CN1005377B - Herbicidal composition and method for destruction undesirable weeds - Google Patents

Abstract

The present invention relates to pphenylacetate, thioesters and acid amide with the following molecular formula, a preparing method thereof, herbicide and a method for killing injurious weeds. The herbicide composed of the compounds can be used for selectively controlling the injurious weeds in crops.

Description

Herbicidal composition and eliminate the method for injurious weed with it

The present invention is the relevant a kind of new compound of selecting activity of weeding that has, a kind of novel preparation method of this compound, (what can be used for various crops a kind ofly has effective herbicide and an a kind of new method of eliminating injurious weed with this new herbicides to a kind of new herbicides of being made up of this new compound.In more detail, the present invention be relevant 2-nitro-5-(2 '-chloro-4 '-the trichloromethyl phenoxy group) phenylacetate, thioesters and acid amides, the preparation method of this compounds, a kind of weed killer herbicide formed by this compounds and the method for eliminating injurious weed with this weed killer herbicide.

Up to now, well-known a kind of weed killer herbicide contain 4-nitro-2 '-chloro-4 '-trifluoromethyl phenyl ether (as the property composition), on the 3-position of this compound, a substituting group is arranged, as hydroxyl, alkoxyl, alkyl, halogen atom, amino, cyano group, carboxyl, alcoxyl carboxyl, carboxyalkyl, alkanoyloxy, carbamyl oxygen base or other diphenyl ether derivative, be commonly referred to ether-type herbicide (referring to, as Japanese patent application, publication number is 58-25641/1983, and corresponding US is 3789276,3888932,3928416 and 4076741).

, any known ether-type herbicide is the good and poor selectivity of activity of weeding often, and perhaps selectivity is good and activity of weeding is poor.Therefore, this class weed killer herbicide can not effectively and fast be controlled the growth of predetermined kind weeds.

Desirable weed killer herbicide also should satisfy following condition except that having above-mentioned good activity of weeding and high selectivity: this weed killer herbicide must be very low to the toxicity of homeothermia animal; The whole growth phase crops all can apply this weed killer herbicide; And, apply weed killer herbicide after, its can be as early as possible decomposes, thus contaminated soil not.Yet, up to the present, also do not find the desirable diphenyl ether herbicide that can satisfy above-mentioned requirements.

Purpose of the present invention:

In view of the foregoing, the inventor furthers investigate for a kind of novel ether-type herbicide of development, this new herbicides does not have the shortcoming of common ether-type herbicide, and the activity of weeding that has selectivity and highly select, that is to say, this new herbicides is foolproof for crops, and can remove any useless plant that grows with crops apace, throughout the growing season can use this weed killer herbicide continuously crops.Result of study found 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) new compound of phenylacetate, thioesters and acid amides, the weed killer herbicide of being made up of this new compound can satisfy above-mentioned requirements, this is a kind of weed killer herbicide through improvement, even this weed killer herbicide consumption seldom, to various crops, all very useful as cotton, soybean, corn, wheat and paddy rice.On this newfound basis, the inventor has finished the present invention.

Therefore, an object of the present invention is to provide 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) new compound of phenylacetate, thioesters and acid amides, this compound has the activity of weeding that a kind of height is selected.

Second purpose of the present invention provides a kind of new method of this compound of preparation.

The 3rd purpose of the present invention provides a kind of novel weed killer herbicide, and this new herbicides has a kind of high selectivity, can eliminate the shortcoming that common ether-type herbicide has, and can be applicable to various crops (no matter these crops vegetative period how).

The 4th purpose of the present invention provides a kind of new method of using this new herbicides to eliminate injurious weed.From describe in detail down and appended claim, those skilled in the art will come into plain view to above-mentioned purpose of the present invention and other purpose, characteristics and advantage.

One of purpose of the present invention provides a kind of novel compound, and this compound can be represented with following molecular formula:

R represents-OR in the following formula ¹,-SR ²Or

R wherein ¹Be unsaturated hydrocarbon residue a kind of aliphatic olefin(e) acid or acetylenic acid, a kind of alicyclic residue, a kind of aromatic hydrocarbons residue, a kind of araliphatic hydrocarbon residue, straight or branched alkyl or alkenyl, this alkyl or alkenyl can be replaced by following groups (at least a): halogen atom, cyano group, hydroxyl, sulfydryl, oxyl, acyloxy, acyl sulfenyl, one replace or unsubstituted amino and a heterocyclic group, or by an at least a straight or branched alkyl that replaces of the carboxyl and the functional group of deriving thereof;

R ²Be a kind of hydrocarbon residue, straight chain or lose alkyl or alkenyl that this alkyl or alkenyl can be replaced by following groups (at least a); Halogen atom, cyano group, hydroxyl, sulfydryl, oxyl, sulfenyl, epoxy radicals, acyl group, acyloxy, acyl sulfenyl, one replace or unsubstituted amino and a heterocyclic group or the straight or branched alkyl that is replaced by carboxyl and the functional group (at least a) of deriving thereof; R ³And R ⁴Be a hydrogen atom, an oxyl or a hydrocarbon residue respectively, said hydrocarbon residue can by a halogen atom, a hydroxyl and a cyano group (at least a) replaces or not replacement, and this hydrocarbon residue can (at least) contain or not contain a kind of mixing atom (promptly being inserted with an oxygen atom or a sulphur atom in the middle of the carbon atom of two vicinities).Surprisingly, a kind of standby or reserve weed killer herbicide that above-claimed cpd generates (comparing) with the weed killer herbicide that the generalization compound with similar structures generates, even its consumption seldom, in the cultivation of various crops, be very effective for the control of injurious weed.

The characteristic of The compounds of this invention is attributable to this compound a group of representing with R (shown in above-listed molecular formula).For instance, in the generalization compound, be a more rudimentary alkyl corresponding to the locational group of above-mentioned R group, as methyl, it is without any substituting group.On the contrary, compound of the present invention is the compound that the above-listed molecular formula of a kind of usefulness is represented, wherein R represents OR ¹,-SR ²Or , here, R ¹It is unsaturated hydrocarbon residue a kind of aliphatic olefin(e) acid or acetylenic acid, a kind of alicyclic residue, a kind of aromatic hydrocarbons residue, a kind of araliphatic hydrocarbon residue, straight or branched alkyl or alkenyl, this alkyl or alkenyl can be replaced by following groups (at least a): a halogen atom, a cyano group, a hydroxyl, a sulfydryl, an oxyl, an epoxy radicals, an acyl group, an acyloxy, an acyl sulfenyl, one replaces or unsubstituted amino and a heterocyclic group, or by an at least a straight or branched alkyl that replaces of the carboxyl and the functional group of deriving thereof;

R ²Be a kind of hydrocarbon residue, straight or branched alkyl or alkenyl, this alkyl can be replaced by following groups (at least a): halogen atom, cyano group, hydroxyl, sulfydryl, oxyl, oxyl, hydrocarbon sulphur, epoxy radicals, acyl group, acyloxy, acyl sulfenyl, one replace or unsubstituted amino and a heterocyclic group or the straight or branched alkyl that is replaced by carboxyl and the functional group (at least a) of deriving thereof; R ³And R ⁴Be a hydrogen atom, an oxyl or a hydrocarbon residue respectively, said hydrocarbon residue can by a halogen atom, a hydroxyl and a cyano group (at least a) replaces or not replacement, and this hydrocarbon residue can (at least) contain or not contain a kind of mixing atom (promptly being inserted with an oxygen atom or a sulphur atom in the middle of the carbon atom of two vicinities).

