CN1005377B - Herbicide composition and method for exterminating harmful weeds using same - Google Patents

Abstract

The present invention relates to a novel compound having selective herbicidal activity, a novel process for the preparation of the compound, a novel herbicide comprising the novel compound (an effective herbicide useful for various crops, and a novel method for the elimination of harmful weeds using the novel herbicide), and more particularly, to 2-nitro-5- (2 '-chloro-4' -trichloromethylphenoxy) phenylacetic acid esters, thioesters and amides, a process for the preparation of the compound, a herbicide comprising the compound, and a method for the elimination of harmful weeds using the herbicide.

Description

Herbicide composition and method for killing harmful weeds using same

The present invention relates to a novel compound having selective herbicidal activity, a novel process for producing the same, a novel herbicide comprising the novel compound (an effective herbicide useful for various crops, and a novel method for destroying harmful weeds with the novel herbicide more specifically, the present invention relates to 2-nitro-5- (2 '-chloro-4' -trichloromethylphenoxy) phenylacetate, thioester and amide, a process for producing the same, a herbicide comprising the same, and a method for destroying harmful weeds with the same.

Heretofore, a herbicide containing 4-nitro-2 '-chloro-4' -trifluoromethylphenyl ether (as a sexual component) having a substituent such as a hydroxyl group, an alkoxy group, an alkyl group, a halogen atom, an amino group, a cyano group, a carboxyl group, an alkoxycarboxyl group, a carboxyalkyl group, an alkanoyloxy group, a carbamoyloxy group or other diphenyl ether derivatives, has been known, and is generally called a diphenyl ether herbicide (see, for example, japanese patent application laid-open No. 58-25641/1983, corresponding U.S. Pat. Nos. 3789276, 3888932, 3928416 and 4076741).

However, any known diphenyl ether herbicide tends to be good in herbicidal activity and poor in selectivity, or good in selectivity and poor in herbicidal activity. Thus, such herbicides are not effective in rapidly controlling the growth of predetermined types of weeds.

In addition to the excellent herbicidal activity and high selectivity described above, the ideal herbicide should also be low in toxicity to warm-blooded animals, be applicable throughout the growth phase of the crop, and be decomposed as soon as possible after application, so as not to contaminate the soil. However, to date, no ideal diphenyl ether herbicide has been found that meets the above requirements.

The purpose of the invention is that:

In view of the above, the inventors have conducted intensive studies for developing a novel diphenyl ether type herbicide which is free from the disadvantages of the conventional diphenyl ether type herbicide and has selective and highly selective herbicidal activity, that is, which is very safe for crops and can rapidly remove any useless plants growing together with the crops, and which can be continuously used throughout the whole growth period of the crops. As a result of the study, it was found that novel compounds of 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate, thioester and amide, and herbicides composed of the novel compounds meet the above-mentioned requirements, are improved herbicides, and are useful for various crops such as cotton, soybean, corn, wheat and rice even in small amounts. Based on this new finding, the inventors completed the present invention.

It is therefore an object of the present invention to provide novel compounds of 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate, thioester and amide, which have a highly selective herbicidal activity.

It is a second object of the present invention to provide a novel process for preparing such compounds.

A third object of the present invention is to provide a novel herbicide which has a high selectivity, eliminates the drawbacks of the conventional diphenyl ether type herbicides, and is applicable to various crops regardless of the growth period of the crops.

It is a fourth object of the present invention to provide a novel method of destroying unwanted weeds using such novel herbicides. The above-described and other objects, features and advantages of the present invention will be apparent to those skilled in the art from the following detailed description and appended claims.

It is an object of the present invention to provide a novel compound which can be represented by the following formula:

wherein R represents-OR ¹、-SR² OR

Wherein R ¹ is an unsaturated hydrocarbon residue, an alicyclic hydrocarbon residue, an aromatic hydrocarbon residue, an araliphatic hydrocarbon residue, a linear or branched alkyl or alkenyl group which may be substituted with (at least one) a halogen atom, a cyano group, a hydroxy group, a mercapto group, a hydrocarbyloxy group, an acyloxy group, an acyl thio group, a substituted or unsubstituted amino group and a heterocyclic group, or a linear or branched alkyl group substituted with at least one of a carboxy group and its derived functional group;

R ² is a hydrocarbon residue, a linear or branched alkyl or alkenyl which may be substituted by (at least one) a halogen atom, a cyano group, a hydroxy group, a mercapto group, a hydrocarbyloxy group, a hydrocarbylthio group, an epoxy group, an acyl group, an acyloxy group, an acyl group, a thio group, a substituted or unsubstituted amino group and a heterocyclic group, or a linear or branched alkyl group substituted by (at least one) a carboxyl group and its derived functional group, R ³ and R ⁴ are each a hydrogen atom, a hydrocarbyloxy group or a hydrocarbon residue, respectively, which may be substituted or unsubstituted by a halogen atom, a hydroxy group and a cyano group (at least one), which may contain (at least) a mixed atom (i.e., two adjacent carbon atoms with an oxygen atom or a sulfur atom interposed therebetween). Surprisingly, the above compounds produce a ready-to-use or back-up herbicide (as compared to herbicides produced from conventional compounds having similar structures), even in small amounts, which is very effective for controlling harmful weeds in cultivation of various crops.

The nature of the compounds of the invention may be attributed to the fact that the compounds have a group represented by R (as shown in the formula above). For example, in a general compound, the group at the position corresponding to the above-mentioned R group is a lower alkyl group such as methyl group, which does not have any substituent. In contrast, the compound of the present invention is a compound represented by the above formula, wherein R represents OR ¹、-SR² ORHere, R ¹ is an unsaturated hydrocarbon residue of an aliphatic olefinic or acetylenic acid, an alicyclic hydrocarbon residue, an aromatic hydrocarbon residue, an araliphatic hydrocarbon residue, a linear or branched alkyl or alkenyl group which may be substituted with (at least one) a halogen atom, a cyano group, a hydroxy group, a mercapto group, a hydrocarbyloxy group, an epoxy group, an acyl group, an acyloxy group, an acyl thio group, a substituted or unsubstituted amino group and a heterocyclic group, or a linear or branched alkyl group substituted with at least one of a carboxyl group and its derived functional group;

R ² is a hydrocarbon residue, a linear or branched alkyl or alkenyl group which may be substituted by (at least one) a halogen atom, a cyano group, a hydroxy group, a mercapto group, a hydrocarbyloxy group, a hydrocarbylthio group, an epoxy group, an acyl group, an acyloxy group, an acyl group, a thio group, a substituted or unsubstituted amino group and a heterocyclic group, or a linear or branched alkyl group substituted by (at least one) a carboxy group and its derivative functional group, R ³ and R ⁴ are each a hydrogen atom, a hydrocarbyloxy group or a hydrocarbon residue, respectively, which may be substituted or unsubstituted by a halogen atom, a hydroxy group and a cyano group (at least one), which may contain (at least) a mixed atom (i.e., two adjacent carbon atoms with an oxygen atom or a sulfur atom interposed therebetween).

