JPH0395170A - New diphenyl ether derivative and herbicide containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X<1> is halogen or 1-3C haloalkyl; X<2> and X<3> are H, halogen, CF3, NO2 or CN; Y is NO2, CN, H or X<1>; A is direct bond, CO2CH(R<1>), C(R<2>)=NOCH(R<3>) (R<1> and R<3> are H or 1-3C alkyl; R<2> is H, 1-4C alkyl or 1-3C alkoxy), etc.; B is formula II (R<5> is halogen, OH, 1-6C acyloxy, benzoyloxy, alkylsulfonyloxy, etc.)]. EXAMPLE:3-(5-(2-Chloro-4-trifluoromethylphenoxy)-2-nitrobenbzoyoloxy)-4- hydroxytetrahydrofuran. USE:A herbicide. PREPARATION:For example, a compound expressed by formula III (Z<1> is halogen) is reacted with a compound expressed by the formula HO-B to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel diphenyl ether derivative and a herbicide containing the same as an active ingredient.

[Prior art] 2. A number of diphenyl ether compounds having herbicidal activity have been proposed, including 4-';chloro-4'-ditrodiphenyl ether (common name: nitrofen). In particular, various herbicides have been produced by conversion of the 41-position and the 3'-1 position (the ortho position of the nitro group in nitrofen). For example, 2,4-dichloro-3'-methoxycarbonyl-4'-nitrodiphenyl ether (common name Hyfenox), sodium 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate salt (common name: acifluorophene-Na), 1-(ethoxycarbonyl)ethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropenzoate (common name: lactofene), 5-(2-chloro) Examples include 4-trifluoromethylphenoxy)-2-nitro-N-methanesulfonylbenzamide (common name: homesaphene). Also, JP-A-56-86179, JP-A-56-108742 and JP-A-60-115
No. 6 and other publications propose diphenyl ethers having a tetrahydrofuran ring in the structural formula. Also, JP-A No. 56-32432, JP-A No. 60-22685
Publication No. 6, JP-A-62201860, JP-A-63
-165359 etc., (substituted) alkyl (5-
The use of (2-chloro-4-trifluoromethylphenoxy)phenyl)ketone derivatives or 2-nitro-5-(substituted phenoxy)penzohydroxymic acid derivatives as herbicides has been proposed.

However, at present, these diphenyl ether herbicides can only be used on relatively limited crops such as rice and soybeans. This is because in the case of conventional diphenyl ether compounds, those with extremely high herbicidal activity tend to have low crop safety, and those with high crop safety tend to have low herbicidal activity. However, in many crop cultivations, both herbicidal activity and crop safety have not been satisfied.

(Problems to be Solved by the Present Invention) As mentioned above, many diphenyl ether compounds having herbicidal activity have been proposed, but safety and satisfactory herbicidal activity for certain crops are still unknown. There are not many herbicides that have these properties, and there is a strong demand for herbicides that have these properties.Also, when considering the impact on the environment, it is desirable to use small amounts of herbicides. Needless to say, the present invention seeks to meet these demands.

[Means for Solving the Problems] As a result of intensive studies on the above problems, the present inventors found that while the compounds of the present invention exhibit high herbicidal activity in upland fields and paddy fields, they have little effect on cultivated crops. It was found that it has the characteristic that it has no effect.

That is, the gist of the present invention is the following general formula (1) (in the above formula, X1 represents a halogen atom or a haloalkyl group having 1 to 3 carbon atoms, X2 and x3 are each the same or different, a hydrogen atom, It represents a halogen atom, a trifluoromethyl group, a nitro group, or a cyano group, Y represents a nitro group, a cyano group, a halogen atom, a haloalkyl group having 1 to 3 carbon atoms, or a hydrogen atom, and A represents a direct bond or , -COZC}I(R') -C(
R2).NOCII(R3) represents a group represented by 1 or 10(.NOR')OCII(R').

In the above group, R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R2 represents a hydrogen atom: an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or
Represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which may be substituted with a halogen atom, and R
3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R4 represents an alkyl group having 91 to 3 carbon atoms, and RS represents a halogen atom; a hydroxyl group; a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, or a halogen atom having 1 to 3 carbon atoms and/or or an aryl group optionally substituted with an alkyl group having 1 to 3 carbon atoms or an acyloxy group having up to 6 carbon atoms optionally substituted with an aryloxy group: a cycloalkyloxy group having 4 to 9 carbon atoms; a halogen a penzoyloxy group which may be substituted with an atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; an alkoxycarponyloxy group having 2 to 7 carbon atoms; an alkylsulfonyloxy group having 1 to 4 carbon atoms; Group: A carbamoyloxy group optionally substituted with an alkyl group having 1 to 4 carbon atoms and/or an alkoxy group having 1 to 4 carbon atoms. ) and herbicides containing this as an active ingredient.

The present invention will be explained in more detail below.

The diphenyl ether derivative used as a herbicide in the present invention is represented by the general formula (I) above.

In the above general formula (1), X1 is a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom, an iodine atom; or a chloromethyl group, a bromomethyl group, a -chloroethyl group, a 2-chloroethyl group, a 2-promoethyl group, - Represents a haloalkyl group having 1 to 3 carbon atoms such as bromoprobyl group, 4-chlorobutyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, etc. , preferably a chlorine atom, a bromine atom, a trifluoromethyl group, a trichloromethyl group, a trifluoroethyl group, a tetrafluoroethyl group, or a pentafluoroethyl group,
Particularly preferred is a chlorine atom or a trifluoromethyl group.

X2 and X3 are the same or different and represent a hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom, or an iodine atom; a trifluoromethyl group; a nitro group; It represents a chlorine atom, a bromine atom, a trifluoromethyl group, a nitro group, or a cyano group, and particularly preferably a hydrogen atom or a chlorine atom.

Y is a nitro group; a cyano group: a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom, an iodine atom; a chloromethyl group,
Bromomethyl group, 1-chlorochel group, 2-chloroethyl group, 2-promoethyl group, 3-promopropyl group, 4
- a haloalkyl group having 1 to 3 carbon atoms such as a chlorobutyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group; or a hydrogen atom, preferably , a nitro group, a cyano group, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, or a hydrogen atom, and particularly preferably a nitro group.

A represents a direct bond or -COzCtl(
R′), -C(R”)・NOC}I(R
”) 1, or -C(・NOR')O(
A group represented by Jl (R") (in the above group, Rl is a hydrogen atom; or a methyl group, an ethyl group, an n-probyl group,
It represents a linear or branched alkyl group having 1 to 3 carbon atoms such as an isoprobyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group. R2 is a hydrogen atom; methoxy group, ethoxy group, n-bropoxy group, isoproboxy group, n-butoxy group, isobutoxy group, se
Straight chain or branched alkoxy groups having 1 to 4 carbon atoms such as c-butoxy group and t-butoxy group, methylthio group, ethylthio group, n-propylthio group, isoprobylthio group, n-
Substituted with a linear or branched alkylthio group having 1 to 4 carbon atoms such as butylthio group, isobutylthio group, sec-butylthio group, t-butylthio group, or halogen atom such as chlorine atom, bromine atom, iodine atom, fluorine atom, etc. A linear or branched chain having 1 to 4 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, etc., which may be Indicates an alkyl group or a straight or branched alkoxy group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, or an isoproboxy group, preferably a hydrogen atom: a carbon that may be substituted with a methoxy group. It represents a linear or branched alkyl group having 1 to 3 carbon atoms or a linear or branched alkoxy group having 1 to 3 carbon atoms, and particularly preferably a methyl group, ethyl group, methoxymethyl group, methoxy group or ethoxy group. R3 represents a hydrogen atom; or a straight or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-probyl group, or an isoprobyl group, preferably a hydrogen atom, a methyl group, or an ethyl group. and particularly preferably represents a hydrogen atom or a methyl group.R4 is
It represents a straight or branched alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, an n-probyl group, or an isobrobyl group, and preferably represents a methyl group. ) is shown.

