WO2001044154A1

WO2001044154A1 - Dihalopropenyloxybenzene derivatives and pesticides containing the same as the active ingredient

Info

Publication number: WO2001044154A1
Application number: PCT/JP2000/008870
Authority: WO
Inventors: Manabu Katsurada; Shinji Kawata; Nobuo Kyomura; Yasushi Shiga; Toshiki Fukuchi; Risa Yamada
Original assignee: Mitsubishi Chemical Corporation
Priority date: 1999-12-17
Filing date: 2000-12-14
Publication date: 2001-06-21
Also published as: AU2023801A

Abstract

Dihalopropenyloxybenzene derivatives represented general formula (I) which have a very excellent effect of controlling pests in the field of agriculture, horticulture, daily life, livestock, pets, etc. (in particular, injurious insects and mites in the fields of agriculture and horticulture) and are highly safe to mammals and fishes wherein A represents aryl, a heterocycle, etc.; W represents oxygen, sulfur, etc.; Q represents aryl, a heterocycle, etc.; R?1, R2, R3, R4, R5 and R6¿ represent each hydrogen, alkyl, etc., or R?1 and R2, R3 and R4, and R5 and R6¿ may form together each alkylidene or alkylenedioxy; p, q and r are each an integer provided that p + q + r is not more than 9; X?1 and X2¿ represent each halogeno, alkyl, etc.; Y represents halogeno, alkyl or haloalkyl; n is an integer of 0 to 2; and Z represents halogeno.

Description

Technical Field Dihalopropenyloxybenzene derivatives and pest control agents containing the same as active ingredients

The present invention relates to a dihalopropenyloxybenzene derivative and an intermediate for producing the same, and a pesticidal agent containing the dihalopropenyloxybenzene derivative as an active ingredient. The present invention relates to pesticides, especially insecticides and acaricides in pets.

The fact that dihalopropenyloxybenzene derivatives have biological activities such as insecticidal and acaricidal activity is disclosed in WO 96Z04228 (corresponding US Patent Publication: US5872137) and W096 / 11909 (corresponding US Patent Publication). : US Pat. No. 5,922,880) and WO 96/33160 (corresponding US patent publication: US 5952386).

However, in each case, only those in which the linking group bonded to the dihalopropenyloxyphenyl group is an oxygen atom, a sulfur atom, or an amino group are described.

However, when the linking group bonded to the dihalopropenyloxyphenyl group is a compound having a substituent having a carbon atom as a linking group, a compound having a carbon atom as a linking group is more preferable than a compound having an oxygen atom, a sulfur atom or an amino group. This is preferable because the variation in synthesizing the compound greatly increases.

On the other hand, the claims of Japanese Patent Application Laid-Open No. 7-188088 (corresponding US Patent Publication: US 5530015) include _C (R ⁴ ) ₂ — , -C (CF ₃ ) ₂ — are described as linear or branched hydrocarbon groups, but specifically disclosed are (substituted) methyl groups having a phenyl group. With only the ren group, the biological effect was also confirmed only for a part of the lotus beetle and the moss, and in Japanese Patent Application Laid-Open No. Hei 7-330651, dihalopro Only the linking group linked to the niloxyphenyl group is described with respect to a specific hydrocarbon group of phenyl—C (CF ₃ ) ₂ —. It was just doing things.

Further, WO98544848 describes that a compound having a difluoroalkenyl group at a terminal is effective as an insecticide and acaricide, and specific examples thereof are shown below. Although there are examples of compounds having a similar structure,

MeO, _kl

_{_{_{- 2 C = CHCH 2 CH 2}}} CH 2 CO-0-N = C (Me) -C- ^ -0-CH 2 CH = CCI 2

There is no evidence of any biological activity for this compound.

As described above, a dihalopropenyloxybenzene derivative having an insecticidal and acaricidal effect is one in which the linking group bonded to the dihalopropenyloxyphenyl group is an oxygen atom, a sulfur atom, or an amino group. However, although a substituent having a carbon atom as a linking group is preferable because a variation in the synthesis of a compound is significantly increased, only a limited number of substituents are known. It has not been done yet.

In the field of insecticides and acaricides, the emergence of new insecticides and acaricides with new structures has been desired one after another due to problems such as resistance to chemicals.

Therefore, among compounds in which the linking group bonded to the dihalopropenyloxyphenyl group is a carbon atom, a compound that is effective as an insecticide or acaricide is found, and is superior to the known compounds as described above. It has been desired to find a compound that has an insecticidal and acaricidal effect and an insecticidal spectrum and that is highly safe for mammals and fish. <Disclosure of Invention>

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a group of compounds in which the linking group bonded to the dihalopropyloxyphenyl group is a group having a carbon atom. That the compound has insecticidal and acaricidal activity, in particular, as a terminal substituent, an aryloxyaryloxy group, a heterocyclicoxyaryloxy group, an aryloxyheterocyclicoxy group, or a heterocyclic group. Cyclic oxyhetero Compounds having a specific substituent, a cyclic oxy group, exhibit high insecticidal and acaricidal effects against insects of the order Coleoptera, such as citrus insects, and are extremely safe for mammals and fish. This led to the completion of the present invention.

That is, the gist of the present invention is represented by the following general formula (I)

[In the above general formula, A represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, a aryl group which may be substituted or substituted. Represents a heterocyclic group which may be

W represents a single bond, an oxygen atom, a sulfur _{atom, - SO-, - S0 2 -} , - NR 7 -, - N = C (R 7) -, - C (R 7) = N0-, - 0N = C (R ⁷ ) ―, — C (R ⁷ ) = N — N = C (R ⁸ ) one, -CO-, — COO—, one ◦ CO-, _NR ⁷ —C0-, — CONR ⁷ — (Where R ⁷ and R ^{8 each} independently represent a hydrogen atom or an alkyl group.),

Q is one S〇 one, one S 0 ₂ —, one N = C (R ⁹ ) one, one C (R ⁹ ) = N 0 —,-0 N = C (R ⁹ ) ―, ― C (R ⁹ ) = N-N two ^{C (R 10) -, -} CO-, -COO -, one 〇- CO-, one NR ⁹ - CO-, one CONR ⁹ -, optionally substituted § aryl group or a substituted, which may have been the good shows the heterocyclic group are (wherein the R ⁹及beauty R ^{1 Q,} it it independently. represents a hydrogen atom or an alkyl group), RR ² , R ³ , R ⁴ , R ⁵ and R ^{6 each} independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an alkoxyalkyl group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be taken together to form an alkylidene group or an alkylenedioxy group,

p, q and r are integers, and p + q + r is 9 or less (where Q is — S 0—, one S〇 ₂ —, one C (R ⁹ ) = NO—, one COO In the case of — or one C0NR ⁹ —, r is 1 or more, and when Q is a phenyl group, r = 0, and Q is — 0N = C (R ⁹ ) one or — 0—CO And q is 1 or more when W is an oxygen atom or a sulfur atom.),

乂¹ and 乂^{2 each} independently represent a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group;

Y represents a halogen atom, an alkyl group or a haloalkyl group,

n represents an integer of 0 to 2, and Z represents a halogen atom. ]

And a pesticidal agent containing the same as an active ingredient, particularly an insecticide and acaricide.

Further, another gist of the present invention is to provide an intermediate of the above-mentioned dihalopropenyloxybenzene derivative represented by the following general formula (II):

[In the above general formula, Q ¹ represents a halogen atom, a hydroxyl group, an aminooxy group, an oxyamino group, an alkoxy group, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group or a haloarylsulfonyloxy group. Indicates that

R ⁵ ′ and R ⁶ ′ each independently represent a hydrogen atom or an alkyl group, r represents an integer of 9 or less,

X ¹ and X ^{2 each} independently represent a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group;

Y represents a halogen atom, an alkyl group or a haloalkyl group,

n represents an integer of 0 to 2, and Z represents a halogen atom. ]

A dihalopropenyloxybenzene derivative represented by

And the following general formula (III)

^--- ( ^m )

[In the above general formula, Q ² represents an oxygen atom or a hydroxyimino group,

Q ³ represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydrazino group or an alkyl group;

1 and AI2 ^each independently represent a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group;

Y represents a halogen atom, an alkyl group or a haloalkyl group,

n represents an integer of 0 to 2, and Z represents a halogen atom. ]

In the dihalopropenyloxybenzene derivative represented by

Hereinafter, the present invention will be described in detail.

The dihalopropenyloxybenzene derivative, which is an active ingredient of the insecticide and acaricide of the present invention, is represented by the above general formula (I).

In the above general formula (I), A is a hydrogen atom; a methyl group which may be substituted, Ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl A chain, branched or cyclic alkyl group such as a cyclohexyl group; an optionally substituted chain, branched or cyclic alkenyl group such as a vinyl group, a propenyl group, a butenyl group or a hexenyl group; An alkynyl group such as an ethynyl group, a butynyl group or a pentenyl group which may be substituted; an aryl group such as a phenyl group or a naphthyl group which may be substituted; or a pyridyl group which may be substituted Thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, furyl group, chenyl group, morphoyl group, benzodioxanyl group, benzofuranyl It represents a heterocyclic group such as a group, and the alkyl group, alkenyl group and alkynyl group preferably have 10 or less carbon atoms.

A is preferably an aryl group or a heterocyclic group which may be substituted, and particularly preferably a phenyl group or a pyridyl group which may be substituted.

Examples of the substituent of the alkyl, alkenyl and alkynyl groups described above A, is not particularly limited as long as it is a group which does not affect the insecticidal activity, specifically, it includes groups that are tables in G ^1.

Examples of the group represented by G ¹ include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group and an n-butoxy group; a trifluoromethoxy group and a difluoromethoxy group. Haloalkoxy groups such as trifluoroethoxy group; aryl groups such as phenyl group and naphthyl group; aryloxy groups such as phenoxy group and naphthyloxy group; pyridyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl. And heterocyclic groups such as a group, a furyl group, a phenyl group, a morphyl group, a benzodioxanyl group, and a benzofuranyl group; and a heterocyclic group such as a pyridyloxy group, a furyloxy group, and a thiazolyloxy group. .

The alkoxy group and haloalkoxy group in G ¹ are preferably those having 4 or less carbon atoms. Incidentally, the aryl group, aryloxy group, heterocyclic group and heterocyclic oxy group exemplified in the above G ¹ further include a halogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, as exemplified above. A substituent selected from the group consisting of a haloalkoxy group, an alkylthio group, a haloalkylthio group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, and a haloalkylsulfonyl group, preferably a halogen atom, an alkyl group, a haloalkyl May be substituted with a substituent selected from the group consisting of a group, an alkoxy group, a haloalkoxy group, an alkylthio group and a haloalkylthio group.

Examples of the substituent of Ariru heterocyclic group group and the above A, is not particularly limited as long as it is a group which can not affect the insecticidal activity, specifically, include groups represented by G ² .

The group represented by G ^2, in addition to the substituents exemplified above G ^1, Shiano group; methylcarbamoyl group, Echiru group, n- propyl group, iso- propyl, n- butyl group, sec- butyl group Haloalkyl groups such as trifluoromethyl group, difluoromethyl group, trifluoromethyl group, dichlorodifluoroethyl group; formyl group; acyl groups such as methylcarbonyl group and ethylcarbonyl group; Acyloxy groups such as acetooxy group and propanoloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, iso-propylthio group and n-butylthio group. Haloalkylthio groups such as trifluoromethylthio and trifluoroethylthio; methylsulfinyl Alkylsulfinyl groups such as phenyl group, ethylsulfinyl group, n-propylsulfinyl group, iso-propylsulfinyl group and n-butylsulfinyl group; haloalkylsulfinyl groups such as trifluoromethylsulfinyl group and trifluoroethylsulfinyl group Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group; and trifluoromethylsulfonyl group, trifluoroethylsulfonyl group and the like; A haloalkylsulfonyl group. Two adjacent substituents of these substituents are joined together to form a methylenedioxy group, an ethylenedioxy group. And may form a condensed ring with an aryl group or a heterocyclic group.

Alkyl groups in G ^2, a haloalkyl group, an alkoxy group, a haloalkoxy group, § sill group, Ashiruokishi group, an alkoxycarbonyl group, an alkylthio group, Haroaru Kiruchio group, alkylsulfinyl group, haloalkylsulfinyl group, an alkyl sulfonyl group and haloalkylsulfonyl group Are preferably those having 4 or less carbon atoms.

G ² is preferably a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, or a haloalkylthio group. (When two adjacent substituents of these substituents together form And may form a condensed ring with an aryl group or a heterocyclic group.), Or a phenyl group, a phenoxy group, or a phenylthio group. Group, pyridyl group, pyridyloxy group or pyridylthio group (the above-mentioned phenyl group, phenoxy group, phenylthio group, pyridyl group, pyridyloxy group and pyridylthio group are a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, Select from the group consisting of alkylthio and haloalkylthio May be substituted with substituents) it is.

Incidentally, Ariru groups exemplified above G ^2, Ariruokishi group, Ariruchio group, heterocyclic group, heterocyclic Okishi group and heterocyclic Chio group further that looks as though it exemplified above, halogen atom, hydroxyl group, Shiano group An alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, a formyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkylthio group, a haloalkylthio group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group and a haloalkylsulfur A substituent selected from the group consisting of a honyl group, preferably a substituent selected from the group consisting of a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group and a haloalkylthio group. Is also good.

W is a single bond, an oxygen atom, a sulfur atom, one SO—, — S0 ₂ —, — NR ⁷ —, — N 2 C (R ⁷ ) one, -C (R ⁷ ) = N0_, — ON = C ( R ⁷ ) one, one C (R ⁷ ) = N one N = C (R ⁸ ) one, -CO-, _C00—, — 0-CO-, one NR ⁷ — CO-, Represents one of CONR ⁷ —, and is preferably an oxygen atom or a sulfur atom.

R ⁷ and R ^{8 each} independently represent a hydrogen atom or an alkyl group, and preferably have 4 or less carbon atoms as the alkyl group.

Q is one SO —, — S 0 ₂ —, — N = C (R ⁹ ) one, — C (R ⁹ ) = NO-, — ON = C (R ⁹ ) —,-C (R ⁹ ) = N— N2 C (R ¹⁰ ) —, —CO—, one COO one, — 0—CO—, one NR ⁹ —CO—, — CONR ^9— or, optionally substituted, phenyl group, naphthyl An aryl group such as a group, or an optionally substituted furyl group, chenyl group, pyrrolyl group, oxazolyl group, oxazolinyl group, isooxazolyl group, isooxazolinyl group, thiazolyl group, thiazolinyl group, isothiazolyl group, isothiazolinyl group Group, imidazolyl group, imidazolinyl group, pyrazolyl group, vilazolinyl group, oxaziazolyl group, oxadiazolinyl group, thiadiazolyl group, thiadiazolinyl group, oxadiazolinyl group, pyridyl group, pyrazyl group, pyrimidyl group, virididyl group Group, triazyl group, benzoxazolyl group, benzothiazolyl group and the like, and the aryl group and the heterocyclic group are a halogen atom and a hydroxyl group as exemplified in the description of the substituent A. , Cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, hoframyl, acyl, acyloxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl And a substituent selected from the group consisting of a haloalkylsulfonyl group, preferably a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, an alkylsulfinyl group, a haloalkylsulfur Group, may be substituted with a substituent selected from the group consisting of alkylsulfonyl group and Haroarukirusu Ruhoniru group.

R ⁹ and R ^{1Q each} independently represent a hydrogen atom or an alkyl group, and preferably has 4 or less carbon atoms as the alkyl group.

Q is preferably 1 C (R ⁹ ) = N0—, 1 0N = C (R ⁹ ) —, -0-C ◦—, or an optionally substituted aryl group or heterocyclic group. More preferably an aryl group or a heterocyclic group which may be substituted, Particularly preferred are groups represented by the following Q-1, Q-2, Q-3, Q-4 or Q-5.

Above Q_ l, in Q-2 or ^{^{Q- 5, R 12, R 13}} , R 14, R 15, R 16, R 17 and R ^18, which it independently hydrogen atom; a fluorine atom, a chlorine atom A halogen atom such as a bromine atom; a methyl group, an ethyl group, an _n -propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, It is a linear, branched or cyclic alkyl group such as a cyclic propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or the like, and the alkyl group preferably has 6 or less carbon atoms. R ^{12 to} R ¹⁸ are preferably a hydrogen atom, a methyl group or an ethyl group.

RR ² , R ³ , R ⁴ , R ⁵ and R ^{6 each} independently represent a hydrogen atom; methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl A chain, branched or cyclic alkyl group such as a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; A chain, branched or cyclic alkenyl group such as an enyl group, a butenyl group, and a hexenyl group; an alkynyl group such as an ethynyl group, a petenyl group, and a pentynyl group; Alkoxy group; alkenyloxy group such as propenyloxy group, butenyloxy group, hexenyloxy group; alkynyloxy group such as petinyloxy group, pentynyloxy group; methoxymethyl group, ethoxyl group Indicates alkoxyalkyl group such as a group, main Tokishechiru group, also, R ¹ and R ^2, R ³ and R ^4, R ⁵ and R ^6, which it together such connexion, Echiriden group, such Puropiri Den group An alkylidene group; or an alkylenedioxy group such as a methylenedioxy group or an ethylenedioxy group. The alkyl group, alkenyl group, alkynyl group, alkoxy group, alkenyloxy group, alkynyloxy group and alkoxyalkyl group preferably have 6 or less carbon atoms.

RR ² , RR ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom, a methyl group or an ethyl group.

p, q and r are integers, preferably 5 or less, particularly preferably 3 or less. p + q + r represents a 9 or less, preferably 6 or less (however, Q is one SO-, One S0 ₂ -, one C (R ⁹⁾ = NO_ one COO- or a CON R ⁹ - In the case of, r is 1 or more, and when Q is a phenyl group, r = 0, Q is _ON = C (R ⁹ ) one or —0—CO—, and W is In the case of an oxygen atom or a sulfur atom, q is 1 or more).

X ¹ and X ² are each independently a hydrogen atom; a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group And alkyl groups such as sec-butyl group, t-butyl group, etc .; or haloalkyl groups such as trifluoromethyl group, difluoromethyl group, trichloromethyl group and dichlorodifluoroethyl group. Those having 4 or less carbon atoms are preferred.

X ¹ and X ² are preferably a halogen atom or an alkyl group, and particularly preferably a halogen atom or a methyl group.

Y represents a halogen atom, an alkyl group or a haloalkyl group, preferably has 4 or less carbon atoms as the alkyl group or the haloalkyl group, and n represents an integer of 0 to 2, preferably n = 0. .

Z represents a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, and is preferably a chlorine atom. Z may be different halogen atoms.

Among the compounds represented by the above general formula (I), a preferable combination of the substituents is p = 0, and the A—W— group may be substituted, and may be an aryl group such as a phenoxy phenoxy group. Optionally substituted, heterocyclic oxyaryloxy group such as pyridyloxyphenoxy group; optionally substituted An aryloxy heterocyclic oxy group such as a phenoxypyridyloxy group; or an optionally substituted heterocyclic oxy group such as a pyridyloxypyridyloxy group.

Substituents for the above aryloxyaryl, heterocyclic oxyaryloxy, aryloxyheterocyclic oxy and heterocyclic oxyheterocyclic oxy groups are each independently And a halogen atom, a hydroxyl group, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, a formyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkylthio group, a haloalkylthio group, an alkyl group A sulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, and a haloalkylsulfonyl group, preferably a haloalkyl group, a haloalkoxy group, or a haloalkylthio group.

The above alkyl group, haloalkyl group, alkoxy group, haloalkoxy group, acyl group, acyloxy group, alkoxycarbonyl group, alkylthio group, haloalkylthio group, alkylsulfinyl group, haloalkylsulfinyl group, alkylsulfonyl group and haloalkylsulfonyl group are preferable. Has 4 or less carbon atoms,

Preferred specific examples of the above A—W— group include a 4- (3-trifluoromethyl-1-pyridyloxy) phenoxy group, a 4- (4-trifluoromethyl-12-pyridyloxy) phenoxy group, and a 4- (5- Trifluoromethyl-1- (2-pyridyloxy) phenoxy group, 4- (4-trifluoromethylphenoxy) phenoxy group, 4- (3-trifluoromethylphenoxy) phenoxy group, 4— (4— Trifluoromethoxyphenoxy) phenoxy group and the like.

The compound of the present invention represented by the general formula (I) can be produced by combining known reactions. For example, according to the production method represented by the following reaction formulas 11 to 14, the compound can be efficiently produced. Can be manufactured.

In the reaction formula, L is a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; an alkylsulfonyloxy group such as a methanesulfonyloxy group and an ethanesulfonyloxy group; or a benzenesulfonyloxy group and P-toluenesulfonyl Oxy group And represents a reelsulfonyloxy group, preferably a chlorine atom, a bromine atom, a methanesulfonyloxy group, or a P-toluenesulfonyloxy group.

R ¹⁹ is a hydrogen atom; methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl building group, a cyclobutyl group, a cyclopentyl group, a linear, branched or cyclic alkyl group such as a cyclohexyl ^{group, a, W, X 1,} X 2, Y, Z, RR 2, R 3, R 4, ^{^{^{R 5, R 6, R 9}}} , R 12, R 13, R 14, R 15, n, p, q and r are the as defined in one general formula (I).

The dihaloprovenyloxybenzene derivative represented by the general formula (la) can be produced by the method of the following Reaction Formula 1 or 2.

Reaction formula 1 1 H ₂ CH = CZ ₂

The dihalopropenyloxybenzene derivative of the general formula (la) can be obtained by reacting the oxime derivative (IV) with a halogen derivative or a sulfonate derivative (Ila) in an inert solvent in the presence of a base.

Examples of the base to be used include: alkali metal hydrides such as sodium hydride; alkali metal alcoholates such as sodium methylate; alkali metal carbonates such as carbon dioxide; Metal tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline.

If necessary, add a quaternary catalyst such as tetra-n-butylammonium bromide to the reaction system. A catalyst such as a ammonium salt or a crown ether such as 18-crown-6-ether may be added in an amount of 0.01 to 1 equivalent to the oxime derivative (IV).

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, polar solvents such as Ν, Ν-dimethylformamide and acetonitrile are preferred. C The halogen derivative or sulfonate derivative (Ila) used in the reaction is 0.5 to 0.5% of the oxime derivative (IV). The reaction is carried out at 0 to 150 ° C, preferably 10 to 100 ° C, in an amount of up to 10 equivalents, preferably 1 to 3 equivalents.

汉 / heart-type-2

The dihalopropenyloxybenzene derivative of the general formula (la) can also be obtained by subjecting a carbonyl derivative (V) and an oxamine derivative (lib) to a dehydration reaction in an inert solvent.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; dimethyl ether, tetrahydrofuran, Ethers such as dioxane; Esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol

-Polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, acetic acid, and other polar solvents or water. Is also good. Of these, alcohols such as methanol and ethanol are preferred.

The oxyamine derivative (lib) used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the carbonyl derivative (V), and is used at 0 to 100 ° C, preferably 10 ° C to The reaction takes place at the boiling point.

The dihalopropenyloxybenzene derivative represented by the general formula (lb) can be produced by the method of the following reaction formula 3 or 4.

5U heart type 1 3

The dihalopropenyloxybenzene derivative represented by the general formula (lb) can be obtained by reacting a oxime derivative (Ilia) with a halogen derivative or a sulfonate derivative (VI) in an inert solvent in the presence of a base.

Examples of the base to be used include: alkali metal hydrides such as sodium hydride; alkali metal alcoholates such as sodium methylate; alkali metal carbonates such as carbon dioxide rim; Metal hydroxides such as potassium rim; tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline.

If necessary, add a quaternary catalyst such as tetra-n-butylammonium bromide to the reaction system. A catalyst such as ammonium salt or a crown ether such as 18-crown-6-ether may be added in an amount of 0.01 to 1 equivalent to the oxime derivative (Ilia).

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol, and propanol; ketones such as acetone and methylethyl ketone; Ν, Ν-dimethylformamide, Ν-methylbiphenyl Examples thereof include polar solvents such as don, dimethylsulfoxide, and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, polar solvents such as Ν, Ν-dimethylformamide and acetonitrile are preferred. _{C The} halogen derivative or sulfonate derivative (VI) used in the reaction is 0.5 to 10% more than the oxam derivative (Ilia). The reaction is carried out at a double equivalent, preferably 1 to 3 equivalents, at 0 to 150 ° C, preferably 10 to 100 ° C.

