JP2971584B2 - Phenylamine derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel phenylamine derivative useful as a herbicide.

[0002]

2. Description of the Related Art One group of compounds conventionally used as herbicides includes dichloro-substituted diphenyl ether compounds used as a submerged soil treatment agent, and trifluoro group used as a foliage treatment agent. There are diphenyl ether compounds substituted with a methyl group. However, the herbicidal activity of the latter was generally higher than that of the former, but its application was mainly limited to foliage treatment. As the cause,
The latter compounds that have been developed so far have been characterized by the lack of selective herbicidal activity between control broadleaf plants and grasses.

[0003]

Accordingly, the present inventors have sought a compound which has a high herbicidal activity while compensating for the above-mentioned drawbacks, and which exhibits a high selective herbicidal activity, particularly against broadleaf weeds. As a result, the novel phenylamine derivative exhibited high herbicidal activity against a wide variety of grass species including broadleaf weeds, and was found to be applicable to a wide range of herbicidal situations, thereby completing the present invention.

[0004]

That is, the present invention provides a compound represented by the general formula (1):

Embedded image X ₃ | {wherein, z is = C-(where, X ₃ is a hydrogen atom, a halogen atom or halogen substitution or unsubstituted alkyl group) or represents nitrogen atom, X ₁ and X ₂ are different A represents a nitro group, R represents an unsubstituted alkoxyalkyl group, an unsubstituted alkenyloxyalkyl group, an alkynyloxyalkyl group, a halogen-substituted or unsubstituted phenoxyalkyl group, tetrahydrofurfuryl Group, furfuryl group or thienylmethyl group. And a phenylamine derivative represented by｝.

In the present invention, in the above general formula (1), X
_When X ₃ represented by the formula of ₁ , X ₂ , A or Z represents a halogen atom, the halogen atom is chlorine, bromine, fluorine,
It may be each atom of iodine.

In the above general formula (1), X ₁ , X ₂ or Z
When X ₃ represented by the formula represents an alkyl group, the alkyl group is not particularly limited, and a known alkyl group can be selected. The alkyl group generally preferably used is preferably a linear or branched one having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, and n-
Propyl group, iso-propyl group, n-butyl group, is
Examples include an o-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

The above alkyl group may be substituted by halogen. The halogen-substituted alkyl group is not particularly limited, but is preferably an alkyl group in which all or some of the hydrogen atoms in the alkyl group are halogen-substituted. As the halogen atom, those exemplified above can be used without any particular limitation. More specifically, examples of the halogen-substituted alkyl group generally most preferably used include a chloromethyl group, a bromomethyl group, a fluoromethyl group, an iodomethyl group, a dichloromethyl group,
Chlorodifluoromethyl group, difluoromethyl group, trichloromethyl group, trifluoromethyl group, chloroethyl group,
Examples include a bromomethyl group, a fluoroethyl group, a dichloroethyl group, a dibromoethyl group, a difluoroethyl group, a trichloroethyl group, a trifluoroethyl group, a perfluoroethyl group, a perfluoropropyl group, and the like.

In the general formula (1), when A represents an alkoxycarbonyl group, the alkoxycarbonyl group is not particularly limited, and a known one can be selected. Alkoxycarbonyl groups that are generally preferably employed are those having 1 to 1 carbon atoms of alkoxy.
Ten, preferably one to four, linear or branched ones are suitable. Specific examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-proponylcarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, te
rt-butoxycarbonyl group, pentyloxycarbonyl group, heptyloxycarbonyl group, decyloxycarbonyl group and the like.

In the general formula (1), when R represents an alkoxyalkyl group, the alkoxyalkyl group is not particularly limited, and a known one can be selected. In general, those preferably and preferably employed are those having a straight or branched chain having 2 to 10 carbon atoms in the alkoxyalkyl group. Specific examples of the most preferably used methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, iso-propoxyethyl group, n-butoxyethyl group, iso-butoxyethyl group, tert-butoxyethyl group Methoxypropyl group, ethoxypropyl group, n-propoxypropyl group, iso-propoxypropyl group, n-butoxypropyl group, iso-butoxypropyl group, tert-
Butoxypropyl, methoxybutyl, ethoxybutyl, n-propoxybutyl, iso-propoxybutyl, n-butoxybutyl, iso-butoxybutyl, tert-butoxybutyl and the like.

