JP2011042611A - Acaricide and new urea compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acaricide that has a sure effect and is safely usable, a new urea compound or a salt thereof that becomes an active ingredient of acaricide. <P>SOLUTION: The acaricide comprises at least one kind of a compound represented by formula (I) (wherein, R<SP>1</SP>is alkyl or the like; R<SP>2</SP>is alkyl or the like; R<SP>3</SP>is a halogen atom or the like; R<SP>4</SP>is a hydrogen atom or the like; R<SP>5</SP>is alkyl or the like; m and n are each an integer of 0-2; X is N=CN or the like; and A is O or the like) or its salt as an active ingredient. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an acaricide, a novel urea compound useful as an active ingredient of an acaricide, and a salt thereof.

  Many acaricides have been used in the past, but their effectiveness is insufficient, their use is restricted due to drug resistance problems, phytotoxicity and contamination of plants, and human fish In many cases, it is not always a satisfactory acaricide because of its high toxicity. Accordingly, there is a demand for the development of a new acaricide that can be used safely and has few such drawbacks.

In relation to the present invention, Patent Document 1 describes a compound having a skeleton similar to the compound of the present invention.
However, this document does not describe that the compound has acaricidal activity or the compound of the present invention.
WO2007 / 015533 pamphlet

  This invention makes it a subject to provide the novel urea compound useful as an active ingredient of an acaricide, an acaricide which is reliable and can be used safely, and its salt.

As a result of intensive studies to solve the above problems, the present inventors have found that a compound represented by the following formula (I) has an excellent acaricidal activity, and have completed the present invention.
That is, the present invention firstly has the formula (I)

[Wherein, R ¹ represents a C1-20 alkyl group or a C1-20 haloalkyl group.
R ² is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an unsubstituted or substituted amino group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C2 20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted aryl group, unsubstituted or substituted C1-20 acyl group, unsubstituted or substituted C1-20 A thioacyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C2-20 alkenyloxy group, an unsubstituted or substituted C2-20 alkynyloxy group, an unsubstituted or substituted group Aryloxy group, unsubstituted or substituted heteroyloxy group, unsubstituted Or a substituted C1-20 alkylthio group, an unsubstituted or substituted C2-20 alkenylthio group, an unsubstituted or substituted C2-20 alkynylthio group, an unsubstituted or substituted arylthio group, Unsubstituted or substituted heteroylthio group, unsubstituted or substituted C1-20 alkylsulfinyl group, unsubstituted or substituted arylsulfinyl group, unsubstituted or substituted C1-20 alkylsulfonyl group, none A substituted or substituted arylsulfonyl group or an unsubstituted or substituted heterocyclic group is represented.

R ³ represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a mercapto group, an unsubstituted or substituted amino group, an unsubstituted or substituted C 1-20 alkyl group, an unsubstituted or substituted C 2- 20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted aryl group, unsubstituted or substituted C1-20 acyl group, unsubstituted or substituted C1-20 A thioacyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C2-20 alkenyloxy group, an unsubstituted or substituted C2-20 alkynyloxy group, an unsubstituted or substituted group Aryloxy group, unsubstituted or substituted heteroyloxy group, unsubstituted Or a substituted C1-20 alkylthio group, an unsubstituted or substituted C2-20 alkenylthio group, an unsubstituted or substituted C2-20 alkynylthio group, an unsubstituted or substituted arylthio group, Unsubstituted or substituted heteroylthio group, unsubstituted or substituted C1-20 alkylsulfinyl group, unsubstituted or substituted arylsulfinyl group, unsubstituted or substituted C1-20 alkylsulfonyl group, none A substituted or substituted arylsulfonyl group or an unsubstituted or substituted heterocyclic group is represented.

R ⁴ is a hydrogen atom, a cyano group, a formyl group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C1-20 acyl group, or an unsubstituted or substituted phenyl group Represents.
R ⁵ represents an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted amino group, the formula (a)

An unsubstituted or substituted nitrogen-containing heterocyclic group represented by formula (b)

(In the formula, R ⁸ and R ⁹ are each independently an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-6 cycloalkyl group, a C2-6 alkenyl group, an unsubstituted group. Or a substituted phenyl group, or an unsubstituted or substituted heterocyclic group, or R ⁸ and R ⁹ are bonded together to form a nitrogen atom, an oxygen atom, or a sulfur atom; A 4- to 8-membered hetero ring which may contain 4), a pyrrolidin-2-yl group having an unsubstituted or substituted group, a phenyl group having an unsubstituted or substituted group, An unsubstituted or substituted C3-8 cycloalkyl group or an unsubstituted or substituted C1-20 alkylthio group is represented.

X represents a group represented by the formula: N—CN, or a group represented by the formula: N—OR ′ (R ′ represents a hydrogen atom or an unsubstituted or substituted C1-20 alkyl group). To express.
n represents any integer of 0 to 2, and m represents any integer of 0 to 2. However, m + n ≦ 2.

A represents an oxygen atom, a sulfur atom, or a group represented by the formula: NQ (Q is a cyano group, an unsubstituted or substituted C1-20 alkyl group, or a formula: OR ¹⁰ ; R ^10. Represents a hydrogen atom, an unsubstituted or substituted C1-10 alkyl group having a substituent. ] An acaricide which contains at least one of the compounds represented by the above or a salt thereof as an active ingredient.
Secondly, the present invention relates to the formula (I-1)

(In the formula, R ¹ represents a C1-20 alkyl group or a C1-20 haloalkyl group.
R ²¹ represents an unsubstituted or substituted C1-20 alkyl group.
R ³ represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a mercapto group, an unsubstituted or substituted amino group, an unsubstituted or substituted C 1-20 alkyl group, an unsubstituted or substituted C 2- 20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted aryl group, unsubstituted or substituted C1-20 acyl group, unsubstituted or substituted C1-20 A thioacyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C2-20 alkenyloxy group, an unsubstituted or substituted C2-20 alkynyloxy group, an unsubstituted or substituted group Aryloxy group, unsubstituted or substituted heteroyloxy group, unsubstituted Or a substituted C1-20 alkylthio group, an unsubstituted or substituted C2-20 alkenylthio group, an unsubstituted or substituted C2-20 alkynylthio group, an unsubstituted or substituted arylthio group, Unsubstituted or substituted heteroylthio group, unsubstituted or substituted C1-20 alkylsulfinyl group, unsubstituted or substituted arylsulfinyl group, unsubstituted or substituted C1-20 alkylsulfonyl group, none A substituted or substituted arylsulfonyl group or an unsubstituted or substituted heterocyclic group is represented.

R ⁴ is a hydrogen atom, a cyano group, a formyl group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C1-20 acyl group, or an unsubstituted or substituted phenyl group Represents.
R ⁶ and R ⁷ are each independently a hydrogen atom, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C2-20 alkenyl group, an unsubstituted or substituted C2-20. An alkynyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted C1-20 alkoxy group, or an unsubstituted or substituted C1-20 alkylthio group is represented. R ⁶ and R ⁷ may be combined to form an unsubstituted or substituted ring. Furthermore, the ring may contain a hetero atom in addition to the nitrogen atom bonded to the group represented by the formula: —N (R ⁴ ) —C (═O) —. )
The urea compound shown by these, or its salt is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the novel aurea compound and its salt useful as an active ingredient of an acaricide which an effect is reliable and can be used safely are provided.

Hereinafter, the present invention will be described in detail.
According to a first aspect of the present invention, the acaricide is characterized by containing as an active ingredient at least one of the compounds represented by the formula (I) (hereinafter sometimes referred to as “compound (I)”) or a salt thereof. It is an agent.

(1) Compound (I)
In formula (I), R ¹ represents a C1-20 alkyl group or a C1-20 haloalkyl group.
Examples of the C1-20 alkyl group of R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl. Group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group and the like.

Examples of the C1-20 haloalkyl group for R ¹ include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, 2, Examples include 2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group and the like.
Among these, ^{R 1,} preferably a C1~20 haloalkyl group, more preferably a C1~6 haloalkyl group, more preferably C1~6 fluoroalkyl group.

R ² is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an unsubstituted or substituted amino group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C2 20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted aryl group, unsubstituted or substituted C1-20 acyl group (acyl group is carbon number of carbonyl group) This is the number of carbon atoms excluding atoms. The same applies hereinafter.), C1-20 thioacyl group having no substituent or substituent (the carbon number of the thioacyl group is the number of carbon atoms excluding the carbon atom of the thiocarbonyl group) The same shall apply hereinafter.), C1-20 alkoxy group having an unsubstituted or substituted group, C2-20 having an unsubstituted or substituted group. An alkenyloxy group, an unsubstituted or substituted C2-20 alkynyloxy group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted heteroyloxy group, an unsubstituted or substituted C1 ~ 20 alkylthio groups, unsubstituted or substituted C2-20 alkenylthio groups, unsubstituted or substituted C2-20 alkynylthio groups, unsubstituted or substituted arylthio groups, unsubstituted or substituted heteroylthio groups Group, unsubstituted or substituted C1-20 alkylsulfinyl group, unsubstituted or substituted arylsulfinyl group, unsubstituted or substituted C1-20 alkylsulfonyl group, unsubstituted or substituted arylsulfonyl Group or unsubstituted young Ku represents a heterocyclic group having a substituent.

Examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the unsubstituted or substituted amino group include an amino group; a mono C1-C6 alkylamino group such as a methylamino group and an ethylamino group; a diC1-C6 alkylamino group such as a dimethylamino group and a diethylamino group; Groups, acylamino groups such as benzoylamino groups; phenylamino groups optionally having substituents such as phenylamino groups and 4-methylphenylamino groups; and the like.

The C1~20 alkyl group C1~20 alkyl group having unsubstituted or substituted, the same ones as exemplified for R ¹ can be mentioned.

  Examples of the C2-20 alkenyl group of the unsubstituted or substituted C2-20 alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1 -Methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl- Examples include 2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.

  Examples of the C2-20 alkynyl group of the unsubstituted or substituted C2-20 alkynyl group include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl 2-propynyl group, 2-methyl-3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3- A pentynyl group, 1-hexynyl group, 1,1-dimethyl-2-butynyl group and the like can be mentioned.

  Substituents for C1-20 alkyl group, C2-20 alkenyl group, C2-20 alkynyl group include halogen atoms such as fluorine atom and chlorine atom; C1-6 alkoxy groups such as methoxy group and ethoxy group; phenyl group, 4 -An unsubstituted or substituted aryl group such as a methylphenyl group;

  Examples of the aryl group of the unsubstituted or substituted aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  The C1-20 acyl group of an unsubstituted or substituted C1-20 acyl group is a C1-20 alkylcarbonyl group such as an acetyl group or a propionyl group (the carbon number of the alkylcarbonyl group excludes the carbon atom of the carbonyl group) C2-20 alkenylcarbonyl groups such as allylcarbonyl group, crotylcarbonyl group, etc. (the carbon number of the alkenylcarbonyl group is the number of carbon atoms excluding the carbon atom of the carbonyl group); C2-20 alkynylcarbonyl group such as propargylcarbonyl group (the carbon number of alkynylcarbonyl group is the number of carbon atoms excluding the carbon atom of carbonyl group); arylcarbonyl group such as benzoyl group; and the like.

  The C1-20 thioacyl group of an unsubstituted or substituted C1-20 thioacyl group includes a C1-20 alkylthiocarbonyl group such as a thioacetyl group or a thiopropionyl group (the carbon number of the alkylthiocarbonyl group is the carbon atom of the thiocarbonyl group). C2-20 alkenylthiocarbonyl group such as allylthiocarbonyl group, crotylthiocarbonyl group, etc. (The carbon number of the alkenylthiocarbonyl group is the number of carbon atoms excluding the carbon atom of the thiocarbonyl group.) A C2-20 alkynylthiocarbonyl group such as a propargylthiocarbonyl group (the carbon number of the alkynylthiocarbonyl group is the number of carbon atoms excluding the carbon atom of the thiocarbonyl group); a thiobenzoyl group, etc. Arylthiocarbonyl group; and the like.

  Examples of the C1-20 alkoxy group of the unsubstituted or substituted C1-20 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a t-butoxy group. .

Examples of the C2-20 alkenyloxy group of the unsubstituted or substituted C2-20 alkenyloxy group include an allyloxy group and a crotyloxy group.
Examples of the C2-20 alkynyloxy group of the unsubstituted or substituted C2-20 alkynyloxy group include a propargyloxy group.

  Examples of the aryloxy group of the unsubstituted or substituted aryloxy group include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

Examples of the heteroyloxy group of the unsubstituted or substituted heteroyloxy group include 2-pyridyloxy group, 3-pyridyloxy group, 4-pyridyloxy group, 2-imidazolyloxy group, 4-imidazolyloxy group, and the like. Can be mentioned.
Examples of the C1-20 alkylthio group of the unsubstituted or substituted C1-20 alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, and a t-butylthio group. .

Examples of the C2-20 alkenylthio group of the unsubstituted or substituted C2-20 alkenylthio group include an allylthio group and a crotylthio group.
Examples of the C2-20 alkynylthio group of the unsubstituted or substituted C2-20 alkynylthio group include a propargylthio group.

Examples of the arylthio group of the unsubstituted or substituted arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.
Examples of the heteroylthio group of the unsubstituted or substituted heteroylthio group include a 2-pyridylthio group, a 3-pyridylthio group, a 4-pyridylthio group, a 2-imidazolylthio group, and a 4-imidazolylthio group.

Examples of the C1-20 alkylsulfinyl group of the unsubstituted or substituted C1-20 alkylsulfinyl group include a methylsulfinyl group and an ethylsulfinyl group.
Examples of the arylsulfinyl group of the unsubstituted or substituted arylsulfinyl group include a phenylsulfinyl group, a 1-naphthylsulfinyl group, and a 2-naphthylsulfinyl group.

Examples of the C1-20 alkylsulfonyl group of the unsubstituted or substituted C1-20 alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.
Examples of the arylsulfonyl group of the unsubstituted or substituted arylsulfonyl group include a phenylsulfonyl group, a 1-naphthylsulfonyl group, and a 2-naphthylsulfonyl group.

  In addition, the heterocyclic group of an unsubstituted or substituted heterocyclic group includes a saturated or unsaturated cyclic compound group having at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom in the ring. Is mentioned.

Specifically, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 3-pyridyl group, 4-pyridazyl group, 2- (1, 3,5-triazyl) group, 3- (1,2,4-triazyl) group, 5- (1,2,4-triazyl) group, 6- (1,2,4-triazyl) group, etc. A group of ring compounds;
2-thienyl group, 3-thienyl group, 2-furyl group, 3-furyl group, 3-pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 3- (1,2,4-triazolyl) group, 5- (1,2,4-triazolyl) group, 2-pyrazyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group 4-isothiazolyl group, 5-isothiazolyl group, 2- (1,3,4-thiadiazolyl) group, 3- (1,2,4-thiadiazolyl) group, 5- (1,2,4-thiadiazolyl) group, 5- (1,2,3-thiadiazolyl) group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, -(1,3,4-oxadiazolyl) group, 3- (1,2,4-oxadiazolyl) group, 5- (1,2,4-oxadiazolyl) group, 5- (1,2,3-oxadiazolyl) group And the like, and the like.

  C1-20 acyl group (excluding arylcarbonyl group), C1-20 thioacyl group, C1-20 alkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy group, C1-20 alkylthio group, C2-20 alkenyl Examples of the substituent for the thio group, C2-20 alkynylthio group, C1-20 alkylsulfinyl group, C1-20 alkylsulfonyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom; phenyl group, 4-methylphenyl group An unsubstituted or substituted aryl group such as;

  Examples of the substituent of the aryl group, arylcarbonyl group, aryloxy group, heteroyloxy group, arylthio group, heteroylthio group, arylsulfinyl group, arylsulfonyl group, and heterocyclic group include C1-6 such as methyl group and ethyl group. Alkyl group; C1-6 haloalkyl group such as trifluoromethyl group; halogen atom such as fluorine atom, chlorine atom and bromine atom; C1-6 alkoxy group such as methoxy group and ethoxy group; phenyl group, 4-methoxyphenyl group and the like An unsubstituted or substituted aryl group; a nitro group; and the like.

Among these, as R ² , a cyano group, a nitro group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C1 ~ 20 acyl groups are preferred, unsubstituted or substituted C1-20 alkyl groups are more preferred, and unsubstituted or substituted C1-6 alkyl groups are even more preferred.

R ³ is a hydrogen atom, a nitro group, a hydroxyl group, a mercapto group, and the same as R ² above (halogen atom, unsubstituted or substituted amino group, unsubstituted or substituted C1-20 alkyl group, Unsubstituted or substituted C2-20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted aryl group, unsubstituted or substituted C1-20 acyl group, A substituted or substituted C1-20 thioacyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C2-20 alkenyloxy group, an unsubstituted or substituted C2-20 alkynyl Oxy group, unsubstituted or substituted aryloxy group, unsubstituted or substituted Teloyloxy group, unsubstituted or substituted C1-20 alkylthio group, unsubstituted or substituted C2-20 alkenylthio group, unsubstituted or substituted C2-20 alkynylthio group, unsubstituted or substituted An arylthio group having an unsubstituted or substituted heteroylthio group, an unsubstituted or substituted C1-20 alkylsulfinyl group, an unsubstituted or substituted arylsulfinyl group, an unsubstituted or substituted C1-20 alkyl A sulfonyl group, an unsubstituted or substituted arylsulfonyl group, or an unsubstituted or substituted heterocyclic group).
Among these, as R ³ , a halogen atom is preferable, and a fluorine atom is particularly preferable.

R ⁴ is a hydrogen atom, a cyano group, a formyl group, C1-20 alkyl group having the same unsubstituted or substituted with said ^{R 2,} C1-20 acyl group having unsubstituted or substituted group similar to the ^{R 2} Or an unsubstituted or substituted phenyl group.
Examples of the substituent of the unsubstituted or substituted phenyl group for R ⁴ include those exemplified as the substituent for the aryl group of R ² .
Among these, as R ⁴ , a hydrogen atom, a formyl group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C1-20 acyl group is preferable, and a hydrogen atom, C1-20 alkyl is preferable. Group, a C1-20 acyl group is more preferred.

