s, 3H), 4.26 and 4.67 (s, 2H), 4.52 (s, 2H), 6, 82 / ^ 8.23 (m, 6H)

-CH ₃ -CH ₂ COOC ₂ H ₅

1.5276

1.23 and 1.26 (t, 3H), 3.15 and

3.32

3H), 4,11 and 4,14 (q, 2ΗΓ

4.23 and 4.62 (s, 2H 6.77 ~ 8.20 (m, 6H)

4.49 (s, 2H;

-CH ~ ³⁰ 1.5219

0.87 and (m, 2H), 3.99 and 4.61 (s, 8.11 (in.

0.90 3.13 4.03 2H), 6H)

and

3H), 3.30 (t 2H), 4.48 (s,

1.22 ^ 1.93 (s, 3H), 4.23 and 2H), 6.78 ^

-GH.

₀ 2

brown gums 2,39 (s, 3H), 3,08 and 3,30 (s, 3H), like substance 4,22 and 4,53 (s, 2H), 4,33 (s, 2H),

6.78-7.06 (m, 6H), 9.00 (bs, 3H)

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"30 1,5106

5

1.24 (t, 3H), 1.38 and 1.48 and 1.58 (d, 6H), 3.15 and 3.29 (s, 3H), 4.18 (q, 2H), 4, 23 and 4.66 (s, 2H), 4.60 ^ 5.27 (m, 2H), 6.83 * ~8.22 (m, 6H)

35 -CH 3 -CH ₂ COSCH ₃ Melting point ( ⁰ C) 70 λ, / 72 2.20 (s, 4.25 and 6.80 ~ 8, (t 3H), 2H), and and -'S, 3H), 4.69 17 (m, 3.15 and (s, 2H), 6H) 3.31 4.47 (s, and 3H), 4,55 3.67 4.62 ( s, 2H), , 26 and (m, 3H), 36 -CH 3 -CH ₀ COSC ₀ H ₁ - (L ί D Melting point 61.5 ^ 62.5 1.18 (see (s) (s, 3.15 and 4.51 (s, 6.90 ^ 8, and (see IH), 3H), 4.23 6.86 ' 2.73 (q, and 4.59 "8.13 (m, 2H), (see 6H) 3,14 and 2H), 4,45 3H), 2H), 3.29 and 4.52 s, 5H), s, 2H), 37 -CH 3 -CH ₂ COSCH ₂ CH = CH ₂ Melting point 52 ^ 55 3.17 4.26 6.85 3.31 2H). 19 (m, (s, 3H), 4.57 (s, 6H) 3.44 2H), (i.e., 2H), 4.91 ^ 6, 4 04 , 13 and 49 ^ 4,84 38 -CH 3 -CH ₂ COSCH ₂ COuCH ₃ 30 1.5478 1.28 3.29 (m, 3j32 4.54 20 (m, (s, 3H), (s, 2H), 6H) 3,60 4,49 and and ( 39 -CH 3 -CHCOSCH ₃ 30 1.5395 1.50 (d, 3H), 3H), 4.23 and 6.82 ^ 8.16 (m. 2.15 4.57 6H) (see (s. 3 4

-CH-

30

"D

CHCOSCH ₂ COOCh ₃ 1.5367

1.31 and 1.52 (d, 3H), 3.17 and 3.31 (s, 3H), 3.55 and 3.62 (s, 2H), 3.67 (s, 3H), 4, 25 and 4.53 (s, 2H), 6.82- * 8.17 (m, 6H)

CH.

0 H

-CH ₂ CNH ₂

Gummy substance

3.14 and 3.29 (s, 3H), 4.20 and 4.52 (s, 2H), 4.33 (s, 2H), 5.97 (b, 2H), 6, 70-8, 05 (m, 6H)

N) Ul O)

-CH-

-CH ₂ GNHCH ₃

Gum 2,82 (d, 3H), 3,20 and 3,31 (s, 3H), 4,23 and 4,58 (s, 2H), 4,43 and 4,48 (s, 2H), 6.27 (m, IH), 6.80 ^ 8.14 (m, 6H)

CH.

0 Il

CH,

-CH ₉ CNHC-CC = CH

ax

Rubbery substance 1.63 (s, 6H), 3.19 and 3.32 (s, 3H), 4.22 and 4.50 (s, 2H), 4.35 and 4.42 (s, 2H), 6.22 (b, IH), 6.30-8.15 (m, 6H)

CH.

0 U

-CH ₂ CN

CH, gum type substance 2.83 and 2.90 and 2.97 (s, 6H), 3.16 and 3.23 (s, 3H), 4.22 and 4.75 (s, 2H), 4.48 and 4.58 (s, 2H), 6.76 ^ 3.09 (ffl, 6H)

CH.

CH,

CH ₃ OCH.

melting point

(OC)

85 ^ 83 3.17 and 3.23 (s, 6H), 3.67 (s, 3Ii), 4.86 (s, 2H), 4.53 and 4.70 (s, 2H), 6.77Λ > 8,13 (m, 6H)

4.23 and

CH.

CH,

-CHCONH,

Gum-like substance 1,32 and 1,52 (d, 3H), 3,17 and 3,30 (s, 3H), 4,23 and 4,44 (s, 2H), 3,30 ^ 3,72 (m , IH), 5.88 (b, 2H), 6.78 ^ 8.13 (m, 6H)

CH.

CH_

-CHCONHCH.