In the general formula (1), when R represents an alkenyloxyalkyl group, the alkenyloxyalkyl group is not particularly limited, and a known one can be selected. In general, the alkenyloxyalkyl group preferably preferably has 2 to 2 carbon atoms.
It has 10 linear or branched chains. Specific examples of the most preferably used ones include a 2- (allyloxy) ethyl group and 2- (3-butenyl-2-oxy)
Ethyl group, 2- (2-butenyl-1-oxy) ethyl group, 2- (3-methyl-2-butenyl-1-oxy) ethyl group, 2- (2-methyl-2-propenyl-1-oxy) Ethyl group, 2- (3-butenyl-1-oxy) ethyl group, 2- (4-pentenyl-2-oxy) ethyl group,
2- (2-methyl-3-butenyl-1-oxy) ethyl group, 2- (2-methyl-3-pentenyl-1-oxy)
Ethyl group, 2- (allyloxy) propyl group, 2- (3
-Butenyl-2-oxy) propyl group, 2- (2-butenyl-1-oxy) propyl group, 2- (3-methyl-2
-Butenyl-1-oxy) propyl group, 2- (2-methyl-2-propenyl-1-oxy) propyl group, 2-
(3-butenyl-1-oxy) propyl group, 2- (4-
Pentenyl-2-oxy) propyl group, 2- (2-methyl-3-butenyl-1-oxy) propyl group, 2- (2
A -methyl-3-pentenyl-1-oxy) propyl group,
3- (allyloxy) propyl group, 3- (3-butenyl-2-oxy) propyl group, 3- (2-butenyl-1-
Oxy) propyl, 2- (3-methyl-2-butenyl-1-oxy) propyl, 3- (2-methyl-2-propenyl-1-oxy) propyl, 3- (3-butenyl-1- An oxy) propyl group, 3- (4-pentenyl-
2- (oxy) propyl group, 3- (2-methyl-3-butenyl-1-oxy) propyl group, 3- (2-methyl-3)
-Pentenyl-1-oxy) propyl group and the like.

In the general formula (1), when R represents an alkynyloxyalkyl group, the alkynyloxyalkyl group is not particularly limited, and a known one can be selected. Generally, the alkynyloxyalkyl group preferably preferably has 2 to 2 carbon atoms.
Ten straight or branched ones are preferred. Specific examples of the most preferably used ones include 2-
(2-propynyl-1-oxy) ethyl group, 2- (3-
Butynyl-2-oxy) ethyl group, 2- (3-pentynyl-2-oxy) ethyl group, 2- (2-propynyl-1)
-Oxy) ethyl group, 3- (3-butynyl-2-oxy) propyl group, 3- (3-pentynyl-2-oxy)
Propyl group, 3- (2-propynyl-1-oxy) propyl group, 3- (3-butynyl-2-oxy) propyl group, 2- (3-pentynyl-2-oxy) propyl group,
2- (2-propynyl-1-oxy) propyl group, 2-
(3-butynyl-2-oxy) propyl group, 2- (3-
And a pentynyl-2-oxy) propyl group.

In the general formula (1), when R represents a phenoxyalkyl group, the phenoxyalkyl group is not particularly limited, and a known phenoxyalkyl group can be employed. Generally, the phenoxyalkyl group preferably employed preferably has a total of 7 to 12 carbon atoms. More specifically, those most preferably used include a phenoxymethyl group, a phenoxyethyl group,
Phenoxypropyl group, phenoxybutyl group and the like.

In the general formula (1), when R represents a substituted alkoxyalkyl group, a substituted alkenyloxyalkyl group or a substituted phenoxyalkyl group, the substituent is not particularly limited, and is an inert group which does not participate in the reaction in the present invention. Substituents can be used. Specific examples of particularly preferred substituents include halogen atoms such as chlorine, bromine, iodine, and fluorine; nitro groups; hydroxyl groups; methyl groups, ethyl groups, and n.
-Propyl group, iso-propyl group, n-butyl group, i
alkyl groups such as so-butyl group and t-butyl group; alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, iso-propoxy group and n-butoxy group; methylthio group, ethylthio group and n-propolthio group , An alkylthio group such as n-butylthio group; a chloromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group,
A halogenoalkyl group such as a trifluoroethyl group and a pentafluoroethyl group; and a phenyl group.

