JPH09263572A - Dihalopropene compound, its use and production intermediate thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new dihalopropene compound excellent in insecticidal and acaricidal activity, useful as an insecticide and an acaricide for agriculture. SOLUTION: A dihalopropene compound is shown by formula I [R, R<2> , R<3> are each a halogen or a (halo)alkyl; R<4> is H or an alkyl; R<5> and R<6> are each H, an alkyl or CF3 ; R<7> is a halogen, an alkyl or CF3 ; R<8> and R<9> are each H, a (halo)alkyl, an alkenyl, etc.; Q<1> is a single bond, etc.; Q<2> is a single bond, O, etc.; X is Cl or Br; Y is O, NH, etc.; Z is O, S, etc.; (l) is 0-4; (p) is 0-6; (r) is 0-2] such as 3,5-dichloro-4-[4-[4-(1-piperidinylcarbonyl)phenoxy] butyloxy]-1-(3,3-dichloro-2-propenyloxy)benzene. The compound of formula I is obtained, for example, by reacting a compound of formula II (L is a halogen) with a compound of formula III. The compound of formula I is also obtained by using a new intermediate of formula IV.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a dihalopropene compound, its use and an intermediate for its production.

2. Description of the Related Art It has been described, for example, in JP-A-49-1526, that some propene compounds can be used as an active ingredient of insecticides.

However, these compounds are not always sufficient as active ingredients of insecticides in terms of insecticidal efficacy and the like.

[0002]

In view of the above situation, the present inventors have conducted extensive studies to find a compound having an excellent insecticidal effect, and as a result, the dihalopropene compound represented by the following general formula 1 is excellent. It has been found that the present invention has insecticidal and acaricidal activities, and has completed the present invention. That is,
The present invention has the general formula

Embedded image {In the formula, R, R ² and R ³ each independently represent a halogen atom, a haloalkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ and R
⁶ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group, and R ⁷
Represents a halogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group. R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or 3 to 6 carbon atoms.
An alkenyl group, a haloalkenyl group having 3 to 6 carbon atoms,
Alkynyl group having 3 to 4 carbon atoms, haloalkynyl group having 3 to 4 carbon atoms, cycloalkylalkyl group having 4 to 8 carbon atoms, cycloalkenylalkyl group having 6 to 8 carbon atoms or alkoxyalkyl group having 3 to 4 carbon atoms Represents, or represents a cycloalkynyl group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 2 carbon atoms, or R ⁸ and R ⁹ are bonded to each other at the terminal, It represents an alkylene group having 4 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 2 or an alkenylene group having 4 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 2 carbon atoms. Q ¹ represents a single bond, or
Represents T, where T is a general formula

Embedded image [In the formula, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group, and A represents an oxygen atom, an S (O) _n group, NR
¹² groups, C (= O) G groups or GC (= O) groups (where n
Represents an integer of 0 to 2, R ¹² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, G represents an oxygen atom or an NR ¹³ group, and R ¹³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Represents a group. ) And s represents an integer from 0 to 6. ] It represents the group shown by. Q ² represents a single bond, an oxygen atom or an NR ¹⁴ group (wherein R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). Each X independently represents a chlorine atom or a bromine atom. Y represents an oxygen atom, an NH group or a sulfur atom. Z represents an oxygen atom, a sulfur atom or NR ¹⁵ , and R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. l (el) represents an integer of 0 to 4, and p
Represents an integer of 0 to 6, and r represents an integer of 0 to 2. } The dihalopropene compound (henceforth the compound of this invention) shown by these, and the insecticide and acaricide which contain it as an active ingredient are provided.

The present invention further provides compounds of general formula 3 which are useful as intermediates in the preparation of some of the compounds of the invention.

Embedded image [In the formula, R and R ² are each independently a halogen atom, a haloalkyl group having 1 to 3 carbon atoms, or a C 1
Represents an alkyl group from 1 to 3. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ and R ⁶
Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group, and R
¹⁸ represents a carboxyl group or an amino group. A is
Oxygen atom, S (O) _n group, NR ¹² group, C (= O) G group or GC (= O) group (wherein n represents an integer of 0 to 2 and R ¹² represents a hydrogen atom or a carbon number of 1). To G3 represent an alkyl group, G represents an oxygen atom or an NR ¹³ group, and R ¹³
Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), X each independently represents a chlorine atom or a bromine atom, and p represents an integer of 0 to 6. ] A compound represented by the above; among them, a compound in which R ¹⁸ is a carboxyl group; a compound in which A is an oxygen atom; R and R ² are each independently a halogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ , R ⁵ and R ⁶
Each is a hydrogen atom, and p is 2 or 3.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound of the present invention and / or the compound of the general formula 3 (general formula [III]), R,
The halogen atom represented by R ² , R ³ and R ⁷ is
Fluorine atom, chlorine atom, bromine atom or iodine atom, and the alkyl group having 1 to 6 carbon atoms represented by R ⁸ and R ⁹ includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 2-ethylbutyl group, 1-methylpentyl group Group, 1-ethylbutyl group, 3
-Methylpentyl group, 1,3-dimethylbutyl group and the like, and the alkylene group having 2 to 6 carbon atoms and bonded to each other represented by R ⁸ and R ⁹ means an ethylene group, a trimethylene group, a tetramethylene group, A pentamethylene group or a hexamethylene group, and the alkenylene group having 4 to 6 carbon atoms, which is represented by R ⁸ and R ⁹ and is bonded to each other at the terminals, is, for example, a 2-butenylene group or a 2-pentenylene group, and R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
The alkyl group having 1 to 3 carbon atoms represented by R ⁷ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is a methyl group, an ethyl group, an n-propyl group or an isopropyl group,
The alkyl group having 1 or 2 carbon atoms in R ⁸ and R ⁹ is a methyl group or an ethyl group, and R, R ² , R ³ ,
The haloalkyl group having 1 to 3 carbon atoms represented by R ⁸ and R ⁹ includes, for example, trifluoromethyl group, difluoromethyl group, bromodifluoromethyl group, 2,2,2-trifluoroethyl group, 2-fluoro Ethyl group, 2-chloroethyl group, 2-bromoethyl group, 1-fluoroethyl group, 1-chloroethyl group, 1-bromoethyl group, 2,2,3,
3,3-pentafluoropropyl group, 3,3,3-trifluoropropyl group, 1-fluoropropyl group, 2-chloropropyl group, 3-bromopropyl group,

The alkenyl group having 3 to 6 carbon atoms represented by R ⁸ and R ⁹ includes, for example, allyl group, homoallyl group, isopropenyl group, 2-butenyl group, 1-methyl-2-propenyl group and prenyl group. , 3-methyl-3-butenyl group, 1-ethyl-2-propenyl group, 2-ethyl-2-propenyl group, 2-pentenyl group, 2-methyl-
2-butenyl group, 1-methyl-2-butenyl group, 2-methyl-3-butenyl group, 4-pentenyl group, 1-methyl-3-butenyl group, 1-ethyl-2-propenyl group, 1
-Propyl-2-propenyl group, 3-hexenyl group, 2
-Isopropyl-2-propenyl group, 2-ethyl-2-
Butenyl group, 2-methyl-2-pentenyl group, 1-ethyl-2-butenyl group, 1-methyl-4-pentenyl group,
1,3-dimethyl-2-butenyl group, 2-hexenyl group,
4-hexenyl group, 5-hexenyl group, 1-n-propyl-2-propenyl group and the like, and the haloalkenyl group having 3 to 6 carbon atoms represented by R ⁸ and R ⁹ is, for example, 3-chloro- 2-propenyl group, 3-bromo-2-
Propenyl group, 2-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3,3-dichloro-2-propenyl group, 3,3-dibromo-2-propenyl group, 3,3-difluoro-2 -Propenyl group, 2-chloromethyl-2-
Propenyl group, 4-chloro-2-butenyl group, 4-chloro-2-butenyl group, 3-chloro-4,4,4-trifluoro-2-butenyl group, 4-bromo-3-fluoro-4,4
-Difluoro-2-butenyl group, 3,4,4,4-tetrafluoro-2-butenyl group, 4,4-dichloro-3-butenyl group, 4,4-dibromo-3-butenyl group, 3-chloro- Two
-Butenyl group, 6,6-dichloro-5-hexenyl group and the like, and the alkynyl group having 3 to 4 carbon atoms represented by R ⁸ and R ⁹ includes, for example, 2-propynyl group and 1-methyl-2- A propynyl group, a 2-butynyl group, a 3-butynyl group, etc.,

The haloalkynyl group having 3 to 4 carbon atoms represented by R ⁸ and R ⁹ is, for example, 3-chloro-2.
-Propynyl group, 3-bromo-2-propynyl group, 4-
Chloro-2-butynyl group, 3-chloro-1-methyl-2
-Propynyl group, 3-bromo-1-methyl-2-propynyl group, 4-chloro-3-butynyl group, 4-bromo-3
A butynyl group and the like, and the alkoxyalkyl group having 3 to 4 carbon atoms represented by R ⁸ and R ⁹ is, for example,
Ethoxymethyl group, n-propyloxymethyl group, isopropyloxymethyl group, 2-methoxyethyl group, 1-
Methoxyethyl group, 2-ethoxyethyl group, 1-ethoxyethyl group, 3-methoxypropyl group, 2-methoxypropyl group, 1-methoxypropyl group, 2-methoxy-1
And a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 2 carbon atoms and is a methylethyl group or the like and is represented by R ⁸ and R ⁹ includes, for example, cyclopropyl group and cyclobutyl group. Group, a cyclopentyl group, a cyclohexyl group, a 2-methylcycloxyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group and the like, and a cycloalkylalkyl group having 4 to 8 carbon atoms represented by R ⁸ and R ^9. Is a cyclopropylmethyl group, a cyclobutylmethyl group, a 2-cyclopropylethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a 2-cyclohexylethyl group, or the like, and has 6 to 8 carbon atoms represented by R ⁸ and R ^9. The cycloalkenylalkyl group of is a (1-cyclopentenyl) methyl group,
Examples include a (1-cyclohexenyl) methyl group and a 2- (1-cyclohexenyl) ethyl group.

In a preferred embodiment of the compound of the present invention, R and R ² are each independently a halogen atom or an alkyl group having 1 to 3 carbon atoms, and r = 0.
A compound wherein R and R ² are each independently a chlorine atom, a bromine atom or an alkyl group having 1 to 3 carbon atoms, and r = 0; R and R ² are both chlorine atoms And a compound in which r = 0; a compound in which Y and Z are both oxygen atoms; a compound in which Q ¹ is a single bond;
A compound in which s = 0 in a compound in which Q ¹ is T; Q
^A compound in which ² is a single bond; a compound in which Q ² is an oxygen atom; a compound in which Q ² is NR ¹⁴ ; a compound in which s = 0 in a compound in which Q ¹ is T and Q ² is a single bond A compound in which A is an oxygen atom; A is an oxygen atom, 1 (el) = 0, and p = 2 to 4;
A compound in which R ⁴ , R ⁵ and R ⁶ are both hydrogen atoms; R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 3 carbon atoms. 6
Is an alkenyl group or an alkynyl group having 3 to 4 carbon atoms, or a compound in which R ⁸ and R ⁹ are bonded to each other at the terminal and are an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a butenylene group. can give.

Among the compounds of the present invention, examples of particularly preferred compounds include (3) 3,5-dichloro-4- (4- (4- (1-piperidinylcarbonyl) phenoxy) butyloxy) -1
-(3,3-Dichloro-2-propenyloxy) benzene (8) 3,5-dichloro-4- (3- (4- (N, N-
Dipropylcarbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (11) 3,5-dichloro-4- (3- (4- (N, N-
And di (2-propenyl) carbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene. (The number indicates the compound number of the compound of the invention described below.)