Among them, R5 is a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, a fluorine atom; a hydroxyl group: a chlorine atom, a bromine atom,
Halogen atoms such as iodine atom and fluorine atom, methoxy group, ethoxy group, n-broboxy group, isobroboxy group,
Straight chain with 1 to 6 carbon atoms such as n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, isobentyloxy group, t-bentyloxy group, n-hexyloxy group or branched alkoxy group, methoxycarbonyl group, ethoxycarbonyl group, n-
Proboxycarbonyl group, isobroboxycarbonyl group, n-butoxycarbonyl group, isofoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-bentyloxycarbonyl group, n-hexyloxycarbonyl group linear or branched alkoxycarbonyl groups having 2 to 7 carbon atoms, halogen atoms such as 1 to 3 chlorine atoms, bromine atoms, iodine atoms, fluorine atoms, etc., and/or methyl groups, ethyl groups, n-probyl groups , an aryl group such as a phenyl group or a naphthyl group which may be substituted with a linear or branched alkyl group having 1 to 3 carbon atoms such as an isobrobyl group, or an aryloxy group such as a phenoxy group or a naphthyloxy group. A saturated or unsaturated acyloxy group having up to 6 carbon atoms which may have carbon atoms such as a cyclopropylic luponyloxy group, a cyclobutylcarbonyloxy group, a cyclobentylcarbonyloxy group, a cyclohexyl luponyloxy group, a cyclooctylcarbonyloxy group, etc. cycloalkylcarbonyloxy group of numbers 4 to 9; halogen atoms such as chlorine atom, bromine atom, iodine atom, fluorine atom, methyl group, ethyl group, n-probyl group, isobrobyl group, n-butyl group, isobutyl group,
Straight chain or branched alkyl groups having 1 to 4 carbon atoms such as sec-butyl group and t-butyl group, methoxy group, ethoxy group,
a penzoyloxy group optionally substituted with a straight or branched alkoxy group having 1 to 4 carbon atoms, such as n-bropoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group; Methoxyluponyloxy group, ethoxycarbonyloxy group, n-
Proboxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, isobutoxycarbonyloxy group, sec-butoxycarbonyloxy group, t-butoxycarbonyloxy group, n-
Straight chain or branched alkoxycarbonyloxy groups having 2 to 7 carbon atoms such as benzyloxycarbonyloxy group, n-hexyloxyluponyloxy group; methylsulfonyloxy group, ethylsulfonyloxy group, n-probylsulfonyloxy group, isoprobylsulfonyloxy group,
Straight chain or branched alkylsulfonyloxy groups having 1 to 4 carbon atoms such as n-butylsulfonyloxy group, isobutylsulfonyloxy group, sec-butylsulfonyloxy group, t-butylsulfonyloxy group; methyl group, ethyl group, n- Straight chain or branched alkyl groups having 1 to 4 carbon atoms such as probyl group, isobrobyl group, n-butyl group, isobutyl group, sec-butyl group, L-butyl group and/or methoxy group, ethoxy group, n-proboxy group, isopropoxy group, n-butoxy group, isobutoxy group, Sec
A carbamoyloxy group which may be substituted with a straight or branched alkoxy group having 1 to 4 carbon atoms, such as a -butoxy group or a t-butoxy group. Preferably, a chlorine atom, a bromine atom, a fluorine atom; a hydroxyl group: a chlorine atom, a bromine atom, a fluorine atom, a straight-chain or branched alkoxy group having 1 to 3 carbon atoms, a straight-chain or branched alkoxycarbonyl having 2 to 5 carbon atoms; group, 1-3 halogen atoms and/or 1-3 carbon atoms
C2-C4 saturated or unsaturated acyloxy group optionally substituted with an aryl group or an aryloxy group optionally substituted with a straight-chain or branched alkyl group; C4-C7 cyclo Alkyl group: penzoyloxy group optionally substituted with a halogen atom; linear or branched alkoxycarbonyloxy group having 2 to 5 carbon atoms; alkylsulfonyloxy group having 1 to 2 carbon atoms; 1 to 2 carbon atoms represents a carbamoyloxy group which may be substituted with an alkyl group and/or an alkoxy group having 1 to 2 carbon atoms. Particularly preferably, chlorine atom, bromine atom, fluorine atom; hydroxyl group; chlorine atom, fluorine atom,
An alkoxy group having 1 to 2 carbon atoms, an alkoxy group having 2 to 3 carbon atoms, a saturated group having 2 to 4 carbon atoms optionally substituted with a phenyl group optionally substituted with a chlorine atom and/or a methyl group or an acyloxy group containing one double bond; number of carbon atoms. 4-6 cycloalkylcarbonyloxy group: penzoyloxy group optionally substituted with a fluorine atom; alkoxycarbonyloxy group having 2-3 carbon atoms: alkylsulfonyloxy group having 1-2 carbon atoms; 1-2 carbon atoms represents a carbamoyloxy group which may be substituted with 2 alkyl groups and/or an alkoxy group having 1 to 2 carbon atoms.

The compound of the present invention represented by the above general formula (1) can be synthesized, for example, according to the following reaction formula. (1) (II) (1) (In the above reaction formula, Zl represents a halogen atom such as a chlorine atom, bromine atom, fluorine atom, or iodine atom, and X'
X3 Y, A, and B have the same meanings as above. ) The above reaction is carried out without a solvent or in a solvent, in the presence or absence of a base. When using a solvent, suitable solvents include benzene, toluene, ethyl acetate, diethyl ether, diisobrobyl ether, tetrahydrofuran, dioxane, N.I. Examples include N-dimethylformamide, N-methylpyrrolidone, 1,2-dimethoxyethane, methylene chloride, and chloroform. As bases,
Pyridine, picolines, quinoline, N,N-'; methyl(diethyl)aniline, triethylamine, sodium bicarbonate (potassium), sodium carbonate (potassium),
Examples include sodium hydroxide (potassium) and sodium hydride. The reaction temperature is in the range of -30 to 120"C, preferably -10 to 60"C, and the reaction time is in the range of 0.5 to 120"C.
24 hours, usually 1 to 8 hours.

(91 (I a) (1 b) (In the above reaction formula, RS is as defined above except for halogen atoms and hydroxyl groups, and RS! is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a carbon number 2 to 7 alkoxy carbonyl groups, or aryl groups optionally substituted with 1 to 3 halogen atoms and/or alkyl groups having 1 to 3 carbon atoms, 1 to 3 halogen atoms, and/or 1 to 3 carbon atoms; an acyl group having 2 to 6 carbon atoms which may be substituted with an aryloxy group which may be substituted with 3 alkyl groups; a cycloalkylcarbonyl group having 4 to 9 carbon atoms;
A benzoyl group optionally substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; an alkylsulfonyl group having 1 to 4 carbon atoms: 22 represents a halogen atom such as a chlorine atom or a bromine atom, or Rsz represents an acyl group as mentioned above. When it is a group, it indicates a residue forming a symmetrical or mixed acid anhydride, and X'l X"t X31Y,A
indicates the same meaning as above. ) The above reaction is carried out without a solvent or in a solvent, in the presence or absence of a base. When using a solvent, suitable solvents include benzene, toluene, ethyl acetate, diethyl ether, diisobrobyl ether, tetrahydrofuran, dioxane, N.I. Examples include N-dimethylformamide, N-methylpyrrolidone, 1,2-dimethoxy8-ethane, methylene chloride, and chloroform. Bases include biridine, vicolines, quinoline, N,N-dimethyl(diethyl)aniline, triethylamine, sodium hydrogen carbonate (potassium), sodium carbonate (potassium),
Examples include sodium hydroxide (potassium) and sodium hydride. The reaction temperature is in the range of -30 to 120°C, preferably -10 to 60°C, and the reaction time is 0. 5～
24 hours, usually 1 to 8 hours.

(In the above reaction formula, RS3 represents a halogen atom,
, Hydrogen fluoride, hydrogen fluoride complexes such as hydrogen fluoride-pyridine fluoride, hydrogen fluoride-melamine complex, 2-chloro-1.1.
2-trifluorotriethylamone, diethyl-1.1
, 2,3,3.3-hexafluorobrovir amine, diethylaminosulfur triple olide, phenylfluorophosphorane, thionyl chloride, phosphorus oxychloride, hydrogen chloride, thionyl bromide, phosphorus tribromide, hydrogen bromide , phosphorus triiodide, hydrogen iodide, etc.