Reaction formula 1 4

The dihalopropenyloxybenzene derivative of the general formula (lb) can also be obtained by subjecting a carbonyl derivative (Illb) and an oxamine derivative (VII) to a dehydration reaction in an inert solvent.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; Esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, acetic acid, and water. It may be a single solvent or a mixed solvent. Of these, alcohols such as methanol and ethanol are preferred.

The oxyamine derivative (VII) used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the carbonyl derivative (Illb), and 0 to: 100 ° C, preferably 10 ° C to the solvent. The reaction is carried out at a boiling point of.

汉, Equation—5

Ic The dihalopropenyloxybenzene derivative of the general formula (Ic) is obtained by reacting an alcohol (VIII) with a carboxylic acid chloride (IIIc) in a solvent in the presence of a base as shown in Reaction formula-5. Is obtained by

Examples of the base to be used include: alkali metal hydrides such as sodium hydride; alkali metal alkoxides such as sodium methylate; alkali metal alkoxides such as carbonate lime; Metal hydroxides; tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; dimethyl ether, tetrahydrofuran, Ethers such as dioxane; Esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; polar solvents such as Ν, Ν-dimethylformamide, Ν-methylpyrrolidone, dimethyl sulfoxide, and acetonitrile; and water. It may be a single solvent or a mixed solvent.

The alcohol (VIII) used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the carboxylic acid chloride (IIIc), and 0 to 150 ° C, preferably 10 ° C to the solvent. The reaction is carried out at a boiling point of.

、, Equation 1 0

A NH ₂ +

q

IX IIIc

The dihalopropenyloxybenzene derivative of the general formula (Id) can be obtained by reacting an amine (IX) with a carboxylic acid chloride (IIIc) in a solvent in the presence of a base, as shown in Reaction formula-6. Can be

Examples of bases used are: metal hydrides such as sodium hydride; metal alkoxides such as sodium methylate; metal alkoxides such as carbon dioxide; And the like; tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and bicholine.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; ketones such as acetone and methylethyl ketone; Ν, Ν- Examples thereof include polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and acetonitrile, and water, and may be a single solvent or a mixed solvent.

The amine (IX) used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the carboxylic acid chloride (IIIc), and 0 to: 150 ° C, preferably 10 ° C to The reaction takes place at the boiling point of the medium

Reaction Formula 1 7

The dihalopropenyloxybenzene derivative represented by the general formula (Ie) is obtained by halogenating an oxime derivative (Illd) with a halogenating agent in an inert solvent, as shown in Reaction formula-7, and then reacting the olefin derivative in the presence of a base. It is obtained by reacting with (X).

Examples of the halogenating agent to be used include chlorine, bromine, N-chlorosuccinic acid imide, N-bromosuccinic acid imide, sulfuryl chloride and the like.

Examples of bases used include: Alkali metal hydrides such as sodium hydride; Alkali metal alcoholates such as sodium methylate; Alkali metal carbonates such as carbonated lime; Metal hydroxides; tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; Esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol

Ketones such as acetone and methylethylketone; polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and acetonitrile; water; and the like; Or a mixed solvent. Of these, Ν, Ν-dimethylformamide, tetrahydrofuran, toluene and the like are preferred.

The olefin derivative (X) used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the oxime derivative (Illd), and 0 to: 150 ° C, preferably 10 to 100 ° C. The reaction takes place.

Reaction formula 1 -C≡CR ¹⁵ +

XI Hid

The dihalopropenyloxybenzene derivative of the general formula (If) is obtained by halogenating an oxime derivative (Illd) with a halogenating agent in an inert solvent as shown in Reaction formula-8, and then reacting the acetylene derivative in the presence of a base. Obtained by reacting with (XI)

Examples of the base to be used include: alkali metal hydrides such as sodium hydride; alkali metal alcoholates such as sodium methylate; alkali metal carbonates such as carbon dioxide; Metal tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline. Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; Ν, Ν-dimethylformamide, Ν-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, Ν, Ν-dimethylformamide, tetrahydrofuran, toluene and the like are preferred.

The acetylene derivative (XI) used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the oxime derivative (Illd), and 0 to: L50 ° C, preferably 10 to 100 °. The reaction takes place at C.

Reaction formula—9

A-

The dihalopropenyloxybenzene derivative of the general formula (Ig) can be prepared by converting the ester derivative (XII) and the benzamidoxime derivative (Ille) in an inert solvent in the presence of an acid or a base, as shown in Reaction Scheme_9. It is obtained by a condensation reaction. Examples of acids used include brenstead acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid, or tertiary acid. Examples thereof include Lewis acids such as aluminum chloride, boron tribromide, and boron trichloride. Examples of the base to be used include: alkali metal hydrides such as sodium hydride; alkali metal alcoholates such as sodium methylate; alkali metal carbonates such as carbon dioxide; And the like; tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and bicholine.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; dimethyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, solvents such as toluene and tetrahydrofuran are preferred.

The ester derivative (XII) used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the benzamidoxime derivative (Hie), and 0 to 150 ° C, preferably 10 to 100. The reaction is performed at ° C.

Reaction formula—10

The dihalopropenyloxybenzene derivative of the general formula (Ii) undergoes a dehydration reaction between an alcohol (VIII) and an oxadiazolinone derivative (Ih) in a solvent, as shown in Reaction Formula-10. It can be obtained by: Examples of the reagent for performing the dehydration reaction include triphenylphosphine and getyl azodicarbonate.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene and xylene; halogen hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; ethers such as getyl ether, tetrahydrofuran and dioxane. Esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and acetonitrile; It may be a solvent or a mixed solvent.

The alcohol (VIII) used in the reaction is used in an amount of 0.5 to: 10 equivalents, preferably 1 to 3 equivalents to the oxadiazolinone derivative (Ih), and 0 to: 150 ° C, preferably 10 to 10 equivalents. The reaction takes place at 100 ° C.

Reaction formula—1 1

The dihalopropenyloxybenzene derivative represented by the general formula (Ii) can be obtained by converting the compound (VI) and the oxadiazolinone derivative (Ih) in a solvent in the presence of a base, as shown in Reaction Formula-11. By reacting with

Examples of the base to be used include: alkali metal hydrides such as sodium hydride; alkali metal alcoholates such as sodium methylate; alkali metal carbonates such as carbon dioxide; Metal tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline. Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, N, N-dimethylformamide, tetrahydrofuran, toluene and the like are preferred.

The compound (VI) used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the oxadiazolinone derivative (Ih), and 0 to: 150 ° C, preferably 10 to 10 equivalents. The reaction takes place at ~ 100 ° C. The compounds represented by the general formulas (II) and (III) are useful intermediates for producing the compound represented by the general formula (I), as shown in the above Reaction Formulas 1-1 to 11.

In the general formula (II), Q ¹ represents a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a hydroxyl group; an aminooxy group; an oxyamino group; an alkoxy group such as a methoxy group, an ethoxy group, and an n-butoxy group; Alkylsulfonyloxy group such as methanesulfonyloxy group; haloalkylsulfonyloxy group such as trifluoromethanesulfonyloxy group; arylsulfonyloxy group such as benzenesulfonyloxy group and p-toluenesulfonyloxy group; Or a haloarylsulfonyloxy group such as a p-chloro benzenesulfonyloxy group, preferably a halogen atom or an aminooxy group, particularly preferably a bromine atom or an aminooxy group.

R ⁵ ′ and R ⁶ ′ are each independently a hydrogen atom; or a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, etc. The alkyl group is preferably an alkyl group having 4 or less carbon atoms.

r is an integer of 9 or less, preferably 5 or less, particularly preferably an integer of 3 or less It is.

X ¹ , X ² _S Y, Z and n are the same as those described in the general formula (I).

In the above general formula (ΙΠ), Q ² is an oxygen atom or a hydroxyimino group,

Q ³ is a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a hydroxyl group; an amino group; a hydrazino group; or a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, It is an alkyl group such as an n-butyl group, a sec-butyl group and a t-butyl group, and the above-mentioned alkyl group is preferably one having 4 or less carbon atoms.

R ⁵ ′ and R ⁶ ′ are each independently a hydrogen atom; or a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group And the alkyl group is preferably an alkyl group having 4 or less carbon atoms.

r represents an integer of 9 or less, preferably 5 or less, more preferably 3 or less, and particularly preferably 0.

X ¹ , X ² , Y, Ζ, and η are the same as those described in the general formula (I).

The compounds represented by the general formulas (II) and (III) can be produced by combining known reactions. For example, the compounds represented by the general formulas (Ig), (Ha ') s (IIb'), (lie),

The specific compounds represented by (Illb, (IIIc), (IIId), (Ille) ヽ (Illf) and (Illg) are produced by the production method shown in Reaction Schemes 12, 13 and 14. can do.

In the formula, X ¹ , X ² , Y, Ζ, and η are as defined in the general formula (I), and L is as defined in the aforementioned reaction formula-1.

Illb 'Illd

The phenol derivative (XIII) is brominated with bromine, and the resulting 4-bromophenol derivative (XIV) is reacted with chloromethyl methyl ether in the presence of a base to give a 4-methoxymethoxybromobenzene derivative (XV). The 4-methoxy methoxy bromobenzene derivative (XV) is reacted with Ν, Ν-dimethylformamide by a Grignard reaction to obtain a 4-methoxy methoxy benzoaldehyde derivative (XVI). it can.

Further, the 4-methoxymethoxybenzaldehyde derivative (XVI) is hydrolyzed with an acid such as hydrochloric acid to give a phenol derivative (XVII).

The aldehyde derivative (Illb ′) can be obtained by reacting the above-mentioned phenol derivative (XVII) with a trihalopropene derivative or a sulfonyloxydihaprobenyloxybenzene derivative (XVHI) in an inert solvent in the presence of a base. .

Examples of bases used are: metal hydrides such as sodium hydride; metal alkoxides such as sodium methylate; alcohols such as carbon dioxide Metal hydroxides; metal hydroxides such as lithium hydroxide; tertiary amines such as N-methylmorpholine and triethylamine; aromatic bases such as pyridine and picoline.

If necessary, a catalyst such as a quaternary ammonium salt such as tetra-n-butylammonium bromide or a crown ether such as 18-crown-6-ether may be added to the reaction system for the oxime derivative (IV). You may add 0.01 to 1 equivalent.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; dimethyl ether, tetrahydrofuran, dioxane, and the like. Ethers such as ethyl acetate; alcohols such as methanol, ethanol, and propanol; ketones such as acetone and methyl ethyl ketone; Ν, Ν-dimethylformamide, Ν-methylpyrrolidone, and dimethyl sulfoxide. And a polar solvent such as acetonitrile or water, and the solvent may be a single solvent or a mixed solvent. Of these, polar solvents such as Ν, Ν-dimethylformamide and acetonitrile are preferred. C The trihalopropene derivative or sulfonyloxydihalopopenyloxybenzene derivative (XVIII) used in the reaction is a phenol derivative. It is used in an amount of 0.5 to: 10 equivalents, preferably 1 to 3 equivalents to (XVII), and the reaction is carried out at 0 to 150 ° C, preferably 10 to 100 ° C.

The oxime derivative (Hid) can be obtained by reacting the aldehyde derivative (nib ') with hydroxyamine hydrochloride or sulfate in an inert solvent in the presence of a base.

Examples of the base to be used include: Al metal hydrides such as sodium hydride; Alkali metal alcohols such as sodium methylate; Al metal alkali acetate such as acetic acid lime; Carbonate lime, etc. Metal hydroxides; hydroxides such as lithium hydroxide; tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline. Of these, alkali metal acetates such as potassium acetate, alkali metal carbonates such as potassium carbonate, tertiary amines such as triethylamine, and aromatic bases such as pyridine are preferable. Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; Ν, Ν-dimethylformamide, Ν-methylpyrrolid Examples thereof include polar solvents such as don, dimethyl sulfoxide, and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, alcohols such as methanol, ethanol and propanol are preferred. The hydroxyamine hydrochloride or sulfate used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the aldehyde derivative (Illb '), and the base is an aldehyde derivative (Illd). The reaction is carried out at 0.5 to 10 equivalents, preferably 1 to 3 equivalents, 0 to: 150 ° C, preferably 10 ° C to the boiling point of the solvent.

The dihalopropenyloxybenzene derivative represented by the general formula (Ille) can be obtained by halogenating the above oxime derivative (Illd) with a halogenating agent in an inert solvent and reacting with ammonia in the solvent.

Examples of the halogenating agent used include chlorine, bromine, N-chlorosuccinic acid imide, N-bromosuccinic acid imide, sulfuryl chloride and the like.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; dimethyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, ether, N, N-dimethylformamide, tetrahydrofuran, methanol and the like are preferable.

The halogenating agent used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the oxime derivative (Illd), and 0 to: 150 ° C, preferably 10 to; The ammonia is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the oxime derivative (Illd), and the reaction is carried out at 0 to 150 ° C, preferably 10 to 100 ° C. .

Reaction formula—1 3

IIIc nig

The carboxylic acid derivative (Illf) can be obtained by oxidizing the aldehyde derivative (Illb ′) obtained by the method of Reaction Scheme-12 in an inert solvent.

Examples of the oxidizing agent used include oxides of heavy metals such as sodium dichromate and lithium permanganate; and chlorinated oxides such as sodium chlorite. Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; dimethyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, polar solvents such as acetonitrile, tetrahydrofuran, and water are preferred. The oxidizing agent used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the aldehyde derivative (Illb '), and the reaction is carried out at 0 to 150 ° C, preferably 10 to 100 ° C. Will be

The acid chloride derivative (IIIc) is obtained by halogenating the carboxylic acid derivative (Illf) in an inert solvent.

Examples of the halogenating agent used include halogenating agents such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphoryl chloride, oxalyl chloride, and phosgene.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; polar solvents such as Ν, Ν-dimethylformamide, Ν-methylpyrrolidone, dimethylsulfoxide, and acetonitrile; water; and the like; May also be a mixed solvent. Of these, solvents such as dichloromethane are preferred.

The halogenating agent used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the carboxylic acid derivative (Illf), and 0 to: 150 ° C, preferably 10 to 100 ° C. The reaction takes place.

The acyl hydrazide derivative (Illg) is obtained by hydrazide of an acid chloride derivative (IIIc) with hydrazine, hydrazine monohydrate, etc. in an inert solvent as shown in Reaction Scheme-13. can get.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and acetonitrile, or water, and the like. May also be a mixed solvent. Of these, solvents such as tetrahydrofuran are preferred. The hydrazine reagent used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the acid chloride derivative (IIIc), and 0 to: 150 ° C, preferably 10 to: 100 °. The reaction takes place at C.

The oxadiazolinone derivative (Ig) can be obtained by adding the hydrazide derivative (Illg) to an inert solvent in the presence of a base in an inert solvent such as phosgene, diphosgene, triphosgene, carbonyldimidazole, or carbonate. It is obtained by reacting with an agent. Examples of bases used include: Alkali metal hydrides such as sodium hydride; Alkali metal alcoholates such as sodium methylate; Alkali metal acetates such as acetic acid rim; Carbonate rim; Metal hydroxides such as potassium hydroxide; tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline. Of these, alkali metal acetates such as potassium acetate, alkali metal carbonates such as potassium carbonate, tertiary amines such as triethylamine, and aromatic bases such as pyridine are preferable.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; dimethyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, ethers such as tetrahydrofuran are preferred.

The carboxylating agent used in the reaction is 0.5 to 10 equivalents, preferably 1 to 3 equivalents, based on the hydrazide derivative (Illg), and the base is 0.5 to 10 equivalents based on the hydrazide derivative (Illg). The reaction is carried out at a double equivalent, preferably 1 to 3 equivalents, 0 to: 150 ° C, preferably 10 ° C to the boiling point of the solvent. Reaction formula 1 1 4

X lib 'alcohol derivative (lie) can be obtained by reacting an aldehyde derivative (Illb') obtained by the method of Reaction Scheme 11 with a reducing agent in an inert solvent.

Examples of the reducing agent used include lithium aluminum hydride, sodium borohydride and the like.

Ketones such as acetone and methylethyl ketone; polar solvents such as Ν, Ν-dimethylformamide, Ν-methylpyrrolidone, dimethylsulfoxide, and acetonitrile, or water, and the like. Or a mixed solvent. Of these, ethers such as getyl ether, tetrahydrofuran, and dioxane; and alcohols such as methanol, ethanol, and propanol are preferable.

The reducing agent used in the reaction was 0 ::! With respect to the aldehyde derivative (Illb '). ~ 5 times The reaction is carried out at a temperature of -20 to 100 ° C, preferably 0 ° C to the boiling point of the solvent.

The halide derivative (Ila ') is obtained by reacting an alcohol derivative (lie) with a halogenating agent in a solvent-free or inert solvent.

Examples of halogenating agents used include tetrabutylammonium fluoride (TBAF), sulfur tetrafluoride, getylamino sulfur trifluoride, morpholino sulfur trifluoride, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, Hydrochloric acid, phosphorus oxychloride, hydrobromic acid, phosphorus tribromide, thionyl bromide, or a composite reagent of carbon tetrachloride and triphenyliphosphine, a composite reagent of carbon tetrabromide and triphenyliphosphine, etc. Can be Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane are preferred.

The halogenating agent used in the reaction is used in an amount of 0.1 to 5 equivalents, preferably 0.2 to 2 equivalents, relative to the alcohol derivative (lie), and has a boiling point of -20 to 100 ° C, preferably 0 to 100 ° C. The reaction takes place at a temperature.

The sulfonate derivative (Ila ′) can be obtained by reacting the alcohol derivative (lie) with a sulfonylating agent in the absence of a solvent or in an inert solvent in the presence of a base.

Examples of the sulfonylating agent used include methanesulfonyl chloride, p-toluenesulfonyl chloride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride and the like.

Examples of bases used are: metal hydrides such as sodium hydride; Alkali metal carbonates such as carbonated lime; Alkali metal hydroxides such as hydroxylated lime; Tertiary amines such as N-methylmorpholine and triethylamine; Aromatic bases such as pyridine and picolin. Can be

If necessary, a halide derivative (Ila ′) may be added to the reaction system by adding a halide of an alkali metal such as lithium chloride or lithium bromide.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; dimethyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; Ν, Ν-dimethylformamide, Ν-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane are preferred.

The sulfonylating agent used in the reaction is used in an amount of 0.1 to 5 equivalents, preferably 0.2 to 2 equivalents to the alcohol derivative (lie), and is used at a temperature of -20 to 100 ° C, preferably 0 ° C to the solvent. The reaction takes place at the boiling point.

The oxamine derivative (lib ') can be obtained by reacting the halogen derivative or the sulfonate derivative (Ila') with acetohydroxamic acid in an inert solvent in the presence of a base.

Examples of the base to be used include: alkali metal hydrides such as sodium hydride; alkali metal alcohols such as sodium methylate; alkali metal carbonates such as carbon dioxide; lithium metal hydroxide; Metal tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and picoline.

If necessary, a catalyst such as a quaternary ammonium salt such as tetra-n-butylammonium bromide or a crown ether such as 18-crown-6-ether may be added to the reaction system as a halogen derivative or sulfonate derivative ( Ila ') Is also good.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; and getyl ether, tetrahydrofuran and dioxane. Ethers such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. And a polar solvent such as acetonitrile or water, and the solvent may be a single solvent or a mixed solvent. Of these, alcohols such as ethanol are preferred.

The acetate hydroxamic acid used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the halogen derivative or the sulfonate derivative (Ila ′), and 0 to: 150 ° C., preferably The reaction is carried out at a temperature between 10 ° C and the boiling point of the solvent.

The oxamine derivative (lib ') can also be obtained by reacting the fluorimide derivative (XVIII) with hydrazine in an inert solvent.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methylethyl ketone; Ν, Ν-dimethylformamide, Ν-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, alcohols such as ethanol are preferred.

The hydrazine used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents, based on the phthalimide derivative (XVIII), and 0 to 150 ° C, preferably 10 ° C to the boiling point of the solvent. The reaction takes place.

The fluoroimide derivative (XVIII) is obtained by reacting a halogen derivative or a sulfonate derivative (Ila ') with N-hydroxyfluorimide in an inert solvent in the presence of a base. Examples of the base to be used include: alkali metal hydrides such as sodium hydride; alkali metal alcoholates such as sodium methylate; alkali metal carbonates such as carbon dioxide; Metal tertiary amines such as N-methylmorpholine and triethylamine; and aromatic bases such as pyridine and bicholine.

If necessary, a catalyst such as a quaternary ammonium salt such as tetra-n-butylammonium bromide or a crown ether such as 18-crown-6-ether may be added to the reaction system as a halogen derivative or sulfonate derivative (Ila. ') May be added in an amount of 0.01 to 1 equivalent.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone; Examples thereof include polar solvents such as dimethyl sulfoxide and acetonitrile, and water, and may be a single solvent or a mixed solvent. Of these, polar solvents such as N, N-dimethylformamide and acetonitrile are preferred. The N-hydroxyphthalimide used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the halogen derivative or the sulfonate derivative (Ila ′), and is preferably 0 to 150 ° C. Is from 10 to: The reaction is carried out at 100 ° C.

The fluorimidide derivative (XVIII) can also be obtained by reacting an alcohol derivative (lie) with N-hydroxy fluorimidide in an inert solvent in the presence of a dehydrating agent.

Examples of dehydrating agents used include trifenylphosphine and getylazodicarboxylate.

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like; getyl ether, tetrahydrofuran, Ethers such as dioxane; Esters such as ethyl acetate; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; Ν, Ν-dimethylformamide, Ν-methylpyrrolidone, dimethyl sulfoxide, acetonitrile and the like Examples thereof include a polar solvent and water, which may be a single solvent or a mixed solvent. Of these, aromatic hydrocarbons such as benzene, toluene, and xylene, and ethers such as getyl ether, tetrahydrofuran, and dioxane are preferable.

The Ν-hydroxyfluoroimide used in the reaction is used in an amount of 0.5 to 10 equivalents, preferably 1 to 3 equivalents to the alcohol derivative (lie), and is used at -20 to 150 ° C or 0 to The reaction is carried out at a temperature between ° C and the boiling point of the solvent. The pest control agent comprising the compound of the present invention as an active ingredient has an effect of controlling pests, mites, and other pests. It is effective in repelling pests, controlling and controlling pests in a wide range of situations.

In particular, the compound of the present invention is used to repel or eliminate harmful organisms in agriculture, forestry, etc., specifically when cultivating crops, crops, trees, ornamental plants, etc., and in public health situations. · Excellent effect as insecticide and acaricide used for pest control.

Specific usage scenes, target pests, usage methods, and the like are shown below, but the present invention is not limited to the following description. The pests specifically exemplified are not limited to the target pests, and the exemplified pests also include adults, larvae, eggs, and the like.

(A) Agriculture, forestry, etc.

The compound of the present invention can be used for agricultural crops such as food crops (rice, wheat, corn, potatoes, sweet potatoes, beans, etc.), vegetables (brassaceae crops, burrs, eggplants, tomatoes, leeks, etc.), fruit trees (citrus fruits, apples, etc.). , Grapes, thighs, etc., special crops (tobacco, tea, sugar beet, sugar cane, cotton, olive, etc.), pasture and feed crops (sorghum, grasses, legumes, etc.) and ornamental plants ( Damage to plants, flowers, garden trees, etc.) It is effective for repelling and controlling arthropods such as arthropods, molluscs, nematodes and various fungi, especially arthropods such as insects and mites. Furthermore, the compound of the present invention is a pest repellent when storing harvested products from the above-mentioned crops, for example, cereals, fruits, tree nuts, spices, tobacco, and the like, and products that have been subjected to drying, powdering, and the like. It is also effective for extermination. It is also effective in protecting standing trees, fallen trees, processed timber, stored timber, and the like from damage by pests such as termites and beetles.

Specific pests include, for example, those belonging to the phylum Arthropoda, Mollusca and Nematoda: Examples of arthropod phylum insects include the following.