The compound of the present invention can be produced, for example, by the following methods (Production Method A) to (Production Method J). (Production method A) General formula 4

Embedded image [In the formula, R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R
⁸ , R ⁹ , Q ¹ , Q ² , 1, p, r, Y and Z have the same meanings as described above. And a compound represented by the general formula

Embedded image L-CH ₂ CH = CX ₂ [wherein, X represents the same as defined above, L represents a halogen atom (e.g., chlorine atom, bromine atom, an iodine atom), a mesyloxy group or a tosyloxy group . And a halide compound represented by the following formula: The above reaction is preferably performed in the presence of a suitable base in an inert solvent. As the solvent used, acetone, methyl ethyl ketone, ketones such as cyclohexanone, 1,2-dimethoxyethane, tetrahydrofuran,
Ethers such as dioxane, dialkyl (for example, C ₁ -C ₄ ) ether (for example, diethyl ether, diisopropyl ether, etc.), N, N-dimethylformamide,
Halogenated hydrocarbons such as dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane, acetonitrile, nitromethane, dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene; hydrocarbons such as toluene, benzene and xylene; and water. Can be. If necessary, a mixed solvent of these solvents can be used. Examples of the base used include hydroxides of alkali metals or alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, and alkalis such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate. Metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride, calcium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc. Alkali metal alkoxides (for example, C ₁ -C
₄ ), organic bases such as triethylamine and pyridine. If necessary, a catalyst such as an ammonium salt (for example, triethylbenzylammonium chloride) may be added to the reaction system at a ratio of 0.01 to 1 mol based on 1 mol of the compound represented by the general formula (4). The reaction temperature can usually range from -20 ° C to the boiling point of the solvent used in the reaction or 150 ° C, but more preferably from -5 ° C to the boiling point of the solvent used in the reaction or 100 ° C. The molar ratio of the starting material and the base 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. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

(Production Method B) (Y =
In the case of O) The compound represented by the above general formula and the general formula

HO-CH ₂ CH ＝ CX ₂ wherein X represents the same meaning as described above. And the alcohol compound represented by the formula: The above reaction is preferably carried out in the presence of a suitable dehydrating agent, if necessary, in an inert solvent. As the dehydrating agent used, for example, dicyclohexylcarbodiimide,
Dialkyl (eg, C ₁ -C ₄ ) azodicarboxylate (diethyl azodicarboxylate, diisopropyl azodicarboxylate, etc.)-Trialkyl (ex.
C ₁ -C ₂₀ ) phosphine or triarylphosphine (triphenylphosphine, trioctylphosphine,
Tributylphosphine) and the like.
Examples of the solvent used include hydrocarbons such as benzene, xylene, and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chlorobenzene, and dichlorobenzene. Can be given. The reaction temperature can range from -20 ° C to 200 ° C or the boiling point of the solvent used in the reaction. The molar ratio of the raw material and the dehydrating 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. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

(Production Method C) (Y =
When O) General formula 7

Embedded image [In the formula, R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R
⁸ , R ⁹ , Q ¹ , Q ² , 1, p, r, Y and Z have the same meanings as described above. ] The manufacturing method by making the aldehyde compound shown by these react with carbon tetrachloride or carbon tetrabromide. The above reaction is preferably carried out in an inert solvent in the presence of a suitable trialkylphosphine or triarylphosphine, if necessary, in the presence of zinc metal. Examples of the solvent used include hydrocarbons such as benzene, xylene and toluene, diethyl ether,
Examples thereof include ethers such as diisopropyl ether, tetrahydrofuran and dioxane, and halogenated hydrocarbons (excluding carbon tetrabromide and carbon tetrachloride) such as dichloromethane, 1,2-dichloroethane and chlorobenzene. The reaction temperature can range from -30 ° C to the boiling point of the solvent used in the reaction or 150 ° C. The trialkyl (ex. C ₁ -C ₂₀ ) phosphine or triaryl phosphine to be subjected to the reaction includes, for example, triphenyl phosphine and trioctyl phosphine, and the metal zinc used as required is preferably in a dust form. . The molar ratio of the raw material and the reagent to be used in the reaction can be set arbitrarily, but the ratio of carbon tetrabromide (tetrachloride) to 2 moles relative to 1 mole of the aldehyde compound of the general formula 7, trialkylphosphine or triarylphosphine. Is preferably 2 or 4 mol (2 mol when zinc is used) and zinc is preferably 2 mol, or it is advantageous to carry out the reaction at a ratio close to that. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. if needed,
Further purification can be carried out by usual operations such as chromatography, distillation and recrystallization.

(Production Example D) (In the compound of the present invention, Y
= Z = O, and Q ¹ = T (where s = 0, A =
Oxygen atom)) General formula

Embedded image [In the formula, R, R ² , R ³ , r and X have the same meanings as described above. ] The compound represented by

Embedded image [In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , Q ² ,
l, p and L have the same meanings as described above. ] The method of manufacturing by making the compound shown by these react. The above reaction is preferably performed in the presence of a suitable base in an inert solvent. As the solvent used, acetone, methyl ethyl ketone, ketones such as cyclohexanone, 1,2-
Dimethoxyethane, tetrahydrofuran, dioxane,
Ethers such as dialkyl (for example, C ₁ -C ₄ ) ether (for example, diethyl ether, diisopropyl ether, etc.), N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, acetonitrile, nitromethane, dichloromethane,
Examples thereof include halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene, hydrocarbons such as toluene, benzene and xylene, and water.
If necessary, a mixed solvent of these solvents can be used. As the base used, lithium hydroxide,
Alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal or alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate, hydrogen Alkali metal or alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide (for example, C ₁ -C ₄ ), organic bases such as triethylamine and pyridine.
If necessary, an ammonium salt (for example,
A catalyst such as triethylbenzylammonium chloride) is used in an amount of 0.01 mol per mol of the compound represented by the general formula.
It may be added in a proportion of up to 1 mol. The reaction temperature is usually −
The boiling point of the solvent used in the reaction may be in the range of 20 ° C. or 150 ° C., but the temperature of −5 ° C. to the boiling point of the solvent used in the reaction or 100 ° C. is more desirable.
The molar ratio of the starting material and the base 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. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

(Production Example E) (In the compound of the present invention, Y
= Z = O, and Q ¹ = T (where: s = 0, A =
In the case of an oxygen atom) The compound represented by the general formula 8 and the general formula 10

Embedded image [In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , Q ² ,
l and p have the same meanings as described above. And the alcohol compound represented by the formula: The above reaction is preferably carried out in the presence of a suitable dehydrating agent, if necessary, in an inert solvent. As the dehydrating agent used, for example, dicyclohexylcarbodiimide,
Dialkyl (eg, C ₁ -C ₄ ) azodicarboxylate (diethyl azodicarboxylate, diisopropyl azodicarboxylate, etc.)-Trialkyl (ex.
C ₁ -C ₂₀ ) phosphine or triarylphosphine (triphenylphosphine, trioctylphosphine,
Tributylphosphine) and the like.
Examples of the solvent used include hydrocarbons such as benzene, xylene, and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chlorobenzene, and dichlorobenzene. Can be given. The reaction temperature can range from -20 ° C to 200 ° C or the boiling point of the solvent used in the reaction. The molar ratio of the raw material and the dehydrating 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. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

(Production method F) {in the compound of the present invention, Q
¹ = T (where s = 0 and A = oxygen atom)} General formula

Embedded image [In the formula, R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , p, r,
X, Y, Z and L have the same meanings as described above. ] And a compound represented by the general formula [IV] [In the formula, R ⁷ , R ⁸ , R ⁹ , Q ² and l have the same meanings as described above. And a compound represented by the formula: The above reaction is preferably performed in the presence of a suitable base in an inert solvent. Examples of the solvent used include ketones such as acetone, methyl ethyl ketone and cyclohexanone, 1,2-dimethoxyethane, tetrahydrofuran, dioxane and dialkyl (for example, C _1-
C ₄ ) Ethers such as ether (eg, diethyl ether, diisopropyl ether, etc.), N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane, acetonitrile, nitromethane, dichloromethane, chloroform, 1,2-dichloroethane , Halogenated hydrocarbons such as chlorobenzene,
Hydrocarbons such as toluene, benzene and xylene, or water can be used. If necessary, a mixed solvent of these solvents can be used. Examples of the base used include alkali metal or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, and alkali metals such as lithium carbonate, potassium carbonate, sodium carbonate and calcium carbonate. Metal or alkaline earth metal carbonate, lithium hydride,
Alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride, calcium hydride, sodium methoxide, sodium ethoxide, potassium
Examples thereof include alkali metal alkoxides such as tert-butoxide (for example, C ₁ -C ₄ ), organic bases such as triethylamine and pyridine. If necessary, a catalyst such as an ammonium salt (eg, triethylbenzylammonium chloride) may be added to the reaction system in a proportion of 0.01 to 1 mol with respect to 1 mol of the compound represented by the general formula [IV]. The reaction temperature may usually range from -20 ° C to the boiling point of the solvent used in the reaction or 150 ° C, but may range from -5 ° C to the boiling point of the solvent used in the reaction or 100 ° C.
Temperatures up to ° C are more desirable. The molar ratio of the starting material and the base 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. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

(Production method G) {in the compound of the present invention, Q
^{When 1} is T (however, s = 0, A is an oxygen atom)} General formula [V] [In the formula, R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , p, r,
X, Y and Z have the same meanings as described above. ] The method which manufactures by making the compound shown by these and the compound shown by the said general formula [IV] react. The above reaction is preferably carried out in the presence of a suitable dehydrating agent, if necessary, in an inert solvent. As the dehydrating agent used, for example,
Dicyclohexylcarbodiimide, dialkyl (eg C ₁ -C ₄ ) azodicarboxylate (diethylazodicarboxylate, diisopropylazodicarboxylate, etc.)-Trialkyl (ex. C ₁ -C ₂₀ ) phosphine or triarylphosphine (tri Phenylphosphine, trioctylphosphine, tributylphosphine, etc.) and the like. Examples of the solvent used include hydrocarbons such as benzene, xylene, and toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chlorobenzene, and dichlorobenzene. Can be given. The reaction temperature can range from -20 ° C to 200 ° C or the boiling point of the solvent used in the reaction. The molar ratio of the raw material and the dehydrating 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. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

(Production Example H) (in the compound of the present invention, Q
^{When 2} is a single bond) General formula [VI] [In the formula, R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and Q
¹ , 1, p, r, X, Y and Z have the same meanings as described above, V is a chlorine atom, a bromine atom, a hydroxyl group, a methoxy group,
It represents an ethoxy group, a propyloxy group or a 1-imidazolyl group. ] And a carboxylic acid compound represented by the general formula [VII] R ⁸ R ⁹ NH [VII] [wherein, R ⁸ and R ⁹ have the same meanings as described above. ]
A method for producing a compound by reacting with an amine compound represented by: (I) In the general formula [VI], when V represents a chlorine atom, a bromine atom or a 1-imidazolyl group, the reaction solvent may be ethers such as diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene and chloro. Aromatic hydrocarbons such as benzene and pyridine,
Hydrocarbons such as n-hexane, n-heptane, cyclohexane, methylene chloride, chloroform, carbon tetrachloride,
Halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate and methyl acetate, nitriles such as water and acetonitrile, N, N-dimethylformamide,
A polar solvent such as N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, or a mixed solvent thereof can be used. The reaction temperature is -20
The temperature may range from 0 ° C to the boiling point of the solvent used in the reaction or 150 ° C, but a temperature from 0 to 50 ° C is more desirable. Usually, the reaction is carried out in the presence of a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine or the like in a ratio of 1 to 10 mol with respect to 1 mol of the compound represented by [VI]. When performing a two-layer system reaction using water as a solvent, the reaction rate can be usually increased by using a phase transfer catalyst such as tetra-n-butylammonium bromide or benzyltriethylammonium chloride. (Ii) In the general formula [VI], when V represents a hydroxyl group, a methoxy group, an ethoxy group or a propyloxy group, it is usually solvent-free or N, N-dimethylformamide, N, N-dimethylacetamide, N- Polar solvents such as methylpyrrolidone and dimethyl sulfoxide, benzene,
The reaction is carried out in an aromatic hydrocarbon solvent such as toluene, xylene or chlorobenzene at a reaction temperature of 50 to 250 ° C.
If necessary, as a reaction catalyst, for example, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, an acidic substance such as activated silica gel, a basic substance such as pyridine, triethylamine, sodium methoxide, sodium ethoxide, activated alumina, etc. Compound 1 represented by the general formula [VI]
0.0001 to 1 weight can be used with respect to weight. The molar ratio of the raw materials to be subjected to the reaction can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar ratio or a ratio close thereto. (Iii) In the general formula [VI], when V represents a hydroxyl group, it can be produced by the following method. That is, usually in the presence or absence of an inert organic solvent,
Reacting with an amine compound represented by the general formula [VII],
The compound of the present invention is obtained by dehydration condensation. Examples of the dehydrating agent include dicyclohexylcarbodiimide, 1
Examples thereof include carbodiimides such as -ethyl-3- (3-dimethylaminopropyl) carbodiimide and inorganic dehydrating agents such as silicon tetrachloride. Examples of the inert organic solvent include hydrocarbons such as n-pentane, n-hexane, n-heptane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, pyridine and o-dichlorobenzene. , Halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, esters such as ethyl acetate and methyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N- Examples thereof include amides such as methylpyrrolidone, nitriles such as acetonitrile, ethers such as diethyl ether, tetrahydrofuran, dioxane and the like. Reaction temperatures can range from -20 ° C to the boiling point of the solvent used or 150 ° C. Usually, the molar ratio of the starting material and the dehydrating 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. The reaction solution after the completion of the reaction of each of (i), (ii) and (iii) can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