Suitable examples of R ¹ and R ² mentioned above are allyl, 2-butynyl, cyclopentyl, cyclohexyl, phenyl and benzyl. In the case of containing an aryl group among these groups, they may be a substituted group.

The unsaturated hydrocarbon residues of the olefinic or acetylenic acids described above may be a straight chain or a branched chain. Suitable halogen atoms mentioned above are, for example, fluorine atoms, chlorine atoms, bromine atoms and iodine atoms. Hydrocarbyloxy is a group having a structure in which a hydrogen atom of a hydroxyl group is replaced with a hydrocarbon residue such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group. If the hydrocarbon group has an aromatic ring, the aromatic ring may have a substituent.

Suitable hydrocarbyloxy groups as described above are, for example, methoxy, ethoxy, allyloxy, propionyloxy, benzyloxy, o-methylbenzyloxy and the like. A hydrocarbylthio group is a group having a structure in which an oxygen atom of a hydrocarbyloxy group is replaced with a sulfur atom. Suitable hydrocarbon thio groups mentioned above are, for example, methylthio, ethylthio, allylthio, benzylthio and the like. The acyl group, the acyloxy group and the acyl sulfide group mentioned above may be aliphatic groups or aromatic groups, and they may have one substituent. Specific examples of these groups are acetyl, propionyl, benzoyl, acetoxy, butyryloxy, acetylthio and the like. The substituted amino group may be a single substituent or a double substituent. Suitable substituted amino groups as described above are, for example, mono-, di-, methylethylamino, methyl methoxyamino and the like.

The heterocyclic groups described above may be in a fully unsaturated form or in partially or fully saturated form. Suitable heterocyclic groups mentioned above are, for example, groups derived from thiophene, furan, pyrrole, pyridine quinoline, piperazine, imidazole and hydrides thereof.

Further, a suitable example of the above-mentioned R ¹ and R ² is a straight-chain or branched alkyl group having a carboxyl group or a functional group derived therefrom as a substituent.

The term "derivative functional group" is used to denote a group generated from a carboxyl group, which is obtained by conversion of only the carboxyl group in a carboxylic acid compound, and which is generally classified into the same class as the carboxyl group. Examples of such groups are a carboxylate, carboxylate ester, thio halide, amide and the like as described above. These groups are readily available from a carboxyl group in a conventional manner. These groups can be converted to the original carboxyl groups by hydrolysis. In the compounds of the present invention, examples of R ¹ and R ² are straight or branched alkyl groups which contain a substituent of the formula:

Wherein R ⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an alkynyl group, an alkali metal, an alkaline earth metal (in proportion to monovalent alkaline earth metal), ammonium or an alkyl-substituted ammonium.

Wherein R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group or an alkoxy group, respectively.

Examples of the substituent contained in a substituted or unsubstituted alkyl or alkenyl group (represented by R ⁵) are a halogen atom, a cyano group, a lower alkoxy group, an alkenyloxy group, an alkylthio group, an alkenylthio group, an alkynylthio group, a hydroxyl group, an aliphatic acyl group, a carboxylic acid group, an alkoxycarbonyl group, an alkoxyalkoxycarbonyl group, an aminocarbonyl group and the like, as required.

Further, a suitable example of R ² is a straight or branched alkyl group such as methyl, ethyl, propyl, butyl and isopropyl.

Suitable examples of the above-mentioned R ³ and R ⁴ may be a hydrogen atom, a hydrocarbon residue, such as an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, an araliphatic hydrocarbon residue or an alicyclic hydrocarbon residue or a hydrocarbyloxy group in which the above-mentioned hydrocarbon residue is bonded to an oxygen atom. In this connection, the above aliphatic hydrocarbon residues may be saturated or unsaturated, or one of straight-chain or branched. An oxygen atom or a sulfur atom is inserted between (at least a portion of) two adjacent carbon atoms to form an ether linkage or a thioether linkage. The hydrocarbon residue described above may be substituted with one halogen atom, one hydroxyl group and one cyano group (at least one).

Examples of the above-mentioned R ³ and R ⁴ are (already mentioned) a hydrogen atom, methyl group, ethyl group, n-propyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, 2-propenyl group, 2-propyl group, 3-butenyl group, cycloheptyl group, cyclohexyl group, naphthyl group, tolyl group, benzyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 2-butoxyethyl group, 2-methylmercaptoethyl group, 2-butylethyl group, 2-benzylmercaptoethyl group, 2-hydroxy-inner group, 2-hydroxybutyl group, 3-hydroxypropyl group, 2-chloroethyl group, 2-bromoethyl group, p-chlorophenyl group, cyanomethyl group, 2-cyanomethyl group, methoxy group, ethoxy group, allyloxy group, benzyloxy group and the like.

Specific examples of the compounds of the present invention represented by the above formula (I) are as follows:

S-methyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-1-methylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-2-propenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-2 propenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-cyclopropyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-cyclohexyl 2-nitro-5- (2 '-chloro-4' -trifluoropropylphenoxy) thiophenoacetate,

2-Propenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate.

2-Propynyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Cyclopropyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Cyclohexyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

S-phenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-4-chlorophenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-4-methylphenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-4-methoxyphenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-benzyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

1-Methyl-2-propenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

4-Methoxybenzyl phenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Chloroethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Chloromethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate.

2-Hydroxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

S-2-chloroethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-1-methyl-2-hydroxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

2- (4-Methoxybenzyloxy) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2. 3-Epoxypropyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Methyl carbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

S-2-methylcarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

2-Phenylcarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Acetoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Benzoyloxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (N, N-dimethylamino) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (N-methyl-N-methylamino) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Methyl-2-methylhydroxoxyethyl-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

3-Chloro-2-propenyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

N-methyl-4-piperidylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Tetrahydropyranylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Furfuryl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (2-Thienyl) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

3- (3-Pyridyl) propyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Benzyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

4-Methylphenyl 2-nitro-5- (2 ',6' -dichloro-4 ' -trifluoromethylphenoxy) phenylacetate,

2-Trifluoroethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (2-Chlorobenzoic acid) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Bromomethylcarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (3-Methoxyphenylcarbonyl) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate

2-Acetylsulfatoethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Benzoylthioethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Ethoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (2-Propenoxy) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (2-Propynyloxy) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Phenylmethoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

3-Methoxypropyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

3-Ethoxypropane 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate.