As Lepidoptera, for example, the family Noctuidae such as Lotus sycamore, Tobacco beetle, Noctuida japonica, and the evening squirrel; Suga family such as Convolvulus; the Anophelesaceae family such as Cyanococcus serrata and Papilio persicae; Laminariaceae, such as the lycopogon moth moth; Linguridae, such as the lycopodium moth; Laceae, such as the stag beetle; Skashibaga, such as Kosukashiba; Lingiberidae; Lingiberidae such as Kobomimeiga, Nikameichiyu, and Suzuki Helichronogium; Laceae family such as Ichimondisseri; Laceae family such as Papilio japonica; E Sphingidae such as Garasuzume; Mont black killer whale pike killer whale pike moth family, and the like; Chiya de Lymantriidae such as Kuga; Ru can be mentioned such as the United States white Arctiidae such as Arctiidae o

As the Coleoptera, for example, Scarabaeidae, such as Scarabaeidae, Koohanamuguri, and Mamekogane; Occupiidae, such as Citrus longiflora; Occidental Beetle, such as Marcavix beetle; and Coccinellidae, such as Nijyahoshtentu; Coleoptera, Chrysomelidae such as Budtra kamikiri; Chrysomelidae, Chrysomelidae beetle, Rice beetle; And the like. Also, as the Hemiptera, for example, the insects belonging to the order Coleoptera, Scarabaeidae, and the beetles; the beetle family such as the pear beetle; the helicopteridae such as the beetle; the beetle family such as the spider beetle; Berberidae family, such as Nashigumbai, etc .; Memphiidae family, such as Usumi doremikuragame; Lepidoptera, such as Leafhoppers such as Black-headed Leafhoppers; Scarletidae, such as Black-bellied mosquitoes and Tobira-kuronuka; Obahagoromo, such as Aobahagoromo; Phyllomorphidae, such as pear lice; Whitefly, Silverleaf whitefly, etc. Whiteflies; Filophyceae, such as Krysius aphid; Apples, evening aphids, etc .; Aphids; Aphids, such as aphids, momokaa aphids, and okabonoa force aphids; Pterodactylidae, such as Mycariidae; Pterodactylidae, such as rubidium beetle; and Pterodactylidae, such as pear marsupials and porphyra.

Further, as the order of the thrips, there may be mentioned a thrips family, such as Citrus thrips, C. japonica, Thrips thrips, etc .; and a thrips family, such as Thysanoptera thrips, rice thrips, etc.

Examples of the Hymenoptera include honeybees, such as the force of Prague, honeybees, such as apple honeybees, honeybees, such as honeybees, and honeybees, such as rosehip bees.

As the diptera, for example, evening fly, such as soybean midge and fly; fruit fly, such as fruit fly; rice fly, such as rice fly; fly fly, such as D. melanogaster; An example of the genus may also include a fly of the family, such as a green fly.

The Orthoptera includes, for example, grasshoppers such as crickets; crickets such as pine beetles;

As the order of the order Tabanidae, for example, the tabitidae such as the bark beetle; White-spotted beetles, such as mouth snappers.

Examples of the termites include termites such as the evening termites, and examples of the earwigs include examples of the earwigs such as the earwigs.

The following can be exemplified as the arthropod phylum crustacea and spiders. As the isopod of the crustacean, there may be mentioned, for example, the family Acaratidae, such as the cadaver bug.

Examples of the acarid mites of the order of the spiders include the family Dermatophagoides, such as Cyanomycocyidae and Cyclamenophycephalidae; Mycidae, such as barley mites; The mysteries, such as Grape Himehada2; The family Acarinae, such as Citrus saccharidum, the apple saccharidum, and the sarcophagid saccharidum;

As the mollusc phylum gastropods, examples of the gastropods of the gastropods include, for example, the apple ringworm, and the patterns of the eyes include, for example, the African snail, the slug, the slug, the slug, the slug, and the like. it can.

The following can be exemplified as the nematode phantom net and the tail net. Examples of the genus Reticulidae include, for example, Anguinaceae, such as Imogusarecentiyu; Tirencholinex, such as Namiikusekisenyu; Bratyrenchus, such as Kiyu Negusarecentiyu, and Minamigusareceiyu; Heterodela family such as potato cysts; Melody doginae such as Saccharomyces mori; Crykonema family such as ヮ Cenyuyu; Nototilenic family such as Ichigomecenyu; and Aferencoides family such as strawberry Examples can be given.

Examples of the order Gastropodidae include Longidraceae, such as P. elegans, and Trichodulaceae, such as Yumiharicenti. Further, the compound of the present invention is also effective for repelling, controlling and controlling pests that damage trees or affect the vigor of natural forests, plantations and urban green spaces. In such a situation, specific pests include the following. Examples of the arthropod phylum Insecta and Arachnida include the following. Examples of the Lepidoptera include, but are not limited to, such as cephalopoda, gypsy moth, etc .; kalehaga family, such as makkaleha and tsukakareha; mephidae family, e.g., larch; Hirrigidae, such as P. crispinae; Moglitiviga, such as Shimoglitibiga;

As the Coleoptera, for example, Scarabaeidae such as Scarabae beetle and Nagachacogane; Pentatomidae such as Pseudocarabidae; Cerambycidae such as pine beetle; Chrysomelidae such as cedar beetle; Scorpion beetle; Of the worms, such as the weevil family; the weevil family, such as the weevil family; the bark beetle family, such as the pine bark beetle and the bark beetle;

The Hemiptera includes, for example, aphid family such as Todomiao aphid; mosquito aphid family such as Ezomatsu cassabra; marsupiidae family such as cedar marcae aphid;

Examples of the Hymenoptera include honeybees, such as the stag beetle; honeybees, such as the pine sawfly; and honeybees, such as the chestnut bee.

Examples of the dipteran can include, for example, the mothflies, such as the giant squirrel, etc .; the genus Flies, e.g.

Examples of the spiders of the order Arachnida include, for example, Suginohadani and Todoma nohadani.

As the order of the Nematodes of the Nematode Nematoda, there may be mentioned, for example, the family Parasitidae, such as P. japonicus.

The pesticidal composition containing the compound of the present invention as an active ingredient can be used alone or in combination with other active compounds such as insecticides, pesticides, and the like in preparations that are effective in the agricultural and forestry situations described above, and in any use forms prepared by the preparations. It can be used in combination with or as a mixture with mites, nematicides, fungicides, synergists, plant conditioners, herbicides and poison baits. More Illustrative active compounds include, but are not limited to, the following.

Active compounds such as insecticides and acaricides:

Examples of the organic phosphorus agent include dichlorvos, funitrothion, malathion, naled, chlorpyrifos, diazinon, tetrachlorovinphos, fenthion, isoxathion, methidathion, salicion, acephate, dimetone-S-methyl, disulfoton, monochlorthophos, azidinphosimesil. Hosalon, pirimiphos-methyl, protiphos and the like.

Examples of the carbamate include metocalp, fenobucalp, propoxur, kyarvalyl, ethiofencarp, pirimicarb, bendiocalp, carbosulfan, carbofuran, mesomil, thiodicarp and the like. Examples of the organic chlorine agent include lindane, DDT, endosulfan, aldrin, chlordane and the like.

Pyrethroids include, for example, permethrin, cypermethrin, deltamethrin, cyhalothrin, cyfluthrin, aclinatrin, fenvalerate, etofenprox, silafluofen, fluvalinate, flucitrinate, bifenthrin, arelesrin, phenothrin, fenpropatrine Phosphorus, sifenotrin, framethrin, resmethrin, transfluthrin, praletrin, flufenprox, halofanprox, imiprotrin and the like can be mentioned.

Neonicotinoid agents include, for example, imidacloprid, nitembiram, acetamiprid, tefuranitodine, thiamethoxam, thiacloprid and the like.

Examples of insect growth regulators such as fenylpenzyl perea include diflubenzuron, clomouth fluazuron, triflumuron, flufenoxuron, hexaflumuron, lufenuron, tefluvenzuron, buprofezin, tebufenozide, chromafufenozide, methoxfenozide. Cyromazine and the like can be mentioned. Juvenile hormone agents include, for example, pyriproxyfen, phenoxycarp, Soprene, hydroprene and the like can be mentioned.

Insecticidal substances produced by microorganisms include, for example, abamectin, milbemectin, nikkomycin, emamectin penzolate, ivermectin, subinosad and the like.

Examples of other insecticides include cartap, bensultap, chlorf Xnabil, diafentiuron, nicotine sulfate, methaldehyde, fipronil, pimetrozine, indoxacarp, tolfenpyrad and the like.

Active compounds for acaricides include, for example, dicophor, phenylisobromolate, benzomate, tetradiphone, polynactin complex, amitraz, propargyl, fenbutin oxide, tricyclohexyltin hydroxide, tefenfenvirad, pyridapen, fenpyroximate, Pyrimidifen, fenazaquin, clofentegine, hexthiazox, acequinosyl, quinomethionate, phenothocalp, ethoxazole, bifenazate and the like can be mentioned.

Examples of the nematicide active compound include methyl isocyanate, phosphatiazate, oxamil, and mesulfenphos.

Examples of the bait include monofluoroacetic acid, perfurin, coumatetralyl, difacine and the like.

Active compounds for fungicides include, for example, inorganic copper, organocopper, sulfur, maneb, thiuram, thiadiazine, captan, closanilonil, iprobenphos, thiophanatemethyl, benomyl, thiabendazol, iprodione, procymidone, dicyclone , Metalaxyl, sandphan, bileton, triflumizole, fenarimol, triforine, dithianon, triazine, fluazinam, probenazole, dietofencarp, isoprothiolane, pyroquilon, iminoc quinoline acetate, eclomethol, dazomet, clesoxime methyl, etc. Can be mentioned.

Examples of active compounds such as herbicides include bialaphos, sethoxydim, trifluralin, mefenacet and the like.

Active compounds of plant regulators include, for example, indolebutyric acid, ethephon, 4-CPA And the like.

Active compounds of repellents include, for example, karan-3,4-diol, Ν, Ν-getyl-m-triamide (Deet), limonene, linalool, citronellal, menthone, hinokitiol, menthol, graniol, u-capitol, etc. Can be mentioned.

Examples of the active compound of the synergist include bis- (2,3,3,3-tetrachloropropyl) ether and N- (2-ethylhexyl) bisque [2,1,1] hept-5-e -2,3-dicarboximidide, and-[2- (2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene.

The pest control agent of the present invention may be used in any form. For example, a wettable powder, a wettable powder, a water solvent, an emulsion, a liquid, a suspension in water, and a milk in water may be added to the compound of the present invention by adding an agrochemical auxiliary. It is used as a formulation in flowables such as suspending agents, capsules, powders, granules, aerosols, etc. The content of the active ingredient compound such as the compound of the present invention in these preparations is arbitrary, but is usually selected from the range of 0.001 to 99.5% by weight in terms of the total amount of the active ingredients. It may be appropriately determined depending on the conditions. For example, in the case of wettable powders, wettable powders, aqueous solvents, emulsions, liquids, flowables, capsules and the like, about 0.01 to 90% by weight, preferably 1 to 50% by weight, Manufactured to contain about 0.1 to 50% by weight, preferably 1 to 10% by weight for powders and granules, and about 0.001 to 20% by weight, preferably 0.01 to 2% by weight for aerosols and the like. It is preferable to o

The pesticide adjuvants used are used for the purpose of improving pest repellent, controlling and controlling effects, and stabilizing and dispersing. For example, carriers (diluents), spreading agents, emulsifiers, and moisturizers are used. An extender, a dispersant, a disintegrant and the like can be used.

Liquid carriers include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, and sulfoxides such as dimethylsulfoxide. , Methylnaphthalene, cyclohexane, animal and vegetable oils, fatty acids and the like. In addition, solid carriers include clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, Montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like can be used.

Usable surfactants can be used as emulsifiers and dispersants, for example, higher alcohols such as sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkyl esters: polyester, lauryl betaine, etc. Anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and the like can be used.

Also, a spreading agent such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl X diester; a wetting agent such as dialkyl sulfosuccinate; a fixing agent such as carboxymethyl cellulose and polyvinyl alcohol; sodium lignin sulfonate Disintegrants such as sodium lauryl sulfate can be used. For example, in the case of a wettable powder, the active ingredient is mixed with a compound of the general formula (I), a solid carrier, a surfactant and the like to produce a raw powder, and the raw powder is used at a predetermined concentration. Can be diluted with water and applied.

In the case of an emulsion, an undiluted emulsion can be prepared by mixing a solvent and a surfactant with the above compound of the active ingredient, and the undiluted solution can be diluted with water to a predetermined concentration before use. it can.

In the case of a powder, the compound of the active ingredient and the solid carrier can be mixed and applied as it is. In the case of a granule, the compound of the active ingredient, the solid carrier and a surfactant are mixed and used. It can be manufactured by granulation and applied as it is. However, the production method of each of the above-mentioned preparation forms is not limited to the above-mentioned one, and can be appropriately selected by those skilled in the art according to the kind of the active ingredient, the purpose of application, and the like.

The method of use depends on the type and amount of pests, the type of crops and trees, the type of cultivation, and the state of growth, but for arthropods, gastropods, nematodes, etc. In general, 0.1 to 1000 g, preferably 1 to, of active ingredients per 10 ares is applied to places where damage by these pests is occurring or where damage is expected to occur. do it. Specific application methods include, for example, the aforementioned wettable powders, wettable powders for granules, aqueous solvents, emulsions, liquids, suspensions in water, and flowables such as emulsions in water, and capsules, etc., diluted with water. It can be applied to crops, trees, etc. in the range of 10 to 1000 liters per 10 ales depending on the type, cultivation form, and growth condition of the target crop, trees, etc. In the case of powders, granules, and aerosols, the preparations may be applied to crops, trees, etc. within the range of the use described above.

When the target pest mainly infects crops, trees, etc. in the soil, for example, wettable powder, wettable powder, aqueous solvent, emulsion, liquid, suspension in water, emulsion in water, etc. Flowables, capsules, etc. may be diluted with water and applied generally in the range of 5 to 500 liters per 10 ares. At this time, the medicine may be sprayed on the soil surface so as to be evenly distributed over the whole application area, or it may be irrigated into the soil. When the preparation is in the form of a powder or granules, the preparation may be sprayed as it is on the soil surface so as to be uniform over the entire area to be applied. Also, when spraying or irrigation, it may be applied only around seeds, crops, trees, etc. that you want to protect from damage by pests, or plowed during or after spraying to disperse the active ingredient mechanically. Good.

Further, a pesticidal composition containing the compound of the present invention as an active ingredient may be adhered around plant seeds by a known method. Such treatment not only prevents damage by pests in the soil after sowing the seeds, but also protects the foliage, flowers, fruits, etc. of the plants from pest damage after growth. You can do it.

When protecting the above-mentioned trees, fallen trees, processed wood, stored wood, etc. from damage by termites or beetles, for example, oils, emulsions, wettable powders, sol Spraying, injecting, irrigating, applying, spraying the drug in the form of powder, granules, etc. can be mentioned. In such situations, the pesticidal composition containing the compound of the present invention as an active ingredient may be used alone or with other active compounds such as insecticides, acaricides, nematicides, bactericides, repellents and synergists. Can be used in combination with or the like or as a mixture.

The content of the active ingredient compound such as the compound of the present invention in these preparations is optional. However, it is usually 0.0001 to 95% by weight of the total amount of active ingredients, 0.005 to 10% by weight for oils, powders, granules, etc., and 0.01 to 50% by weight for emulsions, wettable powders and sols. Preferably. Specifically, for example, if the combating-controlling termites Ya beetles, etc., the 0.01~100g as an active ingredient compound doses per lm ² may be sprayed on the soil or wood surface.

(B) Livestock industry, fishing industry scene, etc.

The pesticidal composition containing the compound of the present invention as an active ingredient is parasitic on animals such as pets bred in the livestock industry, fisheries industry and at home, internally or externally. It is effective in repelling, exterminating and controlling pests such as arthropods, nematodes, flukes, tapeworms, protozoa, etc., which cause direct harm or damage by spreading diseases. Yes, it can be used to prevent and treat diseases related to these pests. Target animals include vertebrates, for example, live-blooded vertebrates such as cattle, sheep, goats, horses, pigs, and other livestock and farmed fish; and poultry, dogs, cats, mice, rats, Rodents such as hamsters and squirrels; carnivores such as ferrets; and experimental animals such as fish and the like can be mentioned.

Among the pests, the following can be exemplified as Arthropod Insecta and Arachnida.

Examples of dipterans include, but are not limited to, the Afidae family, such as Yamato-abu, Ammetgebu-bu, and Akausiab; the housefly family, such as the chrono, 'e, housefly, and the fly; the dipteromycetes, such as the maize fly; Dermatidae, such as Pterodactylidae, etc .; Dermatidae, such as Lepidoptera purpurea; Drosophilidae, such as Drosophila and Drosophila; Family; examples of the family include the brassicaceae, such as Shinukaka power and Nichinukaka power.

In addition, examples of the Laminariae include the flea family such as cat flea and flea flea.

As for the louses, there may be mentioned Lobaceae lice, such as lice of the night lice and white lice; Lepidoptera of the nits, such as the lice of Maha lice; Lynfidae such as reed lice and the like.

Examples of the acarids of the arthropod spiders include the ticks of the spider mites, e.g., ticks and ticks, such as the ticks and mites; the ticks of the sick mites; the mites of the spider mites; the mites of the spiders; Family: Dermatophagoids such as Dermatophagoides farinae and Trichoderidae; and Dermatophagoids such as Dermatophagoides farinae and Dermatophagoides farinae.

The following can be illustrated as examples of the nematodes of the nematode phylum.

Examples of the order Coleoptera include caterpillars, pig nematodes, pig lungworms, hairy nematodes, caterpillars, and the like.

As the roundworm, for example, roundworm, roundworm of chicken, etc. can be mentioned.

Examples of the flatworm flukes include Schistosoma japonicum, Hepatic flukes, Desert flukes, Lesterum pestisman, and Japanese egg fluke.

Examples of tapeworms include foliate tapeworms, tapeworms, Beneden tapeworms, square tapeworms, striated tapeworms, and tapered tapeworms.

In the protozoan phylum flagellates, as the root flagellates, for example, Histomonas, etc., as the protoflagellate, for example, Leishmania, Trypanosoma, etc., as the polyflagellate, for example, Giardia, etc., and as the Trichomonas, , For example, Trichomonas.

Further, as the amoebices of the fleshytes, for example, Entamoeba, etc., as the pyroplasma of the sporozoa, for example, Theilaria, Babesia, etc., and as the live sporozoa, for example, Eimeria, Plasmodium, Toxoplasma, etc. Can be mentioned. The pesticidal composition containing the compound of the present invention as an active ingredient can be used alone or in combination with other active compounds such as insecticides in any of the above-mentioned preparations effective in the livestock and fisheries fields, and in any use form prepared by the preparation. It can be used in combination or as an admixture with insecticides, acaricides, nematicides, fungicides, synergists, plant conditioners, herbicides, baits and the like. More specific examples of the active compound include, but are not limited to, the substances exemplified in “(A) Agriculture, forestry scene, etc.”.

Specific methods of application include, for example, mixing with feed such as livestock and pets, Orally ingestible pharmaceutical compositions, such as tablets, pills, capsules, pastes, gels, beverages, medicated feed, medicated drinking water, medicated bait, controlled release containing pharmaceutically acceptable carriers and coating materials Orally administered as a large-sized pill, other sustained-release device kept in the gastrointestinal tract, or transdermal as a spray, powder, grease, cream, ointment, emulsion, lotion, spot-on, pour-on, shampoo, etc. Can be given.

For dermal or topical administration, devices attached to animals to control arthropods, locally or systemically (eg, collars, medallions, jars, etc.) can also be used. .

Specific oral and transdermal administration methods when used as an anthelmintic for livestock animals are shown below.However, in the present invention, these administration methods are not necessarily limited to the following description. Absent. When administered orally as a medicinal beverage preparation, it is usually dissolved in a suitable non-toxic solvent or water together with a suspending agent such as bentonite or a wetting agent or other excipients, to give a suspension or What is necessary is just to make a dispersion liquid, and may contain an antifoaming agent as needed. Beverage preparations generally contain the active ingredient in an amount of 0.01 to 1.0% by weight, preferably 0.01 to 0.1% by weight.

For oral administration in a dry solid unit dosage form, capsules, pills or tablets containing a predetermined amount of the active ingredient are usually employed. These forms are used by uniformly mixing the active ingredient with a suitably comminuted diluent, filler, disintegrant and / or binder such as starch, lactose, talc, magnesium stearate, vegetable gum, and the like. Manufactured. In such a unit-use formulation, the weight and content of the anthelmintic may be appropriately determined depending on the type of host animal to be treated, the degree of infection, the type of parasite, and the weight of the host.

When administered via feed, there may be mentioned, for example, a method in which the active ingredient compound is uniformly dispersed in the feed, a method in which the drug is used as a top dressing, or a method in which the drug is used as a pellet. In order to achieve an antiparasitic effect, the final feed usually contains 0.0001 to 0.05% by weight, preferably 0.0005 to 0.01% by weight of the active ingredient compound. When dissolved or dispersed in a liquid carrier vehicle, it may be administered parenterally to animals by intraruminal, intramuscular, intratracheal or subcutaneous injection. Because of parenteral administration, the active compound is preferably mixed with vegetable oils such as peanut oil and cottonseed oil. Such a formulation generally contains the active ingredient compound in an amount of 0.05 to 50% by weight, preferably 0.1 to 0.2% by weight. Further, a preparation mixed with a carrier such as dimethyl sulfoxide or a hydrocarbon-based solvent can be directly or locally administered to the external surface of a livestock animal by spraying or direct injection.

(C) Public health scene, etc.

The pesticidal agent of the present invention has an adverse effect on pests in public health situations such as adversely affecting clothes, food and living environment, causing harm to the human body, and carrying and transmitting pathogens. It is also effective for avoidance, eradication and control for maintaining public health. Specifically, the pesticidal agent of the present invention includes, for example, wood products inside and outside the house itself, wood products such as wooden furniture, stored foods, clothing, books, animal products (skin, wool, wool, feathers, etc.). And repelling, extermination and control of lepidoptera, beetles, spots, cockroaches, flies, mites, etc., which cause damage to plant and plant products (clothing, paper, etc.), which have a negative effect on sanitary life It is valid. Specific examples of pests in such a public health situation include the following.

Examples of the arthropod phylum Insecta include the following.

As Lepidoptera, for example, Pterodaceae, such as Moncidae moth; Power, such as Kunugikarehaga; Rehagaceae, such as Aoiraga; Malagalaceae, such as evening croaker; etc .; Gibionidae such as moths; As the Coleoptera, for example, the family Ceratopogonidae such as Akagamirimidoki; Tenebrionidae, such as Scots beetle; Lentinidae, such as Saw-throat and Lentinus; Lentinidae, such as tobacco and Jinsanshibushi; A family of beetles, such as Marcazobushimushi and Harajirokatsubushimushi; a family of beetles, such as Nisesema ruhibonboshi;

Hymenoptera include, for example, wasp family such as wasp, squirrel family such as octopus, and bee family such as beetle.

Examples of the dipteran include dipteranaceae, such as japonicus, etc .; brassicaceae, such as brassicae; mussuriaceae, such as sesjusuri, etc .; buds, such as ashmadarabu, etc .; Rubiaceae; Mulberry fly, such as Mulberry fly; Mulberry engineering, such as Sentinia fly; Laceae, Musca domestica such as Drosophila melanogaster; Cheese fly, such as cheese fly.

Examples of the order Lepidoptera include a flea family such as a human flea. As the order of the viscera, there may be mentioned, for example, the order of the order Beetle, such as the beetle.

Examples of cockroaches include the cockroach family, such as the cockroach and the cockroach, and the cockroaches family such as the cockroach, the black cockroach, and the black cockroach.

The Orthoptera includes, for example, the family Corrugidae such as Madara Powered Horse and Powered Powered Horse.

Examples of the louse include, but are not limited to, lice of the lice family such as lice of the lice;

As the Hemiptera, for example, bed bugs such as bed bugs; and bugs such as green turtles can be mentioned.

As the termites, for example, the termites of the termites such as the termites and termites; the termites of the termites such as the termites; the termites of the termites such as the termites of the termites; Konakya evening family.

As the spots, for example, spots such as stag beetles and sea stains may be mentioned. Can be.