(Production Method I) (in the compound of the present invention, Q
² = NR ¹⁴ ) (First Step of Manufacturing Method I) General Formula [VIII] [In the formula, R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and Q
¹ , 1, p, r, X, Y and Z have the same meanings as described above. ] And an isocyanate compound represented by the general formula [VI
I]] by reacting with an amine compound represented by the general formula [IX] [In the formula, R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R
⁸ , R ⁹ , Q ¹ , l, p, r, X, Y and Z have the same meanings as described above. ] The urea derivative compound (invention compound) shown by these can be manufactured. As the solvent,
Hydrocarbons such as benzene and toluene, ethers such as diethyl ether, tetrahydrofuran and dioxane,
It is possible to use polar solvents such as N, N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoric triamide, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, and acetonitrile or nitromethane. it can. If necessary, a mixed solvent of these can also be used. The reaction temperature can usually range from -20 ° C to the boiling point of the solvent used in the reaction, but is -5 ° C.
The range 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 desirable to carry out the reaction at an equimolar ratio or a ratio close thereto. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention (R ¹⁴ = H). If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

(Second Step of Production Method I) The urea derivative compound (R ¹⁴ = H) of the general formula [IX] and the general formula [X] R ¹⁴ -L ¹ [X] [wherein, R ¹⁴ is as described above] It has the same meaning (however, it does not represent a hydrogen atom), and L ¹ represents a halogen atom (chlorine atom, bromine atom, iodine atom, etc.). ] The compound of the present invention (R ¹⁴ ≠ H) can be produced by reacting with a halogen compound represented by The reaction is preferably carried out in the presence of a suitable catalyst, in a solvent that does not interfere with the reaction. Examples of the solvent include ketones such as acetone and methyl ethyl ketone, hydrocarbons such as benzene and toluene, ethers such as diethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene. Acetone, acetonitrile, nitromethane or pyridine can be used. If necessary, a mixed solvent of these can also be used. As the base, for example, alkali carbonate such as potassium carbonate, hydride of alkali metal such as sodium hydride, or organic base such as sodium methoxide, sodium ethoxide, triethylamine, pyridine and the like can be used. The reaction temperature is usually in the range of -10 ° C to the boiling point of the solvent. Although the molar ratio of the raw materials can be set arbitrarily, the molar ratio of the general formula [I
X] with respect to 1 mol of the urea derivative compound,
The compound represented by [X] and the base are each 1 to 2
And preferably from 0.9 to 20 mol. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by the usual operations of chromatography, distillation and recrystallization.

(Production Method J) (in the compound of the present invention, Q
² = O) General formula [XI] [In the formula, R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and Q
¹ , 1, p, r, X, Y and Z have the same meanings as described above, and L ² represents a chlorine atom or a bromine atom. ] The method of manufacturing by reacting the compound shown by this, and the amine compound shown by general formula [VII]. The reaction is
It is preferably carried out in the presence of a suitable catalyst in a solvent that does not influence the reaction. As the base, for example, an alkali carbonate such as potassium carbonate, an organic base such as triethylamine, pyridine and the like can be used. If necessary, a catalyst such as an ammonium salt (eg, benzyltriethylammonium 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 and toluene, ethers such as diethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene. Acetone, acetonitrile, nitromethane or the like can be used. If necessary, a mixed solvent of these and a mixed solvent with water can also be used. The reaction temperature can usually range from -20 ° C to the boiling point of the solvent used in the reaction,
The range from -5 ° C 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 desirable to carry out the reaction at an equimolar ratio or a ratio close thereto. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by usual operations such as chromatography, distillation, recrystallization and the like.

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 ((+)-form, (-)-) having biological activity.
) And mixtures thereof in all ratios, and in the case of the compounds of the present invention having geometrical isomerism, the compounds of the present invention include the respective geometrical isomers (cis) having biological activity. Body, trans form) and mixtures thereof in all proportions.

Next, specific examples of the compound of the present invention are shown in Chemical formulas 12 to 45, but the compound of the present invention is not limited thereto. In Chemical formula 12 to Chemical formula 45, R ¹ -is represented by the formula [XII]. And R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ ,
Q ¹ , Q ² , p and l (el) represent those shown in Table 1, Table 2 and Table 3, or those shown in Table 4, Table 5 and Table 6, and n-C ₃ H ₇ and n-Pr represents a n- propyl group, iso-C ₃ H ₇ or iso-Pr
Represents an isopropyl group.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

Embedded image (Continuation of chemical formula 20) (Continuation of chemical formula 20) (Continuation of chemical formula 20) (Continuation of chemical formula 20) (Continuation of chemical formula 20) (Continuation of chemical formula 20)

[Chemical 21]

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Embedded image (Continuation of Chemical 45) (Continuation of Chemical 45) (Continuation of Chemical 45)

[0039]

[Table 1]

[0040]

[Table 2] [In Table 2, R ⁸ and R ⁹ represent those shown in Table 3. ]

[0041]

[Table 3]

[0042]

[0043]

[0044]

[Table 4]

[0045]

[Table 5] (Continued from Table 5)

(Continued from Table 5) (Continued from Table 5) (Continued from Table 5) [In Table 5, R ⁸ and R ⁹ represent those shown in Table 6. ]

[0047]

[Table 6]

The aldehyde compound represented by the general formula (7), which is an intermediate for producing the compound of the present invention, can be produced, for example, according to the scheme (46).

Embedded image [Wherein the symbols have the same meanings as described above. ]

The compound represented by the general formula (4), which is an intermediate for producing the compound of the present invention, can be prepared by, for example, the scheme:
It can be manufactured according to 7 to 51.

Embedded image [In the formula, R, R ¹ , R ² , R ³ , r and L have the same meanings as described above. ]

[0050]

Embedded image [In the formula, R, R ¹ , R ² , R ³ , r and L have the same meanings as described above. ]

(Continuation of Chemical Formula 48) [Wherein, Bz represents a benzyl group, Bnzo represents a benzoyl group, and other symbols have the same meanings as described above. ]

Embedded image [In the formula, R, R ¹ , R ² , R ³ , r and L have the same meanings as described above. ]

[0052]

Embedded image [In the formula, R, R ¹ , R ² , R ³ , r and L have the same meanings as described above. ]

[0053]

Embedded image [In the formula, R, R ¹ , R ² , R ³ , r, L and Z have the same meanings as described above. ] (Continuation of Chemical 51) [In the formula, R, R ¹ , R ² , R ³ , r and L have the same meanings as described above. ]

The compound represented by the general formula (8), which is an intermediate for the production of the compound of the present invention, can be prepared by, for example, the scheme:
2 can be manufactured.

Embedded image [In the formula, R ³ , r, X and L have the same meanings as described above. ]

Among the compounds represented by the general formula 11 and [V], which are intermediates for producing the compounds of the present invention, Y = Z =
The compound of O is, for example, a compound of Scheme 53 or
It can be manufactured according to

Embedded image [In the formula, R ¹⁶ represents an alcohol protecting group (for example, a benzoyl group), R ¹⁷ represents an equivalent of a formyl group (for example, an acetal of a formyl group), Ms represents a mesyl group, Ts represents a tosyl group, and other symbols have the same meanings as described above. ]

[0056]

Embedded image [In the formula, symbols have the same meanings as described above. ]

The halide compound represented by the general formula (5) and the alcohol compound represented by the general formula (6), which are intermediates for producing the compound of the present invention, are commercially available or are produced according to the scheme (55). be able to.

Embedded image [In the formula, L ⁴ represents a mesyloxy group or a tosyloxy group, and L ² and X represent the same meaning as described above. ]

The compound of the general formula [IV], which is an intermediate for the production of the compound of the present invention, can be prepared by, for example, the scheme:
It can be manufactured according to

Embedded image [In the formula, L ⁵ represents a methyl, ethyl or propyl group, and R ¹⁶ represents the same meaning as described above. ]

The compounds represented by the general formulas 9 and 10 which are intermediates for producing the compound of the present invention can be produced, for example, according to the scheme 57.

Embedded image [Wherein the symbols have the same meanings as described above. ] (Continuation of Chemical 57) [Wherein the symbols have the same meanings as described above. ]

The compounds represented by the general formulas [VI], [VIII] and [XI], which are intermediates for producing the compound of the present invention, can be produced, for example, according to Scheme 58.

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The compound represented by the general formula [XIII] used in the scheme 58 is, for example,
It can be produced according to Chemical Formulas 59 to 61.

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The formulas [XIV], [XV], [XVI] and [XVI] used in the schemes 59 to 61 are shown.
The compound represented by the formula [I] can be represented by, for example, the scheme:
It can be manufactured according to

Embedded image * 1): For example, RL Kramer et al, J. Am. Chem. Soc., 4
3, 880 (1921) etc. * 2): For example, LMEllis et al, J. Am. Chem. Soc., 54,
1674 (1932) and the like, wherein the symbols have the same meanings as described above. ]

Examples of harmful insects and harmful mites showing the controlling effect of the compound of the present invention include the following. Hemiptera Pests, Little brown planthopper ( Laodelphax striatellus) , Little brown planthopper ( Nilparvata lugens ), White- tailed planthopper ( Sogatell )
a furcifera) and grasshoppers ( Ne)
photettix cincticeps )
Leafhoppers such as ( Nephotettix virescens) , aphids, stink bugs, whiteflies, scale insects,
Coleoptera , Pyllidae and other insect pests of the order Lepidoptera, Chilo suppressalis , Cobnomeika ( Cn
aphalocrocis medinalis) , European corn bolla
( Ostrinia nubilalis) , Shibatatsuga ( Parapediasia
teterrella ), cotton bollworm (Notarch derogata ), long-spotted moth ( Plodia interpunctella ), and other leaf moths , Spodoptera litura , Spodoptera exigua , Spodoptera
litoralis, armyworm (Pseudaletia separata), cabbage armyworm (Mamestra brassicae), black cutworm (Agrotis
ipsilon) , Trichoplusia spp., Heliothis spp., Helicovapa ( He )
licoverpa spp.), Eariasu genus (Earias spp) Noctuidae such as, cabbage butterfly (Pieris rapae crucivora)
Butterflies such as Adoxophyes
spp.) Tortricidae such as, oriental fruit moth (Grapholih
tha molesta) , codling moss (Cydia pomonella) , moss squid (Carposina niponensis ) and other leaf moths such as Lyonetia spp., Lithocolletis ringoniella
, Etc., Lymantria spp.,
Douga, such as Euprotis spp.
Diamondback moths such as diamondback moth ( Plutella xylostella ), leaf worms such as cotton boll beetle ( Pectinophora gossypiella) , hytrigers such as Hyphantria cunea, moth (Tinea translucens) , moth (Tineola )
Bisslliella) and other dipteran pests such as Culex pipiens, Culex pipiens, etc. Drosophila melanogaster, fly, fly, onion fly, etc., fruit fly, fruit fly, butterfly fly, flies, gnats, sand flies, etc. Such as scarab beetles, weevil, weevil, weevils such as adzuki bean weevils, chafer beetles such as white rice weevil, beetle beetles such as Kokonusutomodoki, beetle beetles such as dwarf beetle, sea urchin beetle, beetles Epilacunas such as bedbugs and pearl oysters
( Epilach-na spp.), Flat beetle, long-tailed beetle, beetle beetle, blue-footed stag beetle, etc. Hymenoptera pests Ants, wasps, wasps, wasps and other wasps, etc. Orthoptera pests Kerala, grasshoppers, etc.Heptoptera pests Human flea, etc. Plant parasitic mites such as Nami mites, mandarin mites, spider mites, apple mites, animal parasitic mites such as Drosophila mites, house dust mites, etc. Furthermore, existing insecticides and pests that have developed resistance to acaricides It is also effective.