Gum type substance 1.32 and 1.51 (d, 3H), 2.78 and 2.82 (d, 3H), 3.22 and 3.33 (s, 3H), 4.23 and 4.43 (s , 2H), 4,42 / ^ 4,85 (m, IH), 5,97 (b, 1H), 6,83 ^ 8,2O (m, 6H)

CH.

CH,

-CHCON

CH ₃ OCH.

Gummy substance 1,23 and 1,44 (d, 3H), 3,08 and 3,13 (s, 3H), 3,13 and 3,25 (s, 2H), 3,63 (s, 3H), 4.20 and 4.48 (s, 2H), 4.83 ^ 5.27 (m, IH), 6.78 ^ 8.08 (m, 6H)

49 CH ₃

-CHCOOCH.

25 ⁿ D 1.5378

1.17 and 1.27 (d, 3H), 3.63 (s, 3H), 3.80 and

3.91 (q, IH), 4.31 and 4.37 and 4.50 and 4.59

(s, 2H), 6, SO-'a, 09 (m, 6H), 8.58 and 8.82 (bs.lH)

-CHCQOC ₀ H ₁

25

ⁿ o

1.5383

1.18 and 1.29 (d, 3H), 1.24 (t, 3H), 3.82 and 4.11 (q, 3H), 4.36 and 4.42 and 4.55 and 4.65 (s, 2H), 6.85 ^ 8.17 (m, 6H), 8.50 (b, IH)

s: singlet, d: doublet, t; Triplet, m: multiplet, b: broad, q: quartet

Table 2

C-CH ₂ -O-R '

Com.

Physical properties ¹ H-NMR spectral data (cT: COCl,)

51 -CH, mp 3.39 (s, 3H), 4.28 (s, 2H), 6.85 ^ 8.20 (m, 6H)

95 ^ 96

-CH ₂ COOH

Melting point °

4.16 (s, 2H), 4, 48 (s, 2H) ₁ 6.84 ^ 8.13 (in, 6H), 10.33 (bs, IH)

CH ₂ COOCH ₃

21.5D 1.5465 3.67 (s, 3H), 4.08 (s, 2H), 4.44 (s, 2H), 6.83 ~ 8.13 (m, 6H)

CH ₂ COOC ₂ H ₅

30 1.5105 1.25 (t, 3H), 4.10 (s, 2H), 4.17 (q, 2H), 4.48 (s, 2H), 6.87-8.20 (m , 6H)

-CH ₂ C 00 C ₃ H ₇ (n)

D 1.5300 0.91 (t, 3H), 1.56 (q, 2H), 4.03 (t, 2H), 4 ', 06 (S ₁ 2H), 4.46 (s, 2H), 6.86 ^ 8.14 (m, 6H)

CH ₃ -CHCOOCH-

30 ⁿ D 1.5190 1.31 (d, 3H), 3.67 (s, 3H), 4.02 (q, lH), 4.42 (d, 2H), 6.85 ^ 3.14 ( m, 6H)

-GHCOOC ₂ H ₅

21.5 D 1.5300 1.20 (t, 3H), 1.26 (d, 3H), 3.90 (q, IH), 4.07 (q, 2H), 4.33 (d, 2H ), 6.78 ^ 8.09 (ro, 6H)

58 CH ₃ -CHC00C ₃ H ₇ (n)

30 1.92 (t, 3H), 1.28 (d, 3H), 1.64 (m, 2H), 3.98 (q, IH), 4.03 (t, 2H), 4.37 and 4,42 (s, 2H), 6,86 ^ 8,13 (rn, 6H)

CH ₃ -CHCOOC

30

D 1.5221 0.80- ^ 1.08 (m, 3H), 1.29 (d, 3H), 1.30 ^ 1.74 (m, 4H), 3.98 (q, IH), 4 , 08 (t, 2H), 4,38 and 4,42 (s, 2H), 6,87 ^ 8,16 (in, 6H)

-Ch ₂ COOCH ₂ CH ₂ OCH ₃

.30 ¹ O 1.5230 3.29 (s, 3H), 3.45 ^ 3.61 (in, 2H), 4.11 (s, 2H), 4.11 ^ 4.29 (m, 2H) , 4.45 (s, 2H), 6.89 ^ 8.15 (in, 6H)

Gum-like 4,13 (s, 2H), 4,44 (s, 2H), 4,53- ^ 6,21 (m, 5H), Substance 6,87 <v8,18 (m, 6H)

-CH ₂ COOCH ₂ C = GH

30

D 1.5410 2.46 ~ 2.53 (m, IH), 4.17 (s, 2H), 4.50 (s, 2H), 4.69 (d, 2H) ₁ 6.90 x 8 _f 19 (ro, 6H)

Gummy 1.25 (t, 3H), 4.17 (q, 2H), 4.22 (s, 2H), substance 4.50 (s, 2H), 4.60 (s, 2H), 6.90 ^ 8,17 (m, 6H)

