JP2008133273A - Nitrogen-containing heterocyclic compound and noxious organism-controlling agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nitrogen-containing heterocyclic compound or the like that can be commercially advantageously synthesized and can be an active ingredient of a noxious organism-controlling agent which achieves sure effects and can be used safely, and a noxious organism-controlling agent comprising the compound as an effective ingredient. <P>SOLUTION: The compound is one represented by formula (I) or a salt thereof. The noxious organism-controlling agent comprises the compound as an effective ingredient thereof. In the formula, W is an oxygen atom or a sulfur atom; X is CH, CH<SB>2</SB>, NH or the like; A<SB>1</SB>-A<SB>4</SB>are each independently a carbon atom or a nitrogen atom; Y is a methyl group or the like; n is an integer of 0-4; R<SB>1</SB>and R<SB>2</SB>are each independently a hydrogen atom, a pyridylmethyl group or the like; Z is an optionally substituted phenyl group or the like; and D is a haloalkyl group or the like. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel nitrogen-containing heterocyclic compound, a salt of this compound, and a pest control agent containing these compounds as active ingredients.

  Conventionally, many pesticides such as insecticides and acaricides have been used, but their efficacy is insufficient, their use is limited due to drug resistance problems, and phytotoxicity to plants. In many cases, it is not always a satisfactory control drug because it causes pollution and pollution, or is highly toxic to livestock fish. Therefore, there is a demand for the development of a drug that can be safely used with few such drawbacks.

  In relation to the present invention, Patent Document 1 describes the following isoxazoline-substituted compound having a skeleton similar to that of the compound of the present invention. However, this document does not describe the compound of the present invention.

(Wherein W ′ represents an oxygen atom or a sulfur atom, A ^a , A ^b and ^Ac each independently represent a carbon atom or a nitrogen atom, Y ′ represents a halogen atom or the like, and n ′ represents 0 Or R ¹ and R ^b each independently represents a hydrogen atom, a C1-12 alkyl group, or the like, R ^c represents a halogen atom or the like, and G ′ represents a phenyl group or the like.)

  Patent Document 2 describes the following compounds. However, in this document, the compound of the present invention is not described, and the use as a pest control agent is not described.

(In the formula, R ^d represents a carboxyl group, a represents an integer of 0 to 5, and R ^e and R ^f represent a C 1-10 alkyl group, etc.)
WO2005 / 085216 pamphlet WO2005 / 105810 pamphlet

  The present invention relates to a novel nitrogen-containing heterocyclic compound that can be an industrially advantageous synthesis, an active ingredient of a pest control agent that can be used safely and safely, and a pest control agent comprising this compound as an active ingredient It is an issue to provide.

  In order to solve the above problems, the present invention firstly provides a compound of formula (I)

[In formula, a dotted line represents a single bond or a double bond. However, one of the two bonds represented by the dotted line is a single bond, and the other represents a double bond.
X represents a group represented by CH, CH ₂ or N (Q).
Q is a hydrogen atom, a C1-C12 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxycarbonyl group, an optionally substituted phenyl group, Or represents the heterocyclic group which may have a substituent.
W represents an oxygen atom or a sulfur atom.
A ₁ , A ₂ , A ₃ and A ₄ each independently represents a carbon atom or a nitrogen atom.

Y represents a halogen atom, cyano group, nitro group, formyl group, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, C1-C6 haloalkyl group, C3-C8 cycloalkyl group, C3-C8 halo group. A cycloalkyl group, a hydroxyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylsulfonyloxy group, an optionally substituted phenylsulfonyloxy group, a mercapto group, a C1-C6 alkylthio group, C1-C6 alkylsulfenyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylthio group, C1-C6 haloalkylsulfenyl group, C1-C6 haloalkylsulfonyl group, optionally substituted phenylthio group, substituted Phenylsulfenyl group which may have a group, Which may be phenylsulfonyl group, an amino group, a mono C1~C6 alkylamino group, di-C1~C6 alkyl amino group, an acylamino group, which may have a substituent phenylamino group, -N = C _{(R 3} ) (OR ₄ ), —CO ₂ R ₃ , —C (═O) N (R ₃ ) (R ₄ ), —C (═S) N (R ₃ ) (R ₄ ), —Si (R ₅ ) (R ₆ ) (R ₇ ), a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.

