JP2008115156A - Pest-controlling agent composition and pest-controlling method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pest-controlling method using a new cyclic amine compound. <P>SOLUTION: The pest-controlling agent contains the cyclic amine compound represented by formula (1) (wherein, X is an oxygen atom or the like; R<SP>1</SP><SB>a</SB>and R<SP>2</SP><SB>a</SB>, R<SP>1</SP><SB>a</SB>and R<SP>4</SP><SB>a</SB>, R<SP>2</SP><SB>a</SB>and R<SP>3</SP><SB>a</SB>, or R<SP>3</SP><SB>a</SB>and R<SP>4</SP><SB>a</SB>form a saturated ring together with each other; R<SP>1</SP><SB>a</SB>, R<SP>1</SP><SB>b</SB>, R<SP>2</SP><SB>a</SB>, R<SP>2</SP><SB>b</SB>, R<SP>3</SP><SB>a</SB>, R<SP>3</SP><SB>b</SB>, R<SP>4</SP><SB>a</SB>, R<SP>4</SP><SB>b</SB>and R<SP>5</SP>forming no saturated ring are each a hydrogen atom or the like; and Cy<SP>1</SP>and Cy<SP>2</SP>are each an aromatic ring which may have a substituent) or the like, and another acaricide. The pest-controlling method uses the cyclic amine compound represented by formula (1) and another acaricide. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pest control composition containing a novel cyclic amine compound and another acaricide as active ingredients, and a pest control method.

  Conventionally, many compounds with insecticidal / miticidal activity are known, but their efficacy is insufficient, their use is restricted due to drug resistance problems, and phytotoxicity and contamination are caused to plants. In many cases, it is difficult to say that it is a satisfactory control agent because it occurs or is highly toxic to human and livestock fish. Therefore, there is a demand for the development of a drug that can be safely used with few such drawbacks.

  As a compound having a skeleton similar to the novel cyclic amine compound used in the present invention, Patent Document 1 discloses the following formula:

(Wherein, X ^a represents —O—, —N (R ^c ) —, —S—, etc., and R ^a represents ^a substituted saturated heterocyclic group, etc.).
Patent Document 2 discloses the following formula:

(Wherein X ^b represents —CH— or the like, Z represents a single bond or the like, R ^f represents an optionally substituted aryl group, or an optionally substituted heteroaryl group, R ^h and R ⁱ together represents-(CH ₂ ) s-, etc.).

However, the compounds described in Patent Documents 1 and 2 are all for pharmaceutical use, and these documents do not describe the use of the pest control composition.
International Publication No. 02/100833 Pamphlet WO05 / 14578 pamphlet

  The present invention comprises a novel cyclic amine compound and other acaricide as active ingredients, has an excellent pest control activity and has no safety problems, and the above-mentioned It is an object of the present invention to provide a method for controlling pests using a cyclic amine compound and other acaricides.

  The present inventors have found that a novel cyclic amine compound having a specific structure has an excellent insecticidal / miticidal activity, and has previously filed a patent application (PCT / JP2006 / 320133).

As a result of further earnest research on the agrochemical preparation containing the cyclic amine compound, the present inventors have found that when the cyclic amine compound and other acaricides are used in combination, a safer and better insecticide with a smaller dosage. -It discovered that the pest control effect which has acaricidal activity could be acquired, and came to complete this invention.
Thus, according to the present invention, the following pest control compositions (1) to (4) are provided.
(1) (A) Formula (1)

(In the formula, X represents an oxygen atom, a sulfur atom, an unsubstituted or substituted nitrogen atom, a sulfinyl group, or a sulfonyl group.
R ¹ _a and R ² _a , R ¹ _a and R ⁴ _a , R ² _a and R ³ _a , or R ³ _a and R ⁴ _a together form a saturated ring.
R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , and R ⁵ that do not form a saturated ring are each independently a hydrogen atom, hydroxyl group Represents a halogen atom, an amino group, a substituted amino group, a nitro group, or an organic group.
Cy ¹ and Cy ² each independently represent an unsubstituted or substituted aromatic group.
However, when R ¹ _a and R ² _a are combined to form a saturated ring, and Cy ¹ is an unsubstituted or substituted phenyl group, Cy ² is unsubstituted or substituted. When it is an aromatic heterocyclic group, Cy ¹ is a phenyl group which may have a substituent, and Cy ² is a pyridin-2-yl group, Cy ² is one or more cyano groups as a substituent. It is a substituted pyridin-2-yl group having )
A pest control composition comprising at least one of a cyclic amine compound represented by the formula: or a salt thereof or an N-oxide thereof; and at least one other acaricide.

(2) R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ that do not form a saturated ring of the cyclic amine compound represented by the formula (1) The pest control composition according to (1), wherein _{b 1} and R ⁵ are an alkyl group, an alkoxycarbonyl group, or an alkoxy group.
(3) In the formula (1), the cyclic amine compound represented by the formula (1) forms a saturated ring by combining R ¹ _a and R ² _a , or R ³ _a and R ⁴ _a together. The pest control composition as described in (1),
(4) The pest according to (1), wherein the cyclic amine compound represented by the formula (1) is a compound having 2 or 3 bridge atoms in the piperidine ring forming the saturated ring in the formula (1). Control agent composition.

According to the second aspect of the present invention, the following pest control method (5) is provided.
(5) A method for controlling pests, comprising using at least one of the cyclic amine compound represented by the formula (1), a salt thereof or an N-oxide thereof, and at least one other acaricide.

ADVANTAGE OF THE INVENTION According to this invention, the pest control composition which contains at least 1 type of the cyclic amine compound which has a novel structure, its salt or its N-oxide, and another acaricide as an active ingredient is provided. Is done.
According to the pest control composition and the pest control method of the present invention, it is possible to obtain a pest control effect having more excellent insecticidal / miticidal activity with a smaller dosage and more safely.

Hereinafter, the pest control composition and the pest control method of the present invention will be described in detail.
1) Pest control composition The pest control composition of the present invention comprises at least one of the cyclic amine compound represented by the above (1), or a salt thereof or an N-oxide thereof, and other acaricides. It contains at least one kind.

In the cyclic amine compound represented by the formula (1), in the formula (1), Cy ¹ represents an unsubstituted or substituted aromatic group.

  Examples of the aromatic group include aromatic hydrocarbon groups such as phenyl group, naphthalen-1-yl group, and naphthalen-2-yl group; furan-2-yl group, furan-3-yl group, and thiophen-2-yl. Group, thiophen-3-yl group, pyrrol-2-yl group, pyrrol-3-yl group, oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, thiazol-2-yl group , Thiazol-4-yl group, thiazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, isoxazol-5-yl group, isothiazol-3-yl group, isothiazole- 4-yl group, isothiazol-5-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group, pyrazol-3-yl group, pyrazo Lu-4-yl group, pyrazol-5-yl group, 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 1,2,3-triazole- 4-yl group, 1,2,4-triazol-3-yl group, 1,2,4-triazol-5-yl group, pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl Group, pyridazin-3-yl group, pyridazin-4-yl group, pyrazin-2-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, 1,3,5- And aromatic heterocyclic groups such as a triazin-2-yl group and a 1,2,4-triazin-3-yl group. Among these, a phenyl group is preferable.

  Specific examples of the substituent of the aromatic group include: hydroxyl group; thiol group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; nitro group; formyl group; amino group, methylamino group, benzyl Unsubstituted or substituted amino groups such as amino group, anilino group, dimethylamino group, diethylamino group, phenylethylamino group; methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl Group, alkyl group such as i-butyl group, t-butyl group, n-pentyl group and n-hexyl group; alkenyl group such as vinyl group, allyl group and 2-methoxy-ethenyl group; ethynyl group, 1-propynyl group , Alkynyl groups such as 2-phenylethynyl group and propargyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, -Alkoxy groups such as butoxy, i-butoxy and t-butoxy; alkenyloxy such as vinyloxy and allyloxy; alkynyloxy such as ethynyloxy and propargyloxy; phenoxy and benzyloxy Aryloxy group; heteroaryloxy group such as 2-pyridyloxy group; chloromethyl group, fluoromethyl group, bromomethyl group, dichloromethyl group, difluoromethyl group, dibromomethyl group, trichloromethyl group, trifluoromethyl group, bromodifluoro Haloalkyl groups such as a methyl group, 1,1,1-trifluoroethyl group, 1-chloroethyl group, 2-chloroethyl group, 1-bromoethyl group, pentafluoroethyl group; fluoromethoxy group, chloromethoxy group, bromomethoxy group, Difluoromethoxy group Haloalkoxy groups such as dichloromethoxy group, dibromomethoxy group, trifluoromethoxy group, trichloromethoxy group, tribromomethoxy group, 1,1,1-trifluoroethoxy group, pentafluoroethoxy group, heptafluoro n-propoxy group; Methylthiocarbonyl group, ethylthiocarbonyl group, n-propylthiocarbonyl group, i-propylthiocarbonyl group, n-butylthiocarbonyl group, i-butylthiocarbonyl group, s-butylthiocarbonyl group, t-butylthiocarbonyl group Alkylthiocarbonyl groups such as;

