JP2000178272A - Benzylpiperidine compound, its production and inseticide for agriculture and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a benzylpiperidine compound having a remarkably excellent insecticidal activity, not injuring useful insects, safe also for environments, etc., and low toxic also for mammalians. SOLUTION: A compound of formula I [R1 is H, a halogen, a l-4C alkyl or the like; R2 is H, OH, a halogen or the like; R3 is a halogen, a 1-4C alkyl or a l-4C alkoxy; Z is 0 or the like; (m) is 0-2; (n) is 0 or 1]. N-[4-(6- chloropyridazin-3-yloxy)benzyl]-4-[bis(4-trifluoromethoxyphenyl) hydroxymethyl]piperidine. The compound of formula I is obtained by reacting a piperidine of formula II with a benzyl halide of formula III (X is a halogen), if necessary, in a solvent (for example, hexane or acetone) in the presence of a base (for example, sodium bicarbonate or potassium hydride) preferably at -20 deg.C to the boiling point of the solvent for 0.5-24 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a benzylpiperidine compound, a method for producing the same, and an agricultural and horticultural insecticide.

[0002]

2. Description of the Related Art In recent years, insect pests have gained resistance due to the long-term use of insecticides, and it has become difficult to control them with conventional insecticides such as organophosphorus agents, carbamates, pyrethroids and the like. A type of drug is required. In addition, from the viewpoint of high insecticidal activity and comprehensive pest management, compounds that do not harm beneficial insects, are safe for the environment, and have low toxicity are desired.

Heretofore, as benzylpiperidine compounds, for example, the following compounds are known to have insecticidal activity.

[0004] US Pat. No. 5,569,664 describes:
General formula (A)

[0005]

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Wherein ^a is an integer of 1 to 3, R ^a and R ^b
Is a phenyl group which may have a substituent, R ^c is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxyalkyl group, an alkoxy group, a cycloalkylalkoxy group, a 5-membered heterocyclic group or a 6-membered heterocyclic group. It is stated that benzylpiperidine compounds have insecticidal activity. However, US Pat. No. 5,569,664 does not disclose a compound in which R ^c in the general formula (A) is a pyridazinyl group or a pyridazinyloxy group.

[0007] WO 96/36228 discloses that in the above general formula (A), a is an integer of 1 to 3,
R ^a and R ^b is a phenyl group substituted by haloalkyl group or a haloalkoxy group, R ^c is a halogen atom as a substituent, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkyl group, haloalkoxy A hetero 5-membered ring group or a hetero 6-membered ring group optionally having an alkyl group or an aminocarbonyl group (these hetero rings may be any of the groups -A- [where A is -O-,-
S- or _{- (CH 2) a - (} . A in the formula are as defined above) or _{^{-O- (CR d R e) b}} - ( wherein R ^d and R ^e are the same or different halogen atom or a methyl group And b represents 1 or 2.) ] To the benzene ring. ) Is known to have insecticidal activity. However, WO 9
JP-A-6 / 36228 discloses that R ^c in general formula (A)
Is a pyridazinyl group or a pyridazinyloxy group, but is not specifically described.

Further, the insecticidal activity of these conventional benzylpiperidine compounds is not sufficient.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a benzylpiperidine compound having a remarkably superior insecticidal activity as compared with conventional benzylpiperidine compounds.

Further, the present invention does not cause harm to beneficial insects, is safe for the environment and the like, and does not adversely affect creatures such as fishes even if they flow into the sea, rivers, lakes and marshes. An object of the present invention is to provide a benzylpiperidine compound which is not toxic to mammals and is also low toxic to mammals.

[0011]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have succeeded in developing a benzylpiperidine compound having remarkably excellent insecticidal activity. Was completed.

According to the present invention, general formula (1)

[0013]

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Wherein R ¹ is a hydrogen atom, a halogen atom,
It represents a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-4 haloalkyl group or a C _1-4 haloalkoxy group. Two R
¹ may be the same or different.

R ² is a hydrogen atom, a hydroxyl group, a halogen atom,
C _1-4 alkyl group, C _1-4 alkoxy group, C _1-4 haloalkyl group, C _1-4 haloalkoxy group, (C _1-4 alkoxy)
Carbonyl group, C _1-4 alkylthio group, C _1-4 alkylsulfonyl group, nitro group, cyano group, phenyl group which may have a substituent, phenoxy group which may have a substituent, group —NR ⁴ R ⁵ (R ⁴ and R ⁵ are the same or different and are each a hydrogen atom, a C _1-4 alkyl group, a (C _1-4 alkyl) carbonyl group, a (C _1-4 alkoxy) carbonyl group, a (C _1-4 alkyl) aminocarbonyl Or a di (C _1-4 alkyl) aminocarbonyl group, or R ⁴ and R ⁵ may be combined with each other to represent a linear C _2-6 alkylene group (the alkylene group _May be substituted with a C _1-4 alkyl group or may contain an oxygen atom in a linear alkylene group.))) Or a group —C (O) N
R ⁶ R ⁷ (R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom,
_{And a 1-4} alkyl group and a C _1-4 alkoxy group. Or R
⁶ and R ⁷ may be bonded to each other to represent a linear C _2-6 alkylene group (the alkylene group may be a C _1-4 alkylene group).
It may be substituted with an alkyl group, or may contain an oxygen atom in a linear alkylene group. )).

R ³ represents a halogen atom, a C _1-4 alkyl group or a C _1-4 alkoxy group. Z is an oxygen atom, group —S (O) _p
-(P represents an integer of 0 to 2) or a group -N (R ⁸ )-
(Wherein R ⁸ represents a hydrogen atom, a C _1-4 alkyl group, a (C _1-4 alkyl) carbonyl group, a (C _1-4 alkoxy) carbonyl group, a (C _1-4 alkyl) aminocarbonyl group or a di (C
_{1-4 represents} an alkyl) aminocarbonyl group. ).

M represents an integer of 0 to 2, and n represents 0 or 1. A benzylpiperidine compound represented by the formula:

Further, according to the present invention, the above general formula (1)
And a process for producing a benzylpiperidine compound represented by the formula:

That is, the benzylpiperidine compound represented by the general formula (1) is a compound represented by the general formula (2)

[0020]

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Wherein R ¹ is as defined above. And a general formula (3)

[0022]

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Wherein R ² , R ³ , m and n are as defined above. X represents a halogen atom. And a benzyl halide represented by the following formula:

The benzylpiperidine compound represented by the above general formula (1) is a compound of the general formula (4)

[0025]

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Wherein R ² , R ³ , Z, m and n are as defined above. R ⁹ represents a C _1-4 alkyl group. N-
Benzyl isonipecotate and general formula (5)

[0027]

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Wherein R ¹ is as defined above. X represents a halogen atom. And a Grignard reagent represented by the following formula:

Further, the present invention provides an agricultural and horticultural insecticide comprising a benzylpiperidine compound represented by the above general formula (1) as an active ingredient.

The benzylpiperidine compound represented by the above general formula (1) of the present invention is not only a drug-sensitive pest,
It has a remarkably excellent insecticidal activity that can also control drug-resistant pests, has low toxicity to others, and does not cause harm that is particularly problematic to beneficial insects and the environment. The compound of the present invention is safe for the environment and the like, and has little risk of adversely affecting organisms such as fish even if it flows into the sea, rivers, lakes and marshes, and is low toxic to mammals.