R ₃ and R ₄ are each independently a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C2-C12 alkynyl group. Group, C2-C12 haloalkynyl group, C1-C12 alkylthio group, hydroxyl group, C1-C12 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, acylamino group, substituent It represents a phenylamino group which may be substituted, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.

R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, or an optionally substituted phenyl group.

n represents an integer of 0 to 4. When n is 2 or more, the plurality of Y may be the same as or different from each other.
When two Ys are adjacent to each other, the two Ys may be bonded together to form a 5-membered ring or a 6-membered ring.

R ₁ and R ₂ are each independently a hydrogen atom, a cyano group, a C1-C12 alkyl group optionally substituted by G, a C3-C12 cycloalkyl group optionally substituted by G, or a G-substituted group. An optionally substituted C2-C12 alkenyl group, a C3-C12 cycloalkenyl group optionally substituted by G, a C2-C12 alkynyl group optionally substituted by G, a mercapto group, a C1-C6 alkylthio group, a C1- C6 alkylsulfonyl group which may have a substituent phenylthio group, a substituted group may phenylsulfonyl group optionally _{having, -SN (R 8) (R} 9), - S (O) 2 N (R _{8) (R 9), -} OR 8, -N (R 8) (R 9), - N = C (R 8) (R 9), - C (= O) R 8, -C (= O) N _(R 8) _{R 9), - C (=} S) R 8, -C (= S) N (R 8) (R 9), - C (= NR 8) R 9, -C (= NR 8) N (R 9 ) (R ₁₀ ), a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.

R ₁ and R ₂ may be bonded together to form a group represented by ═C (R ₈ ) (R ₉ ), and R ₁ and R ₂ are combined together. It may combine to form a 3- to 8-membered ring.

R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, C2 -C12 alkynyl group, C2-C12 haloalkynyl group, C1-C12 alkylthio group, hydroxyl group, C1-C12 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, acylamino group, substituent Represents a phenylamino group which may have a phenyl group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.

G is a halogen atom, a cyano group, a C3-C8 cycloalkyl group, a C3-C8 halocycloalkyl group, a C1-C6 alkylsulfonyloxy group, an optionally substituted phenylsulfonyloxy group, a mercapto group, C1 -C6 alkylthio group, C1-C6 alkylsulfenyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylthio group, C1-C6 haloalkylsulfenyl group, C1-C6 haloalkylsulfonyl group, may have a substituent A good phenylthio group, a phenylsulfenyl group which may have a substituent, a phenylsulfonyl group which may have a substituent, an amino group, —OR ₁₁ , —N (R ₁₁ ) (R ₁₂ ), — N = C (R ₁₁ ) (R ₁₂ ), —C (═O) R ₁₁ , —C (═O) N (R ₁₁ ) (R ₁₂ ) _{, -C (= S) R 11} , -C (= S) N (R 11) (R 12), - C (= NR 11) R 12, -C (= NR 11) N (R 12) (R _{13), - Si (R 14} ) (R 15) (R 16), represents an optionally substituted phenyl group, or an optionally substituted heterocyclic group.

R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, C1-C12 alkyl group, C1-C12 haloalkyl group, C3-C12 cycloalkyl group, C2-C12 alkenyl group, C2-C12 haloalkenyl group, C2 -C12 alkynyl group, C2-C12 haloalkynyl group, C1-C12 alkylthio group, hydroxyl group, C1-C12 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, acylamino group, substituent Represents a phenylamino group which may have a phenyl group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.

R ₁₄ , R _15, and R ₁₆ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, or an optionally substituted phenyl group.

D represents a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, or an aryl group which may have a substituent.
Z represents a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. ] The nitrogen-containing heterocyclic compound or its salt represented by these is provided.
Secondly, the present invention relates to the formula (Ia)

(In the formula, D, Z, R ₁ , R ₂ and W represent the same meaning as described above, and Y ₁ represents a C1-C6 haloalkyl group.)
The nitrogen-containing heterocyclic compound represented by these, or its salt is provided.
Thirdly, the present invention provides a pest control agent containing as an active ingredient at least one of the nitrogen-containing heterocyclic compounds or salts thereof of the present invention.
The pest control agent of the present invention is preferably an insecticide or an acaricide.