When using a solvent, suitable solvents include benzene, toluene, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, diglyme, acetonitrile, methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, N,N-dimethyl Examples include formaldehyde, N-methylpyrrolidone, acetic acid, and water. It is also possible to use a mixture of these. When using bases,
Suitable bases include biridine, vicolins, lutidines, quinoline, tri-lower alkyl alkyls, di-substituted amines such as diisoprobylamine and dicyclohexylamine, and the like. The reaction temperature is in the range of -30 to 200°C, preferably -10 to 150'C, and the reaction time is 0. 1 to 30 hours, usually 0. It is 1 to 12 hours.

(Id)? In the above reaction formula, G is -CO■-, -C(R”)・NO
- or -CONH(OR')- represents a group represented by R! z represents a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom; - indicates Rl; when G is a group represented by 1C(1?'') NO- or 100NFI(OR')1, it indicates R3; A1 indicates G is -CO■
- indicates a group represented by -COZCH(R')1, and G is -C(R'')・NO- or -CONH(OR'
) 1, -C<R”)=NOC}I
(1?')-Mataha-C(・NOR')QC}l (
R') represents a group represented by 1, X l, X", X',
(Y, B, R', R", R' and zg have the same meanings as above.) The above reaction is carried out without a solvent or in a solvent in the presence of a base. When a solvent is used, as a suitable solvent. are methanol, ethanol, 2-propanol, acetone, ethyl methyl ketone, diethyl ether, diisobrobyl ether, ethyl acetate, benzene, toluene, xylene, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, acetonitrile, N,N-dimethyl Examples include formaldehyde, N-methylpyrrolidone, etc. It is also possible to use a mixture of these solvents.

Bases include sodium bicarbonate (potassium), sodium carbonate (potassium), sodium hydroxide (potassium, barium, calcium), viridine, picolines, quinoline, N,N-dimethyl(diethyl)aniline, triethylamine, sodium (potassium). ) Lower alkoxides, sodium (potassium) hydride, metallic sodium, potassium fufluoride, etc. Reaction temperature is -30~
200°C1 is preferably in the range of -10 to 150°C, and the reaction time is 0.5 to 48 hours, usually 1 to 18 hours.

(5) (Ie)? In the above reaction formula, TI represents a group represented by -CH(R')Co■B or R4,
When γ1 is a group represented by Il(R3)COJ, it represents R23; when γ1 is R4, it represents a group represented by -CIl(R3)COzB, and Z3 is a halogen atom, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or It represents an optionally substituted phenylsulfonyloxy group or an alkylsulfonyloxy group such as a trifluoromethanesulfonyloxy group, and A2 is 10 (R
! 3) A group represented by NOCII (R3) or -
Represents a group represented by C(・NOR')OCH(R'), R23 is an alkoxy group having 1 to 4 carbon atoms, and
4 alkylthio group or an alkoxy group having 1 to 4 carbon atoms which may be substituted with a halogen atom, XI,
(X", are methanol, ethanol, 2-propanol, acetone, ethyl methyl ketone, diethyl ether, diisobrobyl ether, edyl acetate, benzene, toluene, xylene, 2-tetrahydrofuran, dioxane, 1,2-dimethoxyethane, acetonitrile, N, Examples include N-dimethylformamide, N-methylpyrrolidone, etc. It is also possible to use a mixture of these solvents.

Bases include sodium bicarbonate (potassium), sodium carbonate (potassium), sodium hydroxide (potassium, barium, calcium), pyridine, vicolins,
Examples include quinoline, N,N-dimethyl(diethyl)aniline, triethylamine, sodium (potassium) lower alkoxides, sodium (potassium) hydride, metallic sodium, potassium fluoride, and the like. The reaction temperature is -30
~200°C, preferably -10~150°C, and the reaction time is 0. It is 5 to 48 hours, usually 1 to 18 hours.

The compound of the present invention thus obtained has isomers such as optical isomers, diastereomers, and geometric isomers. The present invention includes all of these. The compound of the present invention can be used as a herbicide in each of these isomers alone or in any mixture of these isomers.

To apply the compound of the present invention as a herbicide, the active substance itself may be applied, or it may be applied in the form of a permanent agent, granule, emulsion, flowable agent, etc. using a suitable carrier or surfactant according to a conventional method. It is also possible to take As the carrier and surfactant, for example, those described in JP-A-60-25986 can be used. Furthermore, the herbicide containing the compound of the present invention can be applied in combination with other agricultural chemicals used in the same field, such as insecticides, fungicides, herbicides, growth regulators, or fertilizers.

The application amount of the herbicide of the present invention varies depending on the type of compound used, the target weed, the treatment period, the treatment method, and the nature of the soil, but the effective amount is usually 0.000% per hectare. 0 0 5-2 kg, preferably 0.0
A range of 1 to 1 kilogram is suitable.

The target weeds and treatment period for the herbicide of the present invention are, for example, white weeds, pigweed, Japanese knotweed, Japanese knotweed, Japanese knotweed, Japanese knotweed, Japanese chickweed, hotokenoza, Japanese knotweed, Japanese chickweed, golden weed, foxtail grass, Japanese knotweed, Japanese cyperus, etc. in paddy fields. It is possible to control weeds, for example, weeds such as japonica, azalea, japonica, sycamore, chickweed, japonica, japonica, and cypress in both the pre-emergence treatment and the growing season treatment. In addition, the compound of the present invention can be used in, for example, soybean, cotton,
It has very little effect on cultivated crops such as sunflowers, potatoes, rice, wheat, barley, corn, and sugarcane during pre-emergence treatments and during growing season treatments, and can be used as a selective herbicide.

Furthermore, the compound of the present invention can be used to kill weeds that have been difficult to control with existing herbicides, such as Japanese crocodile, Japanese fir tree, wild morning glory, Japanese morning glory, wild mustard, Japanese violet, Japanese daisy, Orosha chrysanthemum, etc. In rice fields, it has high herbicidal activity against, for example, Japanese porphyry, Omodaka, Japanese firefly, and Mizugayari.

The herbicidal activity of the compounds of the present invention varies slightly depending on the type and substitution position of the modified functional group, and furthermore, the herbicidal activity may decrease depending on the advanced growth of weeds and the amount of treatment agent. In such cases, it is possible to further stabilize the herbicidal activity by mixing it with other herbicides, and examples of herbicides that can be suitably mixed include the following.