R ⁵ is an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted amino group, an unsubstituted or substituted nitrogen-containing heterocyclic group represented by the above formula (a), A group represented by the formula (b), an unsubstituted or substituted pyrrolidin-2-yl group, an unsubstituted or substituted phenyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or Represents an unsubstituted or substituted C1-20 alkylthio group.

Wherein the R ^5, C1-20 alkyl group having an unsubstituted or substituted group, an amino group having unsubstituted or substituted, and, as the C1-20 alkylthio group having unsubstituted or substituted, exemplified by the R ² The same groups as mentioned above can be mentioned. Examples of the unsubstituted or substituted phenyl group for R ⁵ include the same groups as those exemplified for R ⁴ .

The nitrogen-containing heterocyclic ring of the nitrogen-containing heterocyclic group having an unsubstituted or substituted group represented by the formula (a) (hereinafter sometimes referred to as “nitrogen-containing heterocyclic group (a)”) of R ⁵ . Is a saturated or unsaturated heterocycle having one or more nitrogen atoms in the ring. The nitrogen-containing heterocycle may contain an oxygen atom and / or a sulfur atom in addition to a nitrogen atom, and has a crosslinked structure, whether it is a monocyclic ring or a condensed ring structure. It may be a thing.

The total number of nitrogen atoms, oxygen atoms and sulfur atoms constituting the nitrogen-containing heterocycle of the nitrogen-containing heterocyclic group (a) is usually 1 to 4, preferably 1 to 3.
The number of carbon atoms constituting the nitrogen-containing heterocycle of the nitrogen-containing heterocyclic group (a) is preferably 10 or less, and more preferably 1-8.

  Specific examples of the nitrogen-containing heterocyclic group (a) include those listed in Table 1 below, but are not limited thereto. The substituents on the nitrogen atom and the atoms constituting the ring are omitted, and only the basic skeleton is shown.

  Among these, pyrrolidin-1-yl is particularly preferable as the nitrogen-containing heterocyclic group (a).

  The substituent of the nitrogen-containing heterocyclic group (a) is not particularly limited. For example, a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a C1-6 alkyl group which may have a substituent such as a methyl group, an ethyl group, a trifluoromethyl group or a benzyl group; an allyl group; A C2-6 alkenyl group optionally having a substituent such as a chloroallyl group; a C2-6 alkynyl group optionally having a substituent such as a propargyl group; a phenyl group, a 4-methylphenyl group, etc. Aryl group optionally having substituent; formyl group;

  An unsubstituted or substituted C1-6 alkylcarbonyl group such as an acetyl group or a trifluoroacetyl group; an unsubstituted or substituted C2-6 alkenylcarbonyl group such as a cinnamyl group; an unsubstituted such as a propargylcarbonyl group; Substituted or substituted C2-6 alkynylcarbonyl group; benzoyl group, 4-chlorobenzoyl group, etc., unsubstituted or substituted arylcarbonyl group; thioacetyl group, etc., unsubstituted or substituted C1-6 An alkylthiocarbonyl group; an unsubstituted or substituted C2-6 alkenylthiocarbonyl group such as an allylthiocarbonyl group; an unsubstituted or substituted C2-6 alkynylthiocarbonyl group such as a propargylthiocarbonyl group; thiobenzoyl A group or the like, unsubstituted or An arylthiocarbonyl group having a substituent; a carboxyl group; a C1-6 alkoxycarbonyl group having an unsubstituted or substituted group such as a methoxycarbonyl group or an ethoxycarbonyl group; an unsubstituted or substituted group such as a vinyloxycarbonyl group A C2-6 alkenyloxycarbonyl group;

  An unsubstituted or substituted C2-6 alkynyloxycarbonyl group such as a propargyloxycarbonyl group; an unsubstituted or substituted aryloxycarbonyl group such as a phenoxycarbonyl group or a 2,4-dichlorophenoxycarbonyl group; Cyano group; amino group, dimethylamino group, acetylamino group and the like, unsubstituted or substituted amino group; nitro group; hydroxyl group; oxo group; thioxo group; methoxy group, ethoxy group, t-butoxy group, etc. C1-6 alkoxy group having an unsubstituted or substituted group; C2-6 alkenyloxy group having an unsubstituted or substituted group such as an allyloxy group or a crotyloxy group; C2-6 having an unsubstituted or substituted group such as a propargyloxy group 6 alkynyloxy group; phenoxy group, 4-methylpheno C1-6 alkylthio having an unsubstituted or substituted group, such as an aryloxy group having an unsubstituted or substituted group such as a thio group; a heteroyloxy group having an unsubstituted or substituted group; a mercapto group; a methylthio group, an ethylthio group, etc. A group: an unsubstituted or substituted C2-6 alkenylthio group such as an allylthio group or a crotylthio group; an unsubstituted or substituted C2-6 alkynylthio group such as a propargylthio group; a phenylthio group, etc. Substituted or substituted arylthio group; unsubstituted or substituted heteroylthio group; methylsulfinyl group and other unsubstituted or substituted C1-6 alkylsulfinyl groups; phenylsulfinyl group and other unsubstituted or substituted groups Arylsulfinyl group having a methylsulfonyl group, etc. , Cl to 6 alkylsulfonyl group having unsubstituted or substituted; or phenyl sulfonyl group, an arylsulfonyl group having unsubstituted or substituted; and a heterocyclic group having unsubstituted or substituted; and the like.

  A substituent of the nitrogen-containing heterocyclic group (a), (unsubstituted or substituted heteroyloxy group, unsubstituted or substituted heteroylthio group, unsubstituted or substituted heterocyclic group); Examples of the heterocyclic ring to be configured include saturated or unsaturated cyclic compounds having at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom in the ring. Specifically, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoleyl, pteridine, acridine, phenanthroline , Phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, indolenine, tetrazaindene, furan and other aromatic heterocycles; , Non-aromatic heterocycles such as piperazine, thiazolidine and trioxane.

Among these, as the substituent of the nitrogen-containing heterocyclic group (a), a halogen atom, an unsubstituted or C1-6 alkyl group having a substituent is preferable, and a halogen atom is more preferable.
Moreover, the nitrogen-containing heterocyclic group (a) may have one or a plurality of substituents at the same or different positions.

In the formula (b), R ⁸ and R ⁹ are each independently an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-6 cycloalkyl group, a C2-6 alkenyl group. Represents an unsubstituted or substituted phenyl group, or an unsubstituted or substituted heterocyclic group.

The C1~6 alkyl group C1~6 alkyl group having unsubstituted or substituted of R ^{8, R 9,} methyl, ethyl, n- propyl, i- propyl, n- butyl, sec- A butyl group, an isobutyl group, a t-butyl group, etc. are mentioned.

  Examples of the substituent for the C1-6 alkyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom; methoxy group, ethoxy group, chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoro. And an alkoxy group which may be substituted with a halogen such as ethoxy group, 1,1-difluoroethoxy group, chloromethoxy group, dichloromethoxy group and trifluoromethoxy group.

The C3~6 cycloalkyl group having unsubstituted or substituted of R ^{8, R 9,} cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethyl-cyclopropyl group, 2 -Chlorocyclopropyl group, 2,2-dichlorocyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

The C2~6 alkenyl group of R ^{8, R 9,} a vinyl group, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl group, 1-methyl-2-propenyl group 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1- Examples include a hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group.

  Examples of the substituent for the C2-6 alkenyl group include those exemplified as the substituent for the C1-6 alkyl group.

As the heterocyclic group of unsubstituted or substituted heterocyclic group of R ⁸ and R ⁹ , 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-oxazolyl group, 2 -Oxazolinyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 3-isoxazolinyl group, 2-thiazolyl group, 2-thiazolinyl group, 3-isothiazolyl group, 3-isothiazolinyl group, 2-pyranyl Group, 4-tetrahydropyranyl group, 1-azetidinyl group, 2-azetidinyl group, 3-azetidinyl group, 2-pyrrolyl group, 2-pyrrolidinyl group, 2-imidazolyl group, 3-pyrazolyl group, 2-imidazolinyl group, 2 -Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-piperidyl group, piperidino group, 2-morpholinyl group, morpho Amino group, 2-piperazinyl group, 2-pyrimidinyl group, 3-pyridazinyl group, 2-pyrazinyl group and the like.

Examples of substituents for phenyl group and heterocyclic group of R ⁸ and R ⁹ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group; chloromethyl group, fluoromethyl group, bromomethyl group, dichloro A haloalkyl group such as a methyl group, difluoromethyl group, dibromomethyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group; Alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group; hydroxy group; nitro group; cyano group; amino group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, Alkoxycals such as n-butoxycarbonyl group and t-butoxycarbonyl group Alkylsulfonyl group; a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom; or a methanesulfonyl group, ethylsulfonyl group, an alkylsulfonyl group such as n- propyl sulfonyl group; and the like.

R ⁸ and R ⁹ may be bonded together to form a 3- to 8-membered heterocycle that may contain 1 to 4 nitrogen, oxygen, or sulfur atoms. .
Examples of the heterocyclic ring include a thiophene ring, a tetrahydrothiophene ring, a thiopyran ring, a tetrahydrothiopyran ring, a 4-oxathiane ring, a thiomorpholine ring, a 1,4-dithiane ring, and a tetrahydrothiopyran-4-one ring.