3- (1-Methylethoxy) propyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

3- (2-Propenoxy) propyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Methyl-2-methylethoxy 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Ethoxy-1-methylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Methyl-2- (1-methylethoxy) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Methyl-2- (2-propenoxy) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Methylthiomethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Ethylthiomethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Methyl ethyl thiomethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethyl phenoxy) phenylacetate,

2-Propenylthiomethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Propargylthiomethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Methylthioethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Ethylsulfanylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (2-Propenylthio) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (2-Propynylthio) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

S-methoxymethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-ethoxymethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-2-methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-2-ethoxyethyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-2- (2-propenoxy) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-3-methoxypropyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-1-methyl-2-methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

S-2-methylthioethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

2, 2-Trifluoroethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Chloro-2-propenyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Carboxymethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Carboxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Methoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Ethoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Isopropoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

S-ethoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

2-Ethoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Methoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Ethoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

S-1-isopropoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

2-Chloroethoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1- (2-Bromoethylcarbonyl) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Cyanomethoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1- (2-Methoxyethoxycarbonyl) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

S-2-ethoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

1- (2-Allyloxyethoxycarbonyl) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (2-Propargyloxycarbonyl) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Methylthioethoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Allylsulfanylethoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1- (2-Propargylthioethoxycarbonyl) ethyl-nitro-5- (2 ', 6-dichloro-4' -trifluoromethylphenoxy) phenylacetate,

2- (2-Hydrocarbon ethoxycarbonyl) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Acetylmethoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1- (2-Acetylethoxycarbonyl) ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2- [ 2-Nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetoacetic acid ] propionic acid,

Carboxymethyl 2- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetyl ] propionate,

Methoxycarbonylmethyl 2- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetyl ] propanoate,

Ethoxycarbonylmethyl 2- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetyl ] propanoate,

2-Methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetyl acetate,

Aminocarbonylmethyl 2- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetyl ] propionate,

1-Allyloxycarbonyl ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

S-propargyloxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate,

2-Chloropropene oxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Sodium 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetyl acetate,

Potassium 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetylthioacetate,

Sodium 2- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate ] propionate,

Ammonium 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

Aminomethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

N-methyl-N-methoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetylacetamide,

N-methyl-2- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate ] propanamide,

N, N-dimethyl-2- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate ] propionic acid amine,

N-methyl-3- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate ] propanamide,

Sodium 2- [ 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate ] propionyloxy acetate,

3-Methoxycarbonylpropyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

1-Methyl-1-ethoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Methyl-3-methoxycarbonylpropyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate,

2-Nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-N-butyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-isopropyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (2-chloroethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (2-hydroxybutyl) -2' -nitro-5- (2 ' -chloro-4 ' -trifluoromethylphenoxy) phenylacetamide,

N-methoxymethyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (2-cyanoethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-allyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (3-chloro-2-propenyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (2-propynyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (4-chlorobenzyl) -2 '-nitro-5' - (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-2-dimethylbenzyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (3, 4-dichlorophenyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (4-methylphenyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-2-naphthyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N, N-dimethyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N-phenyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (2-cyanoethyl) -N-phenyl-2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-isobutyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-N-nonyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (2-hydroxyethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-N-butoxymethyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (2-N-propoxyethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (2-methoxypropyl) -2 '-nitro-5' - (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (2-bromoethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-ethoxycarbonylbenzyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-cyanomethyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N-methoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-ethyl-N-N-propoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-allyl-N-methoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-ethyl-N-allyloxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-N-propyl-N-propargyloxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N-ethoxycarbonylmethoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N- (2-cyanoethoxy) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N, N-diallyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (2-diethoxyethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (2-ethoxyethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (4-methoxy-2 alkenyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N- (3-chloro-2-propenoxy) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-ethyl-N- (2-methoxycarbonylethoxy) -2 '-nitro-5' - (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N- (2-chloroethoxy) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (2-methylthioethyl) -2 '-nitro-5' - (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N- (2-benzylthioethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N- (2-allylsulfanyl-ethyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N- (2-methylthioethoxy) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N- (4-methyl mercaptophenyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-methyl-N- (4-allylmercaptobenzyl) -2 '-nitro-5' - (2 '' -chloro-4 '' -trifluoromethylphenoxy) phenylacetamide,

N-ethyl-N-ethoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide,

N-ethyl-N-methoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide and the like.

All of the above compounds are novel compounds, and none of these compounds is disclosed in any document. The preparation of these compounds, for example, method A and method B, is described below:

Method A:

it is another object of the present invention to provide a process for the preparation of a compound of formula (I):

Wherein R is as defined above,

The preparation method of the compound comprises the following steps:

(1) Heating potassium m-hydroxyphenylacetate and 3-chloro-4-halogenobenzene trifluoride to a temperature of 90℃to 180℃to obtain 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetic acid;

(2) The resulting acid is reacted with at least one compound comprising an alcohol, an amine, a thiol and a halide, each of which has a substituent of formula R (as defined above) to give a compound of the formula:

(II)

wherein R is as defined above.

(3) Nitrifying a compound of formula (II)

In the above step (1), the reaction may be carried out in a solvent such as dimethyl sulfoxide. The reaction temperature is 19-180 ℃, preferably 120-150 ℃. The addition of potassium carbonate can increase the yield of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetic acid. In the above step (2), dehydration, desalination or the like is effected by reacting an acid with an alcohol, an amine, a thiamine or a halide. In the above step (3), the compound of formula (II) can be nitrated with a common nitrating agent such as acetyl nitrate, potassium nitrate in sulfuric acid, a mixed acid of sulfuric acid and nitric acid, and nitronium tetrafluoroborate to produce a compound of formula (I) of the present invention. The nitration is generally carried out at a temperature of about-20 ℃ to 100 ℃, preferably at a temperature of about-10 ℃ to 50 ℃. If desired, the nitration can be carried out in an inert organic solvent such as 1, 2-dichloroethane and other chlorohydrocarbons.

Method B:

Another object of the present invention is to provide a process for producing a compound of the formula (I), which comprises reacting a 2-chloro-4-trifluoromethylphenol compound (formula

(III)

Wherein M is an alkali metal

With a 2-nitro-4-halogenophenylacetic acid compound of formula (N) or a 2-nitric-4-halogenophenylthioacetic acid compound

(IV)

Wherein R is as defined above and Y is a halogen group.

Y is preferably a bromine atom or a fluorine atom. Fluorine atoms are better than bromine atoms.

As mentioned above, the compounds of the present invention can be prepared by reacting an alkali metal salt of 2-chloro-4-trifluoromethylphenol of the formula (III) with phenylacetic acid or thiophenacetic acid of the formula (IV), typically at a temperature of from 0℃to 250℃and preferably from 60℃to 180 ℃. The reaction may be carried out in a suitable solvent such as sulfolane, dimethyl sulfoxide, N-dimethylformamide, hexamethylphosphoric triamide and other inert organic solvents, as desired.

The above methods A and B are specific illustrations of the present invention, and it should be understood that these methods are not limiting of the present invention. The compounds of the present invention can be prepared by various modifications of the commonly known methods for preparing analogous compounds.