The following can be exemplified as arthropod spiders.

As the mites, for example, ticks such as Schulz ticks; Dermatophagoides such as house dust mites; Dermatidae such as Minamimite; Louse ticks such as lice mites; Dermatidae such as Dermatidae; Dermatidae such as Dermatophagoides; Oxodidae; Dermatidae, such as Akatsugamushi; Dermatidae, such as Dermatophagoides farinae and Dermatophagoides farinae; Sugar mites, such as sugar cane. Examples of the true arachnids include, for example, the spiders such as Birch spiders; the spiders such as ash spiders; the spiders such as staghorn spiders and the spider spiders; the spiders spiders such as hiratagmo; the spiders such as the spiders spiders. And the like.

As the scorpiones, there may be mentioned, for example, the scorpion family, such as the scorpion.

As other arthropod phylums, examples of the order of the order Aphididae from the order of the order of the order of the order Aphididae include those of the family Aphididae, such as Tobism and Aoazukade, and examples of the order of the order Gastropoda include, for example, the family Dipteridae.

Examples of the arthropod phylum, Ophiaceae include, for example, Rhododendrons such as toadscomb, and examples of the arthropod, such as Crustacea, include the pallidaceae, such as the pods.

Further, examples of the annelid fauna, Lepidoptera, include the Lamaviridae family such as the Lamavir.

The pesticidal composition of the present invention may be used alone or in the form of any other active compound such as an insecticide, acaricide, nematocide, in a formulation effective in the public health situation described above, and in any use form prepared by the formulation. It can be used in combination with or as an admixture with agents, fungicides, synergists, plant regulators, herbicides, baits and the like. Specific other active compounds include:

The substances listed in “(A) Agriculture, forestry, etc.” can be mentioned, but are not necessarily limited to these.

The form of use of the pesticidal composition of the present invention is optional. When protecting products, etc., spray oils, emulsions, wettable powders, powders, etc., install resin vaporizers, treat smoke and aerosols, install granules, tablets and baits, and install aerosols. It can be controlled by spraying. The amount of the active ingredient compound in these preparations is preferably 0.0001 to 95% by weight.

As for the method of application, for pests such as arthropods that cause direct harm or arthropods that are vectors for disease, etc. Spraying, injection, irrigation, application, dusting, etc., fumigants, mosquito coils, self-burning type smokers, heating fogs such as chemical reaction type aerosols, fogging etc., ULV agents, etc. And the like. In addition, they can be applied in other forms such as granules, tablets or poison bait, or by dripping floating powder, granules, etc. into waterways, wells, reservoirs, water tanks and other running or stationary water. do it.

In addition, it is possible to control mites, which are also pests in agriculture and forestry, in the same manner as described in “(A) Agriculture, forestry, etc.”. It is also effective to use a method in which the active ingredient is mixed in the feces by mixing it in the feed of livestock, and a method in which the active ingredient is volatilized in the air with an electric mosquito trap, etc. is there.

The formulations in these forms of use can also be present as mixtures with other active compounds as described above, for example with pesticides, acaricides, nematicides, fungicides, repellents or synergists. Preferably, these preparations contain the active ingredient compound in a total amount of 0.0001 to 95% by weight. Incidentally, it can be used in combination with other active compounds at the time of use.

When protecting houses and wooden furniture from damage by termites or beetles, for example, spraying, pouring, irrigation, coating, dusting of oils, emulsions, wettable powders, and sols on and around them And a method of spraying a medicine in a use form of a granule or the like. In such situations, the compounds of the present invention may be used alone or in combination with other active compounds such as insecticides, acaricides, nematicides, fungicides, repellents, synergists and the like, or as admixtures. Can be used. The content of the active ingredient compound such as the compound of the present invention in these preparations is optional, but it is usually 0.0001 to 95% by weight in total of the active ingredient, and 0.005 to 10% for oils, powders, granules and the like. %, Preferably 0.01 to 50% by weight in emulsions, wettable powders, sols and the like. Specifically, for example, if the combating-controlling termites Ya beetles, etc., 0.01 to as active ingredient compound doses per lm ^2: LOOG may be sprayed around or directly surface.

When repelling, controlling, or controlling pests that cause harm to the human body or transport or transmit pathogens, besides the above, appropriate orally ingestible pharmaceutical preparations, such as pharmaceuticals Tablets, pills, capsules, pastes, gels, beverages, medicated feed, medicated drinking water, medicated bait, sustained release large pills, and other pills containing an acceptable carrier or coating material to be retained in the gastrointestinal tract It can be administered orally as a sustained release device or the like, or transdermally as a spray, powder, grease, cream, ointment, emulsion, lotion, spot-on, pour-on, shampoo, etc.

Specific formulation and the like can be prescribed in the same manner as described in “(B) Livestock industry, fisheries scene, etc.”.

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Synthesis Example 1 4- (3,3-Dichloro-2-propenyloxy) -1- [1- (3-trifluoromethylphenyl) ethoxyimino] methylbenzene (Synthesis of Compound No. 2 in Table 1)

12.2 g (100 mmol) of 4-hydroxybenzaldehyde, 15.32 g (purity 95%, 100 mmol) of 1,1,3-trichloropropene, 13.8 g (100 mmol) of potassium carbonate, 0.49 g of 18-crown-6-ether ( A mixture of 2 mmol, 0.02 eq) and 100 ml of acetonitrile was refluxed for 5 hours. The residue obtained by evaporating the solvent from the reaction mixture was added with 150 ml of ethyl acetate, washed successively with water, a 5% aqueous sodium carbonate solution and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate 10/1 to 5/1) to obtain 21.14 g. This yielded 4- (3,3-dichloro-2-propenyloxy) benzaldehyde (Compound No. 1 in Table 15). Yield 92%.

n _D ²³ 1.5861

_{Ή NMR (400 MHz, CDC1 3} ) δ 4.75 (2H, d), 6.17 (lH, t), 7.00 (2H, d), 7.86 (2H, d), 9.91 (lH, s).

Mixture of 0.23 g (l mmol) of 4- (3,3-dichloro-2-propenyloxy) benzaldehyde, 0.25 g (1.2 mmol) of 1- (3-trifluoromethylphenyl) ethoxyamine and 2 ml of ethanol Was stirred at room temperature for 18 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate 15/1) to obtain 0.33 g of the title compound. 79% yield.

n _D ²⁴ 1.5515

_{Ή NMR (400 MHz, CDC1 3} ) (5 1.60 (3H, d), 4.66 (2H, d), 5.36 (lH, q), 6.13 (lH, t), 6.85 (2H, d), 7.48 (2H, d), 7.4-7.6 (3H, m), 7.63 (lH, s), 8.09 (lH, s). Synthesis Example 1 4- (3,3-dichloro-2-propenyloxy) -2,6- Dimethyl -l- [l- (3-trifluoromethylphenyl) ethoxyimino] methylbenzene (Synthesis of Compound No. 3 in Table 1)

A solution of 17.58 g (110 mmol) of bromine in 10 ml of acetic acid was added dropwise to a mixture of 12.2 g (100 mmol) of 3,5-dimethylphenol and 70 ml of acetic acid over 15 minutes under ice-cooling. The reaction mixture was stirred at room temperature for 1 hour, poured into iced water and extracted with chloroform (100 ml, 50 ml). The organic layer was washed with water and saturated saline, and dried over anhydrous sodium sulfate. Cold hexane was added to the residue obtained by evaporating the solvent, and the mixture was filtered to obtain 6.58 g of 4-bromo-3,5-dimethylphenol. The mother liquor was recovered, the solvent was distilled off, and the residue obtained was purified by silica gel column chromatography (toluene / ethyl acetate = 15/1 to 10/1) to obtain 3.42 g. 10.0 g total. Yield 50%. mp 110-112 ° C Ή NMR (400 MHz, CDC1 3) 5 2.35 (6H, s), 4.67 (lH, s), 6.59 (2H, s).

4-bromo-3,5-dimethylphenol 6.18 (30.7 11111101), benzyl bromide 5.52 (32.3 mmol), potassium carbonate 4.67 g (33.8 mmol, 1.1 eq), 18-crown-6-ether A mixture of 0.16 g (0.61 mmol, 0.02 eq) of toluene and 30 ml of acetonitrile was refluxed for 2 hours. After evaporating the solvent from the reaction mixture, 100 ml of ethyl acetate was added, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 8.90 g of 4-benzyloxy-2,6-dimethylbromobenzene. Yield 99%.

n _D ²⁴ 1.5940

_{Ή NMR (400 MHz, CDC1 3} ) δ 2.38 (6H, s), 5.01 (2H, s), 6.73 (2H, s), 7.3- 7.5 (5H, m).

A mixture of 0.66 g (27.1 mmol, 1.05 eq) of magnesium and 20 ml of tetrahydrofuran (THF) was refluxed under a stream of nitrogen while a solution of 7.50 g (25.8 mmol) of 4-benzyloxy-2,6-dimethylbromobenzene in 20 ml of THF was added. It was dropped in 20 minutes. The reaction mixture was further refluxed for 10 minutes, cooled on ice, and a solution of 2.26 g (30.9 mmol, 1.2 eq) of dimethylformamide (DMF) in 20 ml of THF was added dropwise over 30 minutes. The reaction mixture was stirred for 30 minutes under ice cooling and for 1 hour at room temperature, poured into a saturated aqueous solution of ammonium chloride and extracted with 100 ml of toluene. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15Zl-9 / l) to obtain 4.90 g of 4-benzyloxy-2,6-dimethylbenzaldehyde. Was. 79% yield.

n _D ²⁴ 1.5988

_{Ή NMR (400 MHz, CDC1 3} ) 5 2.61 (6H, s), 5.11 (2H, s), 6.68 (2H, s), 7.3-7.5 (5H, m), 10.48 (lH, s).

A mixture of 4.30 g (17.9 mmol) of 4-benzyloxy-2,6-dimethylpenzaldehyde, 0.4 g of 10% palladium carbon and 40 ml of ethanol was stirred for 1.5 hours in a hydrogen atmosphere. The reaction mixture was filtered through celite, and the solvent was distilled off from the filtrate to obtain 2.40 g of 2,6-dimethyl-4-hydroxybenzaldehyde (containing 16% of a benzyl alcohol compound). Yield 75%.

mp> 200 ° C (dec) Ή NMR (CDCl ₃ + DMSO-d ₆ ) δ 2.56 (67H, s), 6.55 (2H, s), 10.41 (lH, s). 2,6-dimethyl-4-hydroxybenz with the above purity of 84% Aldehyde 2.10 g (purity 100%, 14.0 mmol), 1,1,3-trichloropropene 7.96 g (purity 95%, 16.88 mmol, 1.2 eq), potassium carbonate 2.51 g (18.2 mmol, 1.3 eq), 18 A mixture of 0.07 g (0.28 mmol, 0.02 eq) of -crown-6-ether and 15 ml of acetonitrile was refluxed for 2 hours. After evaporating the solvent from the reaction mixture, 50 ml of toluene was added, and the mixture was washed with water and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1), and 2.54 g of 2,6-dimethyl-4- (3,3-dichloro-2 -Propenyloxy) benzaldehyde (Compound No. 3 in Table 15) was obtained. Yield 83%.

mp 92-94 ° C

Ή NMR (400 MHz, CDC) 5 2.61 (6H, s), 4.69 (2H, d), 6.15 (lH, t), 6.58 (2H, s), 10.48 (lH, s).

2,6-dimethyl-4- (3,3-dichloro-2-pronenyloxy) benzaldehyde 0.18 g (0.69 mmol), 1- (3-trifluoromethylphenyl) ethoxyamine 0.17 g (0.83 mmol) and A mixture of 1.5 ml of ethanol was stirred at room temperature for 18 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate 15/1) to obtain 0.28 g of the title compound. Yield 91% _c n _D ²⁴ 1.5470.

_{Ή NMR (400 MHz, CDC1 3} ) 1.63 (3H, d), 2.26 (6H, s), 4.61 (2H, d), 5.35 (lH, q), 6.11 (lH, t), 6.54 (2H, s) , 7.46 (lH, dd), 7.53 (lH, d), 7.55 (lH, d), 7.65 (lH, s), 8.38 (lH, s). Synthesis Example 1 2-Chloro-4- (3,3 -Dichloro-2-propenyloxy) -l- [l- (3-trifluoromethylphenyl) ethoxyimino;! Methylbenzene (synthesis of compound No. 4 in Table 1)

2-Hydroxy-4-hydroxybenzaldehyde 10.5 g (67.1 mmol), 1,1,3-trichloropropene 10.3 g (purity 95%, 67.1 mmol), potassium carbonate 11.1 g (80.5 mmol), 18- A mixture of 0.36 g (1.3 mmol) of crown-6-ether, 90 ml of acetonitrile and 10 ml of DMF was refluxed for 5 hours. The residue obtained by evaporating the solvent from the reaction mixture was added with 200 ml of toluene, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate 15/1), and 13.9 g of 2-chloro-4- (3,3-dichloro-2- (Propenyloxy) benzaldehyde (synthesis of compound No. 5 in Table 15) was obtained. C Yield 78%.

mp 68-70 ° C

_{Ή NMR (400 MHz, CDC1 3} ) 5 4.72 (2H, d), 6.15 (lH, t), 6.89 (lH, dd), 6.94 (lH, d), 7.91 (lH, d), 10.34 (lH, s ).

4- (3,3-dichloro-2-propenyloxy) benzaldehyde 0.27 g (l mmol), 1- (3-trifluoromethylphenyl) ethoxyamine 0.25 g (1.2 mmol ) And ethanol (2 ml) was stirred at room temperature for 18 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate 15/1) to quantitatively give the title compound (0.46 g).

n _D ²⁴ 1.5577

_{Ή NMR (400 MHz, CDC1 3} ) (5 1.62 (3H, d), 4.64 (2H, d), 5.37 (lH, q), 6.12 (lH, t), 6.75 (lH, dd), 6.87 (lH, d), 7.47 (lH, dd), 7.54 (lH, d), 7.56 (lH, d), 7.63 (lH, s), 7.72 (lH, d), 8.49 (lH, s). , 6-Dichloro-4- (3,3-dichloro-2-propenyloxy) -l- [l- (3-trifluoromethylphenyl) ethoxyimino] methylbenzene (Compound No. 1 in Table 11) 9)

To a mixture of 20.0 g (122.7 mmol) of 3,5-dichlorophenol and 80 ml of acetic acid at room temperature was added dropwise a solution of 20.6 g (128.8 mmol) of bromine in 10 ml of acetic acid over 15 minutes. The reaction mixture was stirred at room temperature for 1 hour, poured into ice water (160 ml), and extracted with black hole form (150 mix x 2). The organic layer was washed with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off, 50 ml of cold hexane was added to the residue, and the mixture was filtered. 5.0 g of 4-bromo-3,5-dichlorophenol was obtained. The mother liquor was recovered, the solvent was distilled off, and the residue obtained was purified by silica gel column chromatography (hexane / ethyl acetate = 8/1) to obtain an additional 16.7 g. 73% yield.

mp 119-120. C

Ή NMR (400 MHz, CDCl ₃ ) d 5.19 (lH, s), 6.92 (2H, s).

4-bromo-3,5-dichlorophenol 7.0 g (28.9 mmol), cupromethylmethylether 2.56 g (31.8 mmol), potassium carbonate 4.79 g (34.7 mmol), 18-crown-6-ether 0.15 g (0.58 mmol) and a mixture of 30 ml of acetonitrile were stirred at 60-70 ° C for 3 hours. After evaporating the solvent from the reaction mixture, toluene (100 ml) was added, and the mixture was washed with water and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 7.23 g of 4-methoxymethoxy-2,6-dichlorobromobenzene. 87% yield.

mp 65-67 ° C

_{Ή NMR (400 MHz, CDC1 3} ) 5 3.47 (3H, s), 5.14 (2H, s), 7.11 (2H, s).

To a mixture of 1.17 g (48.3 mmol) of magnesium and 10 ml of THF, under a nitrogen stream, 6.90 g (24.1 mmol) of 4-methoxymethoxy-2,6-dichlorobromobenzene and 3.80 g of 1-bromo-3-chloropropane ( A solution of 24.1 mmol) in 20 ml of THF was added dropwise over 30 minutes. At that time, water cooling was performed so that the internal temperature was 40 ° C or less. To the reaction mixture was added 20 mL of THF, and the mixture was further stirred for 30 minutes at an internal temperature of 40 ° C. or lower, cooled with ice, and then a solution of 2.64 g (36.2 mmol) of DMF in 10 mL of THF was added dropwise over 5 minutes. The reaction mixture was stirred at room temperature for 2 hours, poured into a saturated aqueous ammonium chloride solution and extracted with 50 ml of toluene. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / toluene / ethyl acetate = 8/2/1), and 4.45 g of 4-methoxymethoxy-2,6-dichlorobenzene was purified. The aldehyde was obtained. 79% yield.

mp 54-62 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (3.49 (3H, s), 5.22 (2H, s), 7.07 (2H, s), 10.43 (lH, s). A mixture of 3.85 g (16.4 mmol) of 4-methoxymethoxy-2,6-dichlorobenzaldehyde, 10 ml of 3N hydrochloric acid, 10 ml of 2-propanol and 10 ml of THF was stirred at 60 ° C for 2 hours. The solvent was distilled off from the reaction mixture, and to the residue obtained, 100 ml of ethyl acetate was added, washed with water and saturated saline, and dried over anhydrous sodium sulfate. Hexane was added to the crystals obtained by distilling off the solvent, followed by filtration to obtain 2.50 g of 2,6-dichloro-4-hydroxybenzaldehyde. Yield 80%.

mp> 200 ° C (dec)

Ή NMR (400 MHz, CDCl ₃ + DMSO-d ₆ ) d 6.88 (2H, s), 10.37 (lH, s).

2,6-dichloro-4-hydroxybenzaldehyde 2.20 g (11.5 mmol), 1,1,3-trichloropropene 1.76 g (purity 95%, 11.5 mmol), potassium carbonate 1.91 g (13.8 mmol, 1.2 eq) ), 0.06 g (0.23 mmol, 0.02 eq) of 18-crown-6-ether, 15 ml of acetonitrile and 3 ml of DMF were refluxed for 2 hours. After evaporating the solvent from the reaction mixture, 50 ml of toluene was added, and the mixture was washed with water and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane Z ethyl acetate = 15Zl), and 3.25 g of 2,6-dichloro-4- (3,3-dichloro-2- Propenyloxy) benzaldehyde (synthesis of compound No. 7 in Table 15) was obtained. 94% yield.

mp 81-83 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 4.70 (2H, d), 6.14 (lH, t), 6.91 (2H, s), 10.42 (lH, s).

0.30 g (l mmol) of 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzaldehyde, 0.31 g (1.5 mmol) of 1- (3-trifluoromethylphenyl) ethoxyamine and A mixture of 2 ml of ethanol was stirred at room temperature for 18 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate 15/1) to quantitatively obtain the title compound (0.50 g).

n _D ²⁴ 1.5596

Ή NMR (400 MHz, CDCl ₃ ) d 1.65 (3H, d), 4.62 (2H, d), 5.41 (lH, q), 6.10 (lH, t), 6.86 (2H, s), 7.46 (lH, dd ), 7.53 (lH, d), 7.56 (lH, d), 7.66 (lH, s), 8.30 (lH, s). Synthetic Example—5 2,6-Dichloro-4- (3,3-dichloro-2-propenyloxy) -l- [2- (4-trifluoromethylphenyl) ethoxyiminomethyl] benzene (Table — Synthesis of compound No. 48 in 1)

A mixture of 9.45 g (46.3 mmol) of 4-trifluoromethylphenylacetic acid, 0.44 g (2.3 mmol) of? -Toluenesulfonic acid and 100 ml of methanol was refluxed for 1 hour. The solvent was distilled off from the reaction mixture, and to the residue obtained, 100 ml of ethyl acetate was added. The mixture was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 9.58 g of methyl 4-trifluoromethylphenylacetate. 95% yield.

n _D ²⁴ 1.4491

_{Ή NMR (400 MHz, CDC1 3} ) (5 3.71 (3H, s), 7.40 (2H, d), 7.59 (2H, d).

A mixture of 1.60 g (42.1 mmol) of lithium aluminum hydride and 100 ml of THF was added dropwise with a solution of 9.18 g (42.1 mmol) of methyl 4-trifluoromethylphenylacetate in 30 ml of THF over 15 minutes under ice-cooling. . After further stirring for 1 hour under ice cooling, 1.6 ml of water, 1.6 ml of a 15% aqueous sodium hydroxide solution and 4.8 ml of water were added, and the mixture was stirred for 30 minutes. The reaction mixture was filtered through celite, and the residue obtained by evaporating the solvent from the filtrate was purified by silica gel column chromatography (hexane Z ethyl acetate = 3/1 to 2/1) to give 7.16 g of 2- (4-Trifluoromethylphenyl) ethanol was obtained. 90% yield. n _D ²⁴ 1.4609

_{Ή NMR (400 MHz, CDC1 3} ) 0 "1.40 (lH, t), 2.93 (2H, t), 3.90 (2H, td), 7.36 (2H, d), 7.57 (2H, d).

2- (4-trifluoromethylphenyl) ethanol 4.0 g (21.1 mmol), N-hydroxyphthalimide 3.5 g (21.5 mmol), triphenylphosphine 6.6 g (25.3 mmol), toluene 40 ml and THF 8 ml To the mixture was added 11.9 g (27.4 mmol) of a 40% toluene solution of getyl azodicarboxylate under water cooling, and the mixture was stirred at room temperature for 18 hours. Ethyl acetate (50 ml) was added to the reaction mixture, and the mixture was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / toluene / ethyl acetate = 8/2/1), and 5.80 g of-[2- (4-trifluoromethylfuran) was obtained. Enil) Ethoxy] Huimi I got. Yield 82 ° /. .

mp 55-61 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 3.21 (2H, t), 4.47 (2H, t), 7.46 (2H, d), 7.56 (2H, d), 7.7-7.9 (4H, m).

To a mixture of 5.40 g (16.1 mmol) of N- [2- (4-trifluoromethylphenyl) ethoxy] phthalimide and 35 ml of ethanol was added a solution of 1.21 g (24.2 mmol) of hydrazine hydroxide in 5 ml of ethanol. The mixture was refluxed for 2 hours. The reaction mixture was filtered, the solvent was distilled off from the filtrate, 50 ml of ether was added to the residue, and the mixture was washed sequentially with water, saturated aqueous sodium hydrogen carbonate and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 3.00 g of 2- (4-trifluoromethylphenyl) ethoxyamine. Yield 91%. n _D ²⁴ 1.4655

_{Ή NMR (400 MHz, CDC1 3} ) 5 2.96 (2H, t), 3.90 (2H, t), 5.41 (2H, brs), 7.33 (2H, d), 7.55 (2H, d).

2- (4-trifluoromethylphenyl) ethoxyamine 0.31 g (1.5 mmol), 2,6-dichloro-4--4- (3,3-dichloro-2-propenyloxy) benzaldehyde 0.30 g (1.0 mmol) ) And 2 ml of ethanol were stirred at room temperature for 18 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to quantitatively give the title compound (0.49 g). n _D ²⁴ 1.5623

_{Ή NMR (400 MHz, CDC1 3} ) 5 3.12 (2H, t), 4.42 (2H, t), 4.65 (2H, d), 6.12 (lH, t), 6.92 (2H, s), 7.38 (2H, d ), 7.56 (2H, d), 8.25 (lH, s). Synthesis Example 6 4- (3,3-Dichloro-2-propenyloxy) -l- [2- (5-trifluoromethylpyridine-2-yloxy) ) Ethoxyimino] methylbenzene (Synthesis of Compound No. 1 in Table 1-2)

2-chloro-5-trifluoromethylpyridine 25.0 g (138 mmol), ethylene glycol 85.4 g (1.38 mol), potassium hydroxide 11.6 g (207 mmol), 18-crown-6-ether 0.68 A mixture of g (2.75 mmol) and 200 ml of toluene was refluxed for 2 hours. reaction After cooling the mixture, 200 ml of water was added and the layers were separated. The aqueous layer was extracted with 100 ml of toluene, and the organic layer was combined, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1 to 1/2) to obtain 25.84 g of 2- (5-trifluoromethylpyridine-2). -(Yloxy) ethanol was obtained. Yield 91%.

n _D ²³ 1.4619

_{Ή NMR (400 MHz, CDC1 3} ) δ 2.74 (lH, brs), 3.98 (2H, brs), 4.53 (2H, t), 6.89 (lH, d), 7.81 (lH, dd), 8.42 (lH, brs ).