In particular, the benzylpiperidine compound represented by the above general formula (1) of the present invention exhibits high efficacy against various pests at a low dose.

The benzylpiperidine compound represented by the above general formula (1) of the present invention includes its N-oxide and its salt.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, specific examples of the groups represented by R ^{1 to} R ⁹ include the following.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-
Butyl group, isobutyl group, sec-butyl group, tert
And a linear or branched alkyl group having 1 to 4 carbon atoms such as -butyl group.

Examples of the C _1-4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group. And 4 straight-chain or branched alkoxy groups.

C _1-4 haloalkyl groups include, for example, fluoromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, penta Fluoroethyl group, 1-fluoropropyl group, 2-chloropropyl group, 3-fluoropropyl group,
A straight-chain or branched carbon atom having 1 to 9 halogen atoms such as a 3-chloropropyl group, a 1-fluorobutyl group, a 1-chlorobutyl group, a 4-fluorobutyl group, etc.
To 4 alkyl groups.

Examples of the C _1-4 haloalkoxy group include fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, and 2-chloroethoxy. , 1-fluoroethoxy group, 2,2,2
-Trifluoroethoxy group, pentafluoroethoxy group, 1-fluoropropoxy group, 2-chloropropoxy group, 3-fluoropropoxy group, 3-chloropropoxy group, 1-fluorobutoxy group, 1-chlorobutoxy group,
A linear or branched C1-C4 alkoxy group substituted with 1-9 halogen atoms, such as 4-fluorobutoxy group, is mentioned.

Examples of the (C _1-4 alkoxy) carbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, and a sec-butoxycarbonyl group. Group, tert
A straight-chain or branched alkoxycarbonyl group having 1 to 4 carbon atoms, such as a -butoxycarbonyl group.

Examples of the C _1-4 alkylthio group include alkylthio such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, and tert-butylthio. Examples thereof include a linear or branched alkylthio group having 1 to 4 carbon atoms.

Examples of the C _1-4 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an isopropylsulfonyl group and an n-
Butylsulfonyl group, isobutylsulfonyl group, sec
Examples thereof include a linear or branched alkylsulfonyl group having 1 to 4 carbon atoms, such as a -butylsulfonyl group and a tert-butylsulfonyl group.

Examples of the (C _1-4 alkyl) aminocarbonyl group include a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an isopropylaminocarbonyl group, an n-butylaminocarbonyl group and an isobutylaminocarbonyl group. , Sec-butylaminocarbonyl group, tert-butylaminocarbonyl group and the like, an alkylaminocarbonyl in which a nitrogen atom on the aminocarbonyl group is substituted by one linear or branched alkyl group having 1 to 4 carbon atoms Groups.

Examples of the (C _1-4 alkyl) carbonyl group include a methylcarbonyl group, an ethylcarbonyl group,
a linear or branched alkyl moiety having 1 to 4 carbon atoms, such as an n-propylcarbonyl group, an isopropylcarbonyl group, an n-butylcarbonyl group, an isobutylcarbonyl group, a sec-butylcarbonyl group, a tert-butylcarbonyl group; Alkylcarbonyl group which is in the form.

Examples of the di (C _1-4 alkyl) aminocarbonyl group include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a di-isopropylaminocarbonyl group and a di-n
A butylaminocarbonyl group, an N-methyl-N-ethylaminocarbonyl group, an N-methyl-N-n-propylaminocarbonyl group, or the like; And a dialkylaminocarbonyl group in which two branched alkyl groups are substituted.

The phenyl group and the phenoxy group may have 1 to 5, preferably 1 to 3, substituents. Examples of the substituent include a halogen atom, a C _1-4 alkyl group,
_Examples thereof include a _1-4 alkoxy group, a C _1-4 haloalkyl group, a nitro group, and a cyano group.

Examples of the linear C _2-6 alkylene group include an ethylene group, a trimethylene group, a tetramethylene group,
Examples include a pentamethylene group and a hexamethylene group.

The straight-chain alkylene group having 2 to 6 carbon atoms which is substituted by a C _1-4 alkyl group includes, for example, -CH
_{(CH 3) CH 2 -,} - CH (CH 3) (CH 2) 2 -, - CH 2 C
_{H (CH 3) CH 2 -} , - CH (CH 3) (CH 2) 3 -, - CH 2
_{CH (CH 3) (CH 2} ) 2 -, - CH (CH 3) (CH 2) 4 -, -
_{CH 2 CH (CH 3) (} CH 2) 3 -, - (CH 2) 2 CH (CH 3)
_{(CH 2) 2 -, -} (CH 2) 2 CH (C 2 H 5) (CH 2) 2 -, -
(CH ₂ ) ₂ CH (iso-C ₃ H ₇ ) (CH ₂ ) ₂ -,-(CH ₂ ) ₂ C
_{H (tert-C 4 H 9} ) (CH 2) 2 -, - (CH 2) 2 CH (CH 3)
_{(CH 2) 3 -, -} CH 2 CH (CH 3) CH (CH 3) CH 2 CH
_{2 -, - CH 2 CH (} CH 3) CH 2 CH (CH 3) CH 2 -, -
A straight-chain alkylene group having 2 to 6 carbon atoms in which 1 to 2 alkyl groups having 1 to 4 carbon atoms such as (CH ₂ ) ₂ C (CH ₃ ) ₂ (CH ₂ ) _2- are substituted; Can be.

Examples of the linear alkylene group having 2 to 6 carbon atoms containing an oxygen atom include, for example, -CH ₂ OCH
_{2 -, - (CH 2)} 2 O (CH 2) 2 -, - CH 2 OCH 2 OCH 2
_{-, - (CH 2) 2} O (CH 2) 3 -, - (CH 2) O (CH 2) 3 -
And the like, and a straight-chain alkylene group having 2 to 6 carbon atoms containing 1 to 2 oxygen atoms.

The benzylpiperidine compound (1) of the present invention
Among them, two R ¹ are the same or different and are a halogen atom, a C _1-4 haloalkyl group or a C _1-4 haloalkoxy group,
R ² represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group,
_1-4 alkoxy group or C _1-4 haloalkoxy group, Z is an oxygen atom or a group —S (O) _p — (p is the same as above), and m is 0
And a compound in which n is 1, an N-oxide form of the compound or a salt thereof is preferred, and two R ^{1 s}
_{A 1-4} haloalkyl group or a C _1-4 haloalkoxy group, R ² is a halogen atom, Z is an oxygen atom, m is 0 and n is 1, a compound, an N-oxide form of the compound or a salt thereof is more preferable, Two R ^{1 s} are the same or different and each is a trifluoromethyl group or a trifluoromethoxy group, R ² is a chlorine atom,
A compound in which Z is an oxygen atom, m is 0 and n is 1, an N-oxide of the compound or a salt thereof is particularly preferred.

The benzylpiperidine compound (1) of the present invention
Can be produced, for example, according to the following reaction scheme 1.