The herbicidal activity of the compounds of the present invention for preventing and eliminating weeds growing in paddy fields is exemplified as follows, and the compounds of the present invention can be effectively used in paddy fields (including before and after rice seedling transplanting) for a long period of time. In particular, the compounds are useful for effectively and rapidly destroying barnyard grass, a detrimental grass weed growing in paddy fields. Furthermore, if a proper amount of the compound of the present invention is used to effectively kill weeds in a paddy field, the compound has no significant phytotoxicity to paddy rice. In addition, the compounds of the present invention also have excellent herbicidal activity against many weeds such as Shan Haorui (mo no choria), RATALA SPP, chickweed and French sea green which grow in paddy fields. It is noted that the amount of the compound of the present invention is much lower than that of the conventional herbicide, and the ester and thioester compounds of the present invention have excellent herbicidal activity when used in paddy fields (usually, the amount is 0.5 to 100 g/10 acre, preferably, 1.5 to 50 g/10 acre). The amide compound of the present invention also has excellent herbicidal activity when used in rice fields (usually in an amount of 1 to 100 g/10 mu, preferably 5 to 50 g/10 mu). The amount of these compounds used is quite low compared to the usual paddy field herbicides such as 2,4, 6-trichloro-1- (4 '-nitric acid phenoxy) benzene, 2, 4-dichloro-1- (3' -methoxy-4 '-nitric acid phenoxy) benzene and methyl 2-nitro-5- (2' -chloro-4-trichlorophenoxy) benzoate (200 to 250 g/10 acre). As described above, it is apparent that the herbicidal activity of the compounds of the present invention is high as that of ordinary herbicides.

In addition, the compound of the present invention has not only a very high herbicidal activity against weeds in paddy fields, but also a very Gao Chucao activity against weeds on a plateau.

The compounds of the present invention, even in small amounts, have high herbicidal activity against a wide variety of weeds such as quinoa (Iambsquarters), VELVETLEAT, caffeia, homoguava, purslane, rhodomyrtus tomentosa, rush (Sicklepod), stramonium, black nightshade, polygonum, euonymus alatus, piper nigrum (PEPPERGRASS), marestail, comfrey (cllmbing milkweed), chickweed, buckwheat (bindweed) and the like, and weeds belonging to the gramineae such as strongback, cricket grass, green horsetail, bluegrass and the like. It is notable that small amounts of the compounds of the present invention also have high herbicidal activity against such harmful weeds as VELVETLEAT, stramonium, rhodomyrtus tomentosa, quinoa (Iambsquarters) and the like in soybean fields. The characteristics of the compounds of the present invention are exhibited not only by high selectivity against various crops such as soybean and cotton, but also by high selectivity against crops belonging to the family Gramineae, such as rice, corn, wheat and the like, before weed emergence or after weed emergence. Because of its wide range of uses and excellent herbicidal activity, the compound of the present invention is also useful as an effective herbicide in pastures, orchards, lawns and non-crop fields.

Methyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate is a known compound structurally similar to the compounds of the present invention, which has the disadvantage of not having a species selectivity for rice and barnyard grass. On the other hand, the compound of the present invention (unlike the conventional diphenyl ether herbicides) has very high species selectivity for plants belonging to the family Gramineae, in addition to excellent herbicidal activity. Thus, the compounds of the present invention can be said to be very effective, useful herbicides.

As described above, it is apparent that the compounds of the present invention can be used for selectively destroying weeds in crops of rice, cereals such as barley and wheat, corn, soybean and cotton. Moreover, the compounds of the invention can be applied before and after the emergence of the weeds.

The compounds of the present invention are used in a wide range of amounts depending on the method of application of the compound, the application site of the compound and the type of weed to be destroyed. For example, the esters and thioesters of the present invention are used in an amount of 0.5 to 100 g/10 g, preferably 1.5 to 50 g/10 g. The dosage of the amide compound is 1-100 g/10 mu, preferably 5-50 g/10 mu.

In practice, the compounds of the present invention can be used directly as herbicides or formulated into various preparations such as wettable powders, emulsifiable concentrates, granules, powders and the like, and therefore, it is a further object of the present invention to provide a herbicide comprising a herbicidally effective amount of a compound of the formula (I) as a herbicidally active ingredient in admixture with an agriculturally acceptable carrier,

(I)

R in the above formula is defined as above.

In the case of formulating the compound of the present invention into the above-mentioned various preparations, the solid carrier used may be mineral powder (for example, kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite and the like), plant powder (for example, soybean grains, wheat flour, wood flour filler, tobacco leaf powder, precipitated powder, crystalline cellulose and the like) high polymer compound (for example, petroleum resin, polyvinyl chloride, ketone resin and the like), alumina and various waxes. As the liquid carrier, there have been mentioned, for example, alcohols (methanol, ethanol, butanol, 1, 2-ethylene glycol, benzyl alcohol and the like), aromatic hydrocarbons (e.g., toluene, benzene, xylene and the like), chlorinated hydrocarbons (chloroform, carbon tetrachloride, monochlorobenzene and the like), ethers (dioxane, tetrahydrofuran and the like), ketones (acetone, methyl ethyl ketone, cyclohexanone and the like), esters (esters of ethyl acetate, butyl acetate and the like), amides (N, N-dimethylacetamide and the like), nitriles (acetonitrile and the like), ether alcohols (ethylene glycol diethyl ether and the like) and water.

Surfactants used to emulsify, disperse, diffuse and the like the compounds of the present invention may be nonionic, anionic, cationic and zwitterionic. Specific examples of the surfactant used in the present invention are a polyoxyethylene alkyl ether, a polyoxyethylene alkylaryl ether, a polyoxyethylene fatty acid ester, a sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, an ethylene oxide polymer, a propylene oxide polymer, a polyoxyethylene alkyl phosphate, a fatty acid salt, an alkyl sulfate, an alkyl sulfonate, an alkylaryl sulfonate, an alkyl phosphate, a polyoxyethylene alkyl sulfate, a quaternary ammonium salt and an alkoxyamine. It should be noted that the surfactant useful in the present invention is not limited to the above-mentioned compounds. Gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol and the like may also be used as auxiliary additives in the present invention as required.

In addition, in order to increase the herbicidal efficiency, the compounds of the present invention may be used in combination with other herbicidal active ingredients, and in some cases, a synergistic effect may be produced. For example, the following ingredients are mixed with the compounds of the present invention:

(A) Phenoxy herbicides:

2, 4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, butyl 2- [ 4- (5-trifluoromethyl-2-pyridyloxy) propionic acid (including esters and salts thereof), ethyl 2- [ 4- (6-chloro-2-quinoxalinyl) phenoxy ] propionate, and the like.

(B) Diphenyl ether herbicides:

2, 4-dichlorophenyl 4 '-nitrophenyl ether, 2,4, 6-trichlorophenyl 4' -nitrophenyl ether, 2, 4-dichlorophenyl 4 '-nitro-3' -methoxyphenyl ether, 2, 4-dichlorophenyl 3 '-methoxycarbonyl-4' -nitrophenyl ether, 2-chloro-4-trifluoromethylphenyl 3 '-ethoxy-4' -nitrophenyl ether, 5- [ 2-chloro-4-trifluoromethyl) phenoxy ] -2-nitrobenzoic acid sodium, and the like.

(C) Triazine herbicides:

2-chloro-4, 6-bis-ethylamino-1, 3, 5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-triazine, 2-methylsulfanyl-4, 6-bis-ethylamino-1, 3, 5-triazine, and the like.

