JP3306876B2 - Carbamic acid derivative, process for producing the same, intermediate thereof, and pesticidal agent containing the same as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel carbamic acid derivative, a method for producing the same, an intermediate thereof, and a pesticidal composition containing the same as an active ingredient.

[0002]

2. Description of the Related Art It has been reported that certain carbamic acid derivatives have a pest controlling effect, for example, as disclosed in
No. 151929.

[0003]

However, these compounds are not always sufficient as an active ingredient of a pesticide.

[0004]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies to find a compound having a better pest control effect.
The inventors have found that a carbamic acid derivative represented by Chemical Formula 13 (hereinafter, referred to as the compound of the present invention) has extremely high juvenile hormone-like activity, and thus completed the present invention. That is, the present invention provides a compound represented by the general formula:

[0005]

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Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms,
3 haloalkyl groups, 1 to 3 alkoxy group having a carbon atom, 1 to 3 haloalkoxy group having a carbon atom, a cyano group or a nitro group, l represents an integer of 1 to 5, R ² is independently represents a hydrogen atom or a chlorine atom Te, m is Table <br/> the 1, R ³ represents a halogen atom, R ⁴ represents a hydrogen atom or a carbon atom 1-3 alkyl group, R ⁵ is It represents <br/> hydrogen atom, R ⁶ is an alkyl group having 1 to 6 carbon atoms, 1-6 haloalkyl group carbon atoms, 3-6 alkenyl carbon atoms, 3-4 carbon atoms Haloalkenyl group, alkynyl group having 3 to 6 carbon atoms, haloalkynyl group having 3 to 5 carbon atoms, alkoxylalkyl group having 3 to 6 carbon atoms, alkylthioalkyl group having 3 to 6 carbon atoms or carbon the atomic 3-6 cycloalkyl group and table, X represents an oxygen atom, sulfate Atom, a group represented by formula -NH-, the formula -C
(O) - group or a methylene group represented by, Y and Z are each independently, represent <br/> an oxygen atom or a sulfur atom. A carbamic acid derivative represented by the formula
It is intended to provide an intermediate thereof and a pesticidal composition containing the intermediate as an active ingredient.

The compounds of the present invention are markedly different from most conventional insecticides and have excellent juvenile hormone-like activity against insects. In other words, they exhibit effects such as inhibition of metamorphosis into adults, inhibition of hatching of eggs, and sterilization of adults. As a result, the compounds of the present invention include various pests, including pests that have developed resistance to existing pesticides, that is, agricultural and forestry pests,
It mainly acts as a growth regulator, a sterilizing agent, an ovicidal agent or a growth inhibitor against stored grain pests and sanitary pests, and has a high control effect.

In the compound of the present invention represented by the general formula (13), the alkyl group having 1 to 3 carbon atoms represented by R ¹ is a methyl group, an ethyl group, an n-propyl group or an isopropyl group;

The haloalkyl group having 1 to 3 carbon atoms represented by R ¹ includes, for example, trifluoromethyl, difluoromethyl, 2-fluoroethyl, 1-fluoroethyl, 1,2-difluoroethyl 2,2,2-trifluoroethyl group, 2-chloroethyl group, 3-fluoropropyl group, 2-fluoropropyl group, 1-fluoropropyl group, 3-chloropropyl group, 3-bromopropyl group,

The alkoxy group having 1 to 3 carbon atoms represented by R ¹ is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,

The haloalkoxy group having 1 to 3 carbon atoms represented by R ¹ is, for example, a trifluoromethoxy group,
Difluoromethoxy group, bromodifluoromethoxy group,
2-fluoroethoxy group, 2,2,2-trifluoroethoxy group, 2-chloroethoxy group, 1,1,2-trifluoroethoxy group, 3-fluoro-n-propoxy group,
2-chloro-1,1,2-trifluoroethoxy group, 2
-Fluoro-n-propoxy group, 2-chloroethoxy group, 3-chloropropoxy group, 3-bromo-n-propoxy group, 1,1,2,2-tetrafluoroethoxy group, and the like,

The alkyl group having 1 to 3 carbon atoms represented by R ⁴ is a methyl group, an ethyl group, an n-propyl group or an isopropyl group,

The alkyl group having 1 to 6 carbon atoms represented by R ⁶ includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group,
neo-pentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-
Methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,3-dimethylbutyl group and the like;

The haloalkyl group having 1 to 6 carbon atoms represented by R ⁶ includes, for example, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-bromoethyl, Iodoethyl group,
2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 3
-Fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2-chloro-1-methylpropyl group, 3-chloropropyl group, 2-chloropropyl group,
2,3-dichloropropyl group, 1,3-dichloro-2-
Propyl, 3-bromopropyl, 2-bromopropyl, 1-bromo-2-propyl, 2,3-dibromopropyl, 3-iodopropyl, 4-fluorobutyl, 4,4,4- Trifluorobutyl group, 3,3
4,4,4-pentafluoro-2-butyl group, 2,2
3,3,4,4,4-heptafluorobutyl group, 4-chlorobutyl group, 3-chlorobutyl group, 2,3,4-trichlorobutyl group, 4-bromobutyl group, 3-bromobutyl group, 4-iodobutyl group, 5-fluoropentyl group,
5-chloropentyl group, 5-bromopentyl group, 6-fluorohexyl group, 6-chlorohexyl group, 6-bromohexyl group and the like,

The alkenyl group having 3 to 6 carbon atoms represented by R ⁶ includes, for example, allyl, 2-methylallyl, 1,1-dimethyl-2-propenyl, 2-butenyl, 3-butenyl Group, 3-methyl-2-butenyl group,
2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 2-pentenyl group, 2-hexenyl group, 5-hexenyl group and the like,

The haloalkenyl group having 3 to 4 carbon atoms represented by R ⁶ includes, for example, 2,3-dichloroallyl group, 2,3-dibromoallyl group, 2-chloro-2-propenyl group, Chloro-2-propenyl group, 2-bromo-2-propenyl group, 2-chloromethyl-2-propenyl group, 2-chloro-3-butenyl group, 3-chloro-2-
Butenyl group, 4-chloro-2-butenyl group, 4-bromo-2-butenyl group and the like,

The alkynyl group having 3 to 6 carbon atoms represented by R ⁶ includes, for example, 2-propynyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl,
1-ethynylbutyl group, 2-butynyl group, 1-ethyl-
2-butynyl group, 1-propyl-2-butynyl group, 2-
Pentynyl group, 4-methyl-2-pentynyl group, 1-methyl-2-pentynyl group, 2-hexynyl group, 3-hexynyl group, etc.

The haloalkynyl group having 3 to 5 carbon atoms represented by R ⁶ includes, for example, 3-chloro-2-propynyl, 3-chloropropynyl, 3-bromopropynyl, 1-chloro-2 -Butynyl group, 4-chloro-3-butynyl group, 1-bromo-2-butynyl group, 4-bromo-
3-butynyl group, 5-chloro-4-pentynyl group, 5-
Bromo-4-pentynyl group, 1-bromo-2-pentynyl group, 1-bromo-4-pentynyl group and the like,

The alkoxyalkyl group having 3 to 6 carbon atoms represented by R ⁶ includes, for example, 2-methoxyethyl group, 2-ethoxyethyl group, 2-iso-propoxyethyl group, 3-methoxypropyl group , 2-methoxypropyl group, 2-ethoxypropyl group, 3- (n-propoxy) propyl group, 4-methoxybutyl group, 4-ethoxybutyl group,

The alkylthioalkyl group having 3 to 6 carbon atoms represented by R ⁶ includes, for example, 2-methylthioethyl, 2-ethylthioethyl, 3-methylthiopropyl, 2-methylthiopropyl, 2-ethylthiopropyl group, 3- (n-propyl) thiopropyl group, 4-
Methylthiobutyl group, 4-ethylthiobutyl group and the like,

The cycloalkyl group having 3 to 6 carbon atoms represented by R ⁶ is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

As the preferred compounds of the present invention represented by the general formula (13), R ¹ is independently a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group, 1 is 1 or 2, and

[0029]

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Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms,
Represents 3 haloalkyl groups, an alkoxy group having 1 to 3 carbon atoms, a haloalkoxy group having 1 to 3 carbon atoms, a cyano group or a nitro group, 1 represents an integer of 1 to 5, X represents an oxygen atom, A sulfur atom, a group represented by the formula -NH-, a formula -C
It represents a group represented by (O)-or a methylene group. X, which may be substituted with (R ¹ ) l
Is substituted at the 4- or 5-position, R ² is a hydrogen atom or a chlorine atom, m is 1, R ³ is a halogen atom, R ⁴ and R ⁵ are hydrogen atoms, and R ⁶ is a carbon atom 1 to 5
, An alkyl group, a haloalkyl group having 2 carbon atoms, an allyl group, a propargyl group or a methoxyethyl group, X is an oxygen atom or a methylene group, Y is an oxygen atom, and Z is an oxygen atom or a sulfur atom. More preferably, (R ¹ ) l is a fluorine atom (3,5-F ₂ ) or a 3-position or 4-position at both the 3-position and 5-position substitution positions.
Chlorine atoms (3,4-Cl ₂ ), (R
¹⁾ substitution position of the phenyl group comprising an optionally X be substituted by l 4-position, a chlorine atom R ² is a substituted position of hydrogen atom or 5-position (5-Cl), R ³ is a chlorine atom, R ⁴ And R
⁵ is a hydrogen atom, R ⁶ is a methyl group, an ethyl group or a 2-chloroethyl group, X is an oxygen atom or a methylene group, and Y and Z are oxygen atoms. When X is an oxygen atom, (R ¹ ) l is a chlorine atom (3-
Cl), a chlorine atom (4-Cl) or a fluorine atom (4-F) at the 4-position substitution position, and when X is a methylene group, R ¹ may be a hydrogen atom. Still more preferably, (R ¹ ) l is a substitution position of a phenyl group containing X which may be substituted with a fluorine atom (3,5-F ₂ ) or (R ¹ ) l at both the 3-position and 5-position substitution positions. Is the 4-position, R ² is a hydrogen atom or a chlorine atom (5-C
l), R ³ is a chlorine atom, R ⁴ and R ⁵ are a hydrogen atom, R
⁶ is a methyl group or an ethyl group, X is an oxygen atom or a methylene group, and Y and Z are oxygen atoms.
When X is an oxygen atom, (R ¹ ) l is in the 3-position and 4-position.
Both the substitution position at the 3 position may be a chlorine atom (3,4-Cl ₂ ) or a chlorine atom at the 3 position (3-Cl),
When X is a methylene group, R ¹ may be a hydrogen atom.