[0051]

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[Wherein R ¹ , R ² , R ³ , Z, m and n are the same as above. X represents a halogen atom. That is, according to the reaction scheme 1, the piperidine compound (2) and the benzyl halide (3) are reacted, if necessary, in the presence of a solvent and a base, whereby the benzylpiperidine compound of the present invention ( 1) can be obtained.

In the present reaction, the ratio of the piperingin compound (2) to the benzyl halide (3) is not particularly limited and can be appropriately selected from a wide range. Usually, the molar ratio may be at or near the equimolar ratio.

This reaction is usually carried out in a solvent. The solvent is not particularly limited as long as it is inert to the reaction,
For example, hexane, cyclohexane, aliphatic or alicyclic hydrocarbons such as heptane, benzene, chlorobenzene,
Aromatic hydrocarbons such as toluene and xylene, methylene chloride, dichloroethane, chloroform, halogenated hydrocarbons such as carbon tetrachloride, ethyl acetate, esters such as methyl acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, Ketones such as acetone and ethyl methyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylsulfoxide, a mixed solvent of two or more of these, a mixed solvent of one or more of these with water, and the like Can be mentioned.

This reaction may be carried out in the presence of a base (catalyst). As the base, for example, inorganic bases such as sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydride, potassium hydride,
Organic bases such as triethylamine and pyridine can be exemplified. One base can be used alone, or two or more bases can be used in combination. The amount of the base used is not particularly limited and can be appropriately selected from a wide range, but may be usually a stoichiometric amount or an excess thereof, preferably a stoichiometric amount or about 1 to 5 times excess. The amount may be used. When an organic base such as triethylamine or pyridine is used, it can be used as a solvent by using these in a large excess.

This reaction is carried out usually at a temperature from -20 ° C. to the boiling point of the solvent used, and is completed usually in about 0.5 to 24 hours.

The benzylpiperidine compound (1) of the present invention is obtained by reacting benzyl halide (3) with isonipecotic acid ester (6) according to the following reaction process scheme-2 to give N-benzylisonipecotic acid: Ester (4) is obtained, and can be produced by reacting this with Grignard reagent (5).

[0058]

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[Wherein R ¹ , R ² , R ³ , R ⁹ , Z, X, m
And n are the same as above. The reaction between benzyl halide (3) and isonipecotate (6) can be carried out in the same manner as the reaction between piperidine compound (2) and benzyl halide (3).

In the reaction between the N-benzylisonicopetinic acid ester (4) and the Grignard reagent (5), the amount of the Grignard reagent (5) to be used is usually at least 2 equivalents, preferably at least 2 equivalents to the ester (4). What is necessary is just to be 2-5 equivalents. This reaction is usually performed in a solvent, and examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, and ethers such as diethyl ether, tetrahydrofuran, and dioxane. One type of solvent can be used alone, or two or more types can be used in combination. This reaction is carried out at a temperature from -20 ° C to the boiling point of the solvent used, and is usually completed in about 0.5 to 24 hours.

Further, the benzylpiperidine compound (1) of the present invention can also be produced by reacting a piperidine compound (7) with a pyridazine compound (8) according to the following reaction scheme 3.

[0062]

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Wherein R ¹ , R ² , R ³ , Z, X and m are the same as above. The reaction is carried out in a suitable solvent or without a solvent, if necessary, in the presence of a base and / or a catalyst.

The ratio of the piperidine compound (7) to the pyridazine compound (8) is not particularly limited and may be appropriately selected from a wide range.
0.5 to 5 moles, preferably 0.9 mole,
It is preferable to use about 2 mol.

The solvent is not particularly limited as long as it is inert to the present reaction. Examples thereof include aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane and heptane, and aromatic solvents such as benzene, chlorobenzene, toluene and xylene. Group hydrocarbons, methylene chloride, dichloroethane, chloroform, halogenated hydrocarbons such as carbon tetrachloride, etc., esters such as ethyl acetate and methyl acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, acetone, ethyl methyl ketone, etc. Ketones, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylsulfoxide, a mixed solvent of two or more thereof, and a mixed solvent of one or more of these and water.

As the base, conventionally known bases can be widely used, and examples thereof include inorganic bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium hydride and sodium hydride. One base can be used alone, or two or more bases can be used in combination. The base can be used in a stoichiometric amount sufficient for the reaction between the piperidine compound (7) and the pyridazine compound (8) or in an excess thereof, but preferably from a stoichiometric amount to about 5 times excess amount. It is better to use within the range.

As the catalyst, for example, 18-crown-6
And quaternary ammonium salts such as tetrabutylammonium chloride and benzyltriethylammonium chloride. One type of catalyst can be used alone, or two or more types can be used in combination. The catalyst is generally used in an amount of 0.00001 to 10 equivalents, preferably 0.0001 to 1 equivalent, relative to the piperidine compound (7).

The reaction of the piperidine compound (7) with the pyridazine compound (8) can be carried out within a temperature range from usually -20 ° C to the boiling point of the solvent used.
The reaction is generally completed in about 0.5 to 24 hours.

Also, by reacting a benzyl piperidine compound (1a) in which R ² is a chlorine atom in the general formula (1) with a nucleophile such as an alkoxide, an alkyl mercaptide, or a cyanide, R ² is not a chlorine atom. To other benzylpiperidine compounds (1). This reaction can be carried out in the same manner as the reaction between the piperidine compound (2) and the benzyl halide (3).

The benzylpiperidine compound (1) of the present invention
Among the raw material compounds used for producing the compound, piperidine compound (2) and piperidine compound (7) are known compounds. For example, US Pat. No. 5,569,644, International Publication No. 96/36228. Can be synthesized according to the method described in Japanese Patent Application Publication No.

The benzyl halide (3) can be produced according to a known method. Benzyl halide (3a) wherein n is 1 in the general formula (3), for example, 4- (6-chloropyridazin-3-yloxy) benzyl bromide (in the general formula (3), R ² = chlorine atom, m = 0; X = bromine atom) is obtained by reacting p-cresol with 3,6-dichloropyridazine in the presence of a solvent and a base as necessary to obtain 4- (6-chloropyridazin-3-yloxy) toluene; It can be produced by treating this with a halogenating agent such as N-bromosuccinimide. In general formula (3), benzyl halide (3
b) For example, 4- (6-chloropyridazin-3-yl) benzyl bromide (R ² = chlorine atom, m = 0, X = bromine atom in the general formula (3)) is composed of 4-methylacetophenone and glyoxalic acid. And then treated with hydrazine to give 4- (6-hydroxypyridazine-3-
Yl) toluene was obtained and reacted with a chlorinating agent such as phosphorus oxychloride to obtain 4- (6-chloropyridazin-3-yl) toluene, which was treated with a halogenating agent such as N-bromosuccinimide. Can be manufactured.

The Grignard reagent (5) is commercially available or can be easily prepared from a halogenobenzene derivative by a method well known to those skilled in the art.

The isonipecotic acid ester (6) and the pyridazine compound (8) are commercially available or can be prepared by a method well known to those skilled in the art.

The benzylpiperidine compound (1) of the present invention obtained by each of the above methods can be easily isolated and purified from the reaction system by ordinary means such as filtration, solvent extraction, distillation, recrystallization and column chromatography. it can.

