JPH04217647A - Phenylamine derivative - Google Patents

Abstract

PURPOSE:To provide a new phenylamine derivative having high herbicidal activity, exhibiting highly selective herbicidal action especially against broad- leaved weeds and causing little phytotoxicity. CONSTITUTION:A compound of formula I [Z is group of formula II (X3 is H, halogen or alkyl) or N; X1 and X2 are H, halogen or alkyl; A is H, halogen, nitro, etc.; R is alkoxyalkyl, alkenyloxyalkyl, etc.], e.g. 4-(2',4'- dichlorophenoxy)-2-methoxyethylaminonitro-benzene. The compound can be produced by reacting a phenyl derivative of formula III (X4 is halogen or nitro) with an amine derivative of formula RNH2 in the presence or absence of a solvent (e.g. benzene) at -30 to +200 deg.C. The herbicide is effective against paddy field weeds such as barnyard grass and false pimpernel and plowed land weeds such as large crab-grass and green foxtail.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD This invention relates to novel phenylamine derivatives useful as herbicides.

0002

[Prior Art] One group of compounds conventionally used as herbicides include dichloro group-substituted diphenyl ether compounds, which are used as a treatment agent for flooded soil, and trifluorocarbon compounds, which are used as a foliar treatment agent. There are diphenyl ether compounds substituted with methyl groups. However, although the latter's herbicidal activity was generally higher than that of the former, its range of application was mainly limited to foliage treatment. The cause of this is
The latter compounds developed so far had no selective herbicidal activity between control broad-leaved plants and grasses.

0003

[Problems to be Solved by the Invention] Therefore, the present inventors searched for a compound that exhibits high herbicidal activity while compensating for the above-mentioned drawbacks, and in particular exhibits a high degree of selective herbicidal activity against broad-leaved weeds. As a result, it was discovered that a new phenylamine derivative exhibits high herbicidal activity against a wide range of grass species including broad-leaved weeds, and is also applicable to a wide range of weeding situations, leading to the completion of the present invention.

0004

[Structure of the invention]

That is, the present invention General formula (1),

[Chemical formula 2] or an unsubstituted alkyl group) or a nitrogen atom, X1 and X2 are different or similar hydrogen atoms, halogen atoms, halogen-substituted or unsubstituted alkyl groups, A is a hydrogen atom, A halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, R is a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyloxyalkyl group, an alkynyloxyalkyl group, a substituted or unsubstituted phenoxyalkyl group,
Indicates a tetrahydrofurfuryl group, a furfuryl group, and a thienylmethyl group. ) is related to a phenylamine derivative represented by

In the present invention, in the above general formula (1), X
When X3 in the formula 1, X2, A or Z represents a halogen atom, the halogen atom may be a chlorine, bromine, fluorine or iodine atom.

In the above general formula (1), when X1, X2 or X3 in the formula Z represents an alkyl group, the alkyl group is not particularly limited and any known alkyl group may be selected. The alkyl group that is generally suitably employed has 1 to 10 carbon atoms.
A linear or branched chain, preferably 1 to 4 of them, is suitable. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Examples include nonyl group and decyl group.

The above alkyl group may be substituted with halogen. The halogen-substituted alkyl group is not particularly limited, but one in which all or part of the hydrogen atoms in the alkyl group are halogen-substituted is preferable. The halogen atoms listed above can be used without particular limitation. More specific examples of the halogen-substituted alkyl groups that are generally most preferably used include chloromethyl group, bromomethyl group, fluoromethyl group, iodomethyl group, dichloromethyl group,
Chlorodifluoromethyl group, difluoromethyl group, trichloromethyl group, trifluoromethyl group, chloroethyl group,
Examples include bromomethyl group, fluoroethyl group, dichloroethyl group, dibromoethyl group, difluoroethyl group, trichloroethyl group, trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, and the like.