When the compound of the present invention is used as an active ingredient of insecticides and acaricides, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, liquid carrier, gaseous carrier, Oil, emulsion, wettable powder, flowable agent, granule, powder, aerosol, fog agent (fogging etc.), poison bait It is used after being formulated. In these preparations, the compound of the present invention as an active ingredient is usually added in a weight ratio.
It contains 0.01% to 95%. 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.), chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate,
Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (urea, ammonium chloride, etc.) and the like. 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, carbon tetrachloride, etc.), dimethylsulfoxide, vegetable oils such as soybean oil, cottonseed oil and the like. For example, Freon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, and the like can be given. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give. 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 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 a base material for poison baits, for example, grain flour, vegetable oil, sugar, bait components such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene, nordihydroguaiaretic acid, preservatives such as dehydroacetic acid,
Examples include a misfeed prevention agent such as pepper powder, an attractive flavor such as a cheese flavor, and an onion flavor. The preparation thus obtained is used as it is or diluted with water or the like. Also, other insecticides, nematicides, acaricides, fungicides,
Herbicide, plant growth regulator, synergist, fertilizer, soil conditioner,
It can be used simultaneously with or without mixing with animal feed.

Examples of the insecticide, nematicide and acaricide used include fenitrothion [O, O-dimethyl].
O- (3-methyl-4-nitrophenyl) phosphorothioate], fenthion [O, O-dimethyl O- (3
-Methyl-4- (methylthio) phenyl) phosphorothioate], diazinone [O, O-diethyl-O-2-
Isopropyl-6-methylpyrimidin-4-yl phosphorothioate], chloropyrifos [O, O-diethyl-
O-3,5,6-trichloro-2-pyridyl phosphorothioate], acephate [O, S-dimethylacetyl phosphoramidothioate], methidathion [S-2,3
-Dihydro-5-methoxy-2-oxo-1,3,4-
Thiadiazol-3-ylmethyl O, O-dimethyl phosphorodithioate], disulfoton [O, O-diethyl S-2-ethylthioethyl phosphorothioate],
DDVP [2,2-dichlorovinyl dimethyl phosphate], sulphophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate],
Cyanophos [O-4-cyanophenyl O, O-dimethyl phosphorothioate], dioxabenzophos [2-methoxy-4H-1,3,2-benzodioxaphosphinin-2-sulfide], dimethoate [O, O -Dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfone [dimethyl 2,
2,2-trichloro-1-hydroxyethylphosphonate], azinphosmethyl [S-3,4-dihydro-4-
Oxo-1,2,3-benzotriazin-3-ylmethyl O, O-dimethylphosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], ethion [O ,
O, O ', O'-tetraethyl S, S'-methylenebis (phosphorodithioate)], profenophos [O-
Organic compounds such as 4-bromo-2-chlorophenyl O-ethyl S-propyl phosphorothioate].
BPMC (2-sec-butylphenylmethylcarbamate), 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-methyl Carbamate], carbaryl [1-naphthyl-N-methylcarbamate], mesomil [S-methyl-N-
[(Methylcarbamoyl) oxy] thioacetimidate], Ethiophencarb [2- (ethylthiomethyl)]
Phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-
Methylcarbamoyloxy], oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2-]
(Methylthio) acetamide], phenothiocarb [S-
4-phenoxybutyl) -N, N-dimethylthiocarbamate], thiodicarb [3,7,9,13-tetramethyl-5,11-dioxa-2,8,14-trithia-
4,7,9,12-tetra-azapentadeca-3,12
-Diene-6,10-dione, alanicarb [ethyl (Z) -N-benzyl-N-{[methyl (1-methylthioethylideneaminooxycarbonyl) amino] thio}
Carbamate-based compounds such as -β-alaninato], 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) -3- (2,2-dichlorovinyl)
-2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1R
S, 3RS) -3- (2,2-dichlorovinyl) -2,
2-methylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS) -cis-3- (2-chloro-
3,3,3-trifluoroprop-1-enyl) -2,
2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-cyano-3-phenoxybenzyl (1R, 3R) -3 (2,2-dibromovinyl)
-2,2-Dimethylcyclopropanecarboxylate], cycloprothrin [(RS) -α-cyano-3-
Phenoxybenzyl (RS) -2,2-dichloro-1
-(4-ethoxyphenyl) cyclopropanecarboxylate], fluvalinate (α-cyano-3-phenoxybenzyl N- (2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate), Bifensulin (2-methylbiphenyl-3-ylmethyl) (Z)-
(1RS) -cis-3- (2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate, acrinasulin ([1
R- {1α (S ^* ), 3α (Z)}]-2,2-dimethyl-3- [3-oxo-3- (2,2,2-trifluoro-1- (trifluoromethyl) ethoxy- 1-propenyl] cyclopropanecarboxylic acid (S)-(α) -cyano (3-phenoxyphenyl) methyl ester, 2-
Methyl-2- (4-bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether,
Tralomethrin [(1R, 3S) 3 [(1'RS)
(1 ', 1', 2 ', 2'-tetrabromoethyl)]-
2,2-Dimethylcyclopropanecarboxylic acid (S) -α
Pyrethroid compounds such as -cyano-3-phenoxybenzyl ester, silafluofen [4-ethoxyphenyl [3- (4-fluoro-3-phenoxyphenyl) propyl] dimethylsilane, buprofezin (2-tert-
Butyrimino-3-isopropyl-5-phenyl-1,
Thiadiazine derivatives such as 3,5-thiadiazin-4-one), nitroimidazolidines such as imidacloprid (1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-indeneamine), cartap (S, S ') -(2-dimethylaminotrimethylene)
Bis (thiocarbamate)], thiocyclam [N, N-
Nereistoxin derivatives such as dimethyl-1,2,3-trithian-5-ylamine] and bensultap [S, S'-2-dimethylaminotrimethylene di (benzenethiosulfonate)]; acetamidoprid [N-cyano- N-cyanoamidine derivatives such as N'-methyl-N '-(6-chloro-3-pyridylmethyl) acetamidine] and 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 (1,2,3,4,4)
5,6-hexachlorocyclohexane], 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol and other chlorinated hydrocarbon compounds, chlorfluazuron [1
-(3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl)-
3- (2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], flufenoxuron [1 − (4- (2-
Benzoylphenylurea-based compounds such as chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea]
Amitraz [N, N '[(methylimino) dimethylyl] di-2,4-xylysine], chlorodimform [N'-(4-chloro-2-methylphenyl) -N, N
-Dimethylmethinimidamide]; thiourea derivatives such as diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N'-tert-butylcarbodiimide]; bromopropylate [ Isopropyl 4,4'-dibromobenzylate], tetradiphone [4-chlorophenyl 2,4,5
-Trichlorophenyl sulfone], quinomethionate [S, S-6-methylquinoxaline-2,3-diyldithiocarbonate], propargate [2- (4-tert
-Butylphenoxy) cyclohexylprop-2-yl sulfite], fenbutatin oxide [bis [tris (2-methyl-2-phenylpropyl) tin] oxide], hexthiazox [(4RS, 5R
S) -5- (4-Chlorophenyl) -N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-
3-carboxamide], clofentezine [3,6-bis (2-chlorophenyl) -1,2,4,5-tetrazine, pyridathioben [2-tert-butyl-5- (4-te
rt-butylbenzylthio) -4-chloropyridazine-3
(2H) -one], fenpyroximate [tert-butyl (E) -4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl]
Benzoate], tebufenpyrad (N-4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide), polynactin complex (tetranactin, dinactin, trinactin), milbemectin, avermectin, ivermectin , Azadirachtin [AZAD], pyrimidifen [5
-Chloro-N- [2- {4- (2-ethoxyethyl)-
2,3-dimethylphenoxydiethyl] -6-ethylpyrimidin-4-amine, chlorphenapyl [4-bromo-2- (4-chlorophenyl) -1-ethoxymethyl-
5-trifluoromethylpyrrol-3-carbonitrile], tebufenozide [N-tertbutyl-N '-(4-
Ethylbenzoyl) -3,5-dimethylbenzohydrazide] and phenylpyrazole derivatives.

When the compound of the present invention is used as an agricultural insecticide or acaricide, its application amount is usually 0.1 g to 100 g per 10 ares, and the emulsion, wettable powder, flowable agent, etc. are diluted with water. When used, the application concentration is usually 1 ppm to 10000 ppm, and granules, powders, etc. are applied as they are without any dilution. When used as an insecticide or acaricide for epidemic prevention, emulsions, wettable powders, flowables, etc. are usually diluted with water to 0.1 ppm to 500 ppm and applied. Is applied 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 or decreased without being affected by the above range. can do.

[0067]

The present invention will be described in more detail below 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 of Compound (3) by Production Example 1 (Production Method F) 3,5-Dichloro-4- (4-bromobutyloxy)-
0.70 g of 1- (3,3-dichloro-2-propenyloxy) benzene, 0.34 g of 4- (1-piperidinylcarbonyl) phenol, 0.25 g of potassium carbonate and N, N
-10 ml of dimethylformamide was placed in a reaction vessel, stirred at room temperature for 24 hours, and then the reaction solution was poured into water. The mixture was extracted twice with 30 ml of diethyl ether, the ether layers were combined, washed with water, dried over magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography to give 3,5-dichloro-4- (4- (4- (1-piperidinylcarbonyl) phenoxy) butyloxy) -1.
0.66 g of-(3,3-dichloro-2-propenyloxy) benzene was obtained. Yield 73% n _D ^22.5 1.5751 Production of compound (11) by Production Example 2 (Production Method H) 4- (3- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) ) Phenoxy) propyloxy) benzoic acid [intermediate compound 2) produced in Production Example 1 of intermediate described below] 0.47 g, di (2-propenyl) amine
To a mixture of 0.10 g and 10 ml of chloroform was added 0.20 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (WSC) hydrochloride with stirring. After stirring at room temperature for 24 hours, the reaction solution was concentrated to obtain a residue. The residue was subjected to silica gel chromatography to give 3,5-dichloro-4- (3- (4- (N, N-di (2-propenyl) carbamoyl) phenoxy) propyloxy) -1- (3,3- 0.45 g of dichloro-2-propenyloxy) benzene was obtained. Yield 83% n _D ^27.0 1.5612 Production of compound (16) according to Production Example 3 (Production Method I) Triphosgene (2.67 g) was dissolved in a solution of toluene (50 ml) in ice-cooled solution under stirring with 3,5- Dichloro-4-
(4- (4-aminophenoxy) butyloxy) -1-
(3,3-Dichloro-2-propenyloxy) benzene [intermediate compound 10 produced in intermediate production example 2 below]]
2.03 g was added. The reaction solution was heated under reflux for 3 hours with stirring, and then the reaction solution was concentrated to give 4- (4- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) butyloxy). A crude product of phenyl isocyanate was obtained. Tetrahydrofuran was added to the crude product to make 15 ml, and 5 ml of the solution was added to di-
0.17 g of n-propylamine and 10 of tetrahydrofuran
The mixture was slowly added dropwise to the reaction vessel containing the mixture with ml while stirring under ice cooling. After stirring at room temperature for 24 hours, the mixture was concentrated to obtain a residue. The residue was subjected to silica gel chromatography to give 3,5-dichloro-4- (4- (4-
0.77 g of (N, N-dipropylureido) phenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene was obtained. Yield 89% mp 93.5 ° C. Production of compound (27) according to Production Example 4 (Production Method A) 3-Ethyl-5-methyl-4- (3- (4- (N, N-
Dipropylcarbamoyl) phenoxy) propyloxy) phenol 0.43 g, 1,1,3-trichloropropene 0.16 g, potassium carbonate 0.15 g and N, N-dimethylformamide 10 ml were placed in a reaction vessel, and the mixture was allowed to stand at room temperature for 2 hours.
After stirring for 4 hours, the reaction solution is poured into water. It is extracted twice with ethyl acetate, the ethyl acetate layers are combined, washed with water, dried over magnesium sulfate and concentrated to give a residue. The residue was chromatographed on silica gel, 3-ethyl-5-
Methyl 4- (3- (4- (N, N-dipropylcarbamoyl) phenoxy) propyloxy) -1- (3,3-
Dichloro-2-propenyloxy) benzene is obtained.