The benzylpiperidine compound (1) of the present invention
Is easily converted to N-oxide with an organic peroxide such as m-chloroperbenzoic acid or hydrogen peroxide, and also, for example, a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, propionic acid, Salts can be easily formed with organic acids such as succinic acid, malonic acid, fumaric acid, and oxalic acid.

The benzylpiperidine compound (1) of the present invention
Can be used, for example, as an active ingredient of an insecticide.

The benzylpiperidine compound (1) of the present invention
Can be used as it is as an insecticide, but it can also be formulated and used in any form such as oils, emulsions, wettable powders, flowables, granules, powders, aerosols and aerosols. At this time, the content of the benzylpiperidine compound (1) of the present invention is not particularly limited, and the form of the preparation, the kind of the target pest or crop, the degree of damage by the pest, the place of application, the time of application, the method of application, Insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, soil conditioners, etc.) and fertilizers. Although it can be appropriately selected, usually 0.01% of the total amount of the insecticide
The amount may be about 95 to 95% by weight, preferably about 0.1 to 50% by weight.

The benzylpiperidine compound (1) of the present invention
Can be produced according to a known method. For example, the benzylpiperidine compound (1) may be mixed with a carrier such as a solid carrier, a liquid carrier, and a gaseous carrier, and a surfactant and other formulation auxiliaries may be added as necessary.

As the carrier, any of those commonly used in this field can be used.

As the solid carrier, for example, clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite,
Hubasami clay, acid clay, etc.), talcs, ceramics, other inorganic minerals (celite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), and chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, salt ammonium, etc.) And the like, fine powder, granular material, and the like.

Examples of the liquid carrier include water, alcohols (eg, methanol and ethanol), ketones (eg, acetone and methyl ethyl ketone), aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), and fats. Group hydrocarbons (hexane, cyclohexane, kerosene, gas oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amide (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil,
Vegetable oils such as cottonseed oil and the like can be mentioned.

As the gaseous carrier or propellant, for example,
Examples thereof include butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugars and the like. Alcohol compounds and the like can be mentioned.

Examples of pharmaceutical auxiliaries include casein, gelatin, polysaccharides (starch, gum arabic, cellulose compounds, alginic acid, etc.), lignin compounds, bentonite, saccharides, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone). , Polyacrylic acids, etc.)
Fixing agents such as PAP (acidic isopropyl phosphate), BB
H (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil And stabilizers such as fatty acids and esters thereof.

The preparation of the insecticide of the present invention thus obtained may be used as it is, or may be used after being diluted with water or the like. Also, other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, soil conditioners,
They may be used by mixing with animal feed or the like, or may be used simultaneously without mixing.

When the insecticide of the present invention is used for agricultural and horticultural purposes, its application rate is not particularly limited, and the concentration of the active ingredient, the formulation,
Types of target pests and crops, degree of pest damage, location of application, timing of application, method of application, and concomitant chemicals (pesticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, Power agent, soil conditioner, etc.) and the amount and type of fertilizer to be used.
It may be about 0.001 to 100 g per 0 m ^{2. When} the emulsion, wettable powder, flowable and the like are diluted with water and used, the application concentration is usually about 0.1 to 1000 ppm,
Preferably, it may be about 1 to 500 ppm. Granules,
Powders and the like are applied as they are without dilution.

The agricultural and horticultural insecticide of the present invention can be used, for example, for controlling the following pests.

Hemiptera: Leafhopper, Lepidoptera, Trichomeris terrestris, Scarabaeidae, Brown planthopper, Scarabaeidae, Pseudococcidae, Southern green stink bug, Nashigumbai, Onsujin whitefly, Tobacco whitefly,
Silver leaf whitefly, cotton aphid, cotton aphid, scorpion aphid, mosquito stag beetle, sword stag beetle, scorpion stag beetle, turtle stink bug, spider stag beetle, scorpion stag beetle, scorpion beetle, etc.

Lepidoptera: Kimmonhosoga, Chanohosoga,
Konaga, cotton migrant, chanokomokumakimaki, apple kokumakumonhamaki, chahamaki, ginmonhamogriga, citrus hamoglyga, bean squid mog, peach squid mog, cobnomeiga, nikameiga, awanomeiga, yotouga, awayoto, tossinca, narcissus
Noctuid, mugwort, etc.

Coleoptera: Scutellariae, Mamekogane,
Rice weevil, rice weevil, rice beetle beetle, cypress flea beetle, beetle beetle beetle, coconut, beetle beetle, scorpion beetle, adzuki beetle, pine beetle beetle, cricket beetle and the like.

Hymenoptera: Pteridopsis, Lulichrange, etc.

Diptera: Aedes aegypti, Aedes aegypti, bean leaf fly, soybean flies, flies, house flies, urimids, rice flies, flies, etc.

Coleoptera: human flea, dog flea and the like.

Thysanoptera: Thrips palmi, Thrips palmi, Thrips palmi, Thrips palmi, Rice thrips, Thrips thrips, and the like.

Louse: lice, lice, etc.

[0096] Chaptera: Cochate, Hiratate, etc.

Orthoptera: Kera, Tonosama grasshopper, Kobanineago, German cockroach, Black cockroach and the like.

[0098]

EXAMPLES The present invention will now be described specifically with reference to Reference Examples, Production Examples, Formulation Examples and Test Examples.

Reference Example 1 Production of 4- (6-chloropyridazin-3-yloxy) benzyl chloride 6.3 g (0.16 mol) of sodium hydride (60% oil) was suspended in 100 ml of dry dimethylformamide and cooled. Under stirring, 16.2 g (0.15 mol) of p-cresol dissolved in 50 ml of dry dimethylformamide was added dropwise. After stirring for 30 minutes at room temperature, the solution was cooled again,
22.4 g (0.15 mol) of 3,6-dichloropyridazine were added in portions. After stirring at room temperature for 2 hours, the reaction solution was poured into ice water, and the precipitated crystals were separated by filtration. The crude crystals were recrystallized from ethanol to give 3-colorless crystals.
Chloro-6- (4-methylphenoxy) pyridazine 31
g (94% yield).

Melting point 110-111 ° C. ¹ H-NMR (δ ppm / CDCl ₃ ): 2.4 (3H,
s), 7.0 (1H, d, J = 9.1 Hz), 7.1
(2H, d, J = 8.2 Hz), 7.2 (2H, d, J
= 8.2 Hz), 7.5 (1H, d, J = 9.1H)
z).

3.0 g (13.6 mmol) of 3-chloro-6- (4-methylphenoxy) pyridazine, 2.27 g (17.1 mmol) of N-chlorosuccinimide,
A mixture of 0.33 g (1.36 mmol) of benzoyl peroxide and 50 ml of carbon tetrachloride was heated under reflux for 2 hours. After cooling the reaction solution, insolubles were removed by filtration, and the filtrate was washed with water, a saturated aqueous solution of sodium hydrogencarbonate and brine in that order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained crude crystals were recrystallized from hexane / ethyl acetate to give 2.1 g of the title compound as colorless crystals (yield 60%).