In the above general formula (1), when A represents an alkoxycarbonyl group, the alkoxycarbonyl group is not particularly limited and any known alkoxycarbonyl group may be selected. The alkoxycarbonyl group that is generally suitably employed is an alkoxy having 1 to 1 carbon atoms.
A linear or branched chain having 10 pieces, preferably 1 to 4 pieces, is suitable. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-proponylcarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, te
Examples include 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 any known alkoxyalkyl group may be selected. In general, straight-chain or branched alkoxyalkyl groups having a total of 2 to 10 carbon atoms are preferably employed. Specific examples of those most preferably used include methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, iso-propoxyethyl group, n-butoxyethyl group, iso-butoxyethyl group, and tert-butoxyethyl group. , methoxypropyl group, ethoxypropyl group, n-propoxypropyl group, iso-propoxypropyl group, n-butoxypropyl group, iso-butoxypropyl group, tert-
These include butoxypropyl group, methoxybutyl group, ethoxybutyl group, n-propoxybutyl group, iso-propoxybutyl group, n-butoxybutyl group, iso-butoxybutyl group, tert-butoxybutyl group, and the like.

In the general formula (1), when R represents an alkenyloxyalkyl group, the alkenyloxyalkyl group is not particularly limited and any known alkenyloxyalkyl group may be selected. The alkenyloxyalkyl group preferably employed generally has a total carbon number of 2 to
10 linear or branched chains. Specific examples of those most preferably used include 2-(allyloxy)ethyl group, 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-methyl-3-pentenyl-1-oxy)propyl group, 3-
(allyloxy)propyl group, 3-(3-butenyl-2)
-oxy)propyl group, 3-(2-butenyl-1-oxy)propyl group, 2-(3-methyl-2-butenyl-1
-oxy)propyl group, 3-(2-methyl-2-propenyl-1-oxy)propyl group, 3-(3-butenyl-
1-oxy)propyl group, 3-(4-pentenyl-2-
Examples include oxy)propyl group, 3-(2-methyl-3-butenyl-1-oxy)propyl group, and 3-(2-methyl-3-pentenyl-1-oxy)propyl group.

In the general formula (1), when R represents an alkynyloxyalkyl group, the alkynyloxyalkyl group is not particularly limited and any known alkynyloxyalkyl group may be selected. The alkynyloxyalkyl group which is generally suitably employed has a total carbon number of 2 to
10 linear or branched chains are preferred. A specific example of what is most preferably used is 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-
These include butynyl-2-oxy)propyl group, 2-(3-pentynyl-2-oxy)propyl group, and the like.

In the general formula (1), when R represents a phenoxyalkyl group, the phenoxyalkyl group is not particularly limited and any known phenoxyalkyl group can be used. The phenoxyalkyl group which is generally suitably employed has preferably 7 to 12 carbon atoms in total. More specific examples of those most preferably used include phenoxymethyl group, phenoxyethyl group,
These include phenoxypropyl group, phenoxybutyl group, etc.

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 in the present invention, an inert group that does not participate in the reaction is used. Substituents can be used. More specific examples of particularly preferably used substituents include halogen atoms such as chlorine, bromine, iodine, and fluorine; nitro group; hydroxyl group; methyl group, ethyl group,
-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, n-butoxy group; methylthio group, ethylthio group, n-proportio group , an alkylthio group such as n-butylthio group; chloromethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group,
Halogenoalkyl groups such as trofluoroethyl group and pentafluoroethyl group; phenyl group, etc.

More specific examples of the most preferably substituted alkoxyalkyl groups include 3-methoxy-2-chloropropyl group, 3-methoxy-2-bromopropyl group, and 3-methoxy-2-iodo group. 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 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, etc.

More specifically, the substituted alkenyloxyalkyl group most preferably used is 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.

More specific examples of the most preferably substituted phenoxyalkyl groups include chlorophenoxyethyl group, bromophenoxyethyl group, fluorophenoxyethyl group, iodophenoxyethyl group, dichlorophenoxyethyl 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, trimethoxyphegenoxyethyl group, methoxyphenoxyethyl group, ethoxyphenoxyethyl group, isopropoxyphenoxyethyl group, ethylthiophenoxyethyl group, dimethoxyphenoxyethyl group, diethoxyphenoxyethyl group,
Nitrophenoxypropyl group, chlorophenoxypropyl group, bromophenoxypropyl group, fluorophenoxypropyl group, iodophenoxypropyl group, dichlorophenoxypropyl group, trichlorophenoxypropyl group, chloro-methylphenoxypropyl group, bromo-fluorophenoxypropyl group, chloro -ethylphenoxypropyl group, chloro-cyanophenylphenoxypropyl group, chloro-methoxyphenoxypropyl group, methoxycarbonylphenoxypropyl group, trimethylphenoxypropyl group, methylthiophenoxypropyl group,
These include trimethoxyphenoxypropyl group, methoxyphenoxypropyl group, ethoxyphenoxypropyl group, isopropoxyphenoxypropyl group, ethylthiophenoxypropyl group, dimethoxyphenoxypropyl group, diethoxyphenoxypropyl group, nitrophenoxypropyl group, and the like.