Next, some specific examples of the compound of the present invention will be shown below together with the compound number and some physical properties. (1) 3,5-dichloro-4- (2- (4- (1-piperidinylcarbonyl) phenoxy) ethyloxy) -1
-(3,3-Dichloro-2-propenyloxy) benzene n _D ^22.5 1.5821 (2) 3,5-dichloro-4- (3- (4- (1-piperidinylcarbonyl) phenoxy) propyloxy)-
1- (3,3-dichloro-2-propenyloxy) benzene n _D ^22.8 1.5655 (3) 3,5-dichloro-4- (4- (4- (1-piperidinylcarbonyl) phenoxy) butyloxy) -1
-(3,3-Dichloro-2-propenyloxy) benzene n _D ^22.5 1.5713 (4) 3,5-dichloro-4- (3- (3- (1-piperidinylcarbonyl) phenoxy) propyloxy)-
1- (3,3-dichloro-2-propenyloxy) benzene n _D ^25.0 1.5574 (5) 3,5-dichloro-4- (3- (2- (1-piperidinylcarbonyl) phenoxy) propyloxy)-
1- (3,3-dichloro-2-propenyloxy) benzene n _D ^25.0 1.5669 (6) 3,5-dichloro-4- (3- (4- (1-pyrrolidinylcarbonyl) phenoxy) propyloxy)-
1- (3,3-dichloro-2-propenyloxy) benzene n _D ^22.5 1.5751 (7) 3,5-dichloro-4- (3- (4- (3-pyrrolin-1-ylcarbonyl) phenoxy) propyloxy ) -1- (3,3-dichloro-2-propenyloxy) benzene n _D ^24.5 1.5762 (8) 3,5- dichloro -4- (3- (4- (n, N-
Dipropylcarbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene n _D ^22.7 1.5184 (9) 3,5-dichloro-4- (3- (4- (N, N −
Dibutylcarbamoyl) phenoxy) propyloxy)
-1- (3,3-dichloro-2-propenyloxy) benzene n _D ^25.0 1.5378 (10) 3,5-dichloro-4- (3- (4- (N, N-
Diisopropylcarbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene n _D ^25.0 1.5430 (11) 3,5-dichloro-4- (3- (4- (N, N-
Di (2-propenyl) carbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene n _D ^27.0 1.5612 (12) 3,5-dichloro-4- (3- (4- (N-Propylcarbamoyl) phenoxy) propyloxy) -1
-(3,3-Dichloro-2-propenyloxy) benzene mp85.1 ° C (13) 3,5-dichloro-4- (5- (4- (N, N-
Dipropylcarbamoyl) phenoxy) pentyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (14) 3,5-dichloro-4- (3- (4- (N, N-
Dipropylcarbamoyl) phenoxy) propyloxy) -1- (3,3-dibromo-2-propenyloxy) benzene (15) 3,5-dichloro-4- (3- (4- (N, N-
Di (2-propynyl) carbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (16) 3,5-dichloro-4- (4- (4- (N, N) −
Dipropylureido) phenoxy) butyloxy) -1
-(3,3-Dichloro-2-propenyloxy) benzene mp 93.5 ° C (17) 3,5-dichloro-4- (4- (4- (N-propylureido) phenoxy) butyloxy) -1-
(3,3-Dichloro-2-propenyloxy) benzene mp115.1 ° C (18) 3,5-dichloro-4- (4- (4- (N, N-
Dipropylcarbamoyloxy) phenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (19) 3,5-dichloro-4- (4- (4- (N-propylcarbamoyloxy) phenoxy ) Butyloxy-
1- (3,3-dichloro-2-propenyloxy) benzene (20) 3,5-dichloro-4- (4- (4- (N, N-
Dipropylcarbamoyl) phenoxy) butyloxy)
-1- (3,3-dichloro-2-propenyloxy) benzene (21) 3,5-dichloro-4- (4- (4- (N, N-
Di (2-propenyl) carbamoyl) phenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (22) 3,5-dichloro-4- (4- (4- (N, N-
Di (2-propenyl) carbamoyl) phenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (23) 3,5-diethyl-4- (3- (4- (N, N-
Dipropylcarbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (24) 3,5-diethyl-4- (3- (4- (N, N-
Di (2-propynyl) carbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (25) 3,5-diethyl-4- (3- (4- (N, N) −
Di (2-propynyl) carbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (26) 3,5-diethyl-4- (3- (4- (1-py Peridinylcarbonyl) phenoxy) propyloxy)-
1- (3,3-dichloro-2-propenyloxy) benzene (27) 3-ethyl-5-methyl-4- (3- (4-
(N, N-Dipropylcarbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (28) 3-ethyl-5-methyl-4- (3- (4-
(N, N-di (2-propenyl) carbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2)
-Propenyloxy) benzene (29) 3-ethyl-5-methyl-4- (3- (4-
(N, N-di (2-propynyl) carbamoyl) phenoxy) propyloxy) -1- (3,3-dichloro-2)
-Propenyloxy) benzene (30) 3-ethyl-5-methyl-4- (3- (4- (1
-Piperidinylcarbonyl) phenoxy) propyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (31) 3,5-diethyl-4- (4- (4- (N, N-
Dipropylcarbamoyl) phenoxy) butyloxy)
-1- (3,3-dichloro-2-propenyloxy) benzene (32) 3,5-diethyl-4- (4- (4- (N, N-
Di (2-propenyl) carbamoyl) phenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (33) 3,5-diethyl-4- (4- (4- (N, N-
Di (2-propynyl) carbamoyl) phenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (34) 3,5-diethyl-4- (4- (4- (1-piperidi) Nylcarbonyl) phenoxy) butyloxy) -1
-(3,3-Dichloro-2-propenyloxy) benzene (35) 3-ethyl-5-methyl-4- (4- (4-
(N, N-Dipropylcarbamoyl) phenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene (36) 3-ethyl-5-methyl-4- (4- (4-
(N, N-di (2-propenyl) carbamoyl) phenoxy) butyloxy) -1- (3,3-dichloro-2-)
Propenyloxy) benzene (37) 3-ethyl-5-methyl-4- (4- (4-
(N, N-di (2-propynyl) carbamoyl) phenoxy) butyloxy) -1- (3,3-dichloro-2-
Propenyloxy) benzene (38) 3-ethyl-5-methyl-4- (4- (4- (1
-Piperidinylcarbonyl) phenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene

Next, production examples of the intermediate compounds represented by the general formula [VI] and / or the general formula 3 (general formula [III]) will be shown. Intermediate Production Example 1 (Production of Intermediate Compound 2)) 3,5-Dichloro-4- (3-bromopropyloxy)
-1- (3,3-dichloro-2-propenyloxy) benzene 4.91 g, methyl 4-hydroxybenzoate 1.83
g, 1.82 g of potassium carbonate and 50 ml of N, N-dimethylformamide were placed in a reaction vessel, stirred at room temperature for 24 hours, and then the reaction solution was poured into water. Diethyl ether 10
The mixture was extracted twice with 0 ml, the ether layers were combined, washed with water, dried over magnesium sulfate and concentrated to obtain a crude product. This crude product was subjected to silica gel column chromatography,
5.58 g of methyl 4- (3- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) propyloxy) benzoate was obtained. (Yield 96%; n
_D ^22.7 1.5519) methyl 4- (3- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) propyloxy) benzoate (2.50 g) in a mixture of 20 ml of methanol and water. A solution of 0.41 g of potassium oxide in 4 ml of water was added. The reaction solution was heated and refluxed for 12 hours with stirring, then diluted with dilute hydrochloric acid to make the reaction solution acidic, and concentrated to obtain a residue. Water was added to this residue, and ethyl acetate was added to 30.
The mixture was extracted twice with ml, the ethyl acetate layers were combined, washed with water, dried over magnesium sulfate, and concentrated to give crude crystals. The crude crystals were washed with hexane to obtain 1.90 g of 4- (3- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) propyloxy) benzoic acid.
(Yield 78%) m. p. 137.5 ° C

General formula [VI] and / or general formula 3
Some specific examples of the intermediate compound represented by (general formula [III]) will be shown together with the compound number and some physical properties. 1) 4- (2- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) ethyloxy) benzoic acid 2) 4- (3- (2,6-dichloro-4-) (3,3-dichloro-2-propenyloxy) phenoxy) propyloxy) benzoic acid m. p. 137.5 ° C. 3) 4- (4- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) butyloxy) benzoic acid 4) 4- (5- (2,6- Dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) pentyloxy) benzoic acid 5) 3- (3- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) ) Phenoxy) propyloxy) benzoic acid 6) 2- (3- (2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenoxy) propyloxy) benzoic acid 7) 4- (3- (2,6-dichloro-4- (3,3-dibromo-2-propenyloxy) phenoxy) propyloxy) benzoic acid

The isocyanate compound represented by the general formula [VIII] can be produced from the corresponding aniline compound. A production example of this aniline intermediate compound is shown below. Intermediate Production Example 2 (Production of Intermediate Compound 10)) 3,5-Dichloro-4- (4-bromobutyloxy)-
1- (3,3-dichloro-2-propenyloxy) benzene 6.34 g, 4-acetamidophenol 2.27 g,
2.28 g of potassium carbonate and 50 ml of N, N-dimethylformamide were placed in a reaction vessel, stirred at room temperature for 24 hours, and then the reaction solution was poured into water. The mixture was extracted twice with 50 ml of ethyl acetate, the ethyl acetate layers were combined, washed with water, dried over magnesium sulfate, and concentrated to give crude crystals. The crude crystals were washed with hexane, and 3,5-dichloro-4- (4- (4-acetamidophenoxy) butyloxy) -1- (3,3-
4.70 g of dichloro-2-propenyloxy) benzene was obtained. (Yield 64%; mp 135.8 ° C.) 3,5-dichloro-4- (4- (4-acetamidophenoxy) butyloxy) -1- (3,3-dichloro-2
-Propenyloxy) benzene 4.44 g, methanol 1
To a mixture of 20 ml and 30 ml of water was added 20 ml of concentrated hydrochloric acid.
The reaction solution was heated under reflux for 6 hours with stirring, and then the reaction solution was concentrated to obtain a residue. Aqueous sodium hydrogen carbonate solution was added to this residue, and the mixture was extracted twice with 100 ml of ethyl acetate. The ethyl acetate layers were combined, washed with water, dried over magnesium sulfate and concentrated to give a crude product. This crude product was subjected to silica gel column chromatography to give 3,5-dichloro-4-
(4- (4-aminophenoxy) butyloxy) -1-
(3,3-dichloro-2-propenyloxy) benzene
3.84 g was obtained. (Yield 95%) n _D ^22.5 1.5816 Some of the specific examples of the above aniline intermediate compounds are shown together with the compound numbers and some physical properties. 8) 3,5-Dichloro-4- (2- (4-aminophenoxy) ethyloxy) -1- (3,3-dichloro-2-
Propenyloxy) benzene 9) 3,5-dichloro-4- (3- (4-aminophenoxy) propyloxy) -1- (3,3-dichloro-2)
-Propenyloxy) benzene 10) 3,5-dichloro-4- (4- (4-aminophenoxy) butyloxy) -1- (3,3-dichloro-2-
Propenyloxy) benzene n _D ^22.5 1.58161 1) 3,5-Dichloro-4- (5- (4-aminophenoxy) -pentyloxy) -1- (3,3-dichloro-
2-Propenyloxy) benzene 12) 3,5-dichloro-4- (4- (3-aminophenoxy) -butyloxy) -1- (3,3-dichloro-2)
-Propenyloxy) benzene 13) 3,5-dichloro-4- (4- (2-aminophenoxy) -butyloxy) -1- (3,3-dichloro-2)
-Propenyloxy) benzene