Alkylsulfonylamino groups such as methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group, i-propylsulfonylamino group, n-butylsulfonylamino group, t-butylsulfonylamino group; phenylsulfonylamino group, etc. A heteroarylsulfonylamino group such as a piperazinylsulfonylamino group; an alkylcarbonylamino group such as a methylcarbonylamino group, an ethylcarbonylamino group, an n-propylcarbonylamino group, or an i-propylcarbonylamino group; Alkoxycarbonylamino groups such as methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group; fluoromethylsulfonylamino , Chloromethylsulfonylamino group, bromomethylsulfonylamino group, difluoromethylsulfonylamino group, dichloromethylsulfonylamino group, 1,1-difluoroethylsulfonylamino group, trifluoromethylsulfonylamino group, 1,1,1-trifluoro Haloalkylsulfonylamino groups such as ethylsulfonylamino group and pentafluoroethylsulfonylamino group; bis (methylsulfonyl) amino group, bis (ethylsulfonyl) amino group, (ethylsulfonyl) (methylsulfonyl) amino group, bis (n-propyl) Bis (alkylsulfonyl) amino group such as sulfonyl) amino group, bis (i-propylsulfonyl) amino group, bis (n-butylsulfonyl) amino group, bis (t-butylsulfonyl) amino group; (Romethylsulfonyl) amino group, bis (chloromethylsulfonyl) amino group, bis (bromomethylsulfonyl) amino group, bis (difluoromethylsulfonyl) amino group, bis (dichloromethylsulfonyl) amino group, bis (1,1-difluoro) Bis (haloalkylsulfonyl) amino groups such as ethylsulfonyl) amino group, bis (trifluoromethylsulfonyl) amino group, bis (1,1,1-trifluoroethylsulfonyl) amino group, bis (pentafluoroethylsulfonyl) amino group ;

Unsubstituted or substituted hydrazino groups such as hydrazino group, N′-phenylhydrazino group, N′-methoxycarbonylhydrazino group, N′-acetylhydrazino group, N′-methylhydrazino group; methoxycarbonyl group, ethoxycarbonyl Group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and other alkoxycarbonyl groups; phenyl group, 1-naphthyl group, 2-naphthyl group and other aryl groups; benzyl group Aralkyl groups such as phenethyl group;

Furan-2-yl group, furan-3-yl group, thiophen-2-yl group, thiophen-3-yl group, pyrrol-2-yl group, pyrrol-3-yl group, oxazol-2-yl group, oxazole -4-yl group, oxazol-5-yl group, thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, Isoxazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazole-5 Yl group, pyrazol-3-yl group, pyrazol-4-yl group, pyrazol-5-yl group, 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadi Unsaturated complex such as zol-2-yl group, 1,2,3-triazol-4-yl group, 1,2,4-triazol-3-yl group, 1,2,4-triazol-5-yl group 5-membered ring group; unsaturated hetero-5 such as 5-phenyl-5-trifluoromethyl-isoxazolin-3-yl group, 2-furfurylmethyl group, 3-thienylmethyl group, 1-methyl-3-pyrazolomethyl group A membered ring alkyl group;

Pyridin-2-yl group, Pyridin-3-yl group, Pyridin-4-yl group, Pyridazin-3-yl group, Pyridazin-4-yl group, Pyrazin-2-yl group, Pyrimidin-2-yl group, Pyrimidine Unsaturated 4-membered cyclic groups such as -4-yl group, pyrimidin-5-yl group, 1,3,5-triazin-2-yl group and 1,2,4-triazin-3-yl group; Unsaturated hetero 6-membered alkyl group such as pyridylmethyl group, 3-pyridylmethyl group, 6-chloro-3-pyridylmethyl group, 2-pyrimidylmethyl group; tetrahydrofuran-2-yl group, tetrahydrapyran-4-yl group Saturated heterocyclic groups such as piperidin-3-yl group, pyrrolidin-2-yl group, morpholino group, piperidino group, N-methylpiperazinyl group; 2-tetrahydrafuranylmethyl group, 3-piperazylme A saturated heterocyclic alkyl group such as an alkyl group, N-methyl-3-pyrrolidylmethyl group, morpholinomethyl group; N-dimethylaminoiminomethyl group, 1-N-phenyliminoethyl group, N-hydroxyiminomethyl group, N -Unsubstituted or substituted iminoalkyl groups such as methoxyiminomethyl group; unsubstituted or substituted hydrazinocarbonyl groups such as N'-methylhydrazinocarbonyl group, N'-phenylhydrazinocarbonyl group, hydrazinocarbonyl group; aminocarbonyl Group, dimethylaminocarbonyl group, unsubstituted or substituted aminocarbonyl group such as N-phenyl-N-methylaminocarbonyl group; alkylthio group such as methylthio group, ethylthio group, t-butylthio group;

Alkenylthio groups such as ethynylthio group and propargylthio group; arylthio groups such as phenylthio group and 4-chlorophenylthio group; heteroaryl groups such as 2-piperidylthio group and 3-pyridazylthio group Arthio group such as benzylthio group and phenethylthio group; Alkylsulfonyl group such as methylsulfonyl group, ethylsulfonyl group and t-butylsulfonyl group; Alkenylsulfonyl group such as allylsulfonyl group; Alkynylsulfonyl such as propargylsulfonyl group Groups; arylsulfonyl groups such as phenylsulfonyl groups; heteroarylsulfonyl groups such as 2-pyridylsulfonyl groups and 3-pyridylsulfonyl groups; aralkylsulfonyls such as benzylsulfonyl groups and phenethylsulfonyl groups A group represented by the following formula (a) ~ (c); groups;

[In the formulas (a) to (c), R ⁶ and R ⁷ are each independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group, an unsubstituted or substituted heterocyclic group, an unsubstituted or It represents an amino group, a hydrocarbon oxy group, or a hydrocarbon thio group having a substituent. R ⁸ and R ¹¹ each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group, an unsubstituted or substituted heterocyclic group, or an unsubstituted or substituted amino group; ⁹ represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group. R ¹⁰ represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group, or an unsubstituted or substituted heterocyclic group.

R ⁶ and R ⁷ , R ⁸ and R ⁹ , and R ¹⁰ and R ¹¹ may be bonded to form a ring.
Examples of the hydrocarbon group of R ^{6 to} R ¹¹ include alkyl groups such as methyl group, ethyl group, i-propyl group, n-propyl group, n-hexyl group, and n-octyl group; vinyl group, allyl group, 1 -Alkenyl groups such as propenyl group and 2-phenylethenyl group; alkynyl groups such as ethynyl group and propargyl group; aromatic hydrocarbon groups such as phenyl group, 1-naphthyl group and 9-anthracel group it can.

Examples of the heterocyclic group of R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , and R ¹¹ include a furan-2-yl group, a furan-3-yl group, a thiophen-2-yl group, and a thiophen-3-yl group. Pyrrol-2-yl group, pyrrol-3-yl group, oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, thiazol-2-yl group, thiazol-4-yl group, Thiazol-5-yl group, isoxazol-3-yl group, isoxazol-4-yl group, isoxazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazole- 5-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group, pyrazol-3-yl group, pyrazol-4-yl group, pyrazol-5-i Group, 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 1,2,3-triazol-4-yl group, 1,2,4-triazole Unsaturated 5-membered cyclic groups such as -3-yl group and 1,2,4-triazol-5-yl group;

  Unsaturated heterocyclic 5-membered alkyl groups such as 5-phenyl-5-trifluoromethyl-isoxazolin-3-yl group, 2-furfurylmethyl group, 3-thienylmethyl group, 1-methyl-3-pyrazolomethyl group; Pyridin-2-yl group, Pyridin-3-yl group, Pyridin-4-yl group, Pyridazin-3-yl group, Pyridazin-4-yl group, Pyrazin-2-yl group, Pyrimidin-2-yl group, Pyrimidine Unsaturated 4-membered cyclic groups such as -4-yl group, pyrimidin-5-yl group, 1,3,5-triazin-2-yl group and 1,2,4-triazin-3-yl group; Unsaturated hetero 6-membered ring alkyl group such as pyridylmethyl group, 3-pyridylmethyl group, 6-chloro-3-pyridylmethyl group, 2-pyrimidylmethyl group; tetrahydrofuran-2-yl group, tetrahydrapyran-4 Saturated heterocyclic groups such as yl, piperidin-3-yl, pyrrolidin-2-yl, morpholino, piperidino, N-methylpiperazinyl; 2-tetrahydrofuranylmethyl, 3-piperazylmethyl, N -Saturated heterocyclic alkyl groups such as methyl-3-pyrrolidylmethyl group and morpholinomethyl group; and the like.