The most preferably used substituted alkoxyalkyl groups are more specifically exemplified by 3-methoxy-2-chloropropyl, 3-methoxy-2-bromopropyl, 3-methoxy-2-iodo. Propyl group, 3
-Methoxy-2-fluoropropyl group, 2-trifluoromethoxyethyl group, 2-dichloromethoxyethyl group,
2- (2-nitroethoxy) ethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-methylthioethoxy) ethyl group, 2-benzyloxyethyl group , 2- (2-phenylethoxy) ethyl group, 3-ethoxy-2-chloropropyl group, 3-ethoxy-2-bromopropyl group, 3-ethoxy-2-iodopropyl group, 3-ethoxy-2-fluoropropyl Group, 2-trifluoromethoxypropyl group, 2-dichloromethoxypropyl group, 2- (2-nitroethoxy) propyl group, 2- (2-methoxyethoxy) propyl group, 2- (2-ethoxyethoxy) propyl group, 2- (2-methylthioethoxy) propyl group, 2
-Benzyloxypropyl group, 2- (2-phenylethoxy) propyl group and the like.

More specifically, those most preferably used as substituted alkenyloxyalkyl groups are exemplified by 2
-(3-methoxy-2-propenyl-1-oxy) ethyl group, 2- (3-methylthio-2-propenyl-1-oxy) ethyl group, 2- (3-bromo-2-propenyl-
1-oxy) ethyl group, 2- (3-chloro-2-propenyl-1-oxy) ethyl group, 2- (3-iodo-2-
Propenyl-1-oxy) ethyl group, 2- (3-fluoro-2-propenyl-1-oxy) ethyl group, 2- (3
-Trifluoromethoxy-2-propenyl-1-oxy) ethyl group, 2- (3-phenyl-2-propenyl-
1-oxy) ethyl group, 2- (3-methoxy-2-propenyl-1-oxy) propyl group, 2- (3-methylthio-2-propenyl-1-oxy) propyl group, 2-
(3-bromo-2-propenyl-1-oxy) propyl group, 2- (3-chloro-2-propenyl-1-oxy)
Propyl group, 2- (3-iodo-2-propenyl-1-
Oxy) propyl group, 2- (3-fluoro-2-propenyl-1-oxy) propyl group, 2- (3-trifluoromethoxy-2-propenyl-1-oxy) propyl group, 2- (3-phenyl- 2-propenyl-1-oxy) propyl group and the like.

The most preferred examples of the substituted phenoxyalkyl group include, more specifically, chlorophenoxyethyl group, bromophenoxyethyl group, fluorophenoxyethyl group, iodophenoxyethyl group, dichlorophenoxyethyl group, trichlorophenoxyethyl group and trichlorophenoxyethyl group. Phenoxyethyl group, chloro-methylphenoxyethyl group, bromo-fluorophenoxyethyl group, chloro-ethylphenoxyethyl group, chloro-cyanophenylphenoxyethyl group, chloro-methoxyphenoxyethyl group, methoxycarbonylphenoxyethyl group, trimethylphenoxyethyl group , Methylthiophenoxyethyl group, trimethoxyphenogenoxyethyl group, methoxyphenoxyethyl group,
Ethoxyphenoxyethyl group, isopropoxyphenoxyethyl group, ethylthiophenoxyethyl group, dimethoxyphenoxyethyl group, diethoxyphenoxyethyl group, nitrphenoxypropyl group, chlorophenoxypropyl group, bromophenoxypropyl group, fluorophenoxypropyl group, iodophenoxy Propyl group, dichlorophenoxypropyl group, trichlorophenoxypropyl group, chloro-methylphenoxypropyl group, bromo-fluorophenoxypropyl group, chloro-ethylphenoxypropyl group, chloro-cyanophenylphenoxypropyl group, chloro-methoxyphenoxypropyl group,
Methoxycarbonylphenoxypropyl, trimethylphenoxypropyl, methylthiophenoxypropyl, trimethoxyphenoxypropyl, methoxyphenoxypropyl, ethoxyphenoxypropyl, isopropoxyphenoxypropyl, ethylthiophenoxypropyl, dimethoxyphenoxypropyl, dimethoxyphenoxypropyl Ethoxyphenoxypropyl, nitrophenoxypropyl and the like.

