WO2002002515A1 - Hydrazone derivatives effective in pest control or salts thereof - Google Patents

Abstract

Compounds useful in pest control, represented by the general formula [I] wherein A, B and C are each hydrogen, halogeno, trifluoro- methylsulfonyloxy, alkyl, alkylthioalkyl, or the like; X is a single bond, methylene, ethylene, or the like;R?1 and R2¿ are each hydrogen, alkyl, an aldehyde group, alkylcarbonyl, alkoxycarbonyl, or the like; R3 is hydrogen, hydroxyl, alkyl, alkoxy, alkylcarbonyl, or the like; and l, m and n are each an integer of 1 to 5, or the like.

Description

 Description Hydrazone derivative or salt thereof effective in controlling pests

 The present invention relates to a hydrazone derivative or a salt thereof, a production intermediate thereof, and a use thereof. Background art

 Conventionally, various pesticides such as insecticides have been studied. For example, Japanese Patent Application Laid-Open No. 6-157444 discloses a pesticidal agent using a hydrazone derivative. However, the hydrazone derivative disclosed in this publication has one phenyl group at the 2-position of the hydrazone group. Not. Disclosure of the invention

 The present invention provides a novel hydrazone derivative having a chemical structure different from that of a conventionally known hydrazone derivative and having a pesticidal activity, a salt thereof, an intermediate thereof, and a method for producing the hydrazone derivative or a salt thereof. It is intended for.

 Means for Solving the Problems The present inventors have studied and investigated a conventionally known compound and intensively studied to find a compound having excellent insecticidal activity. As a result, the hydrazone derivative represented by the following formula [I] or a salt thereof has excellent insecticidal activity. Have been found, and have led to the present invention.

That is, the present invention relates to the following inventions. 1. A hydrazone derivative represented by the following formula [I] or a salt thereof.

[I]

[Wherein, A, B and C may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, Alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, Arylthio, heteroarylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkenylsulfinyl, arylsulfinyl, heteroarylsulfinyl Group, Archi Sulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynyl Carbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkoxycarbonyloxy, alkenyloxy Carbonyloxy group, alkynyloxycarbonyloxy group, cycloalkyloxycarbonyloxy group, cycloalkenyloxycarbonyloxy group, aryloxycarbonyloxy group, heteroaryloxycarbonyloxy group, 0S0 _Two , nitro or cyano groups, and when A, B or C is present in plurals, they may be the same or different,

X represents a single bond, or — {CR ⁴ (R ⁵ )} _p — or one C (R ⁴ ) = C (R ⁵ ), and R ¹ and R ² are the same or different Hydrogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heteroaryl group, aldehyde group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, hetero § reel carbonyl group, an alkoxy force carbonyl group, § reel O alkoxycarbonyl group, a hetero § reel O alkoxycarbonyl group, C (= 0) N ( R 8) (R 9) group, C (secondary 0) C (= 0) R ⁶ group, S 0 ₂ R ⁷ group, or R ¹ and ^ together form two C (R ¹⁰ ) N (R ¹¹ ) (R ¹² ) Well,

R ³ , R \ and R ⁵ may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a heteroaryl group. , Alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylcarbonyl, cycloalkylcarbonyl, aryl Carbonyl group, heteroarylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, heteroarylarylcarbonyl group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group , Aryloki It represents Cal Boniruokishi group, hetero § reel O alkoxycarbonyl O alkoxy group, a nitro group, or a sheet § cyano group,

Is a hydrogen atom, alkyl group, cycloalkyl group, aryl group, heteroaryl , An alkoxy group, an aryloxy group, a heteroaryloxy group, or an N (R ⁸ ) (R ⁹ ) group,

R ⁷ represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group;

R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a heteroaryl group;

R ¹⁰ _N R ^u and R ¹² may be the same or different and represent a hydrogen atom or an alkyl group;

 1, m and n represent numbers from 1 to 5, and

 P represents a number from 0 to 2. ]

2. Intermediate compound represented by the following formula [ΙΓ].

[Ι Ί

[Wherein A, B 'and C' may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group Alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkene Lucio, arylthio, heteroaryl Monothiol, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkenylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkylsulfonyl, alkenylsulfonyl , Alkynylsulfonyl, cycloalkylsulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkyl Carbonyloxy group, cycloalkenylcarbonyloxy group, arylcarbonylcarbonyl group, heteroarylcarbonylcarbonyl group, alkoxycarbonyloxy group,

Alkenyloxycarbonyloxy, alkynyloxycarbonyloxy, cycloalkyloxycarbonyloxy, cycloalkenyloxycarbonyloxy, aryloxycarbonyloxy, heteroarylcarbonylcarbonyl group, 0s0 ₂ R ⁷ group, a nitro group or a Shiano group, a ', B, and C' one at least of the with the proviso that it has as a substituent a Torifuruorome evening down sulfonyl O alkoxy group, further When multiple A ', B' or C 'are present, they may be the same or different,

X is a single bond or represents one {C (R ⁴ ) (R ⁵ )} _p — or — C (R ⁴ ) = C (R ⁵ ),

R ³ 's R \ and R ⁵ may be the same or different and include a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkyninole group, a cycloalkyl group, a cycloalkenyl group, and an aryl group. Group, heteroaryl group, alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkyloxy group, cycloalkenyloxy group, aryloxy group, heteroaryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group,

Arylcarbonyl group, heteroarylcarbonyl group, alkylcarbonyl Si, cycloalkylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkoxycarbonyloxy, cycloalkyloxycarbonyloxy, aryloxycarbonyloxy, heteroaryl Represents a carbonyloxy group, a nitro group, or a cyano group,

R ⁷ represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group;

 1, m and n represent numbers from 1 to 5, and

 p represents a number from 0 to 2. ]

3. The following equation [11],

 [I]

[Wherein, A, B and C may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, Alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, Arylthio, heteroarylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfiel, cycloalkenylsulfinyl , Arylsulfinyl, heteroarylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroaryl Rusulfonyl group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, cycloalkylcarbonyloxy group, cycloalkenylcarbonyloxy group,

Arylcarbonylcarbonyl, heteroarylcarbonyloxy, alkoxycarbonylcarbonyl, alkenyloxycarbonyloxy, alkynyloxycarbonyloxy, cycloalkyloxycarbonyloxy, cycloalkenyloxy carbonyl O alkoxy group, § reel O alkoxycarbonyl O alkoxy group, Heteroa reel O alkoxycarbonyl O alkoxy group, 0s0 ₂ R ⁷ group, a nitro group or a Shiano group, further in the case where B or C there are a plurality of each of , They can be the same or different

X is a single bond, or represents — {C (R ⁴ ) (R ⁵ )} _p — or — C (R ⁴ ) = C (R ⁵ ) —

R ³ , R \ and R ⁵ may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a heteroaryl group. , An alkoxy group, an alkenyloxy group, an alkynyloxy group, a cycloalkyloxy group, a cycloalkenyloxy group, an aryloxy group, a heteroaryloxy group, an alkylcarbonyl group, a cycloalkylcarbonyl group,

Arylcarbonyl group, heteroarylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, heteroarylcarbonyloxy group, alkoxycarbonyloxy group, cycloalkyl Roxycarbonyloxy, aryloxycarbonyloxy, heteroaryl Represents a carbonyloxy group, a nitro group, or a cyano group; represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group;

 1, m and n represent numbers from 1 to 5, and

 p represents a number from 0 to 2. ] And a compound represented by

The following formula [ΠΙ],

R 2

 [III]

[Wherein R ¹ and R ² may be the same or different, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a heteroaryl group. , Aldehyde group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, C (= 0) N (R ⁸ ) (R ⁹ ) group, C (= 0) C (20) R ⁶ group, S0 ₂ R ⁷ group, or R ¹ and R ² are linked to form 2 C (R ^{1 0} ) N (R ^{1 1} ) (R ^{1 2} )

R ⁶ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or N (R ⁸ )

(R ⁹ ) represents a group,

R ⁷ represents an alkoxy group, a cycloalkyl group, an aryl group, or a heteroaryl group; ^ And may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a heteroaryl group;

Β and R ¹² may be the same or different and represent a hydrogen atom or an alkyl group. A method for producing a hydrazone derivative represented by the formula [I], characterized by reacting a compound represented by the formula [I] with or without a catalyst.

4. The following formula [IV:],

[IV]

[Wherein, A, B and C may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, Alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenyl Thiol, arylthio, heteroarylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkenylsulfinyl, arylsulfinyl, heteroarylsulfinyl Group, Archi Sul Honiru group, § Luque sulfonyl sulfonyl group, alkynyl-sulfonyl group, a cycloalkyl Sulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyl A xyl group,

Arylcarbonylcarbonyl, heteroarylcarbonyloxy, alkoxycarbonylcarbonyl, alkenyloxycarbonyloxy, alkynyloxycarbonyloxy, cycloalkyloxycarbonyloxy, cycloalkenyloxy carbonyl O alkoxy group, § reel O alkoxycarbonyl O alkoxy group, Heteroa reel O alkoxycarbonyl O alkoxy group, 0s0 ₂ R ⁷ group, a nitro group or a Shiano group, further in the case where B or C there are a plurality of each of , They may be the same or different

X is a single bond, or —C (R ⁴ ) (R ⁵ )} _p —or—C (R ⁴ ) = C (R ⁵ ), and

R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an aldehyde group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an arylcarbonyl group , Heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, C (= 0) N (R ⁸ ) (R ^s ), C (= 0) C ( = 0) represents R ⁶ group, or S0 ₂ R ⁷ group,

R ³ , R \ and R ⁵ may be the same or different, and include a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group. , Heteroaryl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylcarbonyl, cycloalkylcarbonyl, aryl Carbonyl group, heteroarylcarbonyl Group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonylcarbonyl group, heteroarylcarbonylcarbonyl group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group Group, heteroaryloxycarbonyloxy group, nitro group, or cyano group,

R ⁶ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or an N (R ⁸ ) (R ⁹ ) group. Represent

R ⁷ represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group;

And ⁹ may be the same or different, and represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a heteroaryl group;

R ¹⁰ R ⁿ _s and R ^12, same with or may be different, represent a hydrogen atom, an alkyl group,

 1, m and n represent numbers from 1 to 5, and

 P represents a number from 0 to 2. ] And a compound represented by

The following equation [V] ヽ

R ^13- Z [V]

[Wherein, R ¹³ represents an aldehyde group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heteroaryloxy group. Carbonyl group, C (

R ⁷ , R ⁸ and R ⁹ represent the same meaning as described above. Wherein the compound represented by the formula [VI] is reacted in the presence of a base.

[VI]

[Wherein, A, B, C, X, \ R ³ , R ¹³ , 1, m and n represent the same meaning as described above. ] The manufacturing method of the hydrazone derivative represented by these.

5. The compound represented by the formula [IV] described in 4 above, and the following formula [VII],

R ^{1 4} Y [VII]

[In the formula, R ¹⁴ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a heteroaryl group, and Y represents a leaving group. A compound represented by the following formula [VIII]:

[

[Wherein, A, B, C, X, R ¹ , R ³ _N R ¹⁴ , 1, m and n represent the same meaning as described above. ] The manufacturing method of the hydrazone derivative represented by these.

6. In the compound represented by the formula [IV] described in the above 4, wherein R ¹ is a hydrogen atom, a compound represented by the following formula [IX],

 [K]

[Wherein, R ¹⁵ represents an alkyl group, and R ^1D , R ¹¹ and R ¹² represent the same meaning as described above. ] The compound represented by the following formula [X],

Three

[X]

Wherein, A, B, CX, R 3, R 1D, R u, R 12, 1, m and n are, to display the same meanings as described above. ] The manufacturing method of the hydrazone derivative represented by these. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail.

 In the present specification, the meaning of each functional group shown in the formula is as follows. The halogen atom means, for example, a fluorine atom, a chlorine atom, a bromine atom and the like. The alkyl group may be linear or branched. Examples of the alkyl group include those having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Preferred examples of such an alkyl group include a methyl group, an ethyl group, an isopropyl group, a butyl group and an isobutyl group. The alkyl group may have a substituent.