Above-mentioned R ¹And R ²Suitable example be: pi-allyl, 2-butynyl, cyclopenta, cyclohexyl, phenyl and benzyl.In these groups, contain under the situation of an arylated alkyl group, they can be the group of a replacement.

Unsaturated hydrocarbon residue above-mentioned olefin(e) acid or acetylenic acid can be a kind of straight chain or a kind of side chain.Above-mentioned suitable halogen atom is: for example: fluorine atom, chlorine atom, bromine atoms and iodine atom.Oxyl is a kind of group with a kind of like this structure, and promptly the hydrogen atom of hydroxyl is replaced by the hydrocarbon residue, this hydrocarbon residue such as alkyl, alkenyl, alkynyl, aryl, aralkyl.If alkyl has an aromatic ring, this aromatic ring can have a substituting group again.

Above-mentioned suitable oxyl is: for example, and methoxyl group, ethyoxyl, allyloxy, propionyloxy, benzyloxy, neighbour-methyl benzyloxy and similar group.Sulfenyl is the group with a kind of like this structure, and promptly the oxygen atom of oxyl is by the displacement of a sulphur atom.Above-mentioned suitable hydrocarbons sulfenyl is: for example, and methyl mercapto, ethylmercapto group, allyl sulfenyl, benzylthio and similar group.Above-mentioned acyl group, acyloxy and acyl sulfenyl can be aliphatic group or aromatic group, and they can have a substituting group.The object lesson of these groups is: acetyl group, propiono, benzoyl, acetoxyl group, butyryl acyloxy, acetylthio and similar group.The amino that replaces can be a single substituting group or a disubstituted group.Above-mentioned suitable substituted-amino, for example, monomethyl amino, dimethylamino, an ethylamino, diethylamino, Methylethyl amino, methyl methoxy base amino and similar group.

Above-mentioned heterocyclic group can be a kind of complete unsaturated form or is saturated form partially or even wholly.Above-mentioned suitable heterocyclic group is: for example, and the group of deriving by thiophene, furans, pyrroles, pyridine quinoline, piperazine, imidazoles and hydride thereof.

In addition, above-mentioned R ¹And R ²Suitable example be a kind of straight or branched alkyl, it has as substituent a kind of carboxyl or its a kind of functional group of deriving.

" derived functionalized groups " this speech is used for representing in a carboxylic acid compound, to have only the group that produced by a carboxyl carboxyl to take place to transform and just can obtain this group, usually they is divided in the class identical with carboxyl.The example of these groups is: above-mentioned a kind of carboxylate, carboxylate, halogenation sulfenyl, amide groups and analog.Be easy to according to a conventional method obtain these groups by a carboxyl.These groups can be transformed into original carboxyl by hydrolysis.In compound of the present invention, R ¹And R ²Example be the straight or branched alkyl, it contains a substituting group, its molecular formula is as follows:

In the formula, R ⁶Be a hydrogen atom, replacement or unsubstituted alkyl, one replace or the ammonium of unsubstituted alkenyl, alkynyl, a kind of alkali metal, a kind of alkaline earth metal (in the ratio of monatomic base earth metal), ammonium or the replacement of a kind of alkyl.

R in the formula ⁶And R ⁷Be a hydrogen atom, an alkyl or an alkoxyl respectively.

On demand, be included in a replacement or unsubstituted alkyl or alkenyl and (use R ⁵Expression) the substituent example in is halogen atom, cyano group, lower alkoxy, alkenyloxy, alkylthio group, alkenyl thio, alkynes alkenylthio group, hydroxyl, aliphatic acyl, carboxylic acid group, alkoxy carbonyl, alkoxyl alkoxy carbonyl, amino carbonyl and similar group.

In addition, R ²Suitable example be a straight or branched alkyl such as methyl, ethyl, propyl group, butyl and isopropyl.

Above-mentioned R ³And R ⁴Suitable example can be a hydrogen atom, a kind of hydrocarbon residue, as aliphatic hydrocarbon residue, aromatic hydrocarbons residue, araliphatic hydrocarbon residue or alicyclic residue or oxyl (wherein, above-mentioned hydrocarbon residue and an oxygen atom bonding) mutually.In this connection, above-mentioned aliphatic hydrocarbon residue can be saturated or unsaturated, or be straight chain or side chain a kind of.Be inserted with an oxygen atom or a sulphur atom two adjacent carbon atoms centres (its part at least) to form an ehter bond or a thioether bond.Above-mentioned hydrocarbon residue can be replaced by a halogen atom, hydroxyl and a cyano group (at least a).

Above-mentioned R ³And R ⁴Example be (mentioning): hydrogen atom, methyl, ethyl, just-propyl group, isobutyl group, just-amyl group, just-hexyl, n-heptyl, the 2-acrylic, the 2-propyl group, the 3-cyclobutenyl, suberyl, cyclohexyl, naphthyl, tolyl, benzyl, the 2-methoxy ethyl, the 2-ethoxyethyl group, the 3-methoxy-propyl, the 2-butoxyethyl group, 2-methyl mercapto ethyl, the 2-butyl ethyl, 2-benzyl mercapto ethyl, base in the 2-hydroxyl, the 2-hydroxybutyl, the 3-hydroxypropyl, the 2-chloroethyl, the 2-bromoethyl, right-chlorphenyl, the cyanogen methyl, 2-cyanogen methyl, methoxyl group, ethyoxyl, allyloxy, benzyloxy and similar group.

Object lesson with the The compounds of this invention of above-mentioned molecular formula (I) expression is as follows:

S-methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-1-Methylethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-2-acrylic 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-2 acrylic 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-cyclopropyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-cyclohexyl 2-nitro-5-(2 '-chloro-4 '-trifluoro propyl phenoxy group) benzene thiacetate,

2-acrylic 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate.

2-propynyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

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

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

S-phenyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-4-chlorphenyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-4-aminomethyl phenyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-4-methoxyphenyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-benzyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

1-methyl-2-acrylic 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

4-methoxy-benzyl phenyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-chloroethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

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

2-ethoxy 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

S-2-chloroethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-1-methyl-2 ethoxy 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

2-(4-methoxyl group benzyloxy base) phenylacetate ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant),

2,3-glycidyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

Methyl carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

S-2-methyl carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

2-phenylcarbonyl group ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-acetate ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-benzoyloxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

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

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

1-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-methyl-2-methyl hydroxyl oxygen base ethyl second-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

3-chloro-2-acrylic 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

N-methyl-4-piperidino methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-oxinane ylmethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

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

The 2-(2-thienyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

The 3-(3-pyridine radicals) propyl group 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

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

4-aminomethyl phenyl 2-nitro-5-(2 ', 6 '-two chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-trifluoroacetic acid base ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2(2-chlorobenzoic acid base) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-bromomethyl carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-(3-methoxyphenyl carbonyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate

2-acetyl sulphur ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-benzoyl sulphur ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-ethoxyethyl group 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

The 2-(2-propenyloxy group) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-(2-propine oxygen) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-phenyl methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

3-methoxy-propyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

3-ethoxy-c 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate.