2- (5-trifluoromethylpyridine-2-yloxy) ethanol 5.00 g (24.2 mmol), -hydroxyfluorimide 3.94 g (24.2 mmol), triphenylphosphine 6.33 g (24.2 mmol), To a mixture of 50 ml of toluene and 10 ml of THF, 12.61 g (29.0 mmol, 1.2 eq) of a 40% toluene solution of getyl azodicarboxylate was added dropwise over 15 minutes under ice-cooling. Stirred for hours. To the reaction mixture was added 100 ml of ethyl acetate, washed successively with water, saturated aqueous sodium hydrogen carbonate and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / toluene / ethyl acetate = 7/2/1 to 4/1/1 to 2/2/1) to give 6.81 g. A 2- (5-Trifluoromethylpyridine-2-yloxy) ethoxy] fluoroimidide was obtained. Yield 79.9%.

mp 117 ° C

_{Ή NMR (400 MHz, CDC1 3} ) δ 4.60 (2H, m), 4.73 (2H, m), 6.81 (lH, d), 7.7- 7.8 (3H, m), 7.8-7.9 (2H, m), 8.40 (lH, brs).

2.88 g (57.7 mmol) of hydrazine hydrate was added to a mixture of 6.40 g (28.8 mmol) of N- [2- (5-trifluoromethylviridine-2-yloxy) ethoxy] phthalimid and 60 ml of ethanol. Refluxed for 2.5 hours. After cooling the reaction mixture, 40 ml of hexane was added and the mixture was filtered. The crystals were washed with 60 ml of hexane / ethanol (1/1), and the residue obtained by evaporating the solvent from the filtrate and washings was removed. Purification by silica gel column chromatography (hexane / getyl ether = 4/1) gave 3.62 g of 2- (5-trifluoromethylpyridine-2-yloxy) ethoxyamine. Yield 57%. n _D ²³ 1.4660

_{Ή NMR (400 MHz, CDC1 3} ) δ 4.02 (2H, m), 4.60 (2H, m), 5.58 (2H, brs), 6.87 (lH, d), 7.78 (lH, dd), 8.43 (lH, brs ).

0.44 g (2.0 mmol) of 2- (5-trifluoromethylviridine-2-yloxy) ethoxyamine, 0.42 g (1.8 mmol) of 4- (3,3-dichloro-2-provenyloxy) benzoaldehyde and 4 ml of ethanol Was stirred at room temperature for 1 hour. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate 20/1) to obtain 0.50 g of the title compound. Yield 63.8%. mp 75-76 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 4.50 (2H, dd), 4.67 (2H, dd), 4.68 (2H, d), 6.15 (lH, t), 6.88 (2H, d), 6.88 (lH, d), 7.52 (2H, d), 7.77 (lH, dd), 8.08 (lH, s), 8.43 (lH, brs). Synthesis example 1 7 4- (3,3-dichloro-2-propenyloxy) -l- [l- [2- (5-Trifluoromethylpyridin-2-yloxy) ethoxy] imino] ethylbenzene (Synthesis of Compound No. 3 in Table 2)

4-hydroxyacetophenone 2.0 g (14.7 mmol), l, l, 3-trichloropropene 2.25 g (purity 95%, 14.7 mmol), potassium carbonate 2.03 g (14.7 mmol), 18-crown-6-e — A mixture of 0.07 g (0.29 mmol) of ter and 15 ml of acetonitrile was refluxed for 4 hours. To the residue obtained by evaporating the solvent from the reaction mixture was added 50 ml of ethyl acetate, washed successively with water, a 5% aqueous sodium carbonate solution and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography-(hexane / ethyl acetate 10/1 to 5/1), and 2.95 g of 4- (3,3-dichloro-2-probe) was purified. Nyloxy) acetophenone (compound No. 8 in Table 15) was obtained. 82% yield.

mp 57 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 2.57 (3H, s), 4.72 (2H, d), 6.16 (lH, t), 6.93 (2H, d), 7.95 (2H, d).

2- (5-trifluoromethylviridine-2-yloxy) ethoxyamine 0.44 g (2.0 mmol), 0.44 g (1.8 mmol) of 4- (3,3-dichloro-2-proenyloxy) acetophenone, 4 ml of ethanol and 1 ml of acetic acid were stirred at room temperature for 15 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate 20/1 to 10/1) to obtain 0.70 g of the title compound. 87% yield.

mp 70-71 ° C

_{Ή NMR (400 MHz, CDC1 3} ) δ 2.20 (3H, s), 4.52 (2H, dd), 4.68 (2H, d), 4.69 (2H, dd), 6.15 (lH, t), 6.87 (2H, d ), 7.60 (2H, d), 7.76 (lH, dd), 8.42 (lH, brs). Synthesis Example—8 4- (3,3-dichloro-2-provenyoxy) -2,6-dimethyl -l -[3- (5-Trifluoromethylpyridine-2-yloxy) propoxyimino] methylbenzene (Synthesis of Compound No. 13 in Table 1-2)

2,6-dimethyl-4- (3,3-dichloro-2-propenyloxy) benzaldehyde 0.30 g (1.16 mmol), 3- (5-trifluoromethylpyridine-2-yloxy) propoxyamine 0.30 g ( A mixture of 1.27 mmol) and 3 ml of ethanol was stirred at room temperature for 16 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.52 g of the title compound. 94% yield.

mp 58 ° C

Ή NMR (400 MHz, CDCl ₃ ) d 2.22 (2H, m), 2.39 (6H, s), 4.32 (2H, t), 4.51 (2H, t), 4.64 (2H, d), 6.14 (lH, t ), 6.58 (2H, s), 6.82 (lH, d), 7.76 (lH, dd), 8.35 (lH, s), 8.42 (lH, brs). Synthesis Example 9 4- (3,3-dichloro-) 2-Propenyloxy) -2,6-dichloro-1--1- [2- (5-trifluoromethylpyridine-2-yloxy) ethoxymino] methylbenzene (Synthesis of Compound No. 16 in Table 1)

2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzaldehyde 0.39 g (1.3 mmol), 2- (5-trifluoromethylpyridine-2-yloxy) ethoxyamine A mixture of 0.32 g (1.43 mmol) and 3 ml of ethanol was stirred at room temperature for 22 hours and refluxed for 30 minutes. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.64 g of the title compound. Yield 98%.

mp 68-69 ° C

Ή NMR (400 MHz, CDCl ₃ ) d 4.55 (2H, m), 4.64 (2H, d), 4.70 (2H, m), 6.12 (lH, t), 6.89 (lH, d), 6.90 (2H, s ), 7.78 (lH, dd), 8.32 (lH, s), 8.43 (lH, brs). Synthesis Example— 10 2-Chloro-4- (3,3-dichloro-2-propenyloxy) -l -[l- [2- (5-Trifluoromethylpyridine-2-yloxy) ethoxy] imino] propylbenzene (Synthesis of Compound No. 19 in Table 1-2)

0.29 g (1.0 mmol), 2- (5-trifluoromethylviridine-2-yloxy) ethoxyamine, 4- (3,3-dichloro-2-propionyloxy) propiophenone (1.1 mmol), a mixture of ethanol 3 ml and acetic acid 0.5 ml was stirred at room temperature for 18 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.43 g of the title compound. E / Z mixture (2/1). 86% yield.

n _D ²⁴ 1.5368

_{Ή NMR (400 MHz, CDC1 3} ) 5 0.97 (3H, t), 1.07 (3H, t), 2.49 (2H, q), 2.71 (2H, q), 4.35 (2H, dd), 4.48 (2H, dd ), 4.56 (2H, dd), 4.6-4.7 (6H, m), 6.13 (lH, t), 6.14 (lH, t), 6.78 (lH, dd), 6.79 (lH, dd), 6.79 (lH, d), 6.88 (lH, d), 6.91 (lH, d), 6.93 (lH, d), 6.97 (lH, d), 7.18 (lH, d), 7.75 (lH, dd), 7.78 (lH, dd) ), 8.40 (lH, brs), 8.43 (lH, brs). Synthetic Example—11,2-Dichloro-4- (3,3-dichloro-2-propenyloxy) -l- [2- (5 -Trifluoromethylpyridine-2-ylthio) ethoxyimino] methylbenzene (Synthesis of Compound No. 22 in Table 1)

2-chloro-5-trifluoromethylpyridine 10.0 g (55.1 mmol), 2-mercaptoethanol 4.3 g (55.1 mmol), potassium carbonate 9.1 g (66.1 mmol) and DMF 50 ml of the mixture was stirred at room temperature for 2 hours. To the reaction mixture was added 150 ml of toluene, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 4/1 to 2/1), and 9.89 g of 5-trifluoromethylpyridine-2-ylthio was purified. Ethanol was obtained. Yield 80%.

n _D ²⁴ 1.5136

_{Ή NMR (400 MHz, CDC1 3} ) (5 3.41 (2H, t), 3.58 (2H, t), 3.96 (2H, dt), 7.36 (lH, d), 7.69 (lH, dd), 8.64 (lH, brs).

5-trifluoromethylviridine-2-ylthioethanol 5.0 g (22.4 mmol), N-hydroxyphthalimide 3.66 g (22.4 mmol), triphenylphosphine 6.46 g (24.7 mmol), THF 8 ml and toluene 40 ml To this mixture was added 12.7 g (29.1 mmol, 1.3 eq) of a 40% solution of getylazodicalboxylate in toluene, and the mixture was stirred at room temperature for 18 hours. To the reaction mixture was added 40 ml of ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / toluene / ethyl acetate = 2 / 2Z1), and 7.43 g of-(5-trifluoromethylviridine-2-ylthiol) was purified. An ethoxy) phthalimid was obtained. 90% yield.

mp 83-85 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 3.63 (2H, t), 4.46 (2H, t), 7.28 (lH, d), 7.66 (lH, dd), 7.7-7.9 (4H, m), 8.52 ( lH, brs).

To a mixture of 7.0 g (19.0 mmol) of N- (5-trifluoromethylpyridine-2-ylthioethoxy) phthalimide and 50 ml of ethanol, 1.43 g (28.5 mmol) of hydrazine hydrate was added, and the mixture was refluxed for 2 hours. The reaction mixture was filtered, the solvent was distilled off from the filtrate, 50 ml of ether was added to the residue, and the mixture was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off to give quantitatively 5-trifluoromethylpyridine-2-ylthioethoxyamine (4.64 g).

n _D ²⁴ 1.5150

Ή NMR (400 MHz, CDCl ₃ ) d 3.49 (2H, t), 3.93 (2H, t), 5.52 (2H, br), 7.29 (lH, d), 7.66 (lH, dd), 8.66 (lH, brs).

5-trifluoromethylpyridine-2-ylthioethoxyamine 0.41 g (1.73 mmol), 2,6-dic-mouth-4- (3,3-dic-mouth-2-propenyloxy) benzaldehyde 0.40 g (1.33 mmol) and 3 ml of ethanol were stirred at room temperature for 18 hours. The residue obtained by evaporating the solvent from the reaction mixture is subjected to silica gel column chromatography.

(Hexane / ethyl acetate = 15/1) to give 0.67 g of the title compound. 97% yield.

n _D ²⁴ 1.5833

Ή NMR (400 MHz, CDC1,) 5 3.60 (2H, t), 4.43 (2H, t), 4.65 (2H, d), 6.12 (lH, t), 6.91 (2H, s), 7.30 (lH, d ), 7.67 (lH, dd), 8.31 (lH, s), 8.67 (lH, brs). Synthetic Example— 12 4- (3,3-dichloro-2-propenyloxy) -l- [3- ( 5-trifluoromethylpyridine-2-yloxy) -2-butylideneaminooxy] ethylbenzene (Synthesis of Compound No. 5 in Table 13)

2-chloro-5-trifluoromethylviridine 10.0 g (55.1 mmol), 2,3-butanediol 24.8 g (275 mmol), hydroxide hydroxide 4.63 g (82.6 mmol), 18-crown-6- A mixture of 0.27 g (1.1 mmol) of ether and 80 ml of toluene was refluxed for 3 hours. After cooling the reaction mixture, 70 ml of toluene and 100 ml of water were added thereto, and the mixture was partitioned. The organic layer was washed with water and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1-: 1/2), and 9.83 g of 3- (5-trifluoromethylpyridine-2) was purified. -(Yloxy) -2-butanol was obtained. Diastereomeric mixture. Yield 76%.

n _D ²³ 1.4565

_{Ή NMR (400 MHz, CDC1 3} ) (5 1.23 (3H, d), 1.26 (3H, d), 1.33 (3H, d), 1.34 (3H, d), 2.50 (lH, d), 2.86 (lH, d), 3.90 (lH, m), 4.03 (lH, m), 5.11 (lH, dt), 5.25 (lH, dt), 6.83 (2H, d), 7.78 (2H, dd), 8.41 (2H, brs ).

3- (5-trifluoromethylpyridine-2-yloxy) but-2-ol 4.0 g (17.0 mmol), -methylmorpholine-N-oxide 2.99 g (25.5 mmol), molecular sieve To a mixture of 2.55 g of 4A powder and 17 ml of dichloromethane was added 0.12 g (0.34 mmol) of TPAP (tetra-n-propylammonium perruthenate), and the mixture was stirred at room temperature for 30 minutes. An exotherm occurred 1-2 minutes after the addition, and the mixture was violently refluxed. The reaction mixture was filtered through celite, the solvent was distilled off from the filtrate, and the residue obtained was purified by silica gel column chromatography (hexane / ethyl acetate = 4/1) to give 3.70 g of 3- (5- Trifluoromethylpyridine-2-yloxy) -2-butanone was obtained. Yield 93%.

n _D ²³ 1.4486

Ή NMR (400 MHz, CDCl ₃ ) d 1.53 (3H, d), 2.20 (3H, s), 5.34 (lH, q), 6.93 (lH, d), 7.81 (lH, dd), 8.36 (lH, brs ).

3- (5-Trifluoromethylpyridine-2-yloxodi) -2-butanone 0.40 g (1.7 mmol), 1- [4- (3,3-dichloro-2-propenyloxy) phenyl] ethoxyamine (Table 1-4 Compound No. l) 0.47 g (1.9 mmol A mixture of 5 ml of ethanol and 1 ml of acetic acid was stirred at room temperature for 18 hours. The residue obtained by distilling off the solvent was subjected to silica gel column chromatography. Purification by chromatography (hexane / ethyl acetate = 15/1) gave 0.76 g of the title compound as a diastereomer mixture, yield 97%.

n _D ²³ 1.5203

Ή NMR (400 MHz, CDCl ₃ ) d 1.45 (3H, d), 1.48 (3H, d), 1.49 (3H, d), 1.50 (3H, d), 1.89 (3H, s), 1.91 (3H, s ), 4.64 (4H, d), 5.18 (lH, q), 5.20 (lH, q), 5.62 (lH, q), 5.67 (lH, q), 6.16 (2H, t), 6.75 (lH, d) , 6.78 (lH, d), 6.82 (2H, d), 6.84 (2H, d), 7.20 (2H, d), 7.23 (2H, d), 7.70 (lH, dd), 7.74 (lH, dd), 8.32 (lH, brs), 8.38 (lH, brs). Synthesis Example 1 13 2,6-dichloro-4- (3,3-dichloro-2-propynyloxy) -l- (4-trifluoro (Romethyl benzylideneaminooxy) methylbenzene (Synthesis of compound No. 3 in Table 1-4)

0.61 g (16 mmol) of sodium borohydride was added to a mixture of 6.0 g (20 mmol) of 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzaldehyde and 40 ml of ethanol. Stir for 1 hour. After evaporating the solvent from the reaction mixture, 100 ml of ethyl acetate was added to the residue, and the mixture was washed successively with 2 N hydrochloric acid, water and saturated saline, and then dried with sulfuric anhydride. Dried over magnesium acid. The solvent was distilled off to give 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzyl alcohol (6.12 g) quantitatively.

mp 83-85 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 1.9 (lH, br), 4.63 (2H, d), 4.89 (2H, s), 6.12 (lH, t), 6.88 (2H, s).

2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzyl alcohol 3.0 g (10 mmol), -hydroxyfluoride imide 1.63 g (10 mmol), triphenylphosphine 2.88 g ( ll mmol), 5 ml of THF and 25 ml of toluene were added with 5.66 g (13 mmol) of a 40% solution of diethylazodicarboxylate in toluene, and the mixture was stirred at room temperature for 4 hours. Ethyl acetate (50 ml) was added to the reaction mixture, and the mixture was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (toluene / ethyl acetate = 10/1), and 3.81 g of-[2,6-dichloro-4- (3,3-dichloromethane) was obtained. -2-propenyloxy) benzyloxy] phthalimid was obtained. Yield 80%.

mp 133-135 ° C

_{Ή NMR (400 MHz, CDC1 3} ) 5 4.62 (2H, d), 5.49 (2H, s), 6.12 (lH, t), 6.87 (2H, s), 7.7-7.8 (4H, m).

To a mixture of 3.5 g (7.34 mmol) of N- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzyloxy] fluoroimidide and 30 ml of ethanol was added hydrazine hydrate 0.73. g (14.7 mmol) was added and the mixture was refluxed for 2 hours. The reaction mixture was filtered, the solvent was distilled off from the filtrate, 50 ml of ether was added to the obtained residue, and the mixture was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off to quantitatively determine 2,6-dimethoxy-4- (3,3-dioxo-2-propenyloxy) benzyloxyamine (Compound No. 6 in Table 14) ( 2.54 g) were obtained.

mp 58-60 ° C

Ή NMR (400 MHz, CDCl ₃ ) i 4.63 (2H, d), 4.93 (2H, s), 5.48 (2H, brs), 6.12 (lH, t), 6.88 (2H, s).

2,6-dichloro-4- (3,3-dichloro-2--2-proenyloxy) benzyloxyamine 0.28 g (0.9 mmol), 0.14 g (0.8 mmol) of 4-trifluoromethylbenzaldehyde and 1.5 ml of ethanol were stirred at room temperature for 2 hours. The residue obtained by evaporating the solvent from the reaction mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.30 g of the title compound. 79% yield.

mp 54-57 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 4.63 (2H, d), 5.45 (2H, s), 6.12 (lH, t), 6.91 (2H, s), 7.61 (2H, d), 7.68 (2H, d), 8.10 (lH, s). Synthesis Example 1 4 3- [2,6-dimethyl-4- (3,3-dichloro-2-propenyloxy) phenyl] -5- (5-triflur Oromethylpyridine-2-yloxy) methylisoxazoline (Synthesis of Compound No. 1 in Table 15)

2-chloro-5-trifluoromethyl pyridine 6.0 g (33.1 mmol), aryl alcohol 2.30 g (39.7 mmol), potassium hydroxide 2.78 g (49.6 mmol), 18-crown-6-ether 0.17 g (0.66 (mmol) and 50 ml of toluene were refluxed for 2 hours. After cooling the reaction mixture, 50 ml of toluene was added, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1), and 4.0 g of 2- (aryloxy) -5-trifluoromethylpyridine was added. Obtained. Yield 60%.

n _D ²⁴ 1.4477

_{Ή NMR (400 MHz, CDC1 3} ) δ 4.90 (2H, ddd), 5.28 (lH, ddt), 5.40 (lH, ddt), 6.08 (lH, ddt), 6.85 (lH, d), 7.77 (lH, dd ), 8.43 (lH, brs).

2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzaldehyde 2.0 g (6.67 mmol), hydroxylamine hydrochloride 0.56 g (8.0 mmol, 1.2 eq), sodium acetic anhydride 0.66 A mixture of g (8.0 mmol, 1.2 eq) and 20 ml of ethanol was refluxed for 3 hours. After evaporating the solvent from the reaction mixture, 50 ml of ethyl acetate was added, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The crystals obtained by evaporating the solvent are filtered, washed with hexane, and 1.78 g of 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzaldoxime I got 85% yield. Ή NMR (400 MHz, CDCl ₃ ) d 4.65 (2H, d), 6.13 (lH, t), 6.92 (2H, s), 8.13 (lH, s), 8.35 (lH, s).

To a mixture of 4- (3,3-dichloro-2-propenyloxy) -2,6-dimethylbenzaldoxime 0.56 g (2.0 mmol), THF 4 ml and DMF 1 ml N-chlorosuccinic acid imid 0.26 g (1.9 mmol) was added and the mixture was stirred at room temperature for 1 hour. A solution of 0.39 g (1.9 mmol) of 2- (aryloxy) -5-trifluoromethylpyridine and 0.20 g (2.0 mmol) of triethylamine in 2 ml of THF was added, and the mixture was further stirred for 16 hours. After evaporating the solvent from the reaction mixture, 5 O ml of ethyl acetate was added to the obtained residue, washed successively with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to obtain 0.63 g of the title compound. Yield 68%.

mp 84-85 ° C

_{Ή NMR (400 MHz, CDC1 3} ) δ 2.30 (6H, s), 3.11 (lH, dd), 3.34 (lH, dd), 4.55 (lH, dd), 4.61 (lH, dd), 4.64 (2H, d ), 5.16 (lH, m), 6.14 (lH, t), 6.62 (2H, s), 6.88 (lH, d), 7.80 (lH, dd), 8.44 (lH, brs). -[2,6-Dichloro-4- (3,3-dichloro-2-propenyloxy) phenyl] -5- (5-trifluoromethylpyridine-2-yloxy) methyl isoxazoline (Table 1) Synthesis of compound No. 3 in 5)

N-chlorosuccinimide 0.27 was added to a mixture of 0.63 g (2.0 mmol) of 2,6-dichloro-4- (3,3-dichloro-2--2-propenyloxy) benzaldoxime, 3 ml of THF and 1 ml of DMF. g (2.0 mmol) was added, and the mixture was stirred at room temperature for 1 hour. A solution of 0.41 g (2.0 mmol) of 2- (aryloxy) -5-trifluoromethylpyridine and 0.20 g (2.0 mmol) of triethylamine in 2 ml of THF was added, and the mixture was further stirred for 16 hours. After evaporating the solvent from the reaction mixture, 50 ml of ethyl acetate was added to the obtained residue, washed successively with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. Hexane was added to the crystals obtained by evaporating the solvent, and the crystals were filtered to obtain 0.90 g of the title compound. 87% yield. mp 119-123 ° C

_{Ή NMR (400 MHz, CDC1 3} ) δ 3.18 (lH, dd), 3.46 (lH, dd), 4.58 (2H, d), 4.66 (2H, d), 5.23 (lH, m), 6.13 (lH, t ), 6.89 (lH, d), 6.93 (2H, s), 7.80 (lH, dd), 8.43 (lH, brs). Synthesis Example 1 16 3- [2,6-dichloro-4- (3,3 -Dichloro-2-propenyloxy) phenyl] -5- (5-trifluoromethylpyridine-2-yloxy) ethyl isoxazoline (Synthesis of Compound No. 5 in Table 15)

2-chloro-5-trifluoromethyl pyridine 6.0 g (33.1 mmol), 3-butene-1-ol 2.86 g (39.7 mmol), potassium hydroxide 2.78 g (49.6 mmol), 18-crown-6- A mixture of 0.17 g (0.66 mmol) of ether and 50 ml of toluene was refluxed for 2 hours. After cooling the reaction mixture, 50 ml of toluene was added, and the mixture was washed with water and a saturated saline solution and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1), and 5.4 g of 2- (3-butene-1-yloxy) -5-trifluoro Oromethyl pyridine was obtained. Yield 75%.

n _D ²⁴ 1.4478

_{Ή NMR (400 MHz, CDC1 3} ) δ 2.55 (2H, dddt), 4.41 (2H, t), 5.11 (lH, ddt), 5.16 (lH, ddt), 5.89 (lH, ddt), 6.81 (lH, d ), 7.76 (lH, dd), 8.43 (lH, brs).