The phenylamine derivative represented by the general formula (1) is a combination of the atoms or groups described for Z, X1, X2, A and R, respectively. More specific examples of those that are particularly easily produced industrially and have good herbicidal activity include 4-(2',4'-dichlorophenoxy)-2-methoxyethylaminonitrobenzene, 4-(2 ',4'-dichlorophenoxy)-2
-ethoxyethylaminonitrobenzene, 4-(2',
4'-dichlorophenoxy)-2-isopropoxyethylaminonitrobenzene, 4-(2',4'-dichlorophenoxy)-2-methoxypropylaminonitrobenzene, 4-(2',4'-dichlorophenoxy)-2-
Ethoxypropylaminonitrobenzene, 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-ethoxypropylaminonitrobenzene, Fluoromethylpyridyl-2-oxy)-2-ethoxyethylaminonitrobenzene and the like.

The phenylamine derivative represented by the general formula (1) of the present invention can be obtained by measurement of infrared absorption spectrum (IR), mass spectrum (MS), 1H-nuclear magnetic resonance spectrum (1H-NMR), and elemental analysis. etc.,
You can check its structure. Examples of typical patterns are as follows.

(a) By measuring the infrared absorption spectrum (IR), characteristic absorption based on ether bond (C-O-C) at 1150-1270 cm-1, 3300-3
Characteristic absorption based on amino groups can be observed at 400 cm-1.

(b) Measure mass spectrum (MS),
By calculating the composition formula corresponding to each observed peak (generally expressed as m/e, which is the ion molecular weight m divided by the ion charge number e), the molecular weight of the compound subjected to measurement and the molecule can be determined. It is possible to know the bonding mode of each atomic group within. That is, when a sample subjected to measurement is expressed by the general formula (1), the molecular ion peak (hereinafter abbreviated as M+) generally follows the isotopic abundance ratio according to the number of halogen atoms contained in the molecule. Since the intensity is observed, the molecular weight of the compound subjected to measurement can be determined.

(c) 1H-nuclear magnetic resonance spectrum (
By measuring 1H-NMR), it is possible to know the bonding mode of hydrogen atoms present in the compound of the present invention represented by the above general formula. X1 in the general formula (1) above,
Regardless of the types of X2, It generally appears as a line.

(d) By elemental analysis, carbon, hydrogen, nitrogen (sulfur and halogen if it contains sulfur and halogen)
By determining the weight of each element and further subtracting the sum of the recognized weight percent of each element from 100, the weight percent of oxygen can be calculated, and the compositional formula of the compound can therefore be determined.

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

The derivatives of the present invention include benzene, ether, alcohol, acetone, N,N-dimethylformamide,
It dissolves well in organic solvents such as dimethyl sulfoxide, but
Insoluble or sparingly 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 any production method may be used. Typical manufacturing methods are as follows.

(a) General formula (2),

[Chemical formula 3] (However, X4 represents a halogen atom or a nitro group, and A, X1, X2 and Z are as shown in general formula (1).) A phenyl derivative represented by general formula (3) RNH2
...(3) (However, R is as shown in general formula (1).) React with the amine derivative represented by the formula (1) in the presence or absence of a solvent, or

(b) General formula (4),

[Chemical 4] (However, X5 represents a halogen atom, X1, X2
and Z are as shown in general formula (1). ) is represented by the general formula (5)

[Chemical formula 5] (However, M represents a hydrogen atom or an alkali metal, and R
and A are as shown in general formula (1). ) in the presence or absence of a solvent, or further,

(c) General formula (6)

[Chemical formula 6] (However, M represents a hydrogen atom or an alkali metal, and
1 , X2 and Z are as shown in general formula (1). ) and the general formula (7)

[Chemical formula 7] (However, X6 represents a halogen atom, and A is the general formula (
As shown in 1). ) can be produced by reacting the phenol derivative represented by () in the presence or absence of a solvent.