Examples of such a substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a cycloalkylcarbonyl group, and a cycloalkenylcarbonyl group. , Arylcarbonyl, heteroarylcarbonyl, alkylcarbo Niloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, cycloalkylcarbonyloxy group, cycloalkenylcarbonyloxy group, arylcarbonylcarbonyl group,

Heteroarylcarbonyloxy, alkoxycarbonyloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, arylaryl, heteroarylthio, alkylsulfinyl, Alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkenylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, Cycloalkenyl sulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, acyl group, amino group, imino group, isocyano group, thionyl group, sulfonic acid group, sulfonyl group Two Norre group, an alkylsulfonyl group, a phosphonyl group, a phosphinyl group, an alkoxy group, § Li one group, cycloalkyl group, cycloalkenyl group, Heteroariru group, etc. can be mentioned, et al are. Examples of the substituent of the alkyl group include a halogen atom, an alkylthio group, an alkenylthio group, an alkynylthio group, a cycloalkylthio group, a cycloalkenylthio group,

Arylthio, heteroarylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkenylsulfinyl, arylsulfiel, heteroarylsulfinyl, alkylsulfonyl, alkenylsulfonyl And alkynylsulfonyl, cycloalkylsulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroarylsulfonyl and the like. In particular, examples of the substituent of the alkyl group include a halogen atom, an alkylthio group having a halogen-substituted alkyl group, an alkylsulfinyl group, and an alkylsulfonyl group. No. Examples of the halogen-substituted alkyl group include, for example, trifluoromethyl group, difluorobromomethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group and the like. Are preferred.

 The alkenyl group may be linear or branched, and for example, an alkenyl group having 2 to 10, preferably 2 to 5 carbon atoms is suitable. Examples of such an alkenyl group include a vinyl group, an aryl group, a 1-methyl-2-propenyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, and a 3-methyl-2 group. —Alkenyl groups such as butenyl group. The alkenyl group may have a substituent. As such a substituent, the substituent in the case of an alkyl group can be similarly used. The alkynyl group may be straight-chain or branched, for example, an alkynyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms. For example, an ethynyl group, a propargyl group, a 1-methyl-1-propynyl group Alkynyl groups such as 1,2-butynyl group and the like can be preferably mentioned. As the alkynyl group, a substituent in the case of an alkyl group can be suitably used as the substituent.

 The cycloalkyl group is a cyclic alkyl group, and examples thereof include a cycloalkyl group having 3 to 10, preferably 3 to 6, carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. The cycloalkyl group may have a substituent. As such a substituent, for example, a substituent in an alkyl group can be similarly used.

 The cycloalkenyl group is a group having an unsaturated bond corresponding to the cycloalkyl group, and includes, for example, a cycloalkenyl group having 5 to 10 carbon atoms, preferably 5 to 6 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group. And the like. The cycloalkenyl group may have a substituent. As such a substituent, for example, a substituent in an alkyl group can be similarly used.

The aryl group is a phenyl group, a naphthyl group, a naphthyl group, etc. -10 groups, preferably a phenyl group, which may have a substituent. The range of the substituent is the same as in the case of the alkyl group.

 The heteroaryl group is a heterocyclic compound containing oxygen, nitrogen, sulfur, and the like, and is a furyl group, a thienyl group, a thiazolyl group, an oxazolyl group, an isoxazolyl group, an oxaziazole group, a pyridyl group, a pyrimidinyl group, or an imidazolyl group. Quinolinyl group, triazolyl group and the like. Such groups include, for example, 2-furyl, 2-phenyl,

 2-oxazolyl group, 3-isoxazolyl group, 1,2,3-oxaziazol-14-yl group, 2-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 3-virazolyl group, 2- For example, a thiazolyl group, a 2-imidazolyl group, a 3- (1,2,4-triazolyl) group, a 2-quinolinyl group, etc., having 1 to 9 carbon atoms, preferably 1 to 5 heteroaryl groups No. The heteroaryl group may have a substituent, and its range is the same as that of the alkyl group.

 Alkyl group, alkenyloxy group, alkynyloxy group, cycloalkyloxy group, cycloalkenyloxy group, aryloxy group, heteroaryloxy group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkyl group The range of the alkenyl group, aryl group, heteroaryl group and the like is as described above. For example, as the alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, an i-butoxy group, and a t-butoxy group are preferably exemplified. Preferable examples of the aryloxy group include a phenoxy group and an aryloxy group such as —naphthyloxy group and —naphthyloxy group.

Examples of the heteroaryloxy group include a 2-furyloxy group, a 2-phenyloxy group, a 2-oxazolyloxy group, a 3-isooxazolyloxy group, and a 1,2,3-oxadiazo group. Lou 4-yloxy, 2-pyridyloxy, 4-pi Lysyloxy group, 2-pyrimidinyloxy group, 4-pyrimidinyloxy group, 3-pyrazolyloxy group, 2-thiazolyloxy group, 2-imidazolyloxy group, 3- (1,2,4-triazolyl) oxy group, A heteroaryl group such as a 2-quinolinyloxy group is preferred.

 Alkyl groups, alkenylthio groups, alkynylthio groups, cycloalkylthio groups, cycloalkenylthio groups, arylthio groups, heteroarylthio groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups The cycloalkenyl group, aryl group, heteroaryl group and the like are as described above. For example, the alkylthio group preferably includes, for example, a methylthio group, an alkylthio group such as an ethylthio group and an isopropylthio group.

 Alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group, cycloalkylcarbonyl group, cycloalkenylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group The ranges of the aryl group and the heteroaryl group are as described above. For example, preferred examples of the alkylcarbonyl group include, for example, an alkylcarbonyl group such as a methylcarbonyl group, an ethylcarbonyl group, and a propylcarbonyl group. Examples of the cycloalkylcarbonyl group include a cyclopropylcarbonyl group, a cycloalkylcarbonyl group such as a cyclopentylcarbonyl group and a cyclohexylcarbonyl group. The arylcarbonyl group preferably includes, for example, a phenylcarbonyl group, a naphthylcarbonyl group, a naphthylcarbonyl group and the like.

Alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyl The range of the alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the cycloalkenyl group, the aryl group and the heteroaryl group in the silyl group is as described above. For example, alkylcarbonyloxy groups include, for example, methylcarbonyloxy group,

Preferable examples include an alkylcarboxy group such as an ethylcarbonyloxy group and a propylcarbonyloxy group. Examples of the cycloalkylcarbonyloxy group include a cycloalkylcarbonyloxy group, a cycloalkylcarbonyloxy group such as a cyclopentylcarbonyloxy group and a cyclohexylcarbonyloxy group. Examples of the arylcarbonyl group include a phenylcarbonyloxy group, a mononaphthylcarbonyloxy group, and a naphthylcarbonyloxy group. Examples of the heteroarylcarbonyloxy group include a pyridylcarbonyl group. And the like.

 An alkyl group in an alkoxycarbonyl group, an alkenyloxycarbonyl group, an alkynyloxycarbonyl group, a cycloalkyloxycarbonyl group, a cycloalkenyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, etc. , Alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group and heteroaryl group are as described above. For example, as the alkoxycarbonyl group, a methoxycarbonyl group, an alkoxycarbonyl group such as an ethoxycarbonyl group, a t-butoxycarbonyl group and the like are preferably exemplified.

Alkyl groups such as alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, cycloalkylcarbonyloxy group, cycloalkenylcarbonyloxy group, arylcarbonylcarbonyl group, heteroarylcarbonyloxy group, etc. , Alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, etc. It is. The range of the alkyl group and the cycloalkyl group in the alkoxycarbonyloxy group, the cycloalkoxycarbonyloxy group and the like is the same as described above.

In OS 0 ₂ R ⁷ group, R ⁷ is an alkyl group, a cycloalkyl group, Ariru or heteroaryl group, these ranges are as described above. In addition, these groups may have a substituent, and the range is as described above. As the substituent, an alkyl group is suitable, and preferably, an alkyl group substituted with a halogen atom such as a fluorine atom is mentioned.

 The leaving group is not particularly limited as long as it is a group that leaves during the reaction, and various known leaving groups can be used. As such a leaving group, for example, a halogen atom or a functional group such as a P-toluenesulfonyloxy group can be preferably exemplified.

 A, B and C are preferably a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group (eg, a halogenated alkyl group such as trifluoromethyl), a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group (Eg, methylthio group), alkylsulfinyl group (eg, methylsulfinyl group), alkylsulfonyl group (eg, methylsulfonyl group), heteroaryloxy group, alkylcarbonyloxy group, arylyl group Carbonyloxy group, heteroarylcarbonyloxy group, alkoxycarbonyloxy group, alkenyloxy group carbonyloxy group,

Alkynyl O alkoxycarbonyl O alkoxy group, a cycloalkyl O alkoxycarbonyl O alkoxy group, a cycloalkenyl O alkoxycarbonyl O alkoxy group, § reel O alkoxycarbonyl O alkoxy group, a hetero § reel O alkoxycarbonyl O alkoxy group, OS 0 ₂ R ⁷ Groups (for example, a trifluoromethylsulfonyloxy group, a methylsulfonyloxy group, etc.), a nitro group, and a cyano group can be preferably exemplified.

R ¹ and R ² are, for example, a hydrogen atom, an alkyl group (eg, a methyl group or an isopropyl group), an alkenyl group, an alkylcarbonyl group (eg, a methyl group). Preferred examples thereof include an alkoxycarbonyl group, an alkoxycarbonyloxy group (eg, a methoxycarbonyloxy group), a C (= 0) N (R ⁸ ) group, and the like.

 The compound of the present invention has a geometric isomer based on a double bond (E, Z), an optical isomer based on an asymmetric carbon (R, S), and a geometric isomer based on a cyclopropane ring (cis, trans). The scope of the compounds of the present invention includes all optical isomers, geometric isomers and mixtures thereof having such insecticidal activity.

The compound of the present invention can be produced, for example, according to the following synthesis scheme. Manufacturing method A

(A),

 [H] [Π] [I]

(Wherein, RR ² _S \ A, B, C, X, 1, m, and n represent the same meaning as described above.) A compound represented by the formula [II] and a compound represented by the formula [III] Is reacted in the presence of, for example, an inert solvent and in the presence or absence of a catalyst to produce a hydrazone derivative represented by the formula [I].

Reaction A— 1. —General formula [II] → General formula [I]

The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction.Examples include alcohols such as methanol, ethanol, propanol, and toluene, dichloromethane, and chloroform. Halogenated hydrocarbons such as form and carbon tetrachloride, and aromatic carbons such as benzene, toluene, xylene, and benzene Hydrides, nitriles such as acetonitrile ゃ, benzonitrile, etc., methylcellulose solvent ゃ, ethers such as dimethyl ether, diglyme, dioxane, tetrahydrofuran, etc., carboxylic acids such as acetic acid, dimethylacetamide, dimethyl Examples include sulfoxide and water. These inert solvents may be used alone or as a mixture.

 Examples of the catalyst used in this reaction include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as paratoluenesulfonic acid, boron trifluoride-ether complex, Lewis acids such as tetrachlorosilane, and bilizine hydrochloride. And acid addition salts of amines such as triethylamine hydrochloride. The amount of the catalyst used may be, for example, 0.01 to 10 mol, preferably 0.1 to 1 mol, based on the compound represented by the formula [Π] in the reaction system. Since this reaction is an equimolar reaction, each reactant may be used in an equimolar amount. However, any of the reactants may be used in excess.

 The reaction temperature may be appropriately selected, for example, from room temperature to the boiling point range of the inert solvent to be used. The reaction time varies depending on the reaction amount, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours. After the completion of the reaction, the target product is produced from the reaction solution containing the target product by a conventional method, for example, solvent distillation, solvent extraction, etc., and if necessary, purification by recrystallization, column chromatography, etc. be able to.

[IV] [V] [VI] (Wherein, II ¹ , R ³ , R ¹³ , A, B, C, X, 1, 1, m, and n represent the same meaning as described above.) A compound represented by the formula [IV]: By reacting the compound represented by [V] with or in the presence of an inert solvent, and in the presence of a base,

A hydrazone derivative represented by [VI] can be produced.

Reaction B— 1. General formula [IV] General formula [VI]

In this reaction, a solvent is not necessarily required, but it is generally preferable to carry out the reaction in an inert solvent.When a solvent is used, it depends on X and the type of base used. Aromatic hydrocarbons such as benzene, toluene, xylene, chlorbenzene, dichlorobenzene, pyridines such as pyridine and picoline, chloroform, carbon tetrachloride, 1,2-dichlorobenzene And other hydrocarbons, aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane, and alcohols such as methanol, ethanol and isopropanol. , N, N-dimethylformamide ゃ, dimethylsulfoxide, etc., non-protonic poles II, biosolvent, tetrahydrofuran ゃ, ethers such as Like or a mixed solvent thereof are used. Bases that can be used in this reaction include, for example, triethylamine, organic bases such as pyridine, 4-N, N-dimethylaminopyridine, N, N-getylaniline, sodium hydride, sodium hydroxide, and potassium carbonate. And inorganic metal bases, such as butyllithium and lithium diisopropylamide. The amount of the base used in this reaction is usually 1 to 10 mol, preferably 1 to 1.5 mol, based on the compound represented by the formula [IV], and the compound represented by the formula [V] The compound represented by the formula is usually 5 to 50 mol, preferably 0.8 to 10 mol. The reaction temperature is, for example, 120 to 200 ° C., preferably 0 to 15 ° C., and the reaction time is usually several minutes to 100 hours. After completion of the reaction, the reaction solution containing the target compound is subjected to a conventional method, for example, solvent distillation or solvent extraction, and then, if necessary, recrystallization or column chromatography. -The desired product can be produced by purification by a method or the like.