Melting point 89-90 ° C. ¹ H-NMR (δ ppm / CDCl ₃ ): 4.6 (2H,
s), 7.2 (3H, m), 7.4 (3H, m).

Reference Example 2 Production of 4- (6-chloropyridazin-3-yl) benzyl bromide To 30 g (0.224 mol) of 4-methylacetophenone was added 42 g (0.457 mol) of glyoxylic acid monohydrate. Stirred at 120 ° C. for 15 hours. After cooling the reaction solution, 200 ml of ethanol and 20 ml of concentrated sulfuric acid were added, and the mixture was heated under reflux. The reaction solution was concentrated under reduced pressure to half the volume, 300 ml of water was added, and the mixture was extracted with 500 ml of ethyl acetate. After the ethyl acetate extract was dried over anhydrous magnesium sulfate, the resulting residue was treated with 100 ml of ethanol and 30 g of hydrazine monohydrate.
(0.6 mol) was added and refluxed for 2 hours. The reaction solution was cooled, and the precipitated crystals were collected by filtration to obtain 14 g of 3-hydroxy-6-p-tolylpyridazine as yellow crystals (yield: 3).
4%).

Melting point: 213 to 216 ° C. ¹ H-NMR (δ ppm / CDCl ₃ ): 2.4 (3H,
s), 7.1 (1H, d, J = 9 Hz), 7.2-7.
4 (2H, m), 7.7-7.9 (3H, m).

10 g (54 mmol) of 3-hydroxy-6-p-tolylpyridazine was added to 50 ml of phosphorus oxychloride, and the mixture was stirred at 80 ° C. for 1 hour and refluxed for 3 hours. The reaction solution was concentrated under reduced pressure, the obtained residue was poured into ice, and extracted with 300 ml of ethyl acetate. The ethyl acetate extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the obtained residue was purified by silica gel chromatography (hexane / ethyl acetate = 4/1), and further recrystallized from hexane / ethyl acetate. As a result, 4.0 g of 3-chloro-6-p-tolylpyridazine was obtained as colorless crystals (yield: 3).
6%).

Melting point: 148 to 151 ° C. ¹ H-NMR (δ ppm / CDCl ₃ ): 2.4 (3H,
s), 7.3 (2H, d, J = 8.0 Hz), 7.5
(1H, d, J = 9.0 Hz), 7.8 (1H, d, J
= 9.0 Hz), 8.0 (2H, d, J = 8.0H)
z).

3.0 g (14.7 mmol) of 3-chloro-6-p-tolylpyridazine, 3.13 g (17.6 mmol) of N-bromosuccinimide, 0.36 g of benzoyl peroxide and 50 ml of carbon tetrachloride The mixture was heated at reflux for 3 hours. After cooling the reaction solution, insolubles were removed by filtration,
The filtrate was washed successively with water, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate / hexane.
3.0 g of the title compound was obtained as colorless crystals (yield: 72).
%).

Melting point 140-150 ° C. ¹ H-NMR (δ ppm / CDCl ₃ ): 4.6 (2H,
s), 7.6 (3H, m), 7.8 (1H, d, J =
8.9 Hz), 8.1 (2H, d, J = 8.3 Hz).

Reference Example 3 N- [4- (pyridazin-3-yloxy) benzyl]
Preparation of ethyl isonipecotate 2.55 g (10 mmol) of 4- (6-chloropyridazin-3-yloxy) benzyl chloride, 1.57 g (10 mmol) of ethyl isonipecotate and 1.52 g (11 mmol) of potassium carbonate were mixed with 50 m of acetonitrile.
and stirred under reflux for 2 days. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure. Silica gel chromatography of the residue (hexane / ethyl acetate = 2/1 to 1/4)
To give 3.16 g of ethyl N- [4- (6-chloropyridazin-3-yloxy) benzyl] isonipecotate as colorless crystals (yield 84%).

¹ H-NMR (δppm / CDCl ₃ ):
1.3 (3H, t, J = 7.1 Hz), 1.6-2.0
(4H, m), 2.0-2.1 (2H, m), 2.2-
2.3 (1H, m), 2.8-2.9 (2H, m),
3.5 (2H, s), 4.1 (2H, q, J = 7.1H)
z), 7.1-7.2 (3H, m), 7.4 (2H,
d, J = 8.5 Hz), 7.5 (1H, d, J = 9.1)
Hz).

N- [4- (6-chloropyridazine-3-
Yloxy) benzyl] ethyl isonipecotate 1.0
g (2.7 mmol) and 0.11 g of sodium hydroxide
(2.7 mmol) in 10 ml of methanol
A catalytic amount of 0% palladium carbon was added, and the mixture was stirred under a hydrogen atmosphere until the reaction was completed. The reaction solution was filtered through celite, and the filtrate was concentrated under reduced pressure. 50 ml of ethyl acetate in the residue
Was added, washed with water and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 0.94 g of the title compound as colorless crystals (quantitative).

¹ H-NMR (δppm / CDCl ₃ ):
1.3 (3H, t, J = 7.1 Hz), 1.6-2.0
(4H, m), 2.0-2.1 (2H, m), 2.2-
2.3 (1H, m), 2.8-2.9 (2H, m),
3.5 (2H, s), 4.1 (2H, q, J = 7.1H)
z), 7.1-7.2 (3H, m), 7.4 (2H,
d, J = 8.5 Hz), 7.4-7.5 (1H, m),
8.9 (1H, d).

Production Reference Example 4 Production of 4- (6-methanesulfonylpyridazin-3-yloxy) benzyl bromide 1.0 g (4.55 mmol) of 3-chloro-6- (4-methylphenoxy) pyridazine and 0 of thiourea .45g
(5.91 mmol) in 10 ml of ethanol,
The mixture was heated under reflux for 2 hours. 0.4 g of sodium hydroxide (10
Mmol), and the mixture was stirred at room temperature for 30 minutes. Then, 0.71 g (5.0 mmol) of methyl iodide was added, and the mixture was stirred for 15 hours. The reaction solution was poured into water, and the precipitated crystals were separated by filtration to obtain 0.95 g of 4- (6-methylthiopyridazin-3-yloxy) toluene as colorless crystals (89% yield).

¹ H-NMR (δppm / CDCl ₃ ):
2.35 (3H, s), 2.65 (3H, s), 6.9
0-7.30 (6H, m).

0.95 g (4.1 mmol) of 4- (6-methylthiopyridazin-3-yloxy) toluene was dissolved in 30 ml of chloroform, and 1.4 g (8.2 mmol) of m-chloroperbenzoic acid was stirred under cooling and stirring. Was added and stirred at room temperature for 2 days. The reaction solution was washed with a saturated aqueous solution of sodium hydrogen carbonate and saturated saline in this order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 4- (6-methanesulfonylpyridazin-3-yloxy) toluene as colorless crystals. 81 g was obtained (83% yield).

¹ H-NMR (δppm / CDCl ₃ ):
2.38 (3H, s), 3.38 (3H, s), 7.1
0 (2H, d, J = 8.35 Hz), 7.26 (2H,
d, J = 8.35 Hz), 7.36 (1H, d, J =
9.20 Hz), 8.13 (1H, d, J = 9.20H)
z).