In the above reaction (a), the molar ratio of the phenyl derivative represented by the general formula (2) and the amine derivative represented by the general formula (3) may be determined as necessary, but usually Equimolar or amine derivative, e.g. 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 determined as necessary, but usually It is common to use an equimolar or slight excess of the phenol derivative, for example 20%, preferably 10%.

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

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

In reactions (b) and (c), a phenol derivative represented by general formula (5) and a phenol derivative represented by general formula (6)
Sodium, potassium, lithium, etc. can be used as the alkali metal of the aryl derivative represented by, but sodium and potassium are generally most suitable.

Reactions (a), (b) and (c) are generally carried out at a temperature in the range of -30 to 200°C, preferably in the range of 5 to 150°C. The reaction time is preferably 0.5 to 40 hours, preferably 3 to 1 hour.
It is best to do this at 0 hours.

The method for isolating and purifying the desired product, the phenylamine derivative, from the reaction system is not particularly limited, and any known method can be employed. The reaction solution is added to ice water, the generated solid is filtered, and the solid is purified by recrystallization or column chromatography. Alternatively, if the solvent is immiscible with water, the reaction solution is added to water and an organic solvent is added. After extracting with water and distilling off the solvent, a method of purifying the residue by recrystallization or column chromatography is preferably used.

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

Of course, auxiliary agents for formulation, such as spreading agents, diluents, surfactants, etc., can be appropriately added and used in a liquid or solid state. In particular, it is often effective to use surfactants to improve dispersibility in water and oil.

[0038] As the surfactant, anionic, cationic or nonionic surfactants which are known to be usable in general herbicide formulations can be suitably used. Examples of those which are particularly preferably used are as follows.

Examples include alkylbenzenesulfonic acids, alkylnaphthalenesulfonic acids, fatty acid sulfonates, polyoxyethylene alkylphenyl ether sulfonates, sodium alkylsulfates, sodium ligninsulfonates, polyalkylnaphthalenesulfonates, and the like.

Typical usage forms of the phenylamine derivative represented by the general formula (1) as herbicides are as follows.

Wettable powders and granules generally contain an inert solid carrier, a surfactant, etc. in addition to the active ingredient represented by the general formula (1). The inert solid carrier is generally a natural or synthetic inorganic powder. Examples of those most preferably used include clays, talc, calcium carbonate, diatomaceous earth, and silica. Usually 1 to 80 parts by weight of active ingredient, 5 to 98 parts by weight of inert solid carrier, 1 to 1
It consists of 5 parts by weight of surfactant. Of course, polyvinyl alcohol, Na carboxymethylcellulose, etc. may be added as necessary.

Emulsions generally consist of a solution of an active ingredient and a surfactant dissolved in a solvent. As the solvent, any known solvent capable of dissolving the active ingredient can be used, and typical examples include xylene, phenoxyethanol, cyclohexanone, solvent naphtha, methylnaphthalene, kerosene, and the like. The above components generally consist of 75 to 20 parts by weight of active ingredient, 10 to 20 parts by weight of surfactant, and 15 to 60 parts by weight of solvent.

Powders are those in which the active ingredient is supported on a 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 inorganic powder.

Flowable preparations are suspension preparations in which water-insoluble active ingredients are pulverized and dispersed in water with the addition of a dispersant and the like. Generally, the most widely used mode is to suspend the active ingredient at a concentration of 20 to 50% by weight.

Furthermore, exothermic agents such as nitrates, nitrites, guanidine salts and potassium chlorate, and exothermic regulators such as alkali metal salts and potassium nitrate are added to the fuming agent.

[0046]

Effect of the Invention The phenylamine derivative represented by the general formula (1) has extremely high activity with herbicides and is effective against various weeds. Examples of weeds whose herbicidal activity is generally effective are as follows.

[0047] For example, golden locust, Japanese oval millet, Japanese oval locust, Japanese cypress, Japanese cyperus, Japanese cypress, Japanese cyperus, Japanese firefly, firefly, Japanese sardine,
Japanese serpent, Hyderico, Japanese cypress, Japanese black bream, Japanese black bream, Japanese cypress, Japanese black violet, Japanese violet, silver pear, black-and-white cypress, Japanese cypress, Japanese cypress, Japanese parsley, Japanese parsley, willow violet, Japanese japonica, ibokusa, starweed, water chickweed, Japanese japonica, Japanese japonica, yellow japonica, Japanese trifoliate, Azemushiro, Paddy field weeds such as Takasaburo, Taucogi, American Meliflower, Prunus japonicus, Sour Capsicum, Japanese azalea, Azena, Aze capsicum, etc.

