TW201536725A - Substituted phenol ether compound and agent for controlling pest - Google Patents

Abstract

An objective of this invention is to provide a novel substituted phenol ether compound with controlling effects to pests, and an agent for controlling pests characterized by including the compound as an active ingredient. A substituted phenol ether compound represented by the following formula (1) is provided as a solution means.

Description

Substituted phenyl ether compound and pest control agent

The present invention relates to a novel substituted phenyl ether compound and a pest control agent containing the compound as an active ingredient.

To date, most of the pest control agents that control pests in agricultural and horticultural scenes or pests such as pets, livestock, etc., but have insufficient control effects, or those who have obtained sufficient effects at the beginning, but pests have The agent is resistant and the control effect is reduced. In addition, even if the pest control agent is sprayed out, it is caused by the external fly or the pest of the egg when it is spread, and new pests are produced. Therefore, the pests generated after the spread need to be able to exert the control effect. Residual effect. Agents that do not have residual effects are laborious and have disadvantages such as resistance to pests due to the high number of spreading. In addition, among the widely used pest control agents, there are not only harmful organisms, but also people who are highly toxic to humans, animals, fish and shellfish, and those who are also toxic to natural enemies, and accumulate in the environment due to difficulty in decomposition. Polluters, there are very few pest control agents that can exert high performance in all aspects. Therefore, to be developed A novel pest control agent, which is resistant to pests that have been widely used in the past, can also exhibit a sufficient control effect with a low dose, and will continue to prevent the effect after spreading, and is useful. The biological safety is high and there is no adverse effect on the environment.

Now, the insecticidal and acaricidal activity of the substituted phenyl ether compound has been known. For example, Patent Document 1 describes a compound having a phenyl ether skeleton similar to the compound of the present invention. In the formula of Patent Document 1, R ² represents only a (C ₁ to C ₆ ) alkyl group, and the haloalkyl group and the cycloalkylalkyl group of A in the formula (1) shown in the present invention are not described.

Further, Patent Documents 2 and 3 describe diphenyl ether compounds useful as insecticides and acaricides. Patent Documents 2 and 3 describe a compound in which two benzene rings directly form an ether bond with an oxygen atom, but there is no description of a compound in which two benzene rings of the present invention form an ether bond with an oxygen atom of a stretch alkyl chain.

Further, Patent Document 4 describes an amidine compound containing a 3-substituted phenyl sulfide which is useful as an insecticidal and acaricidal agent. The compound described in Patent Document 4 has an anthracene skeleton at the third position of the benzene ring of phenyl sulfide, but the substituted phenyl ether skeleton of the present invention is not described. Patent Documents 5 and 6 describe 3-heterocyclic substituted phenyl sulfide compounds useful as insecticidal and acaricidal agents. The compounds described in Patent Documents 5 and 6 have a triazole ring and a pyrazole ring at the third position of the benzene ring of the phenyl sulfide, but the substituted phenyl ether skeleton of the present invention is not described.

Further, an N-substituted aniline compound exhibiting insecticidal activity similar to the present invention has hitherto been known. For example, the compound described in Patent Document 7 has an amine carbonyl group at the 3rd position of aniline, but does not describe a phenoxy group as in the present invention. An alkyl substituted aniline compound.

Further, Patent Document 8 describes an alkylphenyl sulfide compound having a pest control effect. In the general formula [1] of Patent Document 8, R ⁴ represents an alkyl group substituted with a phenyl group (the group may be substituted by R ⁶ ), and therefore represents a compound similar to the compound of the present invention. However, R ⁶ having an amine group corresponding to the characteristic N-substituted aniline skeleton of the compound of the present invention is not described.

Further, Patent Document 9 describes a compound similar to the compound of the present invention. In the general formula of Patent Document 9, A and D" have no description of a haloalkylthio group, a cycloalkylalkylthio group, a haloalkylsulfinyl group, a cycloalkylalkylsulfinyl group, or the like, and there is no insecticide. Record of activity.

[Advanced technical literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. SHO 63-41451

Patent Document 2: Japanese Laid-Open Patent Publication No. 51-79723

Patent Document 3: International Publication No. 2013/111864

Patent Document 4: International Publication No. 2007/131680

Patent Document 5: International Publication No. 2006/043635

Patent Document 6: International Publication No. 2009/051245

Patent Document 7: International Publication No. 2005/021488

Patent Document 8: International Publication No. 2013/157229

Patent Document 9: International Publication No. 1999/062871

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel substituted phenyl ether compound which is safe and effective for controlling pests, and a pest control agent which contains the compound as an active ingredient.

As a result of careful examination of the above-mentioned problems, the inventors of the present invention have found that the substituted phenyl ether compound represented by the following formula (1) has an excellent control effect against harmful organisms, and completed the present invention.

In other words, the first aspect of the invention of the present application relates to a substituted phenyl ether compound represented by the following formula (1).

In the above formula (1), A represents a C ₂ to C ₅ haloalkyl group, a C ₂ to C ₅ haloalkenyl group, or a substituted C ₃ to C ₈ cycloalkyl group C ₁ to C ₄ alkyl group (the group) It may be mono- or polysubstituted by a halogen atom or a C ₁ to C ₃ alkyl group, and n represents an integer of any of 0 to 2.

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkoxy group which may be substituted with a halogen atom, C ₃ to C ₆ cycloalkyl, or an aryl group which may be substituted with a halogen atom. However, X ¹ and X ² cannot be hydrogen atoms at the same time.

Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amine group, a decyl group, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkoxy group which may be substituted with a halogen atom, a halogen atom may be substituted with C ₁ to C ₆ alkylthio group, a halogen atom may be substituted with C ₁ to C ₆ alkylsulfinyl acyl, may be substituted by a halogen atom, a C ₁ to C ₆ alkylsulfonyl group, a C ₁ to C ₆ alkylamino group, a di C ₁ to C ₆ alkylamino group, a C ₁ to C ₆ alkylcarbonyl group, a C ₁ to C ₆ alkoxycarbonyl group, a C ₁ to C ₆ alkoxyiminomethyl group, An aryl group which may be substituted with a halogen atom, a substituted aryloxy group which may be via a halogen atom, a cyano group, a C ₁ to C ₃ alkyl group, a C ₁ to C ₃ haloalkyl group, a C ₁ to C ₃ alkane Oxyl, C ₁ to C ₃ haloalkoxy, C ₁ to C ₃ alkylthio, C ₁ to C ₃ haloalkylthio, C ₁ to C ₃ alkylsulfinyl, C ₁ to C ₃ halo Alkylsulfinyl, C ₁ to C ₃ alkylsulfonyl, C ₁ to C ₃ haloalkylsulfonyl, C ₁ to C ₃ alkylcarbonyl, or C ₁ to C ₃ alkoxycarbonyl monosubstituted or Multi-substituted), substituted arylthio (which may be via a halogen atom, a cyano group, a C ₁ to C ₃ alkyl group, a C ₁ to C ₃ haloalkyl group, a C ₁ to C ₃ alkoxy group, C ₁ To C ₃ haloalkoxy, C ₁ to C ₃ alkane , C ₁ to C ₃ haloalkylthio, C ₁ to C ₃ alkylsulfinyl, C ₁ to C ₃ haloalkylsulfinyl, C ₁ to C ₃ alkylsulfonyl, C ₁ a C ₃ haloalkylsulfonyl group, a C ₁ to C ₃ alkylcarbonyl group, or a C ₁ to C ₃ alkoxycarbonyl mono- or polysubstituted), a substituted arylsulfinyl group (the group may be halogenated) Atom, cyano, C ₁ to C ₃ alkyl, C ₁ to C ₃ haloalkyl, C ₁ to C ₃ alkoxy, C ₁ to C ₃ haloalkoxy, C ₁ to C ₃ alkylthio, C ₁ to C ₃ haloalkylthio, C ₁ to C ₃ alkylsulfinyl, C ₁ to C ₃ haloalkylsulfinyl, C ₁ to C ₃ alkylsulfonyl, C ₁ to C _a monohaloalkylsulfonyl group, an alkylcarbonyl group, or a C ₁ to C ₃ alkoxycarbonyl mono- or polysubstituted), a substituted arylsulfonyl group (the group may be via a halogen atom, a cyano group, C ₁ to C ₃ alkyl, C ₁ to C ₃ haloalkyl, C ₁ to C ₃ alkoxy, C ₁ to C ₃ haloalkoxy, C ₁ to C ₃ alkylthio, C ₁ to C ₃ haloalkyl sulfur a C ₁ to C ₃ alkylsulfinyl group, a C ₁ to C ₃ haloalkylsulfinyl group, a C ₁ to C ₃ alkylsulfonyl group, a C ₁ to C ₃ haloalkylsulfonyl group, a C ₁ to C ₃ alkylcarbonyl group, or a C ₁ to C ₃ alkoxycarbonyl-substituted or mono-substituted), a halogen atom, or may be Substituted C ₇ to C ₁₁ aralkyl group, m represents an integer of any of 1 to 5. When m is an integer of 2 to 5, Y may be the same or different. Further, when m represents an integer of 2 or more, adjacent Ys may be bonded to each other, and are represented by -OCH ₂ O-, -OCF ₂ O-, -OCH ₂ CH ₂ O-, -OCF ₂ CH ₂ O-, Or -OCF ₂ CF ₂ O-.

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted with a halogen atom, a C ₁ to C ₄ alkoxy group which may be substituted with a halogen atom, C ₃ to C ₆ cycloalkyl, C ₁ to C ₄ alkylcarbonyloxy, or benzyloxy, p represents any integer from 1 to 5. Further, when p represents an integer of 2 to 5, R ¹ and R ² on different carbon atoms may be the same or different. Further, R ¹ and R ² on the same carbon atom may be bonded to an oxygen atom or a sulfur atom individually and expressed as (=O) or (=S). Further, R ¹ and R ² on the same carbon atom may be bonded at the same time, and are represented by a C ₁ to C ₄ alkoxyimine group. Further, R ¹ and R ² on the same carbon atom may be bonded to each other to form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring in 2 to 5 alkylene groups.

Z represents an oxygen atom, a sulfur atom, a sulfinylene group, or a sulfonyl group, and q represents an integer of 0 or 1. However, p and q cannot be 1 at the same time.

A second aspect of the invention of the present application relates to a pest control agent containing a substituted phenyl ether compound represented by the above formula (1).

A third aspect of the invention of the present application relates to a production intermediate represented by the following formula (2).

In the above formula (2), A represents a C ₃ to C ₈ cycloalkylmethyl group which may be substituted (the group may be mono- or polysubstituted by a fluorine atom or a C ₁ to C ₃ alkyl group), and n represents 0 or Any one of 1 integers.

X ¹ represents a C ₁ to C ₄ alkyl group, and X ² represents a hydrogen atom, a halogen atom, or a C ₁ to C ₄ alkyl group.

A fourth aspect of the invention of the present application relates to an N-substituted aniline compound represented by the following formula (1-6).

In the above formula (1-6), A ¹⁰⁰ represents a C ₂ to C ₅ haloalkyl group, or a C ₃ to C ₆ cycloalkyl group C ₁ to C ₃ alkyl group, and n represents an integer of any of 0 to 2.

X ¹⁰¹ and X ¹⁰² each independently represent a hydrogen atom, a halogen atom, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted with a halogen atom, or a C ₁ to C ₆ alkoxy group which may be substituted with a halogen atom. However, X ¹⁰¹ and X ¹⁰² cannot be hydrogen atoms at the same time.

Y ¹⁰⁰ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a decyl group, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom, halogen substituted C ₁ to C ₆ alkylthio group, a halogen atom may be substituted with C ₁ to C ₆ alkylsulfinyl acyl, a halogen atom may be substituted with C ₁ to C ₆ alkylsulfonyl groups, C ₁ To a C ₆ alkylcarbonyl group, a C ₁ to C ₆ alkoxycarbonyl group, or a C ₁ to C ₆ alkoxyiminomethyl group, v represents an integer of from 1 to 4. Further, when v represents an integer of 2 to 4, Y ¹⁰⁰ may be the same or different.

R ^101a and R ^102a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted with a halogen atom, or a C ₁ to C ₄ alkoxy group which may be substituted with a halogen atom. Further, R ^101a and R ^102a on the same carbon atom may be bonded to one oxygen atom or sulfur atom individually and expressed as (=O) or (=S). Further, R ^101a and R ^102a on the same carbon atom may be bonded at the same time to represent a C ₁ to C ₄ alkoxyimine group. Further, R ^101a and R ^102a on the same carbon atom may be bonded to each other to form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring in 2 to 5 alkylene groups.

R ^101b and R ^102b each independently represent a hydrogen atom, a halogen atom, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, or a C ₁ to C ₄ alkoxy group which may be substituted with a halogen atom, and u represents 0 or 1 Any one of the integers.

A fifth aspect of the invention of the present application relates to a pest control agent containing the N-substituted aniline compound represented by the above formula (1-6).

According to a fourth aspect of the invention, the compound represented by the following formula (3) is an intermediate for producing an N-substituted aniline compound represented by the above formula (1-6).

In the above formula (3), G represents CO ₂ R ¹⁰³ (R ¹⁰³ represents a C ₁ to C ₄ alkyl group), or CH ₂ OR ¹⁰⁴ (R ¹⁰⁴ represents a hydrogen atom, a C ₁ to C ₄ alkane which may be substituted by a halogen atom A sulfonyl group, or an arylsulfonyl group which may be substituted with a C ₁ to C ₄ alkyl group.

Y ¹⁰¹ and Y ¹⁰² each independently represent a hydrogen atom (except when G represents CO ₂ R ³ ), a halogen atom, or a C ₁ to C ₄ alkyl group which may be substituted with a halogen atom.

W ³ and W ⁴ each independently represent a hydrogen atom, a C ₁ to C ₆ alkylcarbonyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkoxycarbonyl group, or a C ₁ to C ₆ alkyl sulfonate which may be substituted with a halogen atom.醯基.

According to the present invention, it is possible to provide a novel substituted phenyl ether compound which has a controlling effect against harmful organisms, and a pest controlling agent containing a substituted phenyl ether compound.

Hereinafter, the present invention will be described in detail.

The substituted phenyl ether compound of the present invention has a substituted phenyl-substituted alkyl ether skeleton represented by the following formula (1) as a basic skeleton.

In the above formula (1), the halogen atom or the halogen atom as a substituent may be each element of fluorine, chlorine, bromine or iodine. The number of halogen atoms as a substituent may be 1 or more, and when 2 or more, each halogen atom may be the same or different. Further, the substitution position of the halogen atom may be any position.

In the above formula (1), as the C ₂ to C ₅ haloalkyl represented by A, 2-fluoroethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 2 -Bromoethyl, 2,2-difluoroethyl, 1,2-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2,2,2-three Chloroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 2-bromo-2-chloroethyl, 2-chloro-1,1,2,2-tetrafluoroethyl, 1 -chloro-1,2,2,2-tetrafluoroethyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 2-bromopropyl, 3-bromopropyl, 2-bromo- 1-methylethyl, 3-iodopropyl, 2,2,2-trifluoro-1-methylethyl, 2,3-dichloropropyl, 2,3-dibromopropyl, 3,3 , 3-trifluoropropyl, 3,3,3-trichloropropyl, 3-bromo-3,3-difluoropropyl, 3,3-dichloro-3-fluoropropyl, 2,2,3 , 3-tetrafluoropropyl, 1-bromo-3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 2,3-dichloro- 1,1,2,3,3-pentafluoropropyl, 2-chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 2-chloro-1,1-dimethylethyl, 4-bromo Butyl, 3-bromo-2-methylpropyl, 2-bromo-1,1-dimethylethyl, 2,2-dichloro-1,1-dimethylethyl, 2-chloro-1 -Chloromethyl-2-methylethyl, 4,4,4-trifluorobutyl, 3,3,3-trifluoro-1-methylpropyl, 3 ,3,3-trifluoro-2-methylpropyl, 2,3,4-trichlorobutyl, 2,2,2-trichloro-1,1-dimethylethyl, 4-chloro-4 , 4-difluorobutyl, 4,4-dichloro-4-fluorobutyl, 4-bromo-4,4 difluorobutyl, 2,4-dibromo-4,4-difluorobutyl, 3 ,4-Dichloro-3,4,4-trifluorobutyl, 3,3-dichloro-4,4,4-trifluorobutyl, 4-bromo-3,3,4,4tetrafluorobutyl 4-bromo-3-chloro-3,4,4-trifluorobutyl, 2,2,3,3,4,4-hexafluorobutyl, 2,2,3,4,4,4-six Fluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, nonafluorobutyl, 4 - Chlorine-1,1,2,2,3,3,4,4-octafluorobutyl, etc., suitably 2,2,2-trifluoroethyl.

In the above formula (1), examples of the C ₂ to C ₅ haloalkenyl group represented by A include a bromovinyl group, a vinyl chloride group, a 3,3-dichloro-2-propenyl group, and a 3,3,3 group. -trifluoro-1-propenyl, 4,4-difluoro-3-butenyl, 3,4,4-trifluoro-3-butenyl, etc., suitably 3,3,3-trifluoro -1-propenyl.

For (1), it is represented by A may be substituted with a C ₃ to C ₈ -cycloalkyl C ₁ to C ₄ alkyl C ₃ to C ₈ -cycloalkyl C ₁ to C ₄ alkyl portion of the formula , which may be cyclopropylmethyl, 1-cyclopropylethyl, 2-cyclopropylethyl, 1-cyclopropylpropyl, 2-cyclopropylpropyl, 3-cyclopropylpropyl, 1 -cyclopropylbutyl, 2-cyclopropylbutyl, 3-cyclopropylbutyl, 4-cyclopropylbutyl, cyclobutylmethyl, 1-cyclobutylethyl, 2-cyclobutylethyl And a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, and a cyclopropylmethyl group is preferable. The halogen atom as a substituent has the same definition as described above, and the C ₁ to C ₃ alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and a fluorine atom or a group is preferable. base.

In the above formula (1), n represents any one of 0 to 2. When n is 0, the oxygen atom (O) is not added to the sulfur atom (S), and when n is 1, the oxygen atom (O) is added to the sulfur atom (S) to form a sulfinyl group (S=O). ). Further, when n is 2, the oxygen atom (O) is added to the sulfur atom (S) to form a sulfonyl group. (O=S=O).

In the above formula (1), the halogen atom represented by X ¹ and X ² is the same as defined above, and the C ₁ to C ₆ alkyl moiety of the C ₁ to C ₆ alkyl group which may be substituted by a halogen atom is used. , which may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl, 3- A pentyl group, a tertiary pentyl group, a n-hexyl group, an isohexyl group, a 2-hexyl group, a 3-hexyl group and the like are preferable, and a methyl group is preferable.

In the above formula (1), the C ₁ to C ₆ alkoxy moiety of the C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom represented by X ¹ and X ² may, for example, be a methoxy group or a B group. The oxy group, the n-propoxy group, the isopropoxy group, the n-butoxy group, the isobutoxy group, the second-butoxy group, the tertiary-butoxy group and the like are preferably a methoxy group.

In the above formula (1), the C ₃ to C ₆ cycloalkyl group represented by X ¹ and X ² may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group. Propyl.

In the above formula (1), the aryl moiety of the halogen-substituted aryl group represented by X ¹ and X ² may, for example, be a phenyl group or a naphthyl group, and a phenyl group is suitably used.

In the above formula (1), the halogen atom represented by Y is the same as defined above, and a fluorine atom, a chlorine atom or a bromine atom is suitable, and a fluorine atom or a chlorine atom is preferable, and a fluorine atom is most suitable. The C ₁ to C ₆ alkyl moiety of the C ₁ to C ₆ alkyl group which may be substituted by a halogen atom may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group. Secondary butyl, tertiary butyl, pentyl, neopentyl, 2-pentyl, 3-pentyl, tertiary pentyl, hexyl, isohexyl, 2-hexyl, 3-hexyl, etc. methyl.

In the above formula (1), the C ₁ to C ₆ alkoxy moiety of the C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom represented by Y may be a methoxy group, an ethoxy group or a positive group. A propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a 2-butoxy group, a tertiary-butoxy group, etc. are preferable, and a methoxy group or an ethoxy group is preferable.

In the above formula (1), the substituents Y may be a halogen atom represented by C ₁ to C ₆ alkylthio C ₁ to C ₆ alkylthio moieties terms, may be cited methylthio, ethylthio, n The propylthio group, the isopropylthio group, the n-butylthio group, the isobutylthio group, the secondary butylthio group, and the tertiary butylthio group are preferably a methylthio group or an ethylthio group.

In the above formula (1), the C ₁ to C ₆ alkylsulfinyl moiety of the C ₁ to C ₆ alkylsulfinyl group which may be substituted by a halogen atom represented by Y may be a methyl group. Sulfonyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, secondary butylsulfin The base or tertiary butylsulfinyl group is preferably a methylsulfinyl group or an ethylsulfinyl group.

In the above formula (1), the C ₁ to C ₆ alkylsulfonyl moiety of the C ₁ to C ₆ alkylsulfonyl group which may be substituted by a halogen atom represented by Y may be a methylsulfonyl group. Ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, secondary butylsulfonyl, tert-butylsulfonyl More suitably, it may be a methylsulfonyl group or an ethylsulfonyl group.

In the above formula (1), the C ₁ to C ₆ alkylamino group represented by Y may, for example, be a methylamino group, an ethylamino group, a n-propylamino group, an isopropylamine group, a n-butylamino group or an isobutylamino group. The secondary butylamine group and the tertiary butylamine group are preferably a methylamino group or an ethylamine group.

In the above formula (1), the di-C ₁ to C ₆ alkylamino group represented by Y may, for example, be a dimethylamino group, a methylethylamino group, a diethylamino group, a di-n-propylamino group or a methyl group. A propylamino group, ethyl n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-second-butylamino group, di-tertiary butylamine group, preferably dimethylamino group Or diethylamine.

In the above formula (1), the C ₁ to C ₆ alkylcarbonyl group represented by Y may, for example, be an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a amyl fluorenyl group or a pivaloyl group. Etc. The number of carbon atoms of the alkylcarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1), the C ₁ to C ₆ alkoxycarbonyl group represented by Y may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group or a tertiary butyl group. As the oxycarbonyl group or the like, a methoxycarbonyl group or an ethoxycarbonyl group is preferable. The number of carbon atoms of the alkoxycarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1), the alkoxyimidomethyl group represented by Y may, for example, be a methoxyimino group, an ethoxyimino group, a n-propoxyimino group or an isopropyloxy group. A methoxyimine group is preferably a benzylenimino group, a n-butoxyimino group, a tertiary oxyiminoimine group or the like.

In the above formula (1), the aryl moiety of the halogen-substituted aryl group represented by Y may, for example, be a phenyl group or a naphthyl group, and a phenyl group is suitably used.

In the above formula (1), the aryloxy moiety of the substitutable aryloxy group represented by Y may, for example, be a phenoxy group or a naphthyloxy group, and a phenoxy group is preferable. The halogen atom as a substituent means the same definition as described above, and the C ₁ to C ₃ alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or the like, and a C ₁ to C ₃ haloalkane. The base may, for example, be difluoromethyl, trifluoromethyl or 2,2,2-trifluoroethyl, and the C ₁ to C ₃ alkoxy may be methoxy, ethoxy or n-propyl. Examples of the C ₁ to C ₃ haloalkoxy group include an oxy group, an isopropoxy group and the like, and a difluoromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, etc. _{The 1-} to C ₃ alkylthio group may, for example, be a methylthio group, an ethylthio group, a n-propylthio group or an isopropylthio group, and the C ₁ to C ₃ haloalkylthio group may be a difluoromethylthio group. A trifluoromethylthio group, a 2,2,2-trifluoroethylthio group or the like, and a C ₁ to C ₃ alkylsulfinyl group may be a methylsulfinyl group or an ethylsulfinyl group. a propylsulfinyl group, an isopropylsulfinyl group, etc., and a C ₁ to C ₃ haloalkylsulfinyl group may be a difluoromethylsulfinyl group or a trifluoromethylsulfinyl group. , 2,2,2-trifluoroethylsulfinyl, etc., as the C ₁ to C ₃ alkylsulfonyl group, a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group , sulfo acyl isopropyl, etc., C ₁ Halo C ₃ alkylsulfonyl group may be cited terms sulfo acyl difluoromethyl, trifluoromethyl sulfonic acyl, acyl sulfonamide 2,2,2-trifluoroethyl, etc., a C ₁ to C ₃ alkyl The carbonyl group may, for example, be an ethyl carbonyl group or a propyl fluorenyl group. The C ₁ to C ₃ alkoxycarbonyl group may, for example, be a methoxycarbonyl group or an ethoxycarbonyl group, and a fluorine atom or a trifluoromethyl group is preferable.

In the above formula (1), the arylthio group of the substitutable arylthio group represented by Y may, for example, be a phenylthio group or a naphthylthio group, and a phenylthio group is suitably used. a halogen atom as a substituent, a C ₁ to C ₃ alkyl group, a C ₁ to C ₃ haloalkyl group, a C ₁ to C ₃ alkoxy group, a C ₁ to C ₃ haloalkoxy group, a C ₁ to C ₃ alkane Sulfur, C ₁ to C ₃ haloalkylthio, C ₁ to C ₃ alkylsulfinyl, C ₁ to C ₃ haloalkylsulfinyl, C ₁ to C ₃ alkylsulfonyl, C _{The 1} to C ₃ haloalkylsulfonyl group, the C ₁ to C ₃ alkylcarbonyl group, and the C ₁ to C ₃ alkoxycarbonyl group mean the same definition as above, and a fluorine atom or a trifluoromethyl group is preferable.

In the above formula (1), the arylsulfinyl moiety of the substitutable arylsulfinyl group represented by Y may, for example, be a phenylsulfinyl group or a naphthylsulfinyl group. More suitably, a phenylsulfinyl group can be mentioned. a halogen atom as a substituent, a C ₁ to C ₃ alkyl group, a C ₁ to C ₃ haloalkyl group, a C ₁ to C ₃ alkoxy group, a C ₁ to C ₃ haloalkoxy group, a C ₁ to C ₃ alkane a thiol group, a C ₁ to C ₃ haloalkylthio group, a C ₁ to C ₃ alkylsulfinyl group, a C ₁ to C ₃ haloalkylsulfinyl group, a C ₁ to C ₃ alkylsulfonyl group, The C ₁ to C ₃ haloalkylsulfonyl group, the C ₁ to C ₃ alkylcarbonyl group, and the C ₁ to C ₃ alkoxycarbonyl group have the same definitions as described above, and a fluorine atom or a trifluoromethyl group is preferable.

In the above formula (1), the arylsulfonyl moiety of the substitutable arylsulfonyl group represented by Y may, for example, be a phenylsulfonyl group or a naphthylsulfonyl group. A phenylsulfonyl group can be mentioned.

a halogen atom as a substituent, a C ₁ to C ₃ alkyl group, a C ₁ to C ₃ haloalkyl group, a C ₁ to C ₃ alkoxy group, a C ₁ to C ₃ haloalkoxy group, a C ₁ to C ₃ alkane Sulfur, C ₁ to C ₃ haloalkylthio, C ₁ to C ₃ alkylsulfinyl, C ₁ to C ₃ haloalkylsulfinyl, C ₁ to C ₃ alkylsulfonyl, C _{The 1} to C ₃ haloalkylsulfonyl group, the C ₁ to C ₃ alkylcarbonyl group, and the C ₁ to C ₃ alkoxycarbonyl group have the same definitions as described above, and a fluorine atom or a trifluoromethyl group is preferable.

In the above formula (1), the C ₇ to C ₁₁ aralkyloxy moiety of the C ₇ to C ₁₁ aralkyloxy group which may be substituted by a halogen atom represented by Y may be a benzyloxy group or a benzene group. An ethoxy group or the like is preferably a benzyloxy group.

In the above formula (1), m represents any one of 1 to 5. When m is 1, Y is added to any one of the five carbon atoms (C) constituting the phenyl group. Further, when m is 2 to 4, Y is added to the aforementioned carbon atom (C) On any two or three, four carbon atoms, when m is 5, Y is added to all of the aforementioned carbon atoms (C).

In the above combination of Y and m, Y is a fluorine atom, m is 3, and a fluorine atom is preferably added to the 3, 4, and 5 positions of the phenyl group.

In the above formula (1), the halogen atom represented by R ¹ and R ² is the same as defined above, and the C ₁ to C ₆ alkyl moiety of the C ₁ to C ₆ alkyl group which may be substituted by a halogen atom is used. , which may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl, 3- A pentyl group, a tertiary pentyl group, a n-hexyl group, an isohexyl group, a 2-hexyl group, a 3-hexyl group and the like are preferable, and a methyl group or an ethyl group is preferable.

In the above formula (1), the C ₁ to C ₄ alkoxy moiety of the C ₁ to C ₄ alkoxy group which may be substituted by a halogen atom represented by R ¹ and R ² may be a methoxy group or a The oxy group, the n-propoxy group, the isopropoxy group, the n-butoxy group, the isobutoxy group, the second-butoxy group, the tertiary-butoxy group and the like are preferably a methoxy group.

In the above formula (1), the C ₃ to C ₆ cycloalkyl group represented by R ¹ and R ² may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group. Propyl.

In the above formula (1), the alkylcarbonyloxy group represented by R ¹ and R ² may, for example, be an ethoxycarbonyl group, a propenyloxy group, a butoxy group, an isobutyloxy group or a trimethyl group. The methoxy group and the like are preferably an ethoxy group. The number of carbon atoms of the alkylcarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1), p represents any one of 1 to 5. When p is from 1 to 5, each represents a methylene chain, an extended ethyl chain, a propyl chain, a butyl chain, and a benzylidene chain. Further, when p represents an integer of 2 to 5, R ¹ and R ² on different carbon atoms may be the same or different. Further, R ¹ and R ² on the same carbon atom may be bonded to one oxygen atom or sulfur atom, respectively, to represent (=O) or (=S). Further, R ¹ and R ² on the same carbon atom may be bonded at the same time to represent a C ₁ to C ₄ alkoxyimine group, and a methoxyimino group or the like may be mentioned. Further, R ¹ and R ² on the same carbon atom may be bonded to each other to form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring in 2 to 5 alkylene groups.

In the above formula (1), Z represents an oxygen atom, a sulfur atom, a sulfinium group or a sulfonyl group, and preferably an oxygen atom.

In the above formula (1), q represents an integer of 0 or 1. However, p and q cannot be 1 at the same time. When q is 0, Z is not contained in the formula (1), and when q is 1, there is any atomic addition of the above Z.

The N-substituted aniline compound of the present invention is a substituted phenoxyalkyl-substituted aniline skeleton represented by the following formula (1-6) as a basic skeleton.

In the above formula (1-6), the halogen atom or the halogen atom as a substituent may be each element of fluorine, chlorine, bromine or iodine. The number of halogen atoms as a substituent may be 1 or more, and when 2 or more, each halogen atom may be the same or different. Further, the substitution position of the halogen atom may be at any position.

In the above formula (1-6), as the C ₂ to C ₅ haloalkyl represented by A ¹⁰⁰ , 2-fluoroethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl Base, 2-bromoethyl, 2,2-difluoroethyl, 1,2-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2,2, 2-trichloroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 2-bromo-2-chloroethyl, 2-chloro-1,1,2,2-tetrafluoroethyl Base, 1-chloro-1,2,2,2-tetrafluoroethyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 2-bromopropyl, 3-bromopropyl, 2 -bromo-1-methylethyl, 3-iodopropyl, 2,2,2-trifluoro-1-methylethyl, 2,3-dichloropropyl, 2,3-dibromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 3-bromo-3,3-difluoropropyl, 3,3-dichloro-3-fluoropropyl, 2, 2,3,3-tetrafluoropropyl, 1-bromo-3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 2,3- Dichloro-1,1,2,3,3-pentafluoropropyl, 2-chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 2-chloro-1,1-dimethylethyl, 4-bromobutyl, 3-bromo-2-methylpropyl, 2-bromo-1,1-dimethylethyl, 2,2-dichloro-1,1-dimethylethyl, 2- Chloro-1-chloromethyl-2-methylethyl, 4,4,4-trifluorobutyl, 3,3,3-trifluoro-1-methylpropane ,3,3,3-trifluoro-2-methylpropyl, 2,3,4-trichlorobutyl, 2,2,2-trichloro-1,1-dimethylethyl, 4-chloro -4,4-difluorobutyl, 4,4-dichloro-4-fluorobutyl, 4-bromo-4,4-difluorobutyl, 2,4-dibromo-4,4-difluorobutyl , 3,4-dichloro-3,4,4-trifluorobutyl, 3,3-dichloro-4,4,4-trifluorobutyl, 4-bromo-3,3,4,4- Tetrafluorobutyl, 4-bromo-3-chloro-3,4,4-trifluorobutyl, 2,2,3,3,4,4-hexafluorobutyl, 2,2,3,4,4 , 4-hexafluorobutyl, 2,2,3,3,4,4,4 heptafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, nonafluorobutene The base is 4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl, etc., and 2,2,2-trifluoroethyl is preferable.

In the above formula (1-6), the C ₃ to C ₆ cycloalkyl C ₁ to C ₃ alkyl group represented by A ¹⁰⁰ may, for example, be a cyclopropylmethyl group or a 1-cyclopropylethyl group. -cyclopropylethyl, 1-cyclopropylpropyl, 2-cyclopropylpropyl, 3-cyclopropylpropyl, cyclobutylmethyl, 1-cyclobutylethyl, 2-cyclobutylethyl And a cyclopentylmethyl group and a cyclohexylmethyl group are preferably a cyclopropylmethyl group.

In the above formula (1-6), n represents any one of 0 to 2. When n is 0, the oxygen atom (O) is not added to the sulfur atom (S), and when n is 1, the oxygen atom (O) is added to the sulfur atom (S) to form a sulfinyl group (S = O). Further, when n is 2, the oxygen atom (O) is added to the sulfur atom (S) to form a sulfonyl group (O = S = O).

In the above formula (1-6), the halogen atom represented by X ¹⁰¹ and X ¹⁰² represents the same definition as defined above, and the C ₁ to C ₆ alkyl moiety of the C ₁ to C ₆ alkyl group which may be substituted with a halogen atom. In other words, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl, 3 - a pentyl group, a tertiary pentyl group, a n-hexyl group, an isohexyl group, a 2-hexyl group, a 3-hexyl group or the like, and a methyl group is suitably used.

In the above formula (1-6), the C ₁ to C ₆ alkoxy moiety of the C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom represented by X ¹⁰¹ and X ¹⁰² may be a methoxy group. And an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a 2-butoxy group, a tertiary-butoxy group, etc., and a methoxy group is preferable.

In the above formula (1-6), the halogen atom represented by Y ¹⁰⁰ represents the same definition as described above, and the C ₁ to C ₆ alkyl moiety of the C ₁ to C ₆ alkyl group which may be substituted by a halogen atom may be used. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl, 3-pentyl And a tertiary pentyl group, an n-hexyl group, an isohexyl group, a 2-hexyl group, a 3-hexyl group, etc., and a methyl group is suitable.

In the above formula (1-6), the C ₁ to C ₆ alkoxy moiety of the C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom represented by Y ¹⁰⁰ may, for example, be a methoxy group or an ethoxy group. A methoxy group or an ethoxy group is preferable, and a methoxy group or an ethoxy group is suitable, for example, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a 2-butoxy group, and a tertiary-butoxy group.

In the above formula (1-6), in terms of Y atom ¹⁰⁰ may be represented by a halogen-substituted C ₁ to C ₆ alkylthio C ₁ to C ₆ alkylthio moieties can be cited methylthio, ethylthio The base, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, secondary butylthio group, and tertiary butylthio group are preferably a methylthio group or an ethylthio group.

In the above formula (1-6), the C ₁ to C ₆ alkylsulfinyl moiety of the C ₁ to C ₆ alkylsulfinyl group which may be substituted with a halogen atom represented by Y ¹⁰⁰ may be mentioned. Methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, secondary butyl The sulfinyl group and the tertiary butyl sulfinylene group are preferably a methylsulfinyl group or an ethylsulfinyl group.

In the above formula (1-6), the C ₁ to C ₆ alkylsulfonyl moiety of the C ₁ to C ₆ alkylsulfonyl group which may be substituted by a halogen atom represented by Y ¹⁰⁰ may be a methyl group. Sulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, tert-butylsulfonyl, tert-butyl The sulfonyl group is preferably a methylsulfonyl group or an ethylsulfonyl group.

In the above formula (1-6), the C ₁ to C ₆ alkylcarbonyl group represented by Y ¹⁰⁰ may, for example, be an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a pentyl group or a trimethyl ethenyl group. Etc.

The number of carbon atoms of the alkylcarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₁ to C ₆ alkoxycarbonyl group represented by Y ¹⁰⁰ may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group or a n-butoxycarbonyl group. And a tertiary butyloxycarbonyl group or the like is preferably a methoxycarbonyl group or an ethoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₁ to C ₆ alkoxyiminomethyl group represented by Y ¹⁰⁰ may, for example, be a methoxyiminomethyl group or an ethoxyiminomethyl group. , n-propoxyiminomethyl, isopropoxyiminomethyl, n-butoxyiminomethyl, tert-butoxyiminomethyl, suitably methoxy Aminomethyl.

In the above formula (1-6), v represents any one of 1 to 4. When v is 1, Y ^{100 is} added to any one of the six carbon atoms (C) constituting the phenyl group. Further, when v is 2 to 4, Y ^{100 is} added to any two, three or four carbon atoms of the carbon atom (C).

In the above formula (1-6), the halogen atom represented by R ^101a and R ^102a represents the same definition as defined above, and the C ₁ to C ₆ alkyl moiety of the C ₁ to C ₆ alkyl group which may be substituted with a halogen atom. In other words, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl, 3 a pentyl group, a tertiary pentyl group, a n-hexyl group, an isohexyl group, a 2-hexyl group, a 3-hexyl group and the like, and a methyl group or an ethyl group is preferable.

In the above formula (1-6), the C ₁ to C ₄ alkoxy moiety of the C ₁ to C ₄ alkoxy group which may be substituted by a halogen atom represented by R ^101a and R ^102a may be a methoxy group. And an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a 2-butoxy group, a tertiary-butoxy group, etc., and a methoxy group is preferable. Further, R ^101a and R ^102a on the same carbon atom may be bonded to one oxygen atom or sulfur atom individually and expressed as (=O) or (=S). Further, R ^101a and R ^102a on the same carbon atom may be bonded at the same time to represent a C ₁ to C ₄ alkoxyimine group, and a methoxyimino group or the like may be mentioned. Further, R ^101a and R ^102a on the same carbon atom may be bonded to each other to form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring in 2 to 5 alkylene groups.

In the above formula (1-6), the halogen atom represented by R ^101b and R ^102b represents the same definition as defined above, and the C ₁ to C ₆ alkyl moiety of the C ₁ to C ₆ alkyl group which may be substituted with a halogen atom. In other words, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl, 3 a pentyl group, a tertiary pentyl group, a n-hexyl group, an isohexyl group, a 2-hexyl group, a 3-hexyl group and the like, and a methyl group or an ethyl group is preferable.

In the above formula (1-6), the C ₁ to C ₄ alkoxy moiety of the C ₁ to C ₄ alkoxy group which may be substituted by a halogen atom represented by R ^101b and R ^102b may be a methoxy group. And an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a 2-butoxy group, a tertiary-butoxy group, etc., and a methoxy group is preferable.

In the above formula (1-6), u represents an integer of 0 or 1.

In the above formula (1-6), the C ₂ to C ₆ alkenyl moiety of the C ₂ to C ₆ alkenyl group which may be substituted with a halogen atom represented by W ¹ may, for example, be a vinyl group or a 1-propenyl group. 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2 -pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl And 3-hexenyl, 4-hexenyl, 5-hexenyl and the like, and a 2-propenyl group is preferable.

In the above formula (1-6), the C ₂ to C ₆ alkynyl moiety of the C ₂ to C ₆ alkynyl group which may be substituted by a halogen atom represented by W ¹ may, for example, be an ethynyl group or a 1-propynyl group. , propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 1- Pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl-3-pentynyl, 1-hexynyl, 1,1-dimethyl-2-butynyl and the like are preferably a propargyl group.

In the above formula (1-6), the C ₃ to C ₆ cycloalkyl group represented by W ¹ may, for example, be a cyclopropyl group, a 1-methylcyclopropyl group or a 2-methylcyclopropyl group. A 2-dimethylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or the like is preferably a cyclopropyl group.

In the above formula (1-6), the C ₃ to C ₆ cycloalkyl C ₁ to C ₃ alkyl group represented by W ¹ may, for example, be a cyclopropylmethyl group or a 1-cyclopropylethyl group. - cyclopropylethyl, 1-cyclopropylpropyl, 2-cyclopropylpropyl, 3-cyclopropylpropyl, 1-cyclopropylbutyl, 2-cyclopropylbutyl, 3-ring Propyl butyl, 4-cyclopropyl butyl, cyclobutylmethyl, 1-cyclobutylethyl, 2-cyclobutylethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, A cyclooctylmethyl group is preferably a cyclopropylmethyl group.

In the above formula (1-6), the C ₁ to C ₆ alkylcarbonyl moiety of the C ₁ to C ₆ alkylcarbonyl group which may be substituted by a halogen atom represented by W ¹ may, for example, be an ethylidene group or a propyl group. The butyl group, the isobutyl group, the amyl group, the trimethyl ethoxy group and the like are preferably acetyl. The number of carbon atoms of the alkylcarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₂ to C ₆ olefinic carbonyl moiety of the C ₂ to C ₆ olefincarbonyl group which may be substituted by a halogen atom represented by W ¹ may, for example, be an acryloyl group or a methacryl group. A mercapto group or the like is preferable. The number of carbon atoms of the olefinic carbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₂ to C ₆ alkynyl group of the C ₂ to C ₆ alkynyl group which may be substituted by a halogen atom represented by W ¹ may, for example, be proparginyl or methyl propyl. As the alkynyl group, etc., a propynyl group is preferable. The number of carbon atoms of the alkynyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₃ to C ₆ cycloalkylcarbonyl moiety of the C ₃ to C ₆ cycloalkanecarbonyl group which may be substituted by a halogen atom represented by W ¹ may, for example, be a cyclopropanecarbonyl group or a 1- A methylcyclopropanecarbonyl group, a 2-methylcyclopropanecarbonyl group, a 2,2-dimethylcyclopropanecarbonyl group, a cyclobutanecarbonyl group, a cyclopentanecarbonyl group, a cyclohexanecarbonyl group or the like is preferably a cyclopropanecarbonyl group. The number of carbon atoms of the cycloalkylcarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), W is a C ₃ to C ₆ -cycloalkyl C ¹ represented by a halogen atom may be substituted with a C ₃ to C ₆ cycloalkyl, a C ₁ to C ₃ alkylcarbonyl group, _a C ₃ to The alkylcarbonyl moiety may, for example, be cyclopropaneethyl, cyclopropanepropenyl, 2-cyclopropaneethyl, 1-methylcyclopropaneethyl, 2-methylcyclopropane, 2, The 2-dimethylcyclopropaneacetinyl group, the cyclobutaneacetinyl group, the cyclopentaneethenyl group, the cyclohexaneethenyl group, and the like are preferably a cyclopropaneethyl group. The number of carbon atoms of the cycloalkylalkylcarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₁ to C ₆ alkoxycarbonyl moiety of the C ₁ to G ₆ alkoxycarbonyl group which may be substituted by a halogen atom represented by W ¹ may, for example, be a methoxycarbonyl group or an ethoxy group. Carbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, di-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, neopentyloxycarbonyl, 2-pentyloxycarbonyl, A 3-pentoxycarbonyl group or the like is preferably a tertiary butoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₂ to C ₆ alkoxycarbonyl moiety of the C ₂ to C ₆ alkoxycarbonyl group which may be substituted by a halogen atom represented by W ¹ may, for example, be an ethyleneoxycarbonyl group or a 1- A propyleneoxycarbonyl group, a 2-propenyloxycarbonyl group, a 1-buteneoxycarbonyl group, a 2-butoxycarbonyl group, a 3-buteneoxycarbonyl group or the like is preferably an ethyleneoxycarbonyl group. The number of carbon atoms of the oxycarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₂ to C ₆ alkynyloxycarbonyl moiety of the C ₂ to C ₆ alkynyloxycarbonyl group which may be substituted with a halogen atom represented by W ¹ may, for example, be acetyleneoxycarbonyl, 1- Propynyloxycarbonyl, propargyloxycarbonyl, 1-butynyloxycarbonyl, 2-butynyloxycarbonyl, 3-butynyloxycarbonyl, 1-methyl-2-propynyloxycarbonyl, 2-methyl A 3-propynyloxycarbonyl group or the like is preferably a propargyloxycarbonyl group. The number of carbon atoms of the alkynyloxycarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), in terms of W ¹ may be substituted with a halogen atom represented by a C ₃ to C ₆ cycloalkyl oxycarbonyl moiety C ₃ to C ₆ cycloalkyl oxycarbonyl group, may be cited cyclopropyloxy Oxycarbonyl, 1-methylcyclopropoxycarbonyl, 2-methylcyclopropoxycarbonyl, 2,2-dimethylcyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, etc. Suitably, a cyclopropoxycarbonyl group can be mentioned. The number of carbon atoms of the cycloalkyloxycarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), it is represented by W ¹ is a halogen atom may be substituted with a C ₃ to C ₆ cycloalkyl, a C ₁ to C ₃ alkyl oxycarbonyl group, C ₃ to C ₆ cycloalkyl, a C ₁ to The C ₃ alkyloxycarbonyl moiety may, for example, be cyclopropylmethyloxycarbonyl, 1-methylcyclopropylmethyloxycarbonyl, 2-methylcyclopropylmethyloxycarbonyl or 2,2-dimethyl The cyclopropylmethyloxycarbonyl group, the cyclobutylmethyloxycarbonyl group, the cyclopentylmethyloxycarbonyl group, the cyclohexylmethyloxycarbonyl group and the like are preferably a cyclopropylmethyloxycarbonyl group. The number of carbon atoms of the cycloalkylalkyloxycarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₁ to C ₆ alkylamine carbonyl moiety of the C ₁ to C ₆ alkylamine carbonyl group which may be substituted by a halogen atom represented by W ¹ may, for example, be a methylamine carbonyl or ethylamine. A carbonyl group, a n-propylamine carbonyl group, an isopropylamine carbonyl group, a n-butylamine carbonyl group, an isobutylamine carbonyl group, a secondary butylamine carbonyl group, a tertiary butylamine carbonyl group, a n-pentylamine carbonyl group or the like is preferably a methylamine carbonyl group. The number of carbon atoms of the alkylamine carbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), as the di C ₁ to C ₆ alkylamine carbonyl moiety of the di C ₁ to C ₆ alkylamine carbonyl group which may be substituted by a halogen atom represented by W ¹ , a dimethylamine carbonyl group may be mentioned. , methyl ethylamine carbonyl, diethylamine carbonyl, di-n-propylamine carbonyl, methyl n-propylamine carbonyl, ethyl n-propylamine carbonyl, diisopropylamine carbonyl, di-n-butylamine carbonyl, diisobutylamine carbonyl, di- or secondary A dimethylamine carbonyl group, a di-tertiary butylamine carbonyl group or the like is preferable. The number of carbon atoms of the dialkylamine carbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₃ to C ₆ cycloalkylamine carbonyl moiety of the C ₃ to C ₆ cycloalkylamine carbonyl group which may be substituted with a halogen atom represented by W ¹ may, for example, be a cyclopropylamine carbonyl group, 1-methylcyclopropylaminecarbonyl, 2-methylcyclopropylaminecarbonyl, 2,2-dimethylcyclopropylaminecarbonyl, cyclobutylaminecarbonyl, cyclopentylaminecarbonyl, cyclohexylaminecarbonyl, etc., suitably cyclopropylaminecarbonyl . The number of carbon atoms of the cycloalkylamine carbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), W is a C ₃ to C ₆ cycloalkyl C may be represented by a halogen atom, ^a substituted C ₃ to C ₆ cycloalkyl C ₁ to C ₃ alkyl aminocarbonyl C ₁ to C _{The 3} -alkylamine carbonyl moiety may, for example, be cyclopropylmethylaminecarbonyl, 1-methylcyclopropylmethylaminecarbonyl, 2-methylcyclopropylmethylaminecarbonyl, 2,2-dimethylcyclopropylmethyl The amine carbonyl group, the cyclobutylmethylamine carbonyl group, the cyclopentylmethylamine carbonyl group, the cyclohexylmethylamine carbonyl group and the like are preferably a cyclopropylmethylamine carbonyl group. The number of carbon atoms of the cycloalkylalkylamine carbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₁ to C ₆ alkylsulfonyl moiety of the C ₁ to C ₆ alkylsulfonyl group which may be substituted by a halogen atom represented by W ¹ may be methanesulfonate. Sulfhydryl, ethanesulfonyl, n-propanesulfonyl, isopropanesulfonyl, n-butanesulfonyl, isobutanesulfonyl, 2-butanesulfonyl, tert-butanesulfonyl , n-pentanesulfonyl group, etc., more suitable may be methanesulfonyl.

In the above formula (1-6), in terms of W ¹ may be substituted with a halogen atom represented by a C ₃ to C ₆ cycloalkyl alkylsulfonyl moiety cycloalkyl C ₃ to C ₆ alkylsulfonyl group, can be cited Cyclopropanesulfonyl, 1-methylcyclopropanesulfonyl, 2-methylcyclopropanesulfonyl, 2,2-dimethylpropanesulfonyl, cyclobutanesulfonyl, cyclopentanesulfonate A cyclopropanesulfonyl group or the like is preferably a cyclopropanesulfonyl group.

In the above formula (1-6), W is a C ₃ to C ₆ -cycloalkyl C ¹ represented by a halogen atom may be substituted with a C ₃ to C ₆ cycloalkyl, a C ₁ to C ₃ alkylsulfonyl group ₁ The C ₃ alkylsulfonyl moiety may, for example, be cyclopropylmethylsulfonyl, 1-methylcyclopropylmethylsulfonyl, 2-methylcyclopropylmethylsulfonyl, 2 , 2-dimethylcyclopropylmethylsulfonyl, cyclobutylmethylsulfonyl, cyclopentylmethylsulfonyl, cyclohexylmethylsulfonyl, etc., suitably cyclopropylmethylsulfonate醯基.

In the above formula (1-6), the C ₁ to C ₆ alkylaminosulfonyl moiety of the C ₁ to C ₆ alkylaminosulfonyl group which may be substituted with a halogen atom represented by W ¹ may be mentioned. Methylaminosulfonyl, ethylaminosulfonyl, n-propylaminosulfonyl, isopropylaminosulfonyl, n-butylaminosulfonyl, isobutylaminosulfonyl, secondary butylaminesulfonate The mercapto group, the tertiary butylaminosulfonyl group, the n-pentylaminosulfonyl group and the like are preferably a methylaminosulfonyl group.

In the above formula (1-6), the di-C ₁ to C ₆ alkylaminosulfonyl moiety of the di-C ₁ to C ₆ alkylaminosulfonyl group which may be substituted with a halogen atom represented by W ¹ , A dimethylaminosulfonyl group, a methylethylaminosulfonyl group, a diethylaminosulfonyl group, a di-n-propylaminosulfonyl group, a methyl n-propylaminosulfonyl group, an ethyl n-propylaminosulfonate Mercapto, diisopropylaminosulfonyl, di-n-butylaminosulfonyl, diisobutylaminosulfonyl, di- or 2-butylaminosulfonyl, di-tertiary butylaminosulfonyl Etc., a suitable dimethylaminosulfonyl group can be mentioned.

In the above formula (1-6), the aryl moiety of the halogen-substituted aryl group represented by W ¹ may, for example, be a phenyl group, a 1-naphthyl group or a 2-naphthyl group. Phenyl.

In the above formula (1-6), the arylcarbonyl moiety of the halogen atom-substituted aromatic carbonyl group represented by W ¹ may, for example, be a benzamidine group, a 1-naphthylmethyl group or a 2-naphthylmethyl group. More suitable is benzyl sulfhydryl.

In the above formula (1-6), the aryloxycarbonyl moiety of the halogen atom-substituted aryloxycarbonyl group represented by W ¹ may, for example, be a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group or a 2-naphthyloxycarbonyl group. More suitable is phenoxycarbonyl.

In the above formula (1-6), the arylamine carbonyl moiety of the arylamine carbonyl group which may be substituted with a halogen atom represented by W ¹ may, for example, be an aniline carbonyl group, a 1-naphthylamine carbonyl group or a 2-naphthylamine carbonyl group. More suitable is aniline carbonyl.

In the above formula (1-6), the arylsulfonyl moiety of the substitutable arylsulfonyl group represented by W ¹ may, for example, be a phenylsulfonyl group, a 1-naphthalenesulfonyl group, or a 2- A naphthosulfonyl group or the like is preferably a phenylsulfonyl group. The halogen atom as a substituent means the same definition as above, and the C ₁ to C ₃ alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and a chlorine atom or a methyl group is preferable. .

In the above formula (1-6), the C ₁ to C ₆ alkyl moiety of the C ₁ to C ₆ alkyl group which may be substituted by a halogen atom represented by W ² may, for example, be a methyl group, an ethyl group or a n-propyl group. Base, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl, 3-pentyl, tertiary pentyl, n-hexyl, An isohexyl group, a 2-hexyl group, a 3-hexyl group or the like is preferably a methyl group.

In the above formula (1-6), the C ₂ to C ₆ alkenyl moiety of the C ₂ to C ₆ alkenyl group which may be substituted by a halogen atom represented by W ² may, for example, be a vinyl group or a 1-propenyl group. 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2 -pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl And 3-hexenyl, 4-hexenyl, 5-hexenyl and the like, and a 2-propenyl group is preferable.

In the above formula (1-6), the C ₂ to C ₆ alkynyl moiety of the C ₂ to C ₆ alkynyl group which may be substituted by a halogen atom represented by W ² may, for example, be an ethynyl group or a 1-propynyl group. , propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 1-pentynyl , 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl-3-pentynyl, 1-hexynyl, 1,1- A dimethyl-2-butynyl group or the like is preferably a propargyl group.

In the above formula (1-6), the C ₃ to C ₆ cycloalkyl group represented by W ² may, for example, be a cyclopropyl group, a 1-methylcyclopropyl group or a 2-methylcyclopropyl group. A 2-dimethylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or the like is preferably a cyclopropyl group.

In the above formula (1-6), the C ₁ to C ₆ alkoxy C ₁ to C ₃ alkyl group represented by W ² may, for example, be methoxymethyl, ethoxymethyl or n-propoxymethyl. And methoxyethyl, etc., suitably methoxymethyl.

In the above formula (1-6), the C ₁ to C ₆ alkylcarbonyl moiety of the C ₁ to C ₆ alkylcarbonyl group which may be substituted by a halogen atom represented by W ² may, for example, be an ethylidene group or a propyl group. The butyl group, the isobutyl group, the amyl group, the trimethyl ethoxy group and the like are preferably acetyl. The number of carbon atoms of the alkylcarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₁ to C ₆ alkoxycarbonyl moiety of the C ₁ to C ₆ alkoxycarbonyl group which may be substituted by a halogen atom represented by W ² may, for example, be a methoxycarbonyl group or an ethoxy group. Carbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, di-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, neopentyloxycarbonyl, 2-pentyloxycarbonyl, A 3-pentoxycarbonyl group or the like is preferably a tertiary butoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group represented by the above C is the number of carbon atoms of the carbon atom from which the carbonyl group is removed.

In the above formula (1-6), the C ₁ to C ₆ alkylsulfonyl moiety of the C ₁ to C ₆ alkylsulfonyl group which may be substituted by a halogen atom represented by W ² may be methanesulfonate. Sulfhydryl, ethanesulfonyl, n-propanesulfonyl, isopropanesulfonyl, n-butanesulfonyl, isobutanesulfonyl, 2-butanesulfonyl, tert-butanesulfonyl , n-pentanesulfonyl group, etc., more suitable may be methanesulfonyl.

In the above formula (1-6), the arylcarbonyl moiety of the halogen atom-substituted arylcarbonyl group represented by W ² may, for example, be a benzamidine group, a 1-naphthylmethyl group or a 2-naphthylmethyl group. More suitable is benzyl sulfhydryl.

In the above formula (1-6), the arylsulfonyl moiety of the substitutable arylsulfonyl group represented by W ² may, for example, be a phenylsulfonyl group, a 1-naphthalenesulfonyl group, or a 2- A naphthosulfonyl group or the like is preferably a phenylsulfonyl group. The halogen atom as a substituent means the same definition as above, and the C ₁ to C ₃ alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and a chlorine atom or a methyl group is preferable. .

Next, in the first to eighth examples, the examples of the substituted phenyl ether compound represented by the formula (1) are shown, and the phenol compound represented by the formula (2) is shown in the ninth table, but it is not Limited to these compounds. Further, the compounds include optical isomers and compounds containing an E body and a Z body. The compound code is referred to in the following description.

Further, in the examples of the N-substituted aniline compound represented by the formula (1-6), the examples of the aniline compound represented by the formula (3) are shown in Table 12, but the invention is not limited. In these compounds. Further, the compounds include optical isomers and compounds containing an E body and a Z body. The compound code is referred to in the following description.

Furthermore, the following symbols in the table are as follows, which respectively indicate the corresponding bases.

"Me" means methyl, "Et" means ethyl, "Pr" means propyl, "n-Pr" means n-propyl, "i-Pr" means isopropyl, "Bu" means butyl, "n" -Bu" means n-butyl, "Pen" means pentyl, "n-Pn" means n-pentyl, "Hex" means hexyl, "n-Hex" means n-hexyl, "Hep" means heptyl, "s- Bu" means secondary butyl, "i-Bu" means isobutyl, "t-Bu" means tertiary butyl, "c-Pr" means cyclopropyl, "c-Bu" means cyclobutyl, " c-Pen" means cyclopentyl, "neo-Pen" means neopentyl, "c-Hex" means cyclohexyl, "c-Hep" means cycloheptyl, "THF" means tetrahydrofuranyl, "THP" means four. Hydropyridyl group, "Ph" means a phenyl group, "Bn" means a benzyl group, "Ac" means an ethyl group, and "Bz" means a benzinyl group. Further, "H" represents a hydrogen atom. "On TLC" and "under TLC" indicate isomers.

The first table is a specific example of the formula (1) in which q is 0 and p is 1, and the second table is a specific example of the formula (1) in which q is 0 and p is 2, and the third table indicates that q is 0. P is a specific example of the formula (1) of 3, and the fourth table is a specific example of the formula (1) in which q is 0 and p is 4, and the fifth table is a formula (1) in which q is 0 and p is 5. In the specific example, the sixth table is a specific example of the formula (1) in which q is 1, and p is 2, and the seventh table is a specific example of the formula (1) in which q is 1, and p is 3, and the eighth table is This is a specific example of the formula (1) in which q is 1, and p is 4, and the ninth table is a specific example of the formula (2). ^{R 1a, R 1b, R 1c} , R 1d, R 1e represents a particular extension on the alkyl chain substitution position of ^{R 1, R 2a, R 2b} , R 2c, R 2d, R 2e represents a particular extension on the alkyl chain Replace the position of R ² .

The tenth table is a specific example of the formula (1-6) in which u is 0, the eleventh table is a specific example of the formula (1-6) in which u is 1, and the twelfth table is a specific example showing the formula (3). .

In the column "Ym" of the tables, for example, 3-F indicates a fluorine atom substitution at the 3-position of the phenyl group, and 3,4,5-F ₃ indicates a position at the 3, 4, and 5 positions of the phenyl group. Each of the three, a total of three fluorine atoms are substituted, and 2-F-4-Cl means that a fluorine atom is present at the 2-position of the phenyl group, and a chlorine atom is substituted at the 4-position.

Among the compounds represented by the formula (1), a compound represented by the following formula (1-1) is preferred, and a particularly preferred illustrative example is a compound represented by the following formula (1-2).

(In the formula (1-1), n represents an integer of 0 or 1, X ² represents a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and R ^1a and R ^2a each independently represent a fluorine atom, a hydroxyl group, and B. a group, an isopropyl group, an isobutyl group, a methoxy group, an ethoxy group. Further, R ^1a and R ^2a may be bonded to a nitrogen atom to form a methoxyimino group (=NOMe), or may be bonded to each other. Form a 3-member ring, a 5-member ring)

In the formula (1-2), n represents an integer of 0 or 1, and X ² represents a fluorine atom or a chlorine atom.

The compound of the present invention represented by the above formula (1) can be produced according to the production method shown below, but is not limited to these methods.

(In the above formula, A, X ¹ , X ² , Y, R ¹ , R ² , Z, m, p, q are the same meanings as the substituted phenyl ether compound represented by the above formula (1), n means 1 or 2)

The compound of the formula (1c) of the present invention can be produced, for example, by reacting a compound represented by the above formula (1b) with an oxidizing agent.

For the oxidizing agent used in the reaction, for example, hydrogen peroxide, m-chloroperoxybenzoic acid, sodium periodate, OXONE (registered trademark, manufactured by EI DuPont; trade name; potassium hydrogen peroxodisulfate), N -chloroammonium imine, N-bromosuccinimide, tertiary butyl hypochlorite, sodium hypochlorite, oxygen, and the like. The ideal is m-chloroperoxybenzoic acid, hydrogen peroxide, and the like.

The solvent used in the reaction, for example, diethyl ether, tetrahydrogen Ethers such as furan and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N- Aprotic polar solvents such as methyl-2-pyrrolidone and sulfolane; alcohols such as methanol, ethanol, and isopropanol; dichloromethane, chloroform, 1,2-dichloroethane, etc. Halogenated hydrocarbons; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and cycloheptane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid, water, or a mixed solvent thereof. Ideally, dichloromethane, chloroform, water, and the like.

(In the above formula, L represents a leaving group such as a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group or an arylsulfonyloxy group, and A, X ¹ , X ² , Y, R ¹ , R ² , Z, m, p, q are the same meanings as described above, and n represents any integer from 0 to 2)

The compound represented by the formula (1) of the present invention can be, for example, a compound represented by the above formula (2a) and a compound represented by the above formula (4) in the presence of a base, optionally in the presence of a catalyst. Manufactured by the next reaction.

The raw material represented by the above formula (4) is known as a case, and can be obtained by Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., Ltd., and the like. Alternatively, it may be easily produced by a known method described in Experimental Chemistry Lecture, Organic Syntheses, or the like.

The base used in the reaction may, for example, be potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine or diisopropylethylamine. , pyridine and other bases. Ideally, potassium carbonate, triethylamine, potassium hydroxide, sodium hydroxide, and the like.

For the catalyst used in the reaction, for example, tetrabutylammonium bromide or tetrabutylammonium chloride or the like.

The solvent used in the reaction, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, cyclobutyl hydrazine; dichloromethane, chloroform, 1,2-dichloroethane A halogenated hydrocarbon such as an alkane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; water or a mixed solvent thereof. Desirable is N,N-dimethylformamide, dichloromethane or a mixture of water and an organic solvent.

(In the above formula, A, X ¹ , X ² , Y, R ¹ , R ² , Z, m, p, q have the same meanings as described above)

The compound of the formula (1) of the present invention can be, for example, according to Bulletin of the Chemical Society of Japan, 1967, P.936, Bulletin of the Chemical Society of Japan, 1967, P. 2380, etc. In the method described, the compound represented by the above formula (2a) and the compound represented by the above formula (5) are produced by a light-draft reaction.

The raw material represented by the above formula (5) is known as a case, and can be obtained by Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., Ltd., and the like. Alternatively, it may be easily produced by a known method described in Experimental Chemistry Lecture, Organic Syntheses, or the like.

The phosphorus compound used in the present reaction may, for example, be triphenylphosphine, tri-n-butylphosphine, tri-tertiary butylphosphine or phenoxydiphenylphosphine. Desirable are triphenylphosphine, phenoxydiphenylphosphine and the like.

The azodicarboxylate used in the present reaction may, for example, be diethyl azodicarboxylate or diisopropyl azodicarboxylate. It is preferably diethyl azodicarboxylate or the like.

The solvent used in the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; dichloromethane, chloroform, 1,2-dichloroethane A halogenated hydrocarbon such as an alkane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; or a mixed solvent thereof. The ideal is tetrahydrofuran and the like.

(In the above formula, X ³ represents a halogen atom, and A, X ¹ , Y, Z, R ¹ , R ² , Z, n, m, p, q have the same meanings as described above)

The compound represented by the formula (1e) of the present invention can be produced, for example, by reacting a compound represented by the above formula (1d) with a halogenating agent.

The halogenating agent used in the present reaction may, for example, be chlorine, bromine, iodine, N-chloroammonium imine, N-bromosinium imine, N-iodosuccinimide, sulfuryl chloride. ), thionyl chloride, and the like. The ideal is chlorine, bromine, iodine, thiopurine and the like.

The solvent used in the reaction is, for example, a halogenated hydrocarbon such as dichloromethane, chloroform or 1,2-dichloroethane or a mixed solvent thereof. The ideal is dichloromethane or the like.

(In the above formula, PG represents a protecting group such as an alkylcarbonyl group, a halocarbonyl group, an arylcarbonyl group or an alkoxycarbonyl group, and X ¹ , X ² and L have the same meanings as defined above)

The starting material represented by the above formula (6) is a known compound and can be obtained from Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., Ltd., and the like.

The production intermediate represented by the above formula (8) can be reacted in the presence of a base by reacting the compound represented by the above formula (6) with the compound represented by the above formula (7) in the above reaction process 5-1. And manufacturing.

For the base used in the above reaction process 5-1, for example, Potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, pyridine, and the like. The ideal is triethylamine and the like.

The solvent used in the above reaction process 5-1, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; dichloromethane, chloroform, 1, 2 a halogenated hydrocarbon such as dichloroethane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; water or a mixed solvent thereof. The ideal is dichloromethane or the like.

The production intermediate represented by the above formula (9) can be produced by reacting the compound represented by the above formula (8) obtained in the above Reaction Process 5-1 with chlorosulfonic acid, as in the above-mentioned reaction process 5-2. Further, the production intermediate represented by the above formula (9) can be reacted with fuming sulfuric acid by the compound represented by the above formula (8) obtained in the above reaction process 5-1, in the presence of a base and five Manufactured by the reaction of phosphorus oxide.

For the base used in the above reaction process 5-2, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, pyridine Wait. The ideal is potassium carbonate and the like.

The production intermediate represented by the above formula (10), such as the above-mentioned reaction process 5-3, can be obtained by using the compound represented by the above formula (9) obtained by the above reaction process 5-2, and a metal and an acid, lithium aluminum hydride. It is produced by reduction of red phosphorus, iodine and acid.

For the metal used in the above reaction process 5-3, for example, zinc, tin, iron, nickel, or the like. The ideal is zinc, tin, and the like.

For the acid used in the above reaction process 5-3, for example, Hydrochloric acid, sulfuric acid, acetic acid, and the like. Ideally, hydrochloric acid, acetic acid, and the like.

The production intermediate represented by the above formula (11) can be produced by hydrolyzing with an acid or a base by using the compound represented by the above formula (10) obtained by the above reaction process 5-3, as in the above reaction process 5-4. .

The acid used in the above reaction process 5-4 is, for example, hydrochloric acid, sulfuric acid, acetic acid or the like. Ideally, hydrochloric acid, acetic acid, and the like.

The base used in the above reaction process 5-4 is, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, diisopropylethylamine, pyridine or the like. The ideal is sodium hydroxide, potassium hydroxide, and the like.

(In the above formula, A, L, X ¹ and X ^{2 have the} same meanings as described above)

The compound represented by the formula (2b) of the present invention can be, for example, the production intermediate represented by the above formula (11) obtained by the above reaction process 5 and the compound represented by the above formula (12) in the presence of a base. It is produced by reacting in the presence or absence of Rongalite (trade name of BASF Corporation; sodium hydroxymethanesulfinate dihydrate). Moreover, it is also possible to manufacture by reacting in the presence of a catalyst.

The raw material represented by the above formula (12) is known as the case, and can be obtained by Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., Ltd., and the like. Alternatively, the reagents that can be obtained can be easily produced by a known method described in Experimental Chemistry Lecture, Organic Syntheses, and the like.

The amount of the raw material represented by the formula (12) used herein may be appropriately selected from the range of 1 to 5 moles per mole of the compound 1 represented by the formula (11), and is preferably 1.0 to 2.0 moles. ear.

For the base used in the reaction, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, pyridine, sodium hydroxide, Potassium hydroxide and the like. The ideal is potassium carbonate and the like.

The amount of the base to be used herein may be appropriately selected from the range of 0 to 5 moles per mole of the compound 1 represented by the formula (11), and is preferably 0 to 2.0 moles.

For the catalyst used in the reaction, for example, tetrabutylammonium bromide or tetrabutylammonium chloride or the like.

The solvent used in the reaction is, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N , aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, cyclobutyl hydrazine; dichloromethane, chloroform, 1,2-dichloro A halogenated hydrocarbon such as ethane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; water or a mixed solvent thereof. It is preferably N,N-dimethylformamide, a mixture of water and an organic solvent, and the like.

The amount of the solvent to be used may be appropriately selected from the range of 0.1 to 100 liters per mole of the compound 1 represented by the formula (11), and is preferably 1.0 to 5.0 liters.

The reaction temperature may be selected from any range of from -30 ° C to the reflux temperature of the reaction system, and is preferably in the range of from 0 ° C to 150 ° C.

The reaction time varies depending on the reaction temperature, the reaction substrate, the amount of the reaction, etc., and is preferably in the range of 10 minutes to 20 hours.

(In the above formula, A, X ¹ and X ^{2 have the} same meanings as described above, and n represents 1 or 2)

The compound of the formula (2c) of the present invention can be produced, for example, by reacting a compound represented by the above formula (2b) with an oxidizing agent.

For the oxidizing agent used in the present reaction, for example, hydrogen peroxide, m-chloroperoxybenzoic acid, sodium periodate, OXONE (registered trademark, manufactured by EI DuPont Co., Ltd.; trade name; potassium hydrogen peroxodisulfate), N -chloroammonium imine, N-bromosuccinimide, tertiary butyl hypochlorite, sodium hypochlorite, oxygen, and the like. The ideal is m-chloroperic acid, hydrogen peroxide, and the like.

The amount of the oxidizing agent to be used herein may be appropriately selected from the range of 1.0 to 6.0 mol per mol of the compound 1 represented by the formula (2b), and is preferably 1.0 to 2.0 mol.

The solvent used in the reaction, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone and cyclobutyl hydrazine; alcohols such as methanol, ethanol and isopropanol; dichloromethane, chloroform, 1 ,2-dichloroethane Halogenated hydrocarbons; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, cycloheptane; ketones such as acetone, methyl ethyl ketone, cyclohexanone; acetic acid, water, or a mixed solvent thereof . Ideally, dichloromethane, chloroform, water, methanol, ethanol, and the like.

The amount of the solvent to be used may be appropriately selected from the range of 0.1 to 100 liters per mole of the compound 1 represented by the formula (2b), and is preferably 1.0 to 5.0 liters.

The reaction temperature may be selected from any range of from -30 ° C to the reflux temperature of the reaction system, and is preferably in the range of -10 ° C to 50 ° C.

The reaction time varies depending on the reaction temperature, the reaction substrate, the amount of the reaction, etc., and is preferably in the range of 10 minutes to 20 hours.

Further, the compound of the present invention represented by the above formula (1-6) can be produced according to the production method shown below, but is not limited to these methods.

(In the above formula, A ¹⁰⁰ , X ¹⁰¹ , X ¹⁰² , Y ¹⁰⁰ , R ^101a , R ^102a , R ^101b , R ^102b , W ¹ , W ² , v, u represent the formula (1-6) N-substituted aniline compounds have the same meaning, n means 1 or 2)

The compound of the formula (1-6b) of the present invention is, for example, by contacting the compound represented by the above formula (1-6a) with an oxidizing agent, if necessary Manufactured in response to the presence of the medium.

For the oxidizing agent used in the present reaction, for example, hydrogen peroxide, m-chloroperoxybenzoic acid, sodium periodate, OXONE (registered trademark, manufactured by EI DuPont; potassium hydrogen peroxodisulfate), N-chloroamber Yttrium, N-bromosuccinimide, butyl tertiary hypochlorite, sodium hypochlorite, oxygen, and the like. The ideal is m-chloroperoxybenzoic acid, hydrogen peroxide, and the like.

The catalyst used in the reaction is, for example, molybdenum oxide, boric acid, tris(acetonitrile) iron or the like. The ideal is molybdenum oxide or the like.

The solvent used in the reaction, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone and cyclobutyl hydrazine; alcohols such as methanol, ethanol and isopropanol; dichloromethane, chloroform, 1 a halogenated hydrocarbon such as 2-dichloroethane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; a ketone such as acetone, methyl ethyl ketone or cyclohexanone; acetic acid, water, Or such a mixed solvent or the like. Ideally, dichloromethane, chloroform, water, and the like.

(In the above formula, L ¹⁰⁰ represents a leaving group such as a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, or the like, A ¹⁰⁰ , X ¹⁰¹ , X ¹⁰² , Y ¹⁰⁰ R ^101a , R ^102a , R ^101b , R ^102b , W ¹ , W ² , v, u represent the same meaning as described above, and n represents any integer from 0 to 2)

The compound of the formula (1-6) of the present invention can be touched, for example, by the compound represented by the above formula (13) and the compound represented by the above formula (14) in the presence of a base, if necessary. Manufactured in response to the presence of the medium.

The raw material represented by the above formula (14) is known as a case, and a commercially available product can be used. Alternatively, it may be easily produced by a known method described in Experimental Chemistry Lecture, Organic Syntheses, or the like.

The base used in the reaction may, for example, be potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, lithium hydride, sodium amide, triethylamine or diisopropylate. A base such as ethylamine or pyridine. Ideally, potassium carbonate, triethylamine, potassium hydroxide, sodium hydroxide, and the like.

For the catalyst used in the reaction, for example, tetrabutylammonium bromide or tetrabutylammonium chloride or the like.

The solvent used in the reaction is, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N , aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, cyclobutyl hydrazine; dichloromethane, chloroform, 1,2-dichloro Halogenated hydrocarbons such as ethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and cycloheptane; water or a mixed solvent thereof. Desirably, N,N-dimethylformamide, dichloromethane, or a mixture of water and an organic solvent, and the like.

(In the above formula, A ¹⁰⁰ , X ¹⁰¹ , X ¹⁰² , Y ¹⁰⁰ , R ^101a , R ^102a , R ^101b , R ^102b , W ¹ , W ² , n, v, u represent the same meaning as described above)

The compound of the formula (1-6) of the present invention can be, for example, as described in Bulletin of the Chemical Society of Japan, 1967, P. 936, Bulletin of the Chemical Society of Japan, 1967, P. 2380, and the like. The method is carried out by subjecting a compound represented by the above formula (13) to a compound represented by the above formula (15) by a light-relay reaction.

The raw material represented by the above formula (15) is known as a case, and a commercially available product can be used. Alternatively, it may be easily produced by a known method described in Experimental Chemistry Lecture, Organic Syntheses, or the like.

The phosphorus compound used in the present reaction may, for example, be triphenylphosphine, tri-n-butylphosphine, tri-tertiary butylphosphine or phenoxydiphenylphosphine. Desirable are triphenylphosphine, phenoxydiphenylphosphine and the like.

The azodicarboxylate used in the present reaction may, for example, be diethyl azodicarboxylate or diisopropyl azodicarboxylate. It is preferably diethyl azodicarboxylate or the like.

The solvent used in the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; dichloromethane, chloroform, 1,2-dichloroethane Halogenated hydrocarbons such as alkanes; An aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane, or a mixed solvent thereof. The ideal is tetrahydrofuran and the like.

(In the above formula, X ¹⁰³ represents a halogen atom, and A ¹⁰⁰ , X ¹⁰¹ , Y ¹⁰⁰ , R ^101a , R ^102a , R ^101b , R ^102b , W ¹ , W ² , n, v, u represent the same meaning as described above)

The compound represented by the formula (1-6d) of the present invention can be produced, for example, by reacting a compound represented by the above formula (1-6c) with a halogenating agent, if necessary, in the presence of a catalyst.

For the halogenating agent used in the present reaction, for example, chlorine, bromine, iodine, N-chloroammonium imine, N-bromosinium imine, N-iodosuccinimide, thiopurine, sulfoxide Wait. The ideal is chlorine, bromine, iodine, thiopurine and the like.

The catalyst used in the present reaction may, for example, be aluminum chloride or phenyl sulfide. The ideal is aluminum chloride or the like.

The solvent used in the reaction is, for example, a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane or carbon tetrachloride, acetic acid, or a mixed solvent thereof. The ideal is dichloromethane or the like.

(In the above formula, PG ¹⁰⁰ represents a protecting group such as an alkylcarbonyl group, a halocarbonyl group, an arylcarbonyl group or an alkoxycarbonyl group, and X ¹⁰¹ , X ¹⁰² and L ^{100 have the} same meanings as defined above)

The starting material represented by the above formula (16) is a known compound, and a commercially available product can be used.

The production intermediate represented by the above formula (18), such as the above-mentioned reaction process 12-1, can be obtained by reacting a compound represented by the above formula (16) with a compound represented by the above formula (17) in the presence of a base. Manufacturing.

For the base used in the above reaction process 12-1, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, and Isopropylethylamine, pyridine, and the like. Ideally, it is sodium hydroxide, potassium hydroxide, triethylamine, and the like.

The solvent used in the above reaction process 12-1, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; dichloromethane, chloroform, 1, 2 a halogenated hydrocarbon such as dichloroethane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; water or a mixed solvent thereof. It is preferably dichloromethane, or a mixture of water and an organic solvent.

a manufacturing intermediate represented by the above formula (19), as described above The process 12-2 can be produced by reacting the compound represented by the above formula (18) obtained in the above reaction process 12-1 with chlorosulfonic acid. Further, the production intermediate represented by the above formula (19) can be produced by reacting a compound represented by the above formula (18) with fuming sulfuric acid and then reacting with phosphorus pentoxide in the presence of a base.

For the base used in the above reaction process 12-2, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, pyridine, etc. . The ideal is potassium carbonate and the like.

The production intermediate represented by the above formula (20), such as the above-mentioned reaction process 12-3, can be obtained by using the compound represented by the above formula (19) obtained by the above reaction process 12-2, and a metal and an acid, lithium aluminum hydride. It is produced by reduction of red phosphorus, iodine and acid.

For the metal used in the above reaction process 12-3, for example, zinc, tin, iron, nickel, or the like. The ideal is zinc, tin, and the like.

For the acid used in the above reaction process 12-3, for example, hydrochloric acid, sulfuric acid, acetic acid or the like. Ideally, hydrochloric acid, acetic acid, and the like.

The production intermediate represented by the above formula (21), as in the above-mentioned reaction process 12-4, can be produced by hydrolyzing with an acid or a base using the compound represented by the above formula (20) obtained by the above reaction process 12-3. .

For the acid used in the above reaction process 12-4, for example, hydrochloric acid, sulfuric acid, acetic acid or the like. Ideally, hydrochloric acid, acetic acid, and the like.

The base used in the above reaction process 12-4 is, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, diisopropylethylamine, pyridine or the like. The ideal is sodium hydroxide, potassium hydroxide, and the like.

(In the above formula, A ¹⁰⁰ , L ¹⁰⁰ , X ¹⁰¹ , and X ^{102 have the} same meanings as described above)

The compound represented by the above formula (23) can be, for example, the production intermediate represented by the above formula (21) obtained by the above reaction process 12 and the compound represented by the above formula (22) in the presence of a base and Manufactured in the presence or absence of Rongalite (manufactured by BASF Corporation; sodium hydroxymethanesulfinate dihydrate). Moreover, it is also possible to manufacture by reacting in the presence of a catalyst.

The raw material represented by the above formula (22) is known as a case, and a commercially available product can be used. Alternatively, it may be easily produced by a known method described in Experimental Chemistry Lecture, Organic Syntheses, or the like.

For the base used in the reaction, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, pyridine, sodium hydroxide, Potassium hydroxide and the like. The ideal is potassium carbonate and the like.

For the catalyst used in the reaction, for example, tetrabutylammonium bromide or tetrabutylammonium chloride or the like.

The solvent used in the reaction, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N, Aprotic polar solution such as N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, cyclobutazone a halogenated hydrocarbon such as dichloromethane, chloroform or 1,2-dichloroethane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; water or a mixed solvent thereof. It is preferably N,N-dimethylformamide, a mixture of water and an organic solvent, and the like.

(In the above formula, A ¹⁰⁰ , X ¹⁰¹ , and X ^{102 have the} same meaning as described above, and n represents 1 or 2)

The compound represented by the above formula (24) can be produced, for example, by reacting a compound represented by the above formula (23) and an oxidizing agent in the presence of a catalyst as necessary.

For the oxidizing agent used in the reaction, for example, hydrogen peroxide, m-chloroperoxybenzoic acid, sodium periodate, OXONE (registered trademark, manufactured by EI DuPont; potassium hydrogen peroxodisulfate), N-chloroamber Yttrium, N-bromosuccinimide, butyl tertiary hypochlorite, sodium hypochlorite, oxygen, and the like. The ideal is m-chloroperoxybenzoic acid, hydrogen peroxide, and the like.

The catalyst used in the reaction is, for example, molybdenum oxide, boric acid, tris(acetonitrile) iron or the like. The ideal is molybdenum oxide or the like.

The solvent used in the reaction, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N, N-dimethylacetamide, N- Aprotic polar solvents such as methyl-2-pyrrolidone and cyclobutyl hydrazine; alcohols such as methanol, ethanol and isopropanol; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane An aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; a ketone such as acetone, methyl ethyl ketone or cyclohexanone; acetic acid, water or a mixed solvent thereof. Ideally, dichloromethane, chloroform, water, methanol, ethanol, and the like.

(In the above formula, Y ¹⁰⁰ , W ³ , W ⁴ , R ¹⁰³ and v represent the same meaning as described above)

The compound of the formula (27) of the present invention can be produced, for example, by a Fenton reaction of the compound represented by the above formula (25) according to the method described in Tetrahedron, 2011, p. 2323 or the like.

The raw materials represented by the above formulas (25) and (26) are known as appropriate, and can be obtained by Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., Ltd., and the like. Alternatively, the reagents that can be obtained can be easily produced in accordance with a known method described in Experimental Chemistry Lecture, Organic Syntheses, and the like.

For the peroxide used in the present reaction, for example, hydrogen peroxide, hydrogen peroxide-urea complex, tertiary butyl peroxide, peracetic acid, and the like. The ideal is hydrogen peroxide or the like.

Catalyst used in the reaction, for example, iron (II) sulfate, sulfur Ammonium iron (II) ammonium, iron (II) tetrafluoroborate, iron (II) chloride, iron (II) bromide, iron (II) iodide, iron (II) acetate, iron (II) oxalate, double Acetylpyruvate) Iron (II), ferrocene, and the like. The ideal is ferrocene and the like.

The solvent used in the reaction, for example, an aprotic polar solvent such as dimethyl hydrazine, diethyl hydrazine, dipropylene arsenide, diisopropyl hydrazine, diphenyl hydrazine, methyl phenyl hydrazine, or the like Mixed solvent, etc. The ideal is dimethyl hydrazine and the like.

(In the above formula, Y ¹⁰⁰ , W ³ , W ⁴ , R ¹⁰³ and v represent the same meaning as described above)

The compound represented by the formula (28) of the present invention can be, for example, represented by the above formula (28) and the compound represented by the formula (26) according to the method described in Chemical and Pharmaceutical Bulletin, 1999, p. 1013 or the like. The compound is produced by coupling reaction in the presence of copper.

The raw material represented by the above formula (28) is known as a case, and can be obtained by Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., Ltd., and the like. Alternatively, it may be easily produced by a known method described in Experimental Chemistry Lecture, Organic Syntheses, or the like.

The solvent used in the reaction, for example, an aprotic polar solvent such as dimethyl hydrazine, diethyl hydrazine, dipropylene arsenide, diisopropyl hydrazine, diphenyl hydrazine, methyl phenyl hydrazine, or the like Mixed solvent, etc. The ideal is dimethyl hydrazine and the like.

(In the above formula, Y ¹⁰⁰ , W ³ , W ⁴ , and v mean the same meaning as described above)

The compound of the formula (29) of the present invention can be produced by reducing the compound represented by the above formula (27).

The reducing agent used in the present reaction is, for example, sodium borohydride, lithium aluminum hydride, diisobutylaluminum hydride or the like. The ideal is sodium borohydride or the like.

The solvent used in the reaction, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; an alcohol such as methanol, ethanol or isopropanol; Halogenated hydrocarbons such as chloroform or 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and cycloheptane; water, or a mixed solvent thereof. Ideally, tetrahydrofuran and the like.

(In the above formula, R ^104' represents a C ₁ to C ₄ alkylsulfonyl group which may be substituted with a halogen atom, or an arylsulfonyl group which may be substituted with a C ₁ to C ₄ alkyl group, Y ¹⁰⁰ , W ³ , W ⁴ , v, L ¹⁰⁰ represent the same meaning as described above)

The compound of the formula (31) of the present invention, for example, can be borrowed It is produced by reacting a compound represented by the above formula (29) with a compound represented by the above formula (30) in the presence of a base.

For the base used in the reaction, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, lithium hydride, sodium amide, triethylamine, diisopropyl A base such as an amine or a pyridine. The ideal is triethylamine and the like.

The solvent used in the reaction, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, cyclobutyl hydrazine; dichloromethane, chloroform, 1,2-dichloroethane A halogenated hydrocarbon such as an alkane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; water or a mixed solvent thereof. The ideal is dichloromethane or the like.

(In the above formula, W ^{3 '} and W ^{4 '} each independently represent a C ₁ to C ₆ alkylcarbonyl group which may be substituted with a halogen atom, a C ₁ to C ₆ alkoxycarbonyl group, or a C ₁ to C which may be substituted with a halogen atom. ₆ alkylsulfonyl, Y ¹⁰⁰ , v, G, L ¹⁰⁰ means the same meaning as described above)

The compound of the formula (34) of the present invention can be produced, for example, by reacting a compound represented by the above formula (32) with a compound represented by the above formula (33) in the presence of a base. Furthermore, the formula (36) of the present invention is shown. The compound can be produced, for example, by reacting a compound represented by the above formula (34) with a compound represented by the above formula (35) in the presence of a base.

For the base used in the reaction, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, lithium hydride, sodium amide, triethylamine, diisopropyl A base such as an amine or a pyridine. The ideal is triethylamine and the like.

The solvent used in the reaction, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; acetonitrile, N,N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, cyclobutyl hydrazine; dichloromethane, chloroform, 1,2-dichloroethane A halogenated hydrocarbon such as an alkane; an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or cycloheptane; water or a mixed solvent thereof. The ideal is dichloromethane or the like.

In any of the above reaction processes 1 to 19, the desired compound can be obtained by subjecting to usual work in organic synthesis such as extraction, drying, concentration, and purification after completion of the reaction.

Further, the structure of the intended compound can be identified by a known analytical means such as NMR spectroscopy.

Further, the substituted phenyl ether compound of the present invention is not limited by the above production method, and can be produced by any organic synthesis method.

Further, the compound of the present invention exhibits excellent control activity against a wide range of insects, mites, crustaceans, mollusks and nematodes. The compound of the present invention, in particular, exhibits excellent effects on insects and mites Control activity.

Among the compounds of the present invention, the compound represented by the above formula (1-1) is preferred because it exhibits very excellent control activity against guanidines. Further, the compound represented by the above formula (1-2) is particularly preferable because it has excellent residual property against the action of controlling the quinones after the dispersion. Further, the compound represented by the above formula (1-2) has excellent safety in oral administration test to mice. Specific examples of the organism in which the compound of the present invention exerts a control activity can be exemplified as follows.

For example, in the case of insects, Ctenolepisma villosa, Lepisma saccharina, Thermobia domestica, etc., Periplaneta americana, black brown home Periplaneta fuliginosa, Periplaneta japonica, Blattella germanica, Blattella lituricollis, etc., Incisitermes minor, Coptotermes formosanus, Reticulitermes speratus, Odontotermes formosanus, etc., Ruspolia lineosa, Teleogryllus emma, Gryllotalpa orientalis, East Asian migratory locust (Oriental genus) Locusta migratoria), Oxya yezoensis, etc., Trogium pulsatorium, Liposcelis bostrychophila, Liposcelis corrodens, etc., Malophaga (Lipeurus caponis), Menacantus stramineus, Damalinia bovis, Damalinia caprae, etc. The genus Haematopinus eurysternus, Haematopinus suis, Pediculus humanus capitis, Pediculus humanus humanus, Pthirus pubis, etc. Taiwan's Frankliniella intonsa, Frankliniella occidentalis, Heliothrips haemorrhoidalis, Mycterothrips glycines, Scirtothrips dorsalis, Indica (Stenchaetothrips biformis), Thrips palmi, Thrips tabaci, Haplothrips aculeatus, Ponticulothrips diospyrosi, and leaf mites of the genus Hemiptera (Arboridia apicalis), Empoasca onukii, Nephotettix cincticeps, Laodelphax striatella, Nilaparvata lugens, Sogatella furcifera, and green moth (Geisha distinctissima), Diaphorina citri, Viteus vitifoliae, Acyrthosiphon pisum, Aphis craccivora, Aphis (A Phissypii), Aphis pomi, Aphis spiraecola, Aulacorthum solani, Eriosoma lanigerum, Hyalopterus pruni, Lipaphis erysimi, Myzus persicae, Rhopalosiphum padi, Schizaphis graminum, Schizaphis piricola, Toxoptera aurantii, Toxoptera citricida, mandarin Aleurocanthus spiniferus, Bemisia argentifolii, Tobacco meal (Bemisia tabaci), Dialeurodes citri, Trialeurodes vaporariorum, Drosicha corpulenta, Icerya purchasi, and Platycladus orientalis Citri), Planococcus kraunhiae, Pseudococcus comstocki, Ceroplastes ceriferus, Ceroplastes rubens, Aonidiella aurantii ), Diaspidiotus perniciosus, Pseudaulacaspis pentagona, Unaspis yanonensis, Creontiades coloripes, Trigonotylus Caelestialium), Stephanitis nashi, Stephanitis pyrioides, Eysarcoris aeneus, Eysarcoris lewisi, Glaucias subpunctatus, black scorpion (Graphosoma rubrolineatum), Halyomorpha halys, Nezara antennata, rice green pupa (Southern green pheasant) (Nezara viridula), Plautia crossota stali, Caneerius saccharivorus, Togo hemipterus, Leptocorisa chinensis, Riptortus clavatus, rice Cletus punctiger, Rhopalus maculatus, Cimex lectularius, etc., Coleoptera, Anomala albopilosa, Anomala cuprea, Anomala rufocuprea, flower tortoise (Eucetonia pilifera), Gametis jucunda, Heptophylla picea, Popillia japonica, Agriotes ogurae fuscicollis, Ettinus sericeus sericeus, Melanotus fortnumi fortnumi, Anthrenus verbasci, Lasioderma serricorne, Otani Tenebroides mauritanicus), Epuraea domina, Epilachna varivestis, Henosepilachna vigintioctopunctata, Tenebrio molitor, Tribolium castaneum , Anoplophora malasiaca, Monochamus alternatus endai, Xylotrechus pyrrhoderus, Callosobruchus chinensis, Aulacophora femoralis, Cassida nebulosa , Chaetocnema concinna, Diabrotica virgifera virgifera, Diabrotica undecimpunctata howardi, Diabrotica spp., Leptinotarsa decemlineata, Oulema oryzae, Phyllotreta striolata, sweet potato ant (Cylas formicarius), Anthonomus grandis, Euscepes postfasciatus, Hypera postica, Listroderes costirostris, Echinocnemus bipunctatus, rice water Lisorhoplus oryzophilus, Sitophilus zeamais, Sphenophorus venatus vestitus, Tomicus piniperda, Lyctus brunneus, etc. Ceratophyllus gallinae Dog shit (Ctenocephalides Canis), Ctenocephalides felis, Echidnophaga gallinacea, Pulex irritans, Xenopsylla cheopis, etc., Asphondylia yushimai, Aedes Aegypti), Anopheles sinensis, Culex pipiens pallens, Culex quinquefasciatus, Culex tritaeniorhynchus, Bactrocera cucurbitae, Oriental fruit fly (Bactrocera) Dorsalis), Agromyza oryzae, Chromatomyia horticola, Liriomyza huidobrensis, Liriomyza sativae, Liriomyza trifolii, onion Fly (Delia antiqua), Delia platura, Musca domestica, Stomoxys calcitrans, etc., Adoxophyes honmai, Adoxophyes orana fasciata, chaos Archips fuscocupreanus, Cydia pomonella, Gramholita molesta, and Homona magnanima Leguminivora glycinivorella, Pandemis heparana, Tinea translucens, Lyonetia clerkella, Lyonetia prunifoliella malinella, Caloptilia theivora, gold grain Phyllonycter ringoniella, Phyllocnistis citrella, Plutella xylostella, Nokona regalis, Synanthedon hector, Stimpmooda masinissa ), Helcystogramma triannulelum, Pectinophora gossypiella, Carposina sasakii, Chilo suppressalis, Cnaphalocrocis medinalis, Conogethes Punctiferalis), Hellula undalis, Ostrinia furnacalis, Ostrinia nubilalis, Etiella zinckenella, Papilio xuthus, and Pieris rapae crucivora , Farnara guttata guttata, Ascotis selenaria, Arna pseudoconspersa, Lymantria dispar, Hyphantria cunea, Agrotis ipsilon, yellow Agrotis segetum, Autographa nigrisigna, Helicoverpa armigera, Heliothis spp., Mamestra brassicae, armyworm (Mythimna separata), Indica (Naranga aenescens), Spodoptera exigua, Spodoptera litura, etc. Gana), Athalia rosae ruficornis, Dryocosmus kuriphilus, Vespa simillima xanthoptera, Formica japonica, Monomorium pharaonis, red fire ant Solenopsis invicta) and so on.

In the case of apes, Varroa jacobsoni, Dermanyssus gallinae, Ornithonyssus bacoti, Ornithonyssus sylviarum, Amblyomma spp., Australia Boophilus microplus, leather Dermacentor spp., Haemaphysalis flava, Haemaphysalis campanulata, Haemaphysalis longicornis, Ixodes ovatus, Ixodes persulcatus , Rhipicephalus sanguineus, Penthaleus erythrocephalus, Penthaleus major, Phytonemus pallidus, Polyphagotarsonemus latus, Double-leaf scorpion Rs (Tarsonemus bilobatus), Demodex canis, Demodex cati, Oligonychus shinkajii, Panonychus citri, Panonychus mori , Panonychus ulmi, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus urticae, Acaphylla theavagrans, tulip rust (Aceria tulipae), Aculops lycopersici, Aculops pelekassi, Aculus schlechtendali, Calacarus cari Natus), Epitrimerus pyri, Eriophyes chibaensis, Phyllocoptruta oleivora, Rhizoglyphus robini, Tyrophagus putrescentiae, Tyrophagus similis, Knemidokoptes spp., Psoroptes ovis, Notoedres cati, Sarcoptes scabiei, Leptotrombidium akamushi, Cheyletiella blakei, Cheyletiella yasguri, Dermatophagoides farinae, red-backed widow (Latrodectus hasselti) and so on.

In the case of crustaceans, the acidous band Oxidus gracilis of Polydesmida, the Armadolidium vulgare of Isopoda, and the American crayfish of Decapoda (Procambarus) Clarkii), etc., Bourletiella hortensis, etc.

In the case of mollusks, the genus Pomacea canaliculata of Mesogastropoda, the Astratina fulica, the Meghimatium bilineatum, and the Valencian lynx (Stylommatophora). Lehmannina valentiana), snail (Acusta despecta sieboldiana), etc.

In the case of nematodes, Tylenchida's Notch nymphs (Nothotylenchus acris), Meloidogyne incognita, Globodera rostochiensis, and Heterodera glycines, Tylenchulus semipenetrans, Pratylenchus coffeae, Pratylenchus penetrans, Pratylenchus yamagutii, Aphelenchus avenae, Aphelenchoides besseyi , pine wood nematode (Bursaphelenchus xylophilus) and so on.

Others, in the case of animal internal parasites, such as aphids, aphids, etc., filamentous insects, liver flukes, lung flukes, Yokohama, Schistosoma japonicum, hookworms, no hookworms, Aphid (Echinococcus), broad-mouthed mites, etc.

The compound of the present invention can be used as an active ingredient of a pest control agent for agricultural and horticultural use. In addition, the formulation, the guidelines for the preparation of pesticide formulations (edited: Japan Institute of Pesticide Application Law Research, Issue: Association of Japanese Plant Epidemic Prevention, 1997) appropriate carrier, surfactant, fluidity improver, bonding Agents, tackifiers, preservatives, etc.

Further, at the time of formulation, an adjuvant may be formulated.

The agricultural and horticultural pest control agent containing the compound of the present invention can be prepared into any dosage form which is generally used as a pest control agent for agricultural and horticultural pest control.

For example, it can be formulated into a powder, a coarse powder, a DL (driftless type) powder, a flow dust, a microparticle, a fine granule, a granule, a wettable powder, and a wettable granule. A dosage form generally used for a powder, a liquid preparation, a sol (flowable agent), an emulsion, and an oil agent, but is not limited thereto.

For example, in the case of a solid carrier, a mineral powder (kaolin, bentonite, clay, montmorillonite, talc, vermiculite, gypsum, diatomaceous earth, clay, calcium carbonate, white carbon, cerium, ammonium sulfate, Urea, etc.), plant matter powder (crystalline cellulose, etc.), polymer compound (petroleum resin, etc.), alumina, citrate, sugar polymer, and the like.

Further, as the liquid carrier, water, alcohols (methanol, ethanol, n-propanol, ethylene glycol, glycerin, etc.), ethers (diethyl ether, tetrahydrofuran, 1,4-dioxane, 赛路苏) (cellosolve), etc., ketones (methyl ethyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, fatty acid glycerides, etc.), Nitriles, hydrazines (dimethyl hydrazine, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (kerosene, kerosene, cyclohexane) Etc.), aromatic hydrocarbons (benzene, toluene, xylene, solvent naphtha, methyl naphthalene, etc.), petroleum fractions, and the like.

Further, at the time of formulation, the surfactant may be formulated for the purpose of emulsifying, dispersing, solubilizing, wetting, foaming, lubricating, expanding, spreading, disintegrating, and the like. As such a surfactant, a nonionic surfactant (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylphenyl ether, polyoxyethylene aryl phenyl ether, Polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, polyoxyethylene alkylene glycol, polyoxyethylene-polyoxypropylene block polymer, etc.), anionic surfactant (alkyl benzene) Sulfonate, alkylnaphthalene sulfonate, lignosulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, polyoxyalkylene alkyl ether Phosphate ester, polyoxyethylene alkyl ether phosphate salt, polycarboxylate, etc.), cationic surfactant (laurylamine, stearyl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, etc.) Alkylamines, polyoxyethylene alkylamines, etc., and amphoteric surfactants (dialkylaminoethylbetaine, alkyldimethylbenzylbetaine, etc.) are of course not limited to those exemplified Compound.

Further, the fluidity improver may, for example, be isopropyl phosphate or calcium stearate. As the binder, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, carboxymethyl starch, dextrin, polytriglucose can be exemplified. (pullulan), sodium alginate, mannan, pectin, gum tragacanth, mannitol, sorbitol, propylene glycol alginate, guar gum, locust bean gum, Raber gum, Sanxian gum, gelatin, casein, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, ethylene/propylene block polymer, sodium polyacrylate, polyethylene Pyrrolidone, calcium lignosulfonate, and the like. In terms of tackifiers, guar gum, sanxian gum, gum tragacanth, casein, dextrin, colloidal aqueous aluminum citrate, colloidal aqueous magnesium citrate, colloidal aqueous aluminum magnesium citrate, Carboxymethyl cellulose, polyvinyl alcohol and water-soluble cellulose ether. Examples of the preservative include sodium benzylate, potassium sorbate, p-chloro-xylenol, butyl-hydroxybenzylate, and 1,2-benzisothiazolin-3-one.

The content of the compound of the present invention can be appropriately selected depending on the dosage form of the preparation and the method of use. A generally desirable content is in the range of 0.0001 to 90% by weight relative to the total amount of the formulation.

For example, in the case of a powder, it is usually from 0.01 to 50% by weight, preferably from 0.05 to 20% by weight, based on the total amount of the preparation, and in the case of a wettable powder, it is usually from 0.01 to 90% by weight, preferably from 0.01 to 90% by weight, based on the total amount of the preparation. It is 0.1 to 60% by weight, and in the case of an emulsion, it is usually 0.01 to 80% by weight, preferably 0.1 to 70% by weight, based on the total amount of the preparation, and in the case of a flowable agent, usually 0.01 to 60 with respect to the entire amount of the preparation. The weight %, desirably 0.1 to 50% by weight, and in the case of granules, is usually in the range of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the total amount of the preparation.

When the compound of the present invention is used as a pest control agent for agricultural and horticultural use, it may be combined with a fungicide (a fungicide, a bactericide, an antiviral agent, a plant resistance inducer) at the time of preparation or dispersion as necessary. ), Insecticide, acaricide, nematicide, herbicide, bird repellent, growth regulator, fertilizer, soil conditioner, etc., one or more optional ingredients are selected to be a mixed preparation, or mixed in a medicine tank when dispersed Apply in combination.

Among the above-mentioned arbitrary components, the following examples of the bactericide, the insecticide, the acaricide, and the nematicide are shown, but are not limited thereto. Fungicide:

(1) Copper agent

Copper oxychloride, copper sulfate, copper hydroxide, copper sulfate, oxine-copper, and arsenite Copper nonylphenol sulfonate), DBEDC, etc.

(2) Inorganic fungicides

Sulfur, calcium polysulfide, sodium hydrogen carbonate, potassium hydrogen carbonate, silver, and the like.

(3) Organic sulfur fungicide

Ziram, maneb, mancozeb, ambam, polycarbamate, propineb, thiuram ), thiadiazin, zineb, etc.

(4) Organic phosphorus fungicide

IBP, EDDP, tolclofos-methyl, pyrazophos, fosetyl-aluminium, and the like.

(5) Benzimidazole-based fungicide

Carbendazim, thiabendazole, thiophanate-methyl, benomyl, etc.

(6) Dicarboximide fungicide

Iprodione, procymidone, vinclozolin, etc.

(7) Carboxamide is a fungicide

Oxycarboxin, carboxin, mepronil, fluolanil, boscalid, floopyram, furametpyr, race Thifluzamide, penthiopyrad, bixafen, penflufen, fluxapyroxad, isopyrazam, off Tolfenpyrad, sedaxane, and the like.

(8) phenyl guanamine bactericide

Metalaxyl, metalaxyl-M, oxadixyl, furaxaxyl, ofurace, benalaxyl, 右本达乐Benalaxyl-M) et al.

(9) Carboxylic acid amide fungicide

Dimethomorph, flumorph, iprovalicarb, benthiavalicarb-isopropyl, mandipropamid, valifenalate. Wait.

(10) SBI agent

Triflumizole, prochloraz, oxpoconazole fumarate, triadimefon, biconne (bitertanol), myclobutanil, fenbuconazole, hexaconazole, tebuconazole, propiconazole, prothioconazole, difenoconazole, ring Ipoconazole, imibenconazole, cyproconazole, tetraconazole, simeconazole, metconazole, epoxiconazole, ankle Flusilazole, imazalil, fenarimol, triforine, triadimenol, flutriafol, pyrifenox, darfuren Tridemorph), dodemorph, fenpropimorph, fenpropidin, spiroxamine, pyrisoxazole, fenhexamid, valerian Fear (pyributicarb) and the like.

(11) methoxy acrylate (strobilurin) fungicide

Azoxystrobin, kresoxim-methyl, trifloxystrobin, metominostrobin, oressastrobin, pyraclostrobin, enestrobin Enestroburin), dimoxystrobin, picoxystrobin, pyribencarb, fluoxastrobin, and the like.

(12) Anilinopyrimidine fungicide

Cyprodinil, mepanipyrim, pyrimethanil, and the like.

(13) Phenylpyrrole fungicide

Fluodixonil, fenpiclonil, and the like.

(14) Antibiotic fungicide

Kasugamycin, polyoxin, validamycin, streptomycin, oxytetracycline, blasticidin-S, and the like.

(15) Other fungicides

DKF-1001 (agent code), MIF-1002 (agent code), NF-171 (agent code), S-2200 (agent code), SB-4303 (agent code), benzothiadiazole (acibenzolar-S- Methyl), amisulbrom, amitoctradin, isotianil, isofetamid, isoprothiolane, iminoctadine tris (albesilate), Iminoctadine triacetate, echlomezol, ethaboxam, oxolinic acid, captafol, carpropamid, Quinoxin, chinomethionat, captan, chloroneb, chlorothalonil, cyazofamid, diethofencarb, Diclocymet, diclomezine, dithianon, cyflufenamid, diflumetorim, cymoxanil, silthiofam , zoxamide, dazomet, tiadinil, tecloftalam, tebufloquin, dodecane acetate (dodi Ne), triazoxide, tricyclazole, tolprocarb, tolnifanide, hydroxyisoxazole, pyriofenone, pyroquilon, fenoxanil, Fumi Ferimzone, fenpyrazamine, phthalide, bupirimate, famoxadone, fenamidone, fluazinam, fluoride Fluopicolide, fluoroimide, flusulfamide, flutianil, proquinazid, propamocarb hydrochloride, probenazole, Pencycuron, folpet, methasulfocarb, metrafenone, laminarin, and the like.

BAF-1120 (pharmaceutical code), MIF-1002 (agent code), SYJ-264 (agent code), NNF-0721 (agent code), and the like.

Insecticides:

(1) Organophosphorus insecticides

Acephate, azinphos-methyl, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, cyanophos, diazison ), in addition to linear phosphorus (dichlofenthion), dichlorvos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, puffer Ethoprophos, fenamiphos, fenitrothion, fenthion, isofenphos, isoxathion, malathion, methidathion, essay Mevinphos, monocrotophos, naled, oxydemeton-methyl, parathion, parathion-methyl, phenthoate ), phorate, phosalone, Phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propaphos, prothiofos , pyraclofos, pyridaphenthion, quinalphos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiophene Thiometon, trichlorfon, vamidothion, etc.

(2) urethane compounds

Aldicarb, alanycarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, love Ethiofencarb, fenobucarb, fenoxycarb, furathiocarb, isoprocarb, metiocarb, methodyl, Metocarb (metholyl), oxamyl, pirimicarb, propoxur, thiodicarb, triazamate, XMC, xylylcarb, etc. .

(3) Pyrethrin insecticides

Acrinathrin, allethrin, bifenthrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin Cyhalothrin), lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, theta-cypermethrin, Detamethrin, Yihuali (esfenvalerate) etofenprox, fenpropathrin, fenvalerate, flucythrinate, fluvalinate, tau-fluvalinate, fenfenine Halfenprox), metofluthrin, permethrin, phenothrin [(1R)-trans-isomer], pyrethrins, resmethrin, sputum Silafluofen, tefluthrin, tetramethrin, tralmethrin, etc.

(4) Nereis toxin insecticide

Bensultap, cartap hydrochloride, thiocyclam, and the like.

(5) Nicotine (Neonicotinoid) insecticide

Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, etc. .

(6) Diamine-based insecticide

Chlorantraniliprole, cyantraniliprole, flubendiamide, and the like.

Cyclaniliprole et al.

(7) Phenylpyrazole insecticide

Acetyl nitrile (acetoprole), ethiprole, fipronil, flufiprole, pyrafluprole, pyriprol, and the like.

(8) Macrolide lactone

Abamectin, avermectin, indomethacin (emamectin benzoate), lepimectin, milbemectin, spinetoram, spinosad, etc.

(9) Benzylurea (benzoylurea) insecticide

Bistrifluron, chlorfluazuron, diflubenzuron, flulazuron, flucycloxuron, flufenoxuron, hexaflumuron , Lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, etc.

(10) Diacylhydrazine is an insecticide

Chromofozide, halofenozide, methoxyfenozide, tebufenozide, and the like.

(11) Other active ingredients of pesticides

Afidopyropen, azadiractin, buprofezin, chinomethionat, chlorfenapyr, cyclaniliprole, cyromazine, diafenthiuron, gram Dicofol), dienochlor, endosulfan, flometoquin, flonicamid, flufenerim, flupyradifurone, hydramethylnon, hydroprene, Indoxacarb, metaflumizone, metaldehyde, methoprene, methoxychlor, pymetrozine, pyridalyl, Pyrifluquinazone, pyriproxyfen, rotenone, spirotetramat, sulfoxaflor, tolfenpyrad, Sodium oleate, diatomaceous earth, fatty acid glycerides, starch, rapeseed oil, adhesive (polybutylene), mono-fatty acid propylene glycol ester, motor oil (petroleum oil), nicotine sulfate ), iron (III) phosphate, and the like.

Triflumezopyrim, AKD-1193 (agent code), MIE-1209 (agent code), NA-89 (agent code), NC-515 (agent code), ME5382 (agent code), ZDI-2501 (agent code), and the like.

(12) Acaricide

Acequinocyl, amidoflumet, amitraz, bifenazate, bromopropylate, clofentezine, cyenopyrafen, race Cyflumetofen, cyhexatin, etoxazole, fenazaquin, fenbutatin oxide, fenothiocarb, fenpyroximate, pyrimidine Fluacrypyrim, hexythiazox, propargite, pyflubumide, pyrimidifen, pyridaben, spirodiclofen, spiromesifen , tebufenpyrad, tetradifon, and the like.

(13) nematicides

Aldoxycarb, cadusafos, carbam sodium, 1,3-dichloropropene, DCIP, fluorinated fluorene (fluensulfone), fosthiazate, imicyafos, levamisol hydrochloride, mesulfenfos, methyl isothiocyanate, morantel tartrate, Nemadectin and the like.

(14) Other

Viral polyhedrosis virus (NPV), granulosis virus (GV), cytoplasmic polyhedrosis virus (CPV), entopoxvirus (EPV) and other viral agents, derived from Su Bacillus thuringiensis spores and crystallization toxins, and such mixtures, microorganisms used as insecticidal/nematicides, such as Steinernema carpocapsae and Pasteuria penetrans Pesticides, insect pheromone agents, insect attractants, etc.

Example

Hereinafter, the present invention will be more specifically described by a synthesis example, a formulation example, and a test example of a substituted phenyl ether compound, but the present invention is not limited thereto.

[Synthesis Example 1]

1,2,3-Trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]methyl]benzene (1-140) )Synthesis

In a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenol (500 mg, 2.08 mmol) in N,N-dimethylformamide (5 ml) Potassium carbonate (345 mg, 2.50 mmol) and 3,4,5-trifluorobenzyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) (515 mg, 2.29 mmol) were added at room temperature, and the mixture was stirred at the same temperature for 3 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was chromatographed on a gel column (solution solvent: ethyl acetate / n-hexane = 1 / 5). The title compound was obtained as a yellow oil (yield: 624 mg, yield 78%).

[Synthesis Example 2]

1-fluoro-5-methyl-4-(2,2,2-trifluoroethylsulfinyl)-2-[(3,4,5-trifluorophenyl)methoxy]benzene (1 -141) Synthesis

In 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]methyl]benzene (210 mg, In a dichloromethane solution (2 ml) of 0.546 mmol), 70% 3-chloroperoxybenzyl acid (150 mg, 0.608 mmol) was added at 0 ° C and stirred at the same temperature for 1 hour. The reaction mixture was poured into a saturated aqueous solution of sodium hydrogencarbonate and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by silica gel column chromatography (solvent elution elution elution

[Synthesis Example 3]

Synthesis of 1-(cyclopropylmethylthio)-4-fluoro-2-methyl-5-[(3,4,5-trifluorophenyl)methoxy]benzene (1-684)

Instead of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenol, 5-(cyclopropylmethylsulfanyl)-2-fluoro-4-methyl- Phenol was subjected to the same reaction and treatment as in Synthesis Example 1 to give the title compound (yield: 100%) as white crystals.

[Synthesis Example 4]

Synthesis of 1-(cyclopropylmethylsulfinyl)-4-fluoro-2-methyl-5-[(3,4,5-trifluorophenyl)methoxy]benzene (1-685)

Use 1 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]methyl]benzene -(cyclopropylmethylthio)-4-fluoro-2-methyl The title compound (yield: 77%) was obtained as white crystals (yield: 77%).

[Synthesis Example 5]

1,2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethyl]benzene (2 Synthesis of -7)

Add 2-(3) at 0 ° C in a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenol (545 mg, 2.27 mmol) in tetrahydrofuran (5 ml) ,4,5-trifluorophenyl)ethanol (400 mg, 2.27 mmol), triphenylphosphine (714 mg, 2.72 mmol), diethyl azodicarboxylate (2.2 M in toluene, 1.24 ml, 2.73 mmol), Stir at room temperature for 2 hours. The reaction mixture was poured into a saturated aqueous The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc)

[Synthesis Example 6]

1,2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenoxy]ethyl]benzene Synthesis of (2-8)

Use 1 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]methyl]benzene , 2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]benzene, The title compound (yield: 98%) was obtained as white crystals.

[Synthesis Example 7]

1,2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy Synthesis of 1,1,1-dimethylethyl]benzene (2-265)

Add 2-methyl at 0 ° C in 2-methyl-4-methyl-5-(2,2,2-trifluoroethylthio)phenol (410 mg, 1.71 mmol) in toluene (3 mL) -2-(3,4,5-trifluorophenyl)propan-1-ol (350 mg, 1.71 mmol), phenoxydiphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) (570 mg, 2.05 mmol), azo Dicarboxylate (2.2 M in toluene, 0.930 ml, 2.05 mmol) was stirred at room temperature for 2 h. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc)

[Synthesis Example 8]

1,2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenoxy]-1,1 Synthesis of dimethyl-ethyl]benzene (2-266)

Use 1 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]methyl]benzene , 2,3-Trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]-1,1-dimethyl The title compound was obtained as a colorless oil (yield: 21%).

[Synthesis Example 9]

1,2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethoxy]benzene Synthesis of 6-9)

In a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenol (240 mg, 0.999 mmol) in N,N-dimethylformamide (3 ml) Add at room temperature Potassium carbonate (180 mg, 1.30 mmol) and 5-(2-bromoethoxy)-1,2,3-trifluorobenzene (268 mg, 1.05 mmol) were stirred at room temperature for 7 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc

[Synthesis Example 10]

1,2,3-Trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenoxy]ethoxy] Synthesis of Benzene (6-10)

Use 1 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]methyl]benzene , 2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethoxy]benzene, The title compound was obtained as a white crystal (yield: 68%).

[Synthesis Example 11]

1,2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]propoxy]benzene Synthesis of 7-9)

In a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenol (300 mg, 1.25 mmol) in N,N-dimethylformamide (3 ml) Potassium carbonate (224 mg, 1.62 mmol) and 5-(3-bromopropoxy)-1,2,3-trifluorobenzene (403 mg, 1.50 mmol) were added at room temperature and stirred at room temperature for 7 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by hydrazine gel column chromatography (solvent solvent: ethyl acetate / n-hexane = 1/4) to afford white oil. The title compound (yield 440 mg, yield 82%).

[Synthesis Example 12]

1,2,3-Trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenoxy]propoxy] Synthesis of Benzene (7-10)

Use 1 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]methyl]benzene , 2,3-trifluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]propoxy]benzene, The same reaction and treatment as in the Synthesis Example 2 gave the title compound (yield: 80%) of white crystals.

[Synthesis Example 13]

Synthesis of 5-(cyclopropylmethylthio)-2-fluoro-4-methylphenol (9-3)

Potassium carbonate (0.77 g, 5.58) was added at 0 ° C in a solution of 2-fluoro-4-methyl-5-nonylphenol (0.59 g, 3.73 mmol) in N,N-dimethylformamide (10 ml). Methyl), Rongalite (0.13 g, 1.10 mmol), and cyclopropylmethyl bromide (0.60 g, 4.44 mmol). A 1 N aqueous hydrochloric acid solution was poured into the reaction mixture, and ethyl acetate was evaporated. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

[Synthesis Example 14]

1-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-2-fluoro-4-methyl-5-(2,2,2-trifluoroethyl Synthesis of thiol)benzene (2-209)

In a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenol (500 mg, 2.08 mmol) in N,N-dimethylformamide (5 ml) Add at 0 °C Potassium carbonate (374 mg, 2.71 mmol) and [2,2-difluoro-2-(3,4,5-trifluorophenyl)ethyl]trifluoromethanesulfonate (859 mg, 2.50 mmol) at room temperature Stir under 2 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

[Synthesis Example 15]

1-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-2-fluoro-4-methyl-5-(2,2,2-trifluoroethyl Synthesis of Benzenesulfonyl)Benzene (2-210)

In 1-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-2-fluoro-4-methyl-5-(2,2,2-trifluoro Ethylthio)benzene (370 mg, 0.897 mmol) in chloroform (4 ml), 70% 3-chloroperoxybenzyl acid (200 mg, 0.897 mmol) was added at 0 ° C, and stirred at the same temperature for 1 hour. . The reaction mixture was poured into a saturated aqueous solution of sodium hydrogencarbonate and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

[Synthesis Example 16]

1-chloro-2-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-5-methyl-4-(2,2,2-trifluoroethyl Synthesis of thiol)benzene (2-447)

In a solution of 2-chloro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenol (2.00 g, 7.79 mmol) in N,N-dimethylformamide (20 ml) Add potassium carbonate (1.40 g, 10.1 mmol) and [2,2-difluoro-2-(3,4,5-trifluorophenyl) at 0 °C Ethyl]trifluoromethanesulfonate (3.20 g, 9.30 mmol) was stirred at room temperature for 2 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc)

[Synthesis Example 17]

1-chloro-2-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-5-methyl-4-(2,2,2-trifluoroethyl Synthesis of Benzenesulfonyl)Benzene (2-448)

In 1-chloro-2-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-5-methyl-4-(2,2,2-trifluoro Ethylthio)benzene (130 mg, 0.897 mmol) in dichloromethane (4 ml), 70% 3-chloroperoxybenzoic acid (200 mg, 0.897 mmol) was added at 5 ° C, and stirred at room temperature for 3 hours. . The reaction mixture was poured into a saturated aqueous The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

[Synthesis Example 18]

2,2-Difluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethyl]-1,3- Synthesis of benzodioxole (2-3)

Add 2-(0) at 0 ° C in a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenol (300 mg, 1.25 mmol) in tetrahydrofuran (2.5 ml) 2,2-Difluoro-1,3-benzodioxan-5-yl)ethanol (252 mg, 1.25 mmol), triphenylphosphine (360 mg, 1.37 mmol), diethyl azodicarboxylate (2.2 M toluene The liquid, 0.590 ml, 1.50 mmol) was stirred at room temperature for 2 hr. The reaction mixture was poured into a saturated aqueous The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc:

[Synthesis Example 19]

2,2-difluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenoxy]ethyl]-1, Synthesis of 3-benzodioxime (2-4)

Instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]methyl]benzene, use 2 ,2-difluoro-5-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethyl]-1,3-benzene The same reaction and treatment as in Synthesis Example 2 were carried out to give the title compound (yield: 87%) of white crystals.

[Synthesis Example 20]

1-fluoro-5-methyl-2-[2-(4-phenoxyphenyl)ethoxy]-4-(2,2,2-trifluoroethylsulfanyl)benzene (2-747) Synthesis

Add 2-(4) at 0 ° C in a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenol (300 mg, 1.25 mmol) in tetrahydrofuran (5 ml) -Phenoxyphenyl)ethanol (manufactured by Sigma Aldrich Co., Ltd.) (321 mg, 1.50 mmol), triphenylphosphine (652 mg, 1.50 mmol), diethyl azodicarboxylate (2.2 M toluene solution, 0.329 ml, 1.50) Methyl), stirred at room temperature for 2 hours. The reaction mixture was poured into a saturated aqueous The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and then evaporated. concentrate. The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc)

[Synthesis Example 21]

1-fluoro-5-methyl-2-[2-(4-phenoxyphenyl)ethoxy]-4-(2,2,2-trifluoroethylsulfinyl)benzene (2- Synthesis of 748)

Use 1 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]methyl]benzene -Fluoro-5-methyl-2-[2-(4-phenoxyphenyl)ethoxy]-4-(2,2,2-trifluoroethylsulfanyl)benzene, Synthesis and Synthesis Example 2 The same reaction and treatment gave the title compound as white crystals (yield: 74%).

[Synthesis Example 22]

N-[4-[2-[2-Fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]phenyl]acetamide (11- 6) Synthesis

Dichloromethane in 4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethyl]phenylamine (300 mg, 0.835 mmol) Triethylamine (127 mg, 0.918 mmol) and acetonitrile chloride (72.1 mg, 0.918 mmol) were added to the solution (5 ml), and stirred at room temperature for 1 hour. A dilute aqueous hydrochloric acid solution was poured into the reaction mixture, and extracted with chloroform. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

[Synthesis Example 23]

N-[4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]phenyl]carbamic acid tridecyl Ester (11-63) and N-tertiary butoxycarbonyl-N-[4- [2-[2-Fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]phenyl]carbamic acid tert-butyl butyl ester (11-65 )Synthesis

4-[2-[2-Fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethyl]phenylamine (1.00 g, 2.78 mmol) in acetonitrile (10 ml), triethylamine (845 mg, 8.35 mmol), 4-dimethylaminopyridine (34.0 mg, 0.278 mmol) and di-tertiary butyl dicarbonate (1.09 g, 5.01 mmol) were added at 0 °C. ), stirring at room temperature for 15 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by hydrazine gel column chromatography (solvent solvent: ethyl acetate / n-hexane = 1/5) to afford N-[4-[2-[2-fluoro-4- N-butyl butyl 5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]phenyl]carbamate (capacity: 642 mg, yield 50%) and N-third Butoxycarbonyl-N-[4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]phenyl]amino Tertiary butyl formate (received 100 mg, yield 6%).

[Synthesis Example 24]

N-tertiary butoxycarbonyl-N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)benzene Synthesis of ternary butyl oxy]ethyl]phenyl]carbamate (11-71)

Add N-III at 0 ° C in a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenol (400 mg, 1.67 mmol) in tetrahydrofuran (5 ml) Butyloxy-N-[2,6-difluoro-4-(2-hydroxyethyl)phenyl]carbamic acid tert-butyl butyl ester (684 mg, 1.83 mmol), triphenylphosphine (524 mg, 2.00 mmol) , diethyl azodicarboxylate (2.2 M solution in toluene, 0.91 ml, 200 mmol) at room temperature Stir under 2 hours. The reaction mixture was poured into a saturated aqueous The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc:

[Synthesis Example 25]

N-[2,6-Difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]phenyl Synthesis of tert-butyl carbamic acid ester (11-69)

N-tertiary butoxycarbonyl-N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)) To a solution of phenoxy]ethyl]phenyl]carbamic acid tert-butyl butyl ester (550 mg, 0.923 mmol) in acetonitrile (5 ml), cerium (III) bromide (41.4 mg, 92.3 μmol) was added at 50 ° C Stir for 2 hours. Further, cerium (III) bromide (41.4 mg, 92.3 μmol) was added, and the mixture was stirred at 50 ° C for 2 hours. The reaction mixture was poured into a saturated aqueous The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc)

[Synthesis Example 26]

N-[2,6-Difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenoxy]ethyl] Synthesis of phenyl]amino carboxylic acid tert-butyl ketone (11-70)

In N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethyl]benzene Addition of 70% 3- at a temperature of 0 ° C in a solution of dimethyl carbamic acid tributyl acrylate (120 mg, 0.242 mmol) in dichloromethane (3 ml) Chloroperoxybenzyl acid (53.7 mg, 0.218 mmol) was stirred at the same temperature for 1 hour. The reaction mixture was poured into a saturated aqueous solution of sodium hydrogencarbonate and extracted with dichloromethane. The extract was washed with saturated brine, dried over anhydrous sodium sulfate and evaporated. The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

[Synthesis Example 27]

N-tertiary butoxycarbonyl-N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)benzene Synthesis of oxy]methyl]phenyl]aminocarboxylic acid tert-butyl butyl ester (10-25)

Instead of N-tertiary butoxycarbonyl-N-[2,6-difluoro-4-(2-hydroxyethyl)phenyl]carbamic acid tert-butyl butyl ester, N-tertiary butoxycarbonyl-N- [2,6-Difluoro-4-(2-hydroxymethyl)phenyl]carbamic acid tert-butyl butyl ester was subjected to the same reaction and treatment as in the the the the the the %).

[Synthesis Example 28]

N-[2,6-Difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]methyl]phenyl Synthesis of tert-butyl carbazate (10-23)

Instead of N-tertiary butoxycarbonyl-N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)benzene Oxy]ethyl]phenyl]aminocarboxylic acid tert-butyl butyl ester using N-tertiary butoxycarbonyl-N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl -5-(2,2,2-Trifluoroethylthio)phenoxy]methyl]phenyl]carbamic acid tert-butyl butyl ester, the same reaction and treatment as in Synthesis Example 25 were carried out to obtain a yellow oil The title compound (yield 59%).

[Synthesis Example 29]

N-[2,6-Difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenoxy]methyl] Synthesis of phenyl]amino carboxylic acid tert-butyl butyl ester (10-24)

Instead of N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethyl]benzene N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfide) The benzyloxy]methyl]phenyl]carbamic acid tert-butyl butyl ester was reacted and treated in the same manner as in Synthesis Example 26 to give the title compound (yield: 97%).

[Synthesis Example 30]

N-[4-[2-[2-Chloro-4-methyl-5-(cyclopropylmethylthio)phenoxy]ethyl]phenyl]carbamic acid tert-butyl butyl ester (11-442 And N-tertiary butoxycarbonyl-N-[4-[2-[2-chloro-4-methyl-5-(cyclopropylmethylsulfanyl)phenoxy]ethyl]phenyl] Synthesis of tert-butyl carbamic acid ester (11-444)

Instead of 4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]phenylamine, 4-[2-[2- Chloro-5-(cyclopropylmethylsulfanyl)4-methylphenoxy]ethyl]aniline was reacted and treated in the same manner as in Synthesis Example 23 to obtain N-[4-[2- [2-Chloro-4-methyl-5-(cyclopropylmethylsulfanyl)phenoxy]ethyl]phenyl]carbamic acid tert-butyl butyl ester (yield 52%) and yellow oily N - Tert-butyloxycarbonyl-N-[4-[2-[2-chloro-4-methyl-5-(cyclopropylmethylsulfanyl)phenoxy]ethyl]phenyl]aminocarboxylic acid Tertiary butyl ester (5% yield).

[Synthesis Example 31]

N-tertiary butoxycarbonyl-N-[4-[2-[2-chloro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]-1, Synthesis of tert-butyl butyl 1-difluoroethyl]2,6-difluorophenyl]carbamate (11-305)

In a solution of 2-chloro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenol (3.70 g, 15.0 mmol) in N,N-dimethylformamide (50 ml) Add potassium carbonate (2.40 g, 18.0 mmol) and [2-[4-[bis(tris-butoxycarbonyl)amino]3,5-difluorophenyl]-2,2-di at 0 °C Fluoroethyl]trifluoromethanesulfonate (7.90 g, 15.0 mmol) was stirred at room temperature for 2 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

[Synthesis Example 32]

N-[4-[2-[2-chloro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]-1,1-difluoroethyl]2, Synthesis of 3-tert-butyl 6-difluorophenyl]carbamate (11-302)

Instead of N-tertiary butoxycarbonyl-N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio) Benzyloxy]ethyl]phenyl]carbamic acid tert-butyl butyl ester using N-tertiary butoxycarbonyl-N-[4-[2-[2-chloro-4-methyl-5-( Tertiary butyl 2,2,2-trifluoroethylthio)phenoxy]-1,1-difluoroethyl]2,6-difluorophenyl]carbamate, carried out in the same manner as in Synthesis Example 25. Reaction and treatment gave the title compound as white crystals (yield: 44%).

[Synthesis Example 33]

N-[4-[2-[2-Chloro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenoxy]-1,1-difluoroethyl] Synthesis of tert-butyl 2,6-difluorophenyl]carbamate (11-303)

Instead of N-[2,6-difluoro-4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]ethyl]benzene Use of benzyl carbamic acid tert-butyl butyl ester N-[4-[2-[2-chloro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]-1,1-difluoroethyl]2, 3-tert-butyl 6-difluorophenyl]carbamate was reacted and treated in the same manner as in Synthesis Example 26 to give the title compound (yield: 81%).

[Synthesis Example 34]

N-[4-[2-[2-chloro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]-1,1-difluoroethyl]2, Synthesis of 3-tert-butyl 6-difluorophenyl]-N-methyl-aminocarbamate (11-307)

In N-[4-[2-[2-chloro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenoxy]-1,1-difluoroethyl]2 A solution of 6-difluorophenyl]aminocarbamic acid tert-butyl ester (200 mg, 0.365 mmol) in tetrahydrofuran (3 ml) was added 60% sodium hydride (16.1 mg, 0.402 mmol), and stirred at room temperature for 5 min. Methyl iodide (155 mg, 1.09 mmol) was added and stirred at room temperature for 15 hours. The reaction mixture was purified by EtOAcjjjjjjjjjjj

[Synthesis Example 35]

[2-[4-[bis(tris-butoxycarbonyl)amino]3,5-difluorophenyl]-2,2-difluoroethyl]trifluoromethanesulfonate (12-91) synthesis

In the N-tertiary butoxycarbonyl-N-[4-(1,1-difluoro-2-hydroxyethyl)-2,6-difluorophenyl]carbamic acid tert-butyl butyl ester (2.30 g, 5.60 mmol) and triethylamine (680 mg, 6.70 mmol) in dichloromethane (40 ml), trifluoromethanesulfonic acid anhydride (1.70 g, 6.20 mmol) was added at 0 ° C, and stirred at the same temperature for 1 hour. Water was poured into the reaction mixture and extracted with chloroform. Extract The extract was washed with aq. EtOAc (EtOAc m.

[Synthesis Example 36]

N-tertiary butoxycarbonyl-N-[4-(1,1-difluoro-2-hydroxyethyl)-2,6-difluorophenyl]carbamic acid tert-butyl butyl ester (12-41) Synthesis

A solution of ethyl 2-[4-[bis(tris-butoxycarbonyl)amino]-3,5-difluorophenyl]-2,2-difluoroacetate (12.3 g, 27.2 mmol) in tetrahydrofuran ( In 60 ml), sodium borohydride (618 mg, 16.3 mmol) was added at 0 ° C, and stirred at room temperature for 2 hr. The reaction mixture was poured into a dilute aqueous hydrochloric acid solution and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate.

[Synthesis Example 37]

Synthesis of ethyl 2-[4-[bis(tris-butoxycarbonyl)amino]-3,5-difluorophenyl]-2,2-difluoroacetate (12-12)

Add 3-B at 0 ° C in a solution of ethyl 2-(4-amino-3,5-difluorophenyl)-2,2-difluoroacetate (1.00 g, 3.98 mmol) in EtOAc (20 mL) Amine (12.1 g, 11.9 mmol), 4-dimethylaminopyridine (48.6 mg, 0.398 mmol) and di-tert-butyl dicarbonate (1.91 g, 8.76 mmol) were stirred at room temperature for 15 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

[Synthesis Example 38]

Synthesis of ethyl 2-(4-amino-3,5-difluorophenyl)-2,2-difluoroacetate (12-2)

2,6-difluoroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) (15.0 g, 116 mmol), ethyl bromodifluoroacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) (70.7 g, 349 mmol) and ferrocene (2.16 g, 1.16) To a solution of mmol of DMSO (500 ml), hydrogen peroxide (25 ml) was slowly added at room temperature, and stirred at the same temperature for 3 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc:

The ¹ H NMR spectrum (CDCl ₃ ) σ (ppm) value, melting point (° C.), and the like of the above-mentioned synthesis example and the compound of the present invention produced in accordance with the above-mentioned synthesis examples are shown in Table 13. ^{The 1} H NMR data was measured by a JNM-ECS400 spectrometer (manufactured by JEOL Ltd.).

Moreover, the ¹ H NMR spectrum (CDCl ₃ ) σ (ppm) value and the melting point (° C.) of the above-mentioned synthesis example and the compound of the present invention produced according to the above-mentioned synthesis example are shown in Table 14. ^{The 1} H NMR spectrum was measured by a JNM-ECS400 spectrometer (manufactured by JEOL Ltd.).

In the following, the synthesis examples in which the starting materials of the above Synthesis Examples 1 to 38 are synthesized from commercially available products are shown in the synthesis example 1 to the reference synthesis example 21, but are not limited thereto.

[Reference Synthesis Example 1]

Synthesis of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)thio]phenol

Potassium carbonate (2.88 g, at 0 ° C) was added to a solution of 2-fluoro-4-methyl-5-nonylphenol (3.00 g, 19.0 mmol) in N,N-dimethylformamide (30 ml). 20.8 mmol), Rongalite (0.900 g, 7.62 mmol) and 2,2,2-trifluoro-1-iodoethane (4.18 g, 19.9 mmol) were stirred at room temperature for 4 hours. A 1 N aqueous hydrochloric acid solution was poured into the reaction mixture, and ethyl acetate was evaporated. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc:

¹ H NMR spectrum (CDCl ₃ ) σ: 7.16 (1H, d, J = 8.7 Hz), 6.94 (1H, d, J = 11.0 Hz), 5.13 (1H, br.s), 3.31 (2H, q, J) =9.8Hz), 2.37 (3H, s)

[Reference Synthesis Example 2]

Synthesis of 2-fluoro-4-methyl-5-nonylphenol

Adding chlorine at 0 ° C in a solution of 2-fluoro-4-methylphenol (24.96 g, 197.9 mmol) (manufactured by Sigma Alcrich) and triethylamine (26.03 g, 257.3 mmol) in dichloromethane (500 ml) Ethyl formate (23.62 g, 217.7 mmol) was stirred at the same temperature for 2 hours. The reaction mixture was poured into 1N aqueous hydrochloric acid and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous sodium sulfate The obtained oil was added to chlorosulfonic acid (117.00 g, 1000 mmol) at 0 ° C and allowed to react at room temperature for 18 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and evaporated. Red phosphorus (16.99 g, 548.4 mmol) and iodine (1.99 g, 7.84 mmol) were added to the obtained oily acetic acid solution (130 ml) at room temperature, and heated under reflux. hour. Ice water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and evaporated. The obtained oily substance was added to a 10% aqueous potassium hydroxide solution (4 L), and heated under reflux for 3 hr. Concentrated hydrochloric acid was added to the reaction mixture to adjust the pH to 7 and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate (MgSO4)

¹ H NMR spectrum (CDCl ₃ ) σ: 6.94 (1H, d, J = 8.7 Hz), 6.88 (1H, d, J = 11.4 Hz), 4.95 (1H, br.s), 3.20 (1H, br.s ), 2.23 (3 H, s).

[Reference Synthesis Example 3]

Synthesis of 2-(3,4,5-trifluorophenyl)ethanol

In a solution of 1,2,3-trifluoro-5-vinylbenzene (manufactured by Apolo) (1.00 g, 6.32 mmol) in tetrahydrofuran (10 ml), dimethyl sulfide borane was added at 0 ° C (d = 0.800, 0.660 ml, 7.04 mmol), and reacted at room temperature for 12 hours. Water (3.0 ml), 2N aqueous sodium hydroxide solution (15 ml) and 30% hydrogen peroxide water (1.4 ml) were added and stirred at the same temperature for 6 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

¹ H NMR spectrum (CDCl ₃ ) σ: 6.89-6.83 (2H, m), 3.86 (2H, q, J = 6.0 Hz), 2.80 (2H, t, J = 6.0 Hz), 1.41 (1H, br. ).

[Reference Synthesis Example 4]

Synthesis of 2-methyl-2-(3,4,5-trifluorophenyl)propan-1-ol

To a solution of 3,4,5-trifluorobenzyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.00 g, 22.2 mmol) in acetonitrile (40 ml), water (10 ml) and potassium cyanide (1.74) were added at room temperature. g, 26.7 mmol) and 18-crown-6-ether (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.590 g, 2.22 mmol), and stirred at 50 ° C for 3 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by hydrazine gel column chromatography (solvent solvent: ethyl acetate / n-hexane = 1/3) to give a colorless oil (yield: 3.74 g, yield 98%). Sodium hydride (60%, 2.19 g, 54.6 mmol) and methyl iodide (15.5 g, 110 mmol) were added at 0 ° C in a solution of the obtained oil in dimethoxyethane (40 ml) at room temperature Stir for 1 hour. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by hydrazine gel column chromatography (solvent solvent: ethyl acetate / n-hexane = 1/5) to afford white solid (yield: 4.00 g, yield: 92%). 60% aqueous sulfuric acid solution (40 ml) was added to the obtained solid acetic acid solution (20 ml), and the mixture was stirred at 120 ° C for 2 hours, then sodium nitrite (6.90 g, 100 mmol) was added at room temperature, and stirred at 90 ° C for 2 hours. . After pouring ice water into the reaction mixture, the precipitated solid was washed with water, and dried under reduced pressure to give a white solid (yield: 3.86 g, yield: 87%). To a solution of the obtained solid methylene chloride (40 ml) was added EtOAc (3. <RTI ID=0.0></RTI> </RTI> <RTIgt; The reaction solution was concentrated under reduced pressure to give a white solid (4.63 g). To the obtained solid tetrahydrofuran solution (40 ml), lithium aluminum hydride (686 mg, 18.1 mmol) was added at 0 ° C, and the mixture was stirred at room temperature for 1 hour. Inject the diethyl ether into the reaction mixture, add a small amount of water, and stir at room temperature. hour. The precipitate was removed by suction filtration, dried over anhydrous sodium sulfate and evaporated. The concentrate was purified by silica gel column chromatography (solvent elution elution elution elution elution

¹ H NMR spectrum (CDCl ₃ ) σ: 7.01-6.97 (2H, m), 3.57 (2H, s), 1.29 (6H, s).

[Reference Synthesis Example 5]

Synthesis of 5-(2-bromoethoxy)-1,2,3-trifluorobenzene

To a solution of 3,4,5-trifluorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.13 g, 7.63 mmol) in tetrahydrofuran (10 ml), 2-bromo-1-ethanol (1.43 g, 11.4 mmol) was added at 0 °C. Triphenylphosphine (2.20 g, 8.39 mmol) and diethyl azodicarboxylate (2.2 M in toluene, 3.82 ml, 8.41 mmol) were stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure. EtOAc m. 74%).

¹ H NMR spectrum (CDCl ₃ ) σ: 6.58-6.50 (2H, m), 4.22 (2H, t, J = 6.0 Hz), 3.61 (2H, t, J = 60 Hz).

[Reference Synthesis Example 6]

Synthesis of 5-(3-bromopropoxy)-1,2,3-trifluorobenzene

To a solution of 3,4,5-trifluorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.13 g, 7.63 mmol) in tetrahydrofuran (10 ml), 3-bromo-1-propanol (1.73 g, 11.5) was added at 0 °C. Methyl), triphenylphosphine (2.20 g, 8.39 mmol) and diethyl azodicarboxylate (2.2 M in toluene, 3.82 ml, 8.41 mmol) were stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and the concentrate was concentrated. The title compound (yield: 1.39 g, yield 68%) was obtained.

¹ H NMR spectrum (CDCl ₃ ) σ: 6.56-6.48 (2H, m), 4.04 (2H, t, J = 6.0 Hz), 3.57 (2H, t, J = 6.0 Hz), 2.30 (2H, q, J =6.0Hz).

[Reference Synthesis Example 7]

Synthesis of 2,2-difluoro-2-(3,4,5-trifluorophenyl)ethanol

Ethyl 2,2-difluoro-2-(3,4,5-trifluorophenyl)acetate (synthesized according to the method described in Journal of Fluorine Chemistry, 2004, P.509, etc.) (1.00 g, 3.93 mmol) In an ethanol solution (8 ml), sodium borohydride (800 mg, 3.15 mmol) was added at 0 ° C, and stirred at the same temperature for 1 hour. Ice water was poured into the reaction mixture, and extracted with chloroform. The extract was washed with saturated brine and dried over anhydrous sodium sulfate.

¹ H NMR spectrum (CDCl ₃ ) σ: 7.23 - 7.15 (2H, m), 4.00 - 3.92 (2H, m).

[Reference Synthesis Example 8]

Synthesis of [2,2-difluoro-2-(3,4,5-trifluorophenyl)ethyl]trifluoromethanesulfonate

In 2,2-difluoro-2-(3,4,5-trifluorophenyl)ethanol (2.30 g, 10.8 mmol) and triethylamine (1.30 g, 12.8 mmol) in dichloromethane (25 ml) Trifluoromethanesulfonic anhydride (3.40 g, 12.1 mmol) was added at 0 ° C, and stirred at the same temperature for 1 hour. Water was poured into the reaction mixture and extracted with chloroform. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

¹ H NMR spectrum (CDCl ₃ ) σ: 7.23-7.16 (2H, m), 4.67 (2H, t, J = 11.2 Hz).

[Reference Synthesis Example 9]

Synthesis of 2-(2,2-difluoro-1,3-benzodioxan-5-yl)ethanol

Addition of dimethyl sulfide at 0 ° C in a solution of 2,2-difluoro-5-vinyl-1,3-benzodioxole (1.90 g, 10.3 mmol) in tetrahydrofuran (31 ml) Borane (d = 0.80, 1.4 ml, 11.8 mmol) was reacted at room temperature for 7 hours. Water (5.0 ml), 2N aqueous sodium hydroxide solution (24 ml) and 30% hydrogen peroxide water (2.2 ml) were added, and the mixture was stirred at the same temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc)

¹ H NMR spectrum (CDCl ₃ ) σ: 6.99-6.91 (3H, m), 3.87-3.82 (2H, m), 2.85 (2H, t, J = 6.4 Hz), 1.42 (1H, br.s).

[Reference Synthesis Example 10]

Synthesis of 2,2-difluoro-5-vinyl-1,3-benzodioxan

Sodium hydride (190 mg, 8.10 mmol) was added to a solution of methyltriphenylphosphonium bromide (2.20 g, 8.10 mmol) in tetrahydrofuran (20 ml). 2,2-Difluoro-1,3-benzodioxan-5-carbaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.00 g, 5.40 mmol) was stirred at the same temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was chromatographed on a gel column (solution solvent: ethyl acetate / n-hexane = The title compound (yield 580 mg, yield 59%) was obtained.

¹ H NMR spectrum (CDCl ₃ ) σ: 7.15 (1H, d, J = 1.8 Hz), 7.06 (1H, dd, J = 8.2, 1.8 Hz), 6.99 (1H, d, J = 8.2 Hz), 6.66 ( 1H, dd, J = 17.4, 11.0 Hz), 5.66 (1H, dd, J = 17.4 Hz), 5.25 (1H, dd, J = 11.0 Hz).

[Reference Synthesis Example 11]

Synthesis of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)thio]phenol

Potassium carbonate (2.88 g, 20.8) was added at 0 ° C in a solution of 2-fluoro-4-methyl-5-nonylphenol (3.00 g, 19.0 mmol) in N,N-dimethylformamide (30 ml). Methyl), Rongalite (0.900 g, 7.62 mmol) and 2,2,2-trifluoro-1-iodoethane (4.18 g, 19.9 mmol) were stirred at room temperature for 4 h. A 1 N aqueous hydrochloric acid solution was poured into the reaction mixture, and ethyl acetate was evaporated. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc:

¹ H NMR spectrum (CDCl ₃ ) σ: 7.16 (1H, d, J = 8.7 Hz), 6.94 (1H, d, J = 11.0 Hz), 5.13 (1H, br.s), 3.31 (2H, q, J) =9.8Hz), 2.37 (3H, s)

[Reference Synthesis Example 12]

Synthesis of 2-fluoro-4-methyl-5-nonylphenol

2-fluoro-4-methylphenol (24.96 g, 197.9 mmol) (manufactured by Sigma Alcrich) and triethylamine (26.03 g, 257.3 mmol) in dichloromethane (500 ml), chloroformic acid at 0 ° C Ethyl ester (23.62 g, 217.7 mmol) was stirred at the same temperature for 2 hours. The reaction mixture was poured into 1N aqueous hydrochloric acid and extracted with dichloromethane. The extract is washed with saturated saline to make anhydrous sulfur The sodium salt was dried and concentrated under reduced pressure to give a colourless oil (yield 39.22 g, yield 100%). The obtained oil was added to chlorosulfonic acid (117.00 g, 1000 mmol) at 0 ° C and allowed to react at room temperature for 18 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and evaporated. Red phosphorus (16.99 g, 548.4 mmol) and iodine (1.99 g, 7.84 mmol) were added to an acetic acid solution (130 ml) of the obtained oil, and the mixture was refluxed for 2 hr. Ice water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and evaporated. The obtained oily substance was added to a 10% aqueous potassium hydroxide solution (4 L), and heated under reflux for 3 hr. Concentrated hydrochloric acid was added to the reaction mixture to adjust the pH to 7 and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate (MgSO4)

¹ H NMR spectrum (CDCl ₃ ) σ: 6.94 (1H, d, J = 8.7 Hz), 6.88 (1H, d, J = 11.4 Hz), 4.95 (1H, br.s), 3.20 (1H, br.s ), 2.23 (3H, s).

[Reference Synthesis Example 13]

Synthesis of 4-[2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenoxy]ethyl]aniline

Add 2-(0) at 0 ° C in a solution of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenol (6.70 g, 27.9 mmol) in tetrahydrofuran (30 mL) 4-aminophenyl)ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (4.20 g, 30.6 mmol), triphenylphosphine (8.80 g, 33.5 mmol), diethyl azodicarboxylate (2.2 M toluene solution, 15 ml) , 33.0 mmol), stirred at room temperature for 2 hours. Mix the reaction The mixture was poured into a saturated aqueous solution of sodium bicarbonate and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

¹ H NMR spectrum (CDCl ₃ ) σ:: 7.10 (1H, d, J = 8.7 Hz), 7.07 (2H, d, J = 8.2 Hz), 6.95 (1H, d, J = 11.9 Hz), 6.66 (2H) ,d,J=8.7Hz), 4.14(2H,t,J=7.3Hz), 3.26(2H,q,J=9.6Hz), 3.00(2H,t,J=7.3Hz), 2.39(3H,s ).

[Reference Synthesis Example 14]

Synthesis of N-tertiary butoxycarbonyl-N-[2,6-difluoro-4-(2-hydroxyethyl)phenyl]carbamic acid tert-butyl butyl ester

In a solution of N-tertiary butoxycarbonyl-N-(2,6-difluoro-4-vinylphenyl)carbamic acid tert-butyl butyl ester (3.58 g, 10.1 mmol) in tetrahydrofuran (20 ml) Dimethyl sulfide borane (d = 0.850, 1.4 ml, 15.1 mmol) was added at 0 ° C and allowed to react at room temperature for 12 hours. Water (6.0 ml), 2N aqueous sodium hydroxide solution (30 ml) and 30% hydrogen peroxide water (3 ml) were added and stirred at the same temperature for 6 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by silica gel column chromatography (solvent elution: ethyl acetate / hexane = 1/2) to give the title compound (yield: 1.36 g, yield 36%).

¹ H NMR spectrum (CDCl ₃ ) σ: 6.83 (2H, d, J = 8.2 Hz), 3.86 (2H, t, J = 6.0 Hz), 2.86 (2H, t, J = 6.0 Hz), 1.43 (18H, s).

[Reference Synthesis Example 15]

Synthesis of N-tertiary butoxycarbonyl-N-(2,6-difluoro-4-vinylphenyl)carbamic acid tert-butyl butyl ester

60% sodium hydride (700 mg, 17.5 mmol) was added to a solution of methyltriphenylphosphonium bromide (4.85 g, 17.5 mmol) in tetrahydrofuran (40 ml), and stirred at the same temperature for 30 minutes. Further, N-tertiary butoxycarbonyl-N-(2,6-difluoro-4-methylindenylphenyl)carbamic acid tert-butyl butyl ester (4.17 g, 11.7 mmol) was added at 0 ° C. The reaction was carried out for 1 hour at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

¹ H NMR spectrum (CDCl ₃ ) σ: 6.96 (2H, d, J = 8.2 Hz), 6.61 (1H, dd, J = 17.4, 11.0 Hz), 5.77 (1H, d, J = 17.4 Hz), 5.38 ( 1H, d, J = 11.0 Hz), 1.42 (18H, s).

[Reference Synthesis Example 16]

Synthesis of N-tertiary Butyloxycarbonyl-N-[2,6-Difluoro-4-(hydroxymethyl)phenyl]carbamic acid tert-butyl butyl ester

In a tetrahydrofuran solution (30 ml) of N-tertiary butoxycarbonyl-N-(2,6-difluoro-4-methylindenylphenyl)carbamic acid tert-butyl ester (962 mg, 2.69 mmol) Sodium borohydride (81.5 mg, 2.15 mmol) was added at 0 ° C, and stirred at the same temperature for 1 hour. The reaction mixture was poured into a dilute aqueous hydrochloric acid solution and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate.

¹ H NMR spectrum (CDCl ₃ ) σ: 6.96 (2H, d, J = 8.2 Hz), 4.71 (2H, s), 1.42 (18H, s).

[Reference Synthesis Example 17]

Synthesis of N-tertiary Butyloxycarbonyl-N-(2,6-Difluoro-4-methylnonylphenyl)carbamic acid Tertiary Butyl Ester

In a solution of 4-amino-3,5-difluorobenzaldehyde (1.68 g, 10.7 mmol) in acetonitrile (20 ml), triethylamine (3.25 g, 32.1 mmol), 4-dimethyl Aminopyridine (131 mg, 1.07 mmol) and di-tertiary butyl dicarbonate (5.13 g, 23.5 mmol) were stirred at room temperature for 15 hours. Water was poured into the reaction mixture, and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

¹ H NMR spectrum (CDCl ₃ ) σ: 9.94 (1H, s), 7.48 (2H, d, J = 7.3 Hz), 1.43 (18H, s).

[Reference Synthesis Example 18]

Synthesis of 4-amino-3,5-difluorobenzaldehyde

To a solution of 2,6-difluoroaniline (made by Tokyo Chemical Industry Co., Ltd.) (5.00 g, 39.0 mmol) in DMSO (300 ml), copper (II) chloride (10.0 g, 77.0 mmol) and concentrated hydrochloric acid (15 ml) were added. Stir at 90 ° C for 10 hours. Saturated sodium hydrogencarbonate was poured into the reaction mixture and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc:

¹ H NMR spectrum (CDCl ₃ ) σ: 9.73 (1H, s), 7.39 (2H, d, J = 8.4 Hz), 4.33 (2H, br. s).

[Reference Synthesis Example 19]

Synthesis of 4-[2-[2-chloro-5-(cyclopropylmethylsulfanyl)4-methylphenoxy]ethyl]aniline

Add 2-(4-Aminobenzene) at 0 ° C in a solution of 2-chloro-5-(cyclopropylmethylsulfanyl)-4-methylphenol (1.00 g, 4.40 mmol) in tetrahydrofuran (10 mL) Ethyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) (660 mg, 4.80 mmol), triphenylphosphine (1.40 g, 5.20 mmol), diethyl azodicarboxylate (2.2 M toluene solution, 2.36 ml, 5.20 mmol), Stir at room temperature for 2 hours. The reaction mixture was poured into a saturated aqueous The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

¹ H NMR spectrum (CDCl ₃ ) σ: 7.15 (1H, s), 7.10 (2H, d, J = 8.7 Hz), 6.84 (1H, s), 6.66 (2H, d, J = 8.2 Hz), 4.12 ( 2H, t, J = 7.3 Hz), 3.03 (2H, t, J = 7.3 Hz), 2.75 (2H, d, J = 6.9 Hz), 2.29 (3H, s), 1.02-0.97 (1H, m), 0.59-0.54 (2H, m), 0.25-0.21 (2H, m).

[Reference Synthesis Example 20]

Synthesis of 2-chloro-5-(cyclopropylmethylthio)-4-methylphenol

Potassium carbonate (23.6 g, 171 mmol) was added at 0 ° C in a solution of 2-chloro-4-methyl-5-nonylphenol (24.8 g, 142 mmol) in N,N-dimethylformamide (140 ml). , Rongalite (6.57g, 42.6mmol), and cyclopropylmethyl bromide The compound (20.1 g, 149 mmol) was stirred at room temperature for 2 hr. A 1 N aqueous hydrochloric acid solution was poured into the reaction mixture, and ethyl acetate was evaporated. The extract was washed with brine, dried over anhydrous sodium sulfate The concentrate was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc

¹ H NMR spectrum (CDCl ₃ ) σ: 7.26 (1H, s), 6.92 (1H, s), 5.42 (1H, s), 2.81 (2H, d, J = 7.2 Hz), 2.26 (3H, s), 1.12-1.02 (1H, m), 0.63-0.58 (2H, m), 0.29-0.25 (2H, m).

[Reference Synthesis Example 21]

Synthesis of 2-Chloro-4-methyl-5-nonylphenol

In place of 2-fluoro-4-methylphenol, 2-chloro-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and the reaction and treatment with Reference Example 12 were carried out to obtain the title compound as a white crystal. 100%).

¹ H NMR spectrum (CDCl ₃ ) σ: 7.09 (1H, s), 6.95 (1H, s), 5.33 (1H, br.s), 3.29 (1H, br.s), 2.22 (3H, s).

Next, specific examples of the method of formulating the compound of the present invention into an insecticidal or acaricidal agent for agricultural and horticultural use are shown in Formulation Examples 1 to 5.

[Formulation Example 1] Powder

A mixture of the compound of Synthesis Example 1 (2 parts by weight), isopropyl phosphate (1 part by weight) of a fluidity improver, and clay (97 parts by weight) of a solid carrier was pulverized and mixed to obtain an active ingredient 2 % by weight of powder. Further, in addition to the compounds shown in the first to the eighth tables, in place of the compounds of Synthesis Example 1, the respective powders were obtained by the same method.

[Formulation Example 2] wettable powder

The compound of Synthesis Example 1 (20 parts by weight), the sodium alkylbenzenesulfonate (3 parts by weight) of an anionic surfactant, and the polyoxyethylene alkylphenyl ether of a nonionic surfactant (5 parts by weight) The mixture of the clay (72 parts by weight) of the solid carrier was pulverized and mixed uniformly, and a wettable powder containing 20% by weight of the active ingredient was obtained. Further, in addition to the compounds described in the first to the eighth tables, the respective wettable powders were obtained by the same method as the compounds of the first to the eighth examples.

[Formulation Example 3] Emulsion

The compound of Synthesis Example 1 (30 parts by weight), the methylnaphthalene (40 parts by weight) of the liquid carrier, and the polyoxyethylene alkylphenyl ether (30 parts by weight) of the nonionic surfactant were mixed and dissolved to obtain An emulsion containing 30% by weight of the active ingredient. Further, in place of the compounds of the first to eighth examples, in addition to the compounds of the first to eighth examples, the respective emulsions were obtained by the same method.

[Formulation Example 4] Flowability agent

The compound of Synthesis Example 1 (25 parts by weight), the polyoxyethylene alkyl ether of a nonionic surfactant (1 part by weight), and the sodium alkylnaphthalene sulfonate (1 part by weight) of an anionic surfactant were added. A mixture of the scented gum (1 part by weight) of the adhesive and water (72 parts by weight) of the liquid carrier was uniformly mixed to obtain a flowable agent containing 25% by weight of the active ingredient. Further, in addition to the compounds described in the first to the eighth tables, in place of the compound of Synthesis Example 1, the respective flowable agents were obtained by the same method.

[Formulation Example 5] Granules

In the compound of Synthesis Example 1 (5 parts by weight), the surfactant of the laurel sulfur Adding water (15 parts by weight) to a mixture of sodium (1 part by weight), calcium lignin sulfonate (5 parts by weight) of binder, bentonite (30 parts by weight) of solid carrier, and clay (59 parts by weight) The kneading machine was kneaded by a kneading machine, granulated by a granulator, and then dried by a flow dryer to obtain a granule containing 5% by weight of the active ingredient. Further, in addition to the compounds described in the first to the eighth tables, in place of the compound of Synthesis Example 1, the respective granules were obtained by the same method.

Specific examples of the evaluation of the control effect of the pest control agent of the present invention obtained by the above are shown in Test Examples 1 to 7.

[Test Example 1] Control of brown planthopper (Nilaparvata lugens)

The germinated seedlings of rice cultivated in a plastic cup were placed on a turntable, and the emulsion dilution (500 ppm) prepared in accordance with Preparation Example 3 was uniformly dispersed by a spray gun. After air drying, placed in a polycarbonate plastic container with a nylon mesh cover, 10 insect larvae of the 4th instar larvae were placed in each container and allowed to stand in a constant temperature room at 25 ° C. The number of living insects was investigated after 7 days of larvae, and the mortality rate (%) was calculated by the following calculation formula (a). The test was repeated in 2 replicates.

By way of example, the compounds of the aforementioned compound numbers 1-1, 1-2, 1-3, 1-106, 1-140, 1-245, 2-7 exhibit a mortality rate of 80% or more.

Further, the aforementioned compound code is 1-120, 2-3, 2-4, Compounds of 2-727, 2-919, 2-928 exhibit a mortality rate of more than 80%.

Further, the compound of the above compound code 11-284 exhibited a mortality rate of 80% or more.

[Test Example 2] Control test for soybean meal (Aphis craccivora)

For the broad bean seedlings cultivated in plastic cups, the soybean meal (Aphis craccivora) is a wingless adult with 3 insects per cup. One day after the larvae, the broad bean seedlings were placed on a turntable, and the emulsion dilution (500 ppm) prepared in accordance with Preparation Example 3 was uniformly spread by a spray gun. After the treatment, the cells were placed in a constant temperature room (16 hours of illumination) at 25 ° C, and the number of adult and larvae parasitized was examined 4 days after the treatment, and the control price (%) was calculated by the following calculation formula (b). The test was repeated in 2 replicates.

By way of example, the compounds of the above-mentioned compound numbers 1-629, 1-760, 2-166, 2-209, 6-9 exhibit an anti-valence of 80% or more.

Further, the compound of the above compound code 2-3, 2-728, 2-782, 2-794, 2-870, 2-919, 2-920, 2-995, 2-1002 exhibited a control price of 80% or more.

Further, the compound of the above compound code 10-25, 10-62, 10-64, 11-69, 11-70, 11-187 exhibits an anti-valence of 80% or more.

Further, the aforementioned compound codes 11-123, 11-124, 11-128, 11-161, 11-344, 11-376, 11-452, 11-455, 11-465, The compounds of 11-499, 11-502, and 11-511 exhibited an anti-price of more than 80%.

[Test Example 3] Control test for Tetranychus urticae

For the vegetable bean seedlings (Phaseolus vulgaris) cultivated in a plastic cup, 10 female mites were placed in each cup. One day after the larvae were placed on the turntable, the emulsion dilution (500 ppm) prepared in accordance with Preparation Example 3 was evenly spread by a spray gun. After the treatment, the mixture was placed in a constant temperature room (16 hours of illumination) at 25 ° C, and the number of female adults parasitized was examined 8 days after the treatment, and the control price (%) was calculated by the following calculation formula (c). The test was repeated in 2 replicates.

By way of example, the aforementioned compound code 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-17, 1-18, 1-47, 1-48, 1 -53, 1-54, 1-55, 1-56, 1-57, 1-58, 1-61, 1-62, 1-73, 1-74, 1-89, 1-90, 1-95 , 1-96, 1-97, 1-99, 1-100, 1-102, 1-103, 1-106, 1-107, 1-108, 1-109, 1-110, 1-111, 1 -118,1-119, 1-132, 1-140, 1-141, 1-142, 1-147, 1-179, 1-187, 1-188, 1-199, 1-200, 1-209 ,1-210,1-211,1-212,1-213,1-214,1-215,1-216,1-227,1-228,1-237,1-238,1-243,1 -244,1-245,1-246,1-275,1-276,1-288,1-293,1-294,1-305,1-306,1-307,1-308,1-333 , 1-334, 1-372, 1-389, 1-390, 1-403, 1-404,1-409,1-410,1-421,1-422,1-448,1-471,1-472,1-495,1-496,1-508,1-559,1- 560, 1-561, 1-568, 1-569, 1-597, 1-608, 1-609, 1-616, 1-617, 1-628, 1-629, 1-625, 1-653, 1-684,1-685,1-702,1-703,1-708,1-709,1-714,1-715,1-720,1-721,1-722,1-723,1- 736, 1-737, 1-752, 1-753, 1-768, 1-769, 1-921, 1-952, 1-953, 1-954, 1-961, 1-962, 1-963, 2-7,2-8,2-34,2-35,2-58,2-59,2-66,2-67,2-82,2-83,2-93,2-108,2- 116,2-117,2-140,2-141,2-158,2-160,2-162,2-164,2-166,2-167,2-168,2-176,2-184, 2-185,2-186,2-193,2-194,2-200,2-201,2-202,2-203,2-204,2-205,2-206,2-207,2- 208,2-209,2-210,2-211,2-212,2-239,2-240,2-249,2-265,2-266,2-311,2-312,2-339, 2-340,2-363,2-364,2-413,2-414,2-421,2-423,2-431,2-432,2-447,2-448,2-449,2- 450,2-487,2-488,2-497,2-498,2-521,2-522,2-557,2-558,2-591,2-592,2-611,2-612, 2-625,2-626 , 2-639,2-655,2-656,2-699,2-700,3-1,3-2,3-9,3-10,6-3,6-4,6-5,6 -6,6-7,6-8,6-9,6-10,6-39,6-40,6-75,6-76,6-83,6-84,7-9,7-10 The compound exhibits an anti-price of more than 80%.

Also, 1-193, 1-194, 1-964, 1-965, 1-016, 1-117, 1-102, 1-102, 1-1024, 1-126, 1-127, 2-3, 2-4,2-401,2-402,2-405,2-406,2-417,2-439,2-440,2-443,2-444,2-527,2-528,2- 725,2-726,2-727,2-728,2-729,2-730,2-731,2-732,2-733,2-734,2-735,2-736, 2-737,2-738,2-739,2-740,2-743,2-744,2-745,2-746,2-747,2-748,2-749,2-750,2- 757,2-758,2-763,2-764,2-781,2-782,2-783,2-784,2-791,2-792,2-793,2-794,2-801, 2-802,2-803,2-804,2-813,2-814,2-815,2-816,2-817,2-818,2-823,2-824,2-825,2- 826,2-835,2-836,2-837,2-838,2-839,2-840,2-841,2-842,2-843,2-844,2-845,2-846, 2-847,2-848,2-849,2-850,2-851,2-852,2-853,2-855,2-856,2-858,2-860,2-861,2- 862,2-863,2-865,2-866,2-867,2-868,2-869,2-870,2-871,2-872,2-873,2-874,2-875, 2-876,2-877,2-878,2-879,2-880,2-882,2-885,2-886,2-887,2-888,2-889,2-890,2- 891,2-892,2-893,2-894,2-895,2-896,2-897,2-898,2-899,2-900,2-901,2-902,2-903, 2-904,2-905,2-906,2-907,2-908,2-909,2-910,2-911,2-912,2-913,2-914,2-915,2- 916,2-917,2-918,2-919,2-920,2-921,2-922,2-923,2-924,2-925,2-926,2-927,2-928, 2-929,2-930,2-931,2-932,2-933,2-934,2-935,2-936,2-937,2-938,2-939,2-940,2- 941,2-944,2-945,2-946,2-947,2-948,2-949,2-950,2-951,2-960,2-961,2-962,2-963, 2-964,2-965,2-966,2-967,2-968,2-969,2-970,2-971,2-974,2-975,2-976,2-977,2- 978,2-979,2-986,2-987,2-988,2-989,2-994,2-995,2-996,2-997,2-1000,2-1001,2-1004, 2-1005,2-1008,2-1009,2-1010,2-1011,2-1020,2-1021,2-1022,2-1023,2-1024,2-1025,2-1026,2- 1027,2-1030,2-1031, 2-1032,2-1033,2-1034,2-1035,2-1040,2-1041,2-1042,2-1043,2-1046,2-1047,2-1048,2-1049,2- 1050,2-1051,2-1052,2-1053,2-1068,2-1069,2-1070,2-1072,2-1073,2-1074,2-1076,2-1077,2-1078, Compounds of 2-1080, 2-1081, and 2-1082 exhibit an anti-price of more than 80%.

Further, the aforementioned compound code is 10-23, 10-24, 10-25, 10-62, 10-64, 10-65, 10-66, 11-6, 11-15, 11-32, 11-41, 11 -64,11-65,11-69,11-70,11-71,11-85,11-98,11-168,11-174,11-180,11-187,11-191,11-217 , 11-228, 11-284, 11-286, 11-287, 11-289, 11-290, 11-291, 11-302, 11-303, 11-305, 11-307, 11-359, 11 The compounds of -360, 11-362, 11-388, and 11-444 exhibited an anti-price of more than 80%.

Further, the aforementioned compound codes 11-8, 11-11, 11-20, 11-37, 11-46, 11-49, 11-51, 11-52, 11-54, 11-55, 11-58, 11 -59,11-62,11-92,11-123,11-124,11-126,11-128,11-131,11-133,11-137,11-144,11-146,11-147 ,11-156,11-158,11-159,11-161,11-162,11-164,11-170,11-176,11-182,11-185,11-189,11-199,11 -214,11-219,11-221,11-272,11-275,11-298,11-337,11-344,11-346,11-376,11-383,11-392,11-393 , 11-448, 11-449, 11-450, 11-451, 11-452, 11-453, 11-454, 11-455, 11-464, 11-465, 11-468, 11-470, 11 -475, 11-477, 11-478, 11-479, 11-484, 11-485, 11-486, 11-491, 11-494, 11-495, 11-496, 11-497, 11-498 , 11-500, 11-502, 11-503, 11-506, 11-508, 11-509, 11-511, The compounds of 11-512, 11-513, 11-515, 11-517, 11-518, 11-519, 11-520 exhibited a defense price of 80% or more.

Among the above compounds, 1-147, 1-179, 1-214, 1-288, 1-403, 1-409, 1-708, 1-709, 1-921, 1-963, 2-82, 2- 93 performance of more than 80% less than 90% of the price; 1-56, 1-103, 1-216, 1-238, 1-404, 1-472, 1-508, 1-653, 1-721, 1 -723,1-737,1-753,1-768,1-962,2-363,2-364,2-432,2-522,2-700,6-40 performance 90% or more and less than 100% Price control; 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-17, 1-18, 1-47, 1-48, 1-53, 1- 54,1-55,1-57,1-58,1-61,1-62,1-73,1-74,1-89,1-90,1-95,1-96,1-97, 1-99,1-100,1-102,1-106,1-107,1-108,1-109,1-110,1-111,1-118,1-119,1-132,1- 140, 1-141, 1-142, 1-187, 1-188, 1-199, 1-200, 1-209, 1-210, 1-211, 1-212, 1-213, 1-215, 1-227,1-228,1-237,1-243,1-244,1-245,1-246,1-275,1-276,1-293,1-294,1-305,1- 306, 1-307, 1-308, 1-333, 1-34, 1-372, 1-389, 1-390, 1-410, 1-421, 1-422, 1-48, 1-471, 1-495, 1-496, 1-559, 1-560, 1-561, 1-568, 1-69, 1-597, 1-608, 1-609, 1-616, 1-617 , 1-628, 1-629, 1-352, 1-684, 1-685, 1-702, 1-703, 1-714, 1-715, 1-720, 1-722, 1-736, 1 -752,1-769,1-952,1-953,1-954,1-961,2-7,2-8,2-34,2-35,2-58,2-59,2-66 ,2-67,2-83,2-108,2-116,2-117,2-140,2-141,2-158,2-160,2-162,2-164,2-166,2 -167,2-168,2-176,2-184,2-185,2-186,2-193,2-194,2-200,2-201,2-202,2-203,2-204 , 2-205,2-206,2-207,2-208,2-209,2-210,2-211,2-212,2-239,2-240,2-249,2-265,2- 266,2-311,2-312,2-339,2-340,2-413,2-414,2-421,2-423,2-431,2-447,2-448,2-449, 2-450,2-487,2-488,2-497,2-498,2-521,2-557,2-558,2-591,2-592,2-611,2-612,2- 625,2-626,2-639,2-655,2-656,2-699,3-1,3-2,3-9,3-10,6-3,6-4,6-5, 6-6,6-7,6-8,6-9,6-10,6-39,6-75,6-76,6-83,6-84,7-9,7-10 performance 100% Defence prevention.