Examples of the substituent of the unsubstituted or substituted pyrrolidin-2-yl group of R ⁵ include a C1-6 alkyl group such as a methyl group; an ester group such as an Nt-butoxycarbonyl group; a fluorine atom, chlorine Halogen atoms such as atoms; and the like.

Examples of the unsubstituted or substituted C 3-8 cycloalkyl group represented by R ⁵ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Examples of the substituent for the C3-8 cycloalkyl group include the same groups as those exemplified as the substituent for the R ² aryl group and the like.

X represents a group represented by the formula: N—CN or a group represented by the formula: N—OR ′. In the formula, R ′ represents a hydrogen atom or a C1-20 alkyl group having no substituent or a substituent similar to those exemplified for R ² .
n represents any integer of 0 to 2, and m represents any integer of 0 to 2. However, m + n ≦ 2.

A represents an oxygen atom, a sulfur atom, or a group represented by the formula: NQ.
Wherein: Q of N-Q represents a cyano group, an unsubstituted or C1~20 alkyl group having a substituent group, or the formula: a group represented by ^{OR 10.}

Examples of the unsubstituted or substituted C1-20 alkyl group for Q include the same groups as those exemplified for R ² above.
R ^{10 in the} formula: OR ¹⁰ represents a hydrogen atom, an unsubstituted or substituted C 1-10 alkyl group having a substituent.
The R ^10, examples of C1~10 alkyl groups C1~10 alkyl group having unsubstituted or substituted group, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl , S-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group and the like. Examples of the substituent include an unsubstituted or substituted phenyl group such as a phenyl group, a 4-methylphenyl group, and a 2-chlorophenyl group.
In the acaricide of the present invention, the compound (I) is represented by the following formula (Ia)

(Wherein R ^{1 to} R ⁵ , A, and n represent the same meaning as described above).

(2) Compound (I-1) of the present invention
A second aspect of the present invention is a novel urea compound represented by the formula (I-1) or a salt thereof (hereinafter referred to as “the present compound (I-1)”) of the compound (I). Yes.)
In formula (I-1), R ¹ , R ³ and R ⁴ represent the same meaning as described above.

R ²¹ represents an unsubstituted or substituted C1-20 alkyl group. Examples of the C1-20 alkyl group having an unsubstituted or substituted group include the same as those of the C2-20 alkyl group having an unsubstituted or substituted R ² .

R ⁶ and R ⁷ are each independently a hydrogen atom, an unsubstituted or substituted C 1-20 alkyl group, an unsubstituted or substituted C 2-20 alkenyl group, an unsubstituted or substituted C 2- A 20 alkynyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted C1-20 alkoxy group, or an unsubstituted or substituted C1-20 alkylthio group is represented.

R ⁶ and R ⁷ , unsubstituted or substituted C1-20 alkyl group, unsubstituted or substituted C2-20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted C1~20 alkoxy group having an aryl group, unsubstituted or substituted with a group, or, as is C1~20 alkylthio group having unsubstituted or substituted group, the same as those of the corresponding groups exemplified in R ² It is done.

R ⁶ and R ⁷ may be combined to form a 4- to 8-membered ring having no substituent or a substituent. Further, the 4- to 8-membered ring may contain a hetero atom in addition to the nitrogen atom bonded to the group represented by the formula: —N (R ⁴ ) —C (═O) —.

  The compound of the present invention may have an E-Z stereoisomer based on a carbon-nitrogen double bond or an optical isomer based on an asymmetric carbon atom. All bodies are included in the present invention.

(3) Manufacturing method Compound (I) can be manufactured by the manufacturing method shown below, for example.
(Manufacturing method 1)
Among the compounds (I), compounds represented by the following formulas (Ib) and (Ib ′) can be produced by the method shown below.

(In the formula, R ^{1 to} R ³ , R ⁶ , R ⁷ , and n represent the same meaning as described above, and A ′ represents an oxygen atom or a sulfur atom.)
That is, (i) the (thio) urea compound represented by the formula (Ib) by reacting the iso (thio) cyanate compound represented by the formula (1) with the amine compound represented by the formula (2). Can be obtained. (Ii) By reacting an amine compound represented by formula (3) with an iso (thio) cyanate compound represented by formula (2 ′), (thio) represented by formula (Ib ′) A urea compound can be obtained. These reactions can be carried out in the same manner as in known reaction methods in which iso (thio) cyanates and amines are reacted to obtain a (thio) urea compound.

(Manufacturing method 2)
Among the compounds (I), a compound represented by the following formula (Ic) can be produced, for example, by the method shown below.

(Wherein R ^{1 to} R ³ and n represent the same meaning as described above, L represents a leaving group such as a halogen atom, and R ^{5 ′} represents an unsubstituted or substituted C 1-20 alkyl group. .)
That is, an amine compound represented by formula (3) and (carboxylic acid represented by formula (4), acid halide represented by formula (5), or acid anhydride represented by formula (6)) To obtain a compound represented by the formula (Ic).

(Manufacturing method 3)
Moreover, the compound represented by the formula (Ie) can also be obtained by oxidizing the compound represented by the following formula (Id) using an oxidizing agent.

(In the formula, R ^{1 to} R ⁵ and A represent the same meaning as described above, and n ′ represents 1 or 2.)
The oxidizing agent to be used is not particularly limited, and examples thereof include m-chloroperbenzoic acid and peracetic acid.

(Manufacturing method 4)
As shown by the following formula, by reacting the compound represented by the formula (Id) with an oxidizing agent such as cyanamide and iodobenzene diacetate, in the formula (I), A = O, n = 0, m = 1 and X = N-CN (If) can be obtained (see Organic Letters, 2007, 9 (15), 2951, etc.).

(Wherein R ^{1 to} R ⁵ and A represent the same meaning as described above.)
(Manufacturing method 5)
As shown by the following formula, the compound represented by the formula (Id) is S-alkylated by a known method to obtain the compound represented by the formula (Ig), and then the compound represented by the formula (Ig). , Q′—NH ₂ [Q ′ represents a group represented by OR ¹⁰ (where R ¹⁰ represents the same meaning as described above). In the formula (I), a compound (Ih) in which R ⁴ = H, A = NOR ¹⁰ , n = 0, and m = 0 can be obtained.

(In the formula, R ^{1 to} R ³ , R ⁵ and Q ′ represent the same meaning as described above, and R ¹¹ represents an alkyl group.)
(Manufacturing method 6)
As shown by the following formula, (S, S) -dialkyl-N-cyanodithioiminocarbonate (7) is allowed to act on the compound represented by the formula (3 ′) to represent the formula (Ii). A compound can be obtained. In addition, the formula (a ′)

In the formula (I), R ⁴ = H, A = NCN, n = 0, m = 0, and R ⁵ is represented by the formula (a ′).

A compound (Ij) that is an unsubstituted or substituted nitrogen-containing heterocyclic group represented by formula (I) can be obtained (below).

(In the formula, R ^{1 to} R ³ represent the same meaning as described above, and R ¹² represents an alkyl group.)
The salt of compound (I) is not particularly limited as long as it is acceptable in agriculture and horticulture. Examples thereof include salts of inorganic acids such as hydrochlorides, nitrates, sulfates and phosphates of compounds (I); salts of organic acids such as acetic acid, propionic acid and lactic acid.
The salt of compound (I) can be produced, for example, by reacting compound (I) with an inorganic acid or an organic acid.

In any reaction, after completion of the reaction, the desired product can be isolated by carrying out usual post-treatment operations in organic synthetic chemistry and separation and purification.
The structure of the target product can be identified and confirmed by known analytical means such as elemental analysis, NMR spectrum, IR spectrum, and mass spectrum.

(4) Acaricide The acaricide of the present invention contains as an active ingredient at least one of the compound (I) obtained as described above and a salt thereof (hereinafter referred to as “compound (I) etc.”). .

  The amount of the active ingredient in the acaricide of the present invention is not particularly limited, but is preferably 0.01 to 90% by weight, particularly preferably 0.05 to 85% by weight.

Compound (I) and the like have excellent killing, larvicidal, larvicidal and ovicidal action against various mites. The acaricide of the present invention containing the compound (I) or the like as an active ingredient is used as an agro-horticultural acaricide for controlling spider mites parasitizing agricultural or horticultural crops or as a sanitary pest for controlling ticks. It can be used as an acaricide.
The acaricide of the present invention has an excellent acaricidal effect on mites parasitic on agricultural and horticultural crops of acaricide-resistant strains.
Further, the acaricide of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.

  Examples of mites to be controlled by the acaricide of the present invention include, for example, urticae, spider mites, kanzawa spider mites, citrus spider mites, apple spider mites, citrus spider mites, apple rustic mites, tea dust mites, brevipalpas spp. Examples include ticks and mites.

  When the acaricide of the present invention is used as an agricultural and horticultural acaricide, one or more compounds (I) and the like can be used as they are without adding other components. Further, various additives, solid carrier, liquid carrier, gaseous carrier, etc. are further mixed with compound (I) or the like, or compound (I) or the like is impregnated into a base such as a porous ceramic plate or nonwoven fabric. If necessary, a surfactant and other auxiliary agents can be added to prepare a formulation. Such preparations include wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, wettable granules, flowables, aerosols, fumes, heat transpiration agents, smokers, poison baits, microcapsules and the like. It is done.