4- (6-methanesulfonylpyridazine-
3-yloxy) toluene 0.81 g (3.4 mmol), N-bromosuccinimide 0.74 g (4.1 mmol), catalytic amount of benzoyl peroxide and carbon tetrachloride 3
0 ml of the mixture was heated at reflux for 3 hours. After cooling the reaction solution, insoluble materials were removed by filtration, and the filtrate was washed with a saturated aqueous solution of sodium hydrogen carbonate and saturated saline in this order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give the title compound as brown crystals. 0.75 g was obtained (63% yield).

¹ H-NMR (δppm / CDCl ₃ ):
3.38 (3H, s), 4.52 (2H, s), 7.0
-8.2 (6H, m).

Production Example 1 N- [4- (6-chloropyridazin-3-yloxy)
Production of benzyl] -4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine (compound 6) 4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine hydrochloride 0.50 g (1.1 Mmol), 0.27 g (1.1 mmol) of 4- (6-chloropyridazin-3-yloxy) benzyl chloride and 0.32 g (2.3 mmol) of potassium carbonate are suspended in 20 ml of acetonitrile and refluxed for 15 hours. Stirred. After cooling, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure.
The residue was purified by silica gel chromatography (hexane / ethyl acetate = 5/1 to 2/1) to give the title compound, 0.1.
62 g was obtained as an amorphous solid (89% yield).

¹ H-NMR (δppm / CDCl ₃ ):
1.3-1.5 (4H, m), 1.9-2.1 (2H,
m), 2.2 (1H, bs), 2.3-2.5 (1H,
m), 2.9 (2H, m), 3.5 (2H, s), 7.
0-7.2 (7H, m), 7.3 (2H, d, J = 8.
5 Hz), 7.4-7.6 (5H, m).

Production Example 2 N- [4- (pyridazin-3-yloxy) benzyl]
Preparation of 4- [bis (4-trifluoromethylphenyl) hydroxymethyl] piperidine (Compound 15) Grignard reagent prepared from 2.37 g (11 mmol) of 4-bromobenzotrifluoride and 0.28 g (12 mmol) of magnesium To 10 ml of a dry tetrahydrofuran solution under cooling and stirring.
0.90 g of ethyl N- [4- (pyridazin-3-yloxy) benzyl] isonipecotinate dissolved in 0 ml
(2.6 mmol) was added dropwise. After stirring at room temperature for 1 hour, the mixture was heated under reflux for 15 hours. After cooling, the reaction solution was filtered through celite, and the filtrate was concentrated. The residue was purified by silica gel chromatography (chloroform / methanol = 100/1) to give the title compound (0.63 g) as an amorphous solid (yield 41%).

¹ H-NMR (δppm / CDCl ₃ ):
1.3-1.6 (4H, m), 2.0-2.1 (3H,
m), 2.4-2.6 (1H, m), 3.0 (2H,
m), 3.5 (2H, s), 7.1-7.2 (3H,
m), 7.3 (2H, d, J = 8.5 Hz), 7.5
(1H, m), 7.5-7.7 (8H, m), 8.9
(1H, m).

Production Example 3 Production of N- [4- (6-methanesulfonylpyridazin-3-yloxy) benzyl] -4- [bis (4-trifluoromethylphenyl) hydroxymethyl] piperidine (Compound 20) 4- [ Bis (4-trifluoromethylphenyl) hydroxymethyl] piperidine hydrochloride 0.72 g (1.6 mmol), 4- (6-methanesulfonylpyridazine-3-
0.75 g (2.2 mmol) of yloxy) benzyl bromide and 0.6 g (4.4 mmol) of potassium carbonate were suspended in 20 ml of acetonitrile and stirred under reflux for 15 hours. The reaction solution was poured into 30 ml of water and extracted twice with 30 ml of diethyl ether. After washing the combined ether extract with saturated saline, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel chromatography (chloroform / methanol = 100/1) to obtain 0.73 g of the title compound as an amorphous solid (yield 67%).

¹ H-NMR (δppm / CDCl ₃ ):
1.4-1.7 (4H, m), 1.9-2.2 (2H,
m), 2.4 (1H, s), 2.5 (1H, m), 3.
0 (2H, m), 3.4 (3H, s), 3.5 (2H,
s), 7.1 (2H, d, J = 8.5 Hz), 7.4
(2H, d, J = 8.5 Hz), 7.4 (1H, d, J
= 9.1 Hz), 7.5-7.7 (8H, m), 8.2
(1H, d, J = 9.1 Hz).

Production Example 4 N- [4- (p-tolylpyridazin-3-yloxy)
Benzyl] -4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine (Compound No. 1
Preparation of 4) 0.54 g (1.0 mmol) of N- (4-hydroxybenzyl) -4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine, 3-chloro-6
-(P-tolyl) pyridazine 0.20 g (1.0 mmol), potassium carbonate 0.14 g (1.0 mmol) and 18-crown-6 0.03 g (0.11 mmol)
Are suspended in 10 ml of dry dimethyl sulfoxide, and 13
Stirred at 0 ° C. for 15 hours. After cooling, the reaction solution was diluted with 60 ml of ethyl acetate, washed three times with 100 ml of water, further washed with saturated saline, and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was subjected to silica gel chromatography (hexane / ethyl acetate = 4/4).
The resulting product was purified as an amorphous solid to give 0.35 g of the title compound as an amorphous solid (yield 49%).

¹ H-NMR (δppm / CDCl ₃ ):
1.4-1.5 (4H, m), 1.9-2.1 (2H,
m), 2.2 (1H, m), 2.3-2.5 (1H,
m), 2.4 (3H, s), 3.0 (2H, m), 3.
5 (2H, s), 7.1-7.4 (11H, m), 7.
5 (4H, m), 7.8 (1H, d, J = 9.2H
z), 7.9 (2H, d, J = 8.2 Hz).

Production Example 5 N- [4- (6-Methylthiopyridazin-3-yloxy) benzyl] -4- [bis (4-trifluoromethylphenyl) hydroxymethyl] piperidine (Compound 1)
Production of 9) Production Example 1 except that 4- [bis (4-trifluoromethylphenyl) hydroxymethyl] piperidine hydrochloride was used instead of 4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine hydrochloride. In the same manner as in the above, N- [4- (6-chloropyridazin-3-yloxy) benzyl] -4- [bis (4-trifluoromethylphenyl) hydroxymethyl] piperidine was obtained.

0.8 g (1.3 mmol) of N- [4- (6-chloropyridazin-3-yloxy) benzyl] -4- [bis (4-trifluoromethylphenyl) hydroxymethyl] piperidine obtained above. )) And 0.18 g (2.6 mmol) of methyl mercaptan sodium salt were suspended in 30 ml of dry tetrahydrofuran,
The mixture was stirred under reflux for an hour. 30 ml of water was added to the reaction solution, and extracted twice with 30 ml of ethyl acetate. The combined ethyl acetate extract was washed with saturated saline and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel chromatography (benzene / ethyl acetate = 1/2) to obtain 0.3 g of the desired product as an amorphous solid (yield 37). %).