2,6-Dichloro mouth-4- (3,3-dichloro-2-propenyloxy) benzaldoxime 0.63 g (2.0 mmol), THF 3 ml and DMF 1 ml was mixed with N-chlorosuccinimide 0.27 g (2.0 mmol) was added, and the mixture was stirred at room temperature for 1 hour. A solution of 0.43 g (2.0 mmol) of 2- (3-butene-1-yloxy) -5-trifluoromethylviridine and 0.20 g (2.0 mmol) of triethylamine in 2 ml of THF was added, and the mixture was further stirred for 16 hours. After evaporating the solvent from the reaction mixture, 50 ml of ethyl acetate was added to the obtained residue, washed successively with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1 to 5/1) to obtain 0.70 g of the title compound. Yield 66%. mp 90 ° C

_{Ή NMR (400 MHz, CDC1 3} ) δ 2.1-2.2 (lH, m), 2.3-2.4 (lH, m), 3.00 (lH, dd), 3.41 (lH, dd), 4.58 (2H, dd), 4.65 (2H, d), 5.04 (lH, m), 6.13 (lH, t), 6.82 (lH, d), 6.92 (2H, s), 7.77 (lH, dd), 8.44 (lH, brs). Synthesis Example 1 17 3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl-5- (5 -Trifluoromethylviridine-2-ylthio) methyl isoxazoline (Synthesis of Compound No. 9 in Table 1-5)

To a mixture of 1.50 g (8.4 mmol) of 2-mercapto-5-trifluoromethylviridine, 1.50 g (10.9 mmol) of lithium carbonate and 8 ml of DMF was added a solution of 1.22 g (10 mmol) of aryl bromide in 2 ml of DMF. The mixture was stirred at room temperature for 3 hours. The reaction mixture was charged with 50 ml of ethyl acetate, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 1.63 g of 2-arylthio-5-trifluoromethylviridine. Yield 89%.

n _D ²⁷ 1.5048

_{Ή NMR (400 MHz, CDC1 3} ) δ 3.88 (2H, d), 5.15 (lH, d), 5.32 (lH, d), 5.9- 6.0 (lH, m), 7.26 (lH, d), 7.67 (lH , dd), 8.67 (lH, brs).

To a mixture of 0.47 g (1.5 mmol) of 2,6-dichroic-4--4- (3,3-dicloh-2--2-propenyloxy) benzaldoxime, 2 ml of THF and 1 ml of DMF, was added -chlorosuccinic acid imide. 0.20 g (1.5 mmol) was added, and the mixture was stirred at room temperature for 1 hour. A solution of 0.36 g (1.7 mmol) of 2-arylthio-5-trifluoromethylpyridine and 0.23 g (2.3 mmol) of triethylamine in 2 ml of THF was added to the reaction mixture, and the mixture was stirred at room temperature for 18 hours. The solvent was distilled off from the reaction mixture, and to the residue obtained, 50 ml of ethyl acetate was added. The mixture was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.58 g of the title compound. Yield 72%.

n _D ²⁴ 1.5796

_{Ή NMR (400 MHz, CDC1 3} ) δ 3.14 (lH, dd), 3.41 (lH, dd), 3.49 (lH, dd), 3.71 (lH, dd), 4.65 (2H, d), 5.1-5.2 (lH , m), 6.12 (lH, t), 6.91 (2H, s), 7.31 (lH, d), 7.68 (lH, dd), 8.66 (lH, brs). Synthesis Example 1 18 3- [2,6-Dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl -5- [ 2- (4-trifluoromethylpyridine-2-yloxy)] butyl isoxazole (synthesis of compound No. 16 in Table 1-6)

5-Hexin-3-ol 4.91 g (50.0 mmol), 2-chloro-4-trifluoromethylpyridine 9.08 g (50.0 mmol), 18-crown-6 0.26 g (1.0 mmol) were added to toluene (83 ml ) And 4.13 g (75.0 mmol) of potassium hydroxide was added. The mixture was stirred under reflux with heating for 2 hours and allowed to cool to room temperature. Water was added and extracted with hexane. After washing with saturated saline, it was dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated and purified by silica gel column chromatography to obtain 3.66 g (15.5 mmol) of 2- (5-hexyn-3-oxy) -4-trifluoromethylpyridine. Yield 30%.

_{Ή NMR (400 MHz, CDC1 3} ) 5 0.99 (3H, t), 1.89 (2H, dq), 2.00 (IH, t), 2.61 (2H, ddd), 2.65 (2H, ddd), 5.22 (1H, tt ), 6.98 (IH, s), 7.04 (IH, d), 8.27 (IH, d).

2,6-Dic mouth-4- (3,3-Dic mouth propenyl-1-oxy) benzaldoxime (0.47 g, 1.5 mmol) in THF (1.5 ml) and DMF (1.5 ml) After dissolution, TV-chlorosuccinimide (0.24 g, 1.8 mmol) was added. One hour later, a solution of 2- (5-hexyne-3-oxy) -4-trifluoromethylpyridine (0.36 g, 1.5 mmol) and triethylamine (0.23 g, 2.3 mmol) in THF (3 ml) was added. added. After stirring for 17.5 hours, water was added, and the mixture was extracted with ether. After washing with a saturated saline solution, the extract was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by medium pressure silica gel column chromatography to obtain the title compound (0.55 g, 1.1 mmol, 73%).

_{¾ NMR (400 MHz, CDC1 3} ) 6 1.02 (3H, t), 1.75- 1.82 (2H, m), 3.25 (2H, d), 4.65 (2H, d), 5.58 (IH, tt), 6.10 (IH , s), 6.13 (IH, t), 6.93 (2H, s), 6.93 (IH, s), 7.03 (2H, d), 8.26 (2H, d). Synthesis Example 1 93- [2,6 -Dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl-5- (5-trifluoromethylpyridine-2-ylthio) ethyl isoxazole (Table— Synthesis of compound No. 21 in 6)

11.42 g (59.9 mmol) of p-toluenesulfonyl chloride was added to a mixture of 4.0 g (57.1 mmol) of 3-butyn-1-ol and 16 ml of pyridine, and the mixture was stirred under ice cooling for 16 hours. To the reaction mixture was added 100 ml of ethyl acetate, washed sequentially with water, 2N hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 9.80 g of 4-(/?-Toluenesulfonyloxy) -1-butyne. Yield 77%.

To a mixture of 2.50 g (14.0 mmol) of 2-mercapto-5-trifluoromethylpyridine, 2.50 g (18.2 mmol) of carbonated rim and 10 ml of DMF, 3.75 g of 4-(-toluenesulfonyloxy) -1-butyne was added. (16.8 mmol) in 6 ml of DMF was added and stirred at room temperature for 18 hours. To the reaction mixture was added 50 ml of ethyl acetate, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 2.97 g of 2-butynylthio-5-trifluoromethylpyridine. Yield 92%. n _D ²⁷ 1.5087

_{Ή NMR (400 MHz, CDC1 3} ) 5 2.06 (lH, t), 2.65 (2H, dt), 3.39 (2H, t), 7.27 (lH, d), 7.66 (lH, dd), 8.67 (lH, brs ).

2,6-Dichloro mouth-4- (3,3-dichloro-2-pronenyloxy) benzaldoxime 0.32 g (1.0 mmol), 1 ml of THF and 1 ml of DMF were added to a mixture of -chlorosuccinic acid imid 0.14 g ( 1.0 mmol) and stirred at room temperature for 1 hour. To the reaction mixture was added a solution of 0.26 g (ll mmol) of 4- (5-trifluoromethylpyridine-2-ylthio) -1-butyne and 0.15 g (1.5 mmol) of triethylamine in 2 ml of THF, and the mixture was added at room temperature for 18 hours. Stirred. The solvent was distilled off from the reaction mixture, and to the residue obtained, 50 ml of ethyl acetate was added, washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.54 g of the title compound. Yield 99%.

n _D ²⁴ 1.5756

_{Ή NMR (400 MHz, CDC1 3} ) 5 3.30 (2H, t), 3.61 (2H, t), 4.67 (2H, d), 6.14 (lH, t), 6.17 (lH, s), 6.96 (2H, s ), 7.28 (lH, d), 7.68 (lH, dd), 8.69 (lH, brs). Synthesis Example—20 3- [4- (3,3-Dichloro-2-propenyloxy)] phenyl-5- (5-trifluoromethylpyridine-2-ylthio) ethylisoxazole (Table 6 Synthesis of middle compound No. 22)

To a mixture of 0.25 g (1.0 mmol) of 4- (3,3-dichloro-2-propenyloxy) benzaldoxime, 1 ml of THF and 1 ml of DMF, 0.14 g (l.Ommol) of V-chlorosuccinic acid imid Was added and stirred at room temperature for 1 hour. To the reaction mixture, a solution of 0.26 g (l.lmmol) of 4- (5-trifluoromethylpyridine-2-ylthio) -1-butyne and 0.15 g (1.5 mmol) of triethylamine in 2 ml of THF was added, and the mixture was stirred at room temperature for 5 hours. The solvent was distilled off from the reaction mixture, and to the residue obtained, 50 ml of ethyl acetate was added, and the mixture was washed with water, saturated aqueous sodium bicarbonate and brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.29 g of the title compound. Yield 57%.

mp 77-79 ° C

Ή NMR (400 MHz, CDCl ₃ ) d 3.25 (2H, t), 3.59 (2H, t), 4.71 (2H, d), 6.18 (lH, t), 6.35 (lH, s), 6.96 (2H, d ), 7.27 (lH, d), 7.68 (lH, dd), 7.73 (2H, d), 8.69 (lH, brs). Synthesis Example 1 2 1 3- [2-Chloro-4- (3,3-dichloro) -2-propenyloxy)] phenyl-5- (5-trifluoromethylpyridine-2-ylthio) ethyl isoxazole (Synthesis of Compound No.23 in Table 1-6)

To a mixture of 0.28 g (1.0 mmol) of 4- (3,3-diclooxy-2-propenyloxy) penzaldoxime, 1 ml of THF and 1 ml of DMF, 0.14 g of chlorosuccinic acid imide 1.0 mmol), and stirred at room temperature for 1 hour. A solution of 0.26 g (ll mmol) of 4- (5-trifluoromethylviridine-2-ylthio) -1-butyne and 0.15 g (1.5 mmol) of triethylamine in 2 ml of THF was added to the reaction mixture, and the mixture was added at room temperature for 5 hours. Stirred. To the residue obtained by evaporating the solvent from the reaction mixture was added 50 ml of ethyl acetate, and the mixture was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.37 g of the title compound. Yield 72%. mp 58 ° C

Ή NMR (400 MHz, CDCl ₃ ) d 3.27 (2H, t), 3.60 (2H, t), 4.69 (2H, d), 6.16 (lH, t), 6.54 (lH, s), 6.88 (lH, dd ), 7.01 (lH, d), 7.27 (lH, d), 7.67 (lH, d), 7.67 (lH, dd), 8.69 (lH, brs). Synthesis Example 1 22 3- [2,6-dichloro- 4- (3,3-Dichloro-2-propenyloxy)] phenyl-5- (4-trifluoromethylphenoxy) ethyl isoxazole (synthesis of compound No.8 in Table 7)

3.24 g (20 mmol) of 4-trifluoromethylphenol, 1.54 g (22 mmol) of 3-butyn-1-ol, 5.76 g (22 mmol) of triphenyliphosphine, 10 ml of THF and 40 ml of toluene To the mixture was added 10.44 g (24 mmol) of a 40% toluene solution of getyl azodicarboxylate, and the mixture was stirred at room temperature for 18 hours. Toluene was added to the residue obtained by evaporating the solvent from the reaction mixture, and the mixture was filtered. The residue obtained by evaporating the solvent from the filtrate was subjected to silica gel column chromatography (hexane / ethyl acetate = 15/1). Purification gave 2.31 g of 4- (4-trifluoromethylphenoxy) -1-butyne. Yield 54%.

n _D ²⁷ 1.4630

_{Ή NMR (400 MHz, CDC1 3} ) 5 2.06 (lH, t), 2.71 (2H, dt), 4.14 (2H, t), 6.98 (2H, d), 7.55 (2H, d).

2,6-Dichloro mouth-4- (3,3-dichloro-2-provenyloxy) benzaldoxime 0.32 g (1.0 mmol), 1 ml of THF and 1 ml of DMF, \ /: chlorosuccinic acid 0.14 g (1.0 mmol) was added, and the mixture was stirred at room temperature for 30 minutes. To the reaction mixture, a solution of 0.24 g (ll mmol) of 4- (4-trifluoromethylphenoxy) -1-butyne and 0.15 g (1.5 mmol) of triethylamine in 2 ml of THF was added, and the mixture was stirred at room temperature for 18 hours. The solvent was distilled off from the reaction mixture, and to the residue obtained, 50 ml of ethyl acetate was added. The mixture was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.38 g of the title compound. Yield 72%. mp 105-106 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 3.37 (2H, t), 4.39 (2H, t), 4.67 (2H, d), 6.14 (lH, t), 6.22 (lH, s), 6.96 (2H, s), 6.98 (2H, d), 7.55 (2H, d). Synthesis Example 1 23 3- [2,6-Dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl-5 -(4-Chlorobenzoyl) methyl isoxazole (Synthesis of Compound No. 51 in Table 1-7)

To a mixture of 5.0 g (31.5 mmol) of 4-methylbenzene, 5.06 g (41.0 mmol) of potassium carbonate and 20 ml of DMF, was added a solution of 4.88 g (41.0 mmol) of propargyl bromide in 5 ml of DMF. The mixture was stirred at room temperature for 7 hours. The reaction mixture was added with 100 ml of ethyl acetate, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to give 5.71 g of 3- (4-chlorobenzylthio) -1-butyne. Obtained. Yield 92%.

n _D ²⁶ 1.5890

_{Ή NMR (400 MHz, CDC1 3} ) 5 2.30 (lH, t), 3.07 (2H, d), 3.84 (2H, s), 7.28 (4H, s).

2,6-Dichloro mouth-4- (3,3-dichloro-2-propenyloxy) benzaldoxime 0.32 g (1.0 mmol), THF 1 ml and DMF 1 ml was mixed with -chlorosuccinic acid imid. g (1.0 mmol) was added, and the mixture was stirred at room temperature for 30 minutes. To the reaction mixture was added a solution of 0.22 g (l.l mmol) of 3- (4-chlorobenzylbenzyl) -1-butyne and 0.15 g (1.5 mmol) of triethylamine in 2 ml of THF, and the mixture was stirred at room temperature for 18 hours. 50 ml of toluene was added to the reaction mixture, and the mixture was washed with water, saturated aqueous sodium hydrogen carbonate and saturated saline, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.39 g of the title compound. Yield 72%.

n _D ²⁶ 1.6209

Ή NMR (400 MHz, CDCl ₃ ) d 3.69 (2H, s), 3.76 (2H, s), 4.68 (2H, d), 6.15 (lH, t), 6.21 (lH, s), 6.97 (2H, s) ), 7.28 (2H, d), 7.30 (2H, d). Synthesis Example 1 24 3- [2,6-Dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl-5- (4-trifluoromethylphenylthio) ethyl isoxazole (Table — Synthesis of 7 compound No.52)

To a mixture of 1.25 g (7 mmol) of 4-trifluoromethylthiophenol, 1.16 g (8.4 mmol) of carbonic acid rim and 4 ml of DMF, 1.73 g (7.7 mmol) of 4-(?-Toluenesulfonyloxy) -1-butyne Was added and the mixture was stirred at room temperature for 3 hours. To the reaction mixture was added 50 ml of ethyl acetate, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1), and 1.48 g of 4- (4-trifluoromethylphenylthio)- 1-butyne was obtained. Yield 92%.

n _D ²⁷ 1.5112

_{Ή NMR (400 MHz, CDC1 3} ) 5 2.07 (lH, t), 2.54 (2H, dt), 3.15 (2H, t), 7.40 (2H, d), 7.53 (2H, d).

To a mixture of 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzaldoxime 0.32 g (1.0 mmol), 1 ml of THF and 1 ml of DMF was added 0.14 g (1.0 ml) of -chlorosuccinic acid imide. mmol) and stirred at room temperature for 30 minutes. To the reaction mixture was added a solution of 4- (4-trifluoromethylphenylthio) -1-butyne 0.25 g (ll mmol) and triethylamine 0.15 g (1.5 mmol) in 2 ml of THF, and the mixture was stirred at room temperature for 18 hours. . The solvent was distilled off from the reaction mixture, and to the residue obtained, 50 ml of ethyl acetate was added. The mixture was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 15/1) to obtain 0.39 g of the title compound. Yield 72%.

n _D ²⁷ 1.5845

_{Ή NMR (400 MHz, CDC1 3} ) (5 3.19 (2H, t), 3.38 (2H, t), 4.67 (2H, d), 6.14 (lH, t), 6.16 (lH, s), 6.96 (2H, s), 7.43 (2H, d), 7.55 (2H, d). Synthesis Example 1 25 3- [4- (3,3-Dichloro-2-proenyloxy) -2,6-dimethyl] phenyl-5 -[4- (4-Trifluoromethylpyridine-2-yloxy) phenoxy] methyliso Xazole (Synthesis of Compound No. 7 in Table 8)

To a solution of hydroquinone (13.76 g, 125 mmol) in -methylpyrrolidone (60 ml) and DMF (60 ml) was added sodium hydride (60% oil dispersion, 2.40 g, 60.0 mmol) under ice-cooling for 25 minutes. After stirring, the mixture was stirred at room temperature for 15 minutes. A solution of 2-chloro-4--4-trifluoromethylviridine (9.08 g, 50.0 mmol) in DMF (40 ml) was added dropwise over 5 minutes, and the mixture was stirred at 80 ° C for 2 hours. After allowing to cool to room temperature, water was added, and the mixture was washed with saturated brine extracted with ether and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated and purified by silica gel column chromatography to obtain 4- (4-trifluoromethylviridine-2-yloxy) phenol: phenol (8.66 g, 33.9 mmol, 68%).

Ή NMR (400 MHz, CDCl ₃ ) d 7.18-7.24 (8H, m), 8.34 (2H, d).

4- (4-Trifluoromethylpyridine-2-yloxy) phenol (3.00 g, 11.8 mmol) was dissolved in acetone (24 ml), and propargylbutane (1.68 g, 14.1 mmol), potassium carbonate (3.26 g, 23.6 mmol) was added. After heating under reflux for 3 hours, the mixture was allowed to cool to room temperature. Hexane was added, and after filtration, the residue was thoroughly washed with a mixed solvent of hexane and ethyl acetate (2: 1). The filtrate was concentrated, and the obtained solid was recrystallized from hexane to give 4- (4-trifluoromethylviridine-2-yloxy) phenoxypropyne (3.21 g, 10.9 mmol, 93%). Obtained.

mp 90 ° C

Ή NMR (400 MHz, CDC) 2.54 (1H, t), 4.71 (2H, d), 7.02 (2H, d), 7.10 (2H, d), 7.12 (1H, s), 7.18 (1H, d), 8.32 (1H, d).

Dissolve 4- (3,3-dimethyl-2-propenyloxy) -2,6-dimethylbenzaldoxime (1.50 g, 5.47 mmol) in THF (5.5 ml) and DMF (5.5 ml). Cic acid imide (0.73 g, 5.5 mmol) was added. One hour later, a solution of 4- (4-trifluoromethylpyridine--2-yloxy) phenoxypropyne (1.60 g, 5.5 mmol) and triethylamine (0.83 g, 8.2 mmol) in THF (ll ml) was added. Was. After stirring for 12 hours, water was added, and the mixture was extracted with ether. After washing with saturated saline, drying over anhydrous sodium sulfate, filtration, concentration, and purification by medium pressure silica gel column chromatography, the title compound (2.40 g, 4.24 mmol, 78%) was obtained. mp 90 ° C

_{¾ NMR (400 MHz, CDC1 3} ) (5 2.16 (6H, s), 4.66 (2H, d), 5.24 (2H, s), 6.17 (1H, t), 6.30 (1H, s), 6.65 (2H, s), 7.05 (2H, d), 7.12 (2H, d), 7.13 (1H, s), 7.18 (1H, d), 8.32 (1H, d). Synthesis Example 1 26 3- [2,6- Dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl-5- [4- (4-trifluoromethylpyridine-2-yloxy) phenoxy] methyl isoxazole (Compound No. in Table 8) .20 synthesis)

Dissolve 2,6-dic- mouth-4- (3,3-dic-mouth-2-propenyloxy) benzaldoxime (4.72 g, 15.0 mmol) in THF (15 ml) and DMF (15 ml). And -chlorosuccinic acid imide (2.00 g, 15.0 mmol) were added. After 1 hour, a solution of 2-propyn-1-ol (0.84 g, 15 mmol) and triethylamine (2.28 g, 22.5 mmol) in THF (30 ml) was added. After stirring for 20 hours, water was added, and the mixture was extracted with ethyl acetate. After washing with saturated saline, drying over anhydrous sodium sulfate, filtration, concentration, and purification by medium pressure silica gel column chromatography, 3- [2,6-dichloro-4- (3,3-dichloro- 2-Propenyloxy)] phenyl-5-hydroxymethyl isoxazole (4.98 g, 13.4 mmol, 90%) was obtained. n _D ²³ 1.5970

_{Ή NMR (400 MHz, CDC1 3} ) (5 1.26 (1H, brs), 4.67 (2H, d), 4.87 (2H, brs), 6.15 (1H, t), 6.34 (1H, s), 6.96 (2H, s).

. 3- [2,6-Dichloro-4- (3,3-dichloro-2-proenyloxy)] phenyl-5-hydroxymethylisoxazole (4.54 g, 12.3 mmol) was added to dichloromethane (25 ml). ) And added carbon tetrabromide (6.12 g, 18.5 mmol). Under ice-cooling, triphenylphosphine (3.87 g, 14.8 mmol) was added. After 13.5 hours, concentrate and purify by silica gel column chromatography to give 3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy;)] phenyl-5-bromomethyliso- Obtained oxazole (5.05 g, 11.6 mmol, 95%)

(Table—Compound No. 4 in 10).

_{Ή NMR (400 MHz, CDC1 3} ) 5 4.68 (2H, d), 4.70 (2H, s), 6.15 (lH, t), 6.41 (lH, s), 6.97 (2H, s). 5-Bromomethyl-3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)] phenylisoxazole (0.35 g, 0.81 mmol) was dissolved in DMF (3 ml). Carbonated lithium (0.15 g, 1.1 mmol) and 4- (5-trifluoromethyl-2-yloxy) phenol (0.23 g, 0.89 mmol) were added, and the mixture was stirred at 100 ° C for 6 hours. Water was added, extracted with ether, washed with saturated saline and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated and purified by medium pressure silica gel column chromatography to obtain the title compound (0.34 g, 0.56 mmol, 69%).

mp 69-70. C

_{Ή NMR (400 MHz, CDC1 3} ) (5 4.68 (2H, d), 5.25 (2H, s), 6.15 (IH, t), 6.44 (IH, s), 6.97 (2H, s), 7.00 (IH, d), 7.05 (2H, d), 7.11 (2H, d), 7.89 (IH, dd), 8.43 (1H, d). Synthesis Example 1 2 7 3- [2,6-dichloro-4- (3, 3-Dichloro-2-propenyloxy)] phenyl-5- [4- (4-trifluoromethylphenoxy) phenoxy] methyl isoxazole (synthesis of compound No. 41 in Table _8)

4- (4-Trifluoromethylphenoxy) phenol (2.54 g, 10.0 mmol) was dissolved in acetone (20 ml), and propargyl bromide (1.43 g, 12.0 mmol), carbon dioxide was added. (2.76 g, 20.0 mmol) was added. After heating under reflux for 3 hours, the mixture was allowed to cool to room temperature. Hexane was added, and after filtration, the residue was thoroughly washed with ethyl acetate. The filtrate was concentrated and purified by silica gel column chromatography to obtain 4- (4-trifluoromethylphenoxy) phenoxypropyne (2.85 g, 9.75 mmol, 98%).

_{Ή NMR (400 MHz, CDC1 3} ) (5 2.55 (IH, t), 4.70 (2H, d), 6.99 (2H, d), 7.01 (4H, s), 7.55 (2H, d).