(D) Urea herbicides:

3- (3, 4-dichlorophenyl) -1-methoxy-1-methylurea, 3- (2, 2-2-trifluoro-tolyl) -1, 1-dimethylurea, 3- [4- (4-methylphenylethoxy-phenyl) -1-methoxy-1-methylurea, 3- (5-t-butyl-3, 4-thiadiazol-2-yl) -4-hydroxy-1-methyl-2-imidazolone, and the like.

(E) Carbamate herbicides:

Isopropyl N- (3-chlorophenyl) carbamate, methyl N-3, 4-dichlorophenyl) carbamate, 4-chloro-2-butyl N- (3-chloro-phenyl) carbamate, and the like.

(F) Thiol carbamic acid ester herbicides:

S-ethyl N, N-hexamethylenethiocarbamate, S- (4-chloro-benzyl) N, N-diethylthiocarbamate, S-ethyldipropylthiocarbamate, and the like.

(G) Anilide herbicides:

2, 4-dichloropropionylaniline, N-methoxymethyl-2 ',6' -diethyl-2-chloroacetanilide, 2-chloro-2 ',6' -diethyl-N- (butoxymethyl) -acetanilide, 2-chloro-2 ',6' -diethyl-N- (propoxyethyl) -acetanilide, 2- (2-naphthoxy) propionyl-nilide, and the like.

(H) Uracil herbicides:

5-bromo-3-sec-butyl-6-methyluracil, 3-cyclohexyl-5, 6-trimethyleneuracil, and the like.

(I) Pyridinium herbicides:

1,1 '-dimethyl-4, 4' -pyridinium dichloride, 1 '-ethylene-2, 2' -pyridinium dibromide, and the like.

(J) Phosphorus herbicides:

N- (phosphonomethyl) glycine, 0-ethyl, 0- (2-nitro-5-methylphenyl) N-sec-butylaminothioyl phosphate, 0-methyl, 0- (2-nitro-4-methylphenyl) N-isopropylaminothiophosphate, S- (2-methyl-1, 1-piperidylcarbonylmethyl) 0, 0-di-N-propyldithiophosphate, (2-amino-4-methylphosphonobutyl) -alanyl alanine-sodium salt, and the like.

(K) Toluidine herbicide:

2, 2-trifluoro-2, 6-dinitro-N, N-dipropyl-p-toluidine, N- (cyclopropylmethyl) -2, 2-trifluoro-2, 6-dinitro-N-propyl-p-toluidine, etc.

(L) other herbicides:

5-t-butyl-3- (2, 4-dichloro-5-isopropoxyphenyl) -1,3, 4-oxadiazol-2-one, 3-isopropyl-2, 1, 3-benzoazo-dinonyl-4,2,2-dioxide, 2- (2-naphthoxy) -N, N-diethylpropionamide, 3-amino-2, 5-dichlorobenzoic acid, 4-dichlorobenzoyl) -1, 3-dimethylpyrazol-5-yl-p-toluenesulfonate, 2-chloro-N- [ 4-methoxy-6-methyl-1, 3, 5-triazin-2-yl) aminocarbonyl ] -benzenesulfonyl, methyl 2- [4, 6-dimethoxypyrimidin-2-yl) -amino sulfamoylmethyl ] -benzoate, N- (1-methyl-1-phenethyl) -2-bromo-3, 3-dimethylbutylamine, 2- [ 1-N-allyloxy-aminobutylene ] -4-methoxycarbonyl-5, 5-dimethylcyclohex-5-enyl ] -2- (2-hydroxy-1, 3-cyclohex-2-yl) -cyclohexan-ethyl-1- (2-hydroxy-3-propyl) -cyclohexan-5-yl-ethyl-2-methyl.

The aforementioned herbicides are merely examples, and they should not limit the scope of the herbicides used in combination with the compounds of the present invention. The herbicides of the present invention can also be used in combination with pesticides (e.g., pyrethroid-type insecticides), fungicides, plant growth regulators, microbial pesticides and fertilizers.

In addition to the above objects of the present invention, the present invention provides a method for destroying unwanted weeds which comprises spraying onto the weeds a herbicidally effective amount of a compound of the formula

R in the above formula is defined as above.

The herbicide consists of the compound (as an active component of the herbicide) and also comprises an agriculturally suitable carrier (the definition of the carrier is as above). The meaning of the aforementioned "herbicidally effective amount of herbicide" is clear from the above description. The amount of the ester and the thioester used in the present invention is in the range of 0.5 to 100 g/10 g/mu, preferably 1.5 to 50 g/10 g/mu. On the other hand, the dosage of the amide is 1-100 g/10 mu, preferably 5-50 g/10 mu. The methods described above can be used to selectively control unwanted weeds in a desired crop. In the examples which follow, the active compound is employed in the form of a herbicide, the amount of which is indicated in units of "a.i. g/10 acre" which means the amount of one active compound.

Examples:

The present invention will now be described in more detail with reference to examples, which relate to the preparation of the compounds of the present invention and to the methods and effects of use of the compounds of the present invention as herbicides. These examples should not be construed as limiting the scope of the invention in any way.

Example 1:

s-ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate (as compound No, 2) was prepared as follows:

(a) 0.7 g of ethylthiol and 1.2 g of triethylamine are dissolved in 20ml of N, N-dimethylacetamide, 3.5 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetylchloride are added dropwise to the resulting solution at a temperature of 10℃and, after the dropwise addition has ended, the reaction is allowed to proceed at room temperature for 3 hours. After the completion of the reaction, 50ml of water was added to the reaction mixture, followed by extraction twice with diethyl ether (30 ml of diethyl ether each time). The diethyl ether layer was washed with water, dried over anhydrous sodium sulfate, and then diethyl ether was removed by evaporation under reduced pressure, whereby a semi-finished product was obtained. The obtained semi-finished product was purified by a silica gel column (eluting with a mixed solvent of toluene and n-hexane). As a result, 1.9 g of S-ethyl-3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate was obtained.

(B) 1.9 g of S-ethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate prepared in step (a) above was added to 15 g of acetic anhydride, and the mixture was cooled to below 10℃with stirring in an ice bath. Then, 1.5 g of ketone nitrate was slowly added over 5 minutes, and after all of the ketone nitrate was added, the reaction was performed at a temperature of less than 10 ℃ for 1 hour, and then at room temperature for 3 hours, the reaction mixture was poured into an ice bath, followed by 200ml of diethyl ether. An aqueous sodium hydroxide solution was added to neutralize the resultant mixture. The mixture was then acidified with aqueous hydrochloric acid, the ether extract layer was separated, washed with water and dried over anhydrous sodium sulfate, and subsequently, the ether was removed by evaporation under reduced pressure to give a crystalline semi-finished product. The obtained semi-finished product is purified by a silica gel color separation column (eluting by a mixed solvent of toluene and acetone). As a result, 1.1 g of pale yellow S-ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate solid was obtained. The melting point is 82.5-84.2 ℃.