The compound of the present invention represented by the general formula (13) can be produced, for example, by the following method.

[0032] (Process A) represented by the general formula of 13 Luke Rubamin acid derivatives (formula of 16)

[0033]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ ,
X, Y, Z, 1 and m have the same meaning as described above. ] Manufacturing method. General formula 17

[0035]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , X,
Y, Z, 1 and m represent the same meaning as described above. And an amine compound represented by the general formula:

[0037]

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[Wherein R ⁶ and Z have the same meanings as described above, and L ¹ represents a halogen atom. And a carboxylic acid compound represented by the following formula: In the production method A, the reaction is preferably carried out in the presence of a suitable base, if necessary, in a solvent that does not affect the reaction.

As the base, for example, an alkali carbonate such as potassium carbonate or an organic base such as triethylamine or pyridine can be used. If necessary, a catalyst such as an ammonium salt (eg, triethylbenzylammonium chloride) may be added to the reaction system.

Examples of the solvent include ketones such as acetone and methyl ethyl ketone, hydrocarbons such as benzene, hexane and toluene, ethers such as diethyl ether, isopropyl ether, tetrahydrofuran and dioxane, dichloromethane, chloroform and 1,2-dichloroethane. , Halogenated hydrocarbons such as chlorobenzene,
Acetonitrile, nitromethane or dimethylsulfoxide and the like can be used. If necessary, a mixed solvent of these solvents or a mixed solvent with water can also be used.

The reaction temperature can range from -20 ° C to the boiling point of the solvent used in the reaction.
A temperature from to the boiling point of the solvent used in the reaction is more desirable.

The molar ratio of the raw materials can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar or close ratio.

After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by a usual operation such as chromatography, distillation, recrystallization and the like.

The production method (Production Method B) represented by the general formula of 13 Luke Rubamin acid derivatives (formula of 16).

[0045]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , X,
Y, 1 and m have the same meaning as described above. And a general formula R ⁶ -ZH wherein R ⁶ and Z have the same meanings as described above. And a (thio) alcohol-based compound represented by the following formula: In the manufacturing method B,
The reaction is preferably performed in a solvent that does not affect the reaction, if necessary, in the presence of a suitable catalyst.

As the catalyst, for example, an organic base such as triethylamine, pyridine or sodium acetate or an acid such as aluminum chloride, hydrogen chloride or boron trifluoride etherate complex (BF _3. (C ₂ H ₅ ) ₂ O) can be used. it can.

Examples of the solvent include hydrocarbons such as benzene, toluene and hexane, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, N, N-dimethylformamide, dimethyl sulfoxide, hexamethyl phosphoric triamide and the like. Polar solvents, dichloromethane, chloroform, 1,
Halogenated hydrocarbons such as 2-dichloroethane and chlorobenzene, acetonitrile, nitromethane and the like can be used. If necessary, a mixed solvent of these solvents can also be used.

The reaction temperature can usually range from -20 ° C to the boiling point of the solvent used in the reaction.
It is more desirable that the range be from to the boiling point of the solvent used in the reaction.

The molar ratio of the raw materials can be set arbitrarily, but it is advantageous to carry out the reaction at an equimolar ratio or a ratio close thereto.

After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by a usual operation such as chromatography, distillation, recrystallization and the like.

[0052] (Process C) represented by the general formula of 13 Luke Rubamin acid derivatives (formula of 20)

[0053]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ ,
X, Y, Z, 1 and m have the same meaning as described above. ] Manufacturing method. General formula 21

[0055]

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[Wherein, R ¹ , R ² , R ³ , X, Y, l and m have the same meanings as described above, and M ¹ represents an alkali metal atom or a hydrogen atom. And a (thio) phenol compound represented by the general formula:

[0057]

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Wherein R ⁴ , R ⁶ and Z have the same meanings as described above, and L ² represents a halogen atom, a methanesulfonyloxy group or a toluenesulfonyloxy group. And a carboxylic acid compound represented by the following formula: In the production method C, the reaction is preferably performed in an inert solvent in the presence of a suitable base. However, when M ₁ is an alkali metal atom, the presence of a base is not necessarily required.

Examples of the solvent used include methanol, ethanol, propanol, isopropanol,
Lower alcohols such as tertiary butyl alcohol; ketones such as acetone and methyl ethyl ketone; hydrocarbons such as hexane, benzene and toluene; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran and dioxane; N, N-dimethylformamide; Polar solvents such as dimethyl sulfoxide and hexamethylphosphoric triamide, dichloromethane, chloroform, 1,
Examples include halogenated hydrocarbons such as 2-dichloroethane and chlorobenzene, acetonitrile, nitromethane and water. If necessary, a mixed solvent of these solvents can also be used.

Examples of the base to be used include caustic alkalis such as caustic potash and caustic soda, alkali carbonates such as potassium carbonate, alkali metals such as sodium metal, hydrides of alkali metals such as sodium hydride or sodium methoxide, sodium ethoxide. Organic bases such as side, triethylamine and pyridine are exemplified. If necessary, a catalyst such as an ammonium salt (eg, triethylbenzylammonium chloride) may be added to the reaction system.

The reaction temperature can range from -20 ° C to the boiling point of the solvent used in the reaction.
It is more desirable that the range be from to the boiling point of the solvent used in the reaction.

The molar ratio of the starting material and the base to be used for the reaction can be arbitrarily set, but it is advantageous to carry out the reaction in an equimolar ratio or a ratio close thereto.

After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by a usual operation such as chromatography, distillation, recrystallization and the like.

(Production Method D) The carbamic acid derivative represented by the general formula
A carbamic acid derivative in which Z represents a sulfur atom (general formula 23)

[0065]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ ,
X, Y, 1 and m represent the same meaning as described above. ] Manufacturing method. General formula 24

[0067]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , X,
Y, l and m have the same meaning as described above, and M ²⁺ represents an alkali metal ion or a quaternary ammonium ion. A thiocarbamic acid compound represented by the general formula:
R ⁶ -L ³ wherein R ⁶ has the same meaning as described above, and L ³ represents a halogen atom, a methanesulfonyloxy group or a toluenesulfonyloxy group. And a compound represented by the following formula: In the production method D, the reaction is desirably performed in a solvent that does not affect the reaction, if necessary.

Examples of the solvent used include methanol, ethanol, propanol, isopropanol,
Lower alcohols such as tertiary butyl alcohol; ketones such as acetone and methyl ethyl ketone; hydrocarbons such as hexane, benzene and toluene; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran and dioxane; N, N-dimethylformamide; Polar solvents such as dimethyl sulfoxide and hexamethylphosphoric triamide, dichloromethane, chloroform, 1,
Halogenated hydrocarbons such as 2-dichloroethane and chlorobenzene, acetonitrile, nitromethane and the like can be used. If necessary, a mixed solvent of these solvents or a mixed solvent with water can also be used. If necessary, a catalyst such as an ammonium salt (for example, triethylbenzylammonium chloride) may be added to the reaction system.

The reaction temperature can usually range from -20 ° C to the boiling point of the solvent used in the reaction.
It is more desirable that the range be from to the boiling point of the solvent used in the reaction.

The molar ratio of the raw materials can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar ratio or a ratio close thereto.

After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by a usual operation such as chromatography, distillation, recrystallization and the like.

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

The general formula which is a raw material of the compound of the present invention:
A carboxylic acid compound represented by the formula: R ⁶ -ZH [wherein R ⁶ and Z represent the same meaning as described above. A carboxylic acid-based compound represented by the general formula 22 and a general formula R ⁶ -L ³ wherein R ⁶ and L ³ have the same meanings as described above. The compound represented by the formula (I) is a commercially available compound, or is obtained from a commercially available compound, for example, J. Prakt. Chem., 2
1, 124 (1880) and the like, and can be adjusted by an ordinary method based thereon. The amine-based compound represented by the general formula (17), the isocyanate-based compound represented by the general formula (19), the (thio) phenol-based compound represented by the general formula (21), and the compound represented by the general formula (24) are used as raw materials of the compound of the present invention. The thiocarbamic acid-based compound can be produced, for example, by the following general methods (reaction formulas 27 and 28).

[0084]

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[0085]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , X,
Y, l, m and M ² have the same meaning as described above, and M ¹ '
Represents an alkali metal atom. ] And the general formula 29

[0087]

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[Wherein R ¹ , R ² , R ³ , X, Y, 1 and m have the same meaning as described above. ] (Thio)
Phenol compounds [represented by the general formula of 21 (thio) of phenolic compound, equivalent to a case where M ¹ represents a hydrogen atom], for example, conventional methods (Scheme of 30 and the reaction scheme shown below 31) and the like. (A) When Y represents an oxygen atom

[0089]

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[Wherein R ¹ , R ² , R ³ , X, l and m represent the same meaning as described above. (B) when Y represents a sulfur atom

[0091]

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[Wherein R ¹ , R ² , R ³ , X, l and m represent the same meaning as described above. In the above, the reaction formula
In the reaction represented by the chemical formula (30) and the chemical formula (31),
In particular, when R ³ represents a chlorine atom,

[0093]

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[Wherein R ¹ , R ² , l and m have the same meaning as described above. The phenol derivative represented by the general formula is reacted with a chlorinating agent in the presence of a solvent,

[0095]

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Wherein R ¹ , R ² , l and m have the same meaning as described above. ] Can be obtained according to the usual method of synthesizing the phenol derivative represented by the formula

In the above reaction formula, chlorine, t-butyl hypochlorite, sulfuryl chloride or the like can be used as the chlorinating agent. In addition, a solvent can be used if necessary, and examples of the solvent that can be used include dichloromethane, dichloroethane, carbon tetrachloride, benzene, and acetic acid. It goes without saying that the solvent used here is properly used depending on the type of the chlorinating agent. The reaction temperature can range from -78 ° C to the boiling point of the solvent or chlorinating agent (sulfuryl chloride, etc.) used in the reaction. ) Is desirable.
The molar ratio of the raw material and the chlorinating agent to be used for the reaction can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar or close ratio.