1 2 3 1.42 4.43 (d, (s. 3H), 2H), 4th 3.63 5.05 % (S ₁ (q. (dl 3H), IH), 4,11 6,81 -el Jq. 2H), 11 (m, 6H) 64 CH, I 3 -CH ₂ COOCHCOOCh ₃ Gum-like substance 1.33 4.23 6H) (D, 3H), 43 (m 3.57 / V3, »2H), 4, (s, (s, 75 (rn 42 (d 2H), 2H) , 4,, 6, (s, IH), 05 (q, 35 ^ 8, IH), 15 (m, 65 CH, \ 3 -CHCOOCH ₂ Ch ₂ Cl 1.5266 1.31 4.01 4.36 (d. (q. ^ 8) 3H), IH), 14 (m 3.31 (s, 4.13 ** 4,, 6H) 1.43 (d, (d, 2H)) 3H), 32 (m 3,46, 2H) , 4, ' 61 (m, 39 (d, 2H), 2H), 66 CH, -CHCOuCH ₂ CH ₂ OCH ₃ 1.5231 1.22 (q. (Rn, IH), '6H) 3H), 4,40 1.30 (i.e., (d, 2H), 3H). 5.08 3.30 (q. (see IH), 3H), 6.89 ' 3.98 67 ^CH 3 ^CH 3 -CHCOOCHCh ₂ OCH ₃ " 30 1.5165 1.32 (d, (2H), 3H), 5,08 4.03 (q, »v6.22 (m IH),, 3H) 4,41 (d,, 6,37 ^ 8 2H),, 19 (m 4,58,6H) 63 CH, I 3 -CHCOOCH ₂ Ch = CH ₂ Gummy substance 1.33 4.40 (d, (s, 3H), 2H), 2.40 '4.62 48 (m 2H), , IH), 4, 6,83 ~ 8, 03 (q, 17 (B ₁ IH) 6H) 69 CH, »3 -CHCOOCH ₂ CScH "ο ³⁰ 1,5337 1.34 4.42 (d, (d, 3H), 2H), 3,70 4,59 3H), 2H), 4.08 6.87 IH), 12 (rn, 6H) 70 CH, I ³ -CHCOOCh ₂ COOCH ₃ η ³⁰ 1.5220 1.33 (q. (M. (d, IH), 6H) 3H), 4,43 3H), 5.07 3.70 (q. 3H), 4.08 6.87 ^ 8.18 71 CH ₃ CH ₃ -CHCuOCHCOOCH ₃ "ο" 1.5185

(JI O)

1 2 3 1.27 4.43 (m, (β! 6H) 3H) ₁ 2H) ₁ 4 jd. 2H), 09 (m, 3 3H), (q. 6, IH), 85 / ^ 8 , 22 72 CH, I 3 -CHCOSCH ₂ CH = Ch ₂ n ³⁰ 1.5520 1.30 4.04 (Q! 3H) ₁ IH) ₁ , 3.42, 4.95 ' (S! 3H), 2H), 3 6 , 73, 84 « 2H), 20 (m , 6H) 73 CH, I ³ -CHCOSCH ₂ COOCh ₃ Gumiiiiartige substance , 3.68, 4.46

s: singlet, d: doublet, t: triplet, m; Multiplet, b: wide, q: quartet

IS) Ul O)

applications

In the following, some production examples of the herbicidal compositions according to the invention are listed. Production Example 1 Spray Powder)

25 parts by weight of the compound of the present invention, 5 parts by weight of Sorpol 5039 (trade name of a product of Toho Chemical Industry Company, Japan) and 70 parts by weight of talc are thoroughly pulverized and mixed to give a wettable powder. Production Example 2 (emulsifiable concentrate)

5 parts by mass of the compound of the invention, 10 parts by mass of Sorpol 3005® (a product of the Toho Chemical Industry Company, Japan), 45 parts by weight of n-butanol and 4 parts of xylene are mixed thoroughly to give an emulsifiable concentrate.

Production Example 3 (Granules)

1 part by weight of the compound of the invention, 45 parts by weight of bentonite, 44 parts by weight of clay, 5 parts by mass of sodium lignosulfonate and 15 parts by mass of sodium dodecylbenzenesulfonate are thoroughly pulverized and mixed. Water is added to the mixture and the mass is thoroughly kneaded. The kneaded mixture is then granulated, then dried and the granules are obtained

Production Example 4 (Dusts)

1 part by weight of the compound of the invention and 99 parts by weight of clay are carefully pulverized and mixed to give a dust

Application example 1

In the greenhouse, pots each having a surface area of 1/2500 a were filled with soil from the upper soil layer. Seeds of soybeans, horse corn, black rot, woolly honeygrass, common goosefoot, and peppercupyte were placed in each pot.

As a pre-emergence application, a composition was dosed at 25 a. i. g / 10a applied 24 hours after laying out the seed. On the other hand, as a post-emergence application, a composition in a dosage of 10 a. i. g / 10 a when the soybeans and equine maize and the weeds had grown to the two- to three-leaf stage, three- to four-leaf stage or two to two-and-half leaf stage. The herbicidal composition of the present invention was applied as follows. From the compounds listed in Table 3 emulsifiable concentrates were prepared according to the method described in Preparation Example 2. Each of the concentrates so prepared was diluted with 10 liters of water per type of soil from the upper soil layer and then spread using a glass atomizer. 14 days after the application, the degree of herbicidal activity on weeds was observed. Thirty days after the application, the degree of phytotoxicity to crops was observed. The results are shown in Table 3. The values listed in Table 3 are based on the following criteria. 5: perfect inhibition 4: 80% inhibition 3: 60% inhibition "2: 40% inhibition 1: 20% inhibition 0: no effect

Table 3

encryption Millet Herbicidal activity and phytotoxicity Common goose foot Pepper kisses rich Soybean Horse de maize Millet Wolli ges honey gras postemergence Pepper kisses Rich, Soybean Horses corn bin 2 preemergence 4 5 6 7 8th 9 Geese goose foot 11 12 13 no. Wolli ges honey gras 10 1 3