 [IV] [顶] [VI]

(Wherein, R ³ , R ^M , A, B, C, X, Y, 1, m, and n represent the same meaning as described above.) A compound represented by the formula [IV] and a compound represented by the formula [VI I Hydrazone derivative represented by the formula [VI II] can be produced by reacting a compound represented by the formula [VI II] with or in the presence of an inert solvent and in the presence of a base. c Reaction C— 1. General formula [IV] "—General formula [VI II]

In this reaction, a solvent is not necessarily required, but it is generally preferable to carry out the reaction in an inert solvent.When a solvent is used, it depends on the type of base, but generally, for example, benzene, toluene, Aromatic hydrocarbons such as xylene, chlorobenzene, and dichlorobenzene; pyridines such as pyridine and picoline; halogenated hydrocarbons such as chloroform, carbon tetrachloride and 1,2-dichlorobenzene; n- Hexane, aliphatic hydrocarbons such as n-heptane, aliphatic hydrocarbons such as cyclohexane, non-protonic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, Ethers such as getyl ether, water and the like, or a mixed solvent thereof are used. Bases that can be used in this reaction include, for example, organic bases such as triethylamine ピ リ ジ ン, pyridine, 4-N, N-dimethylaminopyridine, N, N-getylaniline, sodium hydride, and sodium hydroxide. Preferable examples include inorganic bases such as thorium and carbon dioxide, and organic metal bases such as butyllithium and lithium diisopropylamide. The amount of the base used in this reaction is usually 1 to 100 mol, preferably 1 to mol, relative to the compound represented by the formula [IV], and is represented by the formula [VI I]. Compounds are usually

The ratio is 0.5 to 100 mol, preferably 0.8 to 10 mol. The reaction temperature is, for example, −78 to 200 ° C., preferably 0 to 150 ° C., and the reaction time is usually several minutes to 100 hours. After completion of the reaction, the target product is purified from the reaction solution containing the target product by a conventional method, for example, solvent distillation or solvent extraction, and if necessary, purified by a recrystallization method, column chromatography, or the like. Can be manufactured. Manufacturing method D

 [W] [K] [X]

(In the formula, R ¹ represents a hydrogen ^{atom, R 3, R 10 R n} s A, B, C, X, 1, m and n are as defined above.)

 By reacting the compound represented by the formula [IV] with the compound represented by the formula [IX] in the presence or absence of an inert solvent, for example, the hydrazone represented by the formula [X] is obtained. Derivatives can be produced.

Reaction D— 1. Formula [IX] "Formula [X]

In this reaction, a solvent is not always necessary, but if a solvent is used, In general, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; halogenated hydrocarbons such as chloroform and carbon tetrachloride and 1,2-dichlorobenzene. And ethers such as tetrahydrofuran and dioxane, or a mixed solvent thereof. The amount of the formula [IX] used in this reaction is usually 0.9 to 100 mol, preferably 1 to 10 mol, relative to the compound represented by the formula [IV]. The reaction temperature is, for example, 0 to 200 ° C., preferably 0 to 150 ° C .; when a solvent is used, it is up to the boiling point of the solvent. The reaction time is usually several minutes to 100 ° C. Time. After the completion of the reaction, the target compound is purified from the reaction solution containing the target compound by a conventional method, for example, solvent distillation or solvent extraction, and if necessary, purified by recrystallization, column chromatography, or the like. Can be manufactured.

 The hydrazone derivative of the present invention may be in the form of a hydrochloride, a bromate, a sulfate, or a salt of an alkali metal such as sodium or potassium.

 Preferred compounds of the present invention are shown in Tables 1 and 2 below. However, the scope of the compounds of the present invention is not limited at all by the compounds exemplified below. In Tables 1 and 2, Ph represents a phenyl group, and Py represents a pyridyl group. In addition, n- means normal, i- means iso-1, s- means secondary 11, t-1 means Yuichi Shari 11, and c-1 means cyclo.

(In the compound represented by the formula [I], when is a single bond and p is 0)

ϋ

<〇 GQ CL XXX X X

or

 X X X X X X X X X Q.

 00 o CM CO Dimension ID CD 00

CM CO dimensions LO (D

 2 7

Replacement form (Rule 26) 瑯 λ

to

Pork

_{41 H C0 2 C 2 H 5} Η 4-CI 4-CI 4-N0 2

42 H CO5 2H5 Η 4-CI 4-CI 4-CF ₃ Glassy

43 H G 2C2H5 Η 4-CI -CH3

44 H Η 4— Cl 4−1 Gl 4— OH

45 H 0〇2 οΗ Η 4-CI 4-CI 4-0C ₃ H ₇ — n vitreous

46 H CO2C2 ΓΊ ^ Η 4— ci 4-CI 4- OCF3 Glassy

47 H GO Η 4-CI 4-CI 4— 0CBrF ₂

48 H. Two. Η 4— CI 4-CI 4-0Ph

49 H Η 4-CI 4-CI 4-θΗλ /> — CF ₃

50 H GO2 2H5 Η 4-CI 4— CI

51 H GO, Η 4— Gl 4— CI 4-. > -CF ₃

52 H Cw ₂ C ₂ H ₅ Η 4-CI 4-CI -0- -CF ₃

 53 H then O2. Η 4-CI 4-CI 4-OCOCHg

 54 H then O2 H Η 4-CI 4-CI 4-OCO CH

Η 4-CI 4— CI 4— OCONHEt 55 H

Η 4-CI 4— CI 4— OCONHEt

56 H Η 4-CI 4-CI 4-SCH ₃ Glassy

57. H and O2 Η Dimensions 4-SOCH3 Glassy

58 H Η 4— δ ϋ G ϋl 4-CI 4— SO _z CH ₃ Glassy

59 H Η 4-CI 4— CI 4— SCF ₃ glassy

60 H Sushi 2 Η 4 1 Gl 4-CI Glassy

61 H Η 4— CI 4— CI H Glassy dimensions

o

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Dimensions £ K X X X X X X X X X X X X

X X X X X X X X X X X X X X X

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Dimension

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Dimensions h-ooHowoo _w ^ "

x x X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

2 9

Replacement paper (β26) ϋ

 Factory

 Dimension

 Dimensions

O

 Dimension

E

 X X X X X X X X X 3: X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X

(M 00 size 10 CD 00 ύ)

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CO Dimension Dimension Dimension

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x X X X X X X X X X X X X X X

0 CL ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ CL

X X X X X X X X X X X X

 31/1

Replacement form (Rule 26)

(In the compound represented by the formula [I], is one of {C (R ⁴ ) (R ⁵ )} _p — (where p is 1 or 2) or one C (R ⁴ ) = C ( R ⁵ ) —

Table 2

ε ε

 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

 IS COH OCQ

O 2 {() CH3oco0 CPH 0〇S〇 =

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SSS0 / T0df / I3d SIS 0 OAV Os ϋ.

Dimension

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X X X X X X X X X X X X X

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() ί0〇H

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xx XX XX XX XX X XX XX XX

X X X X X X D X X X X X X X X

3 4

Replacement form (Rule 26) ¾ ろ 撇 i ；

330 CH ₃ C (= 0) CH ₃ H CH0CH2 H 4— CI 4— OS0 ₂ CF ₃

331 G ₂ H ₅ C (= 0) CH ₃ H CH0CH H 4-CI 4— OS0 ₂ CF ₃

332 = C (CH ₃ ) N (CH ₃ ) CH ₃ H CH0CH2 H 4—C! 4—OS0 ₂ CF ₃

333 = C (C ₂ H ₅ ) N (CH ₃ ) CH ₃ H CH CH2 H 4— CI 4— OS0 ₂ CF ₃

_{334 = C (CH 3) N} (CH 3) HH CH ^ and [ "" Ig H 4- CI 4- OS0 2 CF 3

335 H GO H CH = CH H 4-0S0 ₂ CF ₃

336 HC (= 0) HH CH = CH H 4— CI 4-OS0 ₂ CF ₃

337.CH ₃ C (= 0) HH CH = CH H 4 CI 4-0S0 ₂ CF ₃

338 C (= 0) HC (= 0) HH CH = CH H 4-OS0 ₂ CF ₃

O 339 C (= 0) CH ₃ C (= 0) HH CH = CH H 4-CI 4-OS0 ₂ CF ₃

340 C (= 0) CH ₃ G (= 0) GH ₃ H CH = GH H 4-CI 4-0S0 ₂ CF ₃

341 HC (= 0) CH ₃ H CH = CH H 4— CI 4-OS0 ₂ CF ₃

342 CH ₃ G (= 0) CH ₃ H CH = GH. H 4— CI 4-OS0 ₂ CF ₃

343 G ₂ H ₅ C (= 0) CH ₃ H CH = CH H 4-OS0 ₂ CF ₃

344 = C (CH ₃ ) N (CH ₃ ) CH ₃ H CH = CH H 4-01 4-0S0 ₂ CF ₃

345 = C (C ₂ H ₅ ) N (CH ₃ ) CH ₃ H GH = CH H 4-GI 4-OS0 ₂ CF ₃

346 = C (CH ₃ ) N (CH ₃ ) HH CH = CH H 4-CI 4— OS0 ₂ CF ₃

347 H 〇0 C2H5 H CH ₂ HH 4-0S0 ₂ CF ₃ viscous material

348 H G09C2H5 H CH ₂ 4-CI 4-CI 4— OS0 ₂ CF ₃ viscous material

349 H GO. H CHF 4-CI, 4-0S0 ₂ CF ₃

350 H GO ^ H H CHCI 4-CI 4— CI 4-0S0 ₂ GF ₃

Dimension

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3 5

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X X X X X X X X

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X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

3 7

Replacement paper («126) Dimensions

 Dimension

I

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X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

3 7/1

Replacement form (Rule 26)

3 8

.Replacement paper (Regulation B126) ¾

CO

 00

 The compound represented by the formula [I], which is a starting material for producing the hydrazone derivative represented by the formula [I] of the present invention, is available on the market. It can also be manufactured by the illustrated manufacturing method.

Dimensions Dimensions Dimensions Dimensions

ϋ OO ϋ O

[X I] [Π] EH]

(Wherein, A, B, C, X, 1, m, and n represent the same meaning as described above, represents a hydrogen atom, Q represents a CN group, or a C (= 0) G group, and G represents , A chlorine atom, a bromine atom or an OR ¹⁶ group, and R ¹⁶ represents a lower alkyl group having preferably 1 to 3 carbon atoms, such as a methyl group or an ethyl group.)

 A benzophenone represented by the formula [XI] and a compound represented by the general formula [XI I] are mixed in a suitable solvent such as tetrahydrofuran at 0 ° C. to a reflux temperature, preferably at room temperature. By reacting in the presence of low-valent titanium, a raw material conjugate represented by the general formula [II] can be produced. General description of this production method is described in, for example, Tetrahedron Letters, Vol. 34, No. 18, pp. 2963-2964, 1993 and Te trahedron Letters, Vol. 34, No. 10, pp. 1617-1620, 1993. And referred to herein.

 The pest controlling agent containing the compound of the present invention represented by the above formula [I] effectively acts on, for example, the following pests.

Lepidopteran pests:

Spodopteras such as Lotus Snapper (^ podqptera litura), Apodum (Pseudalitia separata), and Spodoptera (Mamestra brassicae); Agatis such as Agrotis ipsilon, Trichopulcia, Heliotis, Helikoberpa, Nikameiga

(Chilo su £ pressalis) Betula, (Cnaphalocrocis medinalis),

3 9 'Baud error (Ostrinia nubilalis), Shibadzutoga (Parapediasia teterrel la) _s Wa evening Nomeiga (Notarcha derogata), Pyralidae such as Indian meal moth (Plodia interp unctella), white butterfly such as cabbage butterfly (Pieris rapae crucivora), Adokizofiesu genus , Pear moths such as Graphholita molesta and Cydia pomonella, Singing moths such as peach moth (Carpo sina niponensis), Leaf moth moths such as genus Rionetia, and Doga moths such as genus Limantria and X-proctis, Plutella xyloste 11a) Which stags, stag beetles (Pectinophora gossypiella), stag beetles (Hyphantriacunea), squirrels (Tinea trans lucens), and squirrels (Tineola bisselliella).