After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, it can be purified by a usual operation such as chromatography, distillation, recrystallization and the like.

It should be noted that other halogenated (R^ThreeIs a fluorine atom
Or when it represents a bromine atom, etc.) and alkylation (especially
Methylation), for example, Tetrahedron Lett.,Two
7, 4465 (1986), J. Org. Chem.,32, 2358 (1967), Tetra
hedron Lett., 889 (1974), etc.
Can use a method corresponding thereto.

The phenol derivative represented by the general formula (I) can be obtained from commercially available compounds, or can be prepared from commercially available compounds by, for example, the following method (reaction formulas (I) to (I)). can do. (I) when X represents an oxygen atom, a sulfur atom or a group represented by the formula -NH-

[0101]

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[0102] wherein, Ha represents a halogen atom, R ¹²
Represents a hydrogen atom or a methyl group, and R ¹ , R ² , l and m have the same meaning as described above. (II) when X represents a methylene group

[0103]

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[Wherein Ha represents a halogen atom,
R ¹ , R ² , l and m have the same meaning as described above. ]
(III) when X represents a group represented by the formula -C (O)-

[0105]

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[Wherein, R ¹ , R ² , l and m represent the same meaning as described above. ]

Next, the compounds of the present invention which can be produced according to these production methods are shown in Tables 1 to 51. However, these compounds are for illustration only, and the present invention is not limited to these.

Further, among the compounds of the present invention, in the case of a compound having an asymmetric carbon atom, the compound of the present invention is an optically active isomer having a biological activity ((+)-isomer,
(-)-Isomer) and mixtures thereof in all proportions.

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Table 3]

[0112]

[Table 4]

[0113]

[Table 5]

[0114]

[Table 6]

[0115]

[Table 7]

[0116]

[Table 8]

[0117]

[Table 9]

[0118]

[Table 10]

[0119]

[Table 11]

[0120]

[Table 12]

[0121]

[Table 13]

[0122]

[Table 14]

[0123]

[Table 15]

[0124]

[Table 16]

[0125]

[Table 17]

[0126]

[Table 18]

[0127]

[Table 19]

[0128]

[Table 20]

[0129]

[Table 21]

[0130]

[Table 22]

[0131]

[Table 23]

[0132]

[Table 24]

[0133]

[Table 25]

[0134]

[Table 26]

[0135]

[Table 27]

[0136]

[Table 28]

[0137]

[Table 29]

[0138]

[Table 30]

[0139]

[Table 31]

[0140]

[Table 32]

[0141]

[Table 33]

[0142]

[Table 34]

[0143]

[Table 35]

[0144]

[Table 36]

[0145]

[Table 37]

[0146]

[Table 38]

[0147]

[Table 39]

[0148]

[Table 40]

[0149]

[Table 41]

[0150]

[Table 42]

[0151]

[Table 43]

[0152]

[Table 44]

[0153]

[Table 45]

[0154]

[Table 46]

[0155]

[Table 47]

[0156]

[Table 48]

[0157]

[Table 49]

[0158]

[Table 50]

[0159]

[Table 51]

Examples of pests against which the compound of the present invention exerts effects include the following.

Hemiptera pests Planthoppers such as brown planthopper, brown planthopper, brown planthopper, etc., leafhoppers such as black leafhopper, locust leafhopper, black leafhopper, leafhopper leafhopper, leafhopper leafhopper, leafhopper leafhopper such as leafhopper leafhopper, etc. Aphids, stink bugs, whiteflies such as tobacco whiteflies, whiteflies, etc., scale insects, firebugs, psyllids, etc.

Pests such as Lepidopteran pests, P. persicae, P. persicae, P. persicae, P. persicae, P. persicae, P. persicae, P.
Agrotis spp., Heliothis spp., Such as Leaf moths, Hosoga, Kibaga, Dokuga, Uwaba, Kaburayaga, Tamanayaga, etc.
p.), Conaga, Iga, Koiga, etc.

Diptera pests Culex pipiens such as Culex pipiens and Culex pipiens, Aedes aegypti such as Aedes albopictus, Anopheles such as Aedes aegypti, houseflyes such as chironomid, housefly, housefly, blowfly, scallop, and housefly Flies, such as onions and flies, flies, fruit flies, olive flies, drosophila,
Drosophila, flies, blackflies, sand flies, etc.

Coleoptera Pests Corn rootworms such as western corn rootworm and southern corn rootworm, scarab beetles such as dung beetle buddha and himeconega, weevils such as weevil, rice weevil and adzuki weevil, and corn beetle such as black beetle mealworm such, Kisujinomihamushi, Chrysomelidae such as corn rootworm, beetles such, Epilachna genera such as the beetle, Epilachna vigintioctopunctata (Epilachna spp.), Hiratakiimushi such, Naga Shinkuimushi class, beetles, etc.

Reticulate pests German cockroaches, black cockroaches, brown cockroaches, brown cockroaches, cockroaches, etc.

Thrips pests Thrips palmi, Thrips palmi, Thrips palmi, etc.

Hymenoptera pests Ants, wasps such as wasps, etc.

Orthoptera pests Kera, grasshoppers, etc.

Pests of the order Coleoptera, human flea, etc.

Lice harmful insects Human lice, lice, etc.

It is effective against the insects of the order Isoptera, such as the termite Yamato and the house termite. Further, among them, it is more suitable for controlling Hemiptera pests, and exhibits particularly excellent effects on planthoppers and leafhoppers that injure rice crops, and exhibits excellent control effects.

By adding other insecticides and / or miticides, the pest control of the compounds of the present invention can be applied practically to a wider variety of insect pests and a wider variety of applications. Suitable additives include, for example, fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate], fenthion [O, O-dimethyl O- [3-methyl-4- (methylthio) phenyl] Phosphorothioate], diazinon [O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos [O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate ], Acephate [O, S-dimethylacetylphosphoramidothioate], methidathione [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazole-3-]
Ylmethyl O, O-dimethylphosphorodithioate], ethylthiomethone [O, O-diethyl S-2-
Ethylthioethyl phosphorodithioate], DDVP
[2,2-dichlorovinyldimethyl phosphate], sulphophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O, O-dimethyl phosphorothioate], salithion [2-methoxy-4H-
1,3,2-benzodioxaphosphinin-2-sulfide], dimethoate [O, O-dimethyl-S- (N-
Methylcarbamoylmethyl) dithiophosphate], phentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro- 1-hydroxyethylphosphonate], azinphosmethyl [S-3,4-dihydro-4-oxo-1,
2,3-benzotriazin-3-ylmethyl O, O-
Organic phosphorous compounds such as dimethyl phosphorodithioate] and monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate];

BPMC (2-sec-butylphenylmethyl carbamate), benfracarb [ethyl N-
[2,3-dihydro-2,2-dimethylbenzofuran-
7-yloxycarbonyl (methyl) aminothio] -N
-Isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-
Dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1
-Naphthyl-N-methyl carbamate], methomil [S
-Methyl-N-[(methylcarbamoyl) oxy] thioacetimidate], ethiophencarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxy And carbamate compounds such as oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide],

Etofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS) -α-
Cyano-3-phenoxybenzyl (RS) -2- (4-
Chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl) -3-methylbutyrate], fenpropatrin [( RS) -α-
Cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-phenoxybenzyl (1RS, 3RS)-(1RS, 3RS) -3 −
(2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS, 3RS)-(1RS, 3R
S) -3- (2,2-Dichlorovinyl) -2,2-methylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS) -3 -(2-chloro-3,
3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-cyano-m-phenoxybenzyl (1
R, 3R) -3 (2,2-dibromovinyl) -2-dimethylcyclopropanecarboxylate], cycloprothrin [(RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro- Pyrethroid compounds such as 1- (4-ethoxyphenyl) cyclopropanecarboxylate],

Thiadiazine derivatives such as buprofezin (2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-triadiadinan-4-one) and imidacloprid [1- (6-chloro-3-pyridyl) Nitroimidazolidine derivatives such as methyl) -N-nitroimidazolidin-2-ylideneamine, cartap [S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N-dimethyl-1,2,2 Nereistoxin derivatives such as 3-trithian-5-ylamine] and bensultap [S, S'-2-dimethylaminotrimethylene di (benzenethiosulfonate)]; endosulfan [6,7,8,
9,10,10-hexachloro-1,5,5a, 6
9,9a-Hexahydro-6,9-methano-2,4,3
-Benzodioxathiepine oxide], γ-BHC
Chlorinated hydrocarbon compounds such as [1,2,3,4,5,6-hexachlorocyclohexane] and chloroflubron [1- (3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridine) -2-yloxy) phenyl] -3- (2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-
2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], flufenoxuron [1-
Benzoylphenylurea-based compounds such as [4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea], amitraz [N, N '[( Methylimino)
Dimethylidin] di-2,4-xylysine], chlordimeform [N '-(4-chloro-2-methylphenyl)-
N, N-dimethylmethanimidamide] and the like.

When the compound of the present invention is used as an active ingredient of a pesticidal agent, it may be used as it is without adding any component of the present invention, but it is usually used as a solid carrier, a liquid carrier, a gaseous carrier, or a bait. Add surfactants and other formulation auxiliaries as needed, and add oils, emulsions, wettable powders, suspensions in water, emulsions in water, etc., flowables, granules, powders,
Aerosol, self-burning type smoke agent, chemical reaction type smoke agent, heating smoke agent such as perforated ceramic plate smoke agent, ULV agent, poison bait and the like are used.

These preparations usually contain the compound of the present invention as an active ingredient in an amount of 0.001% to 95% by weight.
Examples of the solid carrier used in the formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite, quartz, Sulfur, activated carbon, calcium carbonate, hydrated silica, etc.),
Examples include fine powders or granular materials such as chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, salt ammonium, etc.). Examples of liquid carriers include water, alcohols (methanol, ethanol, etc.) and ketones (acetone, acetone, etc.). Methyl ethyl ketone),
Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile) , Isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, tetrachloride) Carbon), dimethyl sulfoxide, soybean oil, vegetable oils such as cottonseed oil, and the like.
Examples of the gaseous carrier, that is, the propellant include Freon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohols. Derivatives and the like.