  Additives and carriers used are vegetable powders such as soybean grains and wheat flour for the purpose of solid dosage forms; mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay Organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate. For liquid dosage forms, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. Can be used as a solvent. For the purpose of a propellant, gaseous carriers such as butane gas, LPG, dimethyl ether and carbon dioxide can be used.

  Surfactants are added to take a uniform and stable form. The surfactant to be used is not particularly limited. For example, nonionic surfactants such as alkyl ethers added with polyoxyethylene, higher fatty acid esters added with polyoxyethylene, sorbitan higher fatty acid esters added with polyoxyethylene, and tristyryl phenyl ether added with polyoxyethylene , Sulfates of alkylphenyl ethers with addition of polyoxyethylene, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkyl naphthalene sulfonates, copolymers of isobutylene-maleic anhydride Etc.

  The acaricide of the present invention is diluted to a predetermined concentration with water when the formulation is a wettable powder, emulsion, suspension, flowable, aqueous solvent, granular wettable powder, etc. Thus, it can be used as a solution, suspension or emulsion. Moreover, when it is a powder agent and a granule, it can be used by the method of spraying to a plant or soil as it is.

  When the acaricide of the present invention is used as an acaricide for epidemics, the preparation form is an emulsion, a wettable powder, and a flowable agent, and these preparations are diluted with water to a predetermined concentration and applied. be able to. Moreover, when the formulation form is an oil agent, an aerosol, an aerosol, a poison bait, an anti-tick sheet, etc., it can be applied as it is.

  When used as a pest control agent for controlling animal ectoparasites in domestic animals such as cattle and pigs, and pets such as dogs and cats, the compound of the present invention is formulated and used by a method known in veterinary medicine. be able to. For example, for the purpose of systemic control, tablets, capsules, immersion liquid, feed mixing, suppositories, injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) etc. In the case of non-systemic control, an oily or aqueous solution is administered by spraying, pouring-on, dropping-on, etc. The method of mounting | wearing the thing which shape | molded the resin formulation in appropriate shapes, such as a collar and an ear tag, is mentioned. In this case, the compound of the present invention can be usually used at a ratio of 0.01 to 1000 mg per 1 kg of the host animal.

  Needless to say, the acaricide of the present invention alone is sufficiently effective, but other acaricides, fungicides, insecticides / acaricides, herbicides, plant regulators, synergists, fertilizers, soils It can also be used in combination or in combination with one or more improvers, animal feeds, other hygiene pesticides and the like.

  If necessary, mix with other types of herbicides, various insecticides, acaricides, nematicides, fungicides, plant growth regulators, synergists, fertilizers, soil conditioners, etc. It may be applied.

  In particular, when mixed with other pesticides or plant hormones, the cost can be reduced by reducing the amount of applied medicine, the insecticidal spectrum can be expanded by the synergistic action of the mixed drugs, and higher pest control effects can be expected. At this time, a combination with a plurality of known agricultural chemicals is also possible.

  Examples of the type of agricultural chemical used in combination with the compound of the present invention include compounds described in the 2007 Crop Protection Handbook 2007 edition. Specific examples of common names are as follows, but the general names are not necessarily limited to these.

As an active ingredient compound (generic name; including some applications) of fungicides, for example, anilinopyrimidine compounds such as mepanipyrim, pyrimethanil, cyprodinil, etc .;
Pyridinamine compounds such as fluazinam;
Triadimefon, tritermizole, triflumizole, etaconazole, propiconazole, penconazole, luconilole, flusilazole, flusilazole, penconazole, flusilazole. cyproconazole, tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, epoxiconazole ), Tetraconazole, oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol (triadimenol), triadimenol (triadimenol) difenoconazole), fluquinconazole, fenbuconazole, bromconazole, dinicozole, tricyclazole, tricyclazole meconazole), pefurazoate (pefurazoate), ipconazole (ipconazole), imibenconazole (imibenconazole), azole compounds such as imazalil (imazalil);

Quinoxaline-based compounds such as quinomethionate;
Manneb, zineb, manzeb, polycarbamate, metyram, propineb, febam, nabam, th , Dithiocarbamate compounds such as ziram;

Organochlorine compounds such as fthalide, chlorothalonil, quintozen;
Imidol compounds such as benomyl, thiophanate-methyl, carbendazim, thiabendazole, fuberiazole, cyazofamide, etc .;
Cyanoacetamide-based compounds such as cymoxanil;
Metalaxyl (metalaxyl), Metalaxyl-M (metalaxyl-M), Mefenoxam (mefenoxam), Oxadixyl (offalace), Benalaxyl (fur), Benalaxyl-M (x) Phenylamide compounds such as (cyprofuram);
Sulfenic acid-based compounds such as dichlorfluanid;
Nitrophenyl compounds such as dinocap;
Copper-based compounds such as cupric hydroxide and organic copper;
Isoxazole-based compounds such as hymexazole;
Organophosphorus compounds such as fosetyl aluminum (fosetyl-Al), turkey phosmethyl (tolcofos-methyl), S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate ;

N-halogenoalkyl compounds such as captan, captafol, folpet, etc .;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
Benzanilide compounds such as flutolanil, mepronil, zoxamide, thiadinyl;
Carboxin, oxycarboxin, thifluzamide, penthiopyrad, boscalid, fluopicolide, fluopyramen, fluopyram

Piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox;
Carbinol compounds such as fenarimol, flutriafol;
Piperidine-based compounds such as fenpropidine;
Morpholine compounds such as fenpropimorph and tridemorph;
Organotin compounds such as fentin hydroxide and fentin acetate;
Urea compounds such as pencycuron;
Synamic acid compounds such as dimethomorph, flumorph and flumetober;
Phenyl carbamate compounds such as dietofencarb;

Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, cresoxime-methyl, methminophen, methminostrobin, trifloxystrobin, picoxystrobin, picoxyzine Strobilurin-based compounds such as dimoxystrobin, pyraclostrobin, fluoxastrobin, etc .;
Oxazolidinone compounds such as famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Silylamide compounds such as silthiopham;
Amino acid amide carbamate compounds such as iprovalicalcarb, benchavaricarb-isopropyl;

Imidazolidine compounds such as fenamidone;
Hydroxyanilide compounds such as fenhexamide;
Benzenesulfonamide-based compounds such as flusulfamide;
Oxime ether compounds such as cyflufenamide;
Phenoxyamide compounds such as phenoxanil;
Antibiotics such as validamycin, kasugamycin, polyoxins;
Guanidine compounds such as iminoctadin;

  Other compounds include trifluanid, isoprothiolane, pyroquilon, diclomezine, quinoxyspirin, propamocarbine hydrochloride. Dazomet, metham-sodium, nicobifen, metraphenone, UBF-307, diclocymet, proquinazide, amisulbrom amisulbrom, pyribencarb, mandipropamid, 5-chlor-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluor-phenyl)-[1,2, 4] triazolo [1,5-a] pyrimidin, OK-5203, and the like.

  As an active ingredient compound (generic name; including some pending applications) of insecticides, acaricides, nematicides or soil pesticides that are pesticides in the spray solution, for example, profenofos, Dichlorvos, fenamifos, fenitrothion, EPN, diazinon, chlorpyrifos-methyl, acephate, prothiophos, prothiophos, prothiophos Cadusafos, disulfoton, chlorpyrifos Demeton-S-methyl, dimethoate, methamidophos, isoxathion, isofenphos, etionfos, etrimfos, quinalphos, quinalphos Phosphite (dimethylvinphos), sulprofos, thiomethon, bamidithion, pyraclofos, pyridafenthion, pyrimiphosmethylphosphiphophyme phosphiphysophys Phosalone, formothion, malathion, tetrachlorvinphos, chlorfenvinphos, cyanophos, trichlorthone, methithion, methithion , ESP, azinephos-methyl, fenthion, heptenophos, methoxychlor, parathion, monocrotophos, imiciafos, imiparafos Organophosphate compounds such as thione-methyl, terbufos, phosphamidon, phosmet, and phosphate;

Carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, thiomil, ethiophencarb Carbosulfan, benfuracarb, bendiocarb, furatiocarb, isoprocarb, metocarb, xylylcarb, xylylcarb, xylylcarb Fenothiocarb) carbamate compounds such as;

Nereistoxin derivatives such as cartap, thiocyclam, bensultap, sodium thiosultap-sodium;
Organochlorine compounds such as dicophor, tetradiphon, endosulfan, dienochlor, dieldrin;
Organometallic compounds such as fenbutatin oxide and cyhexatin;

Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprothrin , Bifenthrin, flucitrinate, fluvalinate, cycloprotorin, lambda-cyhalothrin, pyrethrins, esphethrins. Valenate (esfenvalerate), tetramethrin (resmethrin), protrifenbute (zetriperperthrin), acrinathrin (alpha) permethrin, alpha cyperthrin (alpha) permethrin , Gamma-cyhalothrin, theta-permethrin, tau-fluvalinate, tralomethrin, profluthrin, beta-cypermethrin cypermethrin), beta-cyfluthrin (beta-cyfluthrin), metofluthrin (metofluthrin), pyrethroid compounds such as phenothrin (phenothrin);

Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, flufenuron, flufluonzuron, flufluonzuron, flufluonzuron ), Bistrifluron, benzoylurea compounds such as fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, phenoxycarb, diofenolan;

Pyridazinone compounds such as pyridaben;
Fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, acetoprole, pyrafluprol
Imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, crothianidin, intefuridin, intefuridin
Hydrazine compounds such as tebufenozide, methoxyphenozide, chromafenozide, halofenozide; and the like;

Other compounds include flonicamid, buprofezin, hexythiazox, imitraz, chlordiform, siroflumine, ziramifene, zilaziofene, zilaziofene, zilaziofene, Chlorfenapyr, indoxacarb, acequinocyl, etoxazole, cyromazine, 1,3-dichloropropene, 1,3-dichloropropene Dithiophenon, benclothiaz, flufenrim, pyridalyl, spirodiclofen, bifenatroet, spiromestrofen, spiromethifen , Clofentezine, fluacrylpyrim, metaflumizone, flubenamide, cyflumethofen, chloranthranylpyrrole (chlorantra) iliprole, cienopyrafen, pyrifluquinazone, phenazaquin, amidoflumet, etholydine, chlorobenzoate (chlorophenoate) and compounds such as ryanodine).