Virazole herbicide 1-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl p-}luenesulfonate, 4-(2,4-dichlorobenzoyl)
-1,3-dimethyl-5-fuunacyloxyvirazole, 4- (2,4-dichloro-3-methylbenzoyl)
-1,3-dimethyl-5-(4-methylphenacyloxy)pyrazole, 4-(2,4-dichlorobenzoyl-
Sulfonylurea herbicides such as 1-methyl-5-phenacyloxyvirazole, dimethyl 2-(4,6-dimethoxypyrimidin-2-ylcarbamoylaminosulfonylmethyl)penzoate, ethyl 5-(4,6-dimethoxypyrimidine-) 2-ylcarbamoylaminosulfonyl)-1-methylvirazole-4-carboxylate, 2-chloro-N-(4-methoxy-6-methyl-1,
3.5-}Ryazin-2-ylaminocarbonyl)benzenesulfonamide, methyl 2-(4-methoxy6-
Methyl-1.3.5-}riazin-2-ylcarbamoylaminosulfonyl)penzoate, methyl 2-(4.
Phenoxy herbicides: 2,4-dichlorophenoxyacetic acid and its derivatives, 4-chloro-2-methylphenoxyacetic acid and its derivatives, 4-(4-chloro-2-methylphenoxy)butyric acid and its derivatives, 4-chloro-2-
S-ethyl methylphenoxythioacetate, 2-(2-naphthoxy)propionanilide, 2-(2,4-dichloro-3-methylphenoxy)probionanilide, 2-
Haloacetanilide herbicides such as (4-(5-}refluoromethyl=2-pyridyloxy)phenoxy]butylpropionate: 2-chloro-2'6'-
Diethyl-N-methoxymethylacetanilide, 2-chloro-2',6'-diethyl-N-butoxymethylacetanilide, 2-chloro-2'-1-ethyl-6'-methyl-N-(2methoxy-1-methylethyl)acetanilide, 2 -chloro-2'6'-diethyl-N-proboxyethyl acetanilide, N-chloroacetyl-N-
(2.6-diethylphenyl)aminoethyl acetate, 2-
Chloro 2',6'-dimethyl N-(3-methoxy-2
-thenylmethyl)acetanilide and other acid ξ-do type herbicides: 3',4'-dichlorobutionanilide, 2'3'-dichloro4-ethoxymethoxybenzanilide, 2-bromo3,3-dimethyl-N
-(α.α-dimethylbenzyl)butyric acid ξ-do, 2-penzothiazol-2-yloxy-N-methylacetanilide, 2',4'-difluoro-2-(3-}lifluoromethylphenoxy)nicotinic acid anilide, Carbamate herbicides such as 2,6-dimethoxy N-(3-(1-ethyl=1-methylpropyl)inxazol-5-yl)penzamide: S-(4-chlorobenzi 7L/
) -N, N-'; ethylthiol carbamate, S
-Ethyl-N,N-hexamethylenethiol carbamate, N,N-hexamethylene-S-isoprobylthiol carbamate, S-benzyl-N-ethyl-N-(1
2-dimethylbucutyl) thiol carbamate, S
- (1-methyl-1-phenethyl)-piveridine l-carbothioate, ○-(3-t-butylphenyl)-
N-(6-methoxypyridin-2-yl)N-methylthiocarbamate, S-ethyl-N,N-di-n-probylthiolcarbamate, S-ethyl-N,N-diisobutylthiolcarbamate, isobropyl N-(3-
chlorophenyl)carbamate, 3-methoxyluponylaminophenyl-N-(3-methylphenyl)carbamate, S-(2,3-dichloroallyl)-N,N-diisobutylthiolcarbamate, S-(2.3 ．．
Urea herbicides such as 3-}liku6loallyl)-N,N-diisobrobylthiol carbamate, methyl N-(4-aminobenzenesulfonyl)carbamate: l-(α,α-dimethylbenzyl)-
3-(4-methylphenyl)urea, 3(penzothiazol-2-yl)-1,3-dimethyluria L 3- (3.
4-dichlorophenyl)-1-methoxy-l-methylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(4-(4-methylphenethyloxy)phenyl) ]-1-methoxy1-methylurea, 3
Diphenyl ether herbicides such as -(4-isoprobylphenyl)-1,i dimethylurea, 1-(2=substituted benzyl)-3-(α,α-dimethylbenzyl)urea:
2,4.6-MJ cloro-4'-nitrodiphenyl ether, 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether, methyl 5-(2,4-dichlorophenoxy)-2- Nitropenzoate, 3- (5-
(2-chloro-4-trifluoromethylphenoxy)
-2-nitroph. [enoxy]tetrahydrofuran, 5-
(2-chloro4-trifluoromethylphenoxy)-
2-21, benzoic acid and its salts, 2-chloro3
'1-ethoxy-4'-2-ditro-4-trifluoromethyldiphenyl ether, l-ethoxycarbonylethyl 5
- (2-chloro-4-1-'J 7fluoronotylphenoxy)-2-nitrobenzoate, 5- (2
-chloro-4-trifluoromethylphenoxy)-N-
Methanesulfonyl-2-nitrobenzamide, methyl 5
- Triazine herbicides such as (2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime 10-acetate, 3-chloro-4-nitrodiphenyl ether, etc.: 2-chloro- 4-ethylamino-6-isopropylaminol 1.3.5-triazine, 2
．． 4-bis(ethylamino)-6-methylthio-1.3
．． 5-1 riazine, 2-ethyl aξ-4-(1.2-
dimethylbrobylamino)-6-methylthio-1.3.
5-triazine, 2,4-bis(isopropylamino)
-6-methylthio-1.3.5-1-riazine, 4-amino-6-t-butyl-3-methylthio-1.2.4-
Triazin-5(4H)-one, 4-aξno6-t-
Butyl-3-ethylthio-1.2.4-triazine-5
(4H) mono, 2-chloro-4,6-bis(ethylamino)-1,3.5-triazine, 2-(2-chloro-4-ethylamino-1,3.5-triazine-6-
Dinitroaniline herbicides such as (ylamino)-2-methylprobionitrile: 2,6-dinitro N,N-
Dibrovir-4-trifluoromethylaniline, N-
(1-ethylprobyl)-3,4-dimethyl-2,6-
Nitrile herbicides such as dinitroaniline, 3,5-dinitro-N,N-dibrobylsulfanilamide: 4-hydroxy-3,5-jodobenzonitrile, 3,5-dibromo-4-hydroxybenzonitrile, 2,S -Phosphorus-containing herbicides such as dichloropenzonitrile 〇,○-diisobrobylphosphor dithioether},
S- (2-Methylbiperidin-1-yl)carbonylmethyl 10,0 dibrobyl phosphorodithioate, N-
(phosphonomethyl)glycine, ammonium (3-amino-3-carboxy)propylmethylphosphinate,
Quaternary ammonium salt herbicides such as sodium (2-amino-4-methylphosphino)butyrylalanylalaninate: 1,1'-ethylene-2
．． Other herbicides such as 2'-bipyridylium dibromide, 1,l'-dimethyl-4,4'-bipyridylium dichloride: 3,6-dichloro-2-methoxybenzoic acid, 3,7-dichloroquinoline -8-carboxylic acid, pentachlorophenol, 2-sec-butyl-4,6-
Dinitrophenol, 2-amino-3-chloro 1,4
-naphthoquinone, 1,2-dihydropyridazine-3.6
-dione, 3-(2-methylphenoxy)pyridazine,
3-isoprobyl-IH-2.1.3-penzothiadiazine-4(3H) one 2.2-dioxide, 2.2-
Dichlorobrobionic acid, 2,2,3,3-tetrafluoroprobionic acid, methyl 6-(4-isopropyl-4-
Methyl-5-oxo-2-imidazolin-2-yl)=
3(4) Monomethylbenzoate, 2-(4-isobrobyl-4-methyl-5-oxo-2-imidazoline-2-
nicotinic acid and its salts, 2-(4-isobrobyl-4-methyl-5-oxo-2-imidazoline-2-
yl) quinoline = 3-carboxylic acid, 5-ethyl-2-(
4-isoprobyl-4-methyl-oxoimidazolin-2-yl)nicotinic acid, 1-methyl-4-(1-methylethyl)-2-(2-methylphenylmethoxy)
-7-Oxabicyclo(2.2.l)hebutane,l-(
3-methylphenyl)-5-phenyl 1f{-1.2
．． 4-Triazole-3-carpoxamide, 2-(N-ethoxybutylimidoyl)-5-(2-ethylthioprobyl)-3-hydroxy-2-cyclohexene-1
-one, 2-(3,5-dichlorophenyl)-2- (
2.2.2-}lichloroethyl)oxirane, N-(
4-chloropenzyloxy)phenyl)-3.4,5.
6-tetrahydrophthalide, N-(4-chloro-2-fluoro-5-probargyloxyphenyl)-3
．． 4.5,6-tetrahydride, 3-(2.
4-dichloro-5-isopropoxyphenyl)5-t-
Butyl-1,3,4-oxadiazole-2 (31{
) mono, 4-methoxy-33'-dimethylbenzophenone, 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-penzofuranyl methanesulfonate, 1-methyl-3-phenyl-5- (3- trifluoromethylphenyl)pyridine-4(1}1) one, 2-(2-
chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone, (E)(E)-2- (1- (3-
Chlorobropen-2-yloxyiminobutyl)-5
- (2-ethylthiopropyl)-3-hydroxy-2
-cyclohexene-l-one, 2-(1-ethoxyiminobyl)-3-hydroxy-5-medithyl-2-diclohexen-l-one, etc. It is also possible to use a mixture of a plurality of these.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Example 1 Preparation of 3-(5-(2-chloro4-trifluoromethylphenoxy)-2-nitropenzoyloxy)-4-hydroxytetrahydrofuran 5-(2-chloro4-trifluoromethylphenoxy )-2 ditrobenzoic acid 3. A mixture of 53 g and thionyl chloride was heated under reflux for 2 hours. After distilling off the excess thionyl chloride, the residue was dissolved in 5 mffi of dry ethyl acetate. On the other hand, 1.52 g of 3,4-dihydroxytetrahydrofuran, 1. 9 7 g
A mixture of 30 ml of ethyl acetate and 30 ml of ethyl acetate was prepared and cooled to O''C. To this was added dropwise the previously obtained solution of the acid chloride in ethyl acetate with stirring.