Next, production examples of the compound represented by the general formula 4 which is an intermediate for producing the compound of the present invention will be shown. Intermediate Production Example 3 (Production of Intermediate Compound 21) Hydroquinone monobenzyl ether (1.07 g) and carbon tetrachloride (500 ml) were placed in a reaction vessel, and t-butyl hypochlorite (1.01 g) was added thereto while stirring under ice cooling. A solution dissolved in 10 ml of carbon chloride was slowly added dropwise. After 24 hours, the reaction solution was poured into water and the organic layer (carbon tetrachloride) was separated. After washing with water, drying over anhydrous magnesium sulfate and concentration, a crude product was obtained. The crude product was subjected to silica gel chromatography to obtain 0.85 g of 2,6-dichloro-4-benzyloxyphenol. (Yield 59%) 8.08 g of 1,3-dibromopropane, 3.04 g of potassium carbonate
And 100 ml of N, N-dimethylformamide were placed in a reaction vessel, and a solution of 5.38 g of 2,6-dichloro-4-benzyloxyphenol in 50 ml of N, N-dimethylformamide was added thereto at room temperature for 2 hours. Dropped. After stirring at room temperature for 1 hour, the reaction solution was filtered through Celite and the filtrate was poured into water. Extraction was performed twice with diethyl ether, the ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography to obtain 6.36 g of 3,5-dichloro-4- (3-bromopropyloxy) -1-benzyloxybenzene. (Yield 82%) 4- (N, N-dipropylcarbamoyl) phenol 0.
66 g, 3,5-dichloro-4- (3-bromopropyloxy) -1-benzyloxybenzene 1.29 g, potassium carbonate 0.50 g and N, N-dimethylformamide 2
0 ml was placed in a reaction vessel and stirred at 40 ° C. for 24 hours,
The reaction solution was poured into water. Extraction was performed twice with diethyl ether, the ether layers were combined, washed with water, dried over magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel column chromatography to give 1.24 g of 3,5-dichloro-4- (3- (4- (N, N-dipropylcarbamoyl) phenoxy) propyloxy) -1-benzyloxybenzene. Got Yield 76% n _D ^24.0 1.5572 3,5-dichloro-4- (3- (4- (N, N-dipropylcarbamoyl) phenoxy) propyloxy) -1
-Benzyloxybenzene 1.06 g and ethyl acetate 4
0 ml was placed in the reaction vessel and the air in the vessel was replaced with nitrogen. 0.30 g of 10% palladium carbon was added, nitrogen in the container was replaced with hydrogen, and the mixture was vigorously stirred at room temperature for 2 hours. After replacing the hydrogen in the container with nitrogen, the reaction solution was filtered through Celite and the filtrate was concentrated to give 3,5-dichloro-4-
0.71 g of (3- (4- (N, N-dipropylcarbamoyl) phenoxy) propyloxy) phenol was obtained. Yield 80% ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 0.68 to 1.10 (6H, brs), 1.42 to 1.79 (4H, br)
s), 2.23 (2H, dt), 3.05-3.55 (4H, brs), 3.48 (1H, s),
4.08 (2H, t), 4.23 (2H, t), 6.56 (2H, s), 6.88 (2H, d), 7.
27 (2H, d) Intermediate Preparation Example 4 (Preparation of Intermediate Compound 39) 2-Ethyl-6-methylaniline 27 g, concentrated sulfuric acid 36 ml
A solution of 16.1 g of sodium nitrite in 50 ml of water was added dropwise thereto while stirring a mixture of 100 ml of water and 100 ml of water at a temperature of 0 ° C to 5 ° C. After the dropping was completed, 150 g of cold water, 1.5 g of urea and 150 g of ice were added thereto. This aqueous solution was added dropwise to a solution in which a mixture of 100 ml of sulfuric acid, 100 ml of water and 150 g of sodium sulfate was heated and stirred at 135 ° C. Simultaneously with the dropwise addition, steam distillation was performed. After the completion of the dropwise addition, the aqueous solution distilled by steam distillation was salted out with sodium chloride, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography to obtain 16 g of 2-ethyl-6-methylphenol (yield 59%). 2-ethyl-
16 g of 6-methylphenol was dissolved in 200 ml of chloroform, stirred at 0 ° C., and 56.6 g of tetrabutylammonium tribromide was added little by little to this solution. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, the residue was dissolved in diethyl ether (300 ml), washed with 10% hydrochloric acid and water, dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. Was. This crude product was subjected to silica gel chromatography to obtain 23 g of 4-bromo-2-ethyl-6-methylphenol (yield 92%). 26 g of 4-bromo-2-ethyl-6-methylphenol, 24.8 g of benzyl bromide and N, N-dimethylformamide 2
To the 00 ml of the mixture, 21.7 g of potassium carbonate was added at room temperature with stirring. After stirring at room temperature for 24 hours, the reaction solution was poured into ice water and extracted twice with 500 ml of diethyl ether. The diethyl ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography to obtain 35.6 g (yield 97%) of 4-bromo-2-ethyl-6-methyl-1-benzyloxybenzene. 4-bromo-2-
Ethyl-6-methyl-1-benzyloxybenzene 35.6
g in 250 ml of tetrahydrofuran and n-butyllithium (hexane solution 1.69) with stirring at -70 ° C.
69 ml of the mol / 1) solution was added dropwise. 2 at -70 ° C
After stirring for an hour, trimethoxyborane 1 was added to the reaction solution.
A solution prepared by dissolving 2.1 g in 50 ml of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the reaction temperature was returned to room temperature, and the mixture was stirred for 1 hour. The reaction solution was poured into ice water, made weakly acidic with 10% aqueous hydrochloric acid, and extracted twice with 500 ml of diethyl ether.
The ether layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated to give a residue. To this residue 120 ml of toluene
Was added, and 33 ml of 30% hydrogen peroxide solution was added dropwise with heating and stirring at 70 ° C. After heating under reflux for 1 hour,
The reaction mixture was returned to room temperature, washed once with water, twice with 10% aqueous ferrous ammonium sulfate, and once with water. The toluene layer was dried over anhydrous magnesium sulfate and then concentrated to give a crude product. Got This crude product was subjected to silica gel chromatography to give 26.2 g (yield 93%) of 3-ethyl-4-benzyloxy-5-methylphenol.
I got To a mixture of 6.3 g of 4-benzyloxy-3-ethyl-5-methylphenol, 3.2 g of triethylamine and 50 ml of chloroform was added dropwise 4.0 g of benzoyl chloride while stirring at 0 ° C. After stirring at room temperature for 6 hours,
The reaction mixture was concentrated under reduced pressure to give a residue. 1 for this residue
100 ml of 0% hydrochloric acid water was added, and the mixture was extracted with 100 ml of ethyl acetate. The ethyl acetate layer was washed successively with a 10% aqueous hydrochloric acid solution, a saturated aqueous solution of sodium hydrogen carbonate and a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give crude 4-benzyloxy-3-ethyl-5-methyl 8.4 g (93% yield) of phenylbenzoate were obtained. Crude 4-benzyloxy-3-ethyl-5-methylphenorbenzoate 8.4
g was dissolved in 100 ml of ethyl acetate, placed in a reaction vessel, and the air in the vessel was replaced with nitrogen. 0.5% of 10% palladium-carbon was added, nitrogen in the container was replaced with hydrogen, and the mixture was vigorously stirred at room temperature for 24 hours. After replacing hydrogen in the vessel with nitrogen, the reaction solution was filtered through celite, and the filtrate was concentrated under reduced pressure to obtain 5.9 g of 2-ethyl-6-methyl-4-benzoyloxyphenol (yield 95%). 2-Ethyl-6-methyl-4-benzoyloxyphenol 0.
24 g, 4- (N, N-dipropylcarbamoyl) -1-
0.34 g of (3-bromopropyloxy) benzene, 0.15 g of potassium carbonate and N, N-dimethylformamide 10
After adding ml to the reaction vessel and stirring at room temperature for 24 hours, water is added to the reaction solution. It is extracted twice with ethyl acetate, the ethyl acetate layers are combined, washed with water, dried over magnesium sulfate and concentrated to give a residue. The residue was subjected to silica gel chromatography to give 3-ethyl-5-methyl-4- (3- (4
-(N, N-dipropylcarbamoyl) phenoxy) propyloxy) phenylbenzoate is obtained. 3-Ethyl-5-methyl-4- (3- (4- (N, N-dipropylcarbamoyl) phenoxy) propyloxy) phenylbenzoate 0.52 g was dissolved in 10 ml of methanol, and 0.072 g of potassium hydroxide was added to water. Add a solution dissolved in 0.70 g and stir at room temperature for 1 hour. Dilute hydrochloric acid was added to the reaction mixture to make it acidic, then the mixture was concentrated, water was added, and the mixture was extracted twice with ethyl acetate. Combine the ethyl acetate layers, wash with water,
After drying over magnesium sulfate, it is concentrated to give a residue. The residue is subjected to silica gel chromatography to give 3-ethyl-5-methyl-4- (3- (4- (N, N-dipropylcarbamoyl) phenoxy) propyloxy) phenol. Next, examples of the compound represented by the general formula 4 which is an intermediate for producing the compound of the present invention are shown. 14) 3,5-Dichloro-4- (2- (4- (1-piperidinylcarbonyl) phenoxy) ethyloxy) phenol 15) 3,5-dichloro-4- (3- (4- (1-piperidyl) Nylcarbonyl) phenoxy) propyloxy) phenol 16) 3,5-dichloro-4- (4- (4- (1-piperidinylcarbonyl) phenoxy) butyloxy) phenol 17) 3,5-dichloro-4- (3 -(3- (1-Piperidinylcarbonyl) phenoxy) propyloxy) phenol 18) 3,5-dichloro-4- (3- (2- (1-piperidinylcarbonyl) phenoxy) propyloxy) phenol 19) 3,5-Dichloro-4- (3- (4- (1-pyrrolidinylcarbonyl) phenoxy) propyloxy) phenol 20) 3,5-dichloro-4- (3- (4- ( 3-pyrrolin-1-ylcarbonyl) phenoxy) propyloxy) phenol 21) 3,5-dichloro-4- (3- (4- (N, N-dipropylcarbamoyl) phenoxy) propyloxy)
Phenol 22) 3,5-dichloro-4- (3- (4- (N, N-dibutylcarbamoyl) phenoxy) propyloxy) phenol 23) 3,5-dichloro-4- (3- (4- (N, N-diisopropylcarbamoyl) phenoxy) propyloxy) phenol 24) 3,5-dichloro-4- (3- (4- (N, N-di (2-propenyl) carbamoyl) phenoxy) propyloxy) phenol 25) 3, 5-dichloro-4- (3- (4- (N-propylcarbamoyl) phenoxy) propyloxy) phenol 26) 3,5-dichloro-4- (5- (4- (N, N-dipropylcarbamoyl) phenoxy ) Pentyloxy)
Phenol 27) 3,5-dichloro-4- (3- (4- (N, N-di (2-propynyl) carbamoyl) phenoxy) propyloxy) phenol 28) 3,5-dichloro-4- (4- ( 4- (N, N-dipropylureido) phenoxy) butyloxy) phenol 29) 3,5-dichloro-4- (4- (4- (N-propylureido) phenoxy) butyloxy) phenol 30) 3,5-dichloro -4- (4- (4- (N, N-dipropylcarbamoyloxy) phenoxy) butyloxy) phenol 31) 3,5-dichloro-4- (4- (4- (N-propylcarbamoyloxy) phenoxy) butyloxy ) Phenol 32) 3,5-dichloro-4- (4- (4- (N, N-dipropylcarbamoyl) phenoxy) butyloxy) phenol 33) 3, - dichloro -4- (4- (4- (N, N- di (2-propenyl) carbamoyl) phenoxy) butyloxy) phenol 34) 3,5-dichloro-4-
(4- (4- (N, N-di (2-propynyl) carbamoyl) phenoxy) butyloxy) phenol 35) 3,5-diethyl-4- (3- (4- (N, N-dipropylcarbamoyl) phenoxy ) Propyloxy)
Phenol 36) 3,5-diethyl-4- (3- (4- (N, N-di (2-propenyl) carbamoyl) phenoxy) propyloxy) phenol 37) 3,5-diethyl-4- (3- ( 4- (N, N-di (2-propynyl) carbamoyl) phenoxy) propyloxy) phenol 38) 3,5-diethyl-4- (3- (4- (1-piperidinylcarbonyl) phenoxy) propyloxy) Phenol 39) 3-ethyl-5-methyl-4- (3- (4- (N,
N-dipropylcarbamoyl) phenoxy) propyloxy) phenol 40) 3-ethyl-5-methyl-4- (3- (4- (N,
N-di (2-propenyl) carbamoyl) phenoxy)
Propyloxy) phenol 41) 3-Ethyl-5-methyl-4- (3- (4- (N,
N-di (2-propynyl) carbamoyl) phenoxy)
Propyloxy) phenol 42) 3-ethyl-5-methyl-4- (3- (4- (1-
Piperidinylcarbonyl) phenoxy) propyloxy) phenol 43) 3,5-diethyl-4- (4- (4- (N, N-dipropylcarbamoyl) phenoxy) butyloxy) phenol 44) 3,5-diethyl-4 -(4- (4- (N, N-di (2-propenyl) carbamoyl) phenoxy) butyloxy) phenol 45) 3,5-diethyl-4- (4- (4- (N, N-di (2- Propynyl) carbamoyl) phenoxy) butyloxy) phenol 46) 3,5-diethyl-4- (4- (4- (1-piperidinylcarbonyl) phenoxy) butyloxy) phenol 47) 3-ethyl-5-methyl-4- (4- (4- (N,
N-dipropylcarbamoyl) phenoxy) butyloxy) phenol 48) 3-ethyl-5-methyl-4- (4- (4- (N,
N-di (2-propenyl) carbamoyl) phenoxy)
Butyloxy) phenol 49) 3-ethyl-5-methyl-4- (4- (4- (N,
N-di (2-propynyl) carbamoyl) phenoxy)
Butyloxy) phenol 50) 3-ethyl-5-methyl-4- (4- (4- (1-
Piperidinylcarbonyl) phenoxy) butyloxy)
Phenol Next, a production example of the intermediate represented by the general formula 8 will be shown. Intermediate Production Example 5 4-hydroxyphenyl benzoate (30.5 g), potassium carbonate (21.6 g), 1,1,3-trichloropropene (20.8 g) and N, N-dimethylformamide (100 ml) were placed in a reaction vessel and stirred at room temperature for 15 hours, The reaction solution was poured into water. The mixture was extracted twice with 150 ml of diethyl ether, the ether layers were combined, washed with water, dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography to give 4- (3,3-dichloro-2-
44.1 g of propenyloxy) phenyl benzoate were obtained. (Yield 96%) 4- (3,3-dichloro-2-propenyloxy) phenyl benzoate (40.1 g) and methanol (400 ml) were placed in a reaction vessel, and 30% potassium hydroxide solution 3 was added under ice cooling.
3 g was slowly added dropwise. After stirring for 1 hour, the mixture was made weakly acidic with 10% hydrochloric acid, and 150 ml of diethyl ether was added under salting out.
It was extracted twice with. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography to give 4-
26.0 g of (3,3-dichloro-2-propenyloxy) phenol was obtained. (Yield 87%) 26.0 g of 4- (3,3-dichloro-2-propenyloxy) phenol and 500 ml of carbon tetrachloride were placed in a reaction vessel, and tert-butyl hypochlorite 2 was added with stirring under ice cooling.
A solution of 7.1 g in 20 ml of carbon tetrachloride was slowly added dropwise. After 24 hours, the reaction solution was poured into water, and the organic layer (carbon tetrachloride layer) was separated. After washing with water, drying over anhydrous magnesium sulfate and concentration, a crude product was obtained. This crude product is subjected to silica gel chromatography to give 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)
11.0 g of phenol was obtained. Yield 32% n _D ^22.5 1.5895 Next, a production example of the intermediate compound represented by the general formula 11 is shown. Intermediate Production Example 6 1,3-dibromopropane 10.6 g, potassium carbonate 5.53 g
And 100 ml of N, N-dimethylformamide were placed in a reaction vessel, and 30.5 g of 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenol was added to N, N-.
A solution of 40 ml of dimethylformamide was slowly added dropwise. After stirring at room temperature for 24 hours, the reaction solution was poured into water. The mixture was extracted twice with 150 ml of diethyl ether, the ether layers were combined, washed with water, dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. The crude product was chromatographed on silica gel to give 3,5-dichloro-4-
11.1 g of (3-bromopropyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene was obtained. Yield 77% n _D ^24.0 1.5693 Intermediate Production Example 7 22.67 g of 1,4-dibromobutane, potassium carbonate 11.06
g and N, N-dimethylformamide (200 ml) were placed in a reaction vessel, and 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) phenol (20.16 g) was added to N, N.
A solution dissolved in 80 ml of N-dimethylformamide was slowly added dropwise. After stirring at room temperature for 24 hours, the reaction solution was poured into water. Extracted twice with 300 ml of diethyl ether,
The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography to give 3,5-dichloro-4
21.77 g of-(4-bromobutyroxy) -1- (3,3-dichloro-2-propenyloxy) benzene was obtained. Yield 74% n _D ^25.0 1.5666 Next, a production example of a compound represented by the general formula [IV] which is a production intermediate of the compound of the present invention will be shown. Intermediate Production Example 8 Methyl 4-hydroxybenzoate 22.8 g, potassium carbonate 2
3.5 g, 25.7 g of benzyl bromide and 250 ml of N, N-dimethylformamide were placed in a reaction vessel and allowed to stand at room temperature for 24 hours.
After stirring for an hour, the reaction solution was filtered through Celite, and the filtrate was added to water. The mixture was extracted twice with diethyl ether, the ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain 35.5 g of methyl 4-benzyloxybenzoate. (Yield 97%) Methyl 4-benzyloxybenzoate (34.7 g) and methanol (200 ml) were placed in a reaction vessel, and 20% aqueous potassium hydroxide solution (85 ml) was added at room temperature. After stirring for 1 hour, 10
The reaction mixture was made weakly acidic with aqueous hydrochloric acid, and the resulting crystals were collected by filtration. The obtained crystals are washed successively with 10% hydrochloric acid and water and dried to give 4-benzyloxybenzoic acid 33.3 g.
I got 5.71 g of 4-benzyloxybenzoic acid and 60 ml of hexane were placed in a reaction vessel, and 7.01 g of thionyl chloride was added dropwise while stirring at room temperature. After stirring under heating under reflux for 2 hours, the mixture was slowly cooled, and the generated crystals were collected by filtration. The obtained crystals were washed with hexane and dried to give 5.34 g of 4-benzyloxybenzoyl chloride. (Yield 86%) 2.23 g of dipropylamine and 20 ml of dichloromethane were put in a reaction vessel, and a mixture of 2.47 g of 4-benzyloxybenzoyl chloride and 10 ml of dichloromethane was slowly added dropwise thereto under ice cooling. After stirring at room temperature for 2 hours, the solvent was distilled off, 10% hydrochloric acid was added to the residue, and the mixture was diluted with ethyl acetate to 2%.
Extracted times. The ethyl acetate layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous magnesium sulfate and concentrated to give 2.69 g of 4- (N, N-dipropylcarbamoyl) -1-benzyloxybenzene. .
(Yield 86%) 2.49 g of 4- (N, N-dipropylcarbamoyl) -1-benzyloxybenzene and 30 ml of ethyl acetate were placed in a reaction vessel, and the air in the vessel was replaced with nitrogen. 10%
Palladium carbon (0.2 g) was added, the nitrogen in the container was replaced with hydrogen, and the mixture was vigorously stirred at room temperature for 2 hours. After replacing the hydrogen in the container with nitrogen, the reaction container was filtered through Celite,
The filter cake was washed with methanol, the filtrate was concentrated, and 4- (N,
1.68 g of N-dipropylcarbamoyl) phenol was obtained. (Yield 95%) mp. 92.7 ° C. Next, a production example of the compound represented by the general formula 9 which is a production intermediate of the compound of the present invention will be shown. Intermediate Production Example 9 8.08 g of 1,3-dibromopropane, 3.04 g of potassium carbonate
And 100 ml of N, N-dimethylformamide were placed in a reaction vessel, and 4.43 g of 4- (N, N-dipropylcarbamoyl) phenol was added to 50 ml of N, N-dimethylformamide.
The solution dissolved in is added dropwise at room temperature over 2 hours. After stirring at room temperature for 24 hours, the reaction solution is filtered through Celite, and the filtrate is poured into water. Extract twice with ethyl acetate, combine ethyl acetate layers, wash with water, dry over anhydrous magnesium sulfate,
Concentrate to give the crude product. The crude product is subjected to silica gel chromatography to give 4- (N, N-dipropylcarbamoyl) -1- (3-bromopropyloxy) benzene.