Furthermore, Bacillus thuringienses aizawai, Bacillus thuringienses kurstaki, Bacillus thuringienses israelensis, Bacillus thuringienses japonensis, Bacillus thuringienses tenebrionis, crystal protein toxin Bacillus Thuringienses generated, entomopathogenic viral agents, entomopathogenic fungus agent, nematode pathogenic fungi agent Microbial pesticides such as avermectin, avermectin, emamectin-benzoate, milbemectin, spinosad, ivermec Down (ivermectin), lepimectin (lepimectin), antibiotics or semisynthetic antibiotics such as and the like;
Natural products such as azadirachtin, rotenone, etc .;
Synergists such as piperonyl butoxide;
Examples include repellents such as deet.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by the following examples. The compound numbers correspond to the compound numbers in Tables 2 to 4 below.

Example 1
Synthesis of 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carboxamide

  0.5 g of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) aniline was dissolved in 15 ml of ethyl acetate, 0.25 g of bis (trichloromethyl) carbonate was added, and the mixture was heated to reflux for 3 hours. . The obtained reaction mixture was concentrated under reduced pressure to obtain 0.55 g of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) isocyanate. 15 ml of benzene is added to 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) isocyanate, and 0.41 g of 3,3,4,4-tetrafluoropyrrolidine hydrochloride and N are added under water cooling. -0.54g of ethyl diisopropylamine was added, and it stirred at room temperature for 6 hours. 1N Hydrochloric acid was added to the reaction mixture under water cooling to separate it, and the organic layer was separated. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was washed with a mixed solvent of diethyl ether and n-hexane to give 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoro). Ethylthio) phenyl] pyrrolidine-1-carboxamide (Compound No. 6) 0.51 g was obtained as white crystals. (Melting point 135-137 ° C)

(Example 2)
Synthesis of 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] pyrrolidine-1-carboxamide

  0.30 g of 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carboxamide was added to 20 ml of chloroform. This was dissolved, 0.22 g of 3-chloroperbenzoic acid was added under ice-water cooling, and the mixture was stirred at room temperature for 3 hours. An aqueous sodium hydrogen carbonate solution was added to the reaction mixture for liquid separation, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate), and 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl- 0.22 g of 5- (2,2,2-trifluoroethylsulfinyl) phenyl] pyrrolidine-1-carboxamide (Compound No. 7) was obtained as white crystals. (Melting point 61-63 ° C)

(Example 3)
Synthesis of 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -N-methylpyrrolidine-1-carboxamide

  0.24 g of 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carboxamide was added to N, N -It melt | dissolved in 10 ml of dimethylformamide, 30 mg of sodium hydrides were added under ice water cooling, and it stirred at room temperature for 10 minutes. Furthermore, 0.16 g of methyl iodide was added under ice water cooling, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate) to obtain 3,3,4,4-tetrafluoro-N- [2-fluoro-4. 0.17 g of -methyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] -N-methylpyrrolidine-1-carboxamide (Compound No. 9) was obtained as white crystals. (Melting point 91-93 ° C)

Example 4
Synthesis of N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] cyclopropanecarboxamide

  Dissolve 0.36 g of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) aniline in 5 ml of dichloromethane, add 0.17 g of cyclopropanecarbonyl chloride and 0.18 g of triethylamine, and stir for 1 hour. did. The obtained reaction mixture was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate) and N- [2-fluoro-4-methyl-5- (2,2,2-trifluoro). Ethylthio) phenyl] cyclopropanecarboxamide (Compound No. 63) (0.46 g) was obtained as white crystals. (Melting point 110-112 ° C)

(Example 5)
S- [4-Fluoro-2-methyl-5- (3,3,4,4-tetrafluoropyrrolidine-1-carbonylamino) phenyl] -S- (2,2,2-trifluoroethyl) -N- Synthesis of cyanosulfilimine

  0.40 g of 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carboxamide was added to 5 ml of acetonitrile. After dissolution, 0.05 g of cyanamide and 0.42 g of iodobenzene diacetate were added and stirred for 3 hours. The obtained reaction mixture was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate), and S- [4-fluoro-2-methyl-5- (3,3,4,4- 0.14 g of tetrafluoropyrrolidine-1-carbonylamino) phenyl] -S- (2,2,2-trifluoroethyl) -N-cyanosulfilimine (Compound No. 159) was obtained as white crystals. (Melting point 98-102 ° C)

(Example 6)
Synthesis of 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carbothioamide

  2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) aniline 1.0 g of triethylamine was added to a solution of 1.20 g in 10 ml of ethyl acetate, and then 0.57 g of thiophosgene. And the whole was stirred for 15 minutes. To the obtained reaction mixture, 3,4 g of 3,3,4,4-tetrafluoropyrrolidine hydrochloride and 1.9 g of diisopropylethylamine were added and stirred at 40 ° C. for 2 hours. After the reaction mixture is concentrated, the concentrate is produced by medium pressure column chromatography (developing solvent: a mixed solvent of n-hexane and ethyl acetate), and 3,3,4,4-tetrafluoro-N- [2- 1.69 g of fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carbothioamide (Compound No. 238) was obtained. Melting point 91-94 ° C

(Example 7)
3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -N'-hydroxypyrrolidine-1-carboxyimidamide Synthesis of (1) methyl 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carbimide Synthesis of thioate

  3,0.84 g of 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carbothioamide in 5 ml of acetonitrile The solution was dissolved in 0.35 g of potassium carbonate and 0.33 g of methyl iodide, and stirred at room temperature for one day. After concentrating the obtained reaction mixture, the concentrate was purified by medium pressure column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate) to obtain methyl 3,3,4,4-tetrafluoro-N. 0.73 g of-[2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carbimidothioate was obtained as an oil.

(2) 3,3,4,4-Tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -N′-hydroxypyrrolidine-1- Synthesis of carboxyimidamide

  Methyl 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1- obtained in (1) Carbimide thioate (0.22 g) was dissolved in ethanol (2.5 ml), hydroxylamine hydrochloride (52 mg) and pyridine (68 mg) were added, and the mixture was stirred at 60 ° C. for 7 hours. The obtained reaction mixture was concentrated, and the concentrate was purified by medium pressure column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate) to obtain (E) -3,3,4,4-tetra. 0.04 g of fluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -N′-hydroxypyrrolidine-1-carboxyimidamide (Compound No. 248, Amorphous) and (Z) -3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -N ′ 0.08 g of -hydroxypyrrolidine-1-carboxyimidamide (Compound No. 249, melting point 80-81 ° C.) was obtained.

(Example 8)
3,3,4,4-tetrafluoro-N- (2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -N'-methoxypyrrolidine-1-carboxyimidamide Synthesis of

  Methyl 3,3,4,4-tetrafluoro-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carbimidothioate 0.22 g Was dissolved in 1.5 ml of ethanol, 63 mg of methoxyamine hydrochloride and 120 mg of pyridine were added, and the mixture was stirred at 60 ° C. for 7 hours. After concentrating the reaction mixture, the concentrate is purified by medium pressure column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate), whereby 3,3,4,4-tetrafluoro-N- [2 0.11 g of -fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -N′-methoxypyrrolidine-1-carboxyimidamide (Compound No. 260, amorphous) was obtained.

Example 9
Synthesis of methyl N′-cyano-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] carbamidothioate

  2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) aniline 1.20 g is dissolved in 7.5 ml of pyridine, and (S, S) -dimethyl-N-cyanodithioiminocarbonate is dissolved. After 1.46 g was added, the mixture was heated to reflux for one day. Ethyl acetate and dilute hydrochloric acid were added to the reaction mixture and the layers were separated, and the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by medium pressure column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate), and N′-cyano-N- (2-fluoro-4-methyl-5- (2, 0.92 g of 2,2-trifluoroethylthio) phenyl) carbamidothioate (Compound No. 251, melting point 134-137 ° C.) was obtained.

(Example 10)
Synthesis of N′-cyano-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carboxyimidamide

  Methyl N′-cyano-N- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] carbamidothioate (0.34 g) was dissolved in 3 ml of acetonitrile, and 0.17 g of pyrrolidine was dissolved. And stirred at 60 ° C. for 10 hours. After concentrating the obtained reaction mixture, the concentrate was purified by medium pressure column chromatography (developing solvent: mixed solvent of n-hexane and ethyl acetate), and N′-cyano-N- [2-fluoro- 0.27 g of 4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] pyrrolidine-1-carboxyimidamide (Compound No. 252, melting point 132-133 ° C.) was obtained.