The 3-(1-methyl ethoxy) propyl group 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

The 3-(2-propenyloxy group) propyl group 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-methyl-2-methyl ethoxy 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-ethyoxyl-1-Methylethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-methyl-2-(1-methyl ethoxy) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-methyl-2-(2-propenyloxy group) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

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

Ethylmercapto group methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-methyl ethylmercapto group methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-propylene sulfenyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-propine sulfenyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-methyl sulphur ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-ethylmercapto group ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-(2-propylene sulfenyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-(2-propine sulfenyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

S-methoxy 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-ethoxyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-2-ethoxyethyl group 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

The S-2-(2-propenyloxy group) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the benzene thiacetate,

S-3-methoxy-propyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

S-1-methyl-2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the benzene thiacetate,

S-2-methylmercaptoethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

2,2,2-trifluoroethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-chlorine 2-acrylic 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

Carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

Methoxycarbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

Ethoxy carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-isopropoxy carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

S-ethoxy carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

2-ethoxy carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-methoxycarbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-ethoxy carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

S-1-isopropoxy carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

2-chlorine ethoxycarbonylmethyl group 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-(2-bromoethyl carbonyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-cyanogen methoxycarbonyl group ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-(2-methoxy ethoxy carbonyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

S-2-ethoxy ethoxy carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

1-(2-allyloxy ethoxy carbonyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-(2-alkynes propoxyl group ethoxy carbonyl) phenylacetate ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant),

2-methyl mercapto ethoxy base carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-allyl sulfenyl ethoxy carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-(2-alkynes rosickyite base oxethyl carbonyl) ethyl-nitro-5-(2 ', 6-two chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-(2-alkyl ethoxy carbonyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-acetyl group methoxycarbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-(2-acetate ethoxy carbonyl) ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid guanidine-acetic acid base) propionic acid,

Carboxyl methyl 2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid base) propionic ester,

Methoxycarbonyl methyl 2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid base) propionic ester,

Ethoxy carbonyl methyl 2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid base) propionic ester,

2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid guanidine-acetic acid yl acetate,

Amino carbonyl methyl 2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid base) propionic ester,

1-allyloxy carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

S-alkynes propoxycarbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene thiacetate,

2-chloropropene oxygen base carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

Sodium 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid yl acetate,

Potassium 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetyl thio acetic acid esters,

Sodium 2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid base) propionic ester,

Ammonium 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid yl acetate,

Ammonia first carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

N-methyl-N-methoxyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid yl acetamide,

N-methyl-2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid base) propionamide,

N, N-dimethyl-2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid base) propionic acid amine,

N-methyl-3-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid ester) propionamide,

Sodium 2-(2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetic acid base) the propionyloxy acetic acid esters,

3-methoxycarbonyl propyl group 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-methyl isophthalic acid-ethoxy carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-methyl-3-methoxycarbonyl propyl group 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl-acetamides,

N-methyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-just-butyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-is different-propyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-chloroethyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-(2-hydroxyl butyl)-2 '-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-methoxy-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-cyanoethyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-pi-allyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-(3-chloro-2-acrylic)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-propinyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-(4-benzyl chloride base)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-2-2-dimethyl benzyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-(3, the 4-dichlorophenyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(4-aminomethyl phenyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-2-naphthyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N, N-dimethyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-phenyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-cyanoethyl)-N-phenyl-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-is different-butyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-just-nonyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-ethoxy)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-just-butoxymethyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-(2-just-the propoxyl group ethyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-methoxy-propyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-bromoethyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-ethoxy carbonyl benzyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-cyanogen methyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-methoxyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-ethyl-N-just-propoxyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-pi-allyl-N-methoxyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-ethyl-N-allyloxy-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-just-propyl group-N-alkynes propoxyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-ethoxycarbonyl methoxy-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-(2-cyanogen ethyoxyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N, N-diallyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-(2-2 ,-diethoxy ethyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-ethoxyethyl group)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-(4-methoxyl group-2 thiazolinyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-(3-chloro-2-propenyloxy group)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-ethyl-N-(2-methoxycarbonyl ethyoxyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-(2-chloroethoxy)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

The N-(2-methylmercaptoethyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-(2-benzylthio ethyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-(2-allyl sulfenyl ethyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-(2-methyl mercapto ethoxy base)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-(4-methyl mercapto phenyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-methyl-N-(4-allyl sulfydryl benzyl)-2 '-nitro-5 '-(2 " chloro-4 "-4-trifluoromethylphenopendant) phenyl acetamide,

N-ethyl-N-ethyoxyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide,

N-ethyl-N-methoxyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide and analog.

More than all compounds all be novel compound, these compounds are all unexposed mistake in any document.The method for making of these compounds, for example, method A and method B are described below:

Method A:

Another object of the present invention provides the preparation method of molecular formula for the compound of (I):

R defines as above in the formula,

The method for making of this compound comprises the following steps:

(1) under 90 °-180 ℃ temperature, between heating one hydroxyphenyl acetate potassium ester and 3-chloro-4-halogeno-benzene trifluoride with obtain 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid;

(2) (these compounds comprise: a kind of alcohol, a kind of amine, a kind of mercaptan and a kind of halide to make the acid that makes and following at least a compound reaction, it is that R(as above defines that these compounds all have molecular formula) substituting group) to obtain a kind of compound, its molecular formula is as follows:

（Ⅱ）

The definition of R as above in the formula.

(3) making molecular formula is that the compound of (II) is nitrated

In above-mentioned steps (1), can in a kind of solvent (as dimethyl alum), react.Reaction temperature is 19 °～180 ℃, is preferably 120 °～150 ℃.Add potash can improve 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) productive rate of phenylacetic acid.In above-mentioned steps (2), produce dehydration, desalination or similarly effect by acid and a kind of alcohol, a kind of amine, a kind of thiamines alcohol or a kind of halide reaction.In above-mentioned steps (3), with a kind of common nitrating agent, as acetyl nitrate, it is that the compound of (II) is nitrated to make a kind of compound of molecular formula of the present invention for (I) that the mixed acid of the potassium nitrate in sulfuric acid, sulfuric acid and nitric acid and tetrafluoro boric acid nitrous can make molecular formula.Usually be about-20 ℃ to 100 ℃ temperature, be preferably in carry out under the temperature that is about-10 ℃～50 ℃ nitrated.As required, can be at a kind of inert organic solvents as 1, carry out nitrated in 2-dichloroethane and other chloro-hydrocarbons.

Method B:

Another object of the present invention provides the preparation method of molecular formula for the compound of (I), and this method comprises makes 2-chloro-4-trifluoromethyl phenolic compounds (molecular formula is as follows)

（Ⅲ）

M is an alkali metal in the formula

With molecular formula be the 2-nitro-4-halogenophenyl acetic acid compound of (N) or 2-nitric acid-4-halogeno-benzene ethyl thioglycollic acid compound reaction

（Ⅳ）

In the following formula definition of R as above, Y is a halogen group.

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

As mentioned above, to make molecular formula be the alkali metal salt of 2-chloro-4-trifluoromethyl phenol of (III) and molecular formula for the phenylacetic acid of (IV) or the reaction alive of deriving of benzene sulphur acetate can make compound of the present invention, carries out this reaction usually under the temperature of 0 °～250 ℃ (being preferably in 60 ℃～180 ℃).As required, can as tetramethylene sulfone, dimethyl sulfoxide (DMSO), N, carry out this reaction in dinethylformamide, hexamethylphosphorictriamide and other inert organic solvents at a kind of suitable solvent.

Above-mentioned method A and B are of the present invention specifying, and should be understood that these methods can not limit the present invention.Compound of the present invention can be made with the various amending methods that are used to prepare the common known method of similar compound.