Examples of pharmaceutical auxiliaries such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers. (Polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.) and the like. Examples of the stabilizer include PAP (acidic isopropyl phosphate), BH
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , A surfactant, a fatty acid or an ester thereof, and the like.

As the base material of the self-combustion type smoke agent, for example, nitrate, nitrite, guanidine salt, potassium chlorate,
Combustion heating agents such as nitrocellulose, ethylcellulose, and wood flour; thermal decomposition stimulants such as alkali metal salts, alkaline earth metal salts, dichromates, and chromates; oxygen supply agents such as potassium nitrate; melamine; wheat starch; And a bulking agent such as diatomaceous earth, and a binder such as synthetic paste. As the base material of the chemical reaction type smoke agent, for example, alkali metal sulfide, polysulfide, hydrosulfide, hydrated salt,
Exothermic agents such as calcium oxide, catalytic agents such as carbonaceous materials, iron carbide, and activated clay; organic blowing agents such as azodicarbonamide, benzenesulfonylhydrazine, dinitrosopentamethylenetetramine, polystyrene, and polyurethane; natural fiber fragments and synthetic fibers And fillers such as pieces.

Examples of the bait bait include bait ingredients such as cereal flour, vegetable essential oil, sugar, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid; preservatives such as dehydroacetic acid; Powder and the like, and inducing flavors such as cheese flavor, onion flavor and the like.

Formulations of flowables (suspension in water or emulsions in water) generally contain 0.5% to 15% of the compound.
% Of a dispersant, 0.1 to 10% of a suspending aid (for example, a protective colloid or a compound imparting thixotropic properties),
Fine water in water containing 1.0% of appropriate adjuvants (eg antifoaming agents, rust inhibitors, stabilizers, spreading agents, penetration aids, antifreezing agents, antibacterial agents, antismoking agents, etc.) To be obtained. It is also possible to use an oil in which the compound hardly dissolves in place of water and use it as a suspension in oil. As the protective colloid, for example, gelatin, casein, gums, cellulose ether, polyvinyl alcohol and the like are used. Examples of the compound imparting thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid and the like.

The preparation thus obtained is used as it is or after dilution with water or the like. Also other pesticides,
They can be used together with or without mixing with nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feeds and the like.

When the compound of the present invention is used as an agricultural pesticide, the application rate is usually 0.001 g to 500 g per 10 ares, preferably 0.1.
g to 500 g. When the emulsion, wettable powder, flowable and the like are diluted with water and used, the application concentration is usually 0.1.
0001 ppm to 1000 ppm, and granules, dusts, etc. are applied as they are without dilution. When used as a pest control agent for epidemic control, emulsions, wettable powders, flowables, etc. are usually diluted with water to 0.0001 ppm to 10,000 ppm and applied, and oils, aerosols, smokers, ULVs, For poison bait, etc., apply as it is.

These application rates and application concentrations differ depending on the type of preparation, application time, application place, application method, type of pest, degree of damage, etc., and may be increased without being related to the above range. Or can be reduced.

[0186]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples, but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention will be shown.

Production Example 1 Production Method of Compound (1) by (Production Method A) A solution prepared by dissolving 0.52 g of 2- (2-chloro-4-phenoxyphenoxy) ethylamine and 1.12 g of ethyl chloroformate in 20 ml of acetone was used. Then, 1.66 g of potassium carbonate was added, and the mixture was heated and refluxed for 24 hours while stirring. After concentration of the reaction solution, the residue was poured into 50 ml of water and extracted twice with 100 ml of ethyl acetate. After drying and concentrating the ethyl acetate solution, the residue was subjected to silica gel chromatography to obtain 0.39 g of ethyl 2- (2-chloro-4-phenoxyphenoxy) ethylcarbamate. Yield: 59% n ²⁴ _D 1.5632

Production Example 2 (Production of Compound (6) of the Present Invention by Production Method B) 0.89 g of 2- (2-chloro-4-phenoxyphenoxy) ethyl isocyanate and several drops of pyridine were dissolved in 10 ml of methanol, and the reaction mixture was dissolved in 10 ml of methanol. Heated to reflux. One hour later, the reaction solution was concentrated, and the residue was subjected to silica gel chromatography to obtain 0.51 g of methyl 2- (2-chloro-4-phenoxyphenoxy) ethylcarbamate. Yield: 52% n ²³ _D 1.5698

Production Example 3 (Production of Compound (8) of the Present Invention by Production Method C) 0.91 g of 2-chloro-5-phenoxyphenol and 20 ml of N, N-dimethylformamide were placed in a reaction vessel, and stirred under stirring. 0.69 g of chloroethyl carbamic acid ethyl ester and 1.14 g of potassium carbonate were added, and 50
Heated at 7 ° C. for 7 hours. The reaction solution was poured into 100 g of ice water,
Extracted twice with 100 ml of ethyl acetate. After drying and concentrating the ethyl acetate solution, the residue was subjected to silica gel chromatography to obtain 0.14 g of ethyl 2- (2-chloro-5-phenoxyphenoxy) ethylcarbamate. Yield: 10% n ²² _D 1.5608

Production Example 4 (Compound (100) by Production Method C)
0.5 g (1.73 mmol) of 2-chloro-4- (3-trifluoromethylphenoxy) phenol and 20 ml of N, N-dimethylformamide are placed in a reaction vessel and stirred.
0.29 g of 2-chloroethylcarbamic acid ethyl ester
(1.90 mmol) and 0.53 g (3.81 mm) of potassium carbonate
ol) and heat at 50 ° C. for 7 hours. The reaction solution was ice water 1
100 g and extracted twice with 100 ml of ethyl acetate.
After drying and concentrating the ethyl acetate solution, the residue was subjected to silica gel chromatography to give 2- [2-chloro-4- (3-
Trifluoromethylphenoxy) phenoxy] ethyl carbamic acid ethyl ester is obtained.

Production Example 5 Compound (11) obtained by (Production Method C)
Production method of 6) 0.65 g (2.25 mmol) of 2-chloro-4- (4-trifluoromethylphenoxy) phenol and N, N-
20 ml of dimethylformamide is placed in a reaction vessel, and stirred with ethyl 2-chloroethylcarbamate ethyl ester 0.3.
8 g (2.47 mmol) and 0.69 g of potassium carbonate (4.9)
5 mmol) and heat at 50 ° C. for 8 hours. The reaction solution is poured into 100 g of ice water and extracted twice with 100 ml of ethyl acetate. After drying and concentrating the ethyl acetate solution, the residue was subjected to silica gel chromatography to give 2- [2-chloro-4-
(4-trifluoromethylphenoxy) phenoxy] ethyl carbamic acid ethyl ester is obtained.

Production Example 6 (Production of Compound (15) of the Present Invention by Production Method D) 1.20 g of 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylamine, 0.81 g of triethylamine and tetrahydrofuran 20 ml was placed in a reaction vessel, and excess carbonyl sulfide was blown in at room temperature with stirring for 30 minutes. Then 0.75 ethyl iodide
g was added dropwise and stirred for 24 hours. The reaction solution was concentrated, and the residue was poured into 100 ml of water and extracted twice with 100 ml of ethyl acetate. The ethyl acetate solution was dried and concentrated, and the residue was subjected to silica gel chromatography to obtain 0.95 g of ethyl 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylthiocarbamate. Yield: 61% n ²¹ _D 1.5707

Production Example 7 Production method of the present compound (153) by (Production method E) 2- [2-Chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid ethyl ester
85 g (2.29 mmol) and 10 ml of methylene chloride are placed in a reaction vessel and cooled to 0 ° C. Under stirring, the internal temperature is 0-5 ° C
0.26 g of triethylamine (2.52 mmo
l) is added. Next, 3 ml of a methylene chloride solution containing 0.36 g (2.29 mmol) of methyl N-chlorosulfenyl-N-methylcarbamate was added dropwise. After completion of the dropwise addition, the temperature is raised to room temperature, and the mixture is stirred for 1 hour. Pour the reaction solution into 500 ml of water,
Extract twice with 500 ml of diethyl ether. The diethyl ether solution is dried over magnesium sulfate and concentrated to obtain a crude product. This crude product was subjected to silica gel column chromatography to give [N- (methoxycarbonylmethylamino) sulfenyl] -2- [4-
(3,5-difluorophenoxy) phenoxy] ethyl carbamic acid ethyl ester is obtained.

Next, some of the compounds of the present invention obtained according to these production methods are shown below together with the compound numbers.