Example 2:

S-1-methyl-ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) thiophenoacetate (Compound No, 3) was prepared as follows:

(a) 3.3 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetic acid were dissolved in 30 ml of methylene chloride and the resulting solution was cooled to below 10℃in a water bath. Then, 2.1 g of N, N' -Dicyclohexylcarbodiimide (DCC) was added followed by 0.8 g of 2-propanethiol. The reaction was carried out at room temperature for 6 hours. After the completion of the reaction, the resultant solid matter was removed by filtration, and the solvent in the filtrate was removed by evaporation under reduced pressure to obtain a semi-finished product. The obtained semi-finished product was purified by a silica gel column (eluting with a mixed solvent of toluene and n-hexane). As a result, 1.6 g of S-1-methylethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate was obtained.

(B) 1.6 g of S-1-methylethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate obtained in the above step (a) was added to 15 g of acetic anhydride, and the mixture was cooled to below 10℃while stirring in an ice bath. Then, 1.2 ketone nitrate was slowly added over 5 minutes, and after all of the ketone nitrate was added, the reaction was performed at a temperature of less than 10 ℃ for 1 hour, and then at room temperature for 3 hours to obtain the desired product. The desired product was isolated from the reaction mixture (isolation procedure was virtually identical to step (b) in example (1)). The obtained semi-finished product was purified by a silica gel chromatography column (eluting with a mixed solvent of toluene and acetone). As a result, 1.1 g of pale yellow S-1-methylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate as a solid having a melting point of 102℃to 104℃was obtained.

Example 3:

2-methoxy-ethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate (compound No. 15) was prepared as follows:

(a) 3.3 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetic acid and 1.5 g of 2-methoxyethanol were dissolved in 50 ml of benzene, followed by the addition of 0.5 g of p-toluenesulfonic acid. The mixture was then heated under reflux for 3 hours. After the completion of the reaction, 50 ml of diethyl ether was added to the reaction mixture. The resultant mixture was washed with water according to a conventional method, dried over anhydrous sodium sulfate, and then the solvent was evaporated under alkaline pressure to obtain 3.9 g of 2-methoxy-ethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate.

(B) 3.9 g of 2-methoxyethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate prepared in step (a) above was added to 35 g of acetic anhydride, and the mixture was cooled to 10℃or below while stirring in an ice bath. Then, 2.9 g of copper nitrate was slowly added over 5 minutes, and after the copper nitrate was completely added, the reaction was performed at a temperature of less than 10 ℃ for 1 hour, and then the reaction was continued at room temperature for another 5 hours to complete the reaction. The reaction mixture was poured into ice, followed by the addition of 200 ml of diethyl ether. An aqueous sodium hydroxide solution was added to neutralize the resultant mixture. The mixture was acidified with an aqueous hydrochloric acid solution, and the ether extract layer was separated, washed with water, dried over anhydrous sodium sulfate, and then ether was removed by evaporation under reduced pressure to give a crystalline semi-finished product. The resulting crystalline semifinished product is recrystallized from a mixed solvent of ethyl acetate and n-hexane. As a result, 3 g of 2-methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate as a white crystalline product having a melting point of 71.9℃to 72.5℃was obtained.

Example 4:

I. 1-methyl-2 methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate (compound No. 17) was prepared as follows:

(a) 3.3 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetic acid and 1.8 g of 1-methoxy-2-propanol were dissolved in 50 ml of benzene, and 0.5 g of p-toluenesulfonic acid was added. Subsequently, the mixture was heated under reflux for 6 hours. After the completion of the reaction, 50 ml of diethyl ether was added to the reaction mixture, and the resultant mixture was washed with water according to a conventional method, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 3.9 g of 1-methyl-2 methoxyethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate.

(B) 3 g of 1-methyl-2-methoxyethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate prepared in step (a) above was dissolved in 15 g of 1, 2-dichloroethane. The resulting solution was added dropwise to a mixed acid (2.4 g of 65% concentrated nitric acid and 3 g of 97% concentrated sulfuric acid) at 40℃over about 10 minutes, after which the reaction was carried out at 40℃for 2.5 hours, after which the reaction mixture was poured into crushed ice and then extracted twice with ethyl acetate (100 ml of ethyl acetate each time) in a conventional manner. Then, the organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crystalline semifinished product. The resulting crystalline product was recrystallized from a mixed solvent of ethyl acetate and n-hexane to give 2.3 g of white 1-methyl-2-methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate having a melting point of 78.9℃to 79.3 ℃.

(II) 1-methyl-2-methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate (compound No. 17) was prepared as follows;

2.3 g of potassium salt of 2-chloro-4-trifluoromethylphenol and 2.7 g of 1-methyl-2-methoxy & & & & & gt nitro-5-fluorophenyl acetate were dissolved in 50ml of dimethyl solfoxide, the resulting solution was heated at 60℃to 70℃under reflux for 5 hours, and after the completion of the reaction, the reaction mixture was poured into 300ml of ice water, followed by extraction with diethyl ether. Then, the ether layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals thus obtained were recrystallized from a mixed solvent of ethyl acetate and n-hexane to give 3.2 g of white 1-methyl-2-methoxyethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate having a melting point of 78.5℃to 79.0 ℃.

Example 5:

methoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate (compound No. 37) was prepared as follows:

(a) 3.3 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetic acid and 1g of methyl glycolate were dissolved in 50 ml of benzene. Then, 0.2 g of p-toluenesulfonic acid was added to the resultant solution, followed by heating under reflux for 3 hours. After the reaction was completed, 50 ml of diethyl ether was added. The resultant reaction mixture was washed with water and dehydrated with anhydrous sodium sulfate in a conventional manner, and the solvent was distilled off under reduced pressure to obtain 3.4 g of methoxycarbonylmethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate.

(B) 3.4 g of methoxycarbonylmethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate obtained in the above step (a) was added to 35 g of anhydrous acetic acid, and cooled to 10℃or lower while stirring in an ice bath. Then, 2.4 g of copper nitrate was slowly added over 5 minutes, and after all of the copper nitrate was added, the reaction was performed at a temperature lower than 10 ℃ for 1 hour, and the reaction was continued at room temperature for 5 hours to complete the reaction. The reaction mixture was placed in an ice bath and 200ml of diethyl ether was added. The reaction mixture was neutralized with aqueous sodium hydroxide solution and then acidified with hydrochloric acid. The diethyl ether layer was separated, washed with water, dried over anhydrous sodium sulfate, and diethyl ether was distilled off under reduced pressure to obtain a semi-finished product. And purifying the prepared semi-finished product by using a silica gel color separation column. As a result, 2.2 g of pale yellow crystals of methoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate were obtained, which had a melting point of 79.2℃to 80.1 ℃.