The compounds of this invention for prevention and eliminate long in the rice field activity of weeding of weeds illustrate as followsly, compound of the present invention can be used for rice field (comprise before the rice seedlings rice transplanting and after the rice transplanting) effectively in over a long time.Particularly, this compound can effectively and promptly be used to eliminate barnyard grass, and this barnyard grass is long a kind of harmful grassy weed in the rice field.And if when eliminating weeds in the rice field effectively with an amount of The compounds of this invention, this compound does not have tangible phytotoxicity to paddy rice.In addition, compound of the present invention also has excellent herbicidal for long many weeds in the rice field as single Hao Rui (mo no choria), ratala spp, Elatine ambigua weeds and the sea green genus of Fu Laoer weeds.Consumption that it should be noted that The compounds of this invention is more much lower than the consumption of common weed killer herbicide, (consumption 0.5～100 gram was/10 ares usually when ester class of the present invention and sulfur ester were used for the rice field, be preferably/10 ares of 1.5～50 grams), have excellent herbicidal.(consumption is/10 ares of 1～100 grams usually, is preferably/10 ares of 5～50 grams) also had excellent herbicidal when amides compound of the present invention was used for the rice field.The consumption of these compounds and common used common herbicides for use in paddy, as 2,4,6-three chloro-1-(4 '-nitric acid phenoxy group) benzene, 2,4-two chloro-1-(3 '-methoxyl groups-4 '-the nitric acid phenoxy group) benzene and methyl 2-nitro-5-(2 '-chloro-4-Trichlorophenoxy), it is quite low that the consumption of benzoic ether (/ 10 ares of 200～250 grams) is compared.As mentioned above, obviously, the activity of weeding of The compounds of this invention and common weed killer herbicide height.

In addition, compound of the present invention not only has very high activity of weeding to the weeds in the rice field, and the weeds on the plateau are also had very high herbicidal activity.

Compound of the present invention, be usage amount seldom, all has high activity of weeding for following multiple weeds, these multiple weeds, as lamb's-quarters (Iambsquarters), Velvetleat, the coffee grass, a high kind Potato drafts a document, kitchen garden, the thorn bur, * the fruit common rush (Sicklepod), datura, black nightshade, the knotweed grass, common agrimony, peppergrass (Peppergrass), marestail, Japanese metaplexis herb is drafted a document (cllmbing milkweed), chickweed, buckwheat all grass (bindweed) and similar weeds, and belong to weeds gramineous as, big * holds grass, yard grass, green meadow pine, annual bluegrass and similar weeds.It should be noted that a spot of compound of the present invention also has high activity of weeding for soybean Tanaka's these injurious weeds such as Velvetleat, datura, thorn bur, lamb's-quarters (Iambsquarters) and similar weeds.The characteristic of The compounds of this invention shows that not only multiple kinds of crops such as soybean and cotton are had high selectivity, and for belonging to crops gramineous, as paddy rice, corn, wheat and similar crops, grow preceding or weeds grow the back and use and all have high selectivity in weeds.Because compound of the present invention has purposes and excellent herbicidal widely, it also can be used as pasture, orchard, lawn and non-cropland a kind ofly has an effective herbicide.

Methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate is and a kind of known compound of The compounds of this invention structural similarity, and this compound has such shortcoming, promptly paddy rice and barnyard grass grass is not had the kind selectivity.On the other hand, compound of the present invention (not as common diphenyl ether herbicide) has very high kind selectivity for belonging to plant gramineous except that having excellent herbicidal.Therefore, we can say that compound of the present invention is a kind of very effective, useful weed killer herbicide.

As mentioned above, obvious compound of the present invention can be used for the weeds of selective elemination length in crops such as paddy rice, cereal such as barley and wheat, corn, soybean and cotton.And compound of the present invention can be used before weeds grow He after growing.

When using compound of the present invention, its amount ranges is very wide, and this depends on the applying method of this compound, the weeds kind that the applied field of this compound is to be eliminated in one's power.For example, ester class of the present invention and sulfur ester, its consumption are/10 ares of 0.5～100 grams, are preferably/10 ares of 1.5～50 grams.Amides compound of the present invention, its consumption are/10 ares of 1～100 grams, are preferably/10 ares of 5～50 grams.

During practical application, compound of the present invention directly can be used as weed killer herbicide or be made into various preparations, but as wet powder, emulsible concentrate, particle, pulvis and analog, therefore, a further object of the invention provides a kind of weed killer herbicide, the molecular formula that this weed killer herbicide contains herbicidally effective amount for a kind of compound (making a kind of herbicidal active component) of (I) and with a kind of agricultural on carrier applicatory mix

（Ⅰ）

The definition of R as above in the following formula.

When compound of the present invention is made into above-mentioned various preparation, used solid carrier can be: the mineral powder (for example, kaolin, bentonite, clay, imvite, talcum, diatomite, mica, vermiculite, gypsum, calcium carbonate, apatite and analog), the plant powder (for example, big beans, wheat flour, wood meal, tobacco leaf powder, heavy powder, crystalline cellulose and analog) high polymeric compound (as Petropols, polyvinyl chloride, ketone resin and analog), also has aluminium oxide and multiple wax.As liquid-carrier, mentioned, alcohols (methyl alcohol for example, ethanol, butanols, 1, the 2-ethylidene glycol, benzylalcohol and similarly pure), aromatic hydrocarbons (as, toluene, benzene, dimethylbenzene and similar benzene), chlorinated hydrocabon (chloroform, carbon tetrachloride, monochloro-benzene and analog), ether (diox, oxolane and analog), ketone (acetone, methyl ethyl ketone, cyclohexanone and analog), ester class (ethyl acetate, the ester of butyl acetate and analog) amide-type (N, N-dimethylacetylamide and analog), nitrile (acetonitrile and similar nitrile), ether alcohol (ethylene glycol ethyl ether and analog) and water.

Make The compounds of this invention produce emulsification, dispersion, diffusion and the used surfactant of similar effect and can be nonionic, anionic, cationic and zwitterionic surfactant.The object lesson of used in the present invention surfactant is a kind of polyoxyethylene alkyl ether, a kind of polyoxyethylene alkyl aryl ether, a kind of polyoxyethylene fatty acid ester, a kind of dehydration sorb (sugar) alcohol ester fat acid esters, a kind of polyoxyethylene dehydration sorb (sugar) alcohol ester fat acid esters, a kind of ethylene oxide polymer, a kind of propylene oxide polymer, a kind of polyxyethylated phosphate, a kind of soap, a kind of alkyl sulfate, a kind of alkylsulfonate, a kind of alkylaryl sulfonates, a kind of alkylphosphonic, a kind of laureth sulfate, a kind of quaternary ammonium salt and a kind of alkoxyamine.Should be noted that can be used for surfactant of the present invention has more than and be limited to above-claimed cpd.Also can make a kind of auxiliary additive with gelatin, casein, mosanom, starch, agar, polyvinyl alcohol and analog as required in the present invention.

In addition,, compound of the present invention use can be mixed with other herbicidal active components, in some cases, a kind of synergistic effect can be produced in order to improve weeding ratio.For example, following ingredients is mixed mutually with compound of the present invention:

(A) phenoxy group type weed killer herbicide:

The 2,4 dichloro benzene ethoxyacetic acid; 2-methyl-4-tomatotone; Butyl 2-(4-(5-trifluoromethyl-2-pyridine oxygen base) propionic acid (comprising its ester class and salt); Ethyl 2-(4-(6-chloro-2-quinoxalinyl) phenoxy group) propionic ester etc.

(B) ether-type herbicide:

2,4 dichloro benzene base 4 '-the nitro phenylate; 2,4,6-trichlorophenyl 4 '-the nitro phenylate; 2,4 dichloro benzene base 4 '-nitro-3 '-the methoxyl group phenylate; 2,4 dichloro benzene base 3 '-methoxycarbonyl-4 '-the nitro phenylate; 2-chloro-4-trifluoromethyl 3 '-ethyoxyl-4 '-the nitro phenylate; 5-(2-chloro-4-trifluoromethyl) phenoxy group)-2-nitrobenzoic acid sodium; Deng.