(1) 2- [2-chloro-4-phenoxyphenoxy] ethyl carbamic acid ethyl ester n ²⁴ _D 1.5632 (2) 2- [2-chloro-4-phenoxyphenoxy] ethyl n-pentyl ethyl carbamate Ester n ²² _D 1.5489 (3) 2- [2-chloro-4-phenoxyphenoxy] ethylcarbamic acid allyl ester n ²⁴ _D 1.5671 (4) 2- [2-chloro-4-phenoxyphenoxy] ethylcarbamine Acid 2-methoxyethyl ester n ²² _D 1.5583 (5) 2- [2-chloro-4-phenoxyphenoxy] ethylcarbamic acid 2-trichloroethyl ester n ²² _D 1.5650 (6) 2- [2-chloro -4-phenoxyphenoxy] ethyl carbamic acid methyl ester n ²³ _D 1.5698 (7) 2- [2-Chloro-4-phenoxyphenoxy] ethyl carbamic acid n-propyl ester Viscous liquid (8) 2- [2-Chloro-4-phenoxyphenoxy] ethyl carbamic acid iso-propyl ester n ²⁴ _D 5542

(9) 2- [2-chloro-4-phenoxyphenoxy] ethyl carbamic acid n-butyl ester n ²² _D 1.5530 (10) 2- [2-chloro-4-phenoxyphenoxy] ethyl carbamic acid iso -Butyl ester n ²² _D 1.5505 (11) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid ethyl ester n ²² _D 1.5420 (12) 2- [2 -Chloro-4- (3-fluorophenoxy) phenoxy] ethylcarbamic acid ethyl ester n ²² _D 1.5498 (13) 2- [2-Chloro-4- (3-methylphenoxy) phenoxy] ethylcarbamic acid ethyl ester n ²⁰ _D 1.5627 (14) 2- [2-chloro-4- (2,4-difluorophenoxy) phenol [Xy] ethyl carbamic acid ethyl ester n ²⁵ _D 1.5089 (15) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylthiol carbamic acid ethyl ester n ²¹ _D 1.5707 ( 16) 2- [2-chloro-4-benzyl-phenoxy] ethylcarbamate San'e Chiruesuteru n ²⁰ _D 1.5648

(17) 2- [2-Chloro-4-benzoylphenoxy] ethylcarbamic acid ethyl ester Viscous liquid (18) 2- [2-Chloro-5-phenoxyphenoxy] ethylcarbamic acid ethyl ester n ²² _D 1.5608 (19) 2- [2-chloro-4-phenoxyphenoxy] ethylthiolcarbamic acid ethyl ester n ^20.8 _D 1.5927 (20) 2- [2,6-dichloro-4- (3,5- Difluorophenoxy) phenoxy] ethyl carbamic acid ethyl ester n ²⁵ _D 1.5361 (21) 2- [2-chloro-4- (3,4-dichlorobenzyl) phenoxy] ethyl carbamic acid ethyl ester n ^22.8 _D 1.5682 (22) 2- [2-chloro-4- (3,5-difluorobenzyl) phenoxy] ethylca Vammin acid ethyl ester n ^26.2 _D 1.5422 (23) 2- [2-chloro-5- (3,5-difluorophenoxy) phenoxy] ethyl ethyl carbamate ester n ^23.3 _D 1.5329 (24) 2- [ 2-chloro-5- (3,4-dichlorophenoxy) phenoxy] ethyl carbamic acid ethyl ester n ²⁴ _D 1.5751 (25) 2- [2,5-dichloro-4- (3,5-difluorophenoxy) phenyl Enoxy] ethyl carbamic acid ethyl ester n ²⁵ _D 1.5421 (26) 2- [2-chloro-4- (3,4-dichlorophenoxy) phenoxy] ethyl carbamic acid ethyl ester n ²⁶ _D 1.5709 (27) 2 -[2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethyl 2,2,2-tric acid B ethyl ester n ^23.5 _D 1.5450 (28) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamate 2-chloroethyl ester n ^23.6 _D 1.5515

(29) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 2,2,2-trifluoroethyl ester n ^23.7 _D 1.5110 (30) 2- (2-chloro-4-benzylphenoxy) ethyl carbamic acid 2-chloroethyl ester n ^22.6 _D 1.5708 (31) 2- (2-chloro-4-benzylphenoxy) ethyl carbamic acid 2,2-dichloroethyl ester n ^22.6 _D 1.5740 (32) 2- (2-chloro-4-benzylphenoxy) ethylcarbamic acid 2,2,2-trifluoroethyl ester n ^22.4 _D 1.5369 (33) 2- (2-chloro-4 - benzyl phenoxy) ethylcarbamate 2, 2,2-trichloroethyl ester n ^20.4 _D 1.5728 (34) 2- 2-chloro-4-benzyl-phenoxy) ethylcarbamate 2 - bromoethyl ester _{^{n 22.5 D 1.5802 (35) 2-}} (2- chloro-4-benzyl-phenoxy) ethylcarbamate 2, 2,2 tribromoethyl Esters m. p. 64.3 ° C. (36) 2- (2-chloro-4-benzylphenoxy) ethylcarbamic acid 2,2,3,3,4,4,4-heptafluoro-n-butyl ester n ^20.5 _D 1.4991 ( 37) 2- (2-Chloro-4-benzylphenoxy) ethylcarbamic acid 2-iodoethyl ester n ²² _D 1.5897 (38) 2- (2-Chloro-4-benzylphenoxy) ethylcarbamic acid 3 bromo-n -Propyl ester n ^21.3 _D 1.5766 (39) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2-chloroethyl ester n ²³ _D 1.5590 (40) 2- [2 -Chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2,2-dichloroethyl ester n ²³ _D 1.5646

(41) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2,2,2-trichloroethyl ester n ²³ _D 1.5562 (42) 2- [2-chloro -4- (3-Chlorophenoxy) phenoxy] ethylcarbamic acid 2,2,2-trifluoroethyl ester n ²³ _D 1.5302 (43) 2- [2-Chloro-4- (3-chlorophenoxy) phenoxy] ethyl Rukarubamin acid 3-chloro -n- propyl ester n ²³ _D 1.5581 (44) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethyl Rukarubamin acid (1-chloromethyl-2-chloro) Ethyl ester n ²³ _D 1.5505 (45) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamine Acid 1,2-dichloroethyl ester n ²³ _D 1.5660 (46) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid (2-chloro-1-methyl) ethyl ester n ²³ _D 1.5642 (47) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2-ethoxyethyl ester n ²³ _D 1.5522 (48) 2- [2-chloro-4- (3-Chlorophenoxy) phenoxy] ethylcarbamic acid (1-trifluoromethyl-2,2,2-trifluoro) ethyl ester m. p. 84.5 ° C (49) 1-methyl-2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid ethyl ester (50) 2- [2-chloro-4-benzylphenoxy Ethylcarbamic acid 2-fluoroethyl ester n ^20.6 _D 1.5598

(51) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 3-chloro-n-propyl ester n ^20.9 _D 1.5682 (52) 2- [2-chloro-4-benzylphenoxy] Ethylcarbamic acid (2-bromo-1-methyl) ethyl ester n ^21.2 _D 1.5721 (53) 2- [2-Chloro-4-benzylphenoxy] ethylcarbamic acid (2-chloro-1-methyl) ethyl ester n ^26.0 _D 1.5630 (54) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 2,2,3,3-tetrafluoro-n-propyl ester n ^24.9 _D 1.5256 (55) 2- [ 2-chloro-4-benzyl-phenoxy] ethylcarbamate 2 - cyanoethyl ester n ^20.7 _D 1.5672 (56) 2- [ - chloro-4-benzyl phenoxy] ethylcarbamate 2, 2,3,3,3-pentafluoro -n- propyl ester n ^20.8 _D 1.5118 (57) 2- [2-chloro-4-benzyl-phenoxy] ethyl Carbamic acid 2-propynyl ester m. p. 70.4 ° C (58) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid (1-trifluoromethyl) ethyl ester n ^21.2 _D 1.5342 (59) 2- [2-chloro-4-benzyl Phenoxy] ethylcarbamic acid 1-methyl-2-propynyl ester n ^21.3 _D 1.5637 (60) 2- [2-Chloro-4-benzylphenoxy] ethylcarbamic acid 2,3-dichloro-n-propyl ester n ²⁴ _D 1.5460 (61) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid isopropyl ester n ^20.7 _D 1.5580

(62) 2- [2-Chloro-4-benzylphenoxy] ethylcarbamic acid (1-trifluoromethyl-2,2,2-trifluoro) ethyl ester m. p. 89.5 ° C (63) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 2-methoxyethyl ester n ^22.4 _D 1.5562 (64) 2- [2-chloro-4- (3-chlorophenoxy) ) Phenoxy] ethyl carbamic acid 2-fluoroethyl ester n ²³ _D 1.5684 (65) 2- [2-chloro-4-benzylphenoxy] ethyl carbamic acid tert-butyl ester n ^22.1 _D 1.5569 (66) 2 -[2-chloro-4-benzylphenoxy] ethylcarbamic acid 1,1-dimethyl-2-propynyl ester n ^22.6 _D 1.5605 (67) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 1, 1-dimethyl-2-propenyl ester n ^21.9 _D 1.5728 (68) 2- [2-chloro-4- (3 Chlorophenoxy) phenoxy] ethyl Rukarubamin acid isopropyl ester n ^20.5 _D 1.5570 (69) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethyl Rukarubamin acid 2-methoxyethyl ester n ^20.5 _D 1.5586 (70) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethyl Rukarubamin acid 2-cyanoethyl ester n ²³ _D 1.5604 (71) 2- [2-chloro-4- (3-chlorophenoxy ) Phenoxy] ethylcarbamic acid 2-bromoethyl ester n ²³ _D 1.5797

(72) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2,2,2-tribromoethyl ester n ²³ _D 1.6002 (73) 2- [2- Chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2-bromo-1-methylethyl ester n ²³ _D 1.5688 (74) 2- [2-Chloro-4- (3-chlorophenoxy) phenoxy] Ethylcarbamic acid 1-fluoromethyl-2-fluoroethyl ester n ²³ _D 1.5553 (75) 2- [2-Chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2,3-dibromo-n- Propyl ester n ²³ _D 1.5902 (76) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarba 2,2,3,3-tetrafluoro-n-propyl ester of lactic acid n ²³ _D 1.5322 (77) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 1- ( Trifluoromethyl) ethyl ester n ²³ _D 1.5368 (78) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2,2,3,3,3-pentafluoro-n- Propyl ester n ²³ _D 1.5149 (79) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2-propynyl ester n ²⁴ _D 1.5690 (80) 2- [2-chloro 4- (3-chlorophenoxy) phenoxy] ethyl Rukarubamin acid 2- butenyl ester n ²⁴ _D 1.5685 (81) 2- [2-chloro-4- 3-chlorophenoxy) phenoxy] ethyl Rukarubamin acid 2-methylpropyl ester n ²⁴ _D 1.5547