The phenylamine derivative represented by the general formula (1) is a combination of the atoms or groups described above for Z, X ₁ , X ₂ , A and R. Especially those that are easily manufactured industrially and have good herbicidal activity,
More specifically, 4- (2 ', 4'-dichlorophenoxy) -2-methoxyethylaminonitrobenzene, 4- (2', 4'-dichlorophenoxy) -2-ethoxyethylaminonitrobenzene, (2 ', 4'
-Dichlorophenoxy) -2-isopropoxyethylaminonitrobenzene, 4- (2 ', 4'-dichlorophenoxy) -2-methoxypropylaminonitrobenzene, 4- (2', 4'-dichlorophenoxy) -2-ethoxypropyl Aminonitrobenzene, 4- (2 ',
4'-dichlorophenoxy) -2-isopropoxypropylaminonitrobenzene, 4- (2'chloro-4'-
Trifluoromethylphenoxy) -2-methoxypropylamino-nitrobenzene, 4- (2'-chloro-4 '
-Trifluoromethylphenoxy) -2-ethoxypropylaminonitrobenzene, 4- (2'-chloro-4 '
-Trifluoromethylphenoxy) -2-isopropoxypropylaminonitrobenzene, 4- (2'-chloro-4'-trifluoromethylphenoxy) -2-methoxyethylaminonitrobenzene, 4- (2'-chloro-
4'-trifluoromethylphenoxy) -2-ethoxyethylaminonitrobenzene, 4- (2'-chloro-
4'-trifluoromethylphenoxy) -2-isopropoxyethylaminonitrobenzene, 4- (3'-chloro-5'-trifluoromethylpyridyl-2-oxy)
-2-methoxypropylaminonitrobenzene, 4-
(3'-chloro-5'-trifluoromethylpyridyl-
2-oxy) -2-ethoxypropylaminonitrobenzene, 4- (3'-chloro-5'-trifluoromethylpyridyl-2-oxy) -2-methoxyethylaminonitrobenzene, 4- (3'-chloro-5 ' -Trifluoromethylpyridyl-2-oxy) -2-ethoxyethylaminonitrobenzene and the like.

The phenylamine derivative represented by the general formula (1) of the present invention can be measured for infrared absorption spectrum (IR), mass spectrum (MS), ¹ H-nuclear magnetic resonance spectrum ( ¹ H-NMR) and Its structure can be confirmed by elemental analysis or the like. The typical patterns are as follows.

(A) By measuring the infrared absorption spectrum (IR), the characteristic absorption at 1150-1270 cm ^{-1 based} on the ether bond (C-O-C), 3300-34
Characteristic absorption and the like based on the amino group can be observed at 00 cm ^-1 .

(B) measuring a mass spectrum (MS);
By calculating a composition formula corresponding to each observed peak (generally, the number represented by m / e obtained by dividing the ion molecular weight m by the charge number e of the ion), the molecular weight of the compound subjected to the measurement and the molecular weight You can know the bonding style of each atomic group within. That is, when the sample subjected to the measurement is represented by the general formula (1), the molecular ion peak (hereinafter abbreviated as M ⁺ ) generally follows the isotope abundance ratio according to the number of halogen atoms contained in the molecule. It is possible to determine the molecular weight of the compound used for the measurement because it is observed at a different intensity.

(C) ¹ H-nuclear magnetic resonance spectrum ( ¹ H
-NMR), it is possible to know the bonding mode of the hydrogen atoms present in the compound of the present invention represented by the above general formula. In the general formula (1), X ₁ , X ₂ ,
Regardless of the type of X ₃ , R, and A, the proton on the benzene ring appears as a multiplet at about 6.0 to 8.5 ppm, and the proton of the amino group is a broad singlet at about 8.2 to 8.5 ppm. It usually appears in.

(D) By elemental analysis, carbon, hydrogen and nitrogen (sulfur and halogen if sulfur and halogen are contained)
Is obtained, and the weight% of oxygen can be calculated by subtracting the sum of the recognized weight% of each element from 100, and thus the composition formula of the compound can be determined.

The phenylamine derivative of the present invention is generally a yellow or tan solid at normal temperature and normal pressure.

The derivatives of the present invention include benzene, ether, alcohol, acetone, N, N-dimethylformamide,
It is well soluble in organic solvents such as dimethyl sulfoxide,
Insoluble or poorly soluble in water.

The method for producing the phenylamine derivative represented by the general formula (1) of the present invention is not particularly limited, and may be produced by any method. An example of a typical manufacturing method is as follows.