Example 6:

s-ethoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate (Compound No. 47) was prepared as follows:

(a) 1.2 g of ethyl glycolate and 1.2 g of triethylamine are dissolved in 20 ml of N, N-dimethylacetamide. To the resulting solution was added dropwise 3.5 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetylchloride at a temperature of 10 ℃. After the dropwise addition of the whole, the reaction was carried out at room temperature for 3 hours to complete the reaction. After the reaction was completed, 50 ml of water was added to the reaction mixture, followed by extraction with diethyl ether 2 times (30 ml of diethyl ether each time). The diethyl ether layer was washed with water and dried over anhydrous sodium sulfate, and diethyl ether was distilled off under reduced pressure to obtain a semi-finished product. The obtained semi-finished product was purified by a silica gel layer separation column to obtain 3.5 g of S-ethoxycarbonylmethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) -thiophenoacetate.

(B) 3.5 g of S-ethoxycarbonylmethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylthioacetate prepared in the above step (a) was added to 35 g of anhydrous acetic acid, and cooled to 10℃or lower while stirring in an ice bath. Then, 2.3 g of copper nitrate was slowly added over 5 minutes, and after the copper nitrate was completely added, the reaction was performed at a temperature of less than 10 ℃ for 1 hour, and then, the reaction was further performed at room temperature for 3 hours to complete the reaction. The process of step (b) of example 1 was repeated to produce a semi-finished product. Purifying the obtained semi-finished product by using a silica gel chromatographic column. As a result, 2.3 g of S-ethoxycarbonylmethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) -thiophenoacetate (refractive index h ₀ ²⁶: 1.5578) was obtained as a pale yellow oil.

Example 7:

1-methoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate (compound No. 48) was prepared as follows:

(a) 3.3 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetic acid and 1.7 g of methyl 2-bromopropionate were dissolved in 30 ml of acetone. Then, 1.4 g of anhydrous potassium carbonate was added to the obtained solution, and stirred at room temperature for 30 minutes. The reaction mixture was then heated under reflux for 30 minutes. After the completion of the reaction, the resultant solid matter was removed by filtration, and acetone was distilled off under reduced pressure to obtain 4 g of 1-methoxycarbonylethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate.

(B) 4 g of 1-methoxycarbonylethyl 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate obtained in the above step (a) was added to 35 g of anhydrous acetic acid, and cooled to 10℃or below while stirring in an ice bath. Then, 2.9 g of copper nitrate was slowly added over 5 minutes, and after all of the copper nitrate was added, the reaction was performed at a temperature lower than 10 ℃ for 1 hour, and the reaction was continued at room temperature for 3 more hours to complete the reaction. The process described in step (b) of example 1 was repeated to produce a semi-finished product. The resulting semi-finished ethyl acetate and n-hexane mixture was recrystallized to obtain 3.1 g of white crystals of 1-methoxycarbonylethyl 2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate having a melting point of 72.1℃to 72.9 ℃.

Example 8:

n-ethyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide (compound No. 59) was prepared as follows:

(a) 0.7 g of ethylamine and 1.5 g of triethylamine are dissolved in 20ml of N, N-dimethylacetamide at 0℃and 3.5 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetyl chloride are added. The reaction was carried out at 0 ℃ for 1 hour and then at room temperature for 3 more hours to complete the reaction. After the completion of the reaction, 50ml of water was added to the reaction mixture, followed by extraction twice with diethyl ether (30 ml of diethyl ether each time), washing the diethyl ether layer with dilute hydrochloric acid and water, drying over anhydrous sodium sulfate, and distilling off diethyl ether under reduced pressure. As a result, 3.5 g of N-ethyl-3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide was obtained.

(B) 3.5 g of N-ethyl-3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide prepared in the above step (a) was added to 35 g of acetic anhydride and cooled to 10℃or below in an ice bath with stirring. 2.9 g of copper nitrate was slowly added over 5 minutes, and after all of the copper nitrate was added, the reaction was performed at a temperature of less than 10℃for 1 hour, and then at room temperature for another 5 hours to complete the reaction. The procedure described in step (b) of example 1 was repeated to obtain a semi-finished product, and the obtained semi-finished product was recrystallized from a mixed solvent of ethyl acetate and N-hexane to obtain 2.5-white N-ethyl-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide having a melting point of 188.7℃to 189.3 ℃.

Example 9:

N-methyl N-methoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide (compound No. 90) was prepared as follows:

(a) 0.9 g of N, O-dimethylhydroxylamine and 1.5 g of triethylamine were dissolved in 20ml of N, N-dimethylacetamide at 5℃and 3.5 g of 3- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetyl chloride were added. The reaction was carried out at a temperature of 5 ℃ for 1 hour and at room temperature for 3 more hours to complete the reaction. After the completion of the reaction, 50ml of water was added to the reaction mixture, followed by extraction twice with diethyl ether (30 ml of diethyl ether each time). The ether layer was washed with dilute hydrochloric acid and water, dried over anhydrous sodium sulfate, and the ether was distilled off under reduced pressure to obtain 3.5 g of N-methyl-N-methoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetate.

(B) 3.5 g of N-methyl-N-methoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide prepared in step (a) above was added to 35 g of acetic anhydride, and the resultant mixture was cooled to 10℃or lower while stirring in an ice bath. Then, 2.9 g of copper nitrate was slowly added over 5 minutes. After the copper nitrate was completely added, the reaction was performed at a temperature of less than 10 ℃ for 1 hour and at room temperature for another 5 hours to complete the reaction. The procedure described in step (b) of example 1 was repeated to obtain a crude crystalline product. The prepared product is recrystallized from a mixture of ethyl acetate and N-hexane to prepare 3.2 white crystals of N-methyl-N-methoxy-2-nitro-5- (2 '-chloro-4' -trifluoromethylphenoxy) phenylacetamide, the melting point of which is 134-135 ℃.

Example 10:

The various compounds of the present invention were prepared by the methods of the examples described above, and the structure, physical properties, elemental analysis results, and high nuclear magnetic resonance (H-NMR) analysis data of these compounds are shown in Table 1. It should be understood that the scope of the invention is not limited to these compounds alone. The numbers for the compounds listed in table 1 may also be used to represent the same compounds in the examples of the invention.

S is single spectral line, d is double spectral line, t is triplet

* Only after preparation, the viscous liquid m: multiplet, b: broad line,

S is a single spectral line, d is a double spectral line and t is a triplet

M is multiplet, b is broad spectrum

Application instance

Preparation example 1 (wettable powder)

25 Parts by weight of the compound of the present invention, 5 parts by weight sorpol 5039,5039 (trade name of a product of Toho chemical industry Co.) and 70 parts by weight of talc were pulverized and thoroughly mixed to prepare a wettable powder.

Preparation example 2 (emulsifiable concentrate)

5 Parts by weight of the compound of the present invention, 10 parts by weight of sorpol X (a product of Toho chemical industry Co.), 45 parts by weight of n-butanol and 40 parts by weight of xylene were thoroughly mixed to prepare an emulsifiable concentrate.