(82) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 3-butynyl ester n ²⁴ _D 1.5591 (83) 2- [2-chloro-4- ( 3-chlorophenoxy) phenoxy] ethylcarbamic acid 2-butynyl ester n ²⁴ _D 1.5636 (84) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2,2,3 3,4,4,4-heptafluoro-n-butyl ester n ²⁴ _D 1.5003 (85) 2- [2-chloro-4- (3-bromophenoxy) phenoxy] ethylcarbamic acid ethyl ester (86) 2 - [2-chloro-4-benzyl-phenoxy] ethylcarbamate 1 - fluoromethyl-2-fluoroethyl ester n ^21.4 _D 1.5460 87) 2- [2-chloro-4-benzyl-phenoxy] ethylcarbamate 2, 3-dibromo -n- propyl ester n ^21.8 _D 1.5800 (88) 2- [2-chloro-4-benzyl-phenoxy] ethylcarbamate Acid 2-ethoxyethyl ester n ^21.2 _D 1.5541 (89) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 1-chloromethyl-2-chloroethyl ester n ^21.3 _D 1.5680 (90) 2 - [2-chloro-4-benzyl-phenoxy] ethylcarbamate 2 - butenyl ester n ^21.3 _D 1.5656 (91) 2- [2-chloro-4-benzyl-phenoxy] ethylcarbamate San'i isopropyl ester n ^21.5 _D 1.5539 (92) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 2 Butynyl ester n ^21.8 _D 1.5728 (93) 2- [2-chloro-4-benzyl-phenoxy] ethylcarbamate 3 - butynyl ester n ^21.6 _D 1.5691

(94) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 3-butenyl ester n ²⁰ _D 1.5650 (95) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 4,4,4-trifluoro-n-butyl ester n ²⁰ _D 1.5311 (96) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 1-methyl-n-propyl ester n ^20.6 _D 5542 (97) 2- [2-Chloro-4-benzylphenoxy] ethylcarbamic acid 1-methoxyethyl ester n ^20.1 _D 1.5550 (98) 2- [2-Chloro-4-benzylphenoxy] ethylcarbamic acid 2- Methyl-3-butenyl ester n ^20.3 _D 1.5661 (99) 2- [2-chloro-4-benzylphenoxy] e Tylcarbamic acid 2-isopropoxyethyl ester n ^20.8 _D 1.5478 (100) 2- [2-Chloro-4- (3-trifluoromethylphenoxy) phenoxy] ethylcarbamic acid ethyl ester (101) 2- [2 -Chloro-4-benzylphenoxy] ethylcarbamic acid 3-methyl-2-butenyl ester n ²⁰ _D 1.5582 (102) 2- [2-Chloro-4-benzylphenoxy] ethylcarbamic acid 2,2-dimethyl- n-propyl ester n ^19.9 _D 1.5481 (103) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid 3,3-dimethyl-n-butyl ester n ^20.4 _D 1.5469 (104) 2- [ 2-chloro-4-benzylphenoxy] ethylcarbamic acid 3-methyl-n-butyl ester ^20.3 _D 1.5495 (105) 2- [2-chloro-4-benzyl-phenoxy] ethylcarbamate 2-methylthioethyl ester n ^20.6 _D 1.5797 (106) 2- [2-fluoro-4-phenoxyphenoxy] Echirukarubami Acid ethyl ester n ^24.0 _D 1.5338

(107) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 2-bromo-1-methylethyl ester n ²¹ _D 1.5506 (108) 2- [ 2-chloro-4- (3-chlorophenoxy) phenoxy] ethyl carbamic acid tert-butyl ester n ²² _D 1.5320 (109) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethyl Carbamic acid 3-butenyl ester n ²² _D 1.5519 (110) 2- [2-Chloro-4- (3-chlorophenoxy) phenoxy] ethyl 1-methyl-n-propyl ester n ^21.5 _D 5582 (111) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2-methoxy-1- Methyl ethyl ester n ^21.5 _D 1.5614 (112) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] an ethyl carbamic acid 1-methyl-2-propenyl ester n ^21.5 _D 1.5573 (113) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 1-methyl-2-propynyl ester n ^21.5 _D 1.5519 (114) 2- [2-chloro-4- (3- Chlorophenoxy) phenoxy] ethylcarbamic acid 1,1-dimethyl-2-propynyl ester n ²³ _D 1.5299 (115) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2 - isopropoxyethyl ester n ^22.5 _D 1.5510

(116) Ethyl 2- [2-chloro-4- (4-trifluoromethylphenoxy) phenoxy] ethylcarbamate (117) 2- [2-Chloro-4- (3-chlorophenoxy) phenoxy Ethylcarbamic acid 1,1-dimethyl-2-propenyl ester n ²³ _D 1.5491 (118) 2- [2-Chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 3-methyl-2 - butenyl ester n ^22.5 _D 1.5648 (119) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] an ethyl carbamate 2,2-dimethyl -n- propyl ester n ^22.5 _D 1.5543 (120) 3,3-dimethyl-n 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamate - butyl ester n ^22.5 _D 1.5693 (121) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] an ethyl carbamate 3-methyl -n- butyl ester n ^22.5 _D 1.5591 (122) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid 2-iodoethyl ester n ^22.5 _D 1.5624 (123) 2- [2-chloro-4- (3-chlorophenoxy) Phenoxy] ethyl carbamic acid 2-methylthioethyl ester n ^22.5 _D 1.5631 (124) 2- [2-chloro-4- (4-fluorophenoxy) phenoxy] ethyl carbamic acid ethyl ester n ²⁴ _D 1.5392 (125 ) 2- [2-Chloro-4- (4-chlorophenoxy) phenoxy] ethyl carbamic acid ethyl ester n ²⁴ _D 1.5528

(126) 1-fluoromethyl-2-fluoroethylester 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamate n ^22.1 _D 1.5284 (127) 2 - [2-chloro-4- (3,5-difluorophenoxy) phenol carboxymethyl] ethyl carbamic acid methyl ester n ^23.5 _D 1.5409 (128) 2- [2-chloro-4- (3,5-difluorophenoxy) phenolate carboxylate] ethylcarbamate 2,3-dibromo -n- propyl ester n ^22.8 _D 1.5634 (129) 2- [2-chloro-4- (3,5-difluorophenoxy) phenol carboxymethyl] ethylcarbamate ethoxyethyl ester n ^23.7 _D 1.5340 (130) 2- [2-chloro-4- (3,5-difluorophenoxy) Fe Carboxymethyl] ethylcarbamate l- trifluoromethyl-2,2,2-trifluoroethyl ester m. p. 78.1 ° C (131) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 2,2,3,3-tetrafluoro-n-propyl ester n ^22.9 _D 1 .5045 (132) 2- [2-Chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 1-trifluoromethylethyl ester n ^23.2 _D 1.5090 (133) 2- [2-chloro 4- (3,5-difluorophenoxy) phenol carboxymethyl] ethylcarbamate 2,2,3,3,3-pentafluoro -n- propyl ester n ^23.2 _D 1.4938 (134) 2- [2-chloro - 4- (3,5-Difluorophenoxy) phenoxy] ethylcarbamic acid 2-propynyl ester n ^23.2 _D 1.5462

(135) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 2-butenyl ester n ^23.2 _D 1.5409 (136) 2- [2-chloro- 4-benzylphenoxy] ethyl carbamic acid methyl ester n ^18.7 _D 1.5748 (137) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethyl carbamic acid 2-methyl-n-propyl ester n ^24.5 _D 1.5304 (138) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 3-butynyl ester n ^24.1 _D 1.5449 (139) 2- [2 - chloro-4- (3,5-difluorophenoxy) phenol carboxymethyl] ethylcarbamate 2-butynyl ester n ^23.6 _D 1. 475 (140) 2,2,3,3,4,4,4-2- [2-chloro-4- (3,5-difluorophenoxy) phenol carboxymethyl] ethylcarbamate Heputafuruo b -n- butyl ester n ^23.6 _D 1.4832 (141) 2- [2-chloro-4- (3,5-difluorophenoxy) phenol carboxymethyl] ethylcarbamate 3-butenyl n ^24.2 _D 1.5408 (142) 2- [2-chloro 4- (3,5-Difluorophenoxy) phenoxy] ethyl carbamate 4,4,4-trifluoro-n-butylester n ^23.7 _D 1.5080 (143) 2- [2-chloro-4- (3 , 5-Difluorophenoxy) phenoxy] ethylcarbamic acid 1-methyl-n-propyl ester m. p. 58.2 ° C

(144) 2- [2-Chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 1-methoxyethyl ester n ^23.5 _D 1.5298 (145) 2- [2-chloro- 4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid ethyl ester n ²⁶ _D 1.5611 (146) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 3- Chloropropyl ester n ^21.2 _D 1.5452 (147) 2- (2-bromo-4-phenoxyphenoxy) ethylcarbamic acid ethyl ester n ^24.0 _D 1.5798 (148) 2- (2-methyl-4-phenoxyphenoxy) Ethyl carbamic acid ethyl ester n ²⁴ _D 1.5568 (149) 2- [2-chloro-4- ( 3-chlorophenoxy) phenoxy] ethylcarbamic acid 4,4,4-trifluoro-n-butyl ester n ²⁴ _D 1.5197 (150) 2- [2-chloro-4-benzylphenoxy] ethylcarbamic acid cyclopentyl ester n ^20.9 _D 1.5691 (151) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylcarbamic acid cyclopentyl ester n ^22.5 _D 1.5632 (152) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylcarbamic acid 2,2-dichloroethyl ester n ^20.6 _D 1.5502 (153) [N- (methoxycarbonylmethylamino) sulfenyl] -2- [4- (3 , 5-Difluorophenoxy) phenoxy] ethylcarbamic acid ethyl ester

Next, an intermediate production example is shown. Intermediate Production Example (Production of Intermediate Compound (204)) 2-Chloro-4- (3-chlorophenoxy) phenol
14.99 g, 4.44 g of chloroacetonitrile, 150 ml of dimethylformamide and 8.94 g of potassium carbonate were placed in a reaction vessel and stirred. After stirring for 5 hours at an internal temperature of 70 to 80 ° C. in an oil bath, the reaction solution was cooled to room temperature. The reaction solution was poured into water and extracted twice with 100 ml of ethyl acetate, and the ethyl acetate solution was washed twice with 200 ml of water. The ethyl acetate solution was dried over magnesium sulfate, filtered and concentrated to give [2-chloro-4- (3-chlorophenoxy) phenoxy] acetonitrile as a crude product in 14.0%.
g was obtained. 14.0 g of this crude product and 200 ml of tetrahydrofuran were placed in a reaction vessel and cooled to 0 ° C. Under stirring, 200 ml of a borane tetrahydrofuran complex (1.0 MTHF solution) was slowly added dropwise while maintaining the internal temperature at 0 to 5 ° C. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred overnight.
The reaction solution was poured into 300 ml of water, and tetrahydrofuran was removed under reduced pressure.
The mixture was extracted three times with 00 ml, and washed with 200 ml each of a 5% aqueous hydrochloric acid solution, water and a 10% aqueous sodium hydroxide solution.
The ethyl acetate solution was dried over magnesium sulfate, filtered and concentrated to give 2- [2-chloro-4
-(3-chlorophenoxy) phenoxy] ethylamine
11.4 g were obtained. 65% yield n ^24.3 _D 1.5842 Next, the following together with the compound numbers several intermediate compounds of the present invention compounds obtained according to these production methods.