  According to the present invention, a novel nitrogen-containing heterocyclic compound or a salt thereof, which can be synthesized industrially advantageously, can be an active ingredient of a pest control agent that can be used safely and safely, and at least one of these compounds. A pest control agent as an active ingredient is provided.

Hereinafter, the present invention will be described in detail.
1) Nitrogen-containing heterocyclic compound represented by formula (I) or salt thereof The first aspect of the present invention is a nitrogen-containing heterocyclic compound represented by formula (I) or a salt thereof.
In the formula (I), W represents an oxygen atom or a sulfur atom.
In the formula (I), A ₁ , A ₂ , A ₃ and A ₄ each independently represent a carbon atom or a nitrogen atom.
In the formula (I), the following formula (A)

Specific examples of the partial structure represented by the following include the following.

  Y is a halogen atom such as a fluorine atom, chlorine atom or bromine atom; cyano group; nitro group; formyl group; C1-C6 alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group; vinyl group, n -C2-C6 alkenyl group such as propenyl group, isopropenyl group and 2-butenyl group; C2-C6 alkynyl group such as propargyl group and 3-butynyl group; C1-C6 haloalkyl such as trifluoromethyl group and pentafluoroethyl group Group: C3-C8 cycloalkyl group such as cyclopropyl group, cyclopentyl group and cyclohexyl group; C3 such as 2-chlorocyclopropyl group, 2,2-dichlorocyclopropyl group, 3-chlorocyclopentyl group and 4-bromocyclohexyl group -C8 halocycloalkyl group; hydroxyl group; methoxy group, ethoxy group, n-propoxy group C1-C6 alkoxy groups such as isopropoxy group, n-butoxy group and t-butoxy group; C1-C6 haloalkoxy groups such as trichloromethoxy group and trifluoromethoxy group; methylsulfonyloxy group, ethylsulfonyloxy group, n- C1-C6 alkylsulfonyloxy group such as propylsulfonyloxy group; phenylsulfonyloxy group optionally having substituents such as phenylsulfonyloxy group and 4-methylphenylsulfonyloxy group; mercapto group; methylthio group, ethylthio group C1-C6 alkylthio groups such as n-propylthio group, isopropylthio group, n-butylthio group and t-butylthio group; C1-C6 alkylsulfuric groups such as methylsulfenyl group, ethylsulfenyl group and n-propylsulfenyl group Phenyl group; methylsulfoni Groups, C1-C6 alkylsulfonyl groups such as ethylsulfonyl group, n-propylsulfonyl group; C1-C6 haloalkylthio groups such as chloromethylthio group, trichloromethylthio group, trifluoromethylthio group; chloromethylsulfenyl group, trichloromethylsulfenyl Group, C1-C6 haloalkylsulfenyl group such as trifluoromethylsulfenyl group; C1-C6 haloalkylsulfonyl group such as chloromethylsulfonyl group, trichloromethylsulfonyl group, trifluoromethylsulfonyl group; phenylthio group, 4-methylphenylthio Group, phenylthio group optionally having substituent such as 2,4-dichlorophenylthio group; substituent such as phenylsulfenyl group, 4-methylphenylsulfenyl group, 2,4-dichlorophenylsulfenyl group Phenylsulfonyl group optionally having substituents such as phenylsulfonyl group, 4-methylphenylsulfonyl group, 2,4-dichlorophenylsulfonyl group; amino group; methylamino Mono-C1-C6 alkylamino groups such as a group, ethylamino group and n-propylamino group; di-C1-C6 alkylamino groups such as a dimethylamino group and a diethylamino group; acylamino groups such as an acetylamino group and a benzoylamino group; phenyl An amino group, a phenylamino group optionally having a substituent such as 4-methylphenylamino group;