(C) triazine type weed killer herbicide:

2-chloro-4,6-pair-ethylamino-1,3,5-triazines; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazines; 2-methyl mercapto-4,6-pair-ethylamino-1,3,5-triazines; Deng.

(D) urea type weed killer herbicide:

3-(3, the 4-dichlorophenyl)-1-methoxyl group-1-methyl urea; 3-(2,2,2-2-three fluoro-*-tolyls)-1, the 1-dimethyl urea; 3-(4-(4-methylbenzene ethyoxyl-phenyl)-1-methoxyl group-1-methyl urea; 3-(5-t-butyl-3,4-thiadiazoles-2-yl)-4-hydroxyl-1-methyl-2-imidazolone; Deng.

(E) carbamate type weed killer herbicide:

Isopropyl N-(3-chlorphenyl) carbamate; Methyl N-3, the 4-dichlorophenyl) carbamate; 4-chloro-2-butyl N-(3-chloro-phenyl) carbamate; Deng.

(F) thiol-carbamate type weed killer herbicide:

The S-ethyl n, N-hexamethyl alkenylthio group carbamate; S-(4-chloro-benzyl) N, N-diethyl sulfide aminocarbamic acid ester; S-ethyl propyl sulfide aminocarbamic acid ester; Deng.

(G) anilide type weed killer herbicide:

2, the 4-stam 34; N-methoxy-2 ', 6 '-diethyl-2-chloroacetanilide; 2-chloro-2 ', 6 '-diethyl-N-(butoxymethyl)-antifebrin; 2-chloro-2 ', 6 '-diethyl-N-(propoxyl group ethyl)-antifebrin; The 2-(2-naphthoxy) propionanilide; Deng.

(H) uracil type weed killer herbicide:

The 5-bromo-3-second month in a season-butyl-6-methyluracil; 3-cyclohexyl-5,6-trimethyl alkene uracil; Deng.

(I) pyridine salt type weed killer herbicide:

1,1 '-dimethyl-4,4 '-the pyridine dichloride; 1,1 '-ethene-2,2 '-the pyridine dibromide; Deng.

(J) phosphorus type weed killer herbicide:

The N-((phosphonomethyl)) amion acetic acid; 0-ethyl, 0-(2-nitro-5-aminomethyl phenyl) N-second month in a season-butyl ammonia sulfenyl phosphate; The 0-methyl, 0-(2-nitro-4-methyl benzene) N-isopropyl ammonia sulfenyl phosphate; The S-(2-methyl isophthalic acid, 1-piperidino carbonyl methyl) 0,0-two-just-the propyl disulfide based phosphates; (2-amino-4-methyl phosphino-butyl)-alanyl-alanine-sodium salt; Deng.

(K) toluidines type weed killer herbicide:

2,2,2-three fluoro-2,6-dinitro-N, N-dipropyl-right-toluidines; N-(cyclopropyl methyl)-2,2,2-three fluoro-2,6-dinitro-N-propyl group-right-toluidines; Deng.

(L) other weed killer herbicide:

5-t-butyl-3-(2,4-two chloro-5-isopropyl phenyls)-1,3,4-oxadiazole *-2-ketone; 3-isopropyl-2,1,3-benzimidazoles dinonyl-4,2,2-dioxide; The 2-(2-naphthoxy)-and N, N-diethyl propionamide; 3-amino-2, the 5-dichlorobenzoic acid; 4-dichloro-benzoyl base)-1,3-dimethyl pyrazole-5-base-right-toluene fulfonate; 2-chloro-N-((4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-yl) amino carbonyl)-phenylamino sulphonyl; Methyl 2-((4,6-dimethoxypyridin-2-yl)-amino based aminosulfonyl ylmethyl) benzoic ether; N-(1-methyl isophthalic acid-phenethyl)-and 2-bromo-3, the 3-amide dimethyl butyrate; 2-(1-N-allyloxy-amino butylidene)-4-methoxycarbonyl-5,5-dimethyl cyclohexane-1,3-diketone sodium salt; 2-(1-(ethoxy imino) butyl)-the 5-(2-ethylsuleenyl propyl)-3-hydroxyl-2-cyclohexane-1-ketone; Deng.

Above-mentioned weed killer herbicide only as an example, they should not limit the scope of the weed killer herbicide that is used in combination with The compounds of this invention.Weed killer herbicide of the present invention also can be used in combination with agricultural chemicals and the chemical fertilizer of insecticide (as pyrethroid type insecticide), fungicide, plant growth regulator, microorganism.

Except that above-mentioned the object of the invention, the present invention also provides a kind of method of eliminating injurious weed, and this method comprises: the following compound of molecular formula that sprays herbicidally effective amount on weeds

The definition of R as above in the following formula.

This weed killer herbicide is made up of above-claimed cpd (as a kind of active component of weed killer herbicide), also contains carrier applicatory on a kind of agricultural (it defines as above).About above-mentioned " weeding is an amount of weed killer herbicide effectively ", its implication can be known by above explanation and know.The amount ranges of ester of the present invention and thioesters is/10 ares of 0.5～100 grams, is preferably/10 ares of 1.5～50 grams.On the other hand, the consumption of acid amides of the present invention is/10 ares of 1～100 grams, is preferably/10 ares of 5～50 grams.Above-mentioned method can be used for Selective Control and wants injurious weed in the crops.Below will be for some embodiment, in these examples, this reactive compound is adopted with the form of weed killer herbicide, the consumption of weed killer herbicide looks like and is meant a kind of amount of reactive compound with the unit representation of "/10 ares of a.i. grams ", " restraining/10 ares ".

Embodiment:

The present invention will be described in more detail now with reference to example, and these examples are using method when making weed killer herbicide about the preparation method of The compounds of this invention with about The compounds of this invention and result of use.These examples must not be regarded as the restriction of the scope of the invention.

Embodiment 1:

Follow these steps to prepare S-ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) thiophenyl acetic acid esters (for compound N o, 2):

(a) 0.7 gram ethanethio and 1.2 gram triethylamines are dissolved in 20 milliliters of N, in the N-dimethylacetylamide, under 10 ℃ temperature, in the solution that generates, dropwise add 3.5 gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyllacetyl chloride, after treating dropwise to add end, reaction has been carried out 3 hours.After reaction finishes, in reaction mixture, add 50 ml waters, then with extracted with diethyl ether secondary (using 30 milliliters of ether) at every turn.Wash ether layer with water, be placed on drying on the anhydrous sodium sulfate, then evaporation under reduced pressure is removed ether, thereby makes a kind of semi-finished product.With silica gel look splitter (mixed solvent with toluene and n-hexane carries out drip washing) the prepared semi-finished product of purifying.As a result, can make 1.9 gram S-ethyl-3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the thiophenyl acetic acid esters.

(b) with 1.9 gram S-ethyl 3-(2 '-chloro-4 of making in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) the thiophenyl acetic acid esters is added in the 15 gram acetic anhydrides, in ice bath, this mixture is cooled to is lower than 10 ℃.Then, in 5 minutes, slowly add 1.5 gram nitric acid ketone, treat that nitric acid ketone all adds after, reacted 1 hour being lower than under 10 ℃ the temperature, at room temperature reacted again 3 hours then, reactant mixture is injected ice bath, then add 200 milliliters of ether.Add the mixture that a kind of sodium hydrate aqueous solution generates with neutralization.Use the aqueous hydrochloric acid solution acidifying mixture then, tell the extracted with diethyl ether layer, wash with water, and be placed on drying on the anhydrous sodium sulfate, subsequently, under reduced pressure, remove ether to obtain a kind of crystallization semi-finished product by evaporation.With silica gel look splitter (mixed solvent with toluene and acetone carries out drip washing) the prepared semi-finished product of purifying.As a result, can make 1.1 the gram flaxen S-ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) thiophenyl acetic acid esters solid.Its fusing point is 82.5 °～84.2 ℃.