Examples of the hydrocarbon oxy group for R ⁶ and R ⁷ include a methoxy group, an ethoxy group, an i-propoxy group, a phenoxy group, and a benzyloxy group. Examples of the hydrocarbon thio group include a methylthio group, an ethylthio group, a phenylthio group, and a benzylthio group.

As the substituent of the functional group contained in R ^{6 to} R ¹¹ , the same examples as those exemplified as the substituent of Cy ¹ can be exemplified.

Z and Y each independently represent an oxygen atom or an unsubstituted or substituted nitrogen atom. As the substituent on the nitrogen atom, it can be exemplified by the same as specific examples, which are exemplified as the substituents of Cy ^1.
Specific examples of the groups represented by the formulas (a) to (c) include the following formulae.

In formula (1), X represents an oxygen atom; a sulfur atom; an unsubstituted or substituted nitrogen atom; a sulfinyl group; a sulfonyl group, and preferably an oxygen atom. In the case of an unsubstituted nitrogen atom, a hydrogen atom is bonded to the nitrogen atom.
When X is a nitrogen atom having a substituent, specific examples of the substituent on the nitrogen atom include the same specific examples as the substituent of Cy ¹ .

In formula (1), R ¹ _a and R ² _a , R ¹ _a and R ⁴ _a , R ² _a and R ³ _a , or R ³ _a and R ⁴ _a together form a saturated ring. , R ¹ _a and R ² _a , or R ³ _a and R ⁴ _a are preferably combined to form a saturated ring, and the number of atoms of the crosslinking site of the piperidine ring forming the saturated ring is 2 or 3 It is preferable.

  The element constituting the cross-linked site of the piperidine ring forming the saturated ring is not particularly limited as long as it is in a chemically acceptable range. Specifically, a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc. can be illustrated. Moreover, it can also comprise combining these 2 or more types within the chemically acceptable range.

  Furthermore, these atoms may have a hydrogen atom or a substituent within a chemically acceptable range, and within a chemically acceptable range, through an oxygen atom, a sulfur atom, a nitrogen atom and a double bond. To form a carbonyl group, a thiocarbonyl group, an imino group, or the like.

R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , and R ⁵ that do not form a saturated ring together are each independently Represents a hydrogen atom, a halogen atom, an unsubstituted or substituted amino group, a nitro group, a hydroxyl group, or an organic group. Specific examples of the halogen atom, unsubstituted or substituted amino group include the same as the specific examples of the substituent of Cy ¹ . The organic group represents a general functional group containing a carbon atom, and specifically includes a cyano group, a formyl group, an alkyl group, an alkoxycarbonyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, an alkylthiocarbonyl group, and an alkylsulfonylamino group. Group; haloalkylsulfonylamino group; bis (alkylsulfonyl) amino group; bis (haloalkylsulfonyl) amino group; aryl group; The organic group is preferably an alkyl group; an alkoxycarbonyl group; an alkoxy group, and more preferably a C _1-6 alkyl group; a C _1-6 alkoxycarbonyl group; a C _1-6 alkoxy group. Specifically, those exemplified as specific examples of the substituent for Cy ¹ can be exemplified.
In the compound represented by the formula (1), the following formula (2)

As specific examples of the piperidine ring represented by the formula, a structure represented by the following formula can be exemplified.

Specific examples of the aromatic group of Cy ² include the same ones listed as specific examples of Cy ¹ . Of these, a pyridazyl group is preferable, and a pyridazin-3-yl group is more preferable.

However, when R ¹ _a and R ² _a are combined to form a saturated ring, and Cy ¹ is an unsubstituted or substituted phenyl group, Cy ² may have an optionally substituted aromatic heterocycle. Represents a cyclic group. When Cy ¹ is an unsubstituted or substituted phenyl group and Cy ² is a pyridin-2-yl group, Cy ² represents a substituted pyridin-2-yl group having one or more cyano groups as a substituent. To express.

When Cy ¹ is an unsubstituted or substituted phenyl group, Cy ² does not include an unsubstituted pyridyl-2-yl group. The substituted pyridin-2-yl group having one or more cyano groups as a substituent means a cyano group or a pyridyl-2-yl group having a cyano group and another substituent as a substituent.

In the compound represented by the formula (1), in the formula (1), when R ¹ _a and R ² _a or R ³ _a and R ⁴ _a together form a saturated ring, the following There are two isomers as shown in formula (3a) to formula (3h).

All of these isomers are included in the present invention. The same applies to the case where R ¹ _a and R ⁴ _a or R ² _a and R ³ _a together form a saturated ring.

  Examples of the salt of the compound represented by the formula (1) include salts of inorganic acids such as hydrochloride, nitrate, sulfate, and phosphate; organic acids such as acetate, lactate, propionate, and benzoate. Salt;

  Moreover, as an N-oxide of the compound represented by the formula (1), a nitrogen atom represented by X of the compound represented by the formula (1), a nitrogen atom of a cyclic amine moiety such as a tropane ring or an isotropane ring Examples thereof include compounds in which is oxidized.

  The compound represented by the formula (1) can be produced, for example, by the method shown below.

(1) Manufacturing method 1
In the formula (1), the compound in which X is an oxygen atom or a sulfur atom is, for example, from the compound represented by the formula (4) (hereinafter referred to as the compound (4)) to methyl as shown in the following formula. After removing a protecting group such as a benzyl group or a benzyl group, a compound represented by the formula (5) is obtained, and then the obtained compound (5) and a compound represented by the formula (6) are generally used. Can be obtained by coupling in a conventional manner.

(Wherein Cy ¹ , Cy ² , X, R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , and R ⁵ are the same as above. (X ^′ represents a leaving group such as a halogen atom, and R ′ represents a protecting group.)
Compound (4), which is a production intermediate, can be produced by a general method as follows.

(In the formula, Cy ¹ , X, R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , R ⁵ and R ′ are the same as above. X ¹ and X ² each independently represents a hydroxyl group or a mercapto group, and X ³ represents a leaving group such as a halogen atom.

  Compound (1) can also be produced by the general method shown below.

(Wherein Cy ¹ , Cy ² , X, R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , and R ⁵ are the same as above. (X ⁴ represents a leaving group such as a halogen atom, and X ⁵ represents a hydroxyl group or a mercapto group.)
Compound (11) as a raw material can be produced by a general method shown in the following reaction formula (IV).

(In the formula, Cy ² , X ⁴ , R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , and R ⁵ have the same meanings as described above. X ⁶ represents a leaving group such as a halogen atom.)

(2) Manufacturing method 2
In the formula (1), the compound represented by the formula (17), in which X is a nitrogen atom which may be substituted, is a compound represented by the formula (15) as shown in the following reaction formula (V). And a compound represented by the formula (16) can be produced by a reductive amination reaction by a general method.

(Wherein, Cy ¹ , Cy ² , R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , and R ⁴ _b represent the same meanings as described above. R ″ represents a substituent on a nitrogen atom such as a hydrogen atom, a trifluoroacetyl group, or a trifluoromethylsulfonyl group.)

  As shown in the following reaction formula (VI), compound (17) can also be produced by subjecting compound (15) and the compound represented by formula (18) to a coupling reaction by a general method. .

(In the formula, Cy ¹ , Cy ² , R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , R ⁵ and R ″ are the same as above. X ⁷ represents a halogen atom; a leaving group such as a sulfonyloxy group.)

  In addition, as shown in the following reaction formula (VII), the compound (17) is obtained by coupling the compound represented by the formula (19) and the compound represented by the formula (20) by a general method. Can also be manufactured.

(Wherein Cy ¹ , Cy ² , X ⁷ , R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , R ⁵ and R ′ 'Means the same as above.)

  The salt of the compound represented by the formula (1) is obtained by adding an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid; an organic acid such as acetic acid, lactic acid, propionic acid or benzoic acid to the compound represented by the formula (1). Can be produced by acting.

  The N-oxide of the compound represented by the formula (1) is produced by allowing a known oxidant such as peracetic acid or m-chloroperbenzoic acid to act on the compound represented by the formula (1). Can do.

  In any reaction, after completion of the reaction, the desired product can be isolated by a usual post-treatment operation in organic synthetic chemistry. If desired, known separation and purification means such as a recrystallization method and column chromatography can be used.