Formulation examples are shown below. Parts represent parts by weight, and the compound of the present invention is represented by the aforementioned compound number. Formulation Example 1 Emulsion 10 parts of each of the compounds (1) to (38) of the present invention were mixed with xylene 3
It is dissolved in 5 parts and 35 parts of dimethylformamide, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzene sulfonate are added to this, and well mixed by stirring to obtain 10% emulsions of each. Formulation Example 2 Wettable powder 20 parts of each of the compounds (1) to (38) of the present invention, 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 for each. Formulation Example 3 Granules To 5 parts of each of the compounds (1) to (38) of the present invention, 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay are added and mixed with sufficient stirring. To do. Then, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated by a granulator, and air-dried to obtain each 5% granule. Formulation Example 4 Dust agent 1 part of each of the compounds (1) to (38) of the present invention was dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder, PA
0.3 parts of P and 93.7 parts of clay are added, and the mixture is stirred and mixed with a juice mixer, and acetone is removed by evaporation to obtain each 1% powder. Formulation Example 5 Flowable Agent 20 parts of each of the compounds (1) to (38) of the present invention and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely ground with a sand grinder (particle size: 3 μm). Below), then in this, xanthan gum
0.05 part and aluminum magnesium silicate 0.1
40 parts of an aqueous solution containing 10 parts of propylene glycol is added, and 10 parts of propylene glycol is further added and mixed with stirring to obtain each 20% suspension in water. Formulation Example 6 Oil agent 0.1 parts of each of the compounds (1) to (38) of the present invention was dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this was deodorized kerosene.
Mix with 89.9 parts to obtain each 0.1% oil solution. Formulation Example 7
Oily aerosol 0.1 parts of each of the compounds (1) to (38) of the present invention, 0.2 parts of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorant kerosene are mixed and dissolved, and the mixture is filled in an aerosol container, and a valve part is attached. After that, 30 parts of propellant (liquefied petroleum gas) is charged under pressure through the valve portion to obtain each oil-based aerosol. Formulation Example 8 Aqueous Aerosol 0.2 parts of each of the compounds (1) to (38) of the present invention, 0.2 part of d-allethrin, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosene and an emulsifier {Atmos 300 (registered by Atlas Chemical Co., Ltd. Trade name)} and one part mixed and dissolved,
50 parts of pure water is filled in an aerosol container, a valve portion is attached, and 40 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve portion to obtain each aqueous aerosol. Formulation Example 9 Mosquito coil Incense 0.3 g of each of the compounds (1) to (38) of the present invention was added with 0.3 g of d-allethrin and dissolved in 20 ml of acetone to prepare a carrier for mosquito coil (tab powder: lees powder: wood powder). Mixed at a ratio of 4: 3: 3)
After uniformly stirring and mixing with 99.4 g, 120 ml of water was added, and the kneaded mixture was molded and dried to obtain each mosquito coil. Formulation Example 10 Electric Mosquito Repellent Mat 0.4 g of each of the compounds (1) to (38) of the present invention, 0.3 g of d-allethrin, and 0.4 g of pipenyl butoxide are dissolved by adding acetone to make a total volume of 10 ml. This solution
0.5 ml of a 2.5 cm x 1.5 cm, 0.3 cm thick electric mat substrate (solid fibril of a mixture of cotton sinter and pulp solidified into a plate) uniformly impregnated with each electric mosquito mat Get the agent. Formulation Example 11 Heating Smoke Agent Each of 100 mg of the compounds (1) to (38) of the present invention is dissolved in an appropriate amount of acetone and impregnated into a 4.0 cm × 4.0 cm, 1.2 cm thick porous ceramic plate to heat and smoke each of them. Get smoke. Formulation Example 12 Poison bait 10 mg of each of the compounds (1) to (38) of the present invention is added with 0.5% acetone.
It is dissolved in 5 ml, and this solution is treated to 5 g of animal solid feed powder (solid feed powder for breeding and breeding CE-2, trade name of CLEA Japan, Inc.) and mixed uniformly. Then air-dry acetone to obtain 0.5% of each bait.