1 2 4 4 4 0 0 1 4 4 4 0 0 2 1 4 4 4 0 0 1 . 4 3 3 0 0 3 3 CJL 5 4 0 0 2 5 4 4 1 0 4 2 4 4 4 0 0 1 5 3 4 0 0 5 1 4 3 - 4 0 0 1 4 3 4 0 0 6 1 4 3 3 0 0 1 4 3 3 0 0 7 2 4 4 4 0 0 1 4 4 3 0 0 8th 2 4 3 4 0 0 ί 4 4 3 0 0 9 4 5 5 5 0 0 4 5 5 5 1 0 10 4 5 5 5 0 0 4 5 5 5 1 0 11 4 5 4 5 0 0 2 5 5 5 0 0 12 2 4 3 4 0 0 1 4 4 3 0 0 13 3 5 4 5 0 0 3 5 5 5 1 0 14 3 5 4 4 0 0 2 5 4 5 0 0 15 3 5 5 5 0 0 4 5 5 5 0 0 16 2 4 5 5 0 0 1 5 3 4 0 0 17 3 5 5  5 0 0 3 CJL 5 5 0 0 18 3 4 4 5 0 0 ν 2 5 4 4 0 0 19 2 4 4 4 0 0 2 5 4 3 0 0 20 2 5 5 4 0 0 1 5 5 4 0 0

encryption blood Herbicidal activity and phytotoxicity WoIIh Gemei- pepper So- Horse blood postemergence Wolli Gemei ffeffer- Yes- horses bin millet preemergence ges ner- knöte Yes- de millet ges ner knöte- borings Corn Droppings honey goose rich borings Corn honey geese rich ne No. grass foot ne grass foot 12 2 3 4 5 6 7 8th 9 10 11 0 13 3 5 5 5 0 0 2 5 5 5 0 0 1 2 5 4 4 0 0 1 5 5 4 0 0 21 2 5 5 5 0 0 1 5 5 5 0 0 22 2 5 5 5 0 0 1 5 4 5 0 0 23 2 5 4 5 0 0 1 5 4 5 0 0 24 1 5 4 5 0 0 1 5 4 5 0 0 25 3 5 5 5 0 0 4 5 5 5 0 0 26 2 5 5 4 0 0 1 5 4 5 0 0 27 2 4 5 4 0 0 1 5 5 4 0 0 28 2 5 4 4 0 0 1 5 4 5 0 0 29 2 5 5 5 0 0 0 5 5 5 0 0 30 2 4 4 4 0 0 0 5 4 4 0 0 31 2 4 4 5 0 0 1 5 4 5 0 0 32 1 4 3 3 0 0 0 5 3 4 0 0 33 2 4 4 3 0 0 3 • 5 4 5 0 0 34 2 4 4 3 0 0 1 5 4 4 0 0 35 2 5 4 5 0 0 2 5 4 5 0 0 36 1 4 4 4 0 0 1 5 4 5 0 0 37 1 4 3 4 0 0 2 5 4 4 0 0 38 1 4 3 4 0 0 1 5 4 4 0 0 39 2 5 4 3 0 0 1 5 4 4 0 0 40 2 5 4 4 0 0 1 5 4 4 0 0 41 3 5 4 4 0 0 2 5 5 4 0 0 42 1 5 4 3 0 0 1 5 4 3 0 0 43 2 5 5 4 0 0 1 5 5 4 0 0 44 1 4 3 3 0 0 1 4 3 3 0 0 45 1 4 3 3 0 0 1 4 3 3 0 0 46 1 4 4 3 0 0 1 5 4 4 0 0 47 2 5 4 5 0 0 4 5 5 5 1 0 48 2 5 4 5 0 0 4 5 5 5 0 0 49 2 4 4 3 0 0 1 4 4 3 1 0 50 3 5 5 4 0 0 2 5 5 5 2 0 51 4 5 5 5 0 0 4 5 5 5 2 ' 1 52 4 5 5 5 0 0 4 5 5 5 0 0 53 3 5 5 5 0 0 2 5 5 5 2 0 54 4 5 5 5 0 0 5 5 5 5 2 1 55 3 5 5 5 0 0 5 5 5 5 2 1 56 3 5 5 4 0 0 4 5 5 5 1 0 57 2 5 5 4 0 0 3 5 5 4 0 0 58 2 4 5 4 0 '0 2 5 5 5 0 0 59 2 5 5 4 0 0 3 4 5 4 0 0 60 2 5 5 4 0 0 3 5 5 4 0 0 61 2 4 4 3 0 0 2 4 4 4 0 0 62 2 4 4 3 0 0 2 4 3 4 0 0 63 4 5 4 5 0 0 3 5 5 5 1 0 64 3 5 5 4 0 0 3 5 5 5 0 0 65 3 5 4 5 0 0 3 4 5 5 1 0 66 4 5 5 5 - 0 0 4 - 5 5 5 1 0 67 4 5 5 5 0 0 4 5 5 5 2 0 68 4 5 5 5 0 0 4 5 5 5 1 0 69 3 4 5 5 0 0 3 5 5 5 0 0 70 2 4 4 5 0 0 2 4 5 4 0 0 71 3 4 5 5 0 0 2 4 5 5 0 72 73 5 Bezugsver 5 5 5 5 4 2 5 5 5 5 3 binding number 1 (See Notes kung 1)