  The structure of the target product can be identified and confirmed by IR spectrum, NMR spectrum, MS spectrum, elemental analysis and the like.

  In the pest control composition of the present invention, the compound represented by the formula (1), a salt thereof, or an N-oxide thereof (hereinafter, these may be referred to as “cyclic amine compounds”) are singly used, Alternatively, two or more can be used in combination with other acaricides described below.

  Specific examples of the cyclic amine compound used in the present invention include those described in (Table 1) to (Table 44) in the specification of PCT / JP2006 / 320133, but are not limited thereto. Absent.

(Other acaricides)
The pest control composition of the present invention contains an acaricide (other acaricide) other than the cyclic amine compound in addition to the cyclic amine compound. Combining a cyclic amine compound with other acaricides produces a higher insecticidal / miticidal effect than when used alone, that is, a synergistic effect, so it is possible to reduce the amount of agricultural chemicals applied or the number of applications Become.

  Other acaricides used in the present invention are not particularly limited as long as they are substances having acaricidal activity for agriculture and horticulture. For example, chlorbenzilate, phenisobromolate, dicophore, amitraz, BPPS, benzomate, hexothiazox, fenbutasine oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentedin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidfen Examples include phenothiocarb, dienochlor, fluacrylpyrim, acequinosyl, bifenazate, etoxazole, spirodiclofen, phenazaquin and the like.

  In using the pesticidal composition of the present invention as an agrochemical formulation such as an acaricide, a form that a general agricultural chemical can take, that is, one or more of a cyclic amine compound, and one other acaricide Alternatively, two or more active ingredients may be dissolved or dispersed in an appropriate liquid carrier depending on the intended use, or mixed or adsorbed with an appropriate solid carrier to obtain an agrochemical formulation having a desired dosage form. .

  When the pest control composition of the present invention is actually applied, it can be used as it is without adding other components, but it is further mixed with a solid carrier, a liquid carrier, a gaseous carrier, or a substrate such as a porous ceramic plate or nonwoven fabric The material can be impregnated and, if necessary, a surfactant and other auxiliary agents can be added.

  In addition, it can be used in the form of general agricultural chemicals for the purpose of use as agricultural chemicals, that is, wettable powder, granule, powder, emulsion, aqueous solvent, suspension, granular wettable powder, flowable, aerosol, fumes, heat transpiration. It can be formulated into a form such as an agent, smoke agent, poison bait, and microcapsule.

  Additives and carriers, if solids are intended, vegetable powders such as soybean grains and wheat flour, mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, benzoic acid Organic and inorganic compounds such as soda, urea and mirabilite are used. For liquid dosage forms, use petroleum fractions such as kerosene, xylene, and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, methyl isobutyl ketone, mineral oil, vegetable oil, and water as solvents. Can be used as As the gaseous carrier used for the propellant, butane gas, LPG, dimethyl ether and carbon dioxide gas can be used.

  Examples of the bait base include bait ingredients such as cereal flour, vegetable oil, sugar and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, and children such as pepper Pest-attracting fragrances such as anti-fouling agents for pets and pets, cheese fragrances and onion fragrances can be used.

  Moreover, in order to take a uniform and stable form in these preparations, a surfactant can be added if necessary. The surfactant is not particularly limited. For example, alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, sorbitan higher fatty acid ester added with polyoxyethylene, and polyoxyethylene added. Nonionic surfactants such as tristyrylphenyl ether, sulfates of alkylphenyl ethers added with polyoxyethylene, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde of alkyl naphthalene sulfonates Examples include condensates and copolymers of isobutylene-maleic anhydride.

  The content ratio of the total amount of the cyclic amine compound and other acaricides in the pesticidal composition of the present invention is usually about 0.1 to 80% by weight based on the total amount of the pesticide. Specifically, for example, when used in an emulsion, solution, wettable powder (eg, granular wettable powder), aqueous suspension preparation or microemulsion, it is usually about 1 to 80% by weight, preferably about 10 to 10% by weight. About 50% by weight is appropriate. For example, when used in oils, powders, etc., it is usually about 0.1 to 50% by weight, preferably about 0.1 to 20% by weight. For example, when used in granules, tablets, jumbo agents, etc., it is usually about 0.5 to 50% by weight, preferably about 0.5 to 10% by weight.

  In the pest control composition of the present invention, the mixing ratio of the cyclic amine compound and the other acaricide is not particularly limited, but is usually 100 by weight ratio of (cyclic amine compound) :( other acaricide). : 1 to 1: 100, preferably 10: 1 to 1:10, more preferably 5: 1 to 1:10.

  The content of additives other than the above active ingredients varies depending on the type or content of the agrochemical active ingredient or the dosage form of the preparation, but is usually about 0.001 to 99.9% by weight, preferably about 1 to 99% by weight. Degree.

The pest control composition of the present invention can be prepared, for example, by any of the following methods.
(I) A method in which at least one cyclic amine compound, at least one other acaricide, and other additives are mixed and formulated as desired.
(Ii) A method in which an agrochemical formulation containing a cyclic amine compound and an agrochemical formulation containing another acaricide are mixed at a predetermined ratio.
(Iii) A method of mixing at least one other acaricide with an agrochemical preparation containing a cyclic amine compound.
(Iv) A method of mixing at least one cyclic amine compound with an agrochemical formulation containing another acaricide.

  When the pest control composition of the present invention is actually used, emulsions, wettable powders, flowables, etc. are diluted with water to a predetermined concentration before application, and oils, aerosols, fumes, poison baits, Tick sheets can be used as they are.

  The pest control composition of the present invention has an insecticidal, larvicidal, larvicidal, and ovicidal action, so it can be used to control crop pests, mites, sanitary pests, storage shell pests, clothing pests, house pests, etc. Can be used. The following organisms can be specifically exemplified as organisms to be controlled.

  Particularly preferred lepidopterous pests, for example, Spodoptera litura, Cyprus, Tamanayaga, Aomushi, Tamanaginuwaba, Konaga, Chanoko Kakumon Hamaki, Chahamaki, Momoshiniga, Nashihimeshinpii, Citrus crested moth, Canohosagaigai, Mykonohigaigai , American white-spotted moth, Japanese white moth, Heliotis genus, Helicoberpa genus, Agrotis genus, Iga, Kodlinga, Cottontail, etc.

Hemiptera pests, for example, peach aphid, cotton aphid, phantom aphid, wheat beetle aphid, hosohelamushi, aokusamemushi, agarine aphid, staghorn aphid, onitsu whitefly, tobacco whitefly, silver leaf whitefly, silver leaf whitefly, Gunby beetle, brown planthopper, Japanese brown planthopper, white-spotted planthopper, leafhopper, etc.
Coleopterous pests, for example, Kisodemi beetle, cucumber beetle, Colorado potato beetle, rice weevil, weevil, azuki beetle, beetle, scallop, diablotica, tobacco, scallop, slatinus, pine moth, Cotton weevil, etc.
Diptera pests, for example, house flies, giant black flies, sentinic flies, fruit flies, citrus flies, sand flies, rice leaf flies, Drosophila melanogaster, sand flies, Spodoptera cabbage, Aedes aegypti, Aedes albopictus, etc.

Thrips-like pests, such as Thrips thrips, Thrips thrips,
Hymenopteran pests, for example, Himeari, Kirosuzubee, Bee, etc.
Straight-eyed pests, such as grasshopper, German cockroach, American cockroach, black cockroach, etc.
Termite pests, such as termites, Yamato termites,
Lepidoptera pests, for example, human fleas, cat fleas, etc., lice eye pests, for example, human lice,
Tick, for example, spider mite, spider mite, kanzawa spider mite, citrus spider mite, apple spider mite, citrus spider mite, apple spider mite, chano mite, brebipalpas spp.

  Plant parasitic nematodes such as, for example, sweet potato nematode, nestle nematode, soybean cyst nematode, rice scented nematode, and pinewood nematode.

  Pests preferably applied are lepidopterous insects, semilepidopterous insects, mites, thrips insects, and coleopterous insects, and particularly preferably mites.

  In recent years, resistance to organophosphates, carbamates and other acaricides has been developed in many pests such as Japanese pests, leafhoppers, leafhoppers, and aphids, causing problems of insufficient efficacy of these drugs. Drugs that are also effective against ticks and mites are desired. The compound of the present invention is an agent having an insecticidal and acaricidal effect that is excellent not only for susceptible strains, but also for insects resistant to organophosphates, carbamates, and pyrethroids, and ticks of other acaricide-resistant strains.

  The compound of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.

  The pest control composition of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contact objects such as ship bottoms and fish nets.