Hemiptera:

Pink mosquitoes, such as the brown beetle (Laodelphax striatellus), brown beetle (Nilaparvata lug ens), and white-lung beetle (Sogatella furcifera), Nephotettix cincticeps) , Whiteflies, scale insects, hornworms, psyllids, etc.

Diptera pests:

Musca domes, Musca doica House flies such as house flies (Muscina stabulans), blowflies, sarcophagid flies, flies and flies, flies (Delia platura), evening flies (Delia antigua) and other flies, fruit flies, fruit flies, and flies , Flies, flies, flies, etc.

4 0 Coleoptera pests:

Corn rootworms such as Western corn worms (Diabrotica virgifera) and Southern corn root worms (Diabrotica undecimpunctata); Coca worms such as Anomalai; cu¾rea; and Anomala rufocuprea; Bil beetles (Sitophilus zeafflais), rice weevil (Lissorhoptr us oryzophilus), alfalfa weevil (Hyperapastica) ヽ ズ キ キ (C chy Beetles, beetles (Aulacophora femoral is), Leaf beetles (yllotreta striolata), D. beetles (Leptinotarsa decemlineata), etc. Kind, Hirayuki Imushi such, Naga Shinkuimushi such, beetle insects, such as Aobaariga evening Staphylinidae (Paederus fuscipes).

Orthoptera Reptile pests:

Chiapa's cockroach (Blattella germanica) Black cockroach (Periplanetafuligin osa) _s .

Thistle pests:

Thrips palm thrips (Thrips palmi), Negia thrips (Thrips tabaci), and thrips hawaiiensis. Squirrels, hornets, squirrels, and bees

Kera, bats, etc.

4 1 Pteratoid pests:

Human flea (Purex irritans).

Lice pests:

Lice, lice (Phthirus pubis), etc.

Isoptera pests:

The termite (Reticulitermes speratus house termite (Coptotermesformo sanus etc.).

 The compounds of the present invention are also effective against pests that have developed resistance to existing insecticides.

 When the compound of the present invention is used as an active ingredient of an insecticide, it may be used as it is without adding any other components, but usually it is necessary to mix it with a solid carrier, a liquid carrier, a gaseous carrier, rice cake, etc. Add surfactants and other formulation auxiliaries, if any, to formulate oils, emulsions, wettable powders, flowables, granules, powders, aerosols, aerosols (fogging, etc.), poison baits, etc. I do. In these preparations, as an active ingredient, the compound of the present invention is usually used in an amount of 0.01 to 95%, preferably 0.5 to 90% by weight based on the mass of the preparation. Have in quantity.

 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.), talc, ceramics, and other inorganic minerals (cericite and , Quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), and fine powders or granules of chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, salt ammonium, etc.).

 Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methylethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.).

Ethylbenzene, methylnaphthylene, etc.), aliphatic hydrocarbons (hexane, cyclo

4 2 Hexane, kerosene, diesel 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.), dimethyl sulfoxide, soybean oil, cottonseed oil And other vegetable oils.

 Examples of the gaseous carrier, that is, the propellant include Freon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.

 Examples of the surfactant include alkyl sulfates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. No.

 Examples of pharmaceutical adjuvants such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, pentonites, sugars, synthetic water-soluble Polymers (polyvinyl alcohol, polyvinyl pyridone, polyacrylic acids, etc.) and the like.

 Stabilizers include, for example, PAP (isopropyl isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methyl phenol), BHA (2-tert-butyl-14-methoxy phenol and a mixture with tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids or esters thereof, and the like.

 Base materials for poison bait include, for example, bait ingredients such as cereal flour, vegetable oil, sugar, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydroguairetic acid; preservatives such as dehydroacetic acid; and pepper powder. And the like, and inducing flavors such as cheese flavor, onion flavor and the like.

 The product obtained in this way may be used as it is or diluted with water etc.

4 3 it can. It can also be mixed or mixed with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feed, etc. They can be used at the same time.

 The insecticides used can be, for example, organophosphorus and carbamate insecticides, pyrethic insecticides or other insecticides.

 Organophosphorus and carbamate insecticides include, for example, fenthion, dinitrothion, diazinon, chlorpyrifos, oxydepphos, bamidione, fentoate, dimethoate, formotion, malathion, trichlorfon, thiomethone, phosmethate, dichlorfos, dichlorfos, epchlorate, dichlorfos, EP , Oxydimetone methyl, Ethione, Dioxabenzophos, Cyanophos, Isoxathione, Pyridafenthione, Hosalone, Methydathione, Sulprophos, Chlorfenvinphos, Tetrachlorvinphos, Dimethylvinphos, Propaphos, Isofenphos, Disulfoton, Profenophos, Viraclofos Monocrotophos, Azinphos-methyl, Aldicarp, Mesomyl, Thiodicarp ', Cal Furan, Levosulfan, Penfracarb, Fratiocarp, Provoquisul, Fuenocaparu, Metrecarb, Isoprocarb, Levalvalyl, Pirimicab, Etiofencarp, Diclofenthion, Pirimiphosmethyl, Quinalphos, Chinalphos, Chlorphos, Redo, M It can be xamyl, aranicarp or chlorethoxyphos.

 Pyrethroid insecticides include, for example, permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, protrin, fulvalinate, cyflutrin, cyhalothrin, It can be flucitrinate, etfenprox, cycloprothrin, tralomethrin, silafluofen, tefluthrin, bifenthrin or acrinatrine.

4 4 Other insecticides include, for example, difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tefluvenzuron, flufenoxuron, fluci cloxuron, puprofezin, pyriproxyfen, lufenuron, cilomazine, methoprene, endosulfan, Difenthiuron, imidacloprid, fipronil, phenoxycarp, cartap, thiocyclam, bensulfap, tebufenozide, chlorphenavir, emamectin benzoate, acetamiprid, nitembiram, pymetrozine, sodium oleate, nicotine sulfate, rotenone, rotenone It can be a microbial pesticide such as oil, rapeseed oil, BT agents or entomopathogenic viruses.

 Examples of the acaricide to be used include, for example, chlorpenzilate, phenisopromoleate, dicophor, amitraz, propargite, benzomate, hexithiax, fenbuxinthoxide, polynactin, quinomethionate, chlorfenson, tetradihon, abamectin, milbemectin. Clofenentine, pyridapen, fenpyroximate, tebufenvirad, pyrimidifene, phenothocalp, dienochlor, ethoxazole or halfenprox.

 The nematicide used may be, for example, phenamiphos, phosthiazate, etoprofos, methylisothiosinate, 1,3-dichloropropene or DCIP.

 Fungicides used include, for example, thiophanate methyl, benomyl, carbendazole, thiabendazole, forvet, thiuram, ziram, zineb, maneb, manzeb, polybutamate, ipropenphos, ezifenfos, fusaride, Propenazole, isoprothiolane, closanilonil, captan, polyoxin, blasticidin S, kasugamycin, streptomycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil, flutolanil, pencyclon, iprozion, limezion , Metalaxyl,

4 5 Triflumizol, triforine, triadimefon, vitelenol, fenarimol, propiconazole, simoxanil, polochloraz, ぺ furazoleto, hexonaconazole, microbufenil, diclomedine, teclofuram, probineb, dithianon, josecilin, osecloline , Procymidone, oxadixyl, guazatine, propamocarp hydrochloride, fluazinam, oxolinic acid, hydroxysoxazole, imipenconazole or mepanipyrim.

 Herbicides used include, for example, diflufenican, propanil, dichloropicolinic acid, dicampa ', picomouth lamb, 2,4-D, 2,4-DB, 2,4-DP, fluoroxypyr, MCPA, MCPP, Triclopyr, diclohop-methyl, phenoxapropetyl, fluazihop-l-butyl, haloxyfop-methyl, quizalofop-ethyl, norflurazon, chlorbropam, desmedifam, femmedipham, propham, falachlor, acetochlor, bushachlor , Metazachlor, metolachlor, pretilachlor, propachlor, oryzalin, trifluralin, acifluorfen, biphenox, fluoroglygofen, fomesafen, halosafen, lactofen, oxyfluorfen, chlortoren, Diperon, Fluomeron, Isopropron, Linuron, Metapentzthiazulone, Aroxydim, Cletodim, Cycloxydim, Sethoxydim, Tracoxisim, Imaze Even Pill, Imazametavenz, Imazavir, Imazaquin, Promoxinil, Diclozenil, Efonyxonamide, Dixonil Melon Sulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, sinosulfuron, metsulfuron-methyl, nicosulfuron, pyrimisulfuron, bilazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, butylate, cycloethyl , Giarate, EPTC ;, Espro-Lup, Molinate, Prosulfocalp, Benthiocalp, Trialate Atora Jin, cyanazine, simazine, simetryn, evening one Butorin, evening one Puchirajin, to

4 6 Xazidinone, metamitron, metribuzin, amitriazole, benfreset, benfurezone, simmethillin, cromazone, cloviralide, difenzoquat, dichopyr, ethofumeset, fluolochloridone, glufosinate, glyphosate, glyphosate, glyphosate , Kink mouth rack, kinmetac, sulfoset or tridiphane.

 When the compound of the present invention is used as an agricultural pesticide, the application rate is, for example, usually 0.1 g to 5000 g, preferably 10 to 1000 g per 10 ares, It is formulated into emulsions, wettable powders, granules, wettable granules, liquids, and flowables. When using emulsions, wettable powders, flowables, wettable powders, etc. diluted with water, the application concentration is usually 0.1 lppn! Ο Ο ρ Ο ρρρm, preferably 1 to 2000 ppm. Granules, powders, etc. are applied as they are without dilution. When used as an insect repellent for epidemics, emulsions, wettable powders, floor pulls, etc. are usually diluted to 0.1 ppm to 10,000 ppm, preferably 1 to 2000 ppm, and applied. For aerosols, poison baits, etc., apply as is. These application rates and application concentrations differ depending on the type of preparation, application time, application place, application method, type of pest, degree of damage, etc., and may be increased without being affected by the above range. Can be reduced.

 Hereinafter, the present invention will be described in more detail with reference to Examples, Formulation Examples, and Test Examples, but the present invention is not limited thereto. First, examples of the compound of the present invention will be described.

47 Example 1 (Production of intermediate compound number II-6 shown in Table 3 below)

よく乾燥した 100mlのフラスコに粉末状の亜鉛 3. 9 g (6 O mol) と乾 燥テトラヒドロフラン 50mlを加え、 撹拌しながら塩化チタン （IV) 3. 3 m 1 (3 Onmol) を加え、 その混合物を窒素気流下 2時間加熱還流した。 室温に戻 した後、乾燥テトラヒドロフラン 10mlに溶解した 4一クロロー 4，一トリフル ォロメ夕ンスルホニルォキシペンゾフエノン 3. 6g ( 1 Onifflol)と 4—クロ口べ ンゾニトリル 1. 4 g (1 Ommol) を 3時間かけて滴下し、 さらに室温で 3時間 撹拌し、 40時間加熱還流した。反応終了後、テトラヒドロフランを減圧留去し、 希塩酸で処理し、 クロ口ホルムで抽出した。 有機層を飽和食塩水で洗浄、 無水硫 酸マグネシゥムで乾燥し、 溶媒を減圧留去した後、 シリカゲルカラムクロマトグ ラフィ一により分離精製して、 目的物である 4'—クロロー 2— (4—クロ口フエ ニル) —2— (4—トリフルォロメタンスルフォニルォキシフエニル） ァセトフ ェノン 2. 8 gをガラス状物質として得た。

3.9 g (6 O mol) of powdered zinc and 50 ml of dry tetrahydrofuran are added to a well-dried 100 ml flask, and titanium (IV) chloride 3.3 m 1 (3 Onmol) is added with stirring, and the mixture is added. Was refluxed for 2 hours under a nitrogen stream. After returning to room temperature, 3.6 g (1 Onifflol) of 4-chloro-1,4-trifluoromethanesulfonyloxybenzophenone dissolved in 10 ml of dry tetrahydrofuran and 1.4 g (1 Ommol) of 4-chlorobenzonitrile Was added dropwise over 3 hours, further stirred at room temperature for 3 hours, and heated under reflux for 40 hours. After completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, treated with dilute hydrochloric acid, and extracted with chloroform. The organic layer was washed with saturated saline, dried over magnesium sulfate anhydride, and the solvent was distilled off under reduced pressure. The residue was separated and purified by silica gel column chromatography to obtain the desired product, 4'-chloro-2- (4-chloro- 2.8 g of mouth phenyl) -2- (4-trifluoromethanesulfonyloxyphenyl) acetophenone was obtained as a glassy material.