Reference compound No. 2 2

(Anmer-

Note 1. Reference No 1:

C = NOCH ₂ COOCH ₃

(PPG 1013)

Note 2. Reference No.2:

COONa

(Acifluorfennatrium)

Application Example 2

A plowed field was divided into plots with an area of 1 per m ^2. Seeds of soybean and horse corn were sown in the soil of each plot as weeds of blackcurrant, common goosefoot, chickweed, woolly honeysuckle, hemp sesbania, morning glory, common datura, teaweed, and spurglass as weeds which were allowed to grow. The postemergence treatment was on stems and leaves when soybeans, horse corn and weeds had reached the two- to three-leaf stage, three- to four-leaf stage, and the three- to five-leaf stage, respectively. The herbicidal composition of the present invention was applied as follows. From the compounds listed in Table 4 emulsifiable concentrates were prepared according to the method described in Preparation Example 2. Each of the concentrates thus prepared was diluted with 10 liters of water per pound of soil from the upper soil layer and then spread by means of a nebulizer. Fourteen days after the application, the degree of herbicidal activity on the weeds was determined. Thirty days after the application, the degree of phytotoxicity on the crops was observed. The results in Table 4 are the same as those in Application Example 1.

Table 4

Do-

bin-

tion

No. (g / 10a)

Herbicidal activity and phytotoxicity

Blood brain of my datura

Gemei ner

goosefoot

Pfef-

FER

knö-

te-

rich

Woolly honey grass

Hemp Trich- Spitz- Tea- Soya- Horseback- burdock weed bean corn

nia winds

1 9 • 2 3 4 CJI 6 7 8th 9 10 11 12 13 20 2 5 5 5 5 5 5 5 5 0 0 10 10 2 5 5 5 5 5 4 5 5 0 0 5 1 5 4 5 5 5 3 5 5 0 0 2.5 0 5 4 4 5 5 2 3 4 0 0 20 2 5 5 5 CJL "5 5 5 5 1 1 18 10 1 5 5 5 5 5 4 5 5 0 0 5 1 5 3 5 5 5 3 5 4 0 0 2.5 0 5 3 4 5 5 2 4 4 0 0 20 2 5 5 5 5 5 3 5 5 0 0 20 10 1 5 5 5 5 5 3 3 5 0 0 5 0 5 4 4 5 5 2 3 4 0 0 2.5 0 5 4 4 5 5 2 2 4 0 0 20 3 5 5 5 5 5 3 5 5 1 0 36 10 2 5 4 5 CJL 5 2 3 5 0 0 5 1 5 3 4 5 5 2 3 4 0 0 2.5 1 5 3 3 5 5 1 2 4 0 0 20 2 5 5 5 5 5 3 4 5 0 0 55 10 1 5 4 5 CJL 5 2 3 5 0 0 5 0 5 3 4 5 5 2 3 4 0 0 2.5 0 4 2 3 , 5 5 1 ' 2 4 0 0 20 1 5 4 5 5 5 4 4 5 0 0 56 10 1 5 3 5 CJL 5 3 4 4 0 0 5 0 4 2 3 4 5 2 3 3 0 0 2.5 0 3 1 2 4 4 0 3 3 0 0 20 1 5 4 5 5 5 4 5 5 1 0 10 1 5 4 5 5 5 4 4 5. 1 0 5 0 5 3 5 5 5 3 4 4 0 0 2.5 0 5 3 5 5 5 3 4 4 0 0

1 2 3 4 5 6 7 δ 9 10 11 12 13 57 20 2 CJL 5 5 Oil Oil Oil 4 Oil 1 0 ΊΟ 2 Oil 4 Oil 5 5 4 4 5 0 0 5 1 5 4 Oil 5 Oil 3 4 4 0 0 2.5 1 αϊ 3 4 4 Oil 3 3 3 0 0

Reference 20 3 4 Oil / - - "C 5 3 5 5 2 4 O 1 connected 10 3 3 4 -cc Oil 2 Oil 5 1 3 O O 5 2 3 3 , Cl 4 1 5 4 1 2 O O No. 1 2.5 2 2 2 - 0 - ( 4 1 Oil 4 1 2 O O (See Notes kung 1) Reference 20 2 Oil 4 5 4 5 5 4 4 O O connected 10 2 5 4 Oil 2 Oil 4 4 3 O O 5 1 4 3 4 1 Oil 4 3 3 O O No. 2 2.5 1 3 3 4 1 Oil 3 3 2 O O (See Notes kung 2) Reference 10 3 5 5 Oil 5 OI 5 Oil 5 3 2 connect 5 2 Oil 5 Oil 5 5 4 Oil Oil 3 1 2.5 1 Oil , 4 5 4 5 3 4 5 2 O No. 3 1.25 1 4 2 4 4 Oil 2 3 4 1 O (See Notes 3 Note 1. Reference No 1: _ COONa (Acifluorfennatrium) ^F 3 ^G - > -N0 ₂

Note 2. Reference No 2:

Note 3. Reference No 3:

egg

ONHSO ₂ CH ₃

(Fotnesafen)

NOCH ₂ COOCH ₃

(PPG-1O13)

Application example 3

In the greenhouse pots, each with a surface of 1 / 500Oa, were filled with soil from a paddy field. Seeds of millet and monochoria. Seeds of broadleaf annual weeds, toothcup (rotala ramosior?) And false pimpernelle, as well as seeds of perennial weeds, "Hotarui" (Scirpus juncoides) were mixed with dry paddy fields and placed on surface soil, and the bulbs of arrowhead and sedge were planted by perennial weeds ,

Reedlings in the trefoil stage were inserted 2 to 3cm deep into the ground. From the compounds listed in Table 5 emulsifiable concentrates were prepared according to the method described in Preparation Example 2. Each of the concentrates thus prepared was diluted with water and applied dropwise with the aid of a pipette when the millet had reached the one-half to one-leaf stage. 21 days after the application, the phytotoxicity to rice plants and the herbicidal activity on the weeds was determined. The results are listed in table. The criteria for the values shown in Table 5 are the same as those in Application Example 1.