After stirring at room temperature for 3 hours, the reaction mixture was washed with water and then with saturated brine, and the organic layer was dried over mirabilite.

After distilling off the solvent, the residue was diluted with the developing solvent ethyl acetate n-
The product was purified by hexane tit silica gel column chromatography to obtain 2.20 g of the compound (Nα2) listed in Table 1. Melting point 92-94°C. IR spectrum (KBr)
c1m-': 3 4 0 0. 1 7 3 5,
1575, 1525, 1315, 1260
, 1130. 1075'H-NMR spectrum (CDC P. 3-TMS)
δ: 2.14 (IH, d). 3.63-4.26(
4H, m), 4.60 (IF ■, quint), 5
．． 43 (IH, q), 7.04-8.1 4 (
6H, m) Example 2 Preparation of 3-(5-(2-chloro-4-trifluoromethylphenoxy)-2-ditropenzoyloxy)-4-methoxyacetoxytetrahydrofuran 5-(2-chloro-4-trifluoro Methylphenoxy)-2-nitrobenzoic acid2. A mixture of 89 g and 2 mf of thionyl chloride was heated under reflux for 2 hours. After distilling off excess thionyl chloride, the residue was dissolved in 4 mf of benzene. On the other hand, 3-hydroxy-4-methoxyacetoxytetrahydrofuran 1. ．． 54g,}ethylamine 1. A mixture of 32g and 5mj2 of Henzen 2 was prepared, and the benzene solution of the acid chloride obtained earlier was added to it.
The mixture was added dropwise at room temperature with stirring. After stirring for 3 hours, the reaction mixture was washed with water and then with saturated brine, and the organic layer was dried over mirabilite. After distilling off the solvent, the residue was purified by silica gel column chromatography using a developing solvent of ethyl acetate and n-hexane 2:3 to obtain the compounds listed in Table 1 (No.
．． 57) 2.60 g was obtained. Melting point 72-72.
5°C IR spectrum (KBr) cm-': 1 7 6
0, 1 7 3 5, 1580, 1530, 132
5.12 80,1130.1080' H-NMR spectrum (CCI4-TMS)
δ: 3.3 2 (3 H, s). 3.9 1
(2 H,s), 3. 7 5, 4. 1
2 (e a ch 2H, m). 3.57,5
．． 54 (eachIH, (1), 7.02-8.07
(6H,m) Example 3 Preparation of 3-acetoxy-4-(5-(2-chloro-4-trifluoromethylphenoxy)-2-ditropenzoyloxy)tetrahydrofuran Obtained as in Example 1 Compounds (N(
12) 0.68 g, triethylamine 0. 2
0 g of acetyl chloride and 10 mf of dry ethyl acetate were added 0.0 g of acetyl chloride while stirring under water cooling. 14 g was added dropwise.

After stirring at room temperature for 5 hours, the reaction mixture was washed with water and then with saturated brine, and the N-containing layer was dried over mirabilite.

After distilling off the solvent, the residue was diluted with the developing solvent ethyl acetate n-
Purified by silica gel column chromatography using hexane 1:2 to obtain the compound listed in Table 1 (k2 6) 0.6
0 g was obtained. Melting point 88-89° CIR spectrum (
KBr) cm-': 1 7 4 0, 1 5
7 51525,1320,1290.12 35.1125.1075'H-NMR spectrum (CC l .-TMS) δ:
1.98 (3H, s), 3.60-4.22 (4
H, m), 5.28, 5.48 (each h l
H, q) , 7.0 2-8.0'5 (6H, m
) Example 4 Preparation of 3-(5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoyloxy)-4-(N-methoxyN-methylcarbamoyloxy)tetrahydrofuran Example 1 Compounds listed in Table 1 (No.
．． 2) 0. After dissolving 80 g in 4 ml of pyridine, 0.8 g of N-methoxy N-methylcarbamoyl chloride was added. 27 g was added. After standing overnight at room temperature, water was added. After neutralizing by adding concentrated hydrochloric acid, extraction was performed using Koichitel (three times). After washing the AlIaN with saturated brine, it was dried with Glauber's salt and the solvent was distilled off.

The residue was purified by silica gel column chromatography using a developing solvent of ethyl acetate and n-hexane in a ratio of 2:3.
0.58 g of the described compound (No. 82) was obtained. Amorphous solid.

IR spectrum (Cap.) cm-': 1 7 4
0, 1 7 2 01580, 1530, 12
20 1280.1130 1080 J-NMR spectrum (CC j2 4-TMS) δ:
3.00 (3H, s). 3.50 (3
H,s). 3.70-4.2 1 (4H, m)
, 5.26, 5.53 (each IH, q)
, 6.97-8.08 (6H, m) Example 5
Preparation of 3-(5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoyloxy)-4-fluorotetrahydrofuran Table 1 obtained as in Example 1 The described compound (Na
2) A mixture of 1.34 g, N, N-diethylaminosulfur trifluoride (1.35 mf) and 15 mj2 of 1,2-dimethoxyethane was stirred at 70'C for 5 hours.

After cooling to room temperature and then to O'C, ethylene glycol 1. Add 5 ml and reduce to 0. The mixture was stirred for 5 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the resulting reaction mixture, which was extracted with ether (3 times). Wash the N-containing layer with water,
The mixture was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a developing solvent of ethyl acetate-n-hexane (l:4) to obtain 1.00 g of the compound (kl 2) listed in Table 1. nnl. 5
430.

1R spectrum (Cap.) cl': 1 7 4
5, 1 5 8 0?530, 1320.
1285. 1130. 1080 'II-NMI? Spectrum (CCN4-TMS)
δ: 3.6 9-4.2 4 (4H, m)
, 5.13 (IH, dm), 5.47 (L
H, m), 6.96-8.05 (6H, m) Example 6 3-chloro-4- (5- (2-chloro-4
- Preparation of 1-lifluoromethylphenoxy)121-ditrobenzoyloxy)tetrahydrofuran The compound listed in Table 1 obtained as in Example 1 (No.
．． 2) 0.67 g, pyridine 0. 2 6 g
and 0.0 ml of thionyl chloride with stirring at room temperature in a mixture of 10 ml of methylene chloride. 38 g was added.

After stirring at room temperature for 5 hours, it was left to stand overnight. After the reaction mixture was concentrated under reduced pressure, ether was added, and the mixture was washed with 2N hydrochloric acid, water, and then saturated brine. After drying the sodium sulfate, the solvent was distilled off, and the residue was developed using ethyl acetate-n-hexane 1:
The compound listed in Table 1 (Nl 120) was purified by silica gel chromatography using silica gel chromatography (Nl 120). 20g
I got it. Amorphous solid.

IR spectrum (Cap.) cm-': 1 7 4
0. 1 5 8 01525.1280,11
25.10 75 II-NMR spectrum (CC poor 4-TMS) δ: 3.
84-4.33 (4H, m), 4.435.
47 (each IH, m), 7.01-8.1
1 (6H, m) Example 7 3-acetoxy4- (2- (5-(2
-Chloro-4-trifluoromethylphenoxy)-2-ditrobenzoyloxy)probionyloxy)te1 Preparation of lahydrofuran 5-(2-chloro-4-trifluoromethylphenoxy)-2-ditrobenzoic acid 1 f: After dissolving in NN-dimethylforml, amide 10rnA, 60% oily sodium hydride 0.81g; 2 4
g was added. After the firing stopped, 3acetoxy4-(
2-Promopropionyloxy)tetrahydrofuran 1
．． 41 g was added and stirred at 100°C for 8 hours. After cooling to room temperature, the mixture was extracted with ether (5 times), and the organic layer was washed with saturated brine. After drying with Glauber's salt, the solvent was distilled off, and the residue was purified by silica gel column chromatography using a developing solvent of ethyl acetate and n-hexane 1:2.
0.70 g of the compound described in 1 (Nα33) was obtained.

viscous liquid.