Preparation example 3 (granule)

1 Part by weight of the compound of the present invention, 45 parts by weight of bentonite, 44 parts by weight of clay, 5 parts by weight of sodium lignin sulfonate and 5 parts by weight of sodium dodecylbenzenesulfonate were pulverized and thoroughly mixed, and water was added to the mixture to thoroughly knead the resultant. Then, the kneaded mixture is granulated and then dried, thereby obtaining desired granules.

Preparation 4 (powder)

1 Part by weight of the compound of the present invention, 99 parts by weight of clay were crushed and thoroughly mixed to form a powder.

Use example 1 (use after weed growth)

Paddy field soil in the greenhouse was filled into each pot with a surface area of 1/5000 acre. 3.0 leaves of rice seedlings (the height of the rice seedlings is 2-3 cm from the soil surface) are transplanted in each pot. Barnyard grass and Shan Herui European seeds, various annual weeds, chinese cypress leaf and maternal weeds seeds, perennial grass, seeds of "Hotarul" (scirpus juncoides) grass were mixed with dry paddy soil and added to the topsoil. When barnyard grass generates 0.5-1.0 leaves, emulsifiable concentrate (prepared in preparation example 2) containing a preset concentration is added into soil drop by using a dropper. After 21 days, phytotoxicity and herbicidal effect of the herbicide on rice were determined. The measurement results are shown in Table 3. The values shown in table 3 are based on the following criteria:

5 complete inhibition

4:80% Inhibition

3:60% Inhibition

2:40% Inhibition

1:20% Inhibition

0 No effect

Injection 1 comparison of Compounds

Number 1

Injection 2 comparison Compounds

Number 2

Injection 3 comparison Compounds

Number 3

Use example 2 (use before weed emergence)

The rice field soil in the greenhouse was filled in each pot with a surface area of 1/5000 acre. Barnyard grass and Shan Herui European seeds, various annual weeds, chinese cypress leaf and maternal weeds seeds, perennial grass, seeds of "Hotarui" (Scripus juncoides) grass were mixed with dry paddy soil and added to the topsoil. Wedge-shaped tubers and FLAT SEDGE were transplanted to face perennial grass. Thereafter, the emulsifiable concentrate having a predetermined concentration (prepared as in preparation example 2) was added dropwise to the soil with a dropper. 3 days later, transplanting rice seedlings with a height of 2-3 cm (calculated from surface soil) and 3 leaves, and measuring phytotoxicity and weeding effect of the herbicide on rice after 15 days later, wherein the measurement results are shown in Table 4, and the standard of the numerical values listed in Table 4 is the same as that of the application example 1.

Injection 4: comparison compound:

Number 4

Use example 3

The pots with a surface area of 1/2500 acre are filled with plateau soil in the greenhouse. Seeds of soybean, corn, large crabgrass, green gray amaranth and "Oinutade" (polygonum nodosum) were sown in each pot.

When the herbicide is used before the weeds grow out, the herbicide can be added 24 hours after sowing, and the herbicide dosage is 30 a.i g/10 acre. On the other hand, when the herbicide is used after the weeds grow, namely, when the soybean, the corn and the weeds grow 2-3 leaves, 3-4 leaves and 2-2.5 leaves respectively, the herbicide is added, and the herbicide dosage is 30 a.i. g/10 acre. The herbicide of the present invention was used by diluting an emulsifiable concentrate (prepared in preparation example 2) containing a predetermined concentration with 15 liters of water (per pot of plateau soil), then sprinkling the herbicide in the soil with a glass sprayer, and after 14 days, observing the herbicidal effect. After 30 days, phytotoxicity to rice was observed, and the results obtained are shown in Table 5, and the standards for the values listed in Table 5 are the same as those used in use example 1.

Use example 2 (use before weed emergence)

The rice field soil in the greenhouse was filled in each pot with a surface area of 1/5000 acre. Barnyard grass and Shan Herui European seeds, various annual weeds, chinese cypress leaf and maternal weeds seeds, perennial grass, seeds of "Hotarui" (Scripus Juncoides) grass were mixed with dry paddy soil and added to the topsoil. Wedge-shaped tubers and FLAT SEDGE were transplanted to face perennial grass. Thereafter, the emulsifiable concentrate having a predetermined concentration (prepared as in preparation example 2) was added dropwise to the soil with a dropper. 3 days later, transplanting rice seedlings with a height of 2-3 cm (calculated from surface soil) and 3 leaves, and measuring phytotoxicity and weeding effect of the herbicide on rice after 15 days later, wherein the measurement results are shown in Table 4, and the standard of the numerical values listed in Table 4 is the same as that of the application example 1.

Claims (7)

1. A herbicide composition comprising an active ingredient, a surfactant and a solvent, wherein the active ingredient is a compound of the following chemical formula I:

(I) In the formula, R represents -OR ¹ , wherein R ¹ is a straight or branched alkyl group substituted by at least one of a hydroxyl group and a hydrocarbyloxy group, or R ¹ is a straight or branched alkyl group substituted by at least one of a carboxyl group and a functional group derived therefrom, The active ingredient, surfactant and solvent are present in the composition in amounts of 5-30%, 10-50% and 40-85% by weight of the composition, respectively. 2. A herbicidal composition according to claim 1, wherein R ¹ is a straight or branched chain alkyl group substituted by a hydrocarbyloxy group. 3. A herbicidal composition according to claim 1, wherein R ¹ is a straight or branched chain alkyl group substituted with at least one of a carboxyl group and a functional group derived therefrom. 4. A herbicidal composition according to claim 1, wherein R ¹ is a straight or branched chain alkyl group substituted by a hydroxy group. 5. A herbicide composition according to claim 1, wherein the active ingredient is at least one compound selected from the group consisting of: 1-Methyl-2-methoxyethyl 2-nitro-5-(2′-chloro-4′-trifluoromethylphenoxy)phenyl acetate, 2-Methoxyethyl 2-nitro-5-(2′-chloro-4′-trifluoromethylphenoxy)phenylacetate, 2-Hydroxyethyl 2-nitro-5-(2′-chloro-4′-trifluoromethylphenoxy)phenylacetate, 1-methoxycarbonylethyl 2-nitro-5-(2′-chloro-4′-trifluoromethylphenoxy)phenylacetate, and 1-Ethoxycarbonylethyl 2-nitro-5-(2′-chloro-4′-trifluoromethylphenoxy)phenylacetate. 6. A method for destroying noxious weeds, which method comprises spraying directly onto said weeds a herbicide composition comprising an active ingredient, a surfactant and a solvent, wherein the active ingredient is a compound of the following formula I: (I) In the formula, R represents -OR ¹ , wherein R ¹ is a straight or branched alkyl group substituted by at least one of a hydroxyl group and a hydrocarbyloxy group, or R ¹ is a straight or branched alkyl group substituted by at least one of a carboxyl group and a functional group derived therefrom, The active ingredient, surfactant and solvent are present in the composition in amounts of 5-30%, 10-50% and 40-85% by weight of the composition, respectively. 7. A method according to claim 6, characterized in that the compound is applied to the paddy field at a dosage of 0.5-100 g/10 acres.