Table 2 shows the structural formulas and physical constants of the compounds used as active ingredients of the acaricide of the present invention obtained in the same manner as in Examples 1 to 10, including the compounds obtained in Examples 1 to 10. To Table 4.
In the table, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, cPr is a cyclopropyl group, cPen is a cyclopentyl group, Ac is an acetyl group, Bu is a butyl group, and Bn is a benzyl group. Respectively. In the table, * represents a bonding position, and [] represents a melting point (° C.).

In the above table, * 1: Compound No. 248 is E-form, * 2: Compound No. 249 is Z-form.
Next, ¹ H-NMR spectrum data is shown. In the following, “s” represents a singlet, “d” represents a doublet, “t” represents a triplet, “br” represents a broad singlet, “q” represents a quartet, and “m” represents a multiplet. Moreover, TMS was used as an internal standard.

(Compound No. 12)
¹ H-NMR (CDCl ₃ , δ ppm) 0.90 (t, 3H), 1.20-1.41 (m, 2H), 1.28 (s, 3H), 1.30 (s, 3H), 1.46-1.82 (m, 2H), 1.89-2.18 (m, 4H), 2.47 (s, 3H), 2.88 (br, 1H), 3.30 (q, 2H), 3.55 (m, 1H), 4.84 (br, 1H), 7.02 (d, 1H), 7.31 (d, 1H)

(Compound No. 13)
¹ H-NMR (CDCl ₃ , δ ppm) 1.89-2.21 (m, 4H), 2.51 (s, 3H), 2.72 (br, 1H), 3.32 (q, 2H), 3.34 (br, 1H), 4.95 (br, 1H), 7.111 (d, 1H), 7.36 (d, 1H), 9.11 (s, 1H)

(Compound No. 30)
¹ H-NMR (CDCl ₃ , δ ppm) 2.07 (m, 4H), 2.42 (s, 3H), 3.38 (q, 2H), 3.64 (t, 4H), 6.54 ( s, 1H), 6.95 (d, 1H), 8.25 (d, 1H)

(Compound No. 33)
¹ H-NMR (CDCl ₃ , δ ppm) 2.31 (m, 2H), 2.39 (s, 3H), 3.39 (q, 2H), 4.11 (t, 4H), 6.04 ( s, 1H), 6.91 (d, 1H), 8.37 (d, 1H)

(Compound No. 47)
¹ H-NMR (CDCl ₃ , δ ppm) 1.33 (t, 3H), 2.41 (s, 3H), 3.38 (q, 2H), 4.26 (q, 2H), 6.73 ( s, 1H), 6.94 (d, 1H), 8.27 (d, 1H)

(Compound No. 48)
¹ H-NMR (CDCl ₃ , δ ppm) 3.36 (q, 2H), 3.68 (q, 2H), 7.97 (s, 1H), 8.75 (s, 1H), 9.45 ( s, 1H)

(Compound No. 51)
¹ H-NMR (CDCl ₃ , δ ppm) 2.18 (m, 4H), 2.30 (s, 3H), 3.28 (q, 2H), 3.33 (m, 1H), 3.76 ( m, 1H), 4.71 (m, 1H), 7.42 (s, 1H), 7.82 (s, 1H), 8.38 (s, 1H)

(Compound No. 52)
¹ H-NMR (CDCl ₃ , δ ppm) 2.41 (s, 3H), 2.48 (m, 2H), 3.39 (q, 2H), 3.73 (t, 2H), 3.85 ( t, 2H), 6.27 (s, 1H), 6.94 (d, 1H), 8.32 (d, 1H)

(Compound No. 53)
¹ H-NMR (CDCl ₃ , δ ppm) 1.62 (m, 2H), 1.89 (m, 1H), 2.12 (m, 1H), 2.35 (m, 1H), 2.41 ( s, 3H), 2.88 (m, 1H), 2.99 (m, 1H), 3.38 (q, 2H), 3.91 (m, 1H), 4.36 (m, 1H), 6.53 (s, 1H), 6.94 (d, 1H), 8.25 (d, 1H)

(Compound No. 54)
¹ H-NMR (CDCl ₃ , δ ppm) 1.62 (m, 2H), 1.97 (m, 2H), 2.27 (m, 1H), 2.41 (s, 3H), 2.91 ( m, 2H), 3.38 (q, 2H), 4.17 (m, 2H), 6.51 (s, 1H), 6.94 (d, 1H), 8.27 (d, 1H)

(Compound No. 56)
¹ H-NMR (CDCl ₃ , δ ppm) 1.98 (m, 2H), 2.03 (m, 1H), 2.34 (s, 3H), 2.47 (m, 1H), 3.35 ( q, 2H), 3.79 (m, 2H), 4.88 (m, 1H), 6.28 (s, H), 6.78 (d, 1H), 7.35 (m, 5H), 8.34 (d, 1H)

(Compound No. 58)
¹ H-NMR (CDCl ₃ , δ ppm) 2.41 (s, 3H), 2.69 (m, 4H), 3.38 (q, 2H), 3.81 (m, 4H), 6.48 ( s, 1H), 6.94 (d, 1H), 8.25 (d, 1H)

(Compound No. 59)
¹ H-NMR (CDCl ₃ , δ ppm) 1.60 (d, 3H), 2.41 (s, 3H), 3.10 (m, 1H), 3.28 (m, 1H), 3.39 ( q, 2H), 3.74 (m, 1H), 3.95 (m, 1H), 5.35 (q, 1H), 6.38 (s, 1H), 6.94 (d, 1H), 8.33 (d, 1H)

(Compound No. 61)
¹ H-NMR (CDCl ₃ , δ ppm) 1.21 (d, 6H), 2.41 (s, 3H), 3.38 (q, 2H), 3.44 (t, 2H), 3.94 ( t, 2H), 4.24 (m, 1H), 6.97 (d, 1H), 8.42 (d, 1H), 10.67 (s, 1H)

(Compound No. 236)
¹ H-NMR (CDCl ₃ , δ ppm) 2.40 (s, 3H), 3.41 (s, 3H), 6.94 (d, 1H), 7.19 (d, 1H), 7.32 ( t, 1H), 7.45-7.53 (m, 2H), 7.59 (d, 1H)

(Compound No. 243)
¹ H-NMR (CDCl ₃ , δ ppm) 1.48 (s, 9H), 1.94 (m, 3H), 2.42 (s, 3H), 2.51 (m, 1H), 3.32 ( q, 2H), 3.43 (m, 2H), 4.48 (m, 1H), 6.95 (d, 1H), 8.53 (d, 1H). 9.50 (s, 1H)

(Compound No. 244)
¹ H-NMR (CDCl ₃ , δ ppm) 2.08-2.21 (m, 3H), 2.41 (s, 3H), 2.55 (m, 1H), 3.36 (q, 1H), 3.49 (m, 2H), 5.02 (m, 1H), 6.94 (d, 1H), 8.10 (d, 1H), 9.17 (s, 1H), 11.04 (s , 1H)

(Compound No. 247)
¹ H-NMR (CDCl ₃ , δ ppm) 2.45 (s, 3H), 3.19 (q, 2H), 7.02 (d, 1H), 7.04-7.09 (m, 2H), 7.34 (d, 1H), 7.39-7.47 (m, 2H)

(Compound No. 248)
¹ H-NMR (CDCl ₃ , δ ppm) 2.41 (s, 3H), 3.31 (q, 2H), 3.92-4.02 (m, 4H), 6.95 (d, 1H), 7.11 (d, 1H)

(Compound No. 254)
¹ H-NMR (CDCl ₃ , δ ppm) 1.86-2.23 (m, 4H), 2.43 (s, 3H), 3.33 (q, 2H), 3.63 (m, 1H), 4.03 (m, 1H), 5.06 (m, 1H), 6.99 (d, 1H), 7.25 (d, 1H)

(Compound No. 258)
¹ H-NMR (CDCl ₃ , δ ppm) 1.32 (m, 1H), 1.66 (m, 1H), 2.25-2.30 (m, 2H), 2.45 (s, 3H), 3.40 (q, 2H), 5.95 (m, 1H), 7.04 (d, 1H), 8.72 (d, 1H), 8.78 (s, 1H)

(Compound No. 260)
¹ H-NMR (CDCl ₃ , δ ppm) 2.42 (s, 3H), 3.31 (q, 2H), 3.55 to 3.65 (m, 4H), 3.89 (s, 3H), 6.41 (s, 1H), 6.97 (d, 1H), 7.41 (d, 1H)

(Compound No. 261)
¹ H-NMR (CDCl ₃ , δ ppm) 1.27 (s, 9H), 2.41 (s, 3H), 3.31 (q, 2H), 3.55 to 3.65 (m, 4H), 6.45 (s, 1H), 6.96 (d, 1H), 7.44 (d, 1H)

(Compound No. 262)
¹ H-NMR (CDCl ₃ , δ ppm) 2.41 (s, 3H), 3.29 (q, 2H), 3.55 to 3.65 (m, 4H), 4.94 (s, 2H), 6.42 (s, 1H), 6.95 (d, 1H), 7.27-7.37 (m, 6H)

(Compound No. 263)
¹ H-NMR (CDCl ₃ , δ ppm) 2.42 (s, 3H), 3.30 (q, 2H), 3.55 to 3.65 (m, 4H), 5.04 (s, 2H), 6.31 (s, 1H), 6.98 (d, 1H), 7.31 (d, 1H)

  Next, formulation examples of acaricides containing these compounds as active ingredients are shown. However, the additives and addition ratios are not limited to these examples, and can be varied in a wide range. is there. Moreover, the part in a formulation Example shows a weight part.