IR spectrum (Cap.) cm-': 1 7 4
0, 1 5 8 0.1530,1320,12
35.11 25 1075 'H-NMR Suhe') Tor (CC l 4-TMS
) δ: 1.58 (31{,s), 1.98 (3H,
s), 3.68, 3.98 (each 2H, m
) , 5.3 0 (3 H, m) , 7.0
0-8.1 1 (6H, m) Example 8 3-acetoxy 4- (1- (5-(2
-chloro4-trifluoromethylphenoxy)-2-nitrophenyl)ethylidene ξ
a) Preparation of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime (mixture of isomers) 5-(2-chloro-4- Trifluoromethylphenoxy)-2-nitroacetophenone 5.20g, ethanol 2 5mj? A mixture of 3.01 g of hydroxylamine hydrochloride, 4.48 g of triethylamine and 30 ml of ethanol was added to a mixture of 25 ml of benzene and the mixture was heated under reflux with stirring for 8 hours. After evaporating the solvent, water was added to the residue, extracted with ether (3 times), and the organic layer was washed with saturated brine (2 times). After drying with Glauber's salt, the solvent was distilled off, and the residue was crystallized by adding n-hexane and grinding. This was collected by filtration to obtain the title compound (compound P1
) was obtained quantitatively.

b) Separation of isomers 5-(2-Chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone 9.12 g, ethanol 50 mf and benzene 40 mj2 were combined;
Hydroxylamine hydrochloride5. 26 g, triethylamine 7. A mixture of 76 g and 50 ml of ethanol was added, and the reaction was carried out in the same manner as in a). Silica gel thin layer chromatography (developing solvent: ethyl acetate/n-hexane 1:4) of the reaction mixture revealed the disappearance of starting materials and R f
0. 3 5 and R f 0. 2B shows the generation of two precepts. After evaporating the solvent, water was added to the residue and extracted with ether (3 times), and the i-layer was washed with saturated brine.

After drying with Glauber's salt, the solvent was distilled off, and separated and purified using silica gel column chromatography with a developing solvent of ethyl acetate and n-hexane 1:3 to obtain a high Rf compound P2) 4.72
g, 1.62 g of low Rf$ fraction (compound P3) and mixtures thereof3. 10 g was obtained. Compounds P2 and P
3 are isomers caused by oxime bonds with each other.

Compound P2 Melting point 130-130.5° CSR spectrum (ir) cm-': 3 3 0 0, 1 5
7 5,1520,1340,1320,12 60,1235.1165.1!20,l075 +I-NMR spectrum (CDC l 3-T gate S) δ
:2.17 (3H, s, CH3), 8.24(
LH, s, color (top) Compound P3 Melting point 1 6 2. 5 - 1 6 3° CIR spectrum (KBr) cm-': 3 2 8
0, 1 5 8 0, 1520, 1320,
1235. 1125 1080' II-NMR spectrum (CDC 1 3-T S)
δ: 2.22 (3H, s, CH3), 7.72
(LH, s, dan and) c) 3-acetoxy1- (1- (5- (2
-Chloro-4-trifluoromethylphenoxy)-2-
Preparation of nitrophenyl)ethylidene ξnoxyacetoxy)tetrahydrofuran (isomer mixture) 6. Oxime compound obtained in a). 50 g, 3-acetoxy-4-promoacetoxytetrahydrofuran 4,65
g1 potassium carbonate 3.10g, potassium iodide 0.6g
A mixture of 35 ml of acetone and 35 ml of acetone was heated under reflux for 12 hours while stirring. After filtering off the inorganic salts, the filtrate was concentrated under reduced pressure, and the residue was applied to a silica gel column with a developing solvent of ethyl acetate-n-hexane (2:5) to form a pale yellow viscous liquid containing the compounds listed in Table 1 ( No. 3 4) 6. 6 g was obtained.

IR spectrum (Cap.) cm-': 1 7 4
0, l 5 7 5, 1520, 1320, 12
60.12 35.1125.1080' It-NMR 7! ．． Vector (CC e a-
TMS) δ: 1.94. 1.99 (total 3H.eac
hs), 2.20 (3H, s). 3.59-3.7
8, 3.9 3-4.0 9 (e a ch2H
, m) , 4.46, 4.65 (total 2H,ea
ch s), 5.26 (2H, m) 6.9 3-
8.2 7 (6H, m)d) Preparation of 3-acetoxy4-(5-(2-chloro=4-trifluoromethylphenoxy)-2-nitrophenyl)ethylideneyξnoxyacetoxy)tetrahydrofuran b)
1.12 g of P2 obtained as described above, 3-acetoxy-4-(promoacetoxy)tetrahydrofuran 0
．． 88g, potassium carbonate 0.50g, potassium iodide 0
．． A mixture of 10 g and 10 mf of acetone was heated under reflux for 6.5 hours with stirring. After filtering off the inorganic salts, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography using a developing solvent of ethyl acetate and n-hexane (1:3) to obtain 0.35 g of the compound (Nα35) listed in Table 1.
I got it. viscous liquid.

[R spectrum (Cap,) cm-': 1 7 4
0, 1 5 7 0, 1520, 1315, 12
60,12 35,1125.1075'+{-NMR spectrum (CC N .-TMS) δ
:1.94 (3}{,s). 2.20 (3H,s)
, 3.67, 4.00 (each, 2H, m) ,
4.63 (2H, s), 5.24 (2H,
m), 6.90-8.13 (6H, m) e) 3-acetoxy4-(5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrophenyl)ethylidene ξnoxy Preparation of (acetoxy)tetrahydrofuran Using P3 as a starting material, the compound (No. 36) listed in Table 1 was obtained in the same manner as in b). viscous liquid.

IR spectrum (Cap.) cm-': 1 7 6
0, 1 7 4 0,1575,1520,13
20.12 60 1235 1125 1075'II-N
MR spectrum (CC f a-TMS) δ: 1. 9
9 (3H, s), 2.18 (3
Hs), 3.69.4.00 (each, 2H, m)
,4.44 (2H,s). 5.23 (2H, m)
, 6.90-8.24 (6H, m) Example 9 Methyl O- (3-acetoxy4-tetrahydrofuryl)oxycarbonylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2 - Preparation of Nitrobenzohydroximate a) Preparation of N-((3-acetoxy4-tetrahydrofuryl)oxycarbonylmethoxy)phthalimide 3-acetoxy4-chloroacetoxytetrahydrofuran 1 3. 4 g, potassium iodide 1 0. 9 6
A mixture of g and 50 mf of acetone was heated to reflux with stirring for 1 hour. After cooling to room temperature, the precipitated salt was filtered off, the filtrate was concentrated under reduced pressure, and 5 mff of N,N-dimethylformamide was added to the residue. On the other hand, N(hydroxy)phthalimide 10. 2 8 g, ground sodium hydroxide2. A mixture of 64 g and 50 mf of N,N-dimethylformamide was stirred at room temperature for 1 hour. To this was added the previously obtained NN-dimethylformamide solution of 3-acetoxy4-iodoacetoxyte-1-lahydrofuran, and the mixture was stirred at room temperature for 5 hours, and then the solvent was distilled off. When water was added to the residue, crystals were precipitated. This was collected by filtration, washed with water, and dried at 55°C for 5 hours to obtain 17.0 g of the title compound.
I got it. Melting point 109-110.5°C [R spectrum (
KBr) cm-': 17 8 5, 1755,
1730,1370,1240.12 10.11B0,1070.870 695 H-NMR spectrum (CDC f ff-TMS) δ
:2.06 (3H, s), 3.70-4.
23 (41L m), 4.87 (2H, s), 5
．． 3 3, 5.4 7 (e a ch,
IH, q). 7.89 (4H, m) b) Preparation of 1-(3-acetoxy-4-tetrahydrofuryl)oxycarponylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzohydroximate 5- (2-chloro4-trifluoromethylphenoxy)-2-nitrobenzoic acid7. 23 g and thionyl chloride7. After heating 14 g of the mixture under reflux for 2 hours, excess thionyl chloride was removed to obtain the acid chloride.