(201) 2- [2-chloro-4-phenoxyphenoxy] ethylamine n ^24.3 _D 1.5911 (202) 2- [2-chloro-4-benzylphenoxy] ethylamine n ^24.3 _D 1.5851 (203) 2- [2-chloro-4- (3,5-difluorophenoxy) phenoxy] ethylamine n ^24.3 _D 1.5620 (204) 2- [2-chloro-4- (3-chlorophenoxy) phenoxy] ethylamine n ^24.3 _D 1.5842 (205) 2- [2-Chloro-4- (3-fluorophenoxy) phenoxy] ethylamine n ^24.3 _D 1.5679 (206) 2- [2-Chloro-4- (3-methylphenoxy) phenoxy] et ethylamine n ^24.3 _D 1.5842 (207) 2- [2-chloro-4- (3-trifluoromethoxy Fe Carboxymethyl) phenoxy] ethylamine (208) 2- [2-chloro-4- (2,4-fluorophenoxy) phenoxy] ethylamine n ^24.3 _D 1.5599 (209) 2- (2-chloro-4-benzoyl-phenoxy) Ethylamine n ²⁵ _D 1.5446 (210) 2- [2-chloro-4- (3,4-dichlorobenzyl) phenoxy] ethylamine n ^24.8 _D 1.5921 (211) 2- [2-chloro-4- (3 , 5-Difluorobenzyl) phenoxy] ethylamine n ^24.8 _D 1.5761 (212) 2- [2,5-Dichloro-4- (3,5-difluorophenoxy) phenoxy] ethylamine n ²³ _D 1.5644 (213) 2- [2,6-dichloro-4- (3,5-difluorophenoxy) phenoxy] ethylamine n ²³ _D 1.57 7 (214) 2- [2-chloro-4- (3-bromophenoxy) phenoxy] et ethylamine (215) 2- [2-chloro-5- (3,4-dichlorophenoxy) phenoxy] ethylamine n ²³ _D 1.5624 (216) 2- [2-chloro-5- (3,5-difluorophenoxy) phenoxy] ethylamine n ²³ _D 1.5884 (217) 2- [2-chloro-4- (4-fluorophenoxy) ) Phenoxy] ethylamine n ²⁵ _D 1.5721 (218) 2- [2-chloro-4- (4-chlorophenoxy) phenoxy] ethylamine n ²⁵ _D 1.5693 (219) 2- [2-chloro-4- (4-trifluoromethylphenoxy) phenoxy] ethylamine (220) 2- [2-chloro-5-phenoxyphenoxy] ethylamine ^24.3 _D 1.5903

Next, preparation examples are shown. The parts represent parts by weight, and the compound of the present invention is represented by the same compound number as described above.

Formulation Example 1 Emulsion Ten parts of each of the compounds (1) to (153) of the present invention were dissolved in 35 parts of xylene and 35 parts of dimethylformamide.
Parts and 6 parts of calcium dodecylbenzenesulfonate were added and mixed well with stirring to obtain 10% emulsions of each.

Formulation Example 2 Wettable powder 20 parts of each of the present compounds (1) to (153) were added to 4 parts of sodium lauryl sulfate and 2 parts of calcium ligninsulfonate.
Parts, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of silicon earth were mixed and stirred with a juice mixer to obtain a 20% wettable powder.

Formulation Example 3 Granules Compounds of the present invention (1) to (34), (36) to (47), (49)
~ (56), (58) ~ (61), (63) ~ (84), (86) ~
(99), (101)-(105), (107)-(115), (117)-
(129), (131)-(142), (144)-(146), (148)-
To 5 parts of (152) were added 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 60 parts of clay, and the mixture was sufficiently stirred and mixed. Next, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain 5% granules.

Formulation Example 4 Granules Compounds of the present invention (35), (48), (57), (62), (130)
5 parts of each of (143) and (5)
, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay, and then sufficiently stirred and mixed. Then, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain 5% granules.

Formulation Example 5 Powder Compounds of the present invention (1) to (34), (36) to (47), (49)
~ (56), (58) ~ (61), (63) ~ (84), (86) ~
(99), (101)-(105), (107)-(115), (117)-
(129), (131)-(142), (144)-(146), (148)-
0.3 parts each of (152), 1 part of synthetic silicon oxide hydrous fine powder, 1 part of trade name Doreless B (manufactured by Sankyo) as a coagulant, and 7.7 parts of clay were mixed well in a mortar, and then mixed with a juice mixer. Stir and mix. 90 parts of cut clay is added to the obtained mixture and mixed in a bag to obtain each dust.

Formulation Example 6 Powder Compounds of the present invention (35), (48), (57), (62), (130)
And (143) each in an amount of 0.3 part and synthetic hydrous silicon oxide fine powder 0.3 part.
After well mixing and mixing 03 parts with a juice mixer, pulverize with a centrifugal pulverizer. 0.97 parts of synthetic hydrous silicon oxide fine powder was added to the obtained pulverized mixture.
1 part (manufactured by Sankyo) and 7.7 parts of clay are added, mixed well in a mortar, and then stirred and mixed with a juice mixer. 90 parts of cut clay is added to the obtained mixture and mixed in a bag,
Obtain each powder.

Formulation Example 7 Powder Compounds of the present invention (1) to (34), (36) to (47), (49)
~ (56), (58) ~ (61), (63) ~ (84), (86) ~
(99), (101)-(105), (107)-(115), (117)-
(129), (131)-(142), (144)-(146), (148)-
(152) 0.3 parts each, Fenitrothion 2 parts as an organic phosphorus compound, synthetic hydrous silicon oxide fine powder 3 parts, Drilles B (manufactured by Sankyo) 1 part as a flocculant, clay 3.7
After mixing the parts well in a mortar, stir and mix with a juice mixer. 90 parts of cut clay is added to the obtained mixture, and the mixture is mixed in a bag to obtain each powder.

Formulation Example 8 Dusts Compounds of the present invention (35), (48), (57), (62), (130)
And (143) each in an amount of 0.3 part and synthetic hydrous silicon oxide fine powder 0.3 part.
After well mixing and mixing 03 parts with a juice mixer, pulverize with a centrifugal pulverizer. To the obtained pulverized mixture, 2 parts of fenitrothion as an organophosphorus compound, 2.97 parts of synthetic silicon-containing hydrous fine powder, 1 part of Doreless B (manufactured by Sankyo) as a coagulant and 3.7 parts of clay are added. After mixing well, stir and mix with a juice mixer. 90 parts of cut clay is added to the obtained mixture and mixed in a bag to obtain each powder.

Formulation Example 9 Powder Compounds of the present invention (1) to (34), (36) to (47), (49)
~ (56), (58) ~ (61), (63) ~ (84), (86) ~
(99), (101)-(105), (107)-(115), (117)-
(129), (131)-(142), (144)-(146), (148)-
(152) 0.3 part each, BP as carbamate compound
MC (O-sec-butylphenyl N-methylcarbamate) 2 parts, synthetic hydrous silicon oxide fine powder 3 parts, trade name Drilles B (manufactured by Sankyo Co., Ltd.) 1 part, clay 3.7 parts are well mixed in a mortar. After that, stir and mix with a juice mixer. 90 parts of cut clay are added to the obtained mixture,
Mix the bags to obtain each powder.

Formulation Example 10 Powder Compounds of the present invention (35), (48), (57), (62), (130)
And (143) each in an amount of 0.3 part and synthetic hydrous silicon oxide fine powder 0.3 part.
After well mixing and mixing 03 parts with a juice mixer, pulverize with a centrifugal pulverizer. BPMC (O-sec-butylphenyl) was added as a carbamate compound to the obtained pulverized mixture.
2 parts of N-methyl carbamate), 2.97 parts of fine powder of synthetic hydrated silicon oxide, 1 part of trade name Doreless B (manufactured by Sankyo) and 3.7 parts of clay as a coagulant, mix well in a mortar and mix with a juice mixer. Stir and mix. 90 parts of cut clay is added to the obtained mixture and mixed in a bag to obtain each powder.

Formulation Example 11 Powder 1 part of each of the present compounds (1) to (153) is dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder and P
0.3 parts of AP and 93.7 parts of Cle are added, and the mixture is stirred and mixed with a juice mixer.
Obtain a powder.

Formulation Example 12 Flowable agent Compounds of the present invention (1) to (34), (36) to (47), (49)
~ (56), (58) ~ (61), (63) ~ (84), (86) ~
(99), (101)-(105), (107)-(115), (117)-
(129), (131)-(142), (144)-(146), (148)-
10 parts of (152) is added to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol, and the mixture is stirred with a mixer to obtain a dispersant. To this, 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate are added, and 10 parts of propylene glycol are further added, followed by gentle stirring and mixing to obtain each 10% emulsion in water.

Formulation Example 13 Flowable agent Compounds of the present invention (35), (48), (57), (62), (130)
And 143 each with 20 parts of sorbitan trioleate
1.5 parts with an aqueous solution 2 containing 2 parts of polyvinyl alcohol
8.5 parts and finely pulverized with a sand grinder (particle size 3
μ or less), and an aqueous solution 4 containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesilicate is contained therein.
0 parts and then 10 parts of propylene glycol are further added and stirred and mixed to obtain a 20% suspension in water.

Formulation Example 14 Oil Preparation 0.1 part of each of the compounds (1) to (153) of the present invention was obtained by adding xylene 5
And 5 parts of trichloroethane, and this is mixed with 89.9 parts of deodorized kerosene to obtain a 0.1% oil solution.