  When the compound of the present invention is used as a pest control composition for controlling animal ectoparasites of domestic animals such as cattle and pigs, and pets such as dogs and cats, the compound of the present invention is well known in veterinary medicine. It can be used as a preparation by a commonly used method such as a method.

As the method, for example, for the purpose of systemic control, administration is performed by tablets, capsules, immersion liquid, feed mixing, suppositories, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), etc. In the case of non-systemic control, an oily or aqueous liquid is administered by spraying, pouring-on, dropping-on, etc. and resin There is a method of wearing a product obtained by shaping the preparation into an appropriate shape such as a collar or an ear tag.
In this case, the compound of the present invention can be used at a ratio of 0.01 to 1000 mg per 1 kg of the host animal.

  In addition, it goes without saying that the pest control composition of the present invention is sufficiently effective alone, but other pest control compositions, fungicides, insecticides, herbicides, plant regulators, synergists, It can also be used in combination or in combination with one or more fertilizers, soil conditioners, animal feeds and the like.

  Representative examples of active ingredients such as bactericides, insecticides, other acaricides, plant growth regulators and the like that can be mixed or used in combination with the pest control composition of the present invention are shown below.

Fungicide:
Captan, folpette, thiuram, ziram, dinebu, manneb, mancozeb, propineb, polycarbamate, chlorothalonine, quintosen, captaphor, iprodione, prosaimidon, fluoroimide, mepronil, flutolanil, pencyclon, oxycarboxyne, fosetyl aluminum, propamocurve, triazimephone, Triadimenol, propiconazole, diclobutrazole, viteltanol, hexaconazole, microbutanyl, flusilazole, etaconazole, fluotrimazole, flutriaphene, penconazole, diniconazole, cyproconazole, phenalimol, triflumizole, prochloraz , Imazalyl, pefazoate, tridemorph, fenpropimorph, triphorin, butio , Pyriphenox, anilazine, polyoxin, metalaxyl, oxadixyl, furaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, benomyl, carbendazim, thiophanate methyl, hymexazole, basic chlorination Copper, basic copper sulfate, fentin acetate, triphenyltin hydroxide, dietofencarb, quinomethionate, binapacryl, lecithin, baking soda, dithianon, dinocup, phenaminosulfur, dichromemedin, guazatine, dodin, IBP, edifenphos, mepanipyrim, fermzone, trichramide , Metasulfocarb, fluazinam, etokinolac, dimethomorph, pyroxylone, teclophthala , Fusalide, phenazine oxide, thiabendazole, tricyclazole, vinclozoline, simoxanyl, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid, cyflufenamide, iminoctazine, cresoxime methyl, triazine, fenhexamide, cyazofamide, cyprodinil, prothioconazole, fenbuconazole, fenbuconazole Roxystrobin, azoxystrobin, hexaconazole, imibenconazole, tebuconazole, difenoconazole, carpropamide.

Insecticide:
Organophosphorus and carbamate insecticides:
Fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidthione, phentoate, dimethoate, formothione, marathon, trichlorfone, thiometone, phosmet, dichlorvos, acephate, EPBP, methyl parathion, oxydimethone methyl, ethion, salicione, cyanophos, isoxathione, cyanophos, isoxathione Methidathione, Sulprophos, Chlorfenvinphos, Tetrachlorvinphos, Dimethylvinphos, Propafos, Isophenphos, Ethylthiomethone, Profenofos, Piracrofos, Monocrotophos, Adinfosmethyl, Aldicarb, Mesomil, Thiodicarb, Carbofuran, Carbosulfan, Benhracarb, Furatiocarb Propoxur, BPMC, M MC, MIPC, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, cartap, thiocyclam, bensultap and the like.

Pyrethroid insecticides:
Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, cycloprotorin, tralomethrin , Silafluophene, acrinatrin, etc.

Benzoylurea and other insecticides:
Diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, metoprene, benzoepin, diafenthiuron, imidacloprid, fipronil, nicotine sulfate, rotenone, metaldehyde, acetamiprid , Chlorfenapyr, nitenpyram, thiacloprid, clothianidin, thiamethoxam, dinotefuran, indoxacarb, pymetrozine, spinosad, emamectin, pyridalyl, tebufenozide, chromafenozide, methoxyphenozide, tolfenpyrad, machine oil, BT, insect pathogen virus, etc.

Nematicides:
Fenamifos, Phostiazate, Kazusafos etc.
Plant growth regulator:
Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA.

2) Pest Control Method The pest control method of the present invention is characterized by using at least one cyclic amine compound represented by the formula (1) and at least one other acaricide.

As a method for specifically implementing the pest control method of the present invention,
(A) A method for spraying the pest control composition of the present invention, (b) a pesticide preparation containing a cyclic amine compound and a pesticide preparation containing another acaricide are mixed at a predetermined ratio immediately before spraying. (Tank mix), method of spraying the resulting mixture, (c) spraying a pesticide preparation containing a cyclic amine compound and a pesticide preparation containing other acaricides on the same control target at almost the same time And the like.

  In the methods (a) to (c), the application amount of the pest control composition of the present invention, the agrochemical formulation containing a cyclic amine compound, and the agrochemical formulation containing other acaricide is particularly limited. It can be set as appropriate according to the type of control target, control time, and the like.

EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to an Example.
(Reference Example 1)
Preparation of 3α- (5-trifluoromethyl-2-pyridyloxy) -8- (5-trifluoromethyl-pyridin-2-yl) -8-azabicyclo [3.2.1] octane

  To a suspension of tropine (14.1 g) and potassium carbonate (1.4 g) in benzene (150 ml) was added chloroformate 2,2,2-trichloroethyl ester (23.3 g) at room temperature, Refluxed for 5 hours. The reaction mixture was cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain (30.1 g) of an oily carbonate (A). This was directly used in the next reaction.

  Next, zinc dust (65 g) was added to a solution of the obtained carbonate (A) in acetic acid (250 ml). The mixture was stirred for 5 minutes and then heated at 80 ° C. for 1 hour. The mixture was cooled to room temperature and filtered through celite. The filtrate was concentrated under reduced pressure to obtain 15.5 g of a crude product of compound (B).

  A suspension of the crude product (5.64 g) of compound (B) obtained above, potassium carbonate (41.5 g) and 2-chloro-5-trifluoromethylpyridine (8.2 g) in acetonitrile (150 ml) was obtained. Refluxed for 3.5 hours. The reaction mixture was cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain (3.5 g) of compound (C) as crystals.

To a solution of compound (C) (0.21 g) in dimethylformamide (DMF) (3 ml) was added 60% sodium hydride (32 mg) under ice cooling, and the whole was stirred for 40 minutes. Next, 2-chloro-5-trifluoromethylpyridine (0.17 g) was added to the mixture, and the mixture was heated to 100 ° C. and stirred overnight. The reaction mixture was cooled to room temperature, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solution: mixed solvent of n-hexane and ethyl acetate) to obtain the title compound (0.06 g).
Melting point: 104-105 ° C

(Reference Example 2)
Preparation of 3α- [2-n-propoxy-4- (trifluoromethyl) phenoxy] -8- [3-fluoro-4- (trifluoromethyl) phenyl] -8-azabicyclo [3.2.1] octane

  To a solution of 4-fluoro-3-hydroxybenzotrifluoride (1.8 g) in DMF (15 ml) was added 60% sodium hydride (0.44 g) under ice cooling, and the whole was stirred for 20 minutes. A solution of iodopropane (1.7 g) in DMF (3 ml) was added, and the mixture was further stirred at room temperature for 4 hours. To the obtained mixture, tropine (1.4 g) and 60% sodium hydride (0.43 g) were added at room temperature, and the mixture was heated to 100 ° C. and stirred overnight. The reaction mixture was cooled to room temperature, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain (1.1 g) of oily compound (D).

To a solution of compound (D) (1.0 g) in methylene chloride (6 ml) was added a solution of chloroformic acid 1-chloroethyl ester (0.83 g) in methylene chloride (4 ml) at room temperature, and the whole volume was refluxed overnight. The reaction mixture was diluted with methylene chloride, washed with saturated aqueous sodium hydrogen carbonate and then with brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain crude carbonate (E). This was used in the next reaction as it was.
Methanol (6 ml) was added to the obtained compound (E) and refluxed for 2.5 hours. The mixture was concentrated under reduced pressure to obtain the crude compound (F). This was treated with alkali to obtain a free amine. This was used in the next reaction as it was.

To a toluene (11 ml) solution of the free form (1 g) of compound (F) obtained above and 4-bromo-2-fluorobenzotrifluoride (0.73 g), t-butoxy sodium (0.4 g), Pd ₂ (Dba) ₃ (13.7 mg) and 2- (dicyclohexylphosphino) -2 ′-(N, N-dimethylamino) biphenyl (17.7 mg) were added and the whole volume was refluxed overnight under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate) to obtain the title compound (0.54 g).