Table 5

Connection no.

Dosage (g / 10a)

Herbicidal action

Chicken millet

--v. ^A ,

Mono Choria

Broadleaf

weeds

hotarui

(scir-

pus

juncoi-

of)

arrowhead

sedge

Phytotoxicity

Rice peas

1 2 3 4 ul 6 7. 8th 9 1 30 CJL αϊ ul 4 2 0 15 4 4 5 5 3 1 0 3 30 ul ul 5 ul 4 5 2 15 ul ul ul ul .3 4 1 6 30 5 ul 5 5 4 4 1 15 4 ul ul ul 3 2 0 9 30 Oil Oil 5 5 4 5 2 15 CJL 5 ul 5 3 4 1 10 30 ul Oil ul ul 4 5 2 15 5 Oil ul ul 3 4 1 14 30 5 5 ul 5 4 4 1 15 4 αϊ ul 5 3 3 0 15 60 οι αϊ ul ul 3 2 2 30 5 5 ul 4 3 2 1 17 60 αϊ 5 ul ul 4 4 2 30 αϊ 5 ul Oil 3 3 1 19 60 5 ul ul 4 2 1 0 30 4 4 ul 3 1 1 0 20 60 Oil αϊ 5 4 3 1 0 30 4 4 5 3 2 1 0 21 60 ul ul ul ul 3 2 1 30 CJL ul 5 4 2 1 0 23 60 ul ul 5 ul 3 4 1 30 ul ul ul 4 2 3 0 24 60 ul ul ul ul 4 4 2 30 5 ul ul 4 3 4 1 27 60 ul ul ul Oil 4 3 1 30 ul 5 ul 4 3 2 1 29 60 Oil ul ul αϊ 4 4 1 30 UI ul ul 4 3 2 0 30 60 Oil Oil ul 4 3 3 1 30 4 Oil ul 3 2 2 0 31 60 CJL 5 5 ul 4 3 1 40 ul 5 ul 4 3 2 1 34 60 ul ul ul 4 3 2 1 40 ul ul CJL 3 2 1 0 35 60 ul ul Oil 4 3 2 0 40 4th 4 ul 3 2 1 0 37 60 ul ul ul 4 2 2 0 40 4 5 ul 3 1 1 0 38 60 ul ul ul 4 3 4 ί 40 4 4, 5 3 1 3 0 40 60 ul ul 5 4 3 3 0 40 4 ul ul 3 2 1 0 41 60 5 5 5 4 3 4 1 40 4 5 ul 3 2 3 0 43 60 ul αϊ ul 4 3 3 0 40 4 4 5 3 2 1 0

encryption do Hiih- mono- Herbicidal action hotarui arrow sedge phyto- bin you ner- Choria Wide- (scir- herb toxic Droppings tion hir- PAGING pus on , zitit No. (G / 1Oaj se engined juncoi- Unkräu of) rice ter pflan Zen

1 2 3 4 cn 6 7 8th 9 44 60 cn CJL cn 4 3 3 1 30 5 5 cn 3 2 1 0 45 60 5 5 5 cn 3 4 2 30 5 cn cn 4 2 3 1 47 60 cn 5 cn 4 3 2 1 30 4 4 B 3 2 1 0 49 60 B 5 5 CJL 4 3 2 30 cn 5 cn 5 3 2 1 50 60 5 cn cn cn 4 3 2 30 5 cn CJL 4 3 2 1 51 30 4 5 5 cn 2 1 0 15 4 4 cn CJL 2 1 0 53 60 cn cn CJL 5 4 3 1 30 4 cn cn 4 3 3 0 54 60 5 cn 5 , 5 4 3 0 30 4 cn 5 3 3 2 0 56 60 cn 5 5 5 2 2 0 30 4 cn cn 4 1 0 0 61 60   5 cn cn B 3 3 1 30 cn 5 5 4 1 2 1 63 60 5 cn B 5 2 3 1 30 4 cn 5 4 2 2 0 65 60 5 CJL CJL 5 3 2 1 30 5 cn cn OI 2 1 1 72 60 5 5 5 5 3 2 1 30 4 5 cn 4 2 1 0

subscription 150 2 3 5 4 2 2 0 verbin 75 1 2 cn 3 1 1 0 dung number 1 (See Notes kung 1) subscription 150 2 CJL 5 4 3 2 0 verbin 75 1 2 5 3 1 1 0 dung No. 2 (See Notes kung 2) subscription 30 5 CJL B B B cn 5 verbin 15 5 5 cn B 4 4 4 dung No. 3 (See Notes kung 3)

Note 1. Reference No. 1 Eq

OGH.