 The compounds obtained in the same manner as in Example 1 are shown in Table 3 below together with the above compounds. Ph in the table means a phenyl group. In addition, n- means normal, i- means iso-one, s- means secondary eleven, t- means Yuichi Shari-11, and c- means cyclo-one. Further, “/” in the column “X” indicates a single bond. Table 3

48

Π-34 4-

Π— 35 4

Π— 36 4

Π— 37 4

H-38 4

Π— 39 4

Π—40

 Π—41

Π—42

 Π— 43 4

Π— 44 4

Π— 45 4-

Π -46 4-

Π-47

 Π-48

 Π-49

 I [one 50

 I [One 51

 U— 52

 Π— 53 2

Π— 54 2,

Π— 55 2-

Π— 56 3

Π— 57 3,

Π— 58 3,

Π— 59 3, 4

H-60 3—

Π— 61 3-

/ s sls:] ld / ol:

Example 2 (Production of Compound No. 2)

トルエン 60mlにトリフルォロメ夕ンスルホン酸 4— [1, 2—ビス一 （4 —クロ口フエニル） 一2—ォキソ一ェチル] フエニルエステル 2. 8 g (5. 6 6漏 ol) とカルバジン酸ェチル 1. 2 g (11. 32蘭 ol) 及び触媒量のパラト ルエンスルホン酸ピリジン塩を溶解し、 8時間加熱還流した。 反応終了後、 トル ェンを減圧留去し、 シリカゲルカラムクロマトグラフィーにより分離精製して、 目的物であるト リフルォロメ夕ンスルホン酸 4一 [1, 2—ビス一 （4—クロ口 フエニル） 一2— (エトキシカルボニルヒドラゾノ） 一ェチル] フエニルエステ ル 1. 9 gをガラス状物質として得た。

Toluene sulfonic acid 4- [1,2-bis (4-chlorophenyl) -12-oxoethyl] phenyl ester in 60 ml of toluene 2.8 g (5.66 leakage ol) and ethyl carbazate 1 2 g (11.32 ol) and a catalytic amount of pyridine p-toluenesulfonate were dissolved and the mixture was refluxed for 8 hours. After the completion of the reaction, toluene was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain the desired product, trifluoromethanesulfonic acid 4- [1,2-bis- (4-chlorophenyl) 1-2]. — (Ethoxycarbonylhydrazono) ethyl] phenylester 1.9 g was obtained as a glassy substance.

 Example 3 (Production of Compound No. 248)

トルエン 20mlにトリフルォロメ夕ンスルホン酸 4一 [1- (4ークロロフ ェニノレ）—2—ォキソ—3—フエニルプロビル]一フエニルエステル 1. 0 g ( 1 ,

Trifluoromethanesulfonic acid 4- [1- (4-chlorophenylinole) -2-oxo-3-phenylphenyl] -phenyl ester 1.0 g (1,

53 98 sol), 0.31 g (2.98 sol) of ethyl carbazate, and a catalytic amount of pyridine p-toluenesulfonate were dissolved and refluxed for 8 hours. After completion of the reaction, toluene was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain the target compound, trifluoromethanesulfonic acid 4- [1- (4-chlorophenyl) -2- (ethoxycarbonylhydra dyl). Zono) 1-3-phenylpropyl] -phenyl ester 0.34 g was obtained as a viscous substance.

Example 4 (Production of Compound No. 242)

エタノール 5 Omlにトリフルォロメタンスルホン酸 4—[ 1， 2—ビス一（4 —クロ口フエニル） 一 2—ォキソーェチル] フエニルエステル 20. 46 g (4 2謹 ol)、 ヒドラジン一水和物 1 Oml及び酢酸 5. Omlを溶解し、 4時間加熱 還流した。 反応終了後、 エタノールと過剰のヒドラジン一水和物を減圧留去し、 シリカゲルカラムクロマトグラフィーにより分離精製して、 目的物であるトリフ ルォロメ夕ンスルホン酸 4一 [1， 2—ビス一 （4—クロ口フエニル） 一 2—ヒ ドラゾノーェチル] フエニルエステル 16. 2gを油状物として得た。

Trifluoromethanesulfonic acid 4- [1,2-bis (4-chlorophenyl) -12-oxoethyl] phenyl ester in 5 Oml of ethanol 20.46 g (42 ol), hydrazine monohydrate 1 Oml and 5. Oml of acetic acid were dissolved and heated under reflux for 4 hours. After completion of the reaction, ethanol and excess hydrazine monohydrate were distilled off under reduced pressure, and the resulting product was separated and purified by silica gel column chromatography to obtain the desired product, trifluorene sulfonic acid 4- [1,2-bis- (4- Phenyl) 1-2-hydrazonoethyl] phenyl ester (16.2 g) was obtained as an oil.

54 Example 5 (Production of Compound No. 181)

テトラヒドロフラン 50mlに卜リフルォロメタンスルホン酸 4一 [1， 2— ビス一 （4—クロ口フエニル） 一2—ォキソ一ェチル] フエニルエステル 3. 1 2 g (6. 19腿 ol)、 卜リエチルァミン 0. 82g (8. 06顧 ol)及び 4ージ メチルアミノビリジン 0. 07g (0. 62mmol) を溶解し、 氷冷撹拌下、 モノ メチルォキサリルクロリ ド 0. 84g (6. 82mmol) を少量のテトラヒドロフ ランに溶解して滴下した。滴下終了後、室温に戻しそのまま反応終了まで撹拌し、 その後水を加え、 酢酸ェチルで抽出し、 希塩酸、 飽和炭酸水素ナトリウム、 飽和 食塩水で洗浄し、 無水硫酸ナトリウムで乾燥した後に溶媒を減圧留去した。 得ら れた油状物を、 シリカゲルカラムクロマトグラフィーにより分離精製して、 目的 物である { — [1, 2—ビス一 （4—クロ口フエニル） 一 2— (4—トリフル ォロメタンスルホニルォキシフエニル） 一ェチリデン] —ヒドラジノ }一ォキソ —酢酸メチルエステル 2. 5 gをガラス状物質として得た。

Trifluoromethanesulfonic acid 4- [1,2-bis (4-chlorophenyl) -12-oxoethyl] phenyl ester in 50 ml of tetrahydrofuran 3.12 g (6.19 t ol), triethylamine Dissolve 0.82 g (8.06 mol) and 0.07 g (0.62 mmol) of 4-dimethylaminoviridine and add 0.84 g (6.82 mmol) of monomethyloxalyl chloride under ice-cooling and stirring. It was dissolved in a small amount of tetrahydrofuran and added dropwise. After completion of the dropwise addition, return to room temperature, stir until the reaction is completed, add water, extract with ethyl acetate, wash with dilute hydrochloric acid, saturated sodium hydrogen carbonate, and saturated saline, dry over anhydrous sodium sulfate, and then distill off the solvent under reduced pressure. I left. The obtained oil was separated and purified by silica gel column chromatography, and the target compound, {— [1,2-bis- (4-chlorophenyl))-2- (4-trifluoromethanesulfonyloxy) was obtained. Phenyl) ethylidene] -hydrazino} oxo-acetic acid methyl ester 2.5 g was obtained as a glass.

55 Example 6 (Production of Compound No. 196)

室温で無水酢酸 1. 62 g (15. 89纖 ol) とギ酸 1. 82g (39. 73m mol) の混合物を 1時間攪拌した後、 氷冷攪拌下、 トリフルォロメ夕ンスルホン酸 4一 [1, 2—ビス一 （4一クロ口フエニル） 一 2—ヒドラゾノ一ェチル] フエ ニルエステル 4. 0 g (7. 94画 ol) のテトラヒドロフラン溶液を滴下した。 滴下終了後、 徐々に室温に戻しながらそのまま反応終了まで攪拌し、 その後氷水 を加え、 ジェチルエーテルで抽出し、 飽和炭酸水素ナトリウム、 飽和食塩水で洗 浄し、 無水硫酸ナトリウムで乾燥した後に溶媒を減圧留去した。 得られた油状物 を、 シリカゲルカラムクロマトグラフィーにより分離精製して、 目的物であるト リフルォロメ夕ンスルホン酸 4— [1, 2—ビス一 （4—クロ口フエニル） 一 2 —ホルミルヒドラゾノ一ェチル] フエニルエステル 3. 5 gをガラス状物質とし て得た。 CI

A mixture of 1.62 g (15.89 fiber) of acetic anhydride and 1.82 g (39.73 mmol) of formic acid was stirred at room temperature for 1 hour, and then stirred under ice-cooling. A solution of 4.0 g (7.94 mol) of bis- (4-chlorophenyl) -12-hydrazonoethyl] phenyl ester was added dropwise. After completion of the dropwise addition, the mixture was stirred until the reaction was completed while gradually returning to room temperature, then ice water was added, extracted with getyl ether, washed with saturated sodium hydrogen carbonate and saturated saline, dried over anhydrous sodium sulfate, and then dried. Was distilled off under reduced pressure. The obtained oily substance was separated and purified by silica gel column chromatography, and the desired product, trifluoromethanesulfonic acid 4- [1,2-bis- (4-chlorophenyl) -12-formylhydrazonoethyl, was obtained. 3.5 g of phenyl ester were obtained as a glassy substance.

56 Example 7 (Production of Compound No. 201)

テトラヒドロフラン 10mlにトリフルォロメ夕ンスルホン酸 4— [1， 2— ビス一 （4—クロ口フエニル）一2—ヒドラゾノ一ェチル]フエニルエステル 2. 0 g (3. 97腿 ol) 及びト リェチルァミン 0. 52 g (5. 16雇 ol) を溶解 し、 氷冷攪拌下、 無水酢酸 0. 44g (4. 37mmol) を滴下した。 滴下終了後、 徐々に室温に戻しながらそのまま反応終了まで攪拌し、 その後氷水を加え、 ジェ チルエーテルで抽出し、 飽和炭酸水素ナトリウム、 飽和食塩水で洗浄し、 無水硫 酸ナトリウムで乾燥した後に溶媒を減圧留去した。 得られた油状物を、 シリカゲ ルカラムクロマトグラフィーにより分離精製して、 目的物であるトリフルォロメ 夕ンスルホン酸 4一 [2—ァセチルヒドラゾノ一 1， 2—ビス一 （4ークロロフ ェニル） 一ェチル] フエニルエステル 2. 09 gをガラス状物質として得た。

In 10 ml of tetrahydrofuran, trifluoromethylsulfonic acid 4- [1,2-bis- (4-chlorophenyl) -12-hydrazonoethyl] phenyl ester 2.0 g (3.97 t ol) and triethylamine 0.52 g (5.16 ol) was dissolved, and under ice-cooling and stirring, 0.44 g (4.37 mmol) of acetic anhydride was added dropwise. After completion of the dropwise addition, the mixture was stirred until the reaction was completed while gradually returning to room temperature, then ice water was added, extracted with ethyl ether, washed with saturated sodium hydrogencarbonate and saturated saline, dried over anhydrous sodium sulfate, and then the solvent was removed. It was distilled off under reduced pressure. The obtained oily substance was separated and purified by silica gel column chromatography, and the desired product, trifluoromethanesulfonate 4- [2-acetylhydrazono-1,2-bis- (4-chlorophenyl) ethyl], was obtained. 2.09 g of the phenyl ester were obtained as a glass.