On the other hand, N-((3-acetoxy-4-tetrahydrofuryl)oxycarponylmethoxy)phthalimide obtained in a) 7. 6 8 g of 100% hydrazine hydrate
．． After heating under reflux for 2 hours with 85 g of benzene and 120 mf of benzene, the mixture was cooled to room temperature and the precipitate was filtered off. 2.26 g of pyridine was added to the obtained filtrate. The previously obtained benzene solution of the acid chloride was added dropwise to this under water cooling. After stirring at room temperature for 4 hours, the reaction mixture was washed with water (twice) and then with saturated brine. After drying the sodium sulfate, the solvent was distilled off, and the residue was mixed with a developing solvent system of ethyl acetate and n-hexane 2:3→2:
1 silica gel column chromatography to obtain 4.30 g of the title compound. Melting point 7 6. 5-9° CIR spectrum (KBr) cm-': 3 3 5
0. l 7 3 51520,1,320,12
35,1130.1080'H-NMR spectrum (CDC Q3-TMS) δ
:2.04, 2.08 (total 30, each, S), 3.
76 4.23 (4H, m), 4.66. 4.8
7 (total 2}1, eachbr, s, s). 5.38
(2H, m)7.0 7-8.2 9 (6H+c
a. 0.4 Hm), 9.37 (c a.
0.6 H, b r. S) C] Methyl O-(3-acetoxy4-tetrahydrofuryl)oxycarponylmethyl 5(2-chloro-4-
Preparation of (trifluoromethylphenoxy)-2-nitropenzohydroxymate b)
-trifluoromethylphenoxy)-2-21-lobenzohydroxymer}6.70g, potassium carbonate 1.31
g, 0.38 g of sodium hydroxide and 30 ml of N,N-dimethylformamide at 65°C.
After stirring for 5 hours, methyl p-}luenesulfonate 2. 66 g were added dropwise. After stirring as it was for 2 hours, the solvent was distilled off under reduced pressure. Water was added to the residue and extracted with ether (3 times). The organic layer was washed with water and saturated brine (2 times each), dried with Glauber's salt, and the solvent was distilled off. The residue was developed using ethyl acetate/n-hexane as a developing solvent.
: After subjecting to silica gel column chromatography of 3, the developing solvent system chloroform-2-propanol 1
It was purified by 5:1 silica gel column chromatography to obtain 1.70 g of the compound (No. 40) listed in Table-1. viscous liquid.

IR spectrum (KBr) cm-': 1 7 4
0. 1 5 7 51525 1315,
1260, 1235. 1170, 112
0. 1095, 1075' II-NMR spectrum (CDC 1 3-TMS)
δ: 2.04 (3H, s), 3.70-4.1
8 (4H, m), 3.93 (3H, s) 4.6
1 (2H, s), 5.38 (2H, m)
, 7.03-8.20 (61{, m) Example 10 (3-acetoxy4-tetrahydrofuryl)oxycarponylmethyl○ -Methyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-di Preparation of trobenzohydroxymate (compound Nα43) a) Preparation of O-methyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzohydroxymate 5-(2-chloro-4 -trifluoromethylphenoxy)-2-nitrobenzoic acid 1 0. After heating a mixture of 85 g and 8.9 g of thionyl chloride under reflux for 2 hours,
Excess thionyl chloride was removed to obtain the acid chloride. on the other hand,
○-Methylhydroxylamine hydrochloride 5.01g in water 1
0 mj2, and add 2.0 mj of sodium hydroxide to this. 8
After adding 8 g dissolved in 3 mj2 of water, 20 mf of ether and 3.0 mf of pyridine were added. 0.4 g was added. The previously obtained benzene solution of the acid chloride was added dropwise to this under water cooling. After stirring at room temperature for 4 hours, the reaction mixture was washed with water and then with saturated brine. After drying the sodium sulfate, the solvent was distilled off, a small amount of ethyl acetate was added to the residue, and then n-hexane was added to obtain crystals. This was collected by filtration to obtain the title compound 7.
15 g (yield: 61.1%) was obtained.

Melting point 165-8°C (with sublimation) IR spectrum (KBr) cm-': 3 1 8 0
, 1 6 5 5, 1575, 1520, 1340
,13 15.1260,1235,1160,1130.10
75 H-NMR spectrum (CDC poor, + DMSO-d
&-TMS) δ: 3.89 (3H.br.sL 7.
06-8.29 (6H, m). 1 1.02
(LH, br. s) b) (3-acetoxy 4-tetrahydro mouth frill)
Preparation of oxycarbonylmethyl O-methyl 5-(2-chloro4-trifluoromethylphenoxy)-2-nitropenzohydroximate 3-acetoxy4-chloroacetoxytetrahydrofuran 2.89 g, potassium iodide 2. A mixture of 16 g and 15 mf of acetone was heated to reflux with stirring for 1 hour. After cooling to the kiln temperature, the precipitated salt was filtered off, and the filtrate was concentrated under reduced pressure. On the other hand, O-methyl 5-(2
-chloro-4-trifluoromethylphenoxy)-2-
Nitrobenzohydroximate 3.91 g, potassium carbonate 2. A mixture of 20 g of N,N-dimethylformado and 20 mf of N,N-dimethylformado was heated at 65°C to Stirred for 5 hours. This is the 3-acetoxy 4-iodoacetoxyte obtained earlier! - After adding lahydrofuran and stirring for 4 hours, the solvent was distilled off under reduced pressure. Water was added to the residue, extracted with ether (3 times), and iii was washed with water and brine (
Once each), the solvent was distilled off after drying with Glauber's salt. The residue was subjected to silica gel column chromatography using a developing solvent of ethyl acetate and n-hexane (1:2), and further purified by silica gel column chromatography using a developing solvent of chloroform-2-probanol (30:1). Compound (No. 4 3) 0. 5 g was obtained. Amorphous solid.

IR spectrum (KBr) cm-': l 7 4
5, 1 5 7 51525, 1320, 1260
1235,1170,1125.1085'H-N R spectrum (CDC iL 3-TMS)
δ: 2.06, 2.07 (total 3H, each, s), 3
．． 68-4.20 (4H, m), 3.87 (3H,
s), 4.93 (2H, q), 5.4 0 (2
H, m). 7.0 3 -8. 1 8 (6
H, m. ) Other compounds listed in Table 1 can also be prepared according to any of the methods shown in Example 1-10 above.

The structures of all the prepared compounds are shown in rR spectra and 'II
- Confirmed by NMR spectrum. For compounds obtained as amorphous solids or viscous liquids other than those shown above, the IR spectrum and 'H-NMR spectrum data are shown in the attached table.

Next, examples of formulations of the compounds of the present invention will be shown. In addition, "department" below,
"%" means "part by weight" and "% by weight J," respectively.

Formulation Example 1 Wettable powder 40 parts of the compound of the present invention listed in Table 1, Curbrex #8
0 (Shionogi & Co., Ltd., trade name), 35 parts of N,N kaolin clay (Tsuchiya Kaolin Co., Ltd., trade name), higher alcohol sulfate ester surfactant Solbol 8070 (Toho Chemical Co., Ltd., trade name) 5 parts. After blending, the mixture was uniformly mixed and ground to obtain a permanent agent containing 40% of the active ingredient.

Formulation Example 2 Emulsion After dissolving 20 parts of the compound of the present invention listed in Table 11 in a mixed solvent consisting of 35 parts of xylene and 30 parts of dimethylformamide, the polyoxyethylene surfactant Sorbol 3005X (Toho Chemical Co., Ltd., trademark) was added to the mixture. 15 parts of the active ingredient were added to obtain an emulsion containing 20% of the active ingredient.

Formulation Example 3 Flowable agent 8 parts of ethylene glycol and Sorbol AC302 mixed in advance with 30 parts of the compound of the present invention listed in Table 11
0 (Toho Chemical Co., Ltd., trade name) 5 parts, xanthan gum 0.
After thoroughly mixing and dispersing the slurry in 56.9 parts of water, this slurry mixture was wet-pulverized with Dynomol (trade name, Shinmaru Enterprises Co., Ltd.) to obtain a stable powder containing 30% effective I got a flowable agent.

Formulation Example 4 Granules 3 parts of the compound of the present invention listed in Table 1, 41 parts of clay (manufactured by Nippon Talc Co., Ltd.), 55 parts of Xtonite (manufactured by Hojun Yoko Co., Ltd.), succinate surfactant Eyarol CT-1 (manufactured by Toho Chemical Co., Ltd.) Co., Ltd., trade name), mix and grind, then add 2 parts of water.
0 parts were added and kneaded.