(A) General formula (2),

Embedded image (However, X ₄ represents a halogen atom or a nitro group,
A, X ₁ , X ₂ and Z are as shown in the general formula (1). The phenyl derivative represented by the general formula (3) RNH ₂ ... (3) (where R is as shown in the general formula (1)) and the presence or absence of a solvent and an amine derivative represented by the general formula (1) React down or

(B) general formula (4),

Embedded image (Where X ₅ represents a halogen atom, and X ₁ , X ₂ and Z are as shown in the general formula (1).) An aryl derivative represented by the general formula (5)

Embedded image (Where M represents a hydrogen atom or an alkali metal;
And A are as shown in the general formula (1). ) With the phenol derivative represented by the presence or absence of a solvent, or

(C) General formula (6)

Embedded image (Where M represents a hydrogen atom or an alkali metal;
₁ , X ₂ and Z are as shown in the general formula (1). )
And the general formula (7)

Embedded image (However, X ₆ represents a halogen atom, and A is as shown in the general formula (1).) It can be produced by reacting a phenol derivative represented by the presence or absence of a solvent.

In the above reaction (a), the charged molar ratio of the phenyl derivative represented by the general formula (2) and the amine derivative represented by the general formula (3) may be appropriately determined as necessary. Equimolar or amine derivative, eg 50%
Preferably, it is generally used in an excess of 20%.

In the above reaction (b), the molar ratio of the aryl derivative represented by the general formula (4) and the phenol derivative represented by the general formula (5) may be appropriately determined as necessary. It is common to use an equimolar or phenol derivative in a slight excess, eg 20%, preferably 10%.

In the above reaction (c), the charged molar ratio of the aryl derivative represented by the general formula (6) and the phenol derivative represented by the general formula (7) may be appropriately determined as necessary. It is common to use an equimolar or aryl derivative in a slight excess, eg, 20%, preferably 10%. The solvent for the reactions (a), (b) and (c) is not particularly limited, and a known solvent can be used. Representative examples generally used preferably include benzene, toluene, xylene, methylene chloride, chloroform, N,
N-dimethylformamide or the like is used.

In the reactions (b) and (c), when M is a hydrogen atom, a hydrogen halide scavenger is usually coexistent in the reaction system in order to scavenge by-produced hydrogen halide. preferable. The hydrogen halide scavenger is not particularly limited, and a known one can be used. Representative examples of hydrogen halide scavengers generally preferably used include trialkylamines such as triethylamine, trimethylamine and tripropylamine; pyridine; sodium alcoholate; sodium carbonate; potassium carbonate; sodium hydroxide; Potassium; sodium hydride and the like.

In the reactions (b) and (c), the phenol derivative represented by the general formula (5) and the phenol derivative represented by the general formula (6)
As the alkali metal of the aryl derivative represented by, sodium, potassium, lithium and the like can be used, but sodium and potassium are generally preferred.

The reaction temperatures of the reactions (a), (b) and (c) are usually carried out in the range of -30 to 200 ° C, but preferably in the range of 5 to 150 ° C. The reaction time is 0.5 to 40 hours, preferably 3 to 1 hour.
It is good to do it in 0 hours.

The method for isolating and purifying the phenylamine derivative as the target product from the reaction system is not particularly limited, and a known method can be employed. The reaction solution is added to ice water, the generated solid is separated by filtration, and the solid is purified by recrystallization or column chromatography, or, if the solvent is not mixed with water, the reaction solution is added to water, and the organic solvent is added. , And the solvent is distilled off, and then the residue is preferably recrystallized or purified by column chromatography.

The phenylamine derivative represented by the general formula (1) of the present invention has activity as a herbicide. The form of use as the herbicide is not particularly limited, and known forms of use can be used as they are. For example, using an inert solid carrier, a liquid carrier, an emulsifying dispersant, or the like, granules, powders, emulsions, wettable powders, flowables, tablets, aerosols, smokers, and the like can be used in any dosage form. it can.

Of course, as an auxiliary in the formulation, for example, a spreading agent, a diluent, a surfactant and the like can be appropriately blended and used in a liquid or solid state. In particular, it is often effective to use a surfactant to improve dispersibility in water or oil.

As the surfactant, anionic, cationic or nonionic surfactants known to be usable in general herbicide preparations can be suitably used. Particularly preferred examples are as follows.

For example, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, fatty acid sulfonate, polyoxyethylene alkyl phenyl ether sulfonate, sodium alkyl sulfate, sodium lignin sulfonate, polyalkyl naphthalene sulfonate, etc.

The following are typical forms of use when the phenylamine derivative represented by the general formula (1) is used as a herbicide.

The wettable powders and granules generally contain an inert solid carrier, a surfactant and the like in addition to the active ingredient represented by the general formula (1). As the inert solid carrier, a natural or synthetic inorganic powder is generally used. Examples of the most preferably used are clays, talc, calcium carbonate, diatomaceous earth, silica and the like. Usually 1-80 parts by weight of active ingredient, 5-98 parts by weight of inert solid carrier, 1-1
Consists of 5 parts by weight of surfactant. Of course, if necessary, polyvinyl alcohol, Na carboxymethyl cellulose, etc. may be added.