57 Example 8 (Production of Compound No. 215)

テトラヒドロフラン 10mlにトリフルォロメ夕ンスルホン酸 4— [1, 2- ビス一 （4—クロ口フエニル） 一2—ホルミルヒドラゾノ一ェチル] フエニルェ ステル 1. 5 g (2. 82mmol)、 N-ェチルジイソプロビルアミン 0. 55 g (4. 23顧 ol)、及び 4—ジメチルアミノビリジン触媒量を溶解し、氷冷攪拌下、無水 酢酸 0. 43 g (4. 23mmol) を滴下した。 滴下終了後、 徐々に室温に戻しな がらそのまま反応終了まで攪拌し、 その後氷水を加え、 ジェチルエーテルで抽出 し、 飽和炭酸水素ナトリウム、 飽和食塩水で洗浄し、 無水硫酸ナトリウムで乾燥 した後に溶媒を減圧留去した。 得られた油状物を、 シリカゲルカラムクロマトグ ラフィ一により分離精製して、 目的物であるトリフルォロメ夕ンスルホン酸 4— [2— （ァセチル一ホルミル一ヒドラゾノ） 一1, 2—ビス一 （4一クロ口フエ ニル） 一ェチル 1 フエニルエステル 0. 80 gをガラス状物質として得た。

1.5 g (2.82 mmol) of trifluoromethanesulfonic acid 4- [1,2-bis (4-chlorophenyl) -12-formylhydrazonoethyl] phenylester in 10 ml of tetrahydrofuran, N-ethyldiisopro 0.55 g (4.23 mol) of viruamine and a catalyst amount of 4-dimethylaminoviridine were dissolved, and 0.43 g (4.23 mmol) of acetic anhydride was added dropwise with stirring under ice-cooling. After completion of the dropwise addition, the mixture is stirred while the temperature is gradually returned to room temperature until completion of the reaction, then ice water is added, extracted with getyl ether, washed with saturated sodium hydrogen carbonate and saturated saline, dried over anhydrous sodium sulfate, and then dried. Was distilled off under reduced pressure. The obtained oily substance was separated and purified by silica gel column chromatography to obtain the desired product, trifluoromethanesulfonic acid 4- [2- (acetyl-formyl-hydrazono) -1,1,2-bis- (4-chromate). Phenyl) 0.81 g of monoethyl 1-phenyl ester was obtained as a glass.

58 Example 9 (Production of Compound No. 214)

To 20 ml of N, N-dimethylformamide was added 1.20 g (2.20 spirit ol) of trifluoromethanesulfonic acid 4- [2-acetylhydrazono-1,2-bis (4-chlorophenyl) -ethyl] phenyl ester. Under ice-cold stirring, add 0.09 g (2.20 tmol) of 60% sodium hydride in several portions, stir as it is for 1 hour, and then add 0.47 g of methyl iodide (3. 30 ol) was dropped. After completion of the dropwise addition, the mixture is gradually cooled to room temperature and stirred until the reaction is completed.After that, ice water is added, extracted with getyl ether, washed with water and saturated saline, dried over anhydrous sodium sulfate, and then the solvent is distilled off under reduced pressure. did. The obtained oil was separated and purified by silica gel gel chromatography, and the desired product, trifluoromethanesulfonate 4- [2- (acetyl-methyl-hydrazono) -1,1,2-bis (4-) Phenyl) ethyl] phenyl ester 60 g was obtained as a glassy substance.

59 Example 10 (Production of Compound No. 237)

トルエン 5mlにトリフルォロメ夕ンスルホン酸 4— [1, 2—ビス一 （4— クロ口フエニル） 一2—ヒドラゾノーェチル] フエニルエステル 1. 0g (1. 98mmo 1)及び 90 %N,N-ジメチルァセトアミドジメチルァセ夕一ル 0. 3 5g (2. 38imol) を溶 し、 4時間加熱還流した。 反応終了後、 トルエンを 減圧留去し、 シリカゲルカラムクロマトグラフィ一により分離精製して、 目的物 であるトリフルォロメタンスルホン酸 4— [1， 2—ビス一 （4—クロ口フエ二 ル） 一2— (1—ジメチルアミノエチリデン一ヒドラゾノ） 一ェチル] フエニル エステル 0. 7 gをガラス状物質として得た。

Trifluoromethanesulfonic acid 4- [1,2-bis (4-chlorophenyl) -12-hydrazonoethyl] phenyl ester in 5 ml of toluene 1.0 g (1.98 mmo 1) and 90% N, N 0.35 g (2.38 imol) of -dimethylacetamide dimethylacetate was dissolved and heated under reflux for 4 hours. After completion of the reaction, the toluene was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain the desired product, trifluoromethanesulfonic acid 4- [1,2-bis- (4-chlorophenol) 12 — (1-Dimethylaminoethylidene-hydrazono) -ethyl] phenyl ester 0.7 g was obtained as a glassy material.

60 Example 11 (Production of Compound No. 9)

テトラヒドロフラン 1 5 0mlに、 トリフルォロメ夕ンスルホン酸 4— [1 , 2—ビス一（4—クロ口フエニル）一 2—ォキソェチル]—フエニルエステル 9.

In 150 ml of tetrahydrofuran, trifluoromethanesulfonic acid 4- [1,2-bis- (4-chlorophenyl) -12-oxoethyl] -phenyl ester 9.

Dissolve 79 g (0.02 mol), pyrrolidone hydrotribromide (PHT) 11.51 g (0.023mo1) and 1.95 g (0.023 mol) of 2-pyrrolidinone for 3 hours Heated to reflux. After completion of the reaction, insolubles were filtered off, and tetrahydrofuran was distilled off under reduced pressure. The residue was dissolved in getyl ether, washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain trifluoromethanesulfonic acid 4- [1-bromo-1,2-). 14.38 g of bis (4-chlorophenyl) -2-oxoethyl] -phenyl ester was obtained as a crude oily product. The obtained trifluoromethanesulfonic acid 4- [1-promo 1,2-bis (4-chlorophenyl) -12-oxoethyl] -phenyl ester 14.3

8 g and 11.52 g (0.067 mol) of silver nitrate were dissolved in 200 ml of 50% aqueous acetone and stirred at room temperature for 3 hours. After the reaction was completed, getyl ether was added to the reaction solution, insolubles were filtered, washed with water and saturated saline, and the solvent was distilled off under reduced pressure. Got

6 1 The oil was purified by silica gel column chromatography to give trifluoromethanesulfonic acid 4- [1,2-bis- (4-chlorophenyl) 1-1-hydroxy-2-oxoethyl] -phenyl ester 6.7 3 g was obtained.

 The resulting trifluoromethanesulfonic acid 4-[[1,2-bis (4-chlorophenyl)]-1-hydroxy-2-oxoethyl] phenyl ester 0.64 g (1.26 ol) Then, 0.19 g (1.89) of ethyl carbazate and a catalytic amount of pyridine p-toluenesulfonate were dissolved in 5 ml of toluene, and the mixture was heated under reflux until the reaction was completed. After completion of the reaction, the toluene was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain the desired product, trifluoromethanesulfonic acid 4- [1,2-bis- (4-chlorophenyl) -1-2- 0.7 g of ethoxycarbonylhydrazono] -1-hydroxyethyl] -phenyl ester was obtained as a glassy substance.

The ¹ H-NMR spectra of the compounds obtained in the same manner as in Examples 2 to 11 are shown in Table 5 below together with the compounds.

6 2 Table 5

Compound No. 1 NMR, (a ppm), (TMS)

1 (CDClj) 1.25 (3H, t) ₎ 4,19 (2H ₎ q), 5.29 (lH ₎ s) ₎ 6.89-6.98 (2H, m) ₎ 7.17-7.39 (llH, m), 7.72 (lH ₎ s )

_{2 (CDC1 3) 1.26 (3H} , t), 4.20 (2H, q), 5.27,5,73 (lH, s, s), 6.83- 6.87 (2H, ra), 7.17-7.39 (10H, m), 7.65,7.88 (lH, s, s)

9 (CDClj) l, 26 (3H ₎ t) _J 4.20 (2H, q), 5.27 _; 5.73 (lH, s, s), 6.83-6,87 (2H, m), 7.17-7.39 (10H ₎ m) , 7.65,7,88 (lH ₎ s, s)

_{10 (CDCl 3) 5.19 (2H} , s)! 5.29 (lH, bs), 6.58 (2H, d) 1 7.15-7.41 (l5H) m)) 7.58 (lH) s)

_{29 (CDC1 3) 1.26 (3H} ) t), 1.98) 2.04 (3H) s, s)) 3.67) 4.1l (2H, s, s), 4.23 (2H, q) J 5.27,5.70 (lH) s, s), 6.82 (2H ₎ d),

 7.09- 7.36 (10H, m), 7.60,7.99 (lH, s, s)

 30 (CDCI3) 1.20-1.28 (9H, m), 2.74-2.83 (lH, m), 3.70,3.73 (2H, s, s), 4.21 (2H, q), 5.26,5.69 (lH, s, s) , 6.78-6.83 (2H, m), 7.07-7.34 (10H, m), 7.58,7.98 (lH, s, s)

 31 (CDCI3) 1.25 (3H, t), 2.43,2.45 (3H, s, s), 3.94 (2H, q), 4.16 (2H, q), 5.25,5J8 (lH, s), 6.85-7.51 (12H , in),

 7.71,8.17 (lH, s, s).

 32 (CDCI3) 1.25 (3H, t), 2.75,2.77 (3H, s, s), 4.10-4.24 (4H, n0,5.26,5.74 (lH, s, s), 6.87,7.13 (2H, d, d ),

 7.19- 7.52 (10H, m), 7.67,7.97 (lH, s, s)

42 (CDCI3) 1.25 (3H, t), 4.21 (2H, q), 5.30 ₎ 5.77 (lH, s _; s), 6.87 ₎ 7.11 (2H ₎ d, d), 7.19-7,57 (10H ₎ m) ₎ 7.66 ₎ 7.90 (lH, s, s)

_{45 (CDCI3) 1.00-1.10 (3H)} m), 1.26 (3H J t), 3.86-4.01 (2H, m)) 4.21 (2H, q), 5.23,5.64 (lH) s, s)) 6.79-7.54 (12H, m) ₎ 7.56,8.03 (lH, s, s)

_{46 (CDCI 3) 1.25 (3H} ) t)) 4.20 (2H, q)) 5.26,5.73 (lH) s J s), 6.83-6.87 (2H J m) J 7.10-7.40 (10H) ni)) 7.66, 7.97 (lH _; s, s)

56 (CDCI3) 1.26 (3H, t), 2.46,2.47 (3H, s, s), 4.21 (2H, q), 5.23,5.66 (lH, s, s), 6.83 (2H, d), 7.06-7.56 (10H, m),

 7.59,7.98 (lH, s, s)

 57. (CDClj) 1.26 (3H, t), 2.72,2.74 (3H, s, s), 4.21 (2H, s, s), 5.29,5.78 (lH, s, s), 6.06,7,12 (2H , d, d), 7.20-7,64 (10H, m),

7.66,7.93 (lH, s, s)

 58 (CDClj) 1.26 (3H, t), 3. (M, 3.06 (3H, s, s), 4.20 (2H, q), 5.29,5.80 (lH, s, s), 6.90,7.11 (2H, d , d), 7.19- 7.95 (llH, m)

59 (CDCI3) 1.26 (3H, t), 4.20 (2H, q), 5.27,5.73 (lH, s, s), 6.83-7.85 (13H, m)

60 (CDC) ₃ ) 1.26 (3H, t), 4.20 (2H, q), 5.23,5.68 (lH, s, s) ₎ 6.84 (2H ₎ d) ₎ 7.08-7.57 (10H ₎ m), 7.63,7.96 (lH, s, s)

61 (CDCI3) 1.25 (3H ₎ t), 4.23 (2H, q) ₎ 5.29,5.73 (lH, s, s), 6.83 (2H ₎ d), 7.09-7.57 (llH, m) ₎ 7.63,8.03 (lH , s, s)

_{62 (CDC1 3) 1.26 (3H} , t), 4.21 (2H, q), 5.29,5.74 (lH, s, s), 6.83 - 7.48 (12H, m), 7.65,7.87 (lH, s, s)

 68 (CDCI3) 1.25 (3H, t), 4.21 (2H, q), 5.29,5.76 (lH, s, s), 6.83-7.51 (12H, m), 7: 68'7.96 (lH, s, s)

71 (CDClj) 1.25 (3H ₎ t) ₎ 4.20 (2H, q) _J 5.25,5.73 (lH ₎ s, s), 6.86 ₎ 7.07 (2H, d, d), 7.13-7.55 (10H ₎ m), 7.67 ₎ 7.91 (lH, s, s) 72 (CDCI3) 1.25 (3H, t), 3.64,3.66 (3H, s, s), 4.20 (2H, q), 5.25,5.68 (lH, s, s), 6.80 -7.55 (12H, m), 7.59, 7.99 (lH, s, s) 74 (CDClj) 1.25 (3H, t), 4.21 (2H, q), 5.34, 5.85 (lH, s, s), 6.87-7.90 (13H, in)

76 (CDCI3) 0.89-0.98 (3H, m) ₎ 1.19-1.38 (5H, m), 1.52-1.63 (2H, m), 2.55-2.65 (2H ₎ m) _J 4.20 (2H, q), 5.27 ₎ 5.74 (lH, s, s) ₎