[0048] For example, upland weeds such as foxtail grass, foxtail grass, pigweed, Japanese knotweed, cyperus japonica, cyperus japonica, black snail, purslane, red clover, oxalis, sycamore, sycamore, japonica, japonica, japonica, japonica, japonica, and shepherd's purse.

The phenylamine derivative represented by the general formula (1) is particularly effective against broad-leaved weeds compared to compounds conventionally used as herbicides, that is, dichloro-substituted or trifluoro-substituted diphenyl ether compounds. It is a compound that has the property of being able to perform highly selective weeding.

[0050] This can now be applied to a wider range of crops than ever before. Furthermore, there is less chemical damage to transplanted rice than ever before.

[0051]

[Examples] In order to explain the present invention more specifically, the present invention will be described below with reference to 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, 2.3 g of 4-chloro-2-methoxyethylamine and 20 ml of dimethyl sulfoxide were added to 120 g of potassium salt of 2,4-dichlorophenol.
The mixture was heated and stirred at ℃ for 4 hours. The reaction solution was added to water, extracted with ethyl acetate, and then concentrated. The residue was recrystallized from hexane-methanol to obtain 1.45 g of a yellow solid. Yield is 85.
It was 0%. The analysis results of the compound thus obtained were as follows.

IR (cm-1): 3360 (NH), 1250 (
-C-O-C)

0055 MS (M+): 357

1H-NMR (σppm; tetramethylsilane standard, deuterium chloroform solvent): 3.41 (s,
3H), 3.48-3.90 (m, 4H), 6.00-
8.30 (m, 7H)

Elemental analysis value (%): C50.20, H3.
80, N7.92 (calculated value C50.44, H3.95,
N7.84)

[0058] These results indicate that the isolated adult organisms
It was confirmed that it was -(2',4'-dichlorophenoxy)-2-methoxyethylaminonitrobenzene.

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

[Chemical formula 8]

IR characteristic absorption, characteristic mass fragment (MASS) and 1H-NMR (
Tetramethylsilane standard, measured with CDCl3, δ:p
pm) data and properties are shown in Table 1.

The compound represented by the general formula (8) was confirmed based on the above analysis results with reference to elemental analysis. The results are shown in Table 1 as X11 to X15, Y and R.

[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 1
．． 0 g and 2.7 g of methoxypropylamine were stirred for 1 hour and then concentrated. The residue was purified by silica gel chromatography (benzene) to obtain 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)

0070 MS (M+): 404

1H-NMR (σppm; tetramethylsilane standard, deuterated chloroform solvent): 1.70-2.
25 (m, 2H), 3.36 (s, 3H), 3.40~
3.75 (m, 4H), 5.98-8.60 (m, 7H
)

Elemental analysis value (%): C50.20, H3
．． 80, N6.70 (calculated value C50.44, H3.98
, N6.92)

From these results, it was determined that the isolated adult organism was 4-(2
It was confirmed to be '-chloro-4'-trifluoromethylamino-nitrobenzene.

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

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

From these analysis results, it was confirmed that the synthesized compound was a compound of general formula (8) shown in X11 to X15, Y, and R in Table 2. For this confirmation, 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)

0083 MS (M+): 405

1H-NMR (σppm; tetramethylsilane standard, deuterated chloroform solvent): 1.89 (t,
2H), 3.28 (s, 3H), 3.35-4.10 (
m, 4H), 7.00-8.35 (m, 6H)

008
5] Elemental analysis value (%): C47.60, H3.85, N
10.78 (calculated value C47.36, H3.73, N10
．． 36)

From these results, it was determined that the isolated adult organism was 4-(2
It was confirmed to be '-chloro-4'-trifluoromethylamino-nitrobenzene.

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

[0088]

[Chemical formula 9]

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

From these analysis results, it was confirmed that the synthesized compound was a compound represented by the general formula (9) shown in X21 to X24, 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 derivatives shown in Tables 1, 2 and 3, 2 parts by weight of polyoxyethylene nonylphenyl ether, 40 parts by weight of fine clay, and 48 parts by weight of Siegrite were pulverized and mixed to give a 10% A hydrating powder was prepared.