Viscous oil
¹ H-NMR (CDCl ₃ , δ ppm): δ 1.08 (t, 3H), 1.81-1.97 (m, 4H), 2.04-2.23 (m, 4H), 2.45 ( q, 2H), 3.97 (t, 2H), 4.19 (brs, 2H), 4.57 (brt, 1H), 6.44-6.51 (m, 2H), 6.76 (d , 1H), 7.13 (s, 1H), 7.16 (d, 1H), 7.38 (t, 1H)

(Reference Example 3)
Preparation of 3α- [5- (trifluoromethyl) -2-pyridyloxy] -8- [2-formyl-4- (trifluoromethyl) phenyl] -8-azabicyclo [3.2.1] octane

  To a solution of tropine (17.6 g) and 2-chloro-5-trifluoromethylpyridine (21.6 g) in DMF (240 ml) at 80 ° C., 60% sodium hydride (5.8 g) was added in portions, The whole volume was stirred at the same temperature for 2 hours. The reaction mixture was cooled to room temperature, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography (NH-gel; using DM-1020, developing solvent: mixed solvent of n-hexane and ethyl acetate) to obtain Compound (G) (25 g).

  Chloroformic acid 2,2,2-trichloroethyl ester (26 g) was added to a suspension of compound (G) (25 g) and potassium carbonate (1.33 g) in benzene (150 ml) at room temperature, and the mixture was heated to reflux for 1 hour. did. The reaction mixture was allowed to cool to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain solid carbonate. This was directly used in the next reaction.

  Zinc dust (42 g) was added to the acetic acid (300 ml) solution of carbonate obtained above, and the whole volume was heated and stirred at 100 ° C. for 1 hour. The reaction mixture was cooled to room temperature and then filtered through celite, chloroform and water were added to the filtrate, and the organic layer was separated. The aqueous layer is weakly alkaline, extracted with chloroform, combined with the previous organic layer, washed with water, dried over anhydrous magnesium sulfate, and the solvent is distilled off under reduced pressure to give the crude compound (H) as (14. 4 g) was obtained.

A suspension of compound (H) (2 g), potassium carbonate (3.04 g) and 2-fluoro-5-trifluoromethylbenzaldehyde (1.41 g) in acetonitrile (30 ml) was refluxed for 3.5 hours. The reaction mixture was cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate) to obtain the title compound (2.77 g).
Melting point: 122-123 ° C

(Reference Example 4)
3α- [2-Isopropoxycarbonyl-4- (trifluoromethyl) phenoxy] -8- [6-cyano-pyridazin-3-yl] -8-azabicyclo [3.2.1] octane Step 1

  Preparation of 3α- [2-isopropoxycarbonyl-4- (trifluoromethyl) phenoxy] -8-azabicyclo [3.2.1] octane (J)

To a solution of tropine (1.0 g) in DMF (20 ml) was added 60% sodium hydride (0.56 g). To this mixture, 4-fluoro-3-isopropoxycarbonylbenzotrifluoride (1.76 g) was added dropwise. The mixture was stirred at room temperature overnight, then poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and filtered, and the filtrate was distilled off under reduced pressure to obtain crude compound (I) (1.15 g). This was directly used in the next reaction.
4-Fluoro-3-isopropoxycarbonylbenzotrifluoride was obtained by isopropyl esterification of commercially available 2-fluoro-5-trifluoromethylbenzoic acid.

  To a solution of crude compound (I) (1.23 g) in benzene (20 ml) was added potassium carbonate (0.05 g) and chloroformic acid 1-chloroethyl ester (0.52 g), and the mixture was heated to reflux for 5 hours. The mixture was cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the concentrate was dissolved in methanol (20 ml), and the whole volume was stirred at room temperature overnight. The solvent was distilled off under reduced pressure to obtain (1.0 g) of a crude compound (J). This was directly used in the next reaction.

Process 2
Preparation of 3α- [2-isopropoxycarbonyl-4- (trifluoromethyl) phenoxy] -8- [6-cyano-pyridazin-3-yl] -8-azabicyclo [3.2.1] octane

A suspension of crude compound (J) (1.0 g), potassium carbonate (1.16 g) and 3-chloro-6-cyanopyridazine (0.39 g) in acetonitrile (30 ml) was heated to reflux for 3 hours. The mixture was cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the concentrate was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate) to obtain crystals (0.18 g). This was further washed with diethyl ether to obtain the title compound (0.04 g).
Melting point: 219-221 ° C

(Reference Example 5)
Preparation of 8β- [2-propoxy-4- (trifluoromethyl) phenoxy] -3- [6- (trifluoromethyl) -pyridin-3-yl] -3-azabicyclo [3.2.1] octane

Process 1
Preparation of N-benzyl-8β- [2-propoxy-4- (trifluoromethyl) phenoxy] -3-azabicyclo [3.2.1] octane (L)

  To a solution of 4-fluoro-3-hydroxybenzotrifluoride (0.50 g) in N, N-dimethylformamide (4 ml) was added 60% sodium hydride (0.12 g) under ice cooling. After the mixture was stirred at room temperature for 30 minutes, 1-iodopropane (0.51 g) was added. The mixture was heated to 90 ° C. and stirred for 30 minutes. To the mixture was added a solution of compound (K) (0.41 g) in DMF (4 ml) and 60% sodium hydride (0.09 g) at room temperature, stirred for 15 minutes, then warmed to 100 ° C. for 2 hours. Stir. The mixture was cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate) to obtain compound (L) as an oil (yield: 0.75 g).

¹ H-NMR (CDCl ₃ , δ ppm): δ 1.05 (t, 3H), 1.75-1.91 (m, 6H), 2.19 (d, 2H), 2.34 (brs, 2H) , 2.74 (d, 2H), 3.51 (s, 2H), 3.96 (t, 2H), 4.33 (s, 1H), 6.94 (d, 1H), 7.07 ( s, 1H), 7.13 (d, 1H), 7.20-7.34 (m, 5H)

Process 2
Preparation of 8β- [2-propoxy-4- (trifluoromethyl) phenoxy] -3- (6-trifluoromethyl-pyridin-3-yl) -3-azabicyclo [3.2.1] octane

To a solution of compound (L) (0.66 g) in ethanol (20 ml) was added 10% palladium-carbon (0.13 g). This suspension was stirred overnight at room temperature under a hydrogen atmosphere (1.01 × 10 ⁵ Pa). The reaction solution was filtered through Celite, and the filtrate was distilled off under reduced pressure to obtain (0.55 g) of the crude compound (M).

3-Bromo-6- (trifluoromethyl) pyridine was derived from commercially available 3-amino-6- (trifluoromethyl) pyridine by a conventional Sandmeyer reaction.
To a solution of the crude compound (M) (0.23 g) in toluene (2 ml) was added 3-bromo-6- (trifluoromethyl) pyridine (0.16 g), sodium t-butoxy (0.1 g), Pd ₂ ( dba) ₃ (6.47 mg), and 2- (dicyclohexylphosphino) -2 ′-(N, N-dimethylamino) biphenyl (8.34 mg) were added and the mixture was heated to reflux overnight under a nitrogen atmosphere. The reaction mixture was cooled, poured into water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate) to obtain the title compound (0.1 g).
Melting point: 79-80 ° C

(Reference Example 6)
8β- [2-isopropylideneaminooxy-4- (trifluoromethyl) phenoxy] -3- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) -3-azabicyclo [3.2. 1] Manufacture of octane

Process 1
Preparation of 3- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) -3-azabicyclo [3.2.1] octane-8β-ol

To a solution of compound (K) (4.32 g) in ethanol (100 ml) was added 10% palladium-carbon (2.6 g). The suspension was heated to 50 ° C. under a hydrogen atmosphere, stirred for 2 hours, and further stirred overnight at room temperature. The reaction solution was filtered through Celite, and the filtrate was distilled off under reduced pressure to obtain a crude compound (N) (2.5 g).
2-Bromo-5- (trifluoromethyl) thiadiazole was derived from commercially available 2-amino-5- (trifluoromethyl) thiadiazole by a conventional Sandmeyer reaction.

  To a solution of crude compound (N) (0.2 g) in acetonitrile (6 ml) was added 2-bromo-5- (trifluoromethyl) -1,3,4-thiadiazole (0.37 g), potassium carbonate (0.65 g). ) And tetra n-butylammonium bromide (10 mg) were added and the mixture was heated to reflux overnight. The mixture was cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate) to obtain the title compound (0.25 g).