6.8g 7.54 (12H, m), 7.59,7.96 (lH, s, s)

 77 (CDClj) 1.28 (3H, t), 4.21 (2H, q), 5.29,5.78 (lH, s, s), 6.59,6.86 (2H, d, d), 7.15_7.54 (10H, m), 7.65, 7.86 (lH, s, s)

78 (CDCl ₃ ) 1.25 (3H, t), 3.81,3.82 (3Hs, s), 4.21 (2H, q), 5.26,5.71 (lH, s, s), 6.81-7.52 (12H, m), 7.65, 7.99 (lH, s, s)

_{79 (CDC1 3) 1.25 (3H} , t), 4.21 (2H, q), 5.03,5.07 (2H, s, s), 5.26,5.70 (lH, s, s), 6.81- 7.52 (17H, m), 7,59,7.96 (lH, s, s)

80 (CDCl ₃ ) 1.26 (3H, t), 4.21 (2H, q), 5.14,5.18 (2H, s, s), 5.26,5.71 (lH, s, s), 6.82-7.56 (16H, m), 7.60, 7.97 (lH, s, s) 81 (CDCI3) 1.26 (3H ₎ t), 4.21 (2H, q) ₎ 5.29, 5.82 (lH, s, s), 6.88 (2H, d), 7.21-7.53 ( 10H, ni) ₎ 7.71 ₎ 7.91 (lH, s, s)

82 (CDCI3) 1.26 (3H, t) ₎ 2.30,2.43 (3H, s, s) ₎ 4.21 (2H, q), 5.26,5.73 (lH, s, s) _J 6.82-7.98 (13H, m)

84 (CDCl3) l.26 (3H, t), 4.2l (2H) q) I 5.31) 5.77 (lH) s I s), 6.81-6.86 (2H) ra), 7.17-7.54 (llH, m)) 7.62,7.94 (lH _J s ₎ s)

85 (CDCl3) l.26 (3H, t), 4.21 (2H 1 q), 5.27) 5.74 (lH J s, s) J 6.88-7.40 (12H, m), 7.67,7.87 (lH, s, s)

 6 3

Replacement paper («! 126) ,

 ) ssos ygz-) (¾Η ¾Ϊ0 S2 H22-1 5ν-1

 ) (Puki 7 HI.s, Hi H.- (¾ 5 (ふ (HIHll H¾sS--

())) Yo HSI S Hio ΗS 05558

169 (CDCI ₃ ; 1.26 (3H, t), .21 (2H, q), 5.35,5.76 (lH ₎ s, s), 5.76-6.99 (lH, in), 7.14-7.41 (12H, m), 7.68 -7.72 (lH, m), 7.57,8 l (lH, s, s)

170 (CDCI ₃ ; 1.28 (3H, t) ₎ 4.21 (2H, q), 5.19,5.68 (lH, s ₎ s), 6.81J.12 (2H, d, d), 7-20-r.43 ( 9H, m), 7.62,7.90 (lH, s, s) 171 (CDCI ₃ : 1.26 (3H, t), 4.21 (2H ₎ q), 5.61,5,86 (lH ₎ s _J s) ₎ 6.88-7.48 (l lH, m), 7.76,7.85 (lH, s, s)

172 (CDCIj 1.23 (3H, t), 4.18 (2H ₎ q) ₎ 5.43 ₎ 5.84 (lH, s, s) ₎ 6.76-7.50 (llH, m), 7.71,7.87 (lH, s, s)

175 (CDC1 ₃ : 1.23 (3H, t), 4.18 (2H, q), 5.49,5.84 (lH, s, s), 6.93--7.48 (llH, m), 7.62-7.67 (lH, m), 7.61, 8.01 (lH, s, s) 177 (CDC1 ₃ 1.26 (3H, t), 4.22 (2H _> q), 5.20,5.71 (lH, s, s) ₎ 6.66,6.90 (2H, d, d), 7.12- 7.41 (9H ₎ m), 7.71,7.81 (lH, s _J s) 178 (CDC1; 1.05 (3H, t), 3.1 -3.23 (2H ₎ m), 5.20 (lH ₎ s), 5.54 (lH, t) , 7.01-7.38 (12H ₎ i] i), 7.60 (lH, s)

_{179 (CDC1; 3.48-3.56 (4H)} m), 5.19 (lH, s)> 6.09 (lH, t), 7.04-7.07 (2H, m), 7.16-7.40 (l 0 H) m), 7.76 (lH ₎ s) 180 (CDCI ₃ : 0.88-1.79 (10H, m), 3.53-3.62 (lH, m), 5.21,5.69 (lH, s ₎ s), 5.58 (lH, d) ₎ 7.06-7.39 (12H, m), 7.52 (lH ₎ s) 181 (CDCI ₃ : 3.86 (3H, s), 5.41 (lH, s), 6.86-6.89 (2H, m), 7.18-7.43 (10H, m), 9.67 (lH _> s)

182 (CDC1 ₃ ; 2.68,2.69 (3H, s, s), 3.45,3.53 (3H, s ₎ s), 5.19 (lH, s), 7.09-7.45 (12H, m)

195 (CDCI; 2.58 (2H, t), 3.50-3.56 (2H, m), 5.37,5.88 (lH ₎ s, s), 6.91-6.95 (2H, ni), 7.14-7.4 (10H, m),

 8.05 (1 H't), 9.99,10.22 (lH, s, s)

196 (CDC1 ₃ ; 5.18,5.73 (lH, s, s), 6.92-7.45 (12H, m), 8.37 (lH, d), 8.61 (lH, d)

201 (CDC1 ₃ 2.06 (3H, s), 5.18,5.78 (lH, s, s), 6.98-7.02 (2H, m), 7.I8-7.42 (10H, m), 8.44,8.79 (lH, s, s)

214 (CDCI3 1.93, 2.17 (3H, s, s), 2.70, 2.9'i (3H, s, s), 5.22, 5.77 (3H, s, s), 6.72-7.48 (12H, m)

215 (CDC1 ₃ : 2.05 (3H, s), 5.18 ₎ 5.78 (lH, s, s), 7.01 (2H, d), 7.19-7.39 (10H, m) ₎ 8.34,8.77 (lH, s)

216 (CDC1 ₃ 1.66, 1.72 (3H, s, s), 2.47 (3H, s), 7.05-7.51 (12H, m), 7.65,7.68 (lH, s, s)

217 (CDC1 ₃ : 2.09 (6H, s), 5.36 (lH, s), 6.91 (2H, dd), 7.24-7.46 (10H ₎ m)

228 (CDCI; 1.02 (3H, t), 2.40 (2H, q), 5.18,5.81 (lH ₎ s, s), 7.02 (2H, d), 7.18-7.44 (10H, m), 8.48,8.86 (lH , s, s) 229 (CDC1 ₃ : 0.78-1.01 (4H, m), 2.15-2.19 (lH, ra) ₎ 5.20 (lH, s), 7.02 (2H, d), 7.20-7.39 (10H, m) _{J 8.59 (lH, s) 230} (CDC1 3: 3.58,3.75 (2H, s, s)) 5.15,5.3 (lH, s, s), 6.90-7.40 (17H, m), 7.97,8.29 (lH, s , s)

237 (CDCI3 1.96,2.04,2.29,2.38 (3H, s, s, s, s), 2.86,2.88 (6H, s, s), 5.37,6.60 (lH, s, s), 7.: U-7.29 (l ₀ H, m),

 7.46-7 50 (2H, m)

242 (CDCI ₃ ; 5.11,5.69 (lH ₎ s, s), 5.29,5.82 (2H ₎ s, s), 7-05-7.37 (12H, m)

243 (CDCI; 5.11,5.69 (lH, s, s), 5.28,5.40 (2H, s, s), 7.07-7.38 (12H, m)

^{. 248 (CDCI 1.23 (3 H} , t), 3.6 3 (2H, q), 4.16 (2H, q), 5.M (lH, s), 6 8 9 (2H, d), 7.14 - 7. 3 0 (l lH, in), 8.03 (lH, s) 347 (CDCI: 1.26 (3H ₎ t) _> 3.65 (2H, q), 4.18 (2H, q), 5.14 (lH, s), 6.85-7.35 ( 13H, m), 7.78 (lH, s)

_{348 (CDC1 3: 1.24 (3H} , t), 3.62 (2H, q)) 4.16 (2H, q), 5.0l (lH, s)) 6.81 (lH, d); 7.13-7.36 (l 0 H, m ), 8.09 (lH, bs) Next, formulation examples are shown. In addition, part represents a mass part. Formulation Example 1 (Wettable powder) 50 parts of the compound of the present invention finely pulverized with a hammer mill to an average particle size of 10 μm, 3 parts of sodium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 10 parts of synthetic hydrous silica After well mixing 35 parts of clay, the mixture was pulverized with a jet mill to obtain each wettable powder. Formulation Example 2 (Emulsion) 10 parts of the compound of the present invention, 9 parts of polyoxyethylene styrenated polyester, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene were uniformly dissolved to obtain respective emulsions. .

6 5

Replacement paper (Rule 2β) Formulation Example 3 (Water dispersible granules)

 Compound 40 finely pulverized with a hammer mill to a particle size of 5 μm 40 parts, Differential clay 23 parts, ammonium sulfate powder 20 parts, sodium ligninsulfonate 5 parts and sodium peryl sulfate

After mixing 1 part, it was further ground by a jet mill. After adding 15 parts of water and mixing, a 0.8 mm screen was extruded into granules, which were dried at 70 ° C. It was cut to a length of about 1 to 1.5 mm and sieved to obtain each wettable powder for granules. Formulation Example 4 (granules)

 To 5 parts of the compound of the present invention, which was pulverized to an average particle size of 10 μm with a hammer mill, 3 parts of sodium ligninsulfonate, 1 part of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 60 parts of clay were added. After sufficiently stirring and mixing, the mixture was ground using a hammer mill. Next, an appropriate amount of water was added to the mixture, and the mixture was further stirred, granulated by an extrusion-type granulator, air-dried, sized and sieved to obtain each granule. Formulation Example 5 (Powder)

 One part of the compound of the present invention finely ground to an average particle size of 8 μm with a hammer mill, 5 parts of synthetic hydrous silicate fine powder, 0.3 part of PAP and 93.7 parts of crane are added and mixed by stirring with a pin mill. Thus, each powder was obtained.

Formulation Example 6 (Floor pull agent)

 Add 10 parts of the compound of the present invention finely pulverized with a hammer mill to an average particle diameter of 8 μm, 3 parts of polyoxyethylene styrene styrenated phenyl ether phosphate ammonium salt, 1 part of silicon defoamer and 36 parts of water. The mixture was stirred with a mixer to obtain a dispersion. This dispersion was finely pulverized by a peas mill to an average particle size of 1.5 m. Then, 40 parts of an aqueous solution containing 0.5 part of xanthan gum and 0.2 part of a preservative was added thereto, and propylene glycol was further added. Then, 10 parts of each flowable agent were obtained by gentle stirring and mixing.

 Next, test examples show that the compound of the present invention is useful as an active ingredient of an insecticide.

6 6 Shown. The compounds of the present invention are indicated by the compound numbers shown in Table 5, and the compounds used as comparative controls are indicated by the following compound symbols.

Compound A: 4'-chloro-1-2-isopropyl-12-phenylacetophenone ethoxycarbonylhydrazone (compound No. 3 described in Table 1 of JP-A-6-157444)

Compound B: 4,1-trifluoromethanesulfonyloxy-1,2,2-dimethyl-2-phenylacetophenone ethoxycarbonylhydrazone (JP-A-6-1574

Compound No. 34 described in Table 1 of No. 44)

Test Example 1 (Insecticidal test on Lotus syrup)

 Each emulsion of the i-conjugate shown in Table 5 obtained according to Formulation Example 2

Diluted with water to 50 Oppm.

 The obtained water dilution is sprayed on Chinese cabbage leaves at the 3-4 leaf stage and air-dried, and then placed in a plastic container of 2 lcmx oko 13 cm x 3 cm depth, in which a lotus leaf (Spod optera litura) 3rd instar Ten larvae were released. It was left in a constant temperature room at 26 ° C with the lid on, and the number of live and dead insects after 48 hours was investigated to determine the mortality. As a result, while the comparative compounds A and B had no effect, the following compounds showed a mortality of 80% or more among the tested compounds of the present invention.