[0093] Application example 1

After filling a 1/8850 are magnetic pot with paddy soil (alluvial loam) well mixed with water and sowing paddy weeds, rice seedlings at the 3-leaf stage (variety: Akinishiki) were transplanted to a depth of 2 cm. Then, water was added to make it submerged to a depth of 2 cm.

Next, 1 of each compound produced in Formulation Example 1
A predetermined amount of the 0% diluted solution was dropped at the time of weed germination. After the treatment, the plants were grown in a greenhouse at an average temperature of 25° C., and the herbicidal effects of each test compound were investigated three weeks later. The results are shown in Table 4.

[0096] However, the broad leaves shown in the table refer to azalea, sycamore, chickweed, and the like. The evaluation was on a 6-level scale, and the herbicidal effect was expressed as a number from 0 to 5 as shown below. 0...Weed suppression rate 0-9%
1 ・・・・Weed suppression rate 10-29%2
... Weed suppression rate 30-49%3 ・
... Weed suppression rate 50-69%4 ...
・・Weed suppression rate 70-89%5 ・・・・
Weed suppression rate 90-100%

Regarding chemical damage to transplanted rice, the ratio of plant height, tiller number, and total weight (air-dried weight) to the untreated plot was calculated, and the worst of the three factors was set as 5, and evaluated on the following 6-level scale from 0 to 5. did. 0 ... Ratio to untreated area 1
00%1 ・・・・Ratio to non-treated area 90
~99%2 ... Ratio to untreated area 8
0-89%3 ・・・・・・ Ratio to untreated area
60-79%4 ・・・・・・ Ratio to untreated area
40-59%5 ・・・・・・ Ratio to untreated area
0-39%

[0098]

[Table 10]

0099

[Table 11]

[0100]

[Table 12]

[0101] Application example 2

[0102] A 1/8850 are magnetic pot is filled with field soil (clay loam), soybean seeds are sown to a depth of 2 to 3 cm, and seeds of various plants such as Japanese wild grass, green grass, and rosinus are sown to a depth of 0.5 to 1 cm. The soybeans were sown at a certain depth, and when the soybeans had grown to the initial leaf development stage, a spreading agent was added to a water diluted solution of the hydrating powder of each compound, and a predetermined amount was sprayed onto the leaves. After treatment, average temperature 25
The herbicidal effects of each test compound were investigated after 2 weeks. The survey results are shown in Table 5. In addition, Table 5
The evaluation of the herbicidal effect is the same as above, and for chemical damage to soybeans, the ratio of plant height and total weight (air dry weight) to the untreated area is calculated, and the worst of the two factors is set as 5, and the following 0
Evaluation was made on a scale of 6 to 5. 0 ... Ratio to untreated area 1
00%1 ・・・・Ratio to non-treated area 90
~99%2 ... Ratio to untreated area 8
0-89%3 ・・・・・・ Ratio to untreated area
60-79%4 ・・・・・・ Ratio to untreated area
40-59%5 ・・・・・・ Ratio to untreated area
0-39%

[0103]

[Table 13]

[0104]

[Table 14]

[0105]

[Table 15]

[0106]

[Table 16]

[0107] Application example 3

[0108] A 1/8850 are magnetic pot was filled with field soil (clay loam), and seeds of various plants such as Japanese shrimp, foxtail grass, green grass, and cottontail were sown to a depth of 0.5 to 1 cm, and then each compound was hydrated. A predetermined amount of a water diluted solution of the agent was sprayed onto the soil. After treatment, the plants were grown in a greenhouse at an average temperature of 25° C., and the herbicidal effects of each test compound were investigated two weeks later. The survey results are shown in Table 6. In addition, the evaluation of the herbicidal effect in Table 6 is the same as above.

[0109]

[Table 17]

[0110]

[Table 18]

[0111]

[Table 19]

[0112]

[Table 20]

[Table 9]

Claims (1)

[Claims] Claim 1: General formula (1), [Formula 1] or an unsubstituted alkyl group) or a nitrogen atom, and X1 and X2 are different or similar hydrogen atoms, halogen atoms, halogen-substituted or unsubstituted represents an alkyl group, A represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, and R represents a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyloxyalkyl group, or an alkynyloxyalkyl group. group, substituted or unsubstituted phenoxyalkyl group,
Indicates a tetrahydrofurfuryl group, a furfuryl group, and a thienylmethyl group. ) Phenylamine derivatives represented by