Formulation Example 1 Wetting agent Compound (I) 40 parts Clay 48 parts Dioctyl sulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts or more are uniformly mixed and finely pulverized to hydrate 40% active ingredient Get the agent.

Formulation Example 2 Emulsion Compound (I) 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts The above components are mixed and dissolved to obtain an emulsion containing 10% active ingredient.

Formulation Example 3 Powder Compound (I) 10 parts Clay 90 parts The above is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.

Formulation Example 4 Granules Compound (I) 5 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Potassium phosphate 1 part The above is pulverized and mixed well, and water is added and kneaded well. Dry to obtain granules with 5% active ingredient.

Formulation Example 5 Suspending agent Compound (I) 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts Wet mill until the following content is obtained to obtain a 10% active ingredient suspension.

Formulation Example 6 Granule wettable compound Compound (I) 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Ligninsulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt
After mixing 5 parts or more uniformly and finely pulverizing, add an appropriate amount of water and knead to make clay. The clay-like product is granulated and then dried to obtain a wettable powder containing 40% of the active ingredient.

Test examples of the obtained acaricide of the present invention are shown below.
(Test Example 1) Efficacy against the spider mite On the first true leaf 7 to 10 days after germination of the green beans seeded in a three-size pot, inoculate 17 female adult spider mite that are resistant to organophosphates and then carry out the formulation. The wettable powder obtained according to the formulation shown in Example 1 was sprayed with a chemical diluted with water so that the compound concentration was 125 ppm. It was placed in a thermostatic chamber at a temperature of 25 ° C. and a humidity of 65%, and the rate of killing insects was examined after 3 days. The test is duplicated. As a result, the following compounds showed a miticide rate of 100%.

Compound numbers: 1, 3, 4, 6, 7, 9, 10, 11, 13, 29, 30, 35, 36, 39, 40, 42, 43, 52, 53, 54, 56, 57, 59, 64 , 65, 238, 239, 240, 247, 248, 249, 250, 257, 258, 263
The miticide rate of chlordiform used as a control was 40%.

(Test Example 2) Efficacy against Haemaphysalis longicornis A 20 mL glass vial was thoroughly washed with acetone by the day before the test and used for the test.
The test compound was dissolved in acetone at 4000 ppm, and a diluted solution having a common ratio of 10 was further prepared with acetone.
0.118 mL of an acetone solution was added to the vial, and the vial was rotated while blowing with a dryer to volatilize acetone to form a thin film of the compound (when using a 400 ppm solution, the concentration was 1 μg / cm ² ).

In this, young ticks (15-40 heads / vial) were inoculated, the lid was quickly closed, and the number of test individuals was counted after the movement of ticks settled down. At this time, unhealthy individuals were excluded.
Thereafter, the sample was left in an observation room (25 ° C., in the dark) for 5 days, and a life-and-death determination was performed over time to calculate an insecticidal rate. As a result, the following compounds showed an insecticidal rate of 90% or more.
Compound numbers: 3, 4, 6, 10

Claims (2)

Formula (I)

[Wherein, R ¹ represents a C1-20 alkyl group or a C1-20 haloalkyl group.
R ² is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an unsubstituted or substituted amino group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C2 20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted aryl group, unsubstituted or substituted C1-20 acyl group, unsubstituted or substituted C1-20 A thioacyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C2-20 alkenyloxy group, an unsubstituted or substituted C2-20 alkynyloxy group, an unsubstituted or substituted group Aryloxy group, unsubstituted or substituted heteroyloxy group, unsubstituted Or a substituted C1-20 alkylthio group, an unsubstituted or substituted C2-20 alkenylthio group, an unsubstituted or substituted C2-20 alkynylthio group, an unsubstituted or substituted arylthio group, Unsubstituted or substituted heteroylthio group, unsubstituted or substituted C1-20 alkylsulfinyl group, unsubstituted or substituted arylsulfinyl group, unsubstituted or substituted C1-20 alkylsulfonyl group, none A substituted or substituted arylsulfonyl group or an unsubstituted or substituted heterocyclic group is represented.
R ³ represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a mercapto group, an unsubstituted or substituted amino group, an unsubstituted or substituted C 1-20 alkyl group, an unsubstituted or substituted C 2- 20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted aryl group, unsubstituted or substituted C1-20 acyl group, unsubstituted or substituted C1-20 A thioacyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C2-20 alkenyloxy group, an unsubstituted or substituted C2-20 alkynyloxy group, an unsubstituted or substituted group Aryloxy group, unsubstituted or substituted heteroyloxy group, unsubstituted Or a substituted C1-20 alkylthio group, an unsubstituted or substituted C2-20 alkenylthio group, an unsubstituted or substituted C2-20 alkynylthio group, an unsubstituted or substituted arylthio group, Unsubstituted or substituted heteroylthio group, unsubstituted or substituted C1-20 alkylsulfinyl group, unsubstituted or substituted arylsulfinyl group, unsubstituted or substituted C1-20 alkylsulfonyl group, none A substituted or substituted arylsulfonyl group or an unsubstituted or substituted heterocyclic group is represented.
R ⁴ is a hydrogen atom, a cyano group, a formyl group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C1-20 acyl group, or an unsubstituted or substituted phenyl group Represents.
R ⁵ represents an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted amino group, the formula (a)

An unsubstituted or substituted nitrogen-containing heterocyclic group represented by formula (b)

(In the formula, R ⁸ and R ⁹ are each independently an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C3-6 cycloalkyl group, a C2-6 alkenyl group, an unsubstituted group. Or a substituted phenyl group, or an unsubstituted or substituted heterocyclic group, or R ⁸ and R ⁹ are bonded together to form a nitrogen atom, an oxygen atom, or a sulfur atom; A 4- to 8-membered hetero ring which may contain 4), a pyrrolidin-2-yl group having an unsubstituted or substituted group, a phenyl group having an unsubstituted or substituted group, An unsubstituted or substituted C3-8 cycloalkyl group or an unsubstituted or substituted C1-20 alkylthio group is represented.
X represents a group represented by the formula: N—CN, or a group represented by the formula: N—OR ′ (R ′ represents a hydrogen atom or an unsubstituted or substituted C1-20 alkyl group). Represent,
n represents any integer of 0 to 2, and m represents any integer of 0 to 2. However, m + n ≦ 2.
A represents an oxygen atom, a sulfur atom, or a group represented by the formula: NQ (Q is a cyano group, an unsubstituted or substituted C1-20 alkyl group, or a formula: OR ¹⁰ ; R ¹⁰ Represents a hydrogen atom, an unsubstituted or substituted C1-10 alkyl group having a substituent. ]
A miticide that contains at least one of the compounds represented by the above or a salt thereof as an active ingredient. Formula (I-1)

(In the formula, R ¹ represents a C1-20 alkyl group or a C1-20 haloalkyl group.
R ²¹ represents an unsubstituted or substituted C1-20 alkyl group.
R ³ represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a mercapto group, an unsubstituted or substituted amino group, an unsubstituted or substituted C 1-20 alkyl group, an unsubstituted or substituted C 2- 20 alkenyl group, unsubstituted or substituted C2-20 alkynyl group, unsubstituted or substituted aryl group, unsubstituted or substituted C1-20 acyl group, unsubstituted or substituted C1-20 A thioacyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C2-20 alkenyloxy group, an unsubstituted or substituted C2-20 alkynyloxy group, an unsubstituted or substituted group Aryloxy group, unsubstituted or substituted heteroyloxy group, unsubstituted Or a substituted C1-20 alkylthio group, an unsubstituted or substituted C2-20 alkenylthio group, an unsubstituted or substituted C2-20 alkynylthio group, an unsubstituted or substituted arylthio group, Unsubstituted or substituted heteroylthio group, unsubstituted or substituted C1-20 alkylsulfinyl group, unsubstituted or substituted arylsulfinyl group, unsubstituted or substituted C1-20 alkylsulfonyl group, none A substituted or substituted arylsulfonyl group or an unsubstituted or substituted heterocyclic group is represented.
R ⁴ is a hydrogen atom, a cyano group, a formyl group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C1-20 acyl group, or an unsubstituted or substituted phenyl group Represents.
R ⁶ and R ⁷ are each independently a hydrogen atom, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C2-20 alkenyl group, an unsubstituted or substituted C2-20. An alkynyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted C1-20 alkoxy group, or an unsubstituted or substituted C1-20 alkylthio group is represented. R ⁶ and R ⁷ may be combined to form a 4- to 8-membered ring having no substituent or a substituent. Further, the 4- to 8-membered ring may contain a hetero atom in addition to the nitrogen atom bonded to the group represented by the formula: —N (R ⁴ ) —C (═O) —. )
Or a salt thereof.