 (1) ヽ (2), (9), (29), (68), (7 IX (85), (87), (90), (95) ヽ (96), (102), (110 ), (133), (143), (145), (146), (153), (157), (158), (160), (161), (162), (163), (164), (165), (166), (167), (170), (177), (196), (201), (214), (215), (216), (217), (228), (229 ), (237), (248), (348)

Test Example 2 (Insecticidal test against Yotuga)

 Compound No. (90) was evaluated for insecticidal activity in the same manner as in Biological Test Example 1.

67 As a result, the compound of the present invention exhibited a mortality of 100%.

Test Example 3 (Insecticidal test on Aedes auricaceae)

 The emulsion of Compound No. (90) obtained according to Formulation Example 2 was diluted with water so that the active ingredient concentration became 500 ppm.

 The obtained water dilution is sprayed on the leaves of the cucumber at the 2-3 leaf stage, air-dried, and then placed in a plastic container having an inner diameter of 9 cm x a depth of 6.5 cm. In the plastic container, there is a cynopodium (Adoxophyes s ^) Ten third-instar larvae were released, capped and allowed to stand in a constant temperature room at 26 ° C, and the number of live and dead insects 48 hours later was investigated to determine the mortality. As a result, the compound of the present invention exhibited a mortality of 90% or more.

Test Example 4 (Insecticidal test on Japanese moth)

 The emulsion of Compound No. (90) obtained according to Formulation Example 2 was diluted with water so that the active ingredient concentration became 500 ppm.

 The resulting water diluted solution was sprayed on Chinese cabbage leaves at the 3-4 leaf stage, air-dried, and then placed in a plastic container having an inner diameter of 9 cm x 6.5 cm in depth, and contained therein a moth (Piute 11a xylostella). ) 10 third-instar larvae were released, covered and allowed to stand in a constant temperature room at 26 ° C. The number of live and dead insects 48 hours later was investigated, and the mortality was determined. As a result, the compound of the present invention exhibited a mortality of 100%. The invention's effect

 The hydrazone derivative of the present invention or a salt thereof has an excellent insecticidal effect. Therefore, an excellent pesticidal agent can be produced using the compound of the present invention.

6 8

Claims

The scope of the claims  1. A hydrazone derivative represented by the following formula [I] or a salt thereof c

[I] [Wherein AB and C may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, an alkenylo Xy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, aryl Alkylthio, heteroarylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkenylsulfinyl, arylsulfinyl, heteroarylsulfinyl, Alkyl Lephonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyl A xy group, a cycloalkylcarbonyloxy group, 6 9 Cycloalkenyl) carbonylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, alkoxycarbonyloxy, alkenyloxycarbonyloxy, alkynyloxycarbonyloxy, cycloalkyloxycarbonyl Okishi group, cycloalkenyl O alkoxycarbonyl O alkoxy group, Ari Ruo alkoxycarbonyl O alkoxy group, a hetero § reel O alkoxycarbonyl O alkoxy group, oso ₂ group, a nitro group or a Shiano group, more a, B or C When there are a plurality of each, they may be the same or different, X is a single bond, or — {C (R ⁴ ) (R ⁵ )} _p — or —C (R ⁴ ) = C (R ⁵ ), and R ¹ and R ² may be the same or different, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an aldehyde group, an alkylcarbonyl group, Cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroarylcarbonyl, C (= 0) N (R ⁸ ) (R ^g ) group, C (= 0) C (= 0) R ⁶ group, S 0 ₂ R ⁷ group, or R ¹ and R ² together, = C (R ¹⁰ ) N ( R ^{1 1} ) and (R ^{1 2} ) R ⁴ and R ⁵ may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, or an alkoxy group. Group, alkenyloxy group, alkynyloxy group, cycloalkyloxy group, cycloalkenyloxy group, aryloxy group, heteroaryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, heteroa Reelcarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, arylcarbonyloxy, heteroarylcarbonyloxy, alkoxycarbonyloxy, cycloalkyloxycarbonyloxy, aryloxy Le 7 0 Represents a bonyloxy group, a heteroaryloxycarbonyloxy group, a nitro group, or a cyano group; R ⁶ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or an N (R ⁸ ) (R ⁹ ) group; R ⁷ represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a heteroaryl group; R ^lfl , R ^u , and Ε / ¾, which may be the same or different, represent a hydrogen atom or an alkyl group,  1, m and η represent numbers from 1 to 5, and  ρ represents a number from 0 to 2. ] 2. The hydrazone derivative according to claim 1, wherein in the formula [I], R ¹ is a hydrogen atom. 3. In the above formula [I], 1 ^ and 1 ^2, hydrazone derivative according to claim 1, wherein both hydrogen atoms. 4. In the above formula [I], Alpha, either Β and C, hydrazone derivative according to claim 1, wherein an 0s0 ₂ CF ₃ group. 7 5. Intermediate compound c represented by the following formula [Π ']

,] Wherein A ', B' and C 'may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group Alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, Arylthio group, heteroarylthio group, alkylsulfinyl group, alkenylsulfinyl group, alkynylsulfinyl group, cycloalkylsulfinyl group, cycloalkenylsulfinyl group, arylsulfinyl group, heteroarylsulfenyl group, alkyl Rusulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynyl Carbonyloxy group, cycloalkylcarbonyloxy group, cycloalkenylcarbonyloxy group, arylcarbonyloxy group, heteroarylcarbonyloxy group, alkoxycarbonyloxy group, alkenyloxycarbonyloxy group, alkynillo Xycarbonyloxy group, cycloalkylo 7 2 Alkoxycarbonyl O alkoxy group, a cycloalkenyl O alkoxycarbonyl O alkoxy group, § Li one Ruo alkoxycarbonyl O alkoxy group, a hetero § reel O alkoxycarbonyl O alkoxy group, 0s0 ₂ R ⁷ group, a nitro group or a Shiano group, A At least one of ', B' and C 'has a trifluoromethanesulfonyloxy group as a substituent, and when a plurality of A', B 'or C' are present, Can be the same or different, And represents a single bond or one of {C (R ⁴ ) (R ⁵ )} _p — or —C (R ⁴ ) = C (R ⁵ ) —, R ³ ′, R \ and R ⁵ may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or an aryl. Group, heteroaryl group, alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkyloxy group, cycloalkenyloxy group, aryloxy group, heteroaryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, a Reelcarbonyl group, heteroarylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, heteroarylphenylcarbonyloxy group, alkoxycarbonyloxy group, cycloalkyloxy group Carbonyloxy group, aryloxy It represents Cal Boniruokishi group, hetero § reel O alkoxycarbonyl O alkoxy group, a nitro group, or a sheet § cyano group, R ⁷ represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group;  1, m and n represent numbers from 1 to 5, and  ϋ represents a number from 0 to 2. ] 7 3 6. A method for producing a hydrazone derivative represented by the formula [I], which comprises the following formula [11]:

[Wherein, A, B and C may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, Alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, Arylthio, heteroarylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkenylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkyl Sulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynyl Carbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, arylcarbonylcarbonyl, heteroarylcarbonyloxy, alkoxycarbonyloxy, alkenyloxycarbonyloxy, alkynyloxy Carbonyloxy group, cycloalkylo 7 4 Xycarbonyloxy, cycloalkenyloxycarbonyloxy, aryloxycarbonyloxy, heteroaryloxycarbonyloxy, oso ₂ R ⁷ represents a group, a nitro group or a cyano group, and when A, B or C is present in plurals, they may be the same or different, X represents a single bond, or —C (R ⁴ ) (R ⁵ )} _p — or one C (R ⁴ ) = C (R ⁵ ), R ³ , R \ and R ⁵ may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a heteroaryl group. Group, alkoxy group, alkenyloxy group, alkynyloxy group, cycloalkyloxy group, cycloalkenyloxy group, aryloxy group, heteroaryloxy group, alkylcarbonyl group, cycloalkylcarbonyl group, aryl Carbonyl group, heteroarylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, heteroarylarylcarbonyl group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group , Aryloki It represents Cal Boniruokishi group, hetero § reel O alkoxycarbonyl O alkoxy group, a nitro group, or a sheet § cyano group, R ⁷ represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group;  1, m and n represent numbers from 1 to 5, and  ϋ represents a number from 0 to 2. And a compound represented by the following formula [Π Ι], 7 5

n [Wherein R ¹ and R ² may be the same or different, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl grave, a heteroaryl group, or an aldehyde. Group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, C (= 0) N (R ⁸ ) (R ⁹ ) SC (= 0) C (= 0) R ^B group, S0 ₂ R ⁷ group, or R ¹ and R ² are linked, and = C (R ¹⁰ ) N (R ^{1 1} ) and (R ^{1 2} ) R ^s represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or an N (R ⁸ ) (R ⁹ ) group; R ⁷ represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a heteroaryl group; R ^1D, R ⁿ s and R ^12, same with or may be different, represent a hydrogen atom, an alkyl group. ] In the presence or absence of a catalyst. 7 6 7. The following formula [IV],

[IV] [Wherein, A, B and C may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, Alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, Arylthio group, heteroaryl-thio group, alkylsulfinyl group, alkenylsulfinyl group, alkynylsulfinyl group, cycloalkylsulfinyl group, cycloalkenylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group , Archi Sulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, cycloalkenylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylcarbonyloxy, alkenylcarbonyloxy , Alkynylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, arylcarbonyloxy, heteroa 7 7 Reelcarbonyloxy group, alkoxycarbonyloxy group, alkenyloxycarbonyloxy group, alkynyloxycarbonyloxy group, cycloalkyloxycarbonyloxy group, cycloalkenyloxycarbonyloxy group, aryloxy alkoxycarbonyl O alkoxy group, a hetero § reel O alkoxycarbonyl O alkoxy group, 0s0 ₂ R ⁷ group, a nitro group or a Shiano group, further a, if the B or C there are a plurality each of even those with the same, May be different, X is a single bond, or represents — {C (R ⁴ ) (R ⁵ )} _p — or — C (R ⁴ ) = C (R ⁵ ) — R ¹ is a chromium atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an aldehyde group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an arylcarbonyl group; Teroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, C (= 0) N (R ⁸ ) (R ⁹ ), C (= 0) C (= 0 ) represents a group R ^6, or S0 ₂ R ⁷ group, R ³ , R \ and R ⁵ may be the same or different, and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a heteroaryl group. , Alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryloxy, heteroaryloxy, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, Heteroarylcarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, heteroarylcarbonylcarbonyl group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxy group It represents Cal Boniruokishi group, hetero § reel O alkoxycarbonyl O alkoxy group, a nitro group, or a sheet § cyano group, 7 8 Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or an N (R ⁸ ) (R ⁹ ) group; R ⁷ represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a heteroaryl group; R ^1D, R ⁿ s and R ^12, same with or may be different, represent a hydrogen atom, an alkyl group,  1, m and n represent numbers from 1 to 5, and  p represents a number from 0 to 2. And a compound represented by the following formula [V], R ^13- Z [V] Wherein R ¹³ is an aldehyde group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxy group. Represents a carbonyl group, C (= 0) N (R ⁸ ) (R ⁹ ) group, C (= 0) C (= 0) R ⁶ group, or S 0 ₂ R ⁷ group, and Z represents a leaving group. , R ⁶ , 1 R ⁸ and R ⁹ represent the same meaning as described above. Wherein the compound represented by the formula [VI] is reacted in the presence of a base. 7 9 (O) n

[VI] [Wherein, A, B, C, X, \ R ¹³ , 1, m, and n represent the same meaning as described above. ] The manufacturing method of the hydrazone derivative represented by these. 8. The compound represented by the formula [IV] according to claim 7, and the following formula [VII], R ^14- Y [VII] [Wherein, R ¹⁴ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an a.laryl group, or a heteroaryl group, and Y represents a leaving group. A compound represented by the following formula [VIII]: 8 0

[Wherein, A, B, C, X, R ¹ , R ³ , R ¹⁴ , 1, m and n represent the same meaning as described above. ] The manufacturing method of the hydrazone derivative represented by these. 9. A compound represented by the formula [IV] according to claim 7, wherein R ¹ is a hydrogen atom, and a compound represented by the following formula [IX],

 [IX] [Wherein, R ¹⁵ represents an alkyl group, and R ^w , R ¹¹ and R ¹² represent the same meaning as described above. ] The compound represented by the following formula [X]: 8 1

[X] Wherein, A, Bs C, X, R 3, R 1D, R ", R 12, 1, m and n are as defined above table be.] The method for producing a hydrazone derivative represented by the.  10. An insecticide comprising the hydrazone derivative according to any one of claims 1 to 4 as an active ingredient. 8 2