Process 2
8β- [2-hydroxy-4- (trifluoromethyl) phenoxy] -3- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) -3-azabicyclo [3.2.1] octane Manufacturing of (Q)

  60% sodium hydride (1.6 g) was added to a solution of 4-fluoro-3-hydroxybenzotrifluoride (6.0 g) in DMF (60 ml) under ice cooling. The mixture was stirred at room temperature for 30 minutes, and chloromethyl methyl ether (3.2 g) was added dropwise under ice cooling. The mixture was warmed to room temperature and stirred for 30 minutes. The mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate) to obtain Compound (O) (6.88 g).

  Compound (N) (0.34 g) was added to a solution of compound (O) (0.36 g) in N, N-dimethylformamide (6 ml). The mixture was warmed to 80 ° C. and 60% sodium hydride (0.07 g) was added. The mixture was heated at 80 ° C. for 2 hours. The mixture was cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate) to obtain Compound (P) (0.28 g).

¹ H-NMR (CDCl ₃ , δ ppm): δ 1.68-1.71 (m, 2H), 2.10-2.13 (m, 2H), 2.62 (brs, 2H), 3.45 ( d, 2H), 3.52 (s, 3H), 3.82 (d, 2H), 4.63 (s, 1H), 5.20 (s, 2H), 7.01 (d, 1H), 7.25 (d, 1H) 7.37 (s, 1H)

  To a solution of compound (P) (0.28 g) in tetrahydrofuran (THF) (4 ml) was added 10% aqueous hydrochloric acid (4 ml) at room temperature. After the mixture was heated to reflux for 1 hour, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain (0.25 g) of the title compound (Q).

¹ H-NMR (CDCl ₃ , δ ppm): δ 1.68-1.79 (m, 2H), 2.05-2.10 (m, 2H), 2.69 (brs, 2H), 3.50 ( d, 2H), 3.89 (d, 2H), 4.67 (s, 1H), 5.58 (s, 1H), 6.97 (d, 1H), 7.15 (d, 1H), 7.21 (s, 1H)

Process 3
8β- [2-isopropylideneaminooxy-4- (trifluoromethyl) phenoxy] -3- (5-trifluoromethyl-1,3,4-thiadiazol-3-yl) -3-azabicyclo [3.2. 1] Manufacture of octane

Compound (R) (0.07 g) was synthesized by using the compound (Q) (0.25 g) by the method described in JP-A No. 2001-81071.
Acetone (0.5 ml) and concentrated hydrochloric acid (1 drop) were added to a solution of compound (R) (0.07 g) in ethanol (1 ml), and the whole was stirred at room temperature for 80 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate) to obtain the title compound (0.05 g).
Melting point: 113-115 ° C

(Reference Example 7)
Preparation of 8β- [2-isopropylideneaminooxy-4- (trifluoromethyl) phenoxy] -3- (5-cyano-pyridin-2-yl) -3-azabicyclo [3.2.1] octane (e)

Process 1
Preparation of 8β-hydroxy-3- (5-cyano-pyridin-2-yl) -3-azabicyclo [3.2.1] octane (S)

  A suspension of 3-azabicyclo [3.2.1] oct-8-ol (0.15 g), potassium carbonate (0.65 g) and 2-chloro-5-cyanopyridine (0.33 g) in acetonitrile (5 ml). Was heated to reflux overnight. The mixture was cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain (0.16 g) of compound (S) having the composition. This was directly used in the next step.

Process 2
Preparation of 8β- [2-methoxymethoxy-4- (trifluoromethyl) phenoxy] -3- (5-cyano-pyridin-2-yl) -3-azabicyclo [3.2.1] octane (T)

  To a solution of 4-fluoro-3-hydroxybenzotrifluoride (0.58 g) in DMF (10 ml) was added 60% sodium hydride (0.14 g) under ice cooling. The mixture was stirred at room temperature for 30 minutes, and chloromethyl methyl ether (0.28 g) was added dropwise under ice cooling. After completion of the dropwise addition, the reaction solution was warmed to room temperature and stirred for 30 minutes, and further heated to 80 ° C. and stirred for 30 minutes. Compound (S) (0.49 g) and 60% sodium hydride (0.13 g) were added to the reaction mixture at 80 ° C., stirred for 30 minutes, then heated to 80 ° C. and stirred for 2 hours. The reaction mixture was cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: mixed solvent consisting of n-hexane and ethyl acetate) to obtain the title compound (T) (0.82 g).

¹ H-NMR (CDCl ₃ , δ ppm): δ 1.55-1.63 (m, 2H), 2.02-2.05 (m, 2H), 2.60 (brs, 2H), 3.13 ( d, 2H), 3.52 (s, 3H), 4.22 (d, 2H), 4.63 (s, 1H), 5.20 (s, 2H), 6.58 (d, 1H), 7.03 (d, 1H) 7.26 (d, 1H), 7.37 (s, 1H), 7.62 (d, 1H) 8.41 (s, 1H)

Process 3
Preparation of 8β- [2-hydroxy-4- (trifluoromethyl) phenoxy] -3- (5-cyano-pyridin-2-yl) -3-azabicyclo [3.2.1] octane (U)

  To a solution of compound (T) (0.82 g) in THF (10 ml) was added 10% aqueous hydrochloric acid (10 ml) at room temperature. The mixture was heated to reflux for 30 minutes, poured into water, and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain (0.74 g) of the title compound (U).

¹ H-NMR (CDCl ₃ , δ ppm): δ 1.62-1.75 (m, 2H), 1.91-1.98 (m, 2H), 2.65 (brs, 2H), 3.17 ( d, 2H), 4.26 (d, 2H), 4.66 (s, 1H), 5.63 (s, 1H), 6.60 (d, 1H), 6.98 (d, 1H), 7.13 (d, 1H) 7.16 (s, 1H), 7.63 (d, 1H) 8.42 (s, 1H)
This product was directly used in the next step without purification.

Process 4
Preparation of 8β- [2-isopropylideneaminooxy-4- (trifluoromethyl) phenoxy] -3- (5-cyano-pyridin-2-yl) -3-azabicyclo [3.2.1] octane (W)

  Using compound (U) (0.74 g), compound (V) was synthesized (0.76 g) by the method described in JP-A No. 2001-81071.

¹ H-NMR (CDCl ₃ , δ ppm): δ 1.55-1.68 (m, 2H), 1.99-2.04 (m, 2H), 2.59 (brs, 2H), 3.13 ( d, 2H), 4.22 (d, 2H), 4.60 (s, 1H), 6.00 (brs, 2H), 6.59 (d, 1H), 6.98 (d, 1H), 7.20 (d, 1H), 7.60 (d, 2H) 8.01 (s, 1H), 8.41 (s, 1H)

To a solution of compound (V) (0.76 g) in ethanol (3 ml) were added acetone (3 ml) and 1 drop of concentrated hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: mixed solvent consisting of n-hexane and ethyl acetate) to obtain the title compound (W) (0.45 g). The structure was confirmed by NMR.
Melting point: 120-122 ° C

(Reference Example 8)
9β- [2-Cyclopropylmethoxy-4- (trifluoromethyl) phenoxy] -7- [6- (trifluoromethyl) -3-pyridazyl] -3-oxa-7-azabicyclo [3.3.1] nonane (AC) manufacturing process 1

Preparation of N-benzyl-3-oxa-7-azabicyclo [3.3.1] nonane-9-ol (Z) To benzylamine (2.2 g), acetic acid (1.2 g), methanol (80 ml), and 90% formalin (5.33 g) was added in order, and compound (X) (2.0 g) was added dropwise while gradually raising the temperature from 20 ° C. to 45 ° C., and the mixture was refluxed for 5.5 hours. Stir overnight.
The solvent was distilled off from the reaction mixture under reduced pressure, and water (100 ml) and concentrated hydrochloric acid (2 ml) were added to the resulting residue, followed by washing with diethyl ether. Sodium hydroxide was added to the aqueous layer to adjust the pH to 7 or more, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (chloroform: methanol = 10: 1 (v / v)) to obtain compound (Y) (4.09 g). )Obtained. Yield 88.5%

  Next, sodium borohydride (1.86 g) was added to a solution of compound (Y) (2.24 g) in 2-propanol (30 ml) at 0 ° C., water (15 ml) was added, and the mixture was warmed to room temperature. Warmed and stirred for one day. The reaction mixture was cooled to 0 ° C., 10% hydrochloric acid (75 ml) was added, and then 45 ml of 10% sodium hydroxide was added at the same temperature. Extraction was performed with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain compound (Z) as a viscous oil (1.56 g). Yield 83.8%

Process 2
Production of compound (AA)

  60% sodium hydride (0.40 g) was added to a DMF (20 ml) solution of the compound (Z) (1.56 g) obtained in step 1, and the mixture was stirred at room temperature for 15 minutes. 4-Fluoro-3- (cyclopropylmethoxy) benzotrifluoride (2.35 g) was added thereto, and the mixture was stirred at 100 ° C. for 3 hours. The reaction mixture was cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a crude compound (AA).