Formulation Example 15 Oily aerosol 0.1 parts of each of the compounds (1) to (153) of the present invention, 0.2 part of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene are mixed and dissolved. Then, after filling in an aerosol container and attaching a valve portion, 30 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve portion to obtain an oily aerosol.

Formulation Example 16 aqueous aerosol 0.2 parts of each of the compounds (1) to (153) of the present invention, 0.2 parts of d-aresulin, 0.2 parts of d-phenothrin, 5 parts of xylene,
An aerosol container is charged with 3.4 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark of Atlas Chemical Co.)} mixed and dissolved, and 50 parts of pure is filled into an aerosol container, a valve part is attached, and injected through the valve part. An aqueous aerosol is obtained by pressure-filling 40 parts of an agent (liquefied petroleum gas).

Formulation Example 17 Heat Smoke Agent 100 mg of each of the present compounds (1) to (153) was dissolved in an appropriate amount of acetone, and impregnated on a 4.0 cm × 4.0 cm, 1.2 cm thick porous ceramic plate. Obtain a heat smoker.

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of a pesticidal agent. The compounds of the present invention are represented by the same compound numbers as described above, and the compounds used for comparison are represented by the compound numbers shown in Table 52.

[0231]

[Table 52]

Test Example 1 Metamorphosis Inhibiting Action on Brown Planthopper Larvae The test compound emulsion obtained in accordance with Formulation Example 1 was diluted to a predetermined concentration with water, and added to a polyethylene cup-planted rice seedling in an amount of 20 ml / 2 pots. Sprayed at a rate. After air-drying, 10 larvae of the brown planthopper, 3rd instar, were released per pot.
After a day, the eclosion inhibition rate was determined. Tables 53 and 54 show the results.
And Table 55.

[0233]

[Table 53]

[0234]

[Table 54]

[0235]

[Table 55]

The compounds (11), (16) and (2) of the present invention
2), (25), (26), (127), (136), and (145) inhibited eclosion 100% at a test concentration of 5 ppb.

Test Example 2 Inhibition of Proliferation Against Black Leafhopper The emulsion of the test compound obtained according to Formulation Example 1 was diluted to a predetermined concentration with water, and rice seedlings (length: about 20 cm) planted in pots (1 / 5000a) ) Was sprayed at a ratio of 40 ml / 2 pots. After air-drying, the pots were covered with a wire mesh gauge, and 10 males and 10 females were released per pot and left in a greenhouse. After about three weeks, the number of surviving nymphs of the next generation was examined, and the growth inhibition rate was determined. The results are shown in Table 56.

[0238]

[Table 56]

Test Example 3 Inhibition of Hatching on Blacktip Leafhopper Eggs Rice seedlings planted in polyethylene cups were covered with cages, and 5 males and 5 females were released to allow adult eggs to be laid for 3 days. After removing the adults, the emulsion of the test compound obtained according to Formulation Example 1 was diluted to a predetermined concentration with water, and sprayed onto rice seedlings on which eggs were laid at a ratio of 20 ml / 2 pots. 14
After the day, the number of hatched larvae was examined, and the hatching inhibition rate was determined. The results are shown in Table 57.

[0240]

[Table 57]

[0241]

EFFECTS OF THE INVENTION The compound of the present invention can be used as a pest of the order Hemiptera, Lepidoptera, Diptera, Coleoptera, Pests of the order, Psitoptera, Orthoptera, Hymenoptera, Hymenoptera, Insecta It has an excellent controlling effect against eye pests, lice pests, isoptera pests and the like, and can be used for various uses as a pest control agent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 313/32 C07C 313/32 323/12 323/12 323/20 323/20 323/43 323/43 323/49 323/49 323/62 323/62 333/04 333/04 333/12 333/12 381/06 381/06 (72) Inventor Koritoshi Umeda 4-2-1 Takashi Takarazuka City, Hyogo Prefecture Sumitomo Chemical Industries, Ltd. (72 ) Inventor Noriotada Matsuo 4-2-1 Takashi Takarazuka City, Hyogo Prefecture Inside Sumitomo Chemical Co., Ltd. (56) Reference JP-A-57-85354 (JP, A) European Patent Application Publication 331529 (EP, A2) J . Med. Chem. 12, Vol. 2 (1969), p. 207-211 (58) Field surveyed (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN) CAOLD (STN)

Claims (6)

(57) [Claims] 1. A compound represented by the general formula: Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, 3 represents a haloalkoxy group, a cyano group or a nitro group, 1 represents an integer of 1 to 5, R ² independently represents a hydrogen atom or a chlorine atom, m represents 1, R ³ represents a halogen atom R ⁴ represents a hydrogen atom or a carbon atom 1 to 3
R ⁵ represents a hydrogen atom, R ⁶ represents an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, and a carbon atom. 3-4 haloalkenyl groups, alkynyl groups of 3-6 carbon atoms, haloalkynyl groups of 3-5 carbon atoms, alkoxylalkyl groups of 3-6 carbon atoms, 3-6 carbon atoms Alkylthioalkyl group or carbon atom 3
Represents 6 to 6 cycloalkyl groups, X represents an oxygen atom, a sulfur atom, a group represented by the formula -NH-, a group represented by the formula -C (O)-or a methylene group, and Y and Z each represent Independently represents an oxygen atom or a sulfur atom. A carbamic acid derivative represented by the formula: 2. A compound represented by the general formula: Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, 3 represents a haloalkoxy group, a cyano group or a nitro group, 1 represents an integer of 1 to 5, R ² independently represents a hydrogen atom or a chlorine atom, m represents 1, R ³ represents a halogen atom R ⁴ represents a hydrogen atom or a carbon atom 1 to 3
X represents an oxygen atom, a sulfur atom,
Represents a group represented by NH—, a group represented by the formula —C (O) —, or a methylene group, and Y represents an oxygen atom or a sulfur atom. And an amine compound represented by the general formula: Wherein R ⁶ is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a haloalkenyl group having 3 to 4 carbon atoms, a carbon atom 3-6 alkynyl groups, haloalkynyl groups of 3-5 carbon atoms, alkoxylalkyl groups of 3-6 carbon atoms, alkylthioalkyl groups of 3-6 carbon atoms or 3-6 carbon atoms Z represents a cycloalkyl group
Represents an oxygen atom or a sulfur atom, and L ¹ represents a halogen atom. The method for producing a carbamic acid derivative according to claim 1, wherein the carbamic acid derivative is reacted with a carboxylic acid compound represented by the formula: 3. A compound represented by the general formula: Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, 3 represents a haloalkoxy group, a cyano group or a nitro group, 1 represents an integer of 1 to 5, R ² independently represents a hydrogen atom or a chlorine atom, m represents 1, R ³ represents a halogen atom R ⁴ represents a hydrogen atom or a carbon atom 1 to 3
X represents an oxygen atom, a sulfur atom,
It represents a group represented by NH-, a group represented by the formula -C (O)-or a methylene group, and Y represents an oxygen atom or a sulfur atom. An isocyanate compound represented by the general formula R
^6- ZH wherein R ⁶ is an alkyl group of 1 to 6 carbon atoms, a haloalkyl group of 1 to 6 carbon atoms,
6 alkenyl groups, 3-4 carbon atoms haloalkenyl group, 3-6 carbon atoms alkynyl group, 3 carbon atoms
5 represents a haloalkynyl group, an alkoxylalkyl group having 3 to 6 carbon atoms, an alkylthioalkyl group having 3 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and Z represents an oxygen atom or a sulfur atom. Represents an atom. The method for producing a carbamic acid derivative according to claim 1, wherein the carbamic acid derivative is reacted with a (thio) alcohol-based compound represented by 4. A compound represented by the general formula: Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, 3 represents a haloalkoxy group, a cyano group or a nitro group, 1 represents an integer of 1 to 5, R ² independently represents a hydrogen atom or a chlorine atom, m represents 1, R ³ represents a halogen atom X is an oxygen atom, a sulfur atom, a formula -NH-
, A group represented by the formula -C (O)-or a methylene group, Y represents an oxygen atom or a sulfur atom,
¹ represents an alkali metal atom or a hydrogen atom. And a (thio) phenol compound represented by the general formula: Wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms,
Haloalkyl group having 1 to 6 carbon atoms, alkenyl group having 3 to 6 carbon atoms, haloalkenyl group having 3 to 4 carbon atoms, alkynyl group having 3 to 6 carbon atoms, 3 to 5 carbon atoms
A haloalkynyl group, an alkoxyalkyl group having 3 to 6 carbon atoms, an alkylthioalkyl group having 3 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and Z represents an oxygen atom or a sulfur atom. L ² represents a halogen atom, a methanesulfonyloxy group or a toluenesulfonyloxy group. The method for producing a carbamic acid derivative according to claim 1, wherein the carbamic acid derivative is reacted with a carboxylic acid compound represented by the formula 5. A compound represented by the general formula: Wherein R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, 3 represents a haloalkoxy group, a cyano group or a nitro group, 1 represents an integer of 1 to 5, R ² independently represents a hydrogen atom or a chlorine atom, m represents 1, R ³ represents a halogen atom R ⁴ represents a hydrogen atom or a carbon atom 1 to 3
X represents an oxygen atom, a sulfur atom,
A group represented by NH-, a group represented by the formula -C (O)-or a methylene group, Y represents an oxygen atom or a sulfur atom, and M2 ⁺ represents an alkali metal ion or a quaternary ammonium ion. And a general formula R ⁶ -L ^{3 wherein} R ⁶ is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms. An alkenyl group, a haloalkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, a haloalkynyl group having 3 to 5 carbon atoms, an alkoxylalkyl group having 3 to 6 carbon atoms, and a total carbon atom L represents an alkylthioalkyl group having 3 to 6 atoms or a cycloalkyl group having 3 to 6 carbon atoms;
³ represents a halogen atom, a methanesulfonyloxy group or a toluenesulfonyloxy group. The method for producing a carbamic acid derivative according to claim 1, wherein Z represents a sulfur atom, among the carbamic acid derivatives according to claim 1. 6. A pesticidal composition comprising the carbamic acid derivative according to claim 1 as an active ingredient.