 NO,

(Ghlormethoxynil)

Note 2. Reference No.2 Cl

Cl

Note 3. Reference No.3

Cl

OOCH.

(Bifenox)

NO,

YET ₀ COOCH ^ -

^F 3 ^C

(PPG-1013)

NO,

Claims (28)

1. A herbicidal composition characterized in that it contains as active ingredient a herbicidally effective amount of a compound of formula
Cl (D contains, in the T ti λ R ^{1 represents} a methyl group or -OH-CAR, wherein A represents an oxygen atom or a sulfur atom, R ^{3 represents} a hydrogen atom or a methyl group, and R ^{4 is} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted by a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a Carboalkoxy group having 2 to 4 carbon atoms; and Y represents an oxygen atom or = NOR ² , in which R ^{2 is} a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or R ⁵ 0 ing is -CH-C-R wherein R ^{5 represents} a hydrogen atom or a methyl group R ⁸ and R ^{6 represents} -BR ⁷ or _jj ^ ⁹ wherein B represents an oxygen atom or a sulfur atom, R ^{7 is} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, a substituted or unsubstituted phenyl group, an alkyl group substituted by a halogen atom or an alkoxy group having 1 to 3 carbon atoms with 1 to 4 carbon atoms, an alkali metal, an alkaline earth metal in a proportion corresponding to the monovalent of the alkaline earth metal, an ammonium group, an ammonium group substituted by an alkyl group having 1 to 4 carbon atoms, or R ¹⁰ O -CH-COR ¹¹ j wherein R ^{10 represents} a hydrogen atom or a methyl group and R ^{11 represents} an alkyl group having 1 to 3 carbon atoms, and R ⁸ and R ^{9 are the} same or different and each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkynyl group having 3 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, besides conventional auxiliary and / or Contain carriers. 2. A herbicidal composition according to item 1, characterized in that R ^{1 is} a methyl group, R ^{5 is} a hydrogen atom, B is an oxygen atom, and R ^{7 is} an alkyl group having 1 to 3 carbon atoms. 3. A herbicidal composition according to item 1, characterized in that R ^{1 is} a methyl group, R ^{5 is} a hydrogen atom, B is an oxygen atom and R ^{7 is} a member which has been selected from the group consisting of a hydrogen atom, an unsubstituted phenyl group, and a chlorine atom substituted alkyl group having 1 to 4 carbon atoms, and an alkali metal group. A herbicidal composition according to item 1, characterized in that R ^{1 is} a methyl group, B is a sulfur atom and R ^{7 is} a member selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a carboalkoxy group having 2 to 3 carbon atoms substituted alkyl group having 1 to 4 carbon atoms comprising group. A herbicidal composition according to item 1, characterized in that R ^{1 represents} a methyl group and R ⁸ and R ^{9 are the} same or different and each independently is a member selected from the group consisting of a hydrogen atom, a methyl group and a methoxy group , 6. A herbicidal composition according to item 1, characterized in that Y and A represent an oxygen atom and R ^{4 represents} an alkyl group having 1 to 3 carbon atoms. 7. A herbicidal composition according to item 1, characterized in that Y is an oxygen atom, R ^{3 is} a methyl group, A is an oxygen atom and R ^{4 is} a member selected from the group consisting of a propargyl group and a chlorine atom or a carboalkoxy group having 2 to 3 Carbon atoms-substituted alkyl group having 2 to 3 carbon atoms. 8. A herbicidal composition according to item 1, characterized in that 5- (2-chloro-4-trifluoromethylphenoxy ^ -nitro-a-methoxyacetophenonoxim-O-iessigsäure, methyl ester) is the active ingredient. A herbicidal composition according to item 1, characterized in that 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, ethyl ester) is the active ingredient. 10. A herbicidal composition according to item 1, characterized in that 5- (2-chloro-4-trifluoromethylphenoxy ^ -nitro-a-methoxyacetophenonoxim-CMessigsäure, 2-chloroethyl ester) is the active ingredient. 11. The herbicidal composition according to item 1, characterized in that 5- (2-chloro-4-trifluoromethylphenoxy ^ nitro-a-methoxyacetophenonoxime O-iacetic acid, phenyl ester) is the active ingredient. 12. A herbicidal composition according to item 1, characterized in that the active ingredient is at least a part of the group consisting of: 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (thioacetic acid , S-ethyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, N-methyl-N-methoxyamide), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (2-propionamide), and 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-o! -Methoxyacetophenone oxime 0- (2-thiopropionic acid, S-methoxycarbonyl-methyl ester). A herbicidal composition according to item 1, characterized in that the active ingredient is at least a part of the group consisting of: 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- ( acetic acid), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (2-propionic acid), agriculturally soluble sodium and potassium salts of 5- (2-chloro-4-trifluoromethylphenoxy ) -2-nitro-a: -methoxy-acetophenone oxime-O- (acetic acid), and agriculturally soluble sodium and potassium salts of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (2-propionic acid). 14. A herbicidal composition according to item 1, characterized in that the active ingredient is at least a part of the group consisting of: ethyl 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) -phenacyloxyacetate, methyl 2- [ 2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -phenacyloxy] propionate, ethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -phenacyloxy] -propionate, n- Propyl 2- [2-chloro-5- (2'-chloro-4'-trifluoromethylphenoxy) -phenacyloxy] propionate, 2-chloroethyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -phenacyloxy] propionate, propargyl 2 [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, and methyl 2- [2- [2'-nitro-5 '- (2 "-chloro-4 "trifluoromethylphenoxy) -phenacyloxylpropionyloxyjpropionat. 15. A method for the destruction of unwanted weeds, characterized by the application to the weeds of a herbicidally effective amount of a compound of formula (I) in the R ^ O R ^{1 represents} a methyl group or ι '<> λ , wherein represent -GH-G-A-R A is an oxygen atom or a sulfur atom, ^% R ^{3 is} a hydrogen atom or a methyl group, and R ^{4 is} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an aynyl group having 3 to 6 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted by a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a carboalkoxy group having 2 to 4 carbon atoms, and Y is a Represents oxygen atom or = NOR ² , wherein represent R ^{2 is} a hydrogen, an alkyl group having 1 to 3 carbon atoms or R ⁵ O -GH-CR ⁰ _f