  The obtained crude compound (AA) was purified by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 2: 3 (v / v)). As a result, the compound (AA-cis) was 0 as a viscous oil. .98 g (yield 32.7%) and 0.76 g (yield 25.4%) of the compound (AA-trans) as viscous oil were obtained.

NMR data of AA-cis:
¹ H-NMR (CDCl ₃ , δ ppm): δ 0.34-0.44 (m, 2H), 0.60-0.67 (m, 2H), 1.26-1.31 (m, 2H), 1.94 (brs, 2H), 2.49 (d, 2H), 3.17 (d, 2H), 3.57 (s, 2H), 3.79 (d, 2H), 3.88 (d , 2H), 4.27 (d, 2H) 4.43 (t, 1H), 6.94 (d, 1H), 7.10 (s, 1H), 7.17 (d, 1H), 7. 20-7.40 (m, 5H)

AA-trans NMR data:
¹ H-NMR (CDCl ₃ , δ ppm): δ 0.39-0.44 (m, 2H), 0.62-0.71 (m, 2H), 1.25-1.35 (m, 1H), 2.04 (brs, 2H), 2.84 (brs, 4H), 3.55 (s, 2H), 3.82 (d, 2H), 3.89 (d, 2H), 4.13 (d , 2H), 4.59 (t, 1H), 6.95 (d, 1H), 7.10 (s, 1H), 7.14 (d, 1H), 7.20-7.42 (m, 5H)
Process 3

  10% Pd / C (0.20 g) was added to a solution of the compound (AA-cis) (0.98 g) obtained in step 2 in ethanol (20 ml), and the whole volume was adjusted to 60 ° C. under a hydrogen atmosphere (atmospheric pressure). And stirred for 6.5 hours. The reaction mixture was filtered, and the filtrate was distilled off under reduced pressure to obtain a debenzylated product (AB) as an oil (0.75 g). Yield 95.9%

¹ H-NMR (CDCl ₃ , δ ppm): δ 0.35-0.40 (m, 2H), 0.60-0.69 (m, 2H), 1.23-1.34 (m, 1H), 1.83 (brs, 2H), 1.99 (brs, 1H), 3.04 (d, 2H), 3.38 (d, 2H), 3.85-3.91 (m, 4H), 4 .35 (d, 2H), 4.59 (t, 1H), 6.95 (d, 1H), 7.10 (s, 1H), 7.12 (d, 1H)

To a solution of the obtained compound (AB) in N-methylpyrrolidone (3 ml), 3-chloro-6- (trifluoromethyl) pyridazine (0.19 g) and DBU (0.15 g) were added, and 120-130 ° C. For 3 hours. After the reaction mixture was cooled to room temperature, water was poured and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 1: 1 (v / v)) to obtain the title compound (AC) (0.24 g). Yield 57%
mp. 93-95 ° C

Formulation Example [Insecticide / Acaricide]
Next, although some examples of the composition of the present invention are shown, the additive and the addition ratio are not limited to these examples, and can be varied in a wide range. The part in a formulation example shows a weight part.

Formulation Example 1 wettable powder cyclic amine compound 10 parts other acaricide 30 parts diatomaceous earth 53 parts higher alcohol sulfate 4 parts alkylnaphthalene sulfonate 3 parts 40% wettable powder is obtained.

Formulation Example 2 Emulsion Cyclic amine compound 10 parts Other acaricide 20 parts Xylene 33 parts Dimethylformamide 30 parts Polyoxyethylene alkyl allyl ether
7 parts or more are mixed and dissolved to obtain an emulsion with 30% active ingredient.

Formulation Example 3 Dust Cyclic amine compound 3 parts Other acaricide 7 parts Talc 89 parts Polyoxyethylene alkyl allyl ether
One part or more is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.

Formulation Example 4 Granules Cyclic amine compound 2 parts Other acaricide 3 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt
1 part Sodium phosphate 1 part The above is pulverized and mixed well, water is added and kneaded well, and then granulated and dried to obtain a granule of 5% active ingredient.

Formulation Example 5 Suspension agent Cyclic amine compound 4 parts Other acaricide 6 parts Sodium lignin sulfonate 4 parts Sodium dodecylbenzenesulfonate 1 part Xanthan gum 0.2 part Water 84.8 parts Wet mill to a micron or less to obtain a 10% active ingredient suspension.

  In each of the following test examples, 8β- [2-cyclopropylmethyleneoxy-4- (trifluoromethyl) phenoxy] -3- (6-trifluoromethyl-pyridazin-3-yl) -3 is used as a cyclic amine compound. -Azabicyclo [3.2.1] octane was used.

Test Example 1 Efficacy Confirmation Test for Spider Mite Ten adult female spider mites that are resistant to acaricide are inoculated on kidney beans placed in a petri dish. A 15% emulsion of a cyclic amine compound and various other acaricide preparations are diluted with water, and a chemical solution in which the concentration of the cyclic amine compound is 0.6 ppm and the compound concentration of various other acaricide preparations is a predetermined amount. And sprayed in a rotary spray tower. Whether placed in a temperature-controlled room with a temperature of 25 ° C and a humidity of 65%, and after examining the life and death of adults 3 days after spraying, removed the adults and whether or not they were able to develop to the adults for the eggs laid in these 3 days Was examined on the 7th day, and the effectiveness of miticide was calculated from the following formula. The results are shown in Table 1 below. In Table 1, α indicates the rate of killing insects after 3 days (rate of killing insects + rate of bitter worms), and β indicates the effectiveness of miticide after 7 days.

(Expected value of Colby)
The degree of synergistic effect was calculated using the judgment formula (below) by the Colby method.
Determination formula: Expected value of Colby (E) = X + Y−XY / 100
In the above formula, X represents the killing rate (%) when other acaricides are applied alone, and Y represents the killing rate (%) when a cyclic amine compound is applied alone.
The calculation results are shown in Table 1.
When the mixed insecticide is applied, the killing rate is greater than E, and it is determined that there is a synergistic effect.
In Table 1, various other acaricide formulations used are as follows.

  From Table 1, when a cyclic amine compound and other acaricides were applied in combination (Examples 1 to 6 = mixed section in Table 1 above), the cyclic amine compound was applied alone (Comparative Example 1). ), And when other miticides are applied alone (single-use section in Table 1 above), it can be seen that remarkably superior acaricide activity is observed.

Claims (5)

Formula (1)

(In the formula, X represents an oxygen atom, a sulfur atom, an unsubstituted or substituted nitrogen atom, a sulfinyl group, or a sulfonyl group.
R ¹ _a and R ² _a , R ¹ _a and R ⁴ _a , R ² _a and R ³ _a , or R ³ _a and R ⁴ _a together form a saturated ring.
R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , and R ⁵ that do not form a saturated ring are each independently a hydrogen atom, hydroxyl group Represents a halogen atom, an amino group, a substituted amino group, a nitro group, or an organic group.
Cy ¹ and Cy ² each independently represent an unsubstituted or substituted aromatic group.
However, when R ¹ _a and R ² _a are combined to form a saturated ring, and Cy ¹ is an unsubstituted or substituted phenyl group, Cy ² is unsubstituted or substituted. When it is an aromatic heterocyclic group, Cy ¹ is an unsubstituted or substituted phenyl group, and Cy ² is a pyridin-2-yl group, Cy ² represents one or more cyano groups as a substituent. It is a substituted pyridin-2-yl group. )
A pest control composition comprising at least one of a cyclic amine compound, a salt thereof, or an N-oxide thereof, and at least one other acaricide. R ¹ _a , R ¹ _b , R ² _a , R ² _b , R ³ _a , R ³ _b , R ⁴ _a , R ⁴ _b , which do not form a saturated ring of the cyclic amine compound represented by the formula (1), and The pest control composition according to claim 1, wherein R ⁵ is an alkyl group, an alkoxycarbonyl group, or an alkoxy group compound. The cyclic amine compound represented by the formula (1) is _a compound obtained by forming a saturated ring by combining R ¹ _a and R ² _a or R ³ _a and R ⁴ _{a in the} formula (1). The pest control composition according to claim 1.   The pest control composition according to claim 1, wherein the cyclic amine compound represented by the formula (1) is a compound having 2 or 3 bridged atoms in the piperidine ring forming the saturated ring in the formula (1). object.   A method for controlling pests, comprising using at least one of the cyclic amine compound represented by the formula (1), a salt thereof, or an N-oxide thereof, and at least one other acaricide.