2,6-Dic-mouth-4- (3,3-Dic-mouth propidinyl-1-oxy) benzaldoxime (0.47 g, 1.5 mmol) was added to THF (1.5 ml) and DMF (1.5 ml). After dissolution, TV-chlorosuccinic acid imide (0.24 g, 1.8 mmol) was added. After 1.5 hours, a solution of 4- (4-trifluoromethylphenoxy) phenoxypropyne (0.44 g, 1.5 mmol) and triethylamine (0.23 g, 2.3 mmol) in THF (3 ml) was added. After stirring for 19 hours, add water and add ether Extracted. After washing with saturated brine, drying over anhydrous sodium sulfate, filtration, concentration, and purification by medium pressure silica gel column chromatography, the title compound (0.62 g, l.Ommol, 68%) was obtained.

mp 79-80 ° C

_{Ή NMR (400 MHz, CDC1 3} ) (5 4.68 (2H, d), 5.25 (2H, s), 6.15 (1H, t), 6.44 (1H, s), 6.97 (2H, s), 6.99 (2H, d), 7.03 (4H, s), 7.55 (2H, d). Synthesis Example 1 28 3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl- 5- (3-trifluoromethylphenoxy) methyl-1,2,4-oxaziazol (Synthesis of compound No. 1 in Table 11)

Dissolve 2,6-dic-mouth-4- (3,3-dichloro-2-propenyloxy) benzaldoxime (8.00 g, 25.4 mmol) in chloroform (100 ml) and THF (10 ml). The ice was given. - chlorosuccinimide imide (5.09 g, 38.1 mmol) was added, and _c concentrated and stirred for 2 hours at room temperature, ether was added and filtered the residue. A methanol solution of ammonia (2.0 M soln., 38 ml, 76 mmol) was added to the obtained ether solution. After stirring at room temperature for 2 hours, the mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. After washing with saturated saline, drying over anhydrous sodium sulfate, filtration, concentration, and purification by silica gel column chromatography, 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) Benzaldoxyamidine (5.48 g, 16.6 mmol, 65%) was obtained (Compound No. 21 in Table 15) mp 65 ° C

_{Ή NMR (300 MHz, CDC1 3} ) 5 4.64 (2H, d), 4.77 (2H, brs), 6.12 (1H, t), 6.89 (1H, s).

2,6-Dichloro mouth-4- (3,3-dichloro-2-propenyloxy) benzaldoxyamidine (2.00 g, 6.06 mmol) was dissolved in THF (30 ml) and the mixture was cooled. Sodium hydride (60% in mineral oil, 0.29 g, 7.3 mmol) was added, and the mixture was stirred at room temperature for 20 minutes and then at 60 ° C for 25 minutes. The mixture was allowed to cool to room temperature, and a solution of ethyl glycolate (1.26 g, 12.1 mmol) in THF (10 ml) was added dropwise. After heating under reflux for 1 hour, the mixture was allowed to cool to room temperature, a saturated aqueous solution of ammonium chloride was added, and the mixture was extracted with ethyl acetate. After washing with saturated saline, anhydrous sulfur After drying over sodium citrate, filtering, concentrating, purifying by silica gel column chromatography, 3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl-5- Hydroxymethyl-1,2,4-oxaziazole (2.24 g, 6.05 mmol, 99%) was obtained.

_{Ή NMR (300 MHz, CDC1 3} ) (5 2.83 (1H, brs), 4.69 (2H, d), 5.00 (2H, s), 6.15 (1H, t), 6.98 (2H, s).

3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl-5-hydroxymethyl-1,2,4-oxaziazol (0.29 g, 0.78 mmol) The residue was dissolved in THF (4 ml), and 3-trifluoromethylphenol (0.14 g, 0.86 mmol) and triphenylphosphine (0.27 g, 1.02 mmol) were added. After cooling on ice, getyl azodicarboxylate (40% solution in PhCH ₃ , 0.44 g, 1.02 mmol) was added dropwise. After stirring at room temperature for 15.5 hours, the mixture was concentrated as it was and purified by silica gel column chromatography to obtain the title compound (0.39 g, 0.76 mmol, 97%).

n _D ²⁶ 1.5570.

_{Ή NMR (400 MHz, CDC1 3} ) (5 4.68 (2H, d), 5.45 (2H, s), 6.14 (1H, t), 6.97 (2H, s), 7.21 (1H, dd), 7.31 (1H, d), 7.36 (1H, dd), 7.45 (1H, dd). Synthesis Example 1 2 9 3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)] phenyl- 5- (5-trifluoromethylviridine-2-yloxy) ethyl-1,3,4-oxaziazol-2-one (Synthesis of Compound No. 1 in Table 12)

Dissolve 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzaldehyde (9.00 g, 30 mmol) in 50 ml of THF and add sodium chlorite (80%, 17.0 g, 150 mmol). A solution of (mmol) in water (50 ml) was added dropwise under ice-cooling. After stirring at room temperature for 2 days, the organic layer was separated. The aqueous layer was acidified by adding concentrated hydrochloric acid, and extracted with ethyl acetate. The combined organic layer was washed with an aqueous solution of sodium thiosulfate and saturated saline, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, purified by silica gel column chromatography (silca gel 200 g, hexane / ethyl acetate = 1/1), and the obtained crystals were washed with hexane to give 2,6-dichloro-4- (3, 3-Dichloropropenyl-1-oxy) benzoic acid (6.95 g, yield 73%) was obtained (compound No. 19 in Table 15). mp 127. C

_{Ή NMR (400 MHz, CDC1 3} ) (5 4.66 (2H, d), 6.13 (1H, t), 6.89 (2H, s).

Thionyl chloride (15 ml) was added to 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzoic acid (5.69 g, 18.0 mmol), and the mixture was heated under reflux for 1 hour. After removing excess thionyl chloride and azeotroping with toluene, the mixture was added to a solution of hydrazine monohydrate (2.91 ml, 60 mmol) in THF (20 ml). After stirring at room temperature for 2 hours, the mixture was concentrated under reduced pressure. Water was added, the resulting crystals were collected by filtration, washed successively with water and hexane, and washed with 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzoylhydrazide (5.45). g, _c mp 116-118 ° _C to obtain a 92% yield)

_{Ή NMR (400 MHz, CDC1 3} ) δ 4.16 (2H, brs), 4.64 (2H, d, J = 6.0 Hz), 6.11 (1H, t, J = 6.0 Hz), 6.86 (2H, s), 7.03 ( 1H, br).

2,6-Dic-mouth-4- (3,3-Dic-mouth-2-propenyloxy) benzoylhydrazide (5.15 g, 15.6 mmol) was dissolved in THF (20 ml), and triethylamine (3.52 ml, 23.4 mmol) and 1,1'-carbonildimidazole (CDI) (3.79 g, 23.4 mmol) were added sequentially. After stirring at room temperature for 2 days, the mixture was concentrated under reduced pressure. 1 N Hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, purified by silica gel column chromatography (silka gel 200 g, hexane / ethyl acetate = 4 / 1-2 / 1), and the obtained crystals were washed with hexane to give 3- [2,6- Dichloro-4- (3,3-dichloro-2-propenyloxy) to 1,3,4-oxaziazol-2-one (5.01 g, yield 90%) was obtained.

mp 169-170 ° C

_{Ή NMR (400 MHz, CDC1 3} ) 5 4.69 (2H, d, J: 6.4 Hz), 6.14 (1H, t, J = 6.4 Hz), 6.96 (2H, s), 8.90 (1H, brs).

3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)]-1,3,4-oxaziazol-2-one (0.71 g, 2.0 mmol), 2- ( 2-Hydroxychetoxy) -5-trifluoromethylpyridine (0.41, 2.0 mmol) and triphenylphosphine (0.52 g, 2.0 mmol) in THF (5 ml) were mixed with getyl azodicarboxylate (60% toluene). Solution, 0.87 g, 2.0 mmol) and stirred at room temperature overnight. Concentrate under reduced pressure, silica gel column Purification by chromatography (silka gel 50 g, hexane / ethyl acetate = 5/1) gave the title compound (0.84 g, yield 77%).

n _D ²⁶ 1.5529

Ή NMR (400 MHz, CDCl ₃ ) d 4.25 (2H, t, J = 5.2 Hz), 4.67 (2H, d, J = 6.4 Hz), 4.77 (2H, t, J = 5.2 Hz), 6.12 (1H, t, J = 6.4 Hz), 6.85 (1H, d, J = 8.8 Hz), 6.93 (2H, s), 7.78 (1H, dd, J = 2.8 and 8.8 Hz), 8.42 (1H, d, J = 2.8 Hz) Synthesis example— 30 2- (5-Trifluoromethylpyridine-2-yloxy) ethyl 3- [2,6-dichloro-4- (3,3-dichloro-2-propenyloxy)] Benzoate (Synthesis of Compound No. 1 in Table 1-3)

Thionyl chloride (5 ml) was added to 2,6-dichloro-4- (3,3-dichloro-2-propenyloxy) benzoic acid (0.63 g, 2.0 mmol), and the mixture was heated under reflux for 30 minutes. After distilling off excess titanium chloride, the mixture was azeotropically distilled with toluene. A toluene solution of the obtained acid chloride was added to 2- (2-hydroxyethoxy) -5-trifluoromethylpyridine (0.41, 2.0 mmol), triethylamine (1.5 ml, 10 mmol) and dichloromethane (5 ml). Was added dropwise to the mixture. After stirring at room temperature overnight, the mixture was heated under reflux for 2 hours. Since the reaction did not end, the mixture was concentrated under reduced pressure, pyridine (1.0 ml, 12 mmol) was added, and the mixture was heated under reflux for 2 hours. Poured into diluted hydrochloric acid and extracted with ethyl acetate. The extract was washed with saturated saline and dried over anhydrous sodium sulfate. Purification by flash chromatography (hexane / ethyl acetate 95/5 (2 min)-grad (10 min)-80/20 (5 min)) gave the title compound (0.46 g, 46% yield). Was. n _D ²⁶ 1.5487

Ή NMR (400 MHz, CDC1,) δ 4.64 (2H, d, J = 6.4 Hz), 4.7-4.8 (4H, m), 6.10 (1H, t, J = 6.4 Hz), 6.85 (2H, s), 6.86 (1H, d, J = 8.8 Hz), 7.78 (1H, dd, J = 2.8 and 8.8 Hz), 8.42 (1H, d, J = 2.8 Hz).

The methods exemplified in the above Examples or the compounds produced according to the methods are exemplified in Tables 1 to 15, but the present invention is not limited to these compounds.

The physical properties in the table indicate the refractive index for liquids, the melting point for solids, and the viscosity for those for which neither measurement was possible.

0 Ϊ: 0-

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n H IJ ί J H JiJ H J a J o Lv

OT QC "T a _u

zz H H IJ ri H J H J a J "J y QC" T U

zz a _u HT

IJ ri HJ H J a J C bhv

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H ^J d J a J cv once * Γ

LZ ri IJ H J & I V

QOCC "Tri Τ T

ij ri ^J a-ri J ^ε J-i bC'J

H IJ IJ ri J

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zz ^u hi IJ ri V oc

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zz ^u r IJ H a J ca O a _u

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0999Ί ^a u H ID ID H 9ΙΛΗ3 ¾0-5 'I ο.ε

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.880 / 00df / X3d Table 1 Continuation of 1

No. GBR ⁹ • X ¹ X ² (Y) „Physical properties

25 0

51 4-CF ₃ CHMeCH ₂ H CI CI H ^N D 1.558

" twenty five

52 4-CF3 CMe ₂ CH ₂ .H CI CI H ^N D 1.5571

twenty five

53 2-CF3 CH ₂ CH ₂ H CI CI H "D 1.5700

twenty five

54 4-OCF3 CH ₂ CH ₂ H CI CI H ¾ 1.5547

" twenty five

55 3-C1 CH ₂ CH ₂ H CI CI H ^N D 1.6070

56 4-C1 CH ₂ CH ₂ H CI CI H mp 40-42 X:

twenty five

58 CH ₂ CM ₂ H CI CI H 1.5811

^F3a n.

O

twenty five

59 4-CF3 CH ₂ CH ₂ CH ₂ H CI CI H 1.5860

".CF NO 10 Me-n 1s

"CF NO 01 Me- n 1

15pCF N 010 H- 0 Me Me- m 124 512 d-

2 3-CF3 0 Me 0 Me Me Viscosity

3 -CF3 0 Me 0 Me Me viscous

4 5-CF3 0 Me 0 Me Me Viscosity

5 6-CF3 0 Me 0 Me Me Viscosity

6 3-CF3 0 H 1 Me Me Viscosity

7 -CF3 〇 H 1 Me Me viscous

8 5-CF3 0 H 1 Me Me viscous

9 5-CF3 0 H 2 Me Me viscous

10 5-CF3 0 H 3 Me Me viscous

twenty three

1 1 5-CF3 0 H 0 CI CI ^N D 1.5660

twenty five

14 5-CF3 0 H 1 CI CI mp 78-80 "C

twenty five

15 4-CF3 0 Me 1 CI CI 1.5534

twenty five

19 5-CF3 S H 1 Me Me viscous

20 5-CF ₃ SH 0 CI CI mp 64-70. C

27

21 5-CF3 S H 1 CI CI 1.5756

22 5-CF3 S H 1 H H mp 77-79 ° C

23 5-CF3 SH 1 CI H mp 58

1 2-CF ₃ 0 1 1 Me Me viscous

2 2-OC (Me) ₂ CH ₂ -3 0 0 1 Me Me Not measured

3 4-C1 0 〇 1 Me Me viscous

4 3,4,5-Me 0 0 1 Me Me Viscosity

5 4-C1 0 s 2 Me Me viscous

6 -CF3 0 s 2 Me Me viscous

7 4-CF3 0 bond 3 CI CI consistency

8 4-CF3 0 2 CI CI mp 105-106 X:

9 4-C1 0 0 2 CI CI mp 141-142 t:

12 4-CF3 0 0 CI CI mp 74-80 X:

¹¹

13 4-e 0 0 CI CI mp 51-56 X:

¹¹

14 4- (:) 0 0 CI CI mp 70-71 t

¹¹

15 4-CN 0 0 CI CI mp 149-150 t:

¹¹

16 4-F 0 0 CI CI mp 58-59

¹¹

17 4-Br 0 0 CI CI mp 59-65 X

¹ :

18 4-Ph 0 0 CI CI mp

¹ 136-138 in

19 4-SMe 0 0 CI CI mp 75-76:

20 4-SOMe 0 0 CI c] Viscosity

21 4-SO ^ e 0 0 CI CI mp 128-130

22 2.3-Me 0 0 CI CI 25

1.5958

23 2,4-Me 0 0 CI CI mp 86-89

24 2.5-Me 0 0 CI CI 25

n _D 1.5980

25 2,6- e 0 0 CI CI 25

1.5906 ΰ α ΰ u G ooo

-

U

3: ΗΗ¾ §s> =. Table 1 Continuation of 7

No. GPW q X 'X ² Physical properties

51 4-C1 1 S 1 CI CI „26

ND 1.6209

52 4-CF ₃ 0 S 2 CI CI 27

"D 1.5845

53 4-C1 0 S 2 CI 27

CI n _D 1.6210

54 4-Me 0 S 1 CI 25

CI 1.6110

55 '4-Me 0 SO 1 CI CI viscous

56 4-Me 0 S0 ₂ 1 CI CI viscous

1 4-CF ₃ N 0 rl Π ri UU ri rl mp

no

2 5-CF ₃ N 0 0 Π U 1 ri i mp yo-iu nnu

3 2 4-CF ₃ CH 〇 HHU ri U Me Me

4 H N u H rl H H U rl U e Me

5 5-C1 N 0 H H H U hi U Me Me Mugi f £

6 3-CF ₃ N 0 HHHH (J ru Me Me

7 4-CF3 N 〇 λ

H H Hu U Hu Me Me mp 90

^ ail ct3

8 5-CF ₃ N 〇 HHHH 0 H 0 Me Me Song Song

9 3-Cl. 5-CF3 N 〇 H H H H 0 H 0 Me Me Viscosity

10 6-CF3 N 〇 H H H H 0 H 0 Me Me

1 1 5-C1 N 〇 H H H H 0 Me (J Me Me

12 3-CF3 N 0 H H H H 0 Me 0 Me Me viscosity 1ϊ

13 4-CF3 N 〇 H H H (J Me u Me Me ¾5 裯

14 5-CF ₃ N 0 HHH ri u Me u Me Me

ri u then 1 mp yy- i uu then Γ3, n HHHH 0 H 0 CI CI 1.5860

_{19 5-CF 3. 6-} Cl N 〇 HHHH 0 H 0 CI CI 1 .5837

20 5-CF3 N 0 H H H H 0 H 0 CI CI mp 69-70

21 6-CF3 N 0 H H H H 0 H 0 CI CI 1.55831

22 5-CF3 N 0 H H Me Me 0 H 0 CI CI 1.55.672

23 -CF3 N 0 Me H H H 0 H 0 CI CI viscous

24 4-CF3 N 〇 H H Me H 0 H 0 CI CI Viscosity

25 5-CF ₃ N 0 Me H Me H 0 H 0 CI CI mp 120-121 X: Table 1 Continuation of 8

No. GDJG, G "G 'C"' P q ' ¹ X ²

26 5-CF ₃ N 0 Me H Me Me 0 H 0 CI CI mp 138-139

27 5-CF3 N 0 Me Me H H 0 H 0 CI CI 26

1.5670

28 5-CF3 N 0 Me Me Me H 0 H 0 CI CI „25 1.5647

29 5-CF3 N 0 CI H H H 0 H 0 CI CI „26

1.5789

30 5-CF3 N 0 CI CI H H 0 H 0 CI CI 27

n _D 1.5842

31 5-CF3 N 0 H H H H 0 Me 0 CI CI 24

1.5690

32 4-C1 N 0 H H H H 0 H 1 Me Me viscous

33 3-CF3 N 0 H H H H 0 H 1 Me Me viscous

34 4-CF3 N 0 H H H H 0 H 1 Me Me viscous

35 5-CF3 N 0 H H H H 0 H 1 Me Me viscous

36 6-CF3 N 0 H H H H '0 H 1 Me Me viscous

37 H CH 0 H H H H 0 H 1 CI CI 20 1.6 107

38 2.4-Me CH 0 H H H H 0 H 0 CI CI 21

1.5963

39 2-CF3 CH 0 H H H H H 0 H 0 CI CI 21

1.5791

40 3-CF3 CH 0 HHHH 0 H 0 CI CI n _D 1.5803

41 4-CF3 CH 0 H H H H 0 H 0 CI CI mp 79-80

42 3-F. 5-CF3 CH 0 H H H H 0 H 0 CI CI 22

1.5740

43 2-Cl, 4-CF3 CH 0 H H H H 0 H 0 CI CI 1.5884

44 4-OCF3 CH 0 H H H H 0 H 0 CI CI 22

1.5761

45 5-CF3 N 0 H H H H 0 H 1 CI CI 20

n _D 1.5691

46 5-CF3 N 0 H H H H 0 Me 1 CI CI 1.5743

47 5-CF3 N 0 HHHH 0 Et 1 CI CI

50 5-CF3 N 〇 HHHH 0 H 3 Me Me Viscosity Table 1 Continuation of 8

No. GDJG, G "G 'G""p R ³ q, X ¹ X ²

51 N 0 H H H 25

5-CF ₃ H 0 H 3 CI CI n, 1.5721

52 5-CF3 CH 0 H H H H 2 H 0 Me Me viscous

53 5-CF3 CH 0 HHHH 2 H 0 CI CI n _D ²⁶ 1.5706

54 4-C1 CH bond H H H H O H 0 Me Me mp 95-96 X:

55 4-Br CH bond H H H H O H 0 Me Me mp 105-106 ° C

1 2 H 1.5773

2 3 H 1.5801

3 3 Me mp 121-123

4 3 H II 1.5737

No. A 'Physical properties

1 n-Pr 1.5709

2 CH ₂ = CH viscous

3 MeOCH ₂ 1.5759

4 CH ^ rn _D ²³ 1.601

5 HOCH ₂ CH ₂ mp 74-75

6 HOCH ₂ CH ₂ CH ₂ 1.5801

No. G D P W Physical properties

_{1 3-CF 3. CH 0} 0 1 n D 1.5570

2 5-CF ₃ NOS 1 mp 69-72. C

3 4-CF, CH 1 NH 2 n 1.5513

1 0 2 1.5529

2 0 3 1.5523

3 1 2 1.5770

4 1 3 1.5649

5 1 4 mp 65-67 ° C

Table 1 1 3 0-CH ₂ CH = CCI ₂ q

No. G D s q Q, physical properties

-CF ₃ N 0 2 0 1.5487

4 5-CF3 N 1 3 〇 1.5633

5 5-CF3 N 1 4 〇 1.5610

6 5-CF3 N 0 2 NH Viscosity

7 5-CF3 N 03 NH mp 108-109

8 3-CF N 1 3 〇 1.5632

No. 0 'R ⁵ X' X ² Physical properties

H ^ O Me H H 1.551 1

H ^ O Et H H 1.5548

-Pr H H 1.5392

H ^ O Me Me H 1.5518

HjNO H CI CI mp 58-60

Br H CI CI n _n 1.6101 oo Rei HON NH_

0 2〇

; D

x

X

X X X 3

1.5861 〇 Hereinafter, preparation examples and test examples of the pesticidal composition of the present invention are shown. The compound numbers used in each test correspond to the compound numbers in Tables 1 to 15.

Formulation Example 1: Water-dispersible powder

20 parts by weight of the compound of the present invention, Carplex # 80 (white carbon, Shionogi & Co., Ltd., trade name) 20 parts by weight, ST kaolin clay (Kaolinite, Tsuchiya Kaolin Co., trade name) 52 weight 5 parts by weight, Lunox P 65 L (Anionic surfactant, Toho Chemical Co., Ltd.) 3 parts by weight, Solpol 904 K (Anionic surfactant, Toho Chemical Co., Ltd.) Of the active ingredient and uniformly mixed and pulverized to obtain a wettable powder containing 20% by weight of the active ingredient. Formulation Example 1 2: Powder

2 parts by weight of the compound of the present invention, 93 parts by weight of clay (manufactured by Nippon Talc Co., Ltd.), 5 parts by weight of Carplex # 80 (white carbon, Shionogi & Co., Ltd., trade name) are uniformly mixed and pulverized. A powder of 2% by weight of the components was obtained. Formulation Example 1: Emulsion

The compound of the present invention was added to 20 parts by weight of a mixed solvent consisting of 35 parts by weight of xylene and 30 parts by weight of dimethylformamide and dissolved. A mixture with an ionic surfactant (Toho Chemical Co., Ltd., trade name) was added in an amount of 15 parts by weight to obtain an emulsion containing an active ingredient of 20% by weight. Formulation Example-4: Flowable

30 parts by weight of the compound of the present invention and 5 parts by weight of Solpol 907 K (same as above), 3 parts by weight of Sorbon T-120 (nonionic surfactant, Toho Chemical Co., Ltd., trade name), ethylene 8 parts by weight of glycol and 44 parts by weight of water are wet-pulverized with a Dynomill (manufactured by Shinmaru Enterprises), and 10 parts by weight of a 1% by weight aqueous solution of xanthangum (natural polymer) is added to the slurry-like mixture and mixed well. By pulverizing, a flowable agent having an active ingredient of 20% by weight was obtained. Test Example 1: Insecticidal effect on larvae of Japanese moth

Formulation Example 11 Cabbage cut leaves (6 cm in diameter) were immersed in a water dilution of the insecticide (wettable powder) of the present invention manufactured according to the formulation of Example 1 for 1 minute. After immersion, it was air-dried, placed in a plastic cup (7 cm inside diameter), and five 3rd instar larvae of the Japanese moth were released into this cup (1 concentration, 2 repetitions). The larvae were kept in a constant temperature room at 25 ° C, and after 4 days from the release, the larvae were examined for viability and agony, and the killing rate (%) was determined with 1/2 of the agony worms dead. The results are shown in Table 16.