wherein R ^{5 represents} a hydrogen atom or a methyl group, and R ' R ⁶ -BR ⁷ or - represents, wherein B represents an oxygen atom or a sulfur atom, R ^{7 is} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an aynyl group having 3 to 6 carbon atoms, a substituted or unsubstituted phenyl group, one substituted by a halogen atom or an alkoxy group having 1 to 3 carbon atoms An alkyl group having 1 to 4 carbon atoms, an alkali metal, an alkaline earth metal in a proportion corresponding to the monovalent of the alkaline earth metal, an ammonium group, one substituted by an alkyl group having 1 to 4 carbon atoms Ammonium group, or R ¹⁰ O -GH GOR ¹ ' wherein R ^{10 represents} a hydrogen atom or a methyl group, and R ^{11 represents} an alkyl group having 1 to 3 carbon atoms, and R ⁸ and R ^{9 are the} same or different and each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aynyl group having 3 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. 16. The method according to item 15, characterized in that R ^{1 represents} a methyl group, R ^{5 represents} a hydrogen atom, B represents an oxygen atom and R ^{7 represents} an alkyl group having 1 to 3 carbon atoms. 17. A method according to item 15, characterized in that R ^{1 represents} a methyl group, R ^{5 represents} a hydrogen atom, B represents an oxygen atom, and R ^{7 is} a member selected from the group consisting of a hydrogen atom, an unsubstituted phenyl group, a through a chlorine atom-substituted alkyl group having 1 to 4 carbon atoms and an alkali metal group. 18. The method according to item 15, characterized in that R ^{1 represents} a methyl group, B represents a sulfur atom, and R ^{7 is} a part selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a by a carboalkoxy group having 2 to 3 carbon atoms substituted alkyl group having 1 to 4 carbon atoms comprising group. 19. The method according to item 15, characterized in that R ^{1 represents} a methyl group and R ⁸ and R ^{9 are the} same or different and each independently is a part selected from the group consisting of a hydrogen atom, a methyl group and a methoxy group. 20. The method according to item 15, characterized in that Y and A represent an oxygen atom and R ^{4 represents} an alkyl group having 1 to 3 carbon atoms. 21. A method according to item 15, characterized in that Y represents an oxygen atom, R ^{3 represents} a methyl group, A represents an oxygen atom and R ^{4 is} a part selected from the group consisting of a propargyl group and a chlorine atom or a carboalkoxy group having 2 to 3 carbon atoms substituted alkyl group having 2 to 3 carbon atoms group was selected. 22. The method according to item 15, characterized in that the compound is 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenonoxime-O- (acetic acid, methyl ester). 23. The method according to item 15, characterized in that the compound is 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenonoxime-O- (acetic acid, ethyl ester). 24. The method according to item 15, characterized in that the compound is 5- (2-chloro-4-trifluoromethylphenoxy ^ nitro-a-methoxyacetophenonoxim-O-iacetic acid, 2-chloroethyl ester). 25. The method according to item 15, characterized in that the compound is 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a: -methoxyacetophenone oxime-O- (acetic acid, phenyl ester). 26. The method according to item 15, characterized in that the compound is at least a part of the following compounds comprising group: 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime O- (thioacetic acid, S-ethyl ester), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime-O- (acetic acid, N-methyl-N-methoxyamide), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a: -methoxyacetophenone oxime-O- (2-propionamide), and 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone oxime 0- (2-thiopropionic acid, S-methoxycarbonyl-methyl ester). 27. Method according to item 15, characterized in that the compound is at least a part of the group comprising the following compounds: 5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (acetic acid), 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-α-methoxyacetophenone oxime-O- (2 propionic acid), agriculturally soluble sodium and potassium salts of 5- (2-chloro-4-trifluoromethylphenoxy) -nitro-a-methoxyacetophenone oxime-O-iacetic acid), and agriculturally soluble sodium and potassium salts of 5- (2 chloro-4-trifluoromethylphenoxy) -2-nitro-a-methoxyacetophenone-0- (2-propionic acid). 28. The method according to item 15, characterized in that the compound is at least a part of the following compounds comprising group: Ethyl 2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenacyloxyacetate, methyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, ethyl 2- [2-nitro -5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, n-propyl 2- [2-chloro-5- (2'-chloro-4'-trifluoromethylphenoxy) phenacyloxy] propionate, 2-chloroethyl 2 [ 2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -phenacyloxy] propionate, propargyl 2- [2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) -phenacyloxy] propionate, and methyl 2- [2- [2'-nitro-5 '- (2 "-chloro-4' trifluoromethylphenoxy) -phenacyloxy] propionyloxy] propionate.