Furthermore, this was extruded through holes with a diameter of 0.6 mm using an extrusion granulator, dried at 60°C for 2 hours, and then
The pellets were cut into 2 mm lengths to obtain granules containing 3% of the active ingredient.

Test Example 1 A small styrofoam pot with a test area of 110 tffIN was filled with upland volcanic ash soil, and after fertilization, each seed of Aobu, Japanese knotweed, Japanese grass, Japanese fir, Japanese violet, corn, wheat, and soybean was added as test plants. Seeds were sown in each pot.

Cultivation management was continued in a humid room, and the growth leaf ages of the test plants were 3rd leaf stage of Aobuscus, 3rd leaf stage of Japanese knotweed, 2nd leaf stage of Japanese knotweed, 2nd leaf stage of Japanese fir tree, 2nd leaf stage of Japanese violet, and 3rd leaf stage of Japanese violet. Permanent preparation and Formulation Example 1 containing the compound of the present invention obtained according to Formulation Example 1 as an active ingredient when reaching the leaf stage, 3.5 leaf stage of corn, 3 leaf stage of wheat, and 1.5 leaf stage of soybean. Comparative compound (A) Sodium 5-(2-
Chloro-4-(trifluoromethyl)phenoxy)2-
Nitropenzoate, comparative compound (B) methyl 5-(2
-Chloro-4-trifluoromethylphenoxy)-2-
Nitroacetophenone oxime 10-acetate and comparative example (C) 2-chloro-4-ethylano-6-isobrobylamino-1,3.5-triazine as an effective amount of a permanent agent per lha 1.0,0.
5,0.25,0.125,0.0625kg with water, and the amount of treated liquid per lha is 50
An amount equivalent to 01 was applied to the stems and leaves using a small power pressurized sprayer.

Thereafter, cultivation was continued in a wet room, and on the 21st day after the chemical treatment, the herbicidal effect and chemical damage to each crop were investigated.

The results are shown in Table-2.

In addition, the evaluation of herbicidal effect is as follows: In addition, the evaluation of drug damage is was determined and expressed as a herbicidal effect coefficient based on the following criteria.

was calculated and expressed as a phytotoxicity coefficient according to the following criteria.

Table 2 Test Example 2 Upland soil treatment test A resin vat with an area of 600 cd was filled with upland volcanic ash soil, and after fertilization, each crop seed of corn, wheat, and soybean was sown and covered with 2 to 3 cm of soil. Furthermore, a soil mixture of weed seeds of crabgrass, whiteweed, Japanese knotweed, Japanese thornweed, and kosendangusa was added uniformly to the surface of this soil, and a permanent agent containing the compound of the present invention obtained in Formulation Example 1 as an effective part was prepared in the same way as Formulation Example 1. A permanent agent containing Comparative Compounds (A) and (B) described in Test Example 1 obtained in Example 1 was diluted with water, and the effective ratio was 1.0, 0.5 per Iha.
0. The soil surface was uniformly treated using a small power pressurized sprayer so that the amount was 25 kg.

Thereafter, cultivation was continued in a greenhouse, and on the 21st day after the chemical treatment, the herbicidal effects and chemical damage to each crop were investigated.

The results are shown in Table-3.

The evaluation of herbicidal effect and phytotoxicity against each crop was expressed in the same manner as in Test Example 1.

Test Example 3 Flooded Soil Treatment Test A resin vat with an area of 400 cal was filled with paddy alluvial clay soil, and after fertilization, an appropriate amount of water was added and plowed to reduce the soil surface to zero. Seeds of weeds such as Japanese grasshopper, grasshopper, and firefly were mixed in a 5 cm layer. In addition, four Kuzugayari tubers per vat were planted on the soil surface.

Furthermore, 2. Two rice seedlings (variety: Akinishiki) at the first leaf stage were transplanted per vat (three plants/plant) and submerged in water for about 30 minutes. A water depth of 5 cm was maintained.

On the 5th day after transplanting paddy rice, the granules containing the compound of the present invention obtained according to Formulation Example 4 and the comparative compounds (A) and (B) described in Test Example 1 obtained in the same manner as Formulation Example 4 were added. The amount of active ingredient in the granules used as an effective precept is 1.0, 0.5.
0.2 5. 0. A predetermined amount was deep submerged on the flooded surface so that the amount was 125 kg/ha.

After the chemical treatment, water leakage was performed at a rate of 3 cm/day for two days, the next day and the day after, and cultivation was then continued at room temperature.

Two days after the chemical treatment, the herbicidal effect and the chemical damage to the transplanted paddy rice were investigated.

The results are shown in Table-4.

In addition, the herbicidal effect and the evaluation of phytotoxicity to transplanted paddy rice were expressed in the same manner as in Test Example 1.

〔Effect of the invention〕

As described above, the compound of the present invention has a very high weed spectrum against annual weeds and perennial weeds, and has a high degree of safety against cultivated crops.

Claims (4)

[Claims] (1) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the above formula, X^1 is a halogen atom or a carbon number of 1 to
3 represents a haloalkyl group, X^2 and X^3 are each the same or different and represent a hydrogen atom, a halogen atom, a trifluoromethyl group, a nitro group or a cyano group,
Y is a nitro group, a cyano group, a halogen atom, and has 1 to 3 carbon atoms.
represents a haloalkyl group or a hydrogen atom, and A represents a direct bond or a group represented by -CO_2CH(R^1)-, -C(R^2)=NOCR(R^3)-
A group represented by or -C(=NOR^4)OCH(R
^3) Indicates a group represented by -, B is ▲ mathematical formula, chemical formula,
There are tables etc. Showing the group represented by ▼. In the above group, R^1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R^2 represents a hydrogen atom; an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or
Represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which may be substituted with a halogen atom, and R
^3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R^4 represents an alkyl group having 1 to 3 carbon atoms; R^5 represents a halogen atom; a hydroxyl group; a halogen atom; Alkoxy group, alkoxycarbonyl group having 2 to 7 carbon atoms, or 1 to 3 halogen atoms and/or 1 carbon number
An aryl group optionally substituted with ~3 alkyl groups or an acyloxy group having up to 6 carbon atoms optionally substituted with an aryloxy group; cycloalkylcarbonyloxy group having 4 to 9 carbon atoms; halogen atom, carbon number Benzoyloxy group which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; an alkoxycarbonyloxy group having 2 to 7 carbon atoms; an alkylsulfonyloxy group having 1 to 4 carbon atoms; a carbon number It represents a carbamoyloxy group which may be substituted with an alkyl group having 1 to 4 carbon atoms and/or an alkoxy group having 1 to 4 carbon atoms. ) Diphenyl ether derivatives represented by (2) The following general formula [I ′] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I ′] (In the above formula, X^1 represents a halogen atom or a trifluoromethyl group, and A represents a direct or a group represented by -CO_2CH(R^1)-, -C(
R^2)=NOCH(R^3)- or -C(=NOR^4)OCH(R^3)-, B is a ▲ mathematical formula, chemical formula, table, etc. Indicates the group represented by ▼. In the above group, R^1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R^2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms optionally substituted with a methoxy group, or an alkyl group having 1 to 3 carbon atoms. It represents an alkoxy group having 1 to 3 carbon atoms, R^3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R^4 represents an alkyl group having 1 to 3 carbon atoms.
3 represents an alkyl group, R^3 is a halogen atom; a hydroxyl group; a halogen atom, an alkoxy group having 1 to 3 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or a halogen atom and/or a halogen atom having 1 to 3 carbon atoms. A phenyl group which may be substituted with 1 to 3 alkyl groups or a saturated carbon number of 2 to 4 carbon atoms or an acyloxy group which may contain one double bond; which may be substituted with a phenoxy group; carbon number 4
~7 cycloalkylcarbonyloxy group; benzoyloxy group optionally substituted with a halogen atom; alkoxycarbonyloxy group having 2 to 5 carbon atoms; 1 to 2 carbon atoms
Alkylsulfonyloxy group; represents a carbamoyloxy group substituted with an alkyl group having 1 to 2 carbon atoms and/or an alkoxy group having 1 to 2 carbon atoms. ) Diphenyl ether derivatives represented by (3) A herbicide containing the diphenyl ether derivative according to claim 1 as an active ingredient. (4) A herbicide containing the diphenyl ether derivative according to claim 2 as an active ingredient.