An emulsion generally comprises a solution in which an active ingredient and a surfactant are dissolved in a solvent. As the solvent, known solvents capable of dissolving the active ingredient can be used. Representative examples thereof include xylene, phenoxyethanol, cyclohexanone, solvent naphtha, methylnaphthalene, kerosene and the like. Each of the above components generally comprises 75 to 20 parts by weight of the active ingredient, 10 to 20 parts by weight of the surfactant, and 15 to 60 parts by weight of the solvent.

Powders are obtained by supporting an active ingredient on natural or synthetic inorganic powder. Generally, it is formulated by mixing 0.5 to 6 parts by weight of the active ingredient and 99.5 to 94 parts by weight of the inorganic powder.

The flowable is a suspension formulation in which the active ingredient insoluble in water is finely divided, and the active ingredient is dispersed in water by adding a dispersant or the like. Generally, the most widely used embodiment is to suspend the active ingredient at a concentration of 20-50% by weight.

Further, a heat generating agent such as a nitrate, a nitrite, a guanidine salt and potassium chlorate and a heat generating agent such as an alkali metal salt and potassium nitrate are added to the smoke agent.

[0046]

The phenylamine derivative represented by the general formula (1) has remarkably high activity with herbicides and is effective against various weeds. Generally, weeds having an effective herbicidal activity are as follows.

For example, dog millet, sand millet, canine millet, kazunokogusa, tamagayatsuri, mizuhanabi, hinagayatsuri, kawarasugana, firefly, harii, tentsuki,
Himetentsuki, Hyderiko, Spodoptera mori, Himekuggu, Kurogwai, Matsubai, Koukiyara, Omodaka, Aginashi, Heramodaka, Urikawa, Hirumshiro, Denjisou, Seri, Yanagitade, Konagi, Ibokusa, Hoshikusa,
Mizohakobe, Himemisohagi, Kikasigusa, Mizumatsuba,
Ginseng, Cloverleaf, Azemushiro, Takasaburo,
Paddy field weeds such as Taucogi, American Sendangusa, Akanumasou, Sawa Pepper, Abnome, Azena and Azechi pepper.

For example, Meishiba, Enokorogusa, Akaza, Inadeta, Cyperaceae, Kogomegayatsuri, Inubiyu, Suberihyuyu, Akatsumekusa, Okabami, Suzumetepo, Suzumeokatabira, Yaegura, Noasagao,
Upland weeds, such as Kawaraketsumei, Karasu no Pea, and Nasuna.

The phenylamine derivative represented by the general formula (1) is particularly useful for broadleaf weeds in comparison with compounds conventionally used as herbicides, that is, dichloro- or trifluoro-substituted diphenyl ether compounds. It is a compound that has the property of being able to perform high selective weeding.

This has made it possible to apply to a wider range of crops than ever before. Furthermore, there is less phytotoxicity on transplanted rice than ever.

[0051]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Preparation of 4- (2 ', 4'-dichlorophenoxy) -2-methoxyethylaminonitrobenzene (Compound No. 1)

2.2 g of potassium salt of 2,4-dichlorophenol, 4-chloro-2-methoxyethylamine
2.3 g and 20 ml of dimethyl sulfoxide were heated and stirred at 120 ° C. for 4 hours. The reaction solution was added to water, extracted with ethyl acetate and concentrated. The residue was recrystallized from hexane-methanol to obtain 1.45 g of a yellow solid. 85.0% yield
Met. The analysis results of the compound thus obtained were as follows.

IR (cm ⁻¹ ): 3360 (NH), 1250 (—C—O—C)

MS (M ⁺ ): 357

¹ H-NMR (σ ppm; based on tetramethylsilane, deuterated chloroform solvent): 3.41 (s, 3
H), 3.48-3.90 (m, 4H), 6.00-6.0.
8.30 (m, 7H)

Elemental analysis value (%): C50.20, H3.
80, N 7.92 (calculated value C 50.44, H 3.95,
N7.84)

These results indicate that the isolated product is 4%
-(2 ', 4'-dichlorophenoxy) -2-methoxyethylaminonitrobenzene was confirmed.

Example 2 Compounds 1 to 53 represented by the following general formula (8) were synthesized in the same manner as in Example 1.