Embodiment 2:

Follow these steps to prepare S-1-methyl-ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene sulphur acetic acid esters (for compound N o, 3):

(a) with 3.3 gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid is dissolved in 30 milliliters of carrene, in water-bath, the solution that generates is chilled to below 10 ℃.Then, add 2.1 gram N, N '-dicyclohexylcarbodiimide (DCC) then, adds 0.8 gram 2-propanethiol.At room temperature reacted 6 hours.After reaction finishes, remove by filter the solid matter of generation, under reduced pressure, evaporation is removed solvent in the filter liquor to make a kind of semi-finished product.With silica gel look splitter (and just-mixed solvent of hexane carry out drip washing) the prepared semi-finished product of purifying with toluene.As a result, make 1.6 gram S-1-Methylethyl 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene sulphur acetic acid esters.

(b) with 1.6 gram S-1-Methylethyl 3-(2 '-chloro-4 of obtaining in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) benzene sulphur acetic acid esters is added in the 15 gram acetic anhydrides, in ice bath, this mixture is cooled to is lower than 10 ℃.Then, in 5 minutes, slowly add 1.2 nitric acid ketone, treat that nitric acid ketone all adds after, reacted 1 hour being lower than under 10 ℃ the temperature, at room temperature react 3 hours then again to make the product of wanting.From reactant mixture, isolate desired product (separating method is in fact identical with step (b) among the embodiment (1)).With silica gel chromatography splitter (mixed solvent with toluene and acetone carries out drip washing) the prepared semi-finished product of purifying.As a result, can make 1.1 gram flaxen S-1-Methylethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene sulphur acetic acid esters knot solid, its fusing point is 102 °～104 ℃.

Embodiment 3:

Follow these steps to prepare 2-methoxyl group-ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate (for compound N o.15):

(a) with 3.3 the gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid and 1.5 the gram 2-methyl cellosolves be dissolved in 50 milliliters of benzene, then add 0.5 the gram right-toluenesulfonic acid.Then, under refluxad make mixture heating 3 hours.After reaction finishes, in reactant mixture, add 50 milliliters of ether.Wash the mixture of generation according to a conventional method with water, be placed on the anhydrous sodium sulfate dryly, subsequently, evaporation removes and desolvates under alkali press strip spare, thus make 3.9 gram 2-methoxyl group-ethyl 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate.

(b) with 3.9 gram 2-methoxy ethyl 3-(2 '-chloro-4 of making in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) phenylacetate is added in the 35 gram acetic anhydrides, in ice bath, mixture is cooled to below 10 ℃.Then, in 5 minutes, slowly add 2.9 gram copper nitrates, treat that copper nitrate all adds after, reacted 1 hour being lower than under 10 ℃ the temperature, at room temperature continue reaction 5 hours then again, so that react completely.Reactant mixture is injected ice, then, add 200 milliliters of ether.Add the mixture that a kind of sodium hydrate aqueous solution is generated with neutralization.Use a kind of this mixture of aqueous hydrochloric acid solution acidifying again, separate the extracted with diethyl ether layer, wash with water, be placed on drying on the anhydrous sodium sulfate, then evaporation under reduced pressure is removed ether, to obtain a kind of crystallization semi-finished product.Make the crystallization semi-finished product that make from ethyl acetate and just-mixed solvent of hexane crystallization again.As a result, can make 3 gram 2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the white crystals product of phenylacetate, its fusing point is 71.9 °～72.5 ℃.

Embodiment 4:

I. follow these steps to prepare 1-methyl-2 methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate (for compound N o.17):

(a) with 3.3 gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid and 1.8 gram 1-methoxyl group-2-propyl alcohol are dissolved in 50 milliliters of benzene, add the right-toluenesulfonic acid of 0.5 gram.Subsequently, under refluxad make this mixture heating 6 hours.After reaction finishes, in reactant mixture, add 50 milliliters of ether, according to a conventional method, wash the mixture that is generated with water, make this mixture dehydration with anhydrous sodium sulfate, under reduced pressure, steam solvent, with obtain 3.9 gram 1-methyl-2 methoxy ethyl 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate.

(b) with 3 gram 1-methyl-2-methoxy ethyl 3-(2 '-chloro-4 of making in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) phenylacetate is dissolved in 15 grams 1, in the 2-dichloroethane.40 ℃, in about 10 minutes, the solution that generates dropwise is added to (concentrated sulfuric acids of the red fuming nitric acid (RFNA) of 2.4 grams 65% and 3 grams 97%) in a kind of mixed acid, after acid to be mixed all adds, reacted 2.5 hours at 40 ℃, after reaction finishes, reactant mixture is injected trash ice, then, according to a conventional method, with ethyl acetate extraction secondary (using 100 milliliters of ethyl acetate) at every turn.Then, wash organic layer with water, be placed on and carry out drying on the anhydrous sodium sulfate, under reduced pressure, steam solvent to obtain the crystallization semi-finished product.Make the crystalline product that makes from ethyl acetate and just-mixed solvent of hexane again crystallization with 1-methyl-2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 of obtaining 2.3 gram whites '-4-trifluoromethylphenopendant) phenylacetate, its fusing point is 78.9 °～79.3 ℃.

(II) follow these steps to prepare 1-methyl-2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate (for compound N o.17);

Sylvite and 2.7 gram 1-methyl-2 methoxy 〈 ﹠﹠ with 2.3 gram 2-chloro-4-trifluoromethyl phenol〉nitro-5-fluorophenyl acetate is dissolved among 50 milliliters of dimethyl solfoxide, at 60 °～70 ℃, under refluxad, the solution that heating generates 5 hours, after reaction finishes, reactant mixture is injected 300 milliliters of frozen water, then use extracted with diethyl ether.Then, wash ether layer with water, on anhydrous sodium sulfate, carry out drying, under reduced pressure, steam solvent to make coarse crystallization.Make prepared coarse crystallization from ethyl acetate and just-mixed solvent of hexane again crystallization with 1-methyl-2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 of obtaining 3.2 gram whites '-4-trifluoromethylphenopendant) phenylacetate, its fusing point is 78.5 °～79.0 ℃.

Embodiment 5:

Follow these steps to prepare methoxycarbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate (for compound N o.37):

(a) with 3.3 the gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid and 1 the gram methyl glycollate be dissolved in 50 milliliters of benzene.Then, the right-toluenesulfonic acid of 0.2 gram is added in the solution of generation, then, heating is 3 hours under refluxing.Reaction adds 50 milliliters of ether after finishing.According to a conventional method, wash the reactant mixture of generation with water, and dewater with anhydrous sodium sulfate, under reduced pressure, steam solvent with obtain 3.4 gram methoxycarbonyl methyl 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate.