Maiichi 1-iX, \ j j),

ί ί 中中 ί ί

(ppm) (Ο / Λ

/ 0me (ppm) / 0 L JUU inn 07 I JUU 1 on Table

JUU 1 no one ί¾ ouu 1 n unu

A ouu uu CO ouu uu

c cnn 1

D OUU 1 1 nUnU i ouu IUU

7

JUU OUU IUU

o nn O uu l uu ¾ 1 c

JUU 丄 UU

Q

OUU 1 UU _¾ OA 1 nn

c

ouu IUU Ό ouu IUU

_{¾ 1¾ 1}

19 1 ΠΠ 0 O cnUnU 1 uu ouu 1 I nUnU o ςηuηu 1 I nUnU ouu 1 uu 丰 — 1 ― n

IUU

0 DUU JU 丰 ~ 1 1 4 OUU 1 uu

17 O

JUU I A

uu DUU

1 Q

10 JUU i 1 n unu 宾一 1 ― JUU IUU

1 Q AC.

UU 1 uu OUU

n OUU 1 uu * ku_ 1 1 ■ 40 JUU 1 nn Table 1 1 21 500 100 1 47 500 100 Table 1 1 22 500 100 Table 1 1 48 500 100 Table 1 1 23 500 100 50 500 100 Table -1-24 500 100 Table-1-51 500 100 Table-1-25 500 100 Table-1-52 500 100 Table-1-26 500 100 Table-1-53 500 100 Table 1-6 (continued) Table 1 1 6 (continued)

Compound concentration insecticidal rate Compound concentration insecticidal rate

No. (ppm) (%) No. (Ppm) (%) Table 1 — 54 500 100 Table 4 1 3 500 100 Table 1 55 500 100 Table 4 1 4 500 100 Table 1 1 56 500 100 1 4 1 5 500 100 1 1 57 500 100 4 1 6 500 100 1 1 58 500 100 1 4 12 500 100 Table 1 1 59 500 100 1 4 13 500 100 Table 2-2 500 100 Table 5-4 500 100 Table 2-3 500 100 Table 5-5 500 100 Table 2-4 500 100 Table 5-6 500 100 Table 2-5 500 100 Table 1 5— 7 500 100 Table 2—6 500 100 Table— 5—8 500 100 Table— 2—7 500 100 Table 5—9 500 100 Table 2—8 500 100 Table— 5—10 500 100 Table 2-9 500 100 o- 12 500 100 Table 2-13 500 100 Table 5-13 500 100 Table 2-16 500 100 Table 6-1 500 100 Table 2-17 500 100 Table 6-2 500 100 Table 2-18 500 100 Table 6-3 500 100 Table 2-19 500 100 Table 6-4 500 100 Table 2-20 500 100 Table 6-5 500 100

21 500 100 Table—6-6 500 100 Table—2-22 500 100 Table 6—7 500 100 Table 3—1 500 100 Table 6—8 500 100 One—2 500 100 Table—6—10 500 100 Table 1 3 _ 5 500 100 Table 1 6—1 1 500 100 Table 1 16 (continued) Table 1 6 (continued)

No. (ppm) (%) No. (ppm) (%) Table 6- 12 500 100 Table 7- 18 500 100 Table 6- 13 500 100 Table 7- 19 500 100

*: A 6 14 500 100 Table one 7 20 500 100 one ₆ - 15 500 100 Table one 7 - 21 500 100

16 500 100 22 500 100

* — ₆ — _{¾ 7} _

17 500 100 23 500 100

* _ ₆ _

18 500 100 Table one 7 24 500 100 Table one 6 20 500 100 Table one 7 25 500 100 Main - ₆ - 21 500 100 Table - 7 - 26 500 100 Main - ₆ - 23 500 100 Table - 7 27 500 100 Table 7-1 500 100 Table 7-28 500 100 Table 7-3 500 100 Table 7-29 500 100 Table 7-4 500. 100 30 500 100 Table 7-5 500 100 Table 1 7— 31 500 100 Table— 7 _ 6 500 100 Table 7—32 500 100 Table— 7— 7 500 100 Table— 7— 33 500 100 Table— 7—8 500 100 Table 7—34 500 100 Table— 7 -9 500 100 Table 7-36 500 100 Table 7-10 500 100 Table-7-37 500 100 Table-7-1 1 500 100 Table 7-38 500 100 Table 7 12 500 100 Table _ 7- 40 500 100 Table 7-13 500 100 Table 7-41 500 100 Table 7-14 500 100 42 500 100 Table 7-16 500 100 Table 7-44 500 100 Table 7-17 500 100 Table 7 7-45 500 100 Table-16 (continued) Table-16 (continued)

No. (ppm) (%) No. (ppm) (%) Table 7- 46 500 100 Table 8-19 500 100 Table 7-47 500 100 Table 8-20 500 100 Table 7-48 500 100 _8-21 500 100 _7-49 500 100 _8-23 500 100 _7-50 500 100 _8-24 500 100 _7-51 500 100 _{¾ 8} _ 29 500 100

52 500 100 Table 8-31 500 100 Table 53 500 100 Table 8-32 500 100

¾ 7-54 500 100 ¾ 8-33 500 100

_¾? _ 55 500 100 ¾ 8-34 500 100 Table ⁿ 3 500 100 Table-8-35 500 100

4 500 100 Table 8—36 500 100 Table ⁿ 5 500 100 Table 8-37 500 100 Table 8—6 500 100 Table 8—38 500 100

_{¾ 8} _

7 500 100 Table 8-39 500 100 Table 8-8 500 100 Table 8-40 500 100

9 500 100 Table 1 8—41 500 100

_{¾ 8} _

10 500 100 Table—8—42 500 100 Table 8—1 1 500 100 Table—8—43 500 100

13 500 100 Table 8-44 500 100 Table 8-14 500 100 45 500 100 Table _ 8-15 500 100 46 500 100

16 500 100 Table 8-47 500 100 Table 8-17 500 100 Table _ 8-48 500 100 Table 8-18 500 100 49 500 100 Table-16 (continued) Table-16 (continued)

No. (ppm) (%) No. (ppm) (%) Table 8-50 500 100 Table 10-6 500 100 Table 8-52 500 100 Table 1 1 500 100 Table 8-53 500 100 table 1 1 1 2 500 100 table 8—54 500 100 table—1 500 3 table 100—8—55 500 100 table—12—1 500 100 table—9—1 500 100 table—12—2 500 100 Table 9 1 2 500 100 Table 12-3 500 100 Table 9 1 3 500 100 1 12 4 500 100

4 500 100 1 500 100

1 500 100 2 500 100

2 500 100 Table 13-3 500 100

4 500 100 4 500 100

5 500 100 5 500 100

Test Example 1 2: Insecticidal effect on the larvae of Lotus spruce

Preparation Example-1 Cabbage cut leaves (diameter 6 cm) were immersed for 1 minute in a water dilution of the insecticide (wettable powder) of the present invention manufactured according to the formulation of Preparation Example 1. After immersion, it was air-dried, placed in a plastic cutlet (7 cm inside diameter), and five third-instar larvae of Spodoptera litura were released into this cup (1 concentration, 2 repetitions). They were kept in a constant temperature room at 25 ° C, and after the release of the insects, the larvae were examined for life and death and their agony. The results are shown in Table 17.

Table—1 7 (continued)

No. (ppm) (%) No. (ppm) (%) Table 1 1 1 100 100 Table 1 28 500 100 Table 1 3 500 100 Table 1 29 500 100 Table 1 1 4 500 100 1 1 30 500 100 1 1 5 500 100 1 1-31 500 100 1 1-7 500 100 1 1 32 500 100 1 1 8 500 100 1 33 500 100 Table 1 1-9 500 100 Table 1 34-100 100 Table 1-10 500 100 Table 1-35 500 100 Table 1-1 1 500 100 Table 1-36 500 100

12 500 100 Table 1 1 1 37 500 100

_Plot 13 500 100 Table 1 1 38 500 100 Table 1-14 500 100 Table 1 39 500 100 Table 1-15 500 100 Table _1-40 500 100 Table _1-16 500 100 Table _1-1 41 500 100

17 500 100 Table 1-42 500 100 Table 1-18 500 100 Table 1-44 500 100 Table 1 _ 19 500 100 Table-1 45 500 100 Table-1 _ 20 500 100 Table-1-46 Table 100-1-21 500 100 Table-1 47 500 100 Table-1-22 500 100 Table-1-48 500 100 Table-1 23 500 100 49 500 100

24 500 100 Table 1-1 50 500 100 Table-1-25 500 100 51 500 100 Table-1-26 500 100 Table-1-52 500 100

27 500 100 Table 1-53 500 100 Table 1 1 7 (continued) Table 1 7 (continued)

No. (ppm) (%) No. (ppm) (%) Table 1-54 500 100 Table 4-2 500 100 Table 1-55 500 100 Table-4 3 500 100 Table-1-56 500 100 Table 4 1 4 500 100 Table 1 1 57 500 100 Table 4 4 5 500 100 Table 1 1 58 58 100 Table 4 4 6 500 100 Table 1 1 59 500 100 Table 4 1 8 500 100 Table 2-2 500 100 Table 4-9 500 100 Table-2-3 500 100 Table 4-1 1 500 100 Table 2-4 500 100 Table-4-12 500 100 Table 2-5 500 100 Table 1-4 13 500 100 Table-2-6 500 100 Table-5-2 500 100 Table 1-7 500 100 Table-5-4 500 100 Table-2-8 500 100 Table-5-5 500 100

ZZ—12 500 100 Table—5-6 500 100 Table—2—13 500 100 Table 5—7 500 100 Table 2—14 500 100 Table—5—8 500 100 Table—2—15 500 100 Table—5 -9 500 100 Table 2-16 500 100 Table 5-10 500 100 Table 2-17 500 100 Table 5-12 500 100 Table-2-18 500 100 Table 5-13 500 100 Table 2- 19 500 100 Table— 6— 1 500 100

^-△-20 500 100 Table 6-2 500 100 Table 2-21 500 100 Table 6-3 500 100 Table-2-22 500 100 Table 6-4 500 100 Table _ 3-5 500 100 Table — 6-5 500 100 Table 1-7 (continued) Table 1 7 (continued)

No. (ppm) (%) No. (ppm) (%) Table 6-6 500 100 Table 7-10 500 100 Table 6-7 500 100 Table 7-1 1 500 100 Table 6-8 500 100 Table 7-12 500 100 Table 6-9 500 100 Table 7-13 500 100 Table 6-10 500 100 Table 7-14 500 100 Table 6-1 1 500 100 Table 7-16 500 100 Table 6-12 500 100 Table-7-17 500 100 Table-6-13 500 100 Table-7-18 500 100 Table-6-14 500 100 Table-7-19 500 100 Table-δ-15 500 100 Table 7 7-20 500 100 Table 6-16 500 100 Table 7-21 500 100 Table 6-17 500 100 Table 7-22 500 100 Table 6-18 500 100 Table 7-23 500 100 Table-6-19 500 100 Table-7-24 500 100 Table-6-20 500 100 Table-7-25 500 100 Table-6-21 500 100 Table-7-26 500 100 Table-7 _ 1 500 100 Table -7-27 500 100 Table 7-2 500 100 Table 7-28 500 100 Table 7-3 500 100 Table 7-29 500 100 Table 7 _ 4 500 100 Table 7-30 500 100 Table- 7—5 500 100 Table 7—31 500 100 Table 7—6 500 100 Table—7—32 Table 100-7-7 500 100 Table-7-33 500 100 Table 7-8 500 100 Table-7-34 500 100 Table 7-9 500 100 Table 7-36 500 100 Table-"(continued) Table-1 7 (continued)

No. (ppm) (%) No. (ppm) (%) Table-7-37 500 100 Table-8-10 500 100 Table-7-38 500 100 Table-8-1 1 500 100 Table-7-40 Table 500-8-12 500 100 Table-7-41 500 100 Table-8-13 500 100 Table-7-42 500 100 Table-8-14 500 100 Table-7-44 500 100 Table-8-15 500 Table 100-7-45 500 100 Table-8-16 500 100 Table-7-46 500 100 Table-8-17 500 100 Table-7-47 500 100 Table-8-18 500 100 Table-7-48 500 100 Table-8-19 500 100-7-49 500 100 Table-8-20 500 100 Table-8-21 500 100 Table-7 51 500 100 Table 8-22 500 100 Table-7 -52 500 100 Table 8-23 500 100 Table-7-53 500 100 Table-8-24 500 100 Table-7-54 500 100 Table-8-25 500 100 Table-7-55 500 100 Table-8-27 Table 100-7-56 500 100 Table 8-28 500 100 Table-8-3 500 100 Table-8-29 500 100 Table-8-4 500 100 Table 8-30 500 100 Table 8-5 500 100 31 500 100 Table-8-6 500 100 Table 8-32 500 100 Table-8 7 500 100 Table _ 8-33 500 100 Table 8-8 50 0 100 Table 8-34 500 100 Table 8-9 500 100 Table 8-35 500 100 (Continued) (continued)

No. (ppm) (%) No. (ppm) (%) Table one 8 36 500 100 Table one 9 one 2 500 100 Table one 8 37 500 100 Table -9 one 3 500 100 Table one ₈ one 38 500 100 Table 9-1 4 500 100 Table 8—39 500 100 Table 10—1 500 100 Primary S—40 500 100 Table 10—2 500 100 Table 8—41 500 100 Table—10—3 500 100 Table 1 8—42 500 100 Primary 10—4 500 100 Table 8—43 500 100 Table—1 1 1 1 500 100 Table 8—44 500 100 Table—1 1—2 500 100 Table—8—45 500 100 Table-1 1 1 3 500 100 Table 8—46 500 100 Table 12—1 500 100 Table 8—47 500 100 Table 12—2 500 100 Table 8—48 500 100 Table 12—3 500 100 8-49 500 100 1-12-4 500 100 8-50 500 100 12-5 500 100 8-51 500 100 13-1 500 100-8-52 500 100 Table 1 13—2 500 100

53 500 100 3 500 100

54 500 100 4 500 100

55 500 100 5 500 100

1 500 100 Test Example 1 3: Acaricidal effect on adult adults

On the cutting leaves (3 cm in diameter) of the wings, 10 female female adults were released. Formulation Example 1 A solution (3.5 ml) obtained by diluting the acaricide (wettable powder) of the present invention prepared according to the formulation of 1 to a predetermined concentration with water was spread on the above-mentioned leaves using a rotary spray tower (Mizuho Rika Chemical Co., Ltd.). ) (1 concentration, 2 replicates). Twenty-four hours after the treatment, adults were examined for viability and the acaricidal rate (%) was determined. The results are shown in Table 18.

Table—1 8

Compound concentration Insecticidal rate

No. IPpm) (%)

19 500 100

20 500 100

8 500 100

16 500 100

Test Example 1 4: Insecticidal effect on the larvae of Anemonium japonicus

Formulation Example 1 An artificial feed (Nippon Nosan Kogyo Co., Ltd.) cut into a water diluent of the insecticide (wettable powder) of the present invention manufactured in accordance with the prescription of 1 and having a diameter of about 5 cm x 1/8 yen and a thickness of 0.5 cm. Sector FL) for 10 seconds. After immersion, they were placed in a plastic cup (inner diameter 4 cm), and five third-instar larvae of the cynoid snail were released into the cup (1 concentration, 2 repetitions). The larvae were kept in a constant temperature room at 25 ° C, and after 5 days from the release, the larvae were examined for viability and agony. The results are shown in Table 19.

Table 1 1 9 Table 1 1 9 (continued)

No. Ippm) (%) No. (ppm) (%) Table 1 1 22 500 100 Table 6—20 500 100 Table 1 1 28 500 100 Table 6—21 500 100 Normal 1—29 500 100 Table 1 7—6 500 100

*: ー 1—36 500 100 Table 7—7 500 100 Main table 48 500 100 Table 7—8 500 100

¾— 1 — 49 500 100 Table 7—11 500 100

* ー 1— 51 500 100 Table 1 7— 12 500 100

1-52 500 100 Table 7-13 500 100

* ₁ ― 轰₇ _

54 500 100 22 500 100 Table 1-58 500 100 Table 7-23 500 100

¾ 16 500 100 29 500 100 Table 4-5 500 100 Table 7-30 500 100 Table 4-6 500 100 Table-7-32 500 100 Table-5-8 500 100 Table-7-40 500 100 Table 1 6— 4 500 100 Table 7— 46 500 100 Table— 6—8 500 100 Table— 7— 48 500 100 Table— 6—9 500 100 Table— 7 ^ 50 500 100 Table 6—10 500 100 Table— 7— 51 500 100 Table— 6—12 500 100 Table— 7— 52 500 100 Table— 6—13 500 100 Table— 7— 53 500 100

14 500 100 Table 7—54 500 100 Table— 6 -15 500 100 Table— 8—3 500 100 Table— 6—16 500 100 Table—8—4 500 100 Table 6—17 500 100 Table— 8—5 500 100

¾— 6 18 500 100 1 8 6 500 100 Table 1-9 (continued) Table 1 9 (continued)

No. (ppm) (%) No. (ppm) (%) Table 8-7 500 100 Table 8-39 500 100 Table 8-8 500 100 Table 8-40 500 100 Table 8-9 500 100 Table 8—41 500 100 Table 8—10 500 100 Table 8—42 500 100 Table 8—1 1 500 100 Table 8—43 500 100 Table—8—12 500 100 Table—8—44 500 100 8-13 500 100 8-45 500 100 8-14 500 100 8-46 500 100 8-16 500 100 8-47 500 100 8-17 500 100 Table 8-48 500 100 Table 8-18 500 100 Table 8-49 500 100 Table 8-19 500 100 Table 8-50 500 100 Table 8-20 500 100 Table 8-51 500 100 Table — 8— 21 500 100 Table— 8— 53 500 100 Table 8—23 500 100 Table 8—54 500 100 Table— 8—24 500 100 Table— 8— 55 500 100 Table— 8— 25 500 100 Table— 9—1 500 100 Table—8—27 500 100 Table 9—1 3 500 100 Table—8—29 500 100 Table—9—4 500 100 Table—8—31 500 100 Table—1 1—1 500 100 Table— 8-32 500 100 Table 12-2 500 100 Table 8-33 500 100 — 12— 3 500 100 Table— 8-34 500 100 Table 13—2 500 100 Table— 8— 35 500 100 Table— 13— 3 500 100 Table 8—36 500 100 Table— 13— 4 500 100 Table— 13—5 500 100 <Industrial applicability>

The pesticidal composition containing the dihalopropene derivative of the present invention as an active ingredient is useful for pests in the fields of agricultural and horticultural use, clothing, eating and drinking, livestock and pets, and particularly harmful insects and mites in agricultural and horticultural activities. It has an extremely excellent controlling effect and is useful as a controlling agent.

Claims

Scope of request General formula (I) below

A

W represents a single bond, an oxygen atom, a sulfur _{atom, - SO-, - S0 2 -} , - NR 7 -, -N = C (R 7) -, -C (R 7) = N0 -, -0N = C (R ⁷ ) —, — C (R ⁷ ) = N — N = C (R ⁸ ) —, -CO-, —COO-, — 0—CO—, — NR ⁷ — CO—, — CONR ⁷ — Wherein R ⁷ and R ^{8 each} independently represent a hydrogen atom or an alkyl group.

Q is-SO-, one S 0 ₂ -,-N = C (R ⁹ )-,-C (R ⁹ ) = N 0-,-ON two C (R ⁹ ) one,-C (R ⁹ ) = ^{N- N = C (R 10)} -, - CO-, -COO -, -0- CO-, - NR 9 - CO-, one CONR ⁹ -, optionally substituted § aryl group or substituted, (Wherein R ⁹ and R ^{1Q each} independently represent a hydrogen atom or an alkyl group),

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 each} independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, Represents an alkoxyalkyl group, and R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be taken together to form an alkylidene group or an alkylenedioxy group,

p, q and r are integers, p + q + r represents the 9 or less (, Q is, - S 0-, one S0 ₂ -, one C (R ⁹⁾ = N0-, one C_〇 0—or one CONR ^9— place In this case, r is 1 or more, and when Q is a phenyl group, r = 0, Q is —ON—C (R ⁹ ) one or —0—CO—, and W is In the case of an oxygen atom or a sulfur atom, q is 1 or more. ),

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group;

Y represents a halogen atom, an alkyl group or a haloalkyl group,

n represents an integer of 0 to 2, and Z represents a halogen atom. ]

A dihalopropenyloxybenzene derivative represented by the formula:

2.p + q + r is 6 or less,

A may be substituted with a substituent selected from G ^1, an alkyl group, § alkenyl group or an alkynyl group, or may be substituted with a substituent selected from G ^2, Ariru group or hetero Ring group

[Wherein G ¹ represents a halogen atom, a hydroxyl group, an alkoxy group, a haloalkoxy group, an aryl group, an aryloxy group, a heterocyclic group or a heterocyclic oxy group (the above aryl group, aryloxy group, heterocyclic group and heterocyclic group) The group consisting of a halogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group and a haloalkylsulfonyl group May be substituted with a more selected substituent.)

G ² is a halogen atom, a hydroxyl group, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, a formyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkylthio group, a haloalkylthio group, an alkyls A rufinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group or a haloalkylsulfonyl group, or an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, a heterocyclicoxy group or a heterocyclic thio group (the above arylyl group, Aryloxy group, arylthio group, heterocyclic group, heterocyclic oxy group and heterocyclic thio group include halogen atom, hydroxyl group, cyano group, alkyl group, haloalkyl group, and alkoxy group. A group selected from the group consisting of a group, a haloalkoxy group, a formyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkylthio group, a haloalkylthio group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group and a haloalkylsulfonyl group. It may be substituted with a substituent. ). 2. The dihalopropenyloxybenzene derivative according to claim 1, wherein the derivative is:

3. Q is a halogen atom, a hydroxyl group, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, a formyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkylthio group, a haloalkylthio group, an alkylsulfinyl group An aryl group or a heterocyclic group which may be substituted with a substituent selected from the group consisting of a haloalkylsulfinyl group, an alkylsulfonyl group and a haloalkylsulfonyl group;

r = 0

3. The dihalopropenyloxy benzene derivative according to claim 1 or 2, characterized in that:

4 Q is a group represented by Q Q-5 shown below.

(Wherein, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^{18 each} independently represent a hydrogen atom, a halogen atom or an alkyl group). 3. The dihalopropenyloxybenzene derivative according to claim 1 or 2, characterized in that:

5. X ¹ and X ² are each independently a halogen atom or a C i —C ₄ alkyl group;

n = 0,

W is an oxygen or sulfur atom

The dihaloprobe2oxybenzene derivative according to any one of claims 1 to 4, characterized in that:

6. Q is a group represented by the following Q-1 to Q-5

(In the formula, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^{18 each} independently represent a hydrogen atom, a halogen atom or an alkyl group.)

p = 0 and

A—W— is an aryloxyaryloxy group, a heterocyclicoxyloxy group, an aryloxyheterocyclicoxy group, or a heterocyclicoxyloxy ringoxy group (wherein Ryloxyaryloxy, heterocyclic oxyaryloxy, aryloxyheterocyclic oxy and heterocyclic oxyheterocyclic oxy are each independently a halogen atom, a hydroxyl group, a cyano group, an alkyl group, A haloalkyl group, an alkoxy group, a haloalkoxy group, a formyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkylthio group, a haloalkylthio group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group and a haloalkylsulfonyl group. May be substituted with a substituent selected from the group It is.)

6. The dihalopropenyloxy benzene derivative according to claim 1 or 5, characterized in that:

7. A pesticidal composition comprising any one of the dihalopropenyloxybenzene derivatives according to claims 1 to 6 as an active ingredient.

8. An insecticide or acaricide comprising any one of the dihalopropenyloxybenzene derivatives according to claims 1 to 6 as an active ingredient.

9. General formula (II) below

(In the above general formula, Q ¹ represents a halogen atom, a hydroxyl group, an aminooxy group, an oxyamino group, an alkoxy group, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, or a halarylsulfonyl group. A hydroxy group,

Y represents a halogen atom, an alkyl group or a haloalkyl group,

n represents an integer of 0 to 2, and Z represents a halogen atom. )

A dihalopropenyloxybenzene derivative represented by the formula:

10. The following general formula (III)

(In the above general formula, Q ² represents an oxygen atom or a hydroxyimino group,

Q ³ represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydrazino group or an alkyl group,

R ⁵ ′ and R ⁶ ′ each independently represent a hydrogen atom or an alkyl group, represents an integer of 9 or less,

Y represents a halogen atom, an alkyl group or a haloalkyl group,

n represents an integer of 0 to 2, and Z represents a halogen atom. )

A dihalopropenyloxybenzene derivative represented by the formula: