JP5616519B1 - Substituted phenyl ether compounds and pest control agents - Google Patents

Abstract

An object of the present invention is to provide a novel substituted phenyl ether compound having a pest control effect and a pest control agent characterized by containing this as an active ingredient. A substituted phenyl ether compound represented by the following formula (1-2) is provided. [Chemical 1] [Selected figure] None

Description

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

  To date, many pesticides have been used to control pests in agricultural and horticultural settings or animals such as pets and livestock. However, the pesticides are not effective enough or are initially effective. Even if it is made, pests become resistant to these drugs, and the control effect may be reduced. In addition, even if a pest control agent is sprayed and controlled, it will fly from the outside or the egg pest will hatch at the time of spraying, generating new pests. Residual properties that exert a control effect on the generated pests are required. Drugs that do not have after-effects are disadvantageous in that the number of sprays increases, which is troublesome and pests can easily acquire resistance. In addition, some of the widely used pest control agents are not only harmful to pests but also have strong toxicity to human livestock and fish and shellfish, and some are toxic to natural enemies. There are very few pest control agents that accumulate in the environment and cause environmental pollution, and exhibit high performance in all aspects. Therefore, even against pests that have acquired resistance to conventionally used pest control agents, they exhibit a sufficient control effect at a low dose, and the control effect continues even after spraying, and against useful organisms. Therefore, the development of a new pest control agent that is highly safe and has no adverse environmental impact is eagerly desired.

By the way, insecticidal and acaricidal activities relating to substituted phenyl ether compounds have been known so far. For example, Patent Document 1 describes a compound having a phenyl ether skeleton similar to the compound according to the present invention. In the general formula of Patent Document 1, R ² represents only a (C ₁ -C ₆ ) alkyl group, and the haloalkyl group and cycloalkylalkyl group of A in Formula (1) shown in the present invention are not described.
Patent Documents 2 and 3 describe diphenyl ether compounds useful as insecticides and acaricides. Patent Documents 2 and 3 are compounds in which two benzene rings form an ether bond directly with an oxygen atom, but the compounds in which two benzene rings form an ether bond with an oxygen atom containing an alkylene chain as in the present invention. There is no description.

  Patent Document 4 describes amidine compounds containing 3-substituted phenyl sulfides useful as insecticides and acaricides. Although the compound described in Patent Document 4 has an amidine skeleton at the 3-position of the benzene ring of phenyl sulfide, there is no description of a substituted phenyl ether skeleton as in the present invention. Patent Documents 5 and 6 describe 3-heterocyclic substituted phenyl sulfide compounds useful as insecticides and acaricides. Although the compounds described in Patent Documents 5 and 6 each have a triazole ring and a pyrazole ring at the 3-position of the benzene ring of phenyl sulfide, there is no description of a substituted phenyl ether skeleton as in the present invention.

Japanese Unexamined Patent Publication No. Sho 63-41451 Japanese Unexamined Patent Publication No. 51-79723 International Patent Publication No. 2013/111864 Pamphlet International Patent Publication No. 2007/131680 Pamphlet International Patent Publication No. 2006/043635 Pamphlet International Patent Publication No. 2009/051245 Pamphlet

  An object of the present invention is to provide a novel substituted phenyl ether compound having a safe and pest control effect and a pest control agent characterized by containing the compound as an active ingredient.

  As a result of intensive studies to solve the above problems, the present inventor has found that the substituted phenyl ether compound represented by the following formula (1) has an excellent control effect against pests, and completes the present invention. It came to.

That is, the 1st aspect of the invention which concerns on this application is related with the substituted phenyl ether compound represented by following formula (1).

In the above formula (1), A is a C _{2 to} C ₅ haloalkyl group, a C _{2 to} C ₅ haloalkenyl group, or an optionally substituted C _{3 to} C ₈ cycloalkyl C _{1 to} C ₄ alkyl group (this group Represents a mono- or poly-substitution with a halogen atom or a C ₁ -C ₃ alkyl group, and n represents an integer of 0 to 2.
X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a cyano group, a C ₁ -C ₆ alkyl group that may be substituted with a halogen atom, or a C ₁ -C ₆ alkoxy that may be substituted with a halogen atom. group, a C ₃ -C ₆ cycloalkyl group or an aryl group optionally substituted by a halogen atom,. However, X ¹ and X ² cannot simultaneously be hydrogen atoms.
Y is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, a formyl group, a substituted C ₁ may be -C ₆ alkyl group by a halogen atom, it is C ₁ may be -C ₆ alkoxy substituted with a halogen atom Group, C ₁ -C ₆ alkylthio group which may be substituted with halogen atom, C ₁ -C ₆ alkylsulfinyl group which may be substituted with halogen atom, C ₁ -C ₆ alkylsulfonyl which may be substituted with halogen atom _group, C 1 -C ₆ alkylamino group, di _C 1 -C ₆ alkylamino _group, C 1 -C ₆ alkylcarbonyl _group, C 1 -C ₆ alkoxycarbonyl _group, C 1 -C ₆ alkoxyiminoalkyl methyl, halogen An aryl group which may be substituted with an atom, an aryloxy group which may be substituted with a halogen atom, or C which may be substituted with a halogen atom _{7 to} C _{11 represents an} aralkyloxy group, and m represents an integer of 1 to 5. When m represents an integer of 2 to 5, Y may be the same or different. 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 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a C ₁ -C ₆ alkyl group that may be substituted with a halogen atom, or a C ₁ -C that may be substituted with a halogen atom. _{4 alkoxy,} C 3 -C ₆ cycloalkyl _group, C 1 -C indicates ₄ alkylcarbonyloxy group or benzoyloxy group,, p represents an integer from 1 to 5. 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 can be each represented by (═O) or (═S) by being bonded to one oxygen atom or sulfur atom. R ¹ and R ² on the same carbon atom can be bonded simultaneously to represent a C ₁ -C ₄ alkoxyimino group. R ¹ and R ² on the same carbon atom can be bonded to each other to form a 3-membered ring, 4-membered ring, 5-membered ring or 6-membered ring with 2 to 5 alkylene groups.
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 2nd aspect of the invention which concerns on this application is related with the pest control agent containing the substituted phenyl ether compound represented by the said Formula (1).

  The 3rd aspect of the invention which concerns on this application is related with the manufacturing intermediate represented by following formula (2).

In the above formula (2), A is optionally substituted C ₃ -C ₈ cycloalkylmethyl group (which may be mono- or polysubstituted by said group fluorine atom or C ₁ -C ₃ alkyl group.) N represents an integer of either 0 or 1.
X ¹ represents a C ₁ -C ₄ alkyl group, and X ² represents a hydrogen atom, a halogen atom, or a C ₁ -C ₄ alkyl group.

  ADVANTAGE OF THE INVENTION According to this invention, the pest control agent containing the novel substituted phenyl ether compound which has the control effect with respect to a pest, and a substituted phenyl ether compound can be provided.

Hereinafter, the present invention will be described in detail.
The substituted phenyl ether compound according to the present invention has a substituted phenyl-substituted alkyl ether skeleton represented by the following formula (1) as a basic skeleton.

  In the formula (1), examples of the halogen atom or the halogen atom as a substituent include each element of fluorine, chlorine, bromine or iodine. The number of halogen atoms as substituents may be 1 or 2 or more, and in the case of 2 or more, each halogen atom may be the same or different. Further, the halogen atom may be substituted at any position.

In the above formula (1), the C ₂ -C ₅ haloalkyl group represented by A includes a 2-fluoroethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 1-bromoethyl group, a 2-bromoethyl group, 2, 2-difluoroethyl group, 1,2-dichloroethyl group, 2,2-dichloroethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 1,1,2,2 -Tetrafluoroethyl group, pentafluoroethyl group, 2-bromo-2-chloroethyl group, 2-chloro-1,1,2,2-tetrafluoroethyl group, 1-chloro-1,2,2,2-tetra Fluoroethyl group, 1-chloropropyl group, 2-chloropropyl group, 3-chloropropyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-1-methylethyl group, 3-iodop Pill group, 2,2,2-trifluoro-1-methylethyl group, 2,3-dichloropropyl group, 2,3-dibromopropyl group, 3,3,3-trifluoropropyl group, 3,3,3 -Trichloropropyl group, 3-bromo-3,3-difluoropropyl group, 3,3-dichloro-3-fluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 1-bromo-3,3 3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, heptafluoropropyl group, 2,3-dichloro-1,1,2,3,3-pentafluoropropyl group, 2- Chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 2-chloro-1,1-dimethylethyl, 4-bromobutyl, 3-bromo-2-methylpropyl, 2-bromo-1,1-di Tylethyl group, 2,2-dichloro-1,1-dimethylethyl group, 2-chloro-1-chloromethyl-2-methylethyl group, 4,4,4-trifluorobutyl group, 3,3,3-trimethyl Fluoro-1-methylpropyl group, 3,3,3-trifluoro-2-methylpropyl group, 2,3,4-trichlorobutyl group, 2,2,2-trichloro-1,1-dimethylethyl group, 4 -Chloro-4,4-difluorobutyl group, 4,4-dichloro-4-fluorobutyl group, 4-bromo-4,4-difluorobutyl group, 2,4-dibromo-4,4-difluorobutyl group, 3 , 4-dichloro-3,4,4-trifluorobutyl group, 3,3-dichloro-4,4,4-trifluorobutyl group, 4-bromo-3,3,4,4-tetrafluorobutyl group, 4-bromo-3-chloro- 3,4,4-trifluorobutyl group, 2,2,3,3,4,4-hexafluorobutyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3 , 3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, nonafluorobutyl group, 4-chloro-1,1,2, 2,3,3,4,4-octafluorobutyl group and the like are mentioned, and 2,2,2-trifluoroethyl group is more preferred.

In the above formula (1), examples of the C ₂ -C ₅ haloalkenyl group represented by A include bromovinyl group, chlorovinyl group, 3,3-dichloro-2-propenyl group, 3,3,3-trifluoro- 1-propenyl group 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group and the like can be mentioned, more preferably 3,3,3-trifluoro-1-propenyl group Is mentioned.

In the above formula (1), as the C ₃ -C ₈ cycloalkyl C ₁ -C ₄ alkyl group moiety of the C ₃ -C ₈ cycloalkyl C ₁ -C ₄ alkyl group represented by A, Cyclopropylmethyl group, 1-cyclopropylethyl group, 2-cyclopropylethyl group, 1-cyclopropylpropyl group, 2-cyclopropylpropyl group, 3-cyclopropylpropyl group, 1-cyclopropylbutyl group, 2-cyclo Propylbutyl group, 3-cyclopropylbutyl group, 4-cyclopropylbutyl group, cyclobutylmethyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, A cyclooctylmethyl group is mentioned, More preferably, a cyclopropylmethyl group is mentioned. Halogen atom as a substituent have the same definition as above, C ₁ -C ₃ alkyl The methyl group, ethyl group, n- propyl group, i- propyl group and the like, more preferably fluorine atom or A methyl group is mentioned.

  In said formula (1), n shows the integer in any one of 0-2. When n is 0, the oxygen atom (O) is not added to the sulfur atom (S), and when n is 1, one oxygen atom (O) is added to the sulfur atom (S) to form a sulfinyl group. (S = O) is formed. When n is 2, two oxygen atoms (O) are added to the sulfur atom (S) to form a sulfonyl group (O = S = O).

In the above formula (1), ^{X 1} and a halogen atom represented by ^{X 2} have the same definition as above, _C 1 -C ₆ alkyl group moiety of the optionally _C 1 -C ₆ alkyl group optionally substituted by a halogen atom As methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl Group, 3-pentyl group, tert-pentyl group, n-hexyl group, i-hexyl group, 2-hexyl group, 3-hexyl group and the like, more preferably methyl group.

In the above formula (1), as the _C 1 -C ₆ alkoxy group moiety of the optionally _C 1 -C ₆ alkoxy group optionally substituted by a halogen atom represented by ^{X 1} and ^{X 2,} a methoxy group, an ethoxy radical, n -Propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, tert-butoxy group, etc. are mentioned, More preferably, a methoxy group is mentioned.

In the above formula (1), examples of the C _{3 to} C ₆ cycloalkyl group represented by X ¹ and X ² include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like, more preferably cyclopropyl group. Groups.

In the above formula (1), examples of the aryl group portion of the aryl group which may be substituted with a halogen atom represented by X ¹ or X ² include a phenyl group and a naphthyl group, and more preferably a phenyl group. Can be mentioned.

In the above formula (1), the halogen atom represented by Y has the same definition as above, preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a fluorine atom or a chlorine atom, and most preferably a fluorine atom. Is preferred. The _C 1 -C ₆ alkyl moiety of the substituted _C 1 may be -C ₆ alkyl group by a halogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, i- Butyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, 2-pentyl group, 3-pentyl group, tert-pentyl group, hexyl group, i-hexyl group, 2-hexyl group, 3-hexyl Group etc. are mentioned, A methyl group is mentioned more suitably.

The above formula (1) in, _C 1 -C ₆ alkoxy group moiety of the optionally _C 1 -C ₆ alkoxy group optionally substituted by a halogen atom represented by Y, a methoxy group, an ethoxy group, n- propoxy group, An i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, a tert-butoxy group, and the like are preferable, and a methoxy group or an ethoxy group is more preferable.

In the above formula (1), as the _C 1 -C ₆ alkylthio group portion of good _C 1 -C ₆ alkylthio group optionally substituted by a halogen atom represented by Y, methylthio group, ethylthio group, n- propylthio group, Examples include i-propylthio group, n-butylthio group, i-butylthio group, sec-butylthio group, and tert-butylthio group, and more preferably methylthio group or ethylthio group.

The formula (1), as the C ₁ -C ₆ alkylsulfinyl group moiety of the substituted C ₁ may be -C ₆ alkylsulfinyl group by a halogen atom represented by Y, methylsulfinyl group, ethylsulfinyl radical, n -Propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, i-butylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, more preferably methylsulfinyl group or ethylsulfinyl group. Can be mentioned.

In the above formula (1), as the C ₁ -C ₆ alkylsulfonyl group moiety good C ₁ -C ₆ alkylsulfonyl group optionally substituted by a halogen atom represented by Y, methylsulfonyl group, ethylsulfonyl radical, n -Propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, more preferably methylsulfonyl group or ethylsulfonyl group. Can be mentioned.

In the above formula (1), the C ₁ -C ₆ alkylamino group represented by Y includes a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, i -A butylamino group, a sec-butylamino group, and a tert- butylamino group are mentioned, More preferably, a methylamino group or an ethylamino group is mentioned.

In the above formula (1), examples of the di C ₁ -C ₆ alkylamino group represented by Y include a dimethylamino group, a methylethylamino group, a diethylamino group, a di-n-propylamino group, a methyl n-propylamino group, Examples include ethyl n-propylamino group, di-i-propylamino group, di-n-butylamino group, dii-butylamino group, disec-butylamino group, and ditert-butylamino group, and more preferably dimethyl. An amino group or a diethylamino group is mentioned.

In the above formula (1), examples of the C ₁ -C ₆ alkylcarbonyl group represented by Y include acetyl group, propionyl group, butyryl group, i-butyryl group, valeryl group, pivaloyl group, and the like. Includes an acetyl group. The number of carbon atoms of the alkylcarbonyl group represented by C is the number of carbon atoms excluding the carbon atoms of the carbonyl group.

In the above formula (1), examples of the C ₁ -C ₆ alkoxycarbonyl group represented by Y include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a tert -A butoxycarbonyl group etc. are mentioned, More preferably, a methoxycarbonyl group or an ethoxycarbonyl group is mentioned. The number of carbon atoms of the alkoxycarbonyl group represented by C is the number of carbon atoms excluding the carbon atoms of the carbonyl group.

In the above formula (1), the C ₁ -C ₆ alkoxyiminomethyl group represented by Y includes a methoxyimino group, ethoxyimino group, n-propoxyimino group, i-propoxyimino group, n-butoxyimino group, Examples thereof include a tert-butoxyimino group, and more preferably a methoxyimino group.

  In the above formula (1), examples of the aryl group portion of the aryl group which may be substituted with a halogen atom represented by Y include a phenyl group and a naphthyl group, and more preferably a phenyl group.

  In the above formula (1), examples of the aryloxy group part of the aryloxy group which may be substituted with a halogen atom represented by Y include a phenoxy group and a naphthyloxy group, and more preferable examples include a phenoxy group. It is done.

In the above formula (1), as the _C 7 _{-C 11} aralkyloxy group portion of the good _C 7 _{-C 11} aralkyloxy group optionally substituted by a halogen atom represented by Y, benzyloxy group, phenethyloxy group and the like More preferably, a benzyloxy group is mentioned.

  In said formula (1), m shows the integer in any one of 1-5. When m is 1, Y is added to any one of the five carbon atoms (C) constituting the phenyl group. In addition, when m is 2 to 4, Y is added to any two or three or four of the carbon atoms (C), and when m is 5, all of the carbon atoms (C) are added. Y is added.

  Among the combinations of Y and m, those in which Y is a fluorine atom, m is 3, and a fluorine atom is added to the 3, 4, and 5 positions of the phenyl group are preferable.

In the above formula (1), ^{R 1} and halogen atom represented by ^{R 2} have the same definition as above, _C 1 -C ₆ alkyl group moiety of the optionally _C 1 -C ₆ alkyl group optionally substituted by a halogen atom As methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, 2-pentyl Group, 3-pentyl group, tert-pentyl group, n-hexyl group, i-hexyl group, 2-hexyl group, 3-hexyl group and the like, more preferably methyl group or ethyl group.

In the above formula (1), as the _C 1 -C ₄ alkoxy group moiety of the optionally _C 1 -C ₄ alkoxy group optionally substituted by a halogen atom represented by ^{R 1} and ^{R 2,} a methoxy group, an ethoxy radical, n -Propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, tert-butoxy group, etc. are mentioned, More preferably, a methoxy group is mentioned.

In the above formula (1), examples of the C _{3 to} C ₆ cycloalkyl group represented by R ¹ and R ² include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like, more preferably cyclopropyl group. Groups.

In the above formula (1), examples of the C ₁ -C ₄ alkylcarbonyloxy group represented by R ¹ and R ² include acetyloxy group, propionyloxy group, butyryloxy group, i-butyryloxy group, pivaloyloxy group, and the like. More preferred is an acetyloxy group. The number of carbon atoms of the alkylcarbonyl group represented by C is the number of carbon atoms excluding the carbon atoms of the carbonyl group.

In said formula (1), p shows the integer in any one of 1-5. When p is 1 to 5, each represents a methylene chain, an ethylene chain, a propylene chain, a butylene chain, or a pentylene chain. 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 can be each represented by (═O) or (═S) by being bonded to one oxygen atom or sulfur atom. R ¹ and R ² on the same carbon atom can be bonded simultaneously to represent a C ₁ -C ₄ alkoxyimino group, and examples thereof include a methoxyimino group. R ¹ and R ² on the same carbon atom can be bonded to each other to form a 3-membered ring, 4-membered ring, 5-membered ring or 6-membered ring with 2 to 5 alkylene groups.

  In said formula (1), Z shows an oxygen atom, a sulfur atom, a sulfinyl group, and a sulfonyl group, and an oxygen atom is mentioned more suitably.

  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 included in the formula (1), and when q is 1, any atom of Z is added.

  Next, representative examples of substituted phenyl ether compounds represented by the formula (1) are shown in Tables 1 to 8 and typical examples of phenol compounds represented by the formula (2) are shown in Table 9. It is not limited. In addition, these compounds include compounds including optical isomers, E isomers, and Z isomers. The compound number is referred to in the following description.

In addition, the following notation in a table | surface represents each applicable group as follows.
“Me” is a methyl group, “Et” is an ethyl group, “Pr” is a propyl group, “n-Pr” is a normal propyl group, “i-Pr” is an isopropyl group, “Bu” is a butyl group, “n-Pr” “Bu” is a normal butyl group, “Pen” is a pentyl group, “n-Pen” is a normal pentyl group, “Hex” is a hexyl group, “n-Hex” is a normal hexyl group, “Hep” is a heptyl group, “s -Bu "is a secondary butyl group," i-Bu "is an isobutyl group," t-Bu "is a tertiary butyl group," c-Pr "is a cyclopropyl group," c-Bu "is a cyclobutyl group," c-Bu ""Pen" is a cyclopentyl group, "neo-Pen" is a neopentyl group, "c-Hex" is a cyclohexyl group, "c-Hep" is a cycloheptyl group, "THF" is a tetrahydrofuryl group, "THP" is a teto group A lahydropyranyl group, “Ph” represents a phenyl group, “Bn” represents a benzyl group, “Ac” represents an acetyl group, and “Bz” represents a benzoyl group. “H” represents a hydrogen atom. “On TLC” and “under TLC” indicate isomers.

Table 1 represents a specific example of the formula (1) in which q is 0 and p is 1, Table 2 represents a specific example of the formula (1) in which q is 0 and p is 2, and Table 3 Represents a specific example of the formula (1) in which q is 0 and p is 3, Table 4 represents a specific example of the formula (1) in which q is 0 and p is 4, and Table 5 represents the q Represents a specific example of the formula (1) in which 0 is 0 and p is 5, Table 6 represents a specific example of the formula (1) in which q is 1 and p is 2, and Table 7 shows that q is 1. Table 8 represents a specific example of Formula (1) in which q is 1 and p is 4, Table 9 represents a specific example of Formula (2). A specific example is shown. R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e represent R ¹ specifying the substitution position on the alkylene chain, and R ^2a , R ^2b , R ^2c , R ^2d , and R ^2e are substitution positions on the alkylene chain R ^{2 in} which is specified.

In the column “Ym” in these tables, for example, 3-F indicates that a fluorine atom is substituted at the 3-position of the phenyl group, and 3,4,5-F ₃ indicates that the phenyl group is 3, 4 , Indicating that a total of three fluorine atoms are substituted, one at the 5-position, and 2-F-4-Cl is substituted with a fluorine atom at the 2-position of the phenyl group and a chlorine atom at the 4-position. Indicates that

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

(In 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 are each independently selected. A fluorine atom, a hydroxyl group, an ethyl group, an isopropyl group, an isobutyl group, a methoxy group, an acetyloxy group, and R ^1a and R ^2a are bonded to one nitrogen atom to form a methoxyimino group (= NOMe). Or they can be bonded together to form a 3-membered or 5-membered ring.)

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

  Although the compound based on this invention represented by the said Formula (1) can be manufactured in accordance with the manufacturing method shown below, it is not limited to these methods.

[Reaction step 1]
(In the above formula, A, X ¹ , X ² , Y, R ¹ , R ² , Z, m, p, q have the same meaning as the substituted phenyl ether compound represented by the above formula (1), and n is 1 or 2 is shown.)

The compound represented by the formula (1c) according to the present invention can be produced, for example, by reacting the compound represented by the above formula (1b) with an oxidizing agent.
Examples of the oxidizing agent used in this reaction include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, oxone (OXONE, trade name of EI DuPont; potassium hydrogen peroxosulfate), N -Chlorosuccinimide, N-bromosuccinimide, tert-butyl dichlorite, sodium hypochlorite, oxygen and the like. Preferred are m-chloroperbenzoic acid and hydrogen peroxide.

  Solvents used in this reaction include, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; acetonitrile, N, N-dimethylformamide, N, N-dimethyl Aprotic polar solvents such as acetamide, N-methyl-2-pyrrolidone and sulfolane; alcohols such as methanol, ethanol and isopropyl alcohol; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; pentane and hexane Aliphatic hydrocarbons such as cyclohexane and cycloheptane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid, water, or a mixed solvent thereof. Preferred are dichloromethane, chloroform, water and the like.

[Reaction step 2]
(In the above formula, L represents a leaving group such as a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, A, X ¹ , X ² , Y, R ¹ , R ² , Z, m, p, and q have the same meaning as described above, and n represents an integer of 0 to 2.)

  The compound represented by the formula (1) according to the present invention includes, for example, a compound represented by the above formula (2a) and a compound represented by the above formula (3) in the presence of a base, if necessary. It can manufacture by making it react in presence.

  The raw material represented by the above formula (3) is known in some cases and can be obtained from Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., etc. Or it can also manufacture easily according to the well-known method as described in an experimental chemistry course, Organic Synthesis, etc. from an available reagent.

  Examples of the base used in this reaction include bases such as potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, and pyridine. Preferred are potassium carbonate, triethylamine, potassium hydroxide, sodium hydroxide and the like.

  Examples of the catalyst used in this reaction include tetrabutylammonium bromide or tetrabutylammonium chloride.

  Solvents used in this reaction include, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; acetonitrile, N, N-dimethylformamide, N, N-dimethyl Aprotic polar solvents such as acetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane; Halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Fats such as pentane, hexane, cyclohexane and cycloheptane Group hydrocarbons, water or a mixed solvent thereof. N, N-dimethylformamide, dichloromethane, or a mixture of water and an organic solvent is preferred.

[Reaction step 3]
(In the above formula, A, X ¹ , X ² , Y, R ¹ , R ² , Z, n, m, p, q have the same meaning as described above.)

  The compound represented by the formula (1) according to the present invention is described in, for example, Bulletin of the Chemical Society of Japan, 1967, p. 936, Bulletin of the Chemical Society of Japan, 1967, p. According to the method described in 2380, the compound represented by the above formula (2a) and the compound represented by the above formula (4) can be produced by Mitsunobu reaction.

  The raw material represented by the above formula (4) is known in some cases and can be obtained from Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., etc. Or it can also manufacture easily according to the well-known method as described in an experimental chemistry course, Organic Synthesis, etc. from an available reagent.

  Examples of the phosphorus compound used in this reaction include triphenylphosphine, tri-n-butylphosphine, tritert-butylphosphine, phenoxydiphenylphosphine, and the like. Preferred are triphenylphosphine and phenoxydiphenylphosphine.

  Examples of the azodicarboxylic acid ester used in this reaction include diethyl azodicarboxylate and diisopropyl azodicarboxylate. Preferred is diethyl azodicarboxylate.

  Examples of the solvent used in this reaction include ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; halogenated carbonization such as dichloromethane, chloroform, and 1,2-dichloroethane. Hydrogens: aliphatic hydrocarbons such as pentane, hexane, cyclohexane, cycloheptane or a mixed solvent thereof. Preferred is tetrahydrofuran.

[Reaction step 4]
(In the above formula, X ³ represents a halogen atom, and A, X ¹ , Y, R ¹ , R ² , Z, n, m, p, q have the same meaning as described above.)

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

  Examples of the halogenating agent used in this reaction include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, sulfuryl chloride, thionyl chloride, and the like. Preferred are chlorine, bromine, iodine, sulfuryl chloride and the like.

  Examples of the solvent used in this reaction include halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and mixed solvents thereof. Preferred is dichloromethane.

[Reaction step 5]
(In the above formula, PG represents a protecting group such as an alkylcarbonyl group, a haloalkylcarbonyl group, an arylcarbonyl group, and an alkoxycarbonyl group, and X ¹ , X ² , and L have the same meaning as described above.)

  The starting material represented by the above formula (5) is a known compound and can be obtained from Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., etc.

  The production intermediate represented by the above formula (7) is obtained by converting the compound represented by the above formula (5) and the compound represented by the above formula (6) into a base as in the above reaction step 5-1. It can be produced by reacting in the presence.

  Examples of the base used in the reaction step 5-1 include potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, pyridine and the like. Preferred is triethylamine.

  Examples of the solvent used in the reaction step 5-1 include ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; dichloromethane, chloroform, 1,2-dichloroethane, and the like. Halogenated hydrocarbons; aliphatic hydrocarbons such as pentane, hexane, cyclohexane and cycloheptane; water or a mixed solvent thereof. Preferred is dichloromethane.

  The production intermediate represented by the above formula (8) comprises, as in the above reaction step 5-2, a compound represented by the above formula (7) obtained in the above reaction step 5-1, and chlorosulfonic acid. It can be produced by reacting. In addition, the production intermediate represented by the above formula (8) is obtained by reacting the fuming sulfuric acid with the compound represented by the above formula (7) obtained by the above reaction step 5-1, and then in the presence of a base. It can be produced by reacting with diphosphorus pentoxide.

  Examples of the base used in the reaction step 5-2 include potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, pyridine and the like. Preferred is potassium carbonate.

  The production intermediate represented by the above formula (9) is a compound represented by the above formula (8) obtained by the above reaction step 5-2, a metal and an acid, as in the above reaction step 5-3. It can be produced by reduction using lithium aluminum hydride or red phosphorus, iodine and an acid.

  Examples of the metal used in the reaction step 5-3 include zinc, tin, iron, and nickel. Zinc and tin are preferable.

  Examples of the acid used in the reaction step 5-3 include hydrochloric acid, sulfuric acid, acetic acid, and the like. Preferred are hydrochloric acid, acetic acid and the like.

  The production intermediate represented by the above formula (10) is obtained by reacting the compound represented by the above formula (9) obtained by the above reaction step 5-3 with the acid or base as in the above reaction step 5-4. It can manufacture by hydrolyzing using.

  Examples of the acid used in the reaction step 5-4 include hydrochloric acid, sulfuric acid, acetic acid, and the like. Preferred are hydrochloric acid, acetic acid and the like.

  Examples of the base used in the reaction step 5-4 include potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, diisopropylethylamine, pyridine and the like. Sodium hydroxide, potassium hydroxide and the like are preferable.

[Reaction step 6]
(In the above formula, A, L, X ¹ and X ² have the same meaning as described above.)

  The compound represented by the formula (2b) according to the present invention includes, for example, a production intermediate represented by the formula (10) obtained by the reaction step 5 and a compound represented by the formula (11). , And in the presence or absence of Rongalite (Rongalite, trade name of BASF; sodium hydroxymethanesulfinate dihydrate). Moreover, it can also manufacture by making it react in presence of a catalyst as needed.

  The raw material represented by the above formula (11) is known in some cases and can be obtained from Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., etc. Or it can also manufacture easily according to the well-known method as described in an experimental chemistry course, Organic Synthesis, etc. from an available reagent.

  The amount of the raw material represented by the formula (11) used here may be appropriately selected from the range of 1 to 5 moles relative to 1 mole of the compound represented by the formula (10). 0 to 2.0 moles.

  Examples of the base used in this reaction include potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, triethylamine, diisopropylethylamine, pyridine, sodium hydroxide, potassium hydroxide and the like. It is. Preferred is potassium carbonate.

  What is necessary is just to select the usage-amount of the base used here from the range of 0-5 mol suitably with respect to 1 mol of compounds represented by Formula (10), Preferably it is 0-2.0 mol.

Examples of the catalyst used in this reaction include tetrabutylammonium bromide or tetrabutylammonium chloride.
Solvents used in this reaction include, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; acetonitrile, N, N-dimethylformamide, N, N-dimethyl Aprotic polar solvents such as acetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane; Halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Fats such as pentane, hexane, cyclohexane and cycloheptane Group hydrocarbons, water or a mixed solvent thereof. N, N-dimethylformamide or a mixture of water and an organic solvent is preferred.

  What is necessary is just to select the usage-amount of the said solvent suitably from the range of 0.1-100 liter with respect to 1 mol of compounds represented by Formula (10), Preferably it is 1.0-5.0 liter.

  What is necessary is just to select reaction temperature from the arbitrary ranges from -30 degreeC to the reflux temperature in a reaction system, Preferably it is the range of 0 degreeC to 150 degreeC.

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

[Reaction step 7]
(In the above formula, A, X ¹ and X ² have the same meaning as described above, and n represents 1 or 2.)

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

  Examples of the oxidizing agent used in this reaction include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, oxone (OXONE, trade name of EI DuPont; potassium hydrogen peroxosulfate), N -Chlorosuccinimide, N-bromosuccinimide, tert-butyl dichlorite, sodium hypochlorite, oxygen and the like. Preferred are m-chloroperbenzoic acid and hydrogen peroxide.

  The amount of the oxidizing agent used here may be appropriately selected from the range of 1.0 to 6.0 mol, preferably 1.0 to 2 with respect to 1 mol of the compound represented by the formula (2b). 0.0 mole.

  Solvents used in this reaction include, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; acetonitrile, N, N-dimethylformamide, N, N-dimethyl Aprotic polar solvents such as acetamide, N-methyl-2-pyrrolidone and sulfolane; alcohols such as methanol, ethanol and isopropyl alcohol; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; pentane and hexane Aliphatic hydrocarbons such as cyclohexane and cycloheptane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid, water, or a mixed solvent thereof. Preferred are dichloromethane, chloroform, water, methanol, ethanol and the like.

  What is necessary is just to select the usage-amount of the said solvent suitably from the range of 0.1-100 liter with respect to 1 mol of compounds represented by Formula (2b), Preferably it is 1.0-5.0 liter.

  What is necessary is just to select reaction temperature from the arbitrary ranges from -30 degreeC to the reflux temperature in a reaction system, Preferably it is the range of -10 degreeC to 50 degreeC.

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

  In any reaction of the above reaction step 1 to reaction step 7, the target compound can be obtained by performing ordinary operations in organic synthesis such as extraction, drying, concentration, and purification after the reaction is completed.

  Moreover, the structure of the target compound can be identified by a known analysis means such as an NMR spectrum.

  In addition, the substituted phenyl ether compound which concerns on this invention is not limited to the said manufacturing method, It can manufacture by arbitrary organic synthesis methods.

Moreover, this invention compound can exhibit the outstanding control activity with respect to a wide range of insects, mites, crustaceans, molluscs, and nematodes. The compound of the present invention exhibits excellent control activity especially against insects and mites.
Among the compounds of the present invention, the compound represented by the above formula (1-1) is preferable because it exhibits a very excellent control activity against mites. Furthermore, the compound represented by the above formula (1-2) is particularly preferable because it is excellent in the residual effect of maintaining the control activity against mites even after spraying. Moreover, the compound represented by the said Formula (1-2) is excellent also in the safety from the oral administration test with respect to a mouse | mouth. Specific examples of the organism in which the compound of the present invention exhibits a controlling activity include the following.

For example, as insects, stigma Yamatosimi (Ctenolepisma villosa), sima (Lepisma saccharina), madara shimi (Thermobia domestica), etc.
Cockroaches (Periplaneta americana), Black cockroaches (Periplaneta furiginosa), Japanese cockroaches (Periplaneta japonica), German cockroaches (Blatella germantica), Buri
American termites (Incitermes minor), termites (Coptothermes formosanus), termites (Reticulitermes supertus), Taito termites (Odontotermes formosanus), etc.
Grasshopper (Ruspolia lineosa), Enma cricket (Teleoglyllus emma), Kera (Gryllotalpa orientalis), Tonosama locust (Locusta migratoria), Kobaneigo (Ezoa)
Chathamate (Trogium pulsatorium), Hiratachate (Liposcelis bostrychofila), Usgro chatter (Liposcelis corrodens), etc.
Chrysanthemum chicks (Lipeurus caponis), chicks (Menacanthus stramineus), bull lice (Damalinia bovis), horse lice (Damalinia caprae), etc.
Louseed cattle lice (Haematopinus eurosternus), swine lice (Haematopinus suis), louse lice (Pediculus humanus capitis), head lice (Pediculus humus pus), thrips pi
Thysanoptera of Hirazuhanaazamiuma (Frankliniella intonsa), western flower thrips (Frankliniella occidentalis), Croton thrips (Heliothrips haemorrhoidalis), soybean thrips (Mycterothrips glycines), yellow tea thrips (Scirtothrips dorsalis), rice thrips (Stenchaetothrips biformis), Minami thrips ( Thrips palmi, Thrips tabaci, Hemithrips aculatus, Phytothrips diospyros i) etc.
Hemiptera of the lid Ten leafhopper (Arboridia apicalis), tea Roh green leafhopper (Empoasca onukii), green rice leafhopper (Nephotettix cincticeps), small brown planthopper (Laodelphax striatella), brown planthopper (Nilaparvata lugens), Sejirounka (Sogatella furcifera), Aobahagoromo (Geisha distinctissima) , Citrus leafworm (Diaphorina citri), grape aphid (Viteus vitifoliae), pea aphid (Acyrthosiphon pisum), bean aphid (Aphis craccivora), cotton aphid (Aphis gossypii), Aphis pomi, Aphis spiraecola, phia aphis, Aphicorthum irani, pteraria eus Peach Aphid (Myzus persicae), Wheat Beetle Rhinoceros (Rhopalosiphum padi), Wheat Midge Aphid (Schizophis graminum), Schizophis piricola (Toxa), Aphid terridium (Tax) Black aphid (Toxoptera citricida), mandarin orange spiny whitefly (Aleurocanthus spiniferus), silverleaf whitefly (Bemisia argentifolii), tobacco whitefly (Bemisia tabaci), mandarin orange whitefly (Dialeurodes citri), greenhouse whitefly (Trialeurodes vaporariorum), giant straw sandals scale insects (Drosicha corpulenta) , Icerya purchasi, Prunococcus citri, Planococcus kraunhiae, Pseudococcus comstocki), Tsunoroumushi (Ceroplastes ceriferus), Rubiroumushi (Ceroplastes rubens), Acamar scale insects (Aonidiella aurantii), no circle scale insects (Diaspidiotus perniciosus), white peach scale (Pseudaulacaspis pentagona), Yano yanonensis (Unaspis yanonensis), red-spotted stink bug (Creontiades coloripes), Trigotylus caestierium, Stephanitis nasti, Stephanitis pyrioides, Tohoku Shirahoshi stink bug (Eysarcoris aeneus), giant thorns Shirahoshi bug (Eysarcoris lewisi), Tsuyaaokamemushi (Glaucias subpunctatus), red streaks stink bugs (Graphosoma rubrolineatum), brown marmorated stink bug (Halyomorpha halys), order Hemiptera (Nezara antennata), southern green stink bug (Nezara viridula), Chabae green bug (Plautia rossota stalei), Kambachabanagamekamemushi (Cavelerius saccharivorus), Kobanebane katsura (Togo hempterus), Spider helicopterin nissis), R. rottorus clavatus, Coleus puntigger, Rhopalus mculatus, Chimex lectularis, etc.
Coleoptera of Aodougane (Anomala albopilosa), cupreous chafer (Anomala cuprea), rufocuprea (Anomala rufocuprea), flower chafer (Eucetonia pilifera), core Oh flower chafer (Gametis jucunda), Nagachakogane (Heptophylla picea), Japanese beetle (Popillia japonica), Tobiiromuna Boletus (Agriotes ogurae fuscicollis), White-headed click (Ectinus sericeus sericeus), Marubitus forumni fortum (Tobacco) Banmushi (Lasioderma serricorne), red flour (Tenebroides mauritanicus), Hime Hirata Keshikisui (Epuraea domina), bean beetle (Epilachna varivestis), the beetle, Epilachna vigintioctopunctata (Henosepilachna vigintioctopunctata), Chai Loco Meno mealworm (Tenebrio molitor), red flour beetle (Tribolium castaneum ), Anophorora malasiaca, Monochmus alternada endai, Xylotrechus pyrrhoderus, Azukizo Musi (Callosobruchus chinensis), cucurbit leaf beetle (Aulacophora femoralis), Kamenokohamushi (Cassida nebulosa), Ten site bi potato beetle (Chaetocnema concinna), Western corn rootworm (Diabrotica virgifera virgifera), Southern corn rootworm (Diabrotica undecimpunctata howardi), Diabrotica (Diabrotica spp.), Colorado potato beetle (Leptinotarsa decemlineata), Rice beetle (Oulema oryzae), Kinojin beetle (Phyllotetta striolata), Arimodoki weevil (Cyl) s formicarius), boll weevil (Anthonomus grandis), Imozoumushi (Euscepes postfasciatus), alfalfa weevil (Hypera postica), vegetable weevil (Listroderes costirostris), rice weevil (Echinocnemus bipunctatus), rice water weevil (Lissorhoptrus oryzophilus), maize weevil (Sitophilus zeamais), Shibao weevil (Sphenophrus venatus vestitus), pine beetle (Tomicus piniperda), slatted beetle (Lyctus brunneus), etc.,
Fleas (Ceraphyllus gallinae), dog fleas (Ctenocephalides canis), cat flea (Ctenocephalides felis), chicken fleas (Echinidophaga gallinacea), human fleas (X)
Diptera of soybean pod gall midge (Asphondylia yushimai), Aedes aegypti (Aedes aegypti), Anopheles sinensis (Anopheles sinensis), mosquito (Culex pipines pallens), Culex quinquefasciatus (Culex quinquefasciatus), Culex (Culex tritaeniorhynchus), melon fly (Bactrocera cucurbitae), oriental fruit fly ( Bactrocera dorsalis, Agromyza oryzae, Namoguri flies (Chromatomya horticola), Liriomyza huidobrensis, Tomatoes Liriomyza sativae), legume leafminer (Liriomyza trifolii), onion maggot (Delia antiqua), seedcorn maggot (Delia platura), housefly (Musca domestica), such as the stable fly (Stomoxys calcitrans),
Lepidoptera of the smaller tea tortrix (Adoxophyes honmai), apple Coca summer fruit tortrix (Adoxophyes orana fasciata), Mi someone summer fruit moth (Archips fuscocupreanus), codling moth (Cydia pomonella), oriental fruit moth (Grapholita molesta), Chahamaki (Homona magnanima), soybean pod borer, Leguminivora glycinivorella (Leguminivora glycinivorella), Pandemis heparana, Tinea translucens, Prunus serrata, Lyonetia pelinella pelaribell Chanohosoga (Caloptilia theivora), the apple leaf miner (Phyllonorycter ringoniella), mandarin orange leafminer (Phyllocnistis citrella), diamondback moth (Plutella xylostella), grapes Sukashiba (Nokona regalis), Kosukashiba (Synanthedon hector), Kakinohetamushiga (Stathmopoda masinissa), Imokibaga (Helcystogramma triannulellum), Cotton beetle (Pectinophora gossypiella), peach sink moth (Carposina sasakii), green moth (Chiro suppressalis), yellow-tailed moth (Cnapha) ocrocis medinalisa, Conogethes puntiferalis, Hyla unipais (Hellula undalis), Eustonia furnalis, European corn borer (Ostrilia peach). White butterfly (Pieris rapae crucivora), Ichimon seiseri (Parnara gutata guttata), Artemisia dasak (Ascotis selenaria), Chadokuga (Arna pseudoconsperga) ), The United States white Arctiidae (Hyphantria cunea), black cutworm (Agrotis ipsilon), Kaburayaga (Agrotis segetum), Tamanagin'uwaba (Autographa nigrisigna), cotton bollworm (Helicoverpa armigera), Heliothis (Heliothis spp. ), Miostra brassicae, Mythimna separata, Naranga aenescens, Spodoptera exigua, Spodopter ur spo
Hymenoptera of Chu range sawfly (Arge pagana), Kaburahabachi (Athalia rosae ruficornis), Kuritamabachi (Dryocosmus kuriphilus), Kiirosuzumebachi (Vespa simillima xanthoptera), Formica japonica (Formica japonica), Iehimeari (Monomorium pharaonis), fire ant (Solenopsis invicta), etc. Is mentioned.

  The mites, bees Hegi Ita mite (Varroa jacobsoni), chicken mites (Dermanyssus gallinae), house dust mite (Ornithonyssus bacoti), Torisashidani (Ornithonyssus sylvialum), Ooyamadani (Amblyomma spp.), Boophilus microplus (Boophilus microplus), Amimemadani (Dermacentor spp. ), Tick ticks (Haemaphysalis flava), winged tick (Haephysalis campanulata), Haephysalis longicornis (Ixodes ovadus tick) sulcatus), Rhipicephalus sanguineus (Rhipicephalus sanguineus), Hakusaidani (Penthaleus erythrocephalus), Mugidani (Penthaleus major), cyclamen dust mites (Phytonemus pallidus), Chanohokoridani (Polyphagotarsonemus latus), streak-but-dust mites (Tarsonemus bilobatus), Inunikibidani (Demodex canis) , Demodex cati, Rice spider mite (Oligonychus shinkajii), Citrus spider mite (Pananychus citri), Mulberry spider mite (Pananychus mori), Apple spider mite ( anonychus ulmi), carmine spider mite (Tetranychus cinnabarinus), kanzawai (Tetranychus kanzawai), two-spotted spider mite (Tetranychus urticae), tea Roh Naga rust mite (Acaphylla theavagrans), Tulip rust mite (Aceria tulipae), tomato rust mite (Aculops lycopersici), mandarin orange rust mite (Aculops pelekassi ), Apple rust mites (Aculus schlettendali), tea rust mites (Calacarus carinatus), pear radish mites (Epitrimerus pyri), green rust mites (Eriophytes chibaensi) ), Citrus last mite (Phyllocoptruta oleivora), the bulb mite, Rhizoglyphus (Rhizoglyphus robini), Tyrophagus (Tyrophagus putrescentiae), spinach Kenna mites (Tyrophagus similis), chicken mites (Knemidokoptes spp. ), Sheep 9,000 mites (Psoroptes ovis), cat foraminous mites (Notoedres cati), SENKOU mites (Sarcoptes scabiei), red mites (Leptotrombidium akamushi), Nekotsumedani (Cheyletiella blakei), Inutsumedani (Cheyletiella yasguri), farinae (Dermatophagoides farinae) , Latrodetectus hasseltii and the like.

As the crustaceans, the Obidu depts (Oxidus gracilis), etc.
Isopods such as Armadillium vulgare,
Ten-legged American crayfish (Procambarus clarkii),
For example, Boletiella hortensis.

As mollusks, primordial string eyes, such as Pomacea canalicula,
Examples include pulmonary African mussel (Achatina falica), slug (Meghiatum bilineatum), chakoura slug (Lehmannina valentiana), and Usuka westmai (Acusta specta sieboldiana).
Nematodes include strawberry nematodes (Notothylenchus acris), sweet potato root nematodes (Meloidogyne incognita), potato cyst nematodes (Globodera rostemisen), soybean cyst nematodes (Heterocernes) Pratylenchus coffea, Pratylenchus penetran, Nepalese nematode (Pratylenchus yamagutii), Nepheline nematode (Aphelenchus avenae), Oxalic (Aphelenchoides besseyi), pine wood nematode (Bursaphelenchus xylophilus), and the like.

  Other animal internal parasites include roundworms, worms, etc., filariae, liver dystomia, lung dystoma, Yokokawa flukes, Schistosoma japonicum, striped worms, striped worms, echinococcus Examples include headworms.

  The compound of the present invention can be used as an active ingredient of agricultural and horticultural pest control agents. For formulation, suitable carriers, surfactants, fluidity improvers, bindings described in the Agricultural Chemicals Formulation Guide (edited by: Japanese Society for Agricultural Chemicals Application Methods, published by Japan Society for Plant Protection, 1997) You may mix | blend an agent, a thickener, antiseptic | preservative, etc.

  The agricultural and horticultural pest control agent containing the compound of the present invention can be formulated into any dosage form generally used as a dosage form for agricultural and horticultural pest control agents. For example, powder, coarse powder, DL (driftless) powder, flow dust, fine granules, fine granules, granules, wettable powder, wettable powder, liquid, sol (flowable), emulsion, and oil However, it is not limited to these.

  For example, mineral carriers (kaolin, bentonite, clay, montmorillonite, talc, vermiculite, gypsum, diatomaceous earth, white clay, calcium carbonate, white carbon, quartz sand, ammonium sulfate, urea, etc.), vegetable powder (crystalline cellulose, etc.) ), Polymer compounds (petroleum resin, etc.), alumina, silicates, sugar polymers and the like.

  Examples of the liquid carrier include water, alcohols (methanol, ethanol, n-propanol, ethylene glycol, glycerol, etc.), ethers (diethyl ether, tetrahydrofuran, 1,4-dioxane, cellosolve, etc.), ketones (methyl ethyl ketone, Cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, fatty acid glycerin ester, etc.), nitriles, sulfoxides (dimethyl sulfoxide, 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, methylnaphthalene, etc.), petroleum fractions, etc. That.

  In preparation, a surfactant can be added for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading, spreading, disintegration, and the like. Such surfactants include nonionic surfactants (polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene aryl phenyl ethers, polyoxyethylene sorbitan alkyl esters, sorbitans). Alkyl esters, polyoxyethylene alkylene glycols, polyoxyethylene-polyoxypropylene block polymers, etc.), anionic surfactants (alkyl benzene sulfonates, alkyl naphthalene sulfonates, lignin sulfonates, alkyl sulfosuccinates, alkyls) Sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, polyoxyalkylene alkyl ether phosphate ester, polyoxy Siethylene alkyl ether phosphates, polycarboxylates, etc.), cationic surfactants (alkylamines such as laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, polyoxyethylene alkylamines, etc.) ), Amphoteric surfactants (dialkylaminoethyl betaine, alkyldimethylbenzyl betaine, etc.), but are not limited to these examples.

  Examples of fluidity improvers include isopropyl phosphate and calcium stearate. Binders include methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, starch, carboxymethyl starch, dextrin, pullulan, sodium alginate, mannan, pectin, tragacanth gum, mannitol, sorbitol, propylene glycol alginate, guar gum Locust bean gum, gum arabic, xanthan gum, gelatin, casein, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, ethylene / propylene block polymer, sodium polyacrylate, polyvinyl pyrrolidone, calcium lignin sulfonate and the like. Examples of thickeners include guar gum, xanthan gum, tragacanth gum, casein, dextrin, colloidal hydrous aluminum silicate, colloidal hydrous magnesium silicate, colloidal hydrous aluminum silicate, carboxymethylcellulose, polyvinyl alcohol and water-soluble cellulose ether. It can be illustrated. Examples of preservatives include sodium benzoate, potassium sorbate, p-chloro-metaxylenol, butyl p-oxybenzoate 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. In general, the preferable content is in the range of 0.0001 to 90% by weight based on the total amount of the preparation.

  For example, in the case of a powder, it is usually 0.01 to 50% by weight, preferably 0.05 to 20% by weight, based on the total amount of the preparation. 0.01 to 90% by weight, preferably 0.1 to 60% by weight. 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. If it is a flowable agent, it is usually 0.01 to 60% by weight, preferably 0.1 to 50% by weight, and preferably 0.1 to 50% by weight, based on the total amount of the formulation. The amount is usually 0.01 to 50% by weight, preferably 0.1 to 20% by weight.

  When the compound of the present invention is used as an agricultural or horticultural pest control agent, a bactericidal agent (a fungicide, a bactericidal agent, an antiviral agent, a plant resistance inducer), at the time of formulation or spraying, if necessary. Mix with one or more optional ingredients selected from insecticides, acaricides, nematicides, herbicides, bird repellents, growth regulators, fertilizers, soil conditioners, etc., or mix with tank mix when spraying It may be applied.

Of the above optional components, representative examples of fungicides, insecticides, acaricides and nematicides are shown below, but are not limited thereto.
Fungicide:
(1) Copper agent: Basic copper chloride, basic sulfur copper, copper hydroxide, copper sulfate, oxine-copper, nonylphenol sulfone Copper (copper nonylphenol sulfate), DBEDC, etc.

(2) Inorganic fungicide Sulfur (sulfer), lime sulfur compound (sodium hydrogen carbonate), potassium hydrogen carbonate (potassium hydrogen carbonate), metallic silver (silver) and the like.

(3) Organic sulfur fungicide ziram, manneb, mancozeb, ambam, polycarbamate, propineb, thiuram, thiazine, india zineb).

(4) Organophosphorous fungicides IBP, EDDP, tolclofos-methyl, pyrazophos, fosetyl-alminium and the like.

(5) Benzimidazole fungicides Carbendazim, thiabendazole, thiophanate-methyl, benomyl and the like.

(6) Dicarboximide fungicides iprodione, procymidone, vinclozolin and the like.

(7) Carboxamide fungicides oxycarboxin, carboxin, mepronil, flutolanil, boscalid, fluopyram, furamethizmza Penthiopyrad, bixafen, penflufen, fluxapyroxad, isopyrazam, tolfenpyrad, sedaxane, etc.

(8) Phenylamide-based fungicides Metalaxyl, metalaxyl-M, oxadixyl, furalaxyl, ofuras, benalaxyl, and nalaxyl.

(9) Carboxylic acid amide type fungicides dimethomorph, flumorph, iprovalicalb, benchavaricarb-isopropyl, mandipropamide, valina f, and valinaproparate.

(10) SBI agents triflumizole, prochloraz, oxpoconazole fumarate, triadimefone, bittertanol, microbutanol, microbutanol , Hexaconazole, tebuconazole, propiconazole, prothioconazole, difenoconazole, iconconole and ibconazole. conazole, cyproconazole, tetraconazole, simconazole, metconazole, flusilazole, flusilazole, fluilazole, flusilazole, fluilazole, flusilazole, fluilazole (Trifoline), triadimenol, flutriafol, pyrifenox, tridemorph, dodemorph, fenpropimorphine, fenpropimorphin npropidin, spiroxamine, pyrisoxazole, fenhexamid, pyributicalcarb and the like.

(11) Strobilurin fungicides azoxystrobin, cresoxime-methyl, trifloxystrobin, methinostrobin, orysastrobrobin, orysastrobrobin Enestroburin, dimoxystrobin, picoxystrobin, pyribencarb, fluoxastrobin and the like.

(12) Anilinopyrimidine fungicide Cyprodinil, mepanipyrim, pyrimethanil and the like.

(13) Phenylpyrrole fungicides such as fludioxonil and fenpiclonil.

(14) Antibacterial fungicide kasugamycin, polyoxin, validamycin, streptomycin, oxytetracycline, blasticidin S (blasticidin-S).

(15) Other fungicides DKF-1001 (code number), MIF-1002 (code number), NF-171 (code number), S-2200 (code number), SB-4303 (code number), acibenzoral S methyl (Acibenzalar-S-methyl), amisulbrom, amethoctrazine, isothianil, isofetamid, isoprothiolane, and iminotine arbityl salt iminotadine triacetate), echromezol, ethaboxam ethaboxam), oxolinic acid, captaphor, carpropamide, quinoxyphen, chinoxythion, chloro, lotanyl, capro Diethofencaeb, diclocymet, diclomezine, dithianon, cyflufenamide, diflumetrim, simoxanyl il), sylthiofam, zoxamide, dazomet, thiadinyl, teclophthalam, tebufloquin, izo, trizol, z tolprocarb, tolmifanide, hydroxyisoxazole, pyriophenone, pyroquilon, fenoxanil, ferimon, ferimon amine), phthalide, bupirimate, famoxadone, fenamidone, fluazinam, fludiolide, fluoridoid, fluoridoid, fluorimide proquinazid, propamocarb hydrochloride, probenazole, pencyclon, holpet, metasulfocarb, metrafenone fenone), laminarin (laminarin), such as.

Insecticide:
(1) Organophosphorus insecticides acephate, azinephos-methyl, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, diaphos, diphos (Diazinon), diclofenthion, dichlorvos, dimethoate, dimethylvinphos, disulfoton, EPN, ethiphos, etiophos, ethophos os), fenitrothion, fenthion, isofenphos, isoxathion, malathion, methidathion, mevinphos, monotophos, monotophos -Methyl (oxydemethon-methyl), parathion (parathion), parathion-methyl (parathion-methyl), phentoate, folate, phosalone, phosmetone, phosphamidone n), phoxim, pirimiphos-methyl, profenofos, propopafos, prothiofos, pyrachlorfos, pyridafenthion (pyrifenthione) Temefos, terbufos, tetrachlorvinphos, thiomethon, trichlorfon, bamidithione and the like.

(2) Carbamate insecticides aldicarb, alaniccarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfofan, carbosulfen (Fenobucarb), phenoxycarb (furoxycarb), furathiocarb, isoprocarb, metiocarb, methomyl, metolcarb, icylcarb, icylcarb arb), propoxur, thiodicarb, triazamate, XMC, xylylcarb and the like.

(3) Pyrethroid insecticides acrinathrin, allethrin, bifenthrin, cycloprothrin, cyfluthrin, beta-cythalthrin, beta-cyfluthrinth. Cyhalothrin (lambda-cyhalothrin), gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, alpha-cypermethrin (theta-methrin) Sfenvalerate, etofenprox, fenpropatrin, fenvalerate, flucitrate, fluvalinate, tau-fulvalate, tau-fluinate Halfenprox, methfluthrin, permethrin, phenothrin [(1R) -trans-isomer], pyrethrin, resmethrin, resmethrin, resmethrin Emissions (tefluthrin), tetramethrin (tetramethrin), such as tralomethrin (tralomethrin).

(4) Nereistoxin insecticides such as bensultap, cartap hydrochloride, thiocyclam and the like.

(5) Neonicotinoid insecticides acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiacloprid.

(6) Diamide-based insecticides such as chlorantraniliprole, cyantraniliprole, and flubendamide.

(7) Phenylpyrazole insecticides such as acetoprole, etiprole, fipronil, flufiprole, pyrafluprole, pyriprole.

(8) Macrolide insecticides: abamectin, avermectin, avermectin benzoate, lepimectin, milbemectin, spinetoram, spinosadrum, spinosaramsp

(9) Benzoylurea insecticides bistrifluron, chlorfluazuron, diflubenzuron, fluazuron, flucyclohexuron, flufenhexuron, flufenoxuron Hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron and the like.

(10) Diacylhydrazine insecticides such as chromafenozide, halofenozide, methoxyphenozide, tebufenozide and the like.

(11) Other active insecticide ingredients Diafenthiuron, dicofol, dienochlor, endosulfan, flomequin, flonicamid, flufenerim di, flupyradion f , Hydramethylnon, hydroprene, indoxacarb, metaflumizone, metaaldehyde, methoprene, methoxychlor, and methoxychlor , Pyrifluquinazone, pyriproxyfen, rotenone, spirotetramat, sulfoxafluor, tolfenpyrad, tolfenpyrad Saw soil, fatty acid glycerides, starch (starch), rapeseed, adhesive (Polybutene), propylene glycol mono fatty acid esters, machine oil (petroleum oil), nicotine sulfate (nicotine-sulfate), phosphoric acid or the like ferric.

(12) Acaricides acequinocyl, amidoflumet, amitraz, bifenazate, bromopropylate, clofentezine (clofente), clofentezine Cyhexatin, etoxazole, fenazaquin, fenbutatin oxide, fenothiocarb, fenpyroximate, fluacrylim , Hexythiazox, propargite, piflubumide, pyrimidifene, pyridaben, spirodicifene, spiromethifen, spiromethifen .

(13) nematicide aldoxycarb, cadusafos, carbam sodium, 1,3-dichloropropene, DCIP, flusulfone, Fosthiazate, imicyafos, levamisole hydrochloride, mesulfenfos, methyl isothiocyanate, nectane mortantel

(14) Others Nuclear polyhedrosis virus (NPV), granule disease virus (GV), cytoplasmic polyhedrovirus virus (CPV), insect pox virus (EPV), etc. , Spore derived from Bacillus thuringiensis and produced crystal toxins, and mixtures thereof, microorganisms used as insecticides and nematicides such as Steinerne carpocapsae and Pasteuria penetrans Pesticides, insect pheromone agents, insect attractants, etc.

  Hereinafter, the present invention will be described more specifically with reference to synthetic examples, formulation examples, and test examples of substituted phenyl ether compounds, 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 of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenol (500 mg, 2.08 mmol) in N, N-dimethylformamide solution (5 ml) and potassium carbonate (345 mg, 2 .50 mmol) and 3,4,5-trifluorobenzyl bromide (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 saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/5) to give the title compound (yield 624 mg, 78%) as a yellow oil.

[Synthesis Example 2] 1-fluoro-5-methyl-4- (2,2,2-trifluoroethylsulfinyl) -2-[(3,4,5-trifluorophenyl) methoxy] benzene (1-141) Synthesis of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] methyl] benzene (210 mg, 0.546 mmol) To a dichloromethane solution (2 ml) was added 70% 3-chloroperbenzoic acid (150 mg, 0.608 mmol) at 0 ° C., and the mixture was stirred at the same temperature for 1 hour. The reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/3) to give the title compound as white crystals (yield 170 mg, 78%).

Synthesis Example 3 Synthesis of 1- (cyclopropylmethylthio) -4-fluoro-2-methyl-5-[(3,4,5-trifluorophenyl) methoxy] benzene (1-684) 2-Fluoro-4 Reaction and treatment similar to those of Synthesis Example 1 using 5- (cyclopropylmethylthio) -2-fluoro-4-methyl-phenol instead of -methyl-5- (2,2,2-trifluoroethylthio) phenol The title compound (yield 100%) was obtained as white crystals.

Synthesis Example 4 Synthesis of 1- (cyclopropylmethylsulfinyl) -4-fluoro-2-methyl-5-[(3,4,5-trifluorophenyl) methoxy] benzene (1-685) 1- (Cyclopropylmethylthio) -4-fluoro instead of 3-trifluoro-5-[[2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] methyl] benzene By performing the same reaction and treatment as in Synthesis Example 2 using -2-methyl-5-[(3,4,5-trifluorophenyl) methoxy] benzene, the title compound as a white crystal (yield 77%) Got.

[Synthesis Example 5] 1,2,3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] ethyl] benzene (2- 7) Synthesis of 2- (3,4,5-)-2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenol (545 mg, 2.27 mmol) in tetrahydrofuran (5 ml) Trifluorophenyl) ethanol (400 mg, 2.27 mmol), triphenylphosphine (714 mg, 2.72 mmol), diethyl azodicarboxylate (2.2 M toluene solution, 1.24 ml, 2.73 mmol) were added at 0 ° C., Stir at room temperature for 2 hours. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 1/9) to obtain the title compound (yield 650 mg, yield 72%) as a colorless oil.

[Synthesis Example 6] 1,2,3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenoxy] ethyl] benzene (2- 8) Synthesis 1,2,3 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] methyl] benzene , 3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] ethyl] benzene and the same reaction as in Synthesis Example 2 and By performing the treatment, 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] -1,1-dimethyl -Ethyl] Synthesis of benzene (2-265) To a toluene solution (3 ml) of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenol (410 mg, 1.71 mmol) Methyl-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), azodicarboxylic acid Diethyl (2.2 M toluene solution, 0.930 ml, 2.05 mmol) was added at 0 ° C. and stirred at room temperature for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/5) to give the title compound (yield 111 mg, 15%) as a colorless oil.

[Synthesis Example 8] 1,2,3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenoxy] -1,1-dimethyl Synthesis of -ethyl] benzene (2-266) 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] methyl] 1,2,3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] -1,1-dimethyl- instead of benzene Ethyl] benzene was used for the same reaction and treatment as in Synthesis Example 2 to obtain the title compound (yield 21%) as a colorless oil.

[Synthesis Example 9] 1,2,3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] ethoxy] benzene (6- 9) Synthesis of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenol (240 mg, 0.999 mmol) in N, N-dimethylformamide solution (3 ml) and potassium carbonate (180 mg) , 1.30 mmol) and 5- (2-bromoethoxy) -1,2,3-trifluorobenzene (268 mg, 1.05 mmol) were added at room temperature and stirred at the same temperature for 7 hours. Water was poured into the reaction mixture and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/4) to obtain the title compound (yield 410 mg, yield 99%) as a white oil.

[Synthesis Example 10] 1,2,3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenoxy] ethoxy] benzene (6- 10) Synthesis 1,2,3 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] methyl] benzene , 3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] ethoxy] benzene and the same reaction as in Synthesis Example 2 and By performing the treatment, the title compound (yield 68%) was obtained as white crystals.

[Synthesis Example 11] 1,2,3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] propoxy] benzene (7- 9) Synthesis of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenol (300 mg, 1.25 mmol) in N, N-dimethylformamide solution (3 ml) and 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 the same temperature for 7 hours. Water was poured into the reaction mixture and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/4) to give the title compound (yield 440 mg, yield 82%) as a white oil.

[Synthesis Example 12] 1,2,3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenoxy] propoxy] benzene (7- 10) Synthesis 1,2,3 instead of 1,2,3-trifluoro-5-[[2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] methyl] benzene , 3-trifluoro-5- [2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenoxy] propoxy] benzene and the same reaction as in Synthesis Example 2 and By performing the treatment, the title compound (yield 80%) was obtained as white crystals.

Synthesis Example 13 Synthesis of 5- (cyclopropylmethylthio) -2-fluoro-4-methylphenol (9-3) 2-Fluoro-4-methyl-5-sulfanylphenol (0.59 g, 3.73 mmol) N, N-dimethylformamide solution (10 ml) was charged with potassium carbonate (0.77 g, 5.58 mmol), Rongalite (0.13 g, 1.10 mmol), and cyclopropylmethyl bromide (0.60 g, 4.44 mmol). The mixture was added at ° C and stirred at room temperature for 4 hours. A 1N aqueous hydrochloric acid solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 1/10) to obtain the title compound (yield 0.50 g, yield 64%) as a yellow oil.

[Synthesis Example 14] 1- [2,2-difluoro-2- (3,4,5-trifluorophenyl) ethoxy] -2-fluoro-4-methyl-5- (2,2,2-trifluoroethyl Synthesis of thio) benzene (2-209) 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenol (500 mg, 2.08 mmol) in N, N-dimethylformamide (5 ml) ) Were added potassium carbonate (374 mg, 2.71 mmol) and [2,2-difluoro-2- (3,4,5-trifluorophenyl) ethyl] trifluoromethanesulfonate (859 mg, 2.50 mmol) at 0 ° C. And stirred at room temperature for 2 hours. Water was poured into the reaction mixture and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/5) to give the title compound as a colorless oil (yield 723 mg, yield 80%).

Synthesis Example 15 1- [2,2-Difluoro-2- (3,4,5-trifluorophenyl) ethoxy] -2-fluoro-4-methyl-5- (2,2,2-trifluoroethyl Synthesis of sulfinyl) benzene (2-210) 1- [2,2-difluoro-2- (3,4,5-trifluorophenyl) ethoxy] -2-fluoro-4-methyl-5- (2,2, To a chloroform solution (4 ml) of 2-trifluoroethylthio) benzene (370 mg, 0.897 mmol), 70% 3-chloroperbenzoic acid (200 mg, 0.897 mmol) was added at 0 ° C. and stirred at the same temperature for 1 hour. did. The reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/3) to give the title compound as white crystals (yield 370 mg, yield 97%).

Synthesis Example 16 1-Chloro-2- [2,2-difluoro-2- (3,4,5-trifluorophenyl) ethoxy] -5-methyl-4- (2,2,2-trifluoroethyl Synthesis of thio) benzene (2-447) 2-chloro-4-methyl-5- (2,2,2-trifluoroethylthio) phenol (2.00 g, 7.79 mmol) in N, N-dimethylformamide (20 ml) to potassium carbonate (1.40 g, 10.1 mmol) and [2,2-difluoro-2- (3,4,5-trifluorophenyl) ethyl] trifluoromethanesulfonate (3.20 g, 9.30 mmol) Was added at 0 ° C. and stirred at room temperature for 2 hours. Water was poured into the reaction mixture and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/5) to give the title compound (yield 3.08 g, yield 88%) as a colorless oil.

Synthesis Example 17 1-chloro-2- [2,2-difluoro-2- (3,4,5-trifluorophenyl) ethoxy] -5-methyl-4- (2,2,2-trifluoroethyl Synthesis of sulfinyl) benzene (2-448) 1-chloro-2- [2,2-difluoro-2- (3,4,5-trifluorophenyl) ethoxy] -5-methyl-4- (2,2, To a dichloromethane solution (4 ml) of 2-trifluoroethylthio) benzene (130 mg, 0.897 mmol), 70% 3-chloroperbenzoic 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 saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate / toluene = 1/30) to obtain the title compound as white crystals (yield 130 mg, yield 100%).

Table 1 shows the ¹ HNMR spectrum (CDCl ₃ ) σ (ppm) value, melting point (° C.) and the like of the synthesis examples and the compounds according to the present invention produced according to the synthesis examples. ¹ HNMR data is measured with a JNM-ECS400 spectrometer (manufactured by JEOL Ltd.).

  Hereinafter, Reference Synthesis Example 1 to Reference Synthesis Example 8 show synthesis examples in which the starting materials of Synthesis Examples 1 to 17 are synthesized from commercially available products, but are not limited thereto.

[Reference Synthesis Example 1] Synthesis of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl) thio] phenol 2-Fluoro-4-methyl-5-sulfanylphenol (3.00 g, 19.0 mmol) in N, N-dimethylformamide (30 ml) in potassium carbonate (2.88 g, 20.8 mmol), Rongalite (0.900 g, 7.62 mmol), and 2,2,2-trifluoro-1 -Iodoethane (4.18 g, 19.9 mmol) was added at 0 ° C and stirred at room temperature for 4 hours. A 1N aqueous hydrochloric acid solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/3) to give the title compound (yield 3.96 g, yield 87%) as a yellow oil.
¹ HNMR 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 = 9.8 Hz), 2.37 (3H, s).

[Reference Synthesis Example 2] Synthesis of 2-fluoro-4-methyl-5-sulfanylphenol 2-fluoro-4-methylphenol (24.96 g, 197.9 mmol) (manufactured by Sigma-Aldrich) and triethylamine (26.03 g, To a dichloromethane solution (500 ml) of 257.3 mmol), ethyl chloroformate (23.62 g, 217.7 mmol) was added at 0 ° C., and the mixture 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 saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a colorless oil (yield 39.22 g, yield 100%). The obtained oil was added to chlorosulfonic acid (117.00 g, 1000 mmol) at 0 ° C. and reacted 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 concentrated under reduced pressure to give a brown oil (yield 46.49 g, yield 78%). 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 oily substance at room temperature, and the mixture was heated to reflux for 2 hours. Ice water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give a brown oil (yield 30.13 g, yield 71%). The obtained oil was added to 10% aqueous potassium hydroxide solution (4 l) and heated to reflux for 3 hours. Concentrated hydrochloric acid was added to the reaction mixture to adjust to pH 7 and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the title compound as a brown oil (yield 16.46 g, yield 94%).
¹ HNMR 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 3] Synthesis of 2- (3,4,5-trifluorophenyl) ethanol 1,2,3-trifluoro-5-vinylbenzene (manufactured by Apollo) (1.00 g, 6.32 mmol) Dimethyl sulfide borane (d = 0.800, 0.660 ml, 7.04 mmol) was added to a tetrahydrofuran solution (10 ml) at 0 ° C. and reacted at room temperature for 12 hours. Water (3.0 ml), 2N aqueous sodium hydroxide solution (15 ml) and 30% aqueous hydrogen peroxide (1.4 ml) were added, and the mixture was 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 saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/3) to give the title compound as a colorless oil (yield 809 mg, yield 73%).
¹ HNMR 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.s).

[Reference Synthesis Example 4] Synthesis of 2-methyl-2- (3,4,5-trifluorophenyl) propan-1-ol 3,4,5-trifluorobenzyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) (5 (00 ml, 22.2 mmol) in acetonitrile (40 ml), water (10 ml), potassium cyanide (1.74 g, 26.7 mmol) and 18-crown-6-ether (Tokyo Chemical Industry Co., Ltd.) (0.590 g, 2.22 mmol) was added at room temperature 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 saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: 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 to a dimethoxyethane solution (40 ml) of the obtained oil at 0 ° C., and the mixture was stirred at room temperature for 1 hour. Stir. Water was poured into the reaction mixture and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 1/5) to obtain a white solid (yield 4.00 g, yield 92%). A 60% aqueous sulfuric acid solution (40 ml) was added to the solid acetic acid solution (20 ml) obtained, and the mixture was stirred at 120 ° C. for 2 hours. did. Ice water was poured into the reaction mixture, and the precipitated solid was washed with water and then dried under reduced pressure to obtain a white solid (yield 3.86 g, yield 87%). Oxalyl chloride (3.36 g, 26.5 mmol) and N, N-dimethylformamide (0.10 mmol) were added to a dichloromethane solution (40 ml) of the obtained solid, and the mixture was refluxed for 1 hour. The reaction solution was concentrated under reduced pressure to obtain a yellow solid (4.63 g). Lithium aluminum hydride (686 mg, 18.1 mmol) was added to the obtained solid tetrahydrofuran solution (40 ml) at 0 ° C., and the mixture was stirred at room temperature for 1 hr. Diethyl ether was poured into the reaction mixture, a small amount of water was added, and the mixture was stirred at room temperature for 1 hour. The precipitate was removed by suction filtration, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/3) to obtain the title compound (yield 3.13 g, yield 87%) as a colorless oil.
¹ HNMR 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 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), triphenylphosphine (2.20 g, 8.39 mmol) and diethyl azodicarboxylate (2.2 M toluene) Solution, 3.82 ml, 8.41 mmol) was added at 0 ° C. and stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/10) to give the title compound as a colorless oil (yield 1.44 g, yield 74%). Got.
¹ HNMR spectrum (CDCl ₃ ) σ: 6.58-6.50 (2H, m), 4.22 (2H, t, J = 6.0 Hz), 3.61 (2H, t, J = 6.0 Hz) ).

[Reference Synthesis Example 6] Synthesis of 5- (3-bromopropoxy) -1,2,3-trifluorobenzene 3,4,5-trifluorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.13 g, 7. 63 mmol) in tetrahydrofuran (10 ml) was added 3-bromo-1-propanol (1.73 ng, 11.5 mmol), triphenylphosphine (2.20 g, 8.39 mmol) and diethyl azodicarboxylate (2.2 M toluene). Solution, 3.82 ml, 8.41 mmol) was added at 0 ° C. and stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/10) to give the title compound as a colorless oil (yield 1.39 g, yield 68%). Got.
¹ HNMR 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 = 6.0 Hz).

[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 ( According to the method described in Journal of Fluorine Chemistry, 2004, P.509 and the like (1.00 g, 3.93 mmol) in ethanol solution (8 ml), sodium borohydride (800 mg, 3.15 mmol) is added to 0. The mixture was added at 0 ° C. and stirred at the same temperature for 1 hour. Ice water was poured into the reaction mixture, and the mixture was extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give the title compound (yield 800 mg, yield 96%) as a colorless oil.
¹ HNMR 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 2,2-difluoro-2- (3,4,5-trifluoro Phenyl) ethanol (2.30 g, 10.8 mmol) and triethylamine (1.30 g, 12.8 mmol) in dichloromethane (25 ml) were added trifluoromethanesulfonic anhydride (3.40 g, 12.1 mmol) 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 saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 1/7) to obtain the title compound (yield 3.20 g, yield 86%) as a yellow oil.
¹ HNMR spectrum (CDCl ₃ ) σ: 7.23-7.16 (2H, m), 4.67 (2H, t, J = 11.2 Hz).

Next, specific examples of a method for formulating the compound of the present invention as an agricultural and horticultural insecticide or acaricide 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) as a fluidity improver and clay (97 parts by weight) as a solid carrier is uniformly ground and mixed. Thus, a powder containing 2% by weight of the active ingredient can be obtained. Furthermore, it can replace with the compound of the synthesis example 1, and each powder agent can be obtained by the same method except using each compound of Table 1-Table 8.

[Formulation Example 2] Wetting Agent Compound (20 parts by weight) of Synthesis Example 1, sodium alkylbenzene sulfonate (3 parts by weight) as an anionic surfactant, and polyoxyethylene alkylphenyl ether (non-ionic surfactant) A wettable powder containing 20% by weight of the active ingredient can be obtained by uniformly crushing and mixing a mixture of 5 parts by weight) and clay (72 parts by weight) as a solid carrier. Furthermore, it can replace with the compound of the synthesis example 1, and can respectively obtain a wettable powder by the same method except using each compound of Table 1-Table 8.

[Formulation Example 3] Emulsion The compound of Synthesis Example 1 (30 parts by weight), methyl naphthalene (40 parts by weight) as a liquid carrier and polyoxyethylene alkylphenyl ether (30 parts by weight) as a nonionic surfactant are mixed and dissolved. By doing so, an emulsion containing 30% by weight of the active ingredient can be obtained. Further, emulsions can be obtained in the same manner except that each compound shown in Tables 1 to 8 is used in place of the compound of Synthesis Example 1.

[Formulation Example 4] Flowable Agent The compound of Synthesis Example 1 (25 parts by weight), polyoxyethylene alkyl ether (1 part by weight) as a nonionic surfactant, and sodium alkylnaphthalene sulfonate (1 as an anionic surfactant) Parts by weight), xanthan gum (1 part by weight) as a thickener, and water (72 parts by weight) as a liquid carrier are uniformly mixed to obtain a flowable agent containing 25% by weight of the active ingredient. Furthermore, it replaces with the compound of the synthesis example 1, and each flowable agent can be obtained by the same method except using each compound of Table 1-Table 8.

[Formulation Example 5] Granule The compound of Synthesis Example 1 (5 parts by weight), sodium lauryl sulfate (1 part by weight) as a surfactant, calcium lignin sulfonate (5 parts by weight) as a binder, bentonite (30 Parts by weight) and clay (59 parts by weight), water (15 parts by weight) is further added and kneaded by a kneader, granulated by a granulator, and further dried by a fluid dryer to obtain an active ingredient. Granules containing 5% by weight can be obtained. Furthermore, it replaces with the compound of the synthesis example 1, and each granule can be obtained by the same method except using each compound of Table 1-Table 8.

Specific examples of the evaluation of the control effect using the pest control agent according to the present invention obtained as described above are shown in Test Examples 1 to 4.
[Test Example 1] Control test against brown planthopper Rice seedlings cultivated in a plastic cup were placed on a turntable, and an emulsion diluted solution (500 ppm) prepared according to Formulation Example 3 was sprayed uniformly with a spray gun. After air-drying, it was placed in a polycarbonate plastic container with a nylon gorge on the lid, and 10 4th instar larvae were released, and placed in a constant temperature room at 25 ° C. Seven days after the release, the number of surviving insects was examined, and the death rate (%) was calculated by the following formula (a). The test was carried out in two consecutive systems.

As a representative example, the compound Nos. 1-1, 1-2, 1-3, 106, 1-140, 1-245, and 2-7 showed a death rate of 80% or more.
[Test Example 2] Control test against bean aphids Three pealess aphids were released on each broad bean seedling cultivated in a plastic cup. One day after the release, this broad bean seedling was placed on a turntable, and an emulsion diluted solution (500 ppm) prepared according to Formulation Example 3 was sprayed uniformly with a spray gun. After the treatment, it was placed in a constant temperature room at 25 ° C. (16 hours illumination), and the number of adults and larvae parasitized 4 days after the treatment was examined, and the control value (%) was calculated by the following formula (b). The test was carried out in two consecutive systems.

  As representative examples, the compounds Nos. 1-629, 1-760, 2-166, 2-209, and 6-9 exhibited a control value of 80% or more.

[Test Example 3] Control test against spider mite Ten adult female spider mites were released at a rate of 10 persimmon seedlings cultivated in plastic cups. One day after the release, the kidney seedlings were placed on a turntable, and an emulsion diluted solution (500 ppm) prepared according to Formulation Example 3 was sprayed uniformly with a spray gun. After the treatment, it was placed in a constant temperature room at 25 ° C. (16 hours illumination), and the number of female adults parasitized 8 days after the treatment was examined, and the control value (%) was calculated by the following formula (c). The test was carried out in two consecutive systems.

  As representative examples, the compound numbers 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, 1-2 8, 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, 1-652, 1-653, 1-684, 1-685, 1-702, 1-703, 1-708, 1- 709, 1-714, 1-715, 1-720, 1-721, 1-722, -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, 312, 2-339, 2-340, 2-363, 2-364, 2-413, 2-414, 2-421, 2-421 -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 show a control value 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 shows a control value of 80% or more and less than 90%, 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 have a control value of 90% or more 100 %, 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, 1-9 1-96, 1-97, 1-99, 1-100, 1-102, 1-106, 1-107, 1-108, 1-109, 1-110, 1-111, 1-1811-119 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, 1-334, 1-372, 1-389, 1-390, 1-410, 1-421, 1-422, 1 -448, 1-471, 1-495, 1-496, 1-559, 1-560 1-561, 1-568, 1-569, 1-597, 1-608, 1-609, 1-616, 1-617, 1-628, 1-629, 1-652, 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, 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 showed a 100% value control.

[Test Example 4] Control test 2 against spider mite
Bean seedlings (second true leaf stage) cultivated in a plastic cup were placed on a turntable, and an emulsion diluted solution (5 ppm) prepared by applying the compound of the present invention according to Formulation Example 3 was sprayed uniformly with a spray gun. After spraying, placed in a constant temperature room at 25 ° C. (16 hours illumination), and 7 days later, 10 adult female spider mite were released on leaf discs cut out from the first true leaf and allowed to stand in a constant temperature room at 25 ° C. . Two days after the release, the number of female adults was examined, and the death rate (%) was calculated by the following formula (d). The test was carried out in two consecutive systems.

  Test Example 4 investigates the residual effect of the compound of the present invention against the spider mite. A 5 ppm emulsion diluent prepared by applying the compound of the present invention according to Formulation Example 3 was sprayed on a bean seedling (second true leaf stage) and allowed to stand for 7 days. Thereafter, 10 spider mites were released on leaf discs prepared by cutting out the first true leaves, and the number of live spider mites surviving two days after the release was examined. The residual effect was investigated by spraying the drug and confirming the control effect after standing for 7 days.

  Table 11 below shows the results of the control test 2 against the spider mite using the compounds in the present specification. In Table 11 below, the compounds described in Reference Examples 1, 3, 5, 7, 13, 14, and 19 to 22 are the control values of 3.3 ppm emulsion dilutions tested by the method according to Test Example 3 above. Since the control activity is further reduced 7 days after spraying, the control test 2 for the spider mite was not conducted.

"Summary of Test Example 4"
The compounds Nos. 2-209, 2-210, 2-447, and 2-448 shown in Examples 1 to 4 have a very excellent mortality rate of 89.5% to 100%, and are spread 7 High control activity was maintained even after days, and the residual effect was excellent.
The compounds of Reference Examples 1, 3, 5, and 7 having a slightly different molecular structure from the compound of Example 1 have a control activity against ticks in a 3.3 ppm emulsion diluted by the method according to Test Example 3 above. The control test 2 against the spider mite was not conducted because it was clear that the control activity after 7 days of spraying was further reduced.

Reference Example 2 using Compound No. 2-8 having a molecular structure in which R ^1a and R ^2a are different from the molecular structure of the compound of Example 2 in that R ^2a is a hydrogen atom Reference Example 4 using Compound No. 2-35 having a different molecular structure, Reference Example 8 using Compound No. 2-266 having a molecular structure in which R ^1a and R ^2a are both methyl groups The mortality was 27.8%, 8.2%, and 4.5%, respectively, which was lower than the mortality of 95.0% in Example 2 and inferior in residual efficacy.
In the molecular structure of the compound of Example 2, a molecule in which the fluorine atoms substituted at the 3, 4 and 5 positions of the benzene ring are changed to fluorine atoms substituted at the 3 and 4 positions, and the number of substitution of fluorine atoms is reduced by one. The death rate of Reference Example 6 using Compound No. 2-204 having a structure was 0%, and no residual effect was observed.

Reference Examples 9 and 10 using Compound Nos. 2-405 and 2-406 having molecular structures different from the molecular structures of Examples 3 and 4 in that R ^1a and R ^2a are both hydrogen atoms are respectively dead. Although the insect ratios were 38.9% and 24.7%, and residual effects were observed, they were inferior to Examples 3 and 4 in which both the dead insect ratio was 100%.
Examples 1 and 2 using compounds having a molecular structure in which X ² is a fluorine atom have 89.5% and 95.0% mortality, respectively, and compounds having a molecular structure in which X ² is a chlorine atom are used. The death rates of Reference Examples 11 and 12 using Compound Nos. 2-557 and 2-558 having a molecular structure in which X ² is a bromine atom, whereas the death rate of both Examples 3 and 4 were 100%. The worm rates were 36.8% and 42.1%, respectively. Among the compounds in which X ² is a halogen atom, a compound in which X ² is a fluorine atom or a chlorine atom showed remarkably superior after-effect as compared with a compound in which X ² is a bromine atom.

  The mortality rates of the compounds used in Reference Examples 15 to 18 described in Tables 11-2 and 11-3 were 10.6%, 47.7%, 15.0%, and 12.5%, respectively. Compared with the compounds used in Examples 1 to 4, the mortality rate was low and the residual effect was poor. In Reference Examples 13, 14, and 19-22, the control test 2 against the spider mite was not performed because the control activity against mites at a concentration of 3.3 ppm tested by the method according to Test Example 3 was low.

Among the compounds shown in Table 11, the four compounds 2-209, 2-210, 2-447, and 2-448 exhibit a very good mortality even after 7 days of spraying. It was confirmed that the difference in the structure caused a great difference in the residual effect.
These four compounds maintained high control activity even after 7 days of spraying, and showed very excellent residual effect. In addition, these four compounds greatly reduced the number of nymph mite individuals radiated 7 days after spraying in only 2 days, and were also excellent in rapid action.

  From the above results, it was confirmed that the pest control agent according to the present invention is useful as a pest control agent in any of the above pests. Moreover, since the compound represented by Formula (1-2) had both residual effect and quick effect, it confirmed that it was especially useful as an acaricide.

  Since the substituted phenyl ether compound according to the present invention has an excellent control effect against pests, the use of this as a pest control agent can effectively control pests. In particular, the compound represented by the formula (1-2) has a residual effect and a rapid effect on mites, and is useful as an active ingredient of an acaricide.

Claims (2)

Formula (1-2):

(In the formula (1-2), n represents an integer of 0 or 1.
X ² represents a fluorine atom or a chlorine atom. )
A substituted phenyl ether compound represented by the formula: An acaricide comprising the substituted phenyl ether compound according to claim 1 as an active ingredient.