¹ H-NMR (δppm / CDCl ₃ ):
1.4-1.6 (4H, m), 1.8 (1H, bs),
2.0-2.1 (2H, m), 2.5 (1H, m),
2.6 (3H, s), 2.9-3.0 (2H, m),
3.5 (2H, s), 7.0 (1H, d, J = 9.2H)
z), 7.1 (2H, d, J = 8.5 Hz), 7.2-
7.3 (3H, m), 7.5 (4H, d, J = 9.0H
z), 7.6 (4H, d, J = 9.0 Hz).

Production Example 6 N- [4- (6-chloropyridazin-3-yloxy)
Production of benzyl] -4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine N-oxide (compound 7) N- [4- (6-chloropyridazin-3-yloxy)
Benzyl] -4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine 0.65 g (1
Was dissolved in 30 ml of methylene chloride, and 0.22 g (1.25 mmol) of m-chloroperbenzoic acid was added under cooling and stirring. After stirring at room temperature for 1 hour, the reaction solution was washed with a 10% aqueous sodium hydroxide solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained crude crystals were washed with hexane / ethyl acetate and dried to give 0.45 g of the title compound as colorless crystals (yield 67%).

Melting point: 197 to 198 ° C. ¹ H-NMR (δ ppm / CDCl ₃ / DMSO-
_{d 6): 1.2-1.4 (2H,} m), 2.0 (1H,
bs), 2.4 (1H, m), 2.8-2.9 (2H,
m), 3.0-3.2 (2H, m), 3.2-3.3
(2H, m), 4.4 (2H, s), 7.0-7.1
(4H, m), 7.2-7.3 (3H, m), 7.5-
7.7 (7H, m).

¹ H-NMR (δppm / DMSO-
_{d 6): 0.9-1.0 (2H,} m), 2.1-2.3
(2H, m), 2.5-2.6 (1H, m), 2.8-
2.9 (2H, m), 3.0-3.2 (2H, m),
4.2 (2H, s), 6.7 (1H, bs), 7.1-
7.2 (6H, m), 7.5-7.6 (7H, m),
7.9 (1H, d, J = 9.2 Hz).

Production Example 7 N- [4- (6-chloropyridazin-3-yloxy)
Preparation of benzyl] -4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine fumarate (compound 10) N- [4- (6-chloropyridazin-3-yloxy)
Benzyl] -4- [bis (4-trifluoromethoxyphenyl) hydroxymethyl] piperidine 0.3 g (0.
A mixture of 46 mmol), 0.053 g (0.46 mmol) of fumaric acid and 30 ml of dehydrated ethanol was heated under reflux for 2 hours. The reaction solution was concentrated under reduced pressure, and further dried under reduced pressure over phosphorus pentoxide for 3 hours to obtain 0.35 g of the title compound as colorless crystals (quantitative).

Melting point: 119-120 ° C., decomposition ¹ H-NMR (δ ppm / DMSO-d ₆ ): 1.2 (2
H, m), 1.5 (2H, m), 2.2 (2H, m),
2.6 (1H, m), 2.9 (2H, m), 3.6 (2
H, s), 6.6 (2H, s), 7.2 (2H, d, J
= 7.8 Hz), 7.3 (4H, d, J = 8.5H)
z), 7.4 (2H, d, J = 7.8 Hz), 7.5
(1H, d, J = 9.2 Hz), 7.6 (4H, d, J
= 8.5 Hz), 8.0 (1H, d, J = 9.2H)
z).

The compounds prepared according to any of the methods described in the above Preparation Examples and their physicochemical properties are shown in Table 1. Tables 2 to 5 show NMR spectrum data of each compound shown in Table 1.

In the measurement of the NMR spectrum data of each compound, tetramethylsilane (TM
S) was used. The measurement of a compound of Compound No. 7 and Compound No. 10 was used DMSO-d ₆ as solvent. In addition, for the measurement of the compound No. 7 and the compound No. 17, these compounds were suspended in CDCl ₃ , and a few drops of DMSO-d ₆ were added to make a clear solution, which was subjected to NMR spectrum measurement. . For the measurement of compounds other than the above, CDCl ₃ was used as a solvent.

[0137]

[Table 1]

[0138]

[Table 2]

[0139]

[Table 3]

[0140]

[Table 4]

[0141]

[Table 5]

Next, preparation examples are shown. It should be noted that simply “parts” means parts by weight.

Formulation Example 1 Emulsion 10 parts of each of the compounds of the present invention were mixed with Solvesso 150 45
And 35 parts of N-methylpyrrolidone, 10 parts of Solpol 3005X (Emulsifier manufactured by Toho Chemical Co., Ltd.) was added and mixed with stirring to obtain 10% emulsions of each.

Formulation Example 2 Wettable powder 20 parts of each of the compounds of the present invention were added to a mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium ligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of clay. The mixture was stirred and mixed with a juice mixer to obtain a 20% wettable powder.

Formulation Example 3 Granules To 5 parts of each of the compounds of the present invention, 2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite and clay 83
The mixture was added and mixed well with stirring. An appropriate amount of water was added, further stirred, granulated with a granulator, and dried by ventilation to obtain 5% granules.

Formulation Example 4 Powder One part of each of the compounds of the present invention was dissolved in an appropriate amount of acetone.
To this, 5 parts of synthetic hydrous silicon oxide fine powder, 0.3 parts of acidic isopropyl phosphate (PAP) and 93.7 parts of clay were added, and mixed by stirring with a juice mixer, and acetone was removed by evaporation to obtain a 1% powder. .

Formulation Example 5 Flowable agent 20 parts of each of the compounds of the present invention, 3 parts of polyoxyethylene tristyryl phenyl ether phosphate triethanolamine, and 20 parts of water containing 0.2 part of RHODORSIL 426R were mixed, and Dynomill was added. After wet pulverization, 8 parts of propylene glycol, xanthan gum 0.3
It was mixed with 60 parts of water containing 2 parts to obtain a 20% suspension in water.

Next, Test Examples show that the compounds of the present invention are useful as active ingredients of insecticides.

Test Example 1 Insecticidal test against Spodoptera litura The chemical solution (200 ppm) was prepared by adding an aqueous solution (100 ppm) of Solpol 355 (manufactured by Toho Chemical Co., Ltd.) to a methanol solution of the test compound, and the chemical solution was cabbage leaf pieces (5 × 5 cm). ) Sprayed on two pieces and air-dried. Put the leaf pieces in a plastic cup lined with filter paper moistened with tap water, release 30 second-instar larvae of the cutworm, Spodoptera litura, cover with a small hole, and put it in a thermostatic chamber at 25 ± 2 ° C and 50% humidity. It was left still. Two days after the treatment, the mortality of Spodoptera litura was examined.

As a result, Compound Nos. 2, 5, 6, 7,
8, 9, 10, 11, 12, 13, 15, 16, 17,
Compounds 18, 19 and 24 showed 100% mortality.

Test Example 2 Comparative Test for Insecticidal Activity against Spodoptera litura The compound of the present invention of compound No. 6 and US Pat.
The insecticidal compound A described in the specification of Japanese Patent No. 644 was subjected to an insecticidal comparative test against Spodoptera litura.