Embedded image

Characteristic absorption by IR of the synthesized compound, characteristic mass fragment (MASS) and ¹ H-NMR (based on tetramethylsilane, measured by CDCl ₃ , δ: pp
m) Data and properties are shown in Table 1, respectively.

The identification of the compound represented by the general formula (8) was carried out based on the results of each analysis described above with reference to elemental analysis. The results are shown as X ₁₁ ~X _15, Y and R in Table 1.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

Example 3 Preparation of 4- (2'-chloro-4'-trifluoromethylphenoxy) -2-methoxypropylamino-nitrobenzene (Compound No. 57)

4- (2'-chloro-4'-trifluoromethylphenoxy) -1,2-dinitrobenzene
After stirring 0 g and 2.7 g of methoxypropylamine for 1 hour, the mixture was concentrated. Residue is silica gel chromatography (benzene)
Purification yielded 1.07 g of a yellow solid. The yield was 95.6%. The analysis results of this compound were as follows.

IR (cm ⁻¹ ): 3360 (NH), 1210 (C—O—C)

MS (M ⁺ ): 404

¹ H-NMR (σ ppm; based on tetramethylsilane, deuterated chloroform solvent): 1.70 to 2.25
(M, 2H), 3.36 (s, 3H), 3.40-3.
75 (m, 4H), 5.98 to 8.60 (m, 7H)

Elemental analysis value (%): C50.20, H3.
80, N 6.70 (calculated C 50.44, H 3.98,
N6.92)

From these results, it was found that the isolated product was 4- (2
'-Chloro-4'-trifluoromethylphenoxy)-
It was confirmed to be 2-methoxypropylamino-nitrobenzene.

Example 4 In the same manner as in Example 3, compounds Nos. 54 to 81 represented by the general formula (8) (excluding Compound No. 57) were synthesized.

Table 2 shows the characteristic absorption of IR, characteristic mass fragment, ¹ H-NMR data and properties of the synthesized compound.

From the results of these analyses, it was confirmed that the synthesized compound was a compound of the general formula (8) represented by X _{11 to} X ₁₅ , Y and R in Table 2. In confirming this, the results of elemental analysis were also referred to.

[0077]

[Table 6]

[0078]

[Table 7]

[0079]

[Table 8]

Example 5 Preparation of 4- (3'-chloro-5'-trifluoromethylpyridyl-2-oxy) -2-methoxypropylamino-nitrobenzene (Compound No. 82)

3.37 g of 4- (3'-chloro-5'-trifluoromethylpyridyl-2-oxy) -2-chloro-nitrobenzene and 8 g of methoxypropylamine were stirred for 1 hour. The reaction solution was concentrated, and the residue was purified by silica gel chromatography (benzene) to obtain 3.0 g of a yellow solid. The yield was 74.0%. The analysis results of this compound were as follows.

IR (cm ⁻¹ ): 3330 (NH), 1240 (—C—O—C)

MS (M ⁺ ): 405

¹ H-NMR (σ ppm; based on tetramethylsilane, deuterated chloroform solvent): 1.89 (t, 2
H), 3.28 (s, 3H), 3.35-4.10.
(M, 4H), 7.00 to 8.35 (m, 6H)

Elemental analysis value (%): C47.60, H3.
85, N10.78 (calculated C47.36, H3.7
3, N10.36)

From these results, it was found that the isolated product was 4- (3
'-Chloro-5'-trifluoromethylpyridyl-2-
(Oxy) -2-methoxypropylamino-nitrobenzene.

Example 6 In the same manner as in Example 4, compounds Nos. 82 to 88 represented by the following general formula (9) were synthesized.

[0088]

Embedded image

Table 3 shows the characteristic absorption of IR, characteristic mass fragment, ¹ H-NMR data and properties of the synthesized compound.

From the results of these analyses, it was confirmed that the synthesized compound was a compound represented by the general formula (9) represented by X _{21 to} X ₂₄ , Y and R in Table 3. In this confirmation, the results of elemental analysis were referred to.

Formulation Example 1

10 parts by weight of the phenylamine derivative, 2 parts by weight of polyoxyethylene nonyl phenyl ether, 40 parts by weight of fine powder clay and 48 parts by weight of siegrite shown in Tables 1, 2 and 3 were pulverized and mixed to give 10%. A wettable powder was prepared.

Application Example 1

A 1/8850 are magnetic pot was filled with paddy soil (alluvial loam) well mixed with water, and paddy field weeds were sown. Then, three-leaf stage rice seedlings (variety: Akinishiki) were transplanted to a depth of 2 cm. Then, water was added to make a 2 cm flooded state.