(b) with 3.4 gram methoxycarbonyl methyl 3-(2 '-chloro-4 of making in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) phenylacetate is added in the 35 gram anhydrous acetic acids, and it is cooled to below 10 ℃.Then, in 5 minutes, slowly add 2.4 gram copper nitrates, treat that copper nitrate all adds after, reacted 1 hour being lower than under 10 ℃ the temperature, at room temperature continue reaction 5 hours again, so that react completely.Reaction mixture is placed in the ice bath, adds 200 milliliters of ether.With sodium hydrate aqueous solution neutralization reaction mixed liquor, use hcl acidifying then.Tell ether layer, wash with water, dry on anhydrous sodium sulfate, under reduced pressure, steam ether to make semi-finished product.The prepared semi-finished product of recycle silicon glue look splitter purifying.As a result, make 2.2 the gram flaxen methoxycarbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) the phenylacetate crystallization, its fusing point is 79.2 °～80.1 ℃.

Embodiment 6:

Follow these steps to prepare S-ethoxy carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) benzene sulphur acetic acid esters (compound N is o.47):

(a) 1.2 gram guanidine-acetic acid ethyl esters and 1.2 gram triethylamines are dissolved in 20 milliliters of N,N-dimethylacetamide.Under 10 ℃ of temperature, in the solution that makes, dropwise add 3.5 the gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyllacetyl chloride.After treating that dropwise annex solution all adds, at room temperature react 3 hours so that react completely.After reaction finishes, in reactant mixture, add 50 ml waters, use extracted with diethyl ether then 2 times (using 30 milliliters of ether) at every turn.Wash ether layer with water and dry on anhydrous sodium sulfate, under reduced pressure, steam ether to make a kind of semi-finished product.With the prepared semi-finished product of silica gel layer splitter purifying with obtain 3.5 gram S-ethoxy carbonyl methyl 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant)-benzene sulphur acetic acid esters.

(b) with 3.5 gram S-ethoxy carbonyl methyl 3-(2 '-chloro-4 of making in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) benzene sulphur acetic acid esters is added in the 35 gram anhydrous acetic acids, is cooled to while stirring below 10 ℃ in ice bath.Then, in 5 minutes, slowly add 2.3 gram copper nitrates, treat that copper nitrate all adds after, reacted 1 hour being lower than under 10 ℃ the temperature, then, at room temperature react 3 hours again so that react completely.The method of the step (b) of repetition embodiment 1 is to make a kind of semi-finished product.With the prepared semi-finished product of silica gel chromatography splitter purifying.As a result, obtain 2.3 the gram flaxen oily S-ethoxy carbonyl methyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant)-benzene sulphur acetic acid esters (refractive index h ₀ ²⁶: 1.5578).

Embodiment 7:

Follow these steps to prepare 1-methoxycarbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate (for compound N o.48):

(a) with 3.3 gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetic acid and 1.7 gram methyl 2 bromopropionic acid esters are dissolved in 30 milliliters of acetone.Then, in the solution that makes, add 1.4 gram Anhydrous potassium carbonates, at room temperature stirred 30 minutes.Then, under refluxad added thermal reaction mixture 30 minutes.After reaction finishes, remove by filter the solid matter of generation, under reduced pressure, steam acetone with obtain 4 gram 1-methoxycarbonyl ethyl 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate.

(b) with 4 gram 1-methoxycarbonyl ethyl 3-(2 '-chloro-4 of making in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) phenylacetate is added in the 35 gram anhydrous acetic acids, is cooled to while stirring below 10 ℃ in ice bath.Then, in 5 minutes, slowly add 2.9 gram copper nitrates, treat that copper nitrate all adds after, reacted 1 hour being lower than under 10 ℃ the temperature, at room temperature continue reaction 3 hours again so that react completely.The described method of step (b) that repeats embodiment 1 is to make a kind of semi-finished product.Make crystallization again in the intermixture of the semi-finished product ethyl acetate that makes and just-hexane, with 1-methoxycarbonyl ethyl 2-nitro-5-(2 '-chloro-4 of making 3.1 gram whites '-4-trifluoromethylphenopendant) the phenylacetate crystallization, its fusing point is 72.1 °～72.9 ℃.

Embodiment 8:

Follow these steps to prepare N-ethyl-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide (for compound N o.59):

(a) with 0.7 the gram ethamine and 1.5 the gram triethylamines be dissolved in 20 milliliters of N,N-dimethylacetamide of 0 ℃, then add 3.5 the gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyllacetyl chloride.Reacted 1 hour at 0 ℃, at room temperature react 3 hours then again so that react completely.After reaction finishes, in reaction mixture, add 50 ml waters, then dry on anhydrous sodium sulfate with watery hydrochloric acid and washing ether layer with extracted with diethyl ether secondary (using 30 milliliters of ether) at every turn, under reduced pressure, steam ether.As a result, can make 3.5 gram N-ethyl-3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide.

(b) with 3.5 gram N-ethyl-3-(2 '-chloro-4 of making in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) phenyl acetamide is added in the 35 gram acetic anhydrides, is cooled to while stirring below 10 ℃ in ice bath.In 5 minutes, slowly add 2.9 gram copper nitrates, treat that copper nitrate all adds after, reacted 1 hour being lower than under 10 ℃ the temperature, at room temperature react 5 hours then again so that react completely.Method described in the step (b) of repetition embodiment 1 is to make semi-finished product, make the semi-finished product that make from ethyl acetate and just-mixed solvent of hexane again crystallization with N-ethyl-2-nitro-5-(2 '-chloro-4 of making 2.5 whites '-4-trifluoromethylphenopendant) phenyl acetamide, its fusing point is 188.7 °～189.3 ℃.

Embodiment 9:

Follow these steps to prepare N-methyl N-methoxyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyl acetamide (for compound N o.90):

(a) with 0.9 the gram N, the O-dimethyl hydroxylamine and 1.5 the gram triethylamines be dissolved in 20 milliliters of N,N-dimethylacetamide of 5 ℃, then add 3.5 the gram 3-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenyllacetyl chloride.Under 5 ℃ temperature, reacted 1 hour, and at room temperature reacted 3 hours again so that react completely.After reaction finishes, in reaction mixture, add 50 ml waters, then with extracted with diethyl ether secondary (using 30 milliliters of ether) at every turn.With watery hydrochloric acid and washing ether layer, dry on anhydrous sodium sulfate, under reduced pressure, steam ether obtain 3.5 gram N-methyl-N-methoxyl group-2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate.

(b) with 3.5 gram N-methyl-N-methoxyl group-2-nitro-5-(2 '-chloro-4 of making in the above-mentioned steps (a) '-4-trifluoromethylphenopendant) phenyl acetamide is added in the 35 gram acetic anhydrides, and the mixture of generation is cooled to below 10 ℃.Then, in 5 minutes, slowly add 2.9 gram copper nitrates.After treating that copper nitrate all adds, reacted 1 hour being lower than under 10 ℃ the temperature, at room temperature react 5 hours again so that react completely.The described method of step (b) that repeats embodiment 1 is to make the coarse crystallization product.Make prepared product from ethyl acetate and just-intermixture of hexane again crystallization with N-methyl-N-methoxyl group-2-nitro-5-(2 '-chloro-4 of making 3.2 whites '-4-trifluoromethylphenopendant) the phenyl acetamide crystallization, its fusing point is 134 °～135 ℃.

Embodiment 10:

Method by the various embodiments described above prepares all cpds of the present invention, and it is as shown in table 1 that the structure of these compounds, physical property, results of elemental analyses and high nuclear magnetic resonnance (H-NMR) are analyzed data.But, should be understood that scope of the present invention is not restricted to these compounds.The label of listed compound also can be used to represent the same compound in the example of the present invention in the table 1.