Further, among the above compounds, 2-939 exhibits an anti-valence of 80% or more and less than 90%; 1-107, 2-850, 2-868, 2-885, 2-887, 2-889, 2-908, 2 -921, 2-927, 1-127, showing more than 90% of the defense price less than 100%; 1-193, 1-194, 1-964, 1-965, 1-016, 1-017, 1-120 ,1-1021,1-1024,1-1026,2-3,2-4,2-401,2-402,2-405,2-406,2-417,2-439,2-440,2 -443,2-444,2-527,2-528,2-725,2-726,2-727,2-728,2-729,2-730,2-731,2-732,2-733 , 2-734,2-735,2-736,2-737,2-738,2-739,2-740,2-743,2-744,2-745,2-746,2-747,2 -748,2-749,2-750,2-757,2-758,2-763,2-764,2-781,2-782,2-783,2-784,2-791,2-792 ,2-793,2-794,2-801,2-802,2-803,2-804,2-813,2-814,2-815,2-816,2-817,2-818,2 -823,2-824,2-825,2-826,2-835,2-836,2-837,2-838,2-839,2-840,2-841,2-842,2-843 ,2-844,2-845,2-846,2-847,2-848,2-849,2-851,2-852,2-853,2-855,2-856,2-858,2 -860,2-861,2-862,2-863,2-865,2-866,2-867 , 2-869, 2-870,2-871,2-872,2-873,2-874,2-875,2-876,2-877,2-878,2-879,2-880,2-882,2- 886,2-888,2-890,2-891,2-892,2-893,2-894,2-895,2-896,2-897,2-898,2-899,2-900, 2-901,2-902,2-903,2-904,2-905,2-906,2-907,2-909,2-910,2-911,2-912,2-913,2- 914,2-915,2-916,2-917,2-918,2-919,2-920,2-922,2-923,2-924,2-925,2-926,2-928, 2-929,2-930,2-931,2-932,2-933,2-934,2-935,2-936,2-937,2-938,2-940,2-941,2- 944,2-945,2-946,2-947,2-948,2-949,2-950,2-951,2-960,2-961,2-962,2-963,2-964, 2-965,2-966,2-967,2-968,2-969,2-970,2-971,2-974,2-975,2-976,2-977,2-978,2- 979,2-986,2-987,2-988,2-989,2-994,2-995,2-996,2-997,2-1000,2-1001,2-1004,2-1005, 2-1008,2-1009,2-1010,2-1011,2-1020,2-1021,2-1022,2-1023,2-1024,2-1025,2-1026,2-1027,2- 1030,2-1031,2-1032,2-1033,2-1034,2-1035,2-1040,2-1041,2-1042,2-1043 2-1046, 2-1047, 2-1048, 2-1049, 2-1050, 2-1051, 2-1052, 2-1053, 2-1068, 2-1069, 2-1070, 2-1072, 2- 1073, 2-1074, 2-1076, 2-1077, 2-1078, 2-1080, 2-1081, 2-1082, 3-53, 3-54 showed 100% price control.

Further, among the above compounds, 11-362 exhibits an anti-price of 80% or more and less than 90%; 11-64, 11-85, 11-174, 11-217, 11-228 exhibits a control of 90% or more and less than 100%. Price; 10-23, 10-24, 10-25, 10-62, 10-64, 10-65, 10-66, 11-6, 11-15, 11-32, 11-41, 11-65, 11-69, 11-70, 11-71, 11-98, 11-168, 11-180, 11-187, 11-191, 11-284, 11-286, 11-287, 11- 289, 11-290, 11-291, 11-302, 11-303, 11-305, 11-307, 11-359, 11-360, 11-388, 11-444 exhibited 100% control.

Further, among the above compounds, 11-383, 11-455, 11-496, 11-497, and 11-518 exhibit 80% or more and less than 90% of the control price; 11-11, 11-20, 11-46, 11 -137,11-161,11-170,11-219,11-452,11-453,11-494,11-495,11-498 exhibiting more than 90% of the defense price less than 100%; 11-8, 11-37,11-49,11-51,11-52,11-54,11-55,11-58,11-59,11-62,11-92,11-123,11-124,11- 126,11-128,11-131,11-133,11-144,11-146,11-147,11-156,11-158,11-159,11-162,11-164,11-176, 11-182, 11-185, 11-189, 11-199, 11-214, 11-221, 11-272, 11-275, 11-298, 11-337, 11-344, 11-346, 11- 376, 11-392, 11-393, 11-448, 11-449, 11-450, 11-451, 11-454, 11-464, 11-465, 11-468, 11-470, 11-475, 11-477, 11-478, 11-479, 11-484, 11-485, 11-486, 11-491, 11-500, 11-502, 11-503, 11-506, 11-508, 11- 509, 11-511, 11-512, 11-513, 11-515, 11-517, 11-519, 11-520 exhibit 100% price control.

[Test Example 4] Control test for two-spotted spider mites 2

The bean sprouts (second leaf stage) cultivated in a plastic cup were placed on a turntable, and the compound of the present invention was uniformly dispersed by a spray gun in accordance with the emulsion dilution (5 ppm) prepared in Formulation Example 3. After spreading, put it in a 25 ° C constant temperature room (16 hours of illumination), after 7 days, on the leaf disc made by cutting the first leaf A leaf disc was placed on the larvae of the larvae and the larvae were placed in a constant temperature room at 25 ° C. The number of female adults was investigated 2 days after the larvae, and the mortality rate (%) was calculated by the following calculation formula (d). The test was repeated in 2 replicates.

Test Example 4 is a study on the residual effect of the compound of the present invention on the spider mites. The compound of the present invention was dispersed in a bean sprout (second leaf stage) in accordance with the 5 ppm emulsion diluent prepared in Formulation Example 3 and allowed to stand for 7 days. Then, on the leaf disc made by cutting the first leaf, 10 mites were placed, and the number of individuals of the two-spotted spider mites survived after 2 days of larvae. Disperse the medicine and confirm the control effect after 7 days of standing, and investigate the residual effect.

In the following Table 15, the results of the above-mentioned control test 2 for the two-spotted spider mites were carried out using the compound in the present specification. Further, in the following Table 15, the compounds described in Reference Examples 1, 3, 5, 7, 13, 14, 19 to 22 are 3.3 ppm emulsion diluents tested in accordance with the method of Test Example 3 above. The control price was low, and the control activity was further reduced after 7 days of spreading. Therefore, the above-mentioned control test for the two-point spider mites was not carried out.

[Summary of Test Example 4]

As shown in Examples 1 to 4, the compound of the above compound code 2-209, 2-210, 2-447, 2-48 was a very excellent dead insect rate of 89.5% to 100%, and remained high after 7 days of spreading. It has excellent residual effect by controlling activity.

Further, the molecular structure of the compound of Example 1 was slightly different from that of the compounds of Reference Examples 1, 3, 5, and 7, since the 3.3 ppm emulsion dilution which was tested in accordance with the method of Test Example 3 above was known to the steroids. The control activity was low, and the control activity after 7 days of spreading was further lowered. Therefore, the above-mentioned control test for the two-spotted spider mites was not carried out.

With respect to the molecular structure of the compound of Example 2, Reference Example 2 having the compound code 2-8 having a different molecular structure in the case where R ^1a and R ^2a are hydrogen atoms was used, and the use was such that R ^2a is a hydrogen atom. Reference Example 4 of Compound No. 2-35 having a different molecular structure, Reference Example 8 having a compound number 2-266 having a different molecular structure in the case where both R ^1a and R ^2a are methyl groups, respectively, The mortality rate was 27.8%, 8.2%, and 4.5%. Compared with the mortality rate of 95.0% in Example 2, the mortality rate was low and the residual efficiency was poor.

In the molecular structure of the compound of Example 2, the death rate of Reference Example 6 using Compound No. 2-204 was 0%, and no residual effect was observed at all. The compound code 2-204 was 3 having a benzene ring. The substituted fluorine atom at the 4th and 5th positions is a compound having a molecular structure in which a fluorine atom is substituted at the 3, 4 position and a substitution number of the fluorine atom is reduced.

Using Reference Examples 9 and 10 of Compound Nos. 2-405 and 2-406, the respective dead insect rates were 38.9%, 24.7%, and although the residual effect was also observed, the examples with the dead insect rate were 100%. Compared with 3,4, the residual property is inferior, and the compound codes 2-405 and 2-406 are molecular structures different from those of the structures of Examples 3 and 4, in which both R ^1a and R ^2a are hydrogen atoms. Compound.

The death rate of Examples 1 and 2 using a compound having a molecular structure in which X ² is a fluorine atom was 89.5% and 95.0%, respectively, compared to Example 3 using a compound having a molecular structure in which X ² is a chlorine atom, The mortality rate of 4 was 100%, and the dead worm rates of Reference Examples 11, 12 using the compound code 2-557, 2-558 having a molecular structure of X ² being a bromine atom were 36.8% and 42.1%, respectively. X ² compound to a halogen atom, X ² is a fluorine atom, chlorine atom, and X ² are bromine atoms as compared with significantly excellent residual effect.

The mortality rates of the compounds used in Reference Examples 15 to 18 described in Tables 15-2 and 15-3 were 10.6%, 47.7%, 15.0%, and 12.5%, respectively, compared with the compounds used in Examples 1 to 4. , the rate of dead insects is low and the residual effect is poor. Further, in Reference Examples 13, 14, 19 to 22, since the control activity against guanidine was low at a concentration of 3.3 ppm which was tested in accordance with the method of Test Example 3 above, the above-mentioned control test 2 for the two-spotted spider mites was not carried out.

Among the compounds shown in Table 15, the four compounds of 2-209, 2-210, 2-447, and 2-48 exhibited a very excellent mortality rate after 7 days of spreading, and it was confirmed that the structure was a little Differences can make a big difference to the residual effect.

These four kinds of compounds also maintained high control activity after 7 days of spreading, and exhibited extremely excellent residual effects. Moreover, the number of individuals of the four kinds of compounds which caused the larvae of the two species of spider mites decreased greatly in only two days after the spread of the four compounds. Quick effect is also excellent.

From the above results, it was confirmed that the pest control agent of the present invention is a useful pest control agent for any of the above-mentioned pests. Further, the compound represented by the formula (1-2) is confirmed to have both residual effect and quick-acting property, and thus is particularly useful as an acaricide.

[Test Example 5] Control test for two-spotted spider mites 3

For the bean sprouts cultivated in plastic cups, 10 female mites were placed in the adult mites. One day after the larvae were placed on the turntable, the emulsion dilution (3.3 ppm) prepared in accordance with Preparation Example 3 was evenly spread by a spray gun. After spreading, it was placed in a constant temperature room (16 hours of illumination) at 25 ° C, and after 8 days of treatment, the number of females parasitic was investigated, and the control price (%) was calculated by the above calculation formula (c). The test was repeated in 2 replicates.

Test Example 5 was carried out by controlling the control of the two-spotted spider mites at 500 ppm in Test Example 3 to a low concentration of 3.3 ppm. In the following Table 16, the results of the above-mentioned control test 3 for the two-spotted spider mites were carried out using the compounds in the present specification.

By way of example, the aforementioned compound code is 2-209,2-210,2-447,2-448,2-909,2-910,2-911,2-912,2-914,2-915,2 Compounds of -916, 2-920 exhibit more than 90% control. As a reference example, the compound of the above compound code 2-7, 2-8, 2-727 has a control price of less than 60%.

[Test Example 6] Control test for the two-spotted spider mites 4

The bean sprouts (second leaf stage) cultivated in a plastic cup were placed on a turntable, and the compound of the present invention was uniformly dispersed by a spray gun in accordance with the emulsion dilution (5 ppm) prepared in Formulation Example 3. After spreading, put it in a constant temperature room at 25 °C (16 hours of illumination). After 7 days, 10 pieces of larvae of the two leaf mites are placed on the leaf disc made by cutting the first leaf, and the chamber is kept at 25 °C. Stand still. The number of female adults was investigated after the second day of the larvae, and the mortality rate (%) was calculated by the above calculation formula (d). The test was repeated in 2 replicates.

Test Example 6 is to investigate the residual effect of the compound of the present invention on the spider mites. The compound of the present invention was dispersed in a bean sprout (second leaf stage) in accordance with the 5 ppm emulsion diluent prepared in Formulation Example 3 and allowed to stand for 7 days. Then, on the leaf disc made by cutting the first leaf, 10 mites were placed, and the number of individuals of the two-pointed spider mites survived after 2 days of larvae. Disperse the drug and investigate the residual effect by confirming the control effect after 7 days of standing. In the following Table 17, the results of the above-mentioned control test 4 for the two-spotted spider mites were carried out using the compounds in the present specification.

By way of example, the compounds of the above-mentioned compound numbers 2-912, 2-914, 2-916, 2-920 exhibit very excellent mortality rates of 86.8% to 100%, and maintain high control activity after 7 days of spreading. Excellent residual effect. For the reference example, the aforementioned compound code 2-8, 2-35, 2-204, 2-266, 2-405, 2-406, 2-557, 2-558, 2-727, 2-728, 2 -729, The mortality rate of the compound of 2-730 is 0 to 42.1%.

[Test Example 7] Control test for two-spotted spider mites 5

The glass dish was filled with 0.3% of the sauerkraut, and the leaf discs of the diameter of 3 cm of the beans were placed three times each. There were 10 adult females of the leaf larvae of the leaf discs. After the larvae, the emulsion dilution (1 ppm) prepared in accordance with Preparation Example 3 was uniformly spread by an automatic dispersing device (manufactured by Ikeda Chemical Co., Ltd.). After the dispersion, the temperature was placed in a constant temperature room at 25 ° C (16 hours of illumination), and the number of living insects was investigated after 3 days, and the mortality rate (%) was calculated by the following calculation formula (e). In the following Table 18, the results of the above-mentioned control test for the two-spotted spider mites were carried out using the compounds in the present specification.

By way of example, the compounds of the aforementioned compound numbers 2-209, 2-210, 2-447, 2-448, 2-920 exhibit very excellent mortality rates of 84% to 100%. For the reference example, the compound of the aforementioned compound code 2-35, 2-266, 2-557, 2-727 has a mortality rate of 0 to 37%.

(industrial availability)

The substituted phenyl ether compound of the present invention has an excellent control effect against harmful organisms, and thus it is used as a pest control agent. When used, it can effectively prevent pests. In particular, the compound represented by the formula (1-2) is useful as an active ingredient of an acaricide because it has both residual and quick-acting properties.

The N-substituted aniline compound of the present invention has an excellent control effect against harmful organisms, and therefore, when it is used as a pest control agent, it can effectively prevent pests.

Claims (29)