Next, 1 of each compound prepared in Formulation Example 1
A predetermined amount of a 0% dilution was dropped when weeds germinated. After the treatment, the plants were grown in a greenhouse at an average temperature of 25 ° C., and after 3 weeks, the results of investigating the herbicidal effect of each test compound are shown in Table 4.

[0096] However, the broad leaves shown in the table refer to Azena, Kikasigusa, Mizohakobe and the like. The evaluation was made in six stages, and the evaluation of the herbicidal effect was represented by a number from 0 to 5 as follows. 0 ····· Weed control rate 0 to 9% 1 ···· Weed control rate 10 to 29% 2 ···· Weed control rate 30 to 49% 3 ···· Weed control rate 50 to 69% 4. ··· Weed control rate 70-89% 5 ···· Weed control rate 90-100%

Regarding the phytotoxicity of transplanted rice, plant height, number of tillers,
The ratio of the total weight (air-dried amount) to the non-treated section was calculated, and the worst of the three factors was set to 5, and evaluated on the following 6 levels from 0 to 5. 0 …… Ratio to non-treatment section 100% 1 …… Ratio to non-treatment section 90-99% 2 …… Ratio to non-treatment section 80-89% 3 …… Untreated section ratio 60-79% 4 ..... Untreated section ratio 40-59% 5 ..... Untreated section ratio 0-39%

[0098]

[Table 10]

[0099]

[Table 11]

[0100]

[Table 12]

Application Example 2

A magnetic pot of 1/8850 are filled with field soil (clay loam), soybean seeds are sown at a depth of 2 to 3 cm, and various plant seeds of Nobie, Aobuille and Kosendangusa are sown at 0.5 to 1 cm. When soybeans were sown at the depth and the soybeans grew during the development of the primary leaves, a spreading agent was added to a water dilution of a wettable powder of each compound, and a predetermined amount of foliage was sprayed. After processing, average temperature 25
The plants were grown in a greenhouse at 2 ° C., and two weeks later, the herbicidal effect of each test compound was investigated. The results are shown in Table 5. Table 5
The evaluation of the herbicidal effect was the same as above. Regarding the phytotoxicity to soybeans, the ratio of the plant height and the total weight (air-dried amount) to the untreated section was calculated, and the worst of the two factors was set to 5, and the following 0 was set.
５5 out of 6 grades. 0 ...... Ratio to non-treatment section 100% 1 ...... Ratio to non-treatment section 90-99% 2 ... ...... Ratio to non-treatment section 80-89% 3 ... Untreated section ratio 60-79% 4 ..... Untreated section ratio 40-59% 5 ..... Untreated section ratio 0-39%

[0103]

[Table 13]

[0104]

[Table 14]

[0105]

[Table 15]

[0106]

[Table 16]

Application Example 3

Field soil (clay loam) is filled in a magnetic pot of 1/8850 are, various kinds of plant seeds such as shrimp, enokorogusa, aoubiyu and kosendangusa are sown at a depth of 0.5 to 1 cm, and then hydration of each compound is carried out. A predetermined amount of a water dilution of the agent was sprayed on the soil. After the treatment, the plants were grown in a greenhouse at an average temperature of 25 ° C., and two weeks later, the herbicidal effect of each test compound was investigated. The results of the survey are shown in Table 6. The evaluation of the herbicidal effect in Table 6 is the same as described above.

[0109]

[Table 17]

[0110]

[Table 18]

[0111]

[Table 19]

[0112]

[Table 20]

[Table 9]

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI C07C 255/59 C07C 255/59 C07D 213/30 C07D 213/30 307/52 307/52 (56) References JP-A-60- 172949 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 217/90 A01N 33/10 A01N 43/36 A01N 43/40 101 C07C 229/56 C07C 255/59 C07D 213 / 30 C07D 307/52 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (1) X ₃ | {wherein, z is = C-(where, X ₃ is a hydrogen atom, a halogen atom or halogen substitution or unsubstituted alkyl group) or represents nitrogen atom, X ₁ and X ₂ are different A represents a nitro group, R represents an unsubstituted alkoxyalkyl group, an unsubstituted alkenyloxyalkyl group, an alkynyloxyalkyl group, a halogen-substituted or unsubstituted phenoxyalkyl group, tetrahydrofurfuryl Group, furfuryl group or thienylmethyl group. A phenylamine derivative represented by｝.