Compound A:

[0153]

Embedded image

An aqueous solution (100 ppm) of Solpol 355 (manufactured by Toho Chemical Co., Ltd.) was added to a methanol solution of the test compound to prepare a drug solution (10 ppm). The following test method is the same as in Test Example 1.

As a result, the compound of the present invention of compound No. 6 showed a mortality of 100%. On the other hand, control compound A had 45
% Mortality.

Test Example 3 Comparative Test of Insecticidal Activity against Japanese Conger The compound of the present invention of compound No. 6 and US Pat. No. 5,569,
The insecticidal compound A described in the specification of Japanese Patent No. 644 was subjected to an insecticidal comparative test against Japanese moth.

An aqueous solution (100 ppm) of Solpol 355 (manufactured by Toho Chemical Co., Ltd.) was added to a methanol solution of the test compound to prepare a drug solution (20 ppm), and the drug solution was sprayed on one cabbage leaf piece (5 × 5 cm). Air dried. Put the leaf pieces in a plastic cup covered with filter paper moistened with tap water, release 15 second instar larvae of the Japanese moth, cover them with small holes, put them in a constant temperature room at 25 ± 2 ° C and 50% humidity. It was left still. Two days after the treatment, the insect mortality and the degree of food damage were examined.

As a result, the compound of the present invention of Compound No. 6 showed a 100% mortality and a cabbage damage of 5%. On the other hand, the control compound A had a mortality of 8% and a cabbage
%Met.

Test Example 4 Comparative test of insecticidal activity against armyworm, compound of the present invention of compound Nos. 6 and 16, and WO96 /
The insecticidal compound B described in No. 36228 was subjected to an insecticidal comparative test against the armyworm.

Compound B:

[0161]

Embedded image

An aqueous solution (100 ppm) of Solpol 355 (manufactured by Toho Chemical Co., Ltd.) was added to a methanol solution of the test compound to prepare a drug solution (10 ppm), and the drug solution was sprayed on two pieces of cabbage leaf (5 × 5 cm). Air dried. Put the leaf pieces in a plastic cup covered with filter paper moistened with tap water, release 20 third-instar larvae of the armyworm, cover with a small hole, put in a constant temperature room at 25 ± 2 ° C and 50% humidity. It was left still. Four days after the treatment, the mortality of the armyworm and the degree of damage to the untreated plot were examined.

As a result, the compounds of the present invention of Compound Nos. 6 and 16 both showed 100% mortality. In addition, the cabbage damage rates of the compounds of the present invention of Compound Nos. 6 and 16 were 20% and 16%, respectively. On the other hand, control compound B had a mortality of 16% and a degree of cabbage damage of 90%.
Met.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Manabe 615 Hanato, Satoura-cho, Satoura-cho, Naruto City, Tokushima Prefecture Inside Naruto Research Laboratories of Otsuka Chemical Co., Ltd. Inside Naruto Research Laboratories Co., Ltd. (72) Inventor Yasuhiro Sasama 615, Hanato, Satoura-cho, Satoura-cho, Naruto City, Tokushima Otsuka Chemical Co., Ltd. F-term in the company Naruto Research Laboratories (reference) 4C063 AA01 BB06 BB08 CC28 DD10 EE03 4H011 AC01 AC02 DA02 DA15 DA16 DD03

Claims (6)

[Claims] 1. A compound of the general formula (1) Wherein R ¹ is a hydrogen atom, a halogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-4 haloalkyl group or
_{1-4 represents a} haloalkoxy group. The two R ¹ 's may be the same or different. R ² is a hydrogen atom, a hydroxyl group, a halogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-4 haloalkyl group, a C _1-4 haloalkoxy group,
(C _1-4 alkoxy) carbonyl group, C _1-4 alkylthio group, C _1-4 alkylsulfonyl group, nitro group, cyano group, phenyl group which may have a substituent, phenoxy group which may have a substituent A group —NR ⁴ R ⁵ (R ⁴ and R ⁵ are the same or different and are a hydrogen atom, a C _1-4 alkyl group,
(C _1-4 alkyl) carbonyl group, (C _1-4 alkoxy)
It represents a carbonyl group, a (C _1-4 alkyl) aminocarbonyl group or a di (C _1-4 alkyl) aminocarbonyl group.
Alternatively, R ⁴ and R ⁵ may be bonded to each other to represent a linear C _2-6 alkylene group (the alkylene group may be substituted with a C _1-4 alkyl group, Or a linear alkylene group may contain an oxygen atom.)) Or a group —C (O) NR ⁶ R ⁷ (R ⁶ and R ⁷ may be the same or different and represent a hydrogen atom, C _{1 -4} alkyl group or C _1-4 alkoxy group, or R ⁶ and R ⁷ may be bonded to each other to form a linear C _2-6 alkylene group (the alkylene group is _May be substituted by a C _1-4 alkyl group, or may contain an oxygen atom in a linear alkylene group.)). R ³ represents a halogen atom, a C _1-4 alkyl group or a C _1-4 alkoxy group. Z
Is an oxygen atom, a group -S (O) _p- (p is an integer of 0 to 2) or a group -N (R ⁸ )-(where R ⁸ is a hydrogen atom, C _1-4
Alkyl group, (C _1-4 alkyl) carbonyl group, (C _1-4
An alkoxy) carbonyl group, a (C _1-4 alkyl) aminocarbonyl group or a di (C _1-4 alkyl) aminocarbonyl group. ). m represents an integer of 0 to 2, and n represents 0 or 1. A benzylpiperidine compound, an N-oxide thereof or a salt thereof. 2. In the above general formula (1), R ¹ is a halogen atom, a C _1-4 haloalkyl group or a C _1-4 haloalkoxy group, R ² is a hydrogen atom, a halogen atom, a C _1-4 alkyl group, C _1-4 alkoxy group or C _1-4 haloalkoxy group, Z
Is an oxygen atom or a group -S (O) _p- (wherein p is as defined above), m is 0 and n is 1, the benzylpiperidine compound, its N-oxide form or its salt. . 3. In the general formula (1), R ¹ is C _1-4
The benzylpiperidine compound according to claim 1, wherein the haloalkyl group or C _1-4 haloalkoxy group, R ² is a halogen atom, Z is an oxygen atom, m is 0 and n is 1, an N-oxide form or a salt thereof. 4. A compound of the general formula (2) Wherein R ¹ is the same as above. And a piperidine compound represented by the general formula (3): Wherein R ² , R ³ , m and n are the same as above. X represents a halogen atom. The method for producing a benzylpiperidine compound according to claim 1, wherein the compound is reacted with a benzyl halide represented by the formula: 5. A compound of the general formula (4) Wherein R ² , R ³ , Z, m and n are the same as above. R ⁹ represents a C _1-4 alkyl group. And N-benzylisonipecotic acid ester represented by the general formula (5): Wherein R ¹ is the same as above. X represents a halogen atom. The method for producing a benzylpiperidine compound according to claim 1, wherein the reaction is carried out with a Grignard reagent represented by the following formula: 6. A pesticide for agricultural and horticultural use comprising the benzylpiperidine compound according to claim 1, 2 or 3 as an active ingredient.