S: singlet, d: two spectral lines, t: triplet

* only after preparation, at room temperature be viscous liquid m: multiplet, b: the wide range line,

S: singlet, d: two spectral lines, t triplet

M: multiplet, b: wide range line

Application example

But preparation example 1(wet powder)

With the The compounds of this invention of 25 parts of weight, the brand name of a kind of product of the sorpol 5039(Toho chemical industrial company of 5 parts of weight) and the talcum of 70 parts of weight pulverize and fully mix to make wettable powder.

The emulsible concentrate of preparation example 2()

With the The compounds of this invention of 5 parts of weight, the sorpol 3005 of 10 parts of weight * (a kind of product of Toho chemical industrial company), 45 parts of weight just-dimethylbenzene of butanols and 40 parts of weight fully mixes to make emulsible concentrate.

Preparation example 3(particle)

With the The compounds of this invention of 1 part of weight, the bentonite of 45 parts of weight, the clay of 44 parts of weight, the neopelex of the Sodium Lignosulphonate of 5 parts of weight and 5 parts of weight are pulverized and are fully mixed, and add entry in mixture, and product is fully kneaded.Then, make the mixture granulation of kneading, then dry, thus obtain desired particle.

Preparation example 4(pulvis)

With the The compounds of this invention of 1 part of weight, pulvis is pulverized and fully be mixed into to the clay of 99 parts of weight.

Making use-case 1(grow the back in weeds uses)

In surperficial face is each basin of 1/5000 are, the paddy soils in the filling greenhouse.In every basin, transplant the paddy rice seedling (counted by native surface, the rice seedlings height is 2～3 centimetres) of 3.0 leaf lobes.With the seed of barnyard grass grass and the seed of single He Ruiou, multiple annual weed, Chinese deciduous cypress leaf genus and Vandellia weeds, the seed and the paddy soils mix of doing of perennial root grass, " Hotarul " (scirpus juncoides) grass, and add in the topsoil.When barnyard grass grass generates 0.5～1.0 leaf lobe, but the emulsifying concentrated solution (being made by preparation example 2) that will contain predetermined concentration dropwise is added in the soil with a dropper.After 21 days, measure phytotoxicity and the herbicidal effect of this weed killer herbicide to paddy rice.Measurement result is as shown in table 3.Numerical value shown in the table 3 is based on following standard:

5: suppress fully

4:80% suppresses

3:60% suppresses

2:40% suppresses

1:20% suppresses

0: to no effect

Annotate 1: comparative compound

Number 1

Annotate 2: comparative compound

Numbers 2

Annotate 3: comparative compound

Numbers 3

Make use-case 2(grow preceding use) in weeds

At surface area is the paddy soils in the filling greenhouse in each basin of 1/5000 are.With the seed of barnyard grass grass and the seed of single He Ruiou, multiple annual weed, Chinese deciduous cypress leaf genus and Vandellia weeds, the seed and the paddy soils mix of doing of perennial root grass, " Hotarui " (Scripus juncoides) grass, and add in the topsoil.Regard to the perennial root grass, transplant the stem tuber and the flat sedge of wedge shape.After this, will contain predetermined concentration (making) with a dropper by preparation example 2 but emulsifying concentrated solution dropwise add and bury.After 3 days, to transplant height be 2～3 centimetres (being counted by topsoil), grow the rice seedlings of 3 leaf lobes, measure phytotoxicity and the herbicidal effect of this weed killer herbicide to paddy rice after 15 days, measurement result is as shown in table 4, in the table 4 standard of listed numerical value with make use-case 1 used standard identical.

Annotate 4: comparative compound:

Numbers 4

Make use-case 3

At surface area is the upland soil in the filling greenhouse in each basin of 1/2500 are.Sow in each basin that soybean, corn, big lady's-grass are drafted a document, the seed of cinerous Amaranthus grass and " Oinutade " (polygonum nodosum).

When using before weeds grow, can add weed killer herbicide at after planting 24 hours, the weed killer herbicide consumption is/10 ares of 30ai grams.On the other hand, when weeds grow the back use, promptly add weed killer herbicide when soybean, corn and weeds grow 2-3 leaf lobe, a 3-4 leaf lobe and 2～2.5 leaf lobes respectively, the weed killer herbicide consumption is/10 ares of 30ai grams.The usage of weed killer herbicide of the present invention is as follows: contain the emulsible concentrate of predetermined concentration (being made by preparation example 2) with 15 premium on currency (every basin upland soil) dilution, then, with a glass sprayer weed killer herbicide is sprinkling upon in the soil, after 14 days, observe and survey herbicidal effect.After 30 days, observation is to the phytotoxicity of paddy rice, and the gained result is as shown in table 5, in the table 5 standard of listed numerical value with make use-case 1 in used standard identical.

Make use-case 2(grow preceding use) in weeds

At surface area is the paddy soils in the filling greenhouse in each basin of 1/5000 are.With the seed of barnyard grass grass and the seed of single He Ruiou, multiple annual weed, Chinese deciduous cypress leaf genus and Vandellia weeds, the seed and the paddy soils mix of doing of perennial root grass, " Hotarui " (Scripus Juncoides) grass, and add in the topsoil.Regard to the perennial root grass, transplant the stem tuber and the flat sedge of wedge shape.After this, will contain predetermined concentration (making) with a dropper by preparation example 2 but emulsifying concentrated solution dropwise add and bury.After 3 days, to transplant height be 2～3 centimetres (being counted by topsoil), grow the rice seedlings of 3 leaf lobes, measure phytotoxicity and the herbicidal effect of this weed killer herbicide to paddy rice after 15 days, measurement result is as shown in table 4, in the table 4 standard of listed numerical value with make use-case 1 used standard identical.

Claims (20)

1, a kind of herbicidal composition comprises a kind of active component, surfactant and solvent, it is characterized in that described active component is the following compound of formula I of a kind of tool,

（Ⅰ）

In the formula, R represents-OR ¹,

R wherein ¹Be one by the straight or branched alkyl that at least a group replaced in hydroxyl and the oxyl, perhaps R ¹By the straight or branched alkyl that at least a group replaced of the carboxyl and the functional group of deriving thereof,

Described active component, surfactant and the solvent amount in composition is respectively 5-30%, 10-50% and 40-85% by the weight of composition.

2, press a kind of herbicidal composition of claim 1, wherein R ¹By a straight or branched alkyl of an oxyl replacement.

3, press a kind of herbicidal composition of claim 1, wherein R ¹By an at least a straight or branched alkyl that replaces of the carboxyl and the functional group of deriving thereof.

4, press a kind of herbicidal composition of claim 1, wherein R ¹By a straight or branched alkyl of a hydroxyl replacement.

5, by a kind of herbicidal composition of claim 1, wherein active component is selected from following at least a compound:

1-methyl-2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-methoxy ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

2-ethoxy 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate,

1-methoxycarbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate, and

1-ethoxy carbonyl ethyl 2-nitro-5-(2 '-chloro-4 '-4-trifluoromethylphenopendant) phenylacetate.

6, eliminate a kind of method of injurious weed, this method comprises that the herbicidal composition that will contain a kind of active component, surfactant and solvent is sprayed directly on on the said weeds, it is characterized in that wherein active component is the following compound of formula I of a kind of tool:

（Ⅰ）

In the formula, R represents-OR ¹,

R wherein ¹Be one by the straight or branched alkyl that at least a group replaced in hydroxyl and the oxyl, perhaps R ¹By an at least a straight or branched alkyl that replaces of the carboxyl and the functional group of deriving thereof,

Described active component, surfactant and the solvent amount in composition is respectively 5-30%, 10-50% and 40-85% by the weight of composition.

7,, it is characterized in that the dosage of described compound administration in the rice field is/10 acres of 0.5-100 grams by a kind of method of claim 6.