Next, it will be shown by test examples that the compound of the present invention is useful as an active ingredient of insecticides and acaricides. The compounds of the present invention are shown by the above compound numbers, and the compounds used for comparison and control are shown by the compound symbols shown in Table 7.

[Table 7] Test Example 1 (Insecticidal test on Spodoptera litura) For 13 g of Spodoptera litura, 2 ml of a 200-fold diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 with water was prepared in a polyethylene cup having a diameter of 11 cm. Soaked in artificial feed. Among them, Lotus armyworm 4
Ten larvae were released, and after 6 days, their mortality was examined to determine the mortality (two repetitions). As a result, the compound of the present invention (2)
(12) each showed a mortality of 80% or more. For it,
The mortality of the compound (A) used as a comparative control was 0%.

Test Example 2 (Insecticidal test against diamondback moth) To the emulsion of the test compound obtained according to Formulation Example 1, water and the spreading agent Rinault (manufactured by Nippon Agricultural Chemicals Co., Ltd.) were added to give an active ingredient concentration of 500 ppm. The potted cabbage (5-leaf stage) was prepared by diluting the spreading agent 1000 times.
Was sprayed with 25 ml per pot. After the treated plant was air-dried, ten 10th instar larvae of the Japanese moth were released. After 4 days, the mortality was investigated. As a result, the compounds (2), (3), (9) and (11) of the present invention each showed a mortality rate of 80% or more. On the other hand, the mortality of the compound (A) used as a comparative control was 0%.

Test Example 3 (Insecticidal test against housefly) The compound to be tested was diluted with acetone to a predetermined concentration, and 10 μg / 0.5 μl of the compound was applied to the back of the adult female housefly ( Musca domestica) 4 days after emergence with a microdropper. Acetone was treated and the mortality was calculated 72 hours later. (1 group 10 heads 3
As a result, the compounds of the present invention (2), (3), (6), (7),
(8), (9), (10), (11), (12) are 100% mortality
showed that. On the other hand, the mortality of the comparative compound (A) is 3.
It was 3%.

Test Example 4 (Acaricidal Test against Nite Mites) A 130 ml plastic cup was filled with sandy loam soil, two seeds of kidney bean were sown per cup, and the seeds were cultivated in the growth room until the primary leaves developed. The adult green spider mite was released to the obtained kidney bean seedlings and allowed to grow in a greenhouse for 6 days, and then a sufficient amount of a water-diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 was used. The foliage was sprayed. Then, after keeping it in a greenhouse for 8 days, its life and death were investigated and the mortality rate was calculated. As a result, the compound of the present invention (1), (2),
(3) and (6) each showed a mortality of 60% or more. On the other hand, the mortality of the compound (A) used as a comparative control was 0%. Test Example 5 (Insecticidal test against Heliothis virescens) 0.2 ml of a water-diluted solution (100 ppm) of the emulsion of the test compound obtained in Production Example 1 was mixed with artificial feed to give H. virescens second-instar larvae. And kept in a plastic container. Ten animals were tested for one treatment. 6-7
The mortality was calculated after a day. As a result, the compound of the present invention (8),
(11) each showed a mortality of 80% or more. On the other hand, the mortality of the compound (A) used as a comparative control was 0%.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 47/30 A01N 47/30 BG C07C 65/28 2115-4H C07C 65/28 235/48 9547 -4H 235/48 235/60 9547-4H 235/60 237/30 9547-4H 237/30 237/32 9547-4H 237/32 271/40 9451-4H 271/40 271/56 9451-4H 271/56 275/30 9451-4H 275/30 275/34 9451-4H 275/34 275/38 9451-4H 275/38 317/16 7419-4H 317/16 317/22 7419-4H 317/22 317/26 7419- 4H 317/26 317/32 7419-4H 317/32 323/09 7419-4H 323/09 323/18 7419-4H 323/18 323/31 7419-4H 323/31 323/60 7419-4H 323/60 C07D 207/06 C07D 207/06 207/20 207/20 211/16 211/16 211/70 211/70 295/18 295/18 Z 295/20 295/20 Z (72) Inventor Keiichi Izumi Takarazuka City, Hyogo Prefecture 4-2-1 Takashi Sumitomo Industrial Co., Ltd. (72) Inventor Noriho Sakamoto 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (72) Inventor Yoshitaka Takano 4-53, Kitahama, Osaka City, Osaka Sumitomo Chemical Gaku Kogyo Co., Ltd. (72) Inventor Yoji Takada 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Gaku Kogyo Co., Ltd.

Claims (28)

[Claims] 1. A general formula [I] {In the formula, R, R ² and R ³ each independently represent a halogen atom, a haloalkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group, R 5 ⁷ represents a halogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group. R ⁸ and R
⁹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a haloalkenyl group having 3 to 6 carbon atoms, or a carbon number. Represents an alkynyl group having 3 to 4 carbon atoms, a haloalkynyl group having 3 to 4 carbon atoms, a cycloalkylalkyl group having 4 to 8 carbon atoms, a cycloalkenylalkyl group having 6 to 8 carbon atoms, or an alkoxyalkyl group having 3 to 4 carbon atoms. Alternatively, it represents a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 2 carbon atoms, or R ⁸ and R ⁹ are bonded to each other at the terminal, 2 carbon atoms that may be substituted with 2 alkyl groups
Represents an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 4 to 6 carbon atoms, which may be substituted with an alkyl group having 1 to 2 carbon atoms. Q ¹ represents a single bond or represents T, and T is represented by the general formula [II] [In the formula, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group, and A represents an oxygen atom, an S (O) _n group, NR ¹² Group, C (= O)
G group or GC (= O) group (wherein n represents an integer of 0 to 2, R ¹² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, G represents an oxygen atom or an NR ¹³ group, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and s represents an integer of 0 to 6. ] It represents the group shown by. Q ² represents a single bond, an oxygen atom or an NR ¹⁴ group (wherein R ¹⁴ represents a hydrogen atom or an alkyl group of 1 to 3). Each X independently represents a chlorine atom or a bromine atom. Y represents an oxygen atom, an NH group or a sulfur atom. Z represents an oxygen atom, a sulfur atom or NR ¹⁵ , and R ¹⁵ is a hydrogen atom or a carbon number of 1 to 3.
Represents an alkyl group. l (el) represents an integer of 0 to 4, p represents an integer of 0 to 6, and r represents an integer of 0 to 2. A dihalopropene compound represented by｝. 2. R and R ² are each independently a halogen atom or an alkyl group having 1 to 3 carbon atoms, and
The dihalopropene compound according to claim 1, wherein r = 0. 3. R and R ² are each independently a halogen atom or an alkyl group having 1 to 3 carbon atoms, and
The dihalopropene compound according to claim 1, wherein r is 1 or 2. 4. The dihalopropene compound according to claim 1, wherein R and R ² are each independently a chlorine atom, a bromine atom or an alkyl group having 1 to 3 carbon atoms, and r = 0. 5. R and R ² are both chlorine atoms, and
The dihalopropene compound according to claim 1, wherein r = 0. 6. The dihalopropene compound according to claim 1, wherein Y and Z are both oxygen atoms. 7. The dihalopropene compound according to claim 4, wherein both Y and Z are oxygen atoms. 8. The dihalopropene compound according to claim 5, wherein both Y and Z are oxygen atoms. 9. The dihalopropene compound according to claim 1, wherein Q ¹ is a single bond. 10. The dihalopropene compound according to claim 1, wherein s = 0 in the compound in which Q ¹ is T. 11. The dihalopropene compound according to claim 1, wherein in the compound in which Q ¹ is T, s = 1 is an integer of 6. 12. The dihalopropene compound according to claim 1, wherein Q ² is a single bond. 13. The dihalopropene compound according to claim 1, wherein Q ² is an oxygen atom. 14. The dihalopropene compound according to claim 1, wherein Q ² is NR ¹⁴ . 15. The dihalopropene compound according to claim 7, wherein s = 0 in the compound in which Q ¹ is T and Q ² is a single bond. 16. The dihalopropene compound according to claim 15, wherein A is an oxygen atom. 17. The dihalopropene compound according to claim 8, wherein s = 0 in the compound in which Q ¹ is T, and Q ² is a single bond. 18. A is an oxygen atom, and l (el)
= 0 and an integer from p = 2 to 4, and
18. The dihalopropene compound according to claim 17, wherein R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms. 19. R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms or an alkynyl group having 3 to 4 carbon atoms, or 19. The dihalopropene compound according to claim 18, wherein R ^8, R ⁹ and R ⁹ are terminally bonded to each other and are an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a butenylene group. 20. An insecticide or acaricide, which comprises the dihalopropene compound according to any one of claims 1 to 19 as an active ingredient. 21. The general formula [III] [In the formula, R and R ² are each independently a halogen atom, a haloalkyl group having 1 to 3 carbon atoms, or a C 1
Represents an alkyl group from 1 to 3. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group, R 5 ¹⁸ represents a carboxyl group or an amino group. A
Is an oxygen atom, S (O) _n group, NR ¹² group, C (= O) G
Group or a GC (= O) group (wherein n represents an integer of 0 to 2, R ¹² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, G represents an oxygen atom or an NR ¹³ group,
R ¹³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), X independently represents a chlorine atom or a bromine atom, and p represents an integer of 0 to 6. ] The compound shown by these. 22. The method according to claim 21, wherein R ¹⁸ is a carboxyl group.
A compound as described. 23. The compound according to claim 22, wherein A is an oxygen atom. 24. R and R ² are each independently a halogen atom or an alkyl group having 1 to 3 carbon atoms;
The compound according to claim 23, wherein ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, and p is 2 or 3. 25. 4- (3- (2,6-dichloro-4-)
(3,3-Dichloro-2-propenyloxy) phenoxy) propyloxy) benzoic acid 26. 3- (3- (2,6-dichloro-4-
(3,3-Dichloro-2-propenyloxy) phenoxy) propyloxy) benzoic acid 27. 2- (3- (2,6-dichloro-4-)
(3,3-Dichloro-2-propenyloxy) phenoxy) propyloxy) benzoic acid 28. 3,5-Dichloro-4- (4- (4-aminophenoxy) butyloxy) -1- (3,3-dichloro-2-propenyloxy) benzene