A substituted phenyl ether compound of the formula (1): In the formula (1), A represents a C ₂ to C ₅ haloalkyl group, a C ₂ to C ₅ haloalkenyl group or a substituted C ₃ to C ₈ cycloalkyl group C ₁ to C ₄ alkyl group (the group may be a halogen atom or a C ₁ to C ₃ alkyl group monosubstituted or polysubstituted), n represents any integer of 0 to 2; X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, and may be substituted by a halogen atom. a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom, a C ₃ to C ₆ cycloalkyl group or an aryl group which may be substituted with a halogen atom; however, both X ¹ and X ² Except in the case of a hydrogen atom; Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amine group, a formazan group, a C ₁ to C ₆ alkyl group which may be substituted with a halogen atom, and a C ₁ which may be substituted with a halogen atom. to C ₆ alkoxy group, a halogen atom may be substituted by a C ₁ to C ₆ alkylthio group, a halogen atom may be substituted with C ₁ to C ₆ alkylsulfinyl acyl, a halogen atom may be substituted with C ₁ to C ₆ alkylsulfonyl, C ₁ to C ₆ alkylamino, di C ₁ to C ₆ alkylamino, C ₁ to C ₆ alkylcarbonyl, C ₁ to C ₆ alkoxycarbonyl, C ₁ to C ₆ alkoxy a benzylamino group, an aryl group which may be substituted with a halogen atom, a aryloxy group which may be substituted (the group may be a halogen atom, a cyano group, a C ₁ to C ₃ alkyl group, C) ₁ to C ₃ haloalkyl, C ₁ to C ₃ alkoxy, C ₁ to C ₃ haloalkoxy, C ₁ to C ₃ alkylthio, C ₁ to C ₃ haloalkylthio, C ₁ to C ₃ -alkylsulfinyl, C ₁ to C ₃ haloalkylsulfinyl, C ₁ to C ₃ alkylsulfonyl, C ₁ to C ₃ haloalkylsulfonyl, C ₁ to C ₃ alkane a carbonyl group or a C ₁ to C ₃ alkoxycarbonyl mono- or polysubstituted), substitutable arylthio group (the group may be via a halogen atom, a cyano group, a C ₁ to C ₃ alkyl group, a C ₁ to C ₃ haloalkyl group) a C ₁ to C ₃ alkoxy group, a C ₁ to C ₃ haloalkoxy group, a C ₁ to C ₃ alkylthio group, a C ₁ to C ₃ haloalkylthio group, a C ₁ to C ₃ alkyl sulfinium group a C ₁ to C ₃ haloalkylsulfinyl group, a C ₁ to C ₃ alkylsulfonyl group, a C ₁ to C ₃ haloalkylsulfonyl group, a C ₁ to C ₃ alkylcarbonyl group or a C ₁ to C group ₃ alkoxycarbonyl mono- or polysubstituted), substituted arylsulfinyl (this group may be via a halogen atom, a cyano group, a C ₁ to C ₃ alkyl group, a C ₁ to C ₃ haloalkyl group, C ₁ to C ₃ alkoxy, C ₁ to C ₃ haloalkoxy, C ₁ to C ₃ alkylthio, C ₁ to C ₃ haloalkylthio, C ₁ to C ₃ alkylsulfinyl, C ₁ to C ₃ alkylsulfinyl halo acyl groups, C ₁ to C ₃ alkylsulfonyl groups, C ₁ to C ₃ halo alkylsulfonyl groups, C ₁ to C ₃ alkyl Or C ₁ to C ₃ alkoxycarbonyl-substituted or mono-substituted), aryl groups may be substituted sulfonylurea group (the group may be a halogen atom, a cyano group, a C ₁ to C ₃ alkyl group, a C ₁ to C ₃ Haloalkyl, C ₁ to C ₃ alkoxy, C ₁ to C ₃ haloalkoxy, C ₁ to C ₃ alkylthio, C ₁ to C ₃ haloalkylthio, C ₁ to C ₃ alkyl Sulfonyl, C ₁ to C ₃ haloalkylsulfinyl, C ₁ to C ₃ alkylsulfonyl, C ₁ to C ₃ haloalkylsulfonyl, C ₁ to C ₃ alkylcarbonyl or C ₁ a C ₇ to C ₁₁ aralkyloxy group which may be mono- or polysubstituted with a C ₃ alkoxycarbonyl group or a halogen atom, m represents an integer of 1 to 5; and, m represents an integer of 2 to 5 Y may be the same or different; and when m is an integer of 2 or more, adjacent Y may be bonded to each other to represent -OCH ₂ O-, -OCF ₂ O-, -OCH ₂ CH ₂ O-, -OCF ₂ CH ₂ O- or -OCF ₂ CF ₂ O-; R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted with a halogen atom, a C ₁ to C ₄ alkoxy group, a C ₃ to C ₆ cycloalkyl group, a C ₁ to C ₄ alkylcarbonyloxy group or a benzyloxy group which may be substituted by a halogen atom, and p represents any integer of 1 to 5; , p means 2 to 5 In the case of an integer, R ¹ and R ² on different carbon atoms may be the same or different; in addition, R ¹ and R ² on the same carbon atom may be bonded to one oxygen atom or sulfur atom individually and expressed as ( = O) or (= S); and, R on the same carbon atom ¹ and R ² may be bonded to simultaneously represents a C ₁ to C ₄ alkoxyimino group; and, R on the same carbon atom, ¹ and R ² may be bonded to each other to form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring in 2 to 5 alkylene groups; Z represents an oxygen atom, a sulfur atom, a sulfinyl group or a sulfonyl group. , q represents any integer of 0 or 1, but p and q cannot be 1 at the same time. The substituted phenyl ether compound according to claim 1, wherein in the above formula (1), A represents a C ₂ to C ₅ haloalkyl group, and n represents an integer of 0 to 2, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a fluorine atom may be substituted with C ₁ to C ₆ alkyl group, a C ₁ to C ₆ alkoxy, cyclopropyl, cyclobutyl, cyclopentyl, Or phenyl (except where X ¹ and X ² are both hydrogen atoms), Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amine group, a C ₁ to C ₆ alkane which may be substituted by a halogen atom group, a halogen atom may be substituted with C ₁ to C ₄ alkoxy group, C ₁ to C ₄ alkylthio group, a C ₁ to C ₄ alkylsulfinyl acyl, a C ₁ to C ₄ alkylsulfonyl group, C ₁ to C ₄ alkylamino group, di C ₁ to C ₄ alkylamino group, C ₁ to C ₄ alkylcarbonyl group, C ₁ to C ₄ alkoxycarbonyl group, C ₁ to C ₄ alkoxyiminomethyl group, a phenyl group substituted with a halogen atom, a phenoxy group which may be substituted with a halogen atom, or a C ₇ to C ₁₁ aralkyloxy group, m represents any integer of 1 to 5, and m represents an integer of 2 to 5, Y May be the same or different, and when m represents an integer of 2 or more, adjacent Ys may be bonded to each other to represent -OCH ₂ O- or -OCF ₂ O- R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a C ₁ to C ₆ alkyl group, a C ₁ to C ₄ alkoxy group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, C ₁ to C ₄ alkylcarbonyloxy or benzyloxy, p represents an integer of 1 to 5, and p represents an integer of 2 to 5, and R ¹ and R ² on different carbon atoms may be the same or not Similarly, R ¹ and R ² on the same carbon atom may be individually bonded to one oxygen atom or sulfur atom to represent (=O) or (=S), and R ¹ and R ² on the same carbon atom. It can be bonded at the same time, and is represented by a C ₁ to C ₄ alkoxyimine group, and R ¹ and R ² on the same carbon atom can be bonded to each other to form a 3-membered ring with 2 to 5 alkylene groups. 4-membered ring, 5-membered ring and 6-membered ring, Z represents an oxygen atom, a sulfur atom, a sulfinyl group or a sulfonyl group, and q represents an integer of 0 or 1 (however, p and q cannot be 1 at the same time). The substituted phenyl ether compound according to claim 1, wherein in the above formula (1), A represents a C ₃ to C ₈ cycloalkyl C ₁ to C ₄ alkyl group which may be substituted ( The group may be mono- or polysubstituted by a halogen atom or a C ₁ to C ₃ alkyl group, and n represents any integer of 0 to 2, and X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, or the like. a C ₁ to C ₆ alkyl group substituted with a fluorine atom, a C ₁ to C ₆ alkoxy group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a phenyl group (however, X ¹ and X ² are each a hydrogen atom) Except for the above), Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amine group, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₄ alkoxy group which may be substituted with a halogen atom, C ₁ to C ₄ alkylthio, C ₁ to C ₄ alkylsulfinyl, C ₁ to C ₄ alkylsulfonyl, C ₁ to C ₄ alkylamino, di C ₁ to C ₄ alkylamino, a C ₁ to C ₄ alkylcarbonyl group, a C ₁ to C ₄ alkoxycarbonyl group, a C ₁ to C ₄ alkoxyiminomethyl group, a phenyl group which may be substituted with a halogen atom, a phenoxy group which may be substituted with a halogen atom, Or C ₇ to C ₁₁ aralkyloxy, m represents any integer from 1 to 5, and m represents an integer from 2 to 5, and Y may be the same or not Similarly, when m represents an integer of 2 or more, adjacent Ys may be bonded to each other to represent -OCH ₂ O- or -OCF ₂ O-; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, Cyano, C ₁ to C ₆ alkyl, C ₁ to C ₄ alkoxy, cyclopropyl, cyclobutyl, cyclopentyl, C ₁ to C ₄ alkylcarbonyloxy or benzyloxy, p represents 1 Any integer up to 5, where p represents an integer from 2 to 5, R ¹ and R ² on different carbon atoms may be the same or different, and R ¹ and R ² may be individually and one on the same carbon atom. An oxygen atom or a sulfur atom is bonded to (=O) or (=S), and R ¹ and R ² on the same carbon atom may be bonded at the same time, and represented as a C ₁ to C ₄ alkoxyimine. R ¹ and R ² on the same carbon atom may be bonded to each other, and 2 to 5 alkyl groups form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring, and Z represents an oxygen atom and sulfur. An atom, a sulfinyl group or a sulfonyl group, and q represents an integer of 0 or 1 (however, p and q cannot be 1 at the same time). The substituted phenyl ether compound according to claim 1, wherein in the above formula (1), A represents a C ₂ to C ₅ haloalkyl group, and n represents any integer of 0 to 2, X ¹ represents a halogen atom, a C ₁ to C ₄ alkyl group or a methoxy group, and X ² represents a hydrogen atom, a halogen atom, a cyano group, a C ₁ to C ₄ alkyl group which may be substituted by a fluorine atom, a methoxy group, a cyclopropyl group Or phenyl, Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amine group, a C ₁ to C ₄ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₄ alkoxy group which may be substituted with a halogen atom, C ₁ to C ₄ alkylthio group, C ₁ to C ₄ alkylsulfinyl group, C ₁ to C ₄ alkylsulfonyl group, C ₁ to C ₄ alkylamino group, di C ₁ to C ₄ alkylamino group a C ₁ to C ₄ alkoxycarbonyl group, a C ₁ to C ₄ alkoxyiminomethyl group or a phenoxy group which may be substituted with a halogen atom, m represents any integer of 1 to 5, and m represents 2 to 5 In the case of an integer, Y may be the same or different, and when m represents an integer of 2 or more, adjacent Y may be bonded to each other to represent -OCH ₂ O- or -OCF ₂ O-, and R ¹ and R ² each independently represent hydrogen. Atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, C ₁ to C ₆ alkyl group, C ₁ to C ₄ alkoxy group or C ₁ to C ₄ alkane A carbonyloxy group, p represents any integer from 1 to 3, and p represents an integer of 2 or 3, and R ¹ and R ² on different carbon atoms may be the same or different, and R ¹ and R on the same carbon atom. ² may be respectively bonded to one oxygen atom to represent (=O), and further, R ¹ and R ² on the same carbon atom may be bonded at the same time to represent a C ₁ to C ₄ alkoxyimine group; R ¹ and R ² on the same carbon atom may be bonded to each other, and 2 to 5 alkyl groups form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring, and Z represents an oxygen atom, and q represents Any integer of 0 or 1 (however, p and q cannot be 1 at the same time). The substituted phenyl ether compound according to claim 1, wherein in the above formula (1), A represents a C ₃ to C ₈ cycloalkyl C ₁ to C ₄ alkyl group which may be substituted ( The group may be mono- or polysubstituted by a halogen atom or a C ₁ to C ₃ alkyl group, n represents any integer of 0 to 2, and X ¹ represents a halogen atom, a C ₁ to C ₄ alkyl group or a methoxy group, X ² represents a hydrogen atom, a halogen atom, a cyano group, a C ₁ to C ₄ alkyl group which may be substituted by a fluorine atom, a methoxy group, a cyclopropyl group or a phenyl group, and Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, Amino group, C ₁ to C ₄ alkyl group which may be substituted by a halogen atom, C ₁ to C ₄ alkoxy group which may be substituted by a halogen atom, C ₁ to C ₄ alkylthio group, C ₁ to C ₄ alkyl sulfinic acid Mercapto, C ₁ to C ₄ alkylsulfonyl, C ₁ to C ₄ alkylamino, di C ₁ to C ₄ alkylamino, C ₁ to C ₄ alkoxycarbonyl, C ₁ to C ₄ alkoxy An iminomethyl group or a phenoxy group which may be substituted by a halogen atom, m represents an integer of 1 to 5, and m represents an integer of 2 to 5, and Y may be the same or different, and m represents an integer of 2 or more. adjacent to each other may be bonded to Y denotes -OCH ₂ O- or -OCF ₂ O-; R ¹ and R ² each independently represent a hydrogen atom, a fluorine , A chlorine atom, a bromine atom, a hydroxyl group, a C ₁ to C ₆ alkyl group, a C ₁ to C ₄ alkoxy groups or C ₁ to C ₄ alkoxy carbonyl group, P represents any one integer of 1 to 3, P 2 represents when integer of 3 or, R on different carbon atoms ¹ and R ² may be the same or different, R on the same carbon atom ¹ and R ² may be an individual with an oxygen atom bonded to and is expressed as (= O) Further, R ¹ and R ² on the same carbon atom may be bonded at the same time to represent a C ₁ to C ₄ alkoxyimine group; in addition, R ¹ and R ² on the same carbon atom may be bonded to each other. 2 to 5 alkyl groups form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring, Z represents an oxygen atom, and q represents an integer of 0 or 1 (however, p and q cannot simultaneously 1). The substituted phenyl ether compound according to claim 1, wherein in the above formula (1), A represents 2,2,2-trifluoroethyl, and n represents any integer of 0 or 1. , X ¹ represents a halogen atom or a C ₁ to C ₄ alkyl, X ² represents a halogen atom, a cyano group or a fluorine atom may be substituted by a C ₁ to C ₄ alkyl group, Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano a C ₁ to C ₄ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₄ alkoxy group which may be substituted by a halogen atom, a C ₁ to C ₄ alkylthio group, a C ₁ to C ₄ alkyl sulfinium group a C ₁ to C ₄ alkylsulfonyl group or a phenoxy group which may be substituted by a halogen atom, m represents any integer of 1 to 5, and m represents an integer of 2 to 5, and Y may be the same or different, m When an integer of 2 or more is represented, adjacent Ys may be bonded to each other to represent -OCF ₂ O-; and R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, and C ₁ to C. ₆ alkyl or C ₁ to C ₄ alkoxy, p represents any integer from 1 to 3, and p represents an integer of 2 or 3, and R ¹ and R ² on different carbon atoms may be the same or different, in R ¹ and R ² on the same carbon atom may be bonded to one oxygen atom individually and expressed as ( =O), R ¹ and R ² on the same carbon atom may be bonded to each other to form a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring with 2 to 5 alkyl groups, Z Indicates an oxygen atom, and q represents an integer of 0 or 1 (however, p and q cannot be 1 at the same time). The substituted phenyl ether compound according to claim 1, wherein in the above formula (1), A represents a cyclopropylmethyl group, n represents an integer of 0 or 1, and X ¹ represents a halogen. atom or a C ₁ to C ₄ alkyl, X ² represents a halogen atom, a cyano group or a fluorine atom may be substituted by a C ₁ to C ₄ alkyl group, Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a halogen may be substituted C ₁ to C ₄ alkyl group, a halogen atom may be substituted with C ₁ to C ₄ alkoxy group, C ₁ to C ₄ alkylthio group, a C ₁ to C ₄ alkylsulfinyl acyl, a C ₁ to a C ₄ alkylsulfonyl group or a phenoxy group which may be substituted by a halogen atom, m represents an integer of 1 to 5, m represents an integer of 2 to 5, Y may be the same or different, and m represents an integer of 2 or more. When adjacent Y may be bonded to each other to represent -OCF ₂ O-, R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a C ₁ to C ₆ alkyl group or C. ₁ to C ₄ alkoxy, p represents any integer from 1 to 3, and p represents an integer of 2 or 3, and R ¹ and R ² on different carbon atoms may be the same or different, on the same carbon atom. R ¹ and R ² may individually with one oxygen atom as represented by junctions (= O) On the same carbon atom of R ¹ and R ² may be bonded to each other to 2-5 alkylene group forming a cyclopropane ring, cyclobutane ring, cyclopentane ring and cyclohexane ring, Z represents an oxygen atom, q represents any integer of 0 or 1 (however, p and q cannot be 1 at the same time). The substituted phenyl ether compound according to claim 1, wherein the compound represented by the formula (1a): Formula (1a) represents the above formula (1) in which q is 0 and p is 2; in this case, R ¹ may be represented by R ^1a and R ^1b , and R ² may be represented by R ^2a and R ^2b ; in formula (1a), A Represents 2,2,2-trifluoroethyl, n represents any integer of 0 or 1, X ¹ represents a halogen atom or a C ₁ to C ₄ alkyl group; X ² represents a halogen atom, a cyano group or may be substituted by a fluorine atom C ₁ to C ₄ alkyl; Y represents a halogen atom, a nitro group, a cyano group, a C ₁ to C ₄ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₄ alkoxy group which may be substituted with a halogen atom, C alkoxy _{of 1} to C ₄ -alkylthio, C ₁ to C ₄ alkylsulfinyl acyl group, C ₁ to C ₄ alkylsulfonyl group or a halogen atom may be substituted phenoxy group, m represents any integer of 1 to 5 When m represents an integer of 2 to 5, Y may be the same or different; and when m represents an integer of 2 or more, adjacent Ys may be bonded to each other to represent -OCF ₂ O-; R ^1a and R ^2a Respectively, respectively, a fluorine atom, a chlorine atom or a bromine atom; and R ^1a and R ^2a on the same carbon atom may be individually bonded to one oxygen atom to represent (=O); R ^1b and R ^2b are independently The ground represents a hydrogen atom or a C ₁ to C ₄ alkyl group. The substituted phenyl ether compound according to claim 8, wherein in the above formula (1a), A represents a cyclopropylmethyl group, n represents an integer of 0 or 1, and X ¹ represents a halogen. atom or a C ₁ to C ₄ alkyl, X ² represents a halogen atom, a cyano group or a fluorine atom may be substituted by a C ₁ to C ₄ alkyl group, Y represents a halogen atom, a nitro group, a cyano group, may be substituted with a halogen atom a C ₁ to C ₄ alkyl group, a halogen atom may be substituted by a C ₁ to C ₄ alkoxy group, C ₁ to C ₄ alkylthio group, a C ₁ to C ₄ alkylsulfinyl acyl, a C ₁ to C ₄ alkyl A sulfonyl group or a phenoxy group which may be substituted by a halogen atom, m represents an integer of 1 to 5, m represents an integer of 2 to 5, Y may be the same or different, and m represents an integer of 2 or more, The adjacent Y may be bonded to each other and represented by -OCF ₂ O-, and R ^1a and R ^2a each independently represent a fluorine atom, a chlorine atom or a bromine atom, and R ^1a and R ^2a on the same carbon atom may be individually and one. The oxygen atom is bonded to represent (=O), and R ^1b and R ^2b each independently represent a hydrogen atom or a C ₁ to C ₄ alkyl group. A phenol compound, which is an intermediate for the production of a substituted phenyl ether compound according to any one of claims 1 to 9, which is a compound represented by the formula (2): In the formula (2), A represents a C ₃ to C ₈ cycloalkylmethyl group which may be substituted (the group may be mono- or polysubstituted by a fluorine atom or a C ₁ to C ₃ alkyl group), and n represents 0 or 1. Any integer; X ¹ represents a C ₁ to C ₄ alkyl group, and X ² represents a hydrogen atom, a halogen atom or a C ₁ to C ₄ alkyl group. The phenol compound according to claim 10, wherein, in the above formula (2), A represents a cyclopropylmethyl group, n represents an integer of 0 or 1, and X ¹ represents a C ₁ to C ₄ alkane. Base, X ² represents a halogen atom. A pest control agent comprising the substituted phenyl ether compound according to any one of claims 1 to 9 as an active ingredient. An insecticide or an acaricide which contains the substituted phenyl ether compound according to any one of claims 1 to 9 as an active ingredient. A substituted phenyl ether compound of the formula (1-3): Formula (1-3) represents that q is 0 and one of Y is a phenoxy group which may be substituted, a phenylthio group which may be substituted, a phenylsulfinyl group which may be substituted or a phenyl group which may be substituted In the above formula (1) in the case of a sulfonyl group, in the formula (1-3), A represents a C ₂ to C ₅ haloalkyl group, a C ₂ to C ₅ haloalkenyl group or a substituted C ₃ to C ₈ naphthenic group. a group C ₁ to C ₄ alkyl (the group may be mono- or polysubstituted by a halogen atom or a C ₁ to C ₃ alkyl group), n represents any integer of 0 to 2; X ¹ and X ² each independently represent hydrogen An atom, a halogen atom, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom, a C ₃ to C ₆ cycloalkyl group or a halogen atom a substituted aryl group; however, except that both X ¹ and X ² represent a hydrogen atom; Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a decyl group, and a C ₁ to C ₆ alkane which may be substituted with a halogen atom. group, a halogen atom may be substituted with C ₁ to C ₆ alkoxy, a halogen atom may be substituted with C ₁ to C ₆ alkylthio group, a halogen atom may be substituted by a C ₁ to C ₆ alkylsulfinyl acyl, a halogen atom may be substituted with C ₁ to C ₆ alkylsulfonyl groups, C ₁ to C ₆ alkylcarbonyl group, C ₁ to C ₆ alkoxycarbonyl group, C ₁ to C ₆ alkyl Imino group, may be substituted by a halogen atom or an aryl group substituted by a halogen atom, C ₇ to C ₁₁ aralkyl group, m represents any integer of 2-5; and, m represents 3-5 In the case of an integer, Y may be the same or different; R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, may pass through a halogen atom Substituted C ₁ to C ₄ alkoxy, C ₃ to C ₆ cycloalkyl, C ₁ to C ₄ alkylcarbonyloxy or benzyloxy, p represents any integer of 1 or 2; in addition, p is 2 When R ¹ and R ² on different carbon atoms may be the same or different; in addition, R ¹ and R ² on the same carbon atom may be bonded to one oxygen atom individually and expressed as (=O); R ¹ and R ² on the same carbon atom may be bonded at the same time to represent a C ₁ to C ₄ alkoxyimine group; further, R ¹ and R ² on the same carbon atom may be bonded to each other to 2 One to five alkylene groups form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring; Z ¹ represents an oxygen atom, a sulfur atom, a sulfinylene group or a sulfonyl group; Y ¹ represents a hydrogen atom or a halogen atom , nitro, cyano, C ₁ to C ₃ alkyl which may be substituted by a halogen atom, may be halogenated a sub-substituted C ₁ to C ₃ alkoxy group, a C ₁ to C ₃ alkylthio group which may be substituted with a halogen atom, a C ₁ to C ₃ alkylsulfinyl group which may be substituted with a halogen atom, may be substituted by a halogen atom C ₁ to C ₃ alkylsulfonyl, C ₁ to C ₃ alkylcarbonyl or C ₁ to C ₃ alkoxycarbonyl, r represents any integer from 1 to 5; Y ¹ may be the same or different. The substituted phenyl ether compound according to claim 14, wherein in the above formula (1-3), A represents a C ₂ to C ₅ haloalkyl group or a cyclopropylmethyl group, and n represents 0. Any integer up to 2, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group (except where X ¹ and X ² both represent a hydrogen atom), and Y represents a hydrogen atom. a halogen atom, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom, a C ₁ to C ₆ alkylthio group which may be substituted by a halogen atom, halogen substituted C ₁ to C ₆ alkylsulfinyl acyl or substituted by a halogen atom a C ₁ to C ₆ alkylsulfonyl group, m represents any integer from 2 to 5, m represents an integer of 3 to 5 When Y may be the same or different, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a hydroxyl group, p represents an integer of 1 or 2, and when p is 2, R ¹ on a different carbon atom and R ² may be the same or different, and R ¹ and R ² on the same carbon atom may be individually bonded to one oxygen atom to represent (=O), and Z ¹ represents an oxygen atom, a sulfur atom, a sulfinylene group or Sulfhydryl group, Y ¹ represents a hydrogen atom, a halogen atom, a nitro group , a cyano group, a C ₁ to C ₃ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₃ alkoxy group which may be substituted by a halogen atom, a C ₁ to C ₃ alkylthio group which may be substituted by a halogen atom, halogen substituted C ₁ to C ₃ alkylsulfinyl acyl, may be substituted by a halogen atom, a C ₁ to C ₃ alkylsulfonyl groups, C ₁ to C ₃ alkylcarbonyl group or a C ₁ to C ₃ alkoxycarbonyl group, r represents any integer from 1 to 3, and when r represents an integer of 2 or 3, Y ¹ may be the same or different. A substituted phenyl ether compound of the formula (1-4): Formula (1-4) represents that one of Y is a phenoxy group which may be substituted at the 4-position on the phenyl ring, a substituted phenylthio group, a substituted phenylsulfinyl group or a substituted group. In the above formula (1-3) in the case of a phenylsulfonyl group, in the formula (1-4), A represents 2,2,2-trifluoroethyl or cyclopropylmethyl, and n represents either 0 or 1. An integer; X ¹ represents a C ₁ to C ₃ alkyl group, X ² represents a halogen atom; Y represents a hydrogen atom, a halogen atom or a C ₁ to C ₃ alkyl group which may be substituted by a halogen atom, and m represents an integer of 2 or 3 And when m is 3, Y may be the same or different; R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or a hydroxyl group, and p represents an integer of 1 or 2; and, when p is 2, R ¹ and R ² on different carbon atoms may be the same or different; in addition, R ¹ and R ² on the same carbon atom may be individually bonded to one oxygen atom to represent (=O); Z ¹ represents oxygen. An atom, a sulfur atom or a sulfinylene group; Y ¹ represents a hydrogen atom, a halogen atom, a cyano group, a C ₁ to C ₃ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₃ alkoxy group which may be substituted by a halogen atom , may be substituted with a halogen atom C ₁ to C ₃ alkylthio group or a halogen atom may be substituted by a C ₁ to C ₃ alkyl Sulfo acyl, r represents any integer from 1 to 3; and, r represents an integer of 2 or 3, Y ¹ may be the same or different. A substituted phenyl ether compound of the formula (1-5): Formula (1-5) shows that q is 0, m is an integer of 2 or more, and adjacent Ys may be bonded to each other to become -OCH ₂ O-, -OCF ₂ O-, -OCH ₂ CH ₂ O-, - In the above formula (1) when OCF ₂ CH ₂ O- or -OCF ₂ CF ₂ O-; in the formula (1-5), A represents a C ₂ to C ₅ haloalkyl group, a C ₂ to C ₅ haloalkenyl group or a C ₃ to C ₈ cycloalkyl C ₁ to C ₄ alkyl group which may be substituted (the group may be mono- or polysubstituted by a halogen atom or a C ₁ to C ₃ alkyl group), and n represents any integer from 0 to 2. X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted with a halogen atom, a C ₁ to C ₆ alkoxy group which may be substituted with a halogen atom, C ₃ a C ₆ cycloalkyl group or an aryl group which may be substituted with a halogen atom; however, except that both X ¹ and X ² represent a hydrogen atom; Y represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a decyl group, or a C ₁ to C ₆ alkyl group substituted by a halogen atom, a C ₁ to C ₆ alkoxy group which may be substituted by a halogen atom, a C ₁ to C ₆ alkylthio group which may be substituted by a halogen atom, a C which may be substituted with a halogen atom ₁ to C ₆ alkylsulfinyl acyl, may be substituted by halogen atom C ₁ to C ₆ alkylsulfonyl group, a C ₁ to C ₆ alkylcarbonyl group, C ₁ to C ₆ alkoxycarbonyl group, a C ₁ to C ₆ Alkoxy An aminomethyl group, an aryl group which may be substituted with a halogen atom or a C ₇ to C ₁₁ aralkyloxy group which may be substituted with a halogen atom, m represents any integer of 3 to 5; further, m represents an integer of 4 or 5. When Y may be the same or different; R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, and a C which may be substituted with a halogen atom. _a C ₁ alkoxy group, a C ₃ to C ₆ cycloalkyl group, a C ₁ to C ₄ alkylcarbonyloxy group or a benzyloxy group, wherein p represents an integer of 1 or 2; in addition, when p is 2, R ¹ and R ² on different carbon atoms may be the same or different; in addition, R ¹ and R ² on the same carbon atom may be bonded to one oxygen atom individually and expressed as (=O); R ¹ and R ² on the carbon atom may be bonded at the same time to represent a C ₁ to C ₄ alkoxyimino group; in addition, R ¹ and R ² on the same carbon atom may be bonded to each other to 2 to 5 The alkyl group forms a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring; Y ² represents a hydrogen atom or a fluorine atom, and t represents an integer of 1 or 2; further, when t is 2, Y ² may be the same Or not the same. The substituted phenyl ether compound according to claim 17, wherein in the above formula (1-5), A represents a C ₂ to C ₅ haloalkyl group or a cyclopropylmethyl group, and n represents 0. Any integer up to 2, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group (except where X ¹ and X ² both represent a hydrogen atom), and Y represents a hydrogen atom. a halogen atom or a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, m represents any integer of 3 to 5, and m represents an integer of 4 or 5, and Y may be the same or different, and R ¹ and R ² respectively Independently represents a hydrogen atom, a halogen atom or a hydroxyl group, p represents any integer of 1 or 2, and when p is 2, R ¹ and R ² on different carbon atoms may be the same or different, and R on the same carbon atom. ¹ and R ² may be independently bonded to one oxygen atom to represent (=O), Y ² represents a hydrogen atom or a fluorine atom, and t represents 1. The substituted phenyl ether compound according to claim 17, wherein in the above formula (1-5), A represents 2,2,2-trifluoroethyl or cyclopropylmethyl, n Any integer from 0 to 1, X ¹ represents a C ₁ to C ₃ alkyl group, X ² represents a halogen atom, Y represents a hydrogen atom, m represents an integer of any of 3 to 5, and R ¹ and R ² are independently represented a hydrogen atom, a halogen atom or a hydroxyl group, p represents an integer of 1 or 2, and when p is 2, R ¹ and R ² on different carbon atoms may be the same or different, and R ¹ and R on the same carbon atom. ² may be individually bonded to one oxygen atom and represented by (=O), Y ² represents a fluorine atom, and t represents 1. A pest control agent containing the substituted phenyl ether compound as described in any one of claims 14 to 19 as an active ingredient. An insecticide or acaricide containing the substituted phenyl ether compound as described in any one of claims 14 to 19 as an active ingredient. An N-substituted aniline compound of the formula (1-6): In the formula (1-6), A ¹⁰⁰ represents a C ₂ to C ₅ haloalkyl group or a C ₃ to C ₆ cycloalkyl group C ₁ to C ₃ alkyl group, and n represents any integer of 0 to 2; X ¹⁰¹ and X ^{And 102} independently represent a hydrogen atom, a halogen atom, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted with a halogen atom, or a C ₁ to C ₆ alkoxy group which may be substituted with a halogen atom; however, X ¹⁰¹ and X ¹⁰² are not simultaneously a hydrogen atom; Y ¹⁰⁰ represents a hydrogen atom, a halogen atom, nitro, cyano, methyl acyl, a halogen atom may be substituted with C ₁ to C ₆ alkyl group, a halogen atom may be substituted with C ₁ to C ₆ alkoxy group, a halogen atom may be substituted with C ₁ to C ₆ alkylthio group, a halogen atom may be substituted with C ₁ to C ₆ alkylsulfinyl acyl, may be substituted by a halogen atom, a C ₁ to C ₆ alkyl a sulfonyl group, a C ₁ to C ₆ alkylcarbonyl group, a C ₁ to C ₆ alkoxycarbonyl group or a C ₁ to C ₆ alkoxyiminomethyl group, and v represents an integer of 1 to 4; further, v represents 2 When it is an integer of 4, Y ¹⁰⁰ may be the same or different; R ^101a and R ^102a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, or may be a halogen-substituted C ₁ to C ₄ alkoxy group; further, R ^101a and R ^102a on the same carbon atom It may be represented by an oxygen atom or a sulfur atom individually as (=O) or (=S); in addition, R ^101a and R ^102a on the same carbon atom may be bonded at the same time to represent a C ₁ to C ₄ alkane. Further, R ^101a and R ^102a on the same carbon atom may be bonded to each other to form a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring in the form of 2 to 5 alkylene groups; R ^101b and R ^102b each independently represent a hydrogen atom, a halogen atom, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom or a C ₁ to C ₄ alkoxy group which may be substituted with a halogen atom, and u represents 0 or 1. Any integer; W ¹ represents a C ₂ to C ₆ alkenyl group which may be substituted by a halogen atom, a C ₂ to C ₆ alkynyl group which may be substituted with a halogen atom, a C ₃ to C ₆ cycloalkyl group, a C ₃ to C ₆ ring Alkyl C ₁ to C ₃ alkyl, methionyl, C ₁ to C ₆ alkylcarbonyl which may be substituted by a halogen atom, C ₂ to C ₆ olefincarbonyl which may be substituted by a halogen atom, C ₂ which may be substituted by a halogen atom To a C ₆ alkynylcarbonyl group, a C ₃ to C ₆ cycloalkanecarbonyl group which may be substituted with a halogen atom, a C ₃ to C ₆ cycloalkyl group which may be substituted with a halogen atom, a C ₁ to C ₃ alkylcarbonyl group, a C which may be substituted with a halogen atom ₁ to C ₆ alkoxycarbonyl group, a halogen atom may be substituted with a C ₂ to C ₆ alkenyloxycarbonyl group, a halogen atom may be taken by A C ₂ to C ₆ alkynyloxycarbonyl group, may be substituted by halogen atom a C ₃ to C ₆ cycloalkyl alkoxycarbonyl group, may be substituted by halogen atom a C ₃ to C ₆ cycloalkyl, a C ₁ to C ₃ alkoxycarbonyl group, may be a C ₁ to C ₆ alkylamine carbonyl group substituted by a halogen atom, a di C ₁ to C ₆ alkylamine carbonyl group which may be substituted with a halogen atom, a C ₃ to C ₆ cycloalkylamine carbonyl group which may be substituted by a halogen atom, may be halogen atom Substituted C ₃ to C ₆ cycloalkyl C ₁ to C ₃ alkylamine carbonyl, C ₁ to C ₆ alkylsulfonyl group which may be substituted by a halogen atom, C ₃ to C ₆ cycloalkyl which may be substituted by a halogen atom a sulfonyl group, a C ₃ to C ₆ cycloalkyl group which may be substituted with a halogen atom, a C ₁ to C ₃ alkylsulfonyl group, a C ₁ to C ₆ alkylaminosulfonyl group which may be substituted with a halogen atom, may be halogenated Atom-substituted di-C ₁ to C ₆ alkylaminosulfonyl, aryl substituted by halogen atom, benzyl which may be substituted by halogen atom, aromatic carbonyl group which may be substituted by halogen atom, benzyl which may be substituted by halogen atom a carbonyl group, an aryloxycarbonyl group which may be substituted with a halogen atom, a benzyloxycarbonyl group which may be substituted with a halogen atom, an arylamine carbonyl group which may be substituted with a halogen atom, a substituted arylsulfonyl group which may be via a halogen atom or C to ₁ C ₃ alkyl mono or polysubstituted) or Halogen atom-substituted benzyl sulfo acyl; W ² represents a hydrogen atom, a halogen atom may be substituted with a C ₁ to C ₆ alkyl, may be substituted with a halogen atom by a halogen atom substituted C ₂ to C ₆ alkenyl group C ₂ to C ₆ alkynyl, C ₃ to C ₆ cycloalkyl, C ₁ to C ₆ alkoxy C ₁ to C ₃ alkyl, C ₁ to C ₆ alkylcarbonyl which may be substituted by a halogen atom, may be a halogen-substituted C ₁ to C ₆ alkoxycarbonyl group, a C ₁ to C ₆ alkylsulfonyl group which may be substituted with a halogen atom, a benzyl group which may be substituted with a halogen atom, an aromatic carbonyl group which may be substituted with a halogen atom, or may be Substituted arylsulfonyl (this group may be mono- or polysubstituted by a halogen atom or a C ₁ to C ₃ alkyl group). The N-substituted aniline compound according to claim 22, wherein, in the above formula (1-6), A ¹⁰⁰ represents 2,2,2-trifluoroethyl or cyclopropylmethyl, and n represents 0. Or any integer of 1, X ¹⁰¹ represents a C ₁ to C ₆ alkyl group, X ¹⁰² represents a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group, and Y ¹⁰⁰ represents a hydrogen atom, a halogen atom or a halogen atom may be substituted C ₁ to C ₆ alkyl, v represents an integer of 1 or 2, when v is 2, Y ¹⁰⁰ may be the same or different, and R ^101a and R ^102a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or The C ₁ to C ₆ alkyl group substituted by a halogen atom, R ^101a and R ^102a on the same carbon atom may be bonded to one oxygen atom individually to represent (=O), and R ^101b and R ^102b represent a hydrogen atom. u represents any integer of 0 or 1, and W ¹ represents a C ₁ to C ₆ alkylcarbonyl group which may be substituted by a halogen atom, a C ₃ to C ₆ cycloalkylcarbonyl group, a C ₁ to C ₆ alkoxycarbonyl group which may be substituted with a halogen atom. a C ₃ to C ₆ cycloalkoxycarbonyl group, a C ₁ to C ₆ alkylamine carbonyl group, a C ₁ to C ₆ alkylsulfonyl group which may be substituted by a halogen atom, a phenyl group which may be substituted by a halogen atom, may be halogen atom Substituted benzinyl, phenoxy substituted by halogen atom Group, a halogen atom may be substituted benzyloxycarbonyl group, a halogen atom may be substituted aniline may be carbonyl or phenyl substituted acyl sulfonamide (which can be a single group substituted with a halogen atom or a C ₁ to C ₃ alkyl or substituted And W ² represents a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ alkylcarbonyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkoxycarbonyl group which may be substituted with a halogen atom, may be substituted by a halogen atom a C ₁ to C ₆ alkylsulfonyl group, a benzyl group, a benzinyl group which may be substituted with a halogen atom or a phenylsulfonyl group which may be substituted (the group may be a halogen atom or a C ₁ to C ₃ alkyl group) Replace or replace). The N-substituted aniline compound according to claim 22, wherein, in the above formula (1-6), A ¹⁰⁰ represents 2,2,2-trifluoroethyl or cyclopropylmethyl, and n represents 0. Or any integer of 1, X ¹⁰¹ represents a C ₁ to C ₄ alkyl group, X ¹⁰² represents a halogen atom, Y ¹⁰⁰ represents a hydrogen atom or a halogen atom, v represents an integer of 1 or 2, and when v is 2, Y ¹⁰⁰ may be the same or different, R ^101a and R ^102a each independently represent a hydrogen atom a halogen atom or a hydroxyl group, R ^101a on the same carbon atom and R ^102a may be an individual with an oxygen atom bonded to and is expressed as (= O), R ^101b and R ^102b represent a hydrogen atom, u represents any integer of 0 or 1, and W ¹ represents a C ₁ to C ₆ alkylcarbonyl group which may be substituted by a halogen atom, a C ₃ to C ₆ cycloalkylcarbonyl group, and may be substituted by a halogen atom. C ₁ to C ₆ alkoxycarbonyl group, a halogen atom may be substituted with C ₁ to C ₆ alkylsulfonyl group, a benzyl or acyl may be a C ₁ to C ₃ alkyl-substituted phenyl sulfonic acyl, W ² represents a hydrogen atom, a C ₁ to C ₆ alkyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkylcarbonyl group, may be substituted with halogen atoms C ₁ to C ₆ alkoxycarbonyl group by, may be substituted by a halogen atom C ₁ to C ₆ alkylsulfonyl group, a benzyl or acyl may be a C ₁ to C ₃ A phenyl group substituted with a sulfo acyl. A pest control agent containing the N-substituted aniline compound according to any one of claims 22 to 24 as an active ingredient. An insecticide or acaricide containing the N-substituted aniline compound according to any one of claims 22 to 24 as an active ingredient. An aniline compound which is a compound represented by the formula (3): In the formula (3), G represents CO ₂ R ¹⁰³ (R ¹⁰³ represents a C ₁ to C ₄ alkyl group) or CH ₂ OR ¹⁰⁴ (R ¹⁰⁴ represents a hydrogen atom, a C ₁ to C ₄ alkyl sulfonate which may be substituted by a halogen atom A mercapto group or an arylsulfonyl group which may be substituted with a C ₁ to C ₄ alkyl group; Y ¹⁰¹ and Y ¹⁰² each independently represent a hydrogen atom (except where G represents CO ₂ R ¹⁰³ ), a halogen atom or may be a halogen atom-substituted C ₁ to C ₄ alkyl group; W ¹⁰³ and W ¹⁰⁴ each independently represent a hydrogen atom, a C ₁ to C ₆ alkylcarbonyl group which may be substituted by a halogen atom, a C ₁ to C ₆ alkoxycarbonyl group or a halogenizable group. Atom-substituted C ₁ to C ₆ alkylsulfonyl. A substituted phenyl ether compound of the formula (1-2): In the formula (1-2), n represents any integer of 0 or 1, and X ² represents a fluorine atom or a chlorine atom. An acaricide comprising the substituted phenyl ether compound described in claim 28 of the patent application as an active ingredient.