_{-N = CH (OCH 3),} - N = CH (OCF 3), - N = C (CH 3) (OCH 3), - N = C (Ph) (OCH 3), - N = CH (OcPr) _{, -N = CH (OCH 2 CH} = CH 2), - N = CH (OCH 2 CH = CCl 2), - N = Table with CH (OPh) -N such _{= C (R 3) (OR} 4) A group to be
A group represented by —CO ₂ R ₃ such as —CO ₂ H, —CO ₂ CH ₃ , —CO ₂ cPr, —CO ₂ CF ₃ , —CO ₂ CH ₂ CH═CH ₂ , —CO ₂ Ph;
_{-C (= O) NH 2,} -C (= O) NH (CH 3), - C (= O) NH (Ph), - C (= O) NH (CH 2 CH = CH 2), - C A group represented by —C (═O) N (R ₃ ) (R ₄ ) such as (═O) N (CH ₃ ) ₂ , —C (═O) N (CH ₃ ) (OCH ₃ );
_{-C (= S) NH 2,} -C (= S) NH (CH 3), - C (= S) NH (Ph), - C (= S) NH (CH 2 CH = CH 2), - C _{(= S) N (CH 3} ) 2, -C (= S) N (CH 3) (OCH 3) -C such _{(= S) N (R 3} ) group represented by _{(R 4);
-Si (CH 3) 3, -Si} (C 2 H 5) 3, -Si (CH 3) 2 (Ph), - Si (t-C 4 H 9) (CH 3) 2, -Si (CH 3 ) (Ph) ₂ or the like group represented by —Si (R ₅ ) (R ₆ ) (R ₇ );
A phenyl group which may have a substituent such as a phenyl group, a 4-methylphenyl group, a 2-fluorophenyl group, a 2,4-dichlorophenyl group or a 2,4,6-trimethylphenyl group; Represents an optionally substituted heterocyclic group.

  The heterocyclic group for Y is not particularly limited as long as it is a heterocyclic group containing at least one hetero atom in the ring. Here, examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of atoms constituting the ring of the heterocyclic group is preferably 3 to 8, more preferably 5 or 6. Furthermore, the heterocyclic group may be a saturated heterocyclic group or an unsaturated heterocyclic group, but an unsaturated heterocyclic group is preferable in terms of having excellent pest control activity. An unsaturated nitrogen-containing heterocyclic group is more preferable.

  Examples of such an unsaturated nitrogen-containing heterocyclic group include heterocyclic groups having 1 to 3 nitrogen atoms in the ring, and optionally having 1 or 2 oxygen atoms or sulfur atoms. It is done.

  Specific examples of the unsaturated nitrogen-containing heterocyclic group include pyrrol-2-yl group, pyrrol-3-yl group, pyrazol-3-yl group, pyrazol-4-yl group, oxazol-2-yl group, and oxazole. -4-yl group, oxazol-5-yl group, thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group, isoxazol-4-yl group, isoxazol-5-yl group, Isothiazol-2-yl group, isothiazol-4-yl group, isothiazol-5-yl group, triazol-3-yl group, triazol-5-yl group, 1,3,4-oxadiazole-2- Yl group, 1,2,4-oxadiazol-3-yl group, 1,2,4-oxadiazol-5-yl group, 1,3,4-thiadiazol-2-yl group, 1,2,4 4-thiadiazo -3-yl group, 1,2,4-thiadiazol-5-yl 5-membered unsaturated nitrogen-containing heterocyclic ring group such as a group;

  Pyridin-2-yl group, Pyridin-3-yl group, Pyridin-4-yl group, Pyridazin-3-yl group, Pyridazin-4-yl group, Pyrimidin-2-yl group, Pyrimidin-4-yl group, Pyrimidine 6-membered unsaturated nitrogen-containing heterocyclic group such as -5-yl group, pyrazin-2-yl group and triazin-2-yl group.

  The heterocyclic group may have a substituent at any position. Such substituents include: cyano group; nitro group; formyl group; halogen atom such as fluorine atom, chlorine atom and bromine atom; C1-C6 alkyl group such as methyl group, ethyl group, n-propyl group and isopropyl group; C1-C6 alkoxy group such as ethoxy group; C3-C8 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group; C3-C8 cycloalkyloxy such as cyclopropyloxy group, cyclopentyloxy group, cyclohexyloxy group Group: C3-C8 cycloalkyl C1-C6 alkyl group such as cyclopropylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group; C3-C8 cycloalkyl C1-C6 alkoxy such as cyclopropylmethoxy group, cyclopentylmethoxy group, cyclohexylmethoxy group, etc. Base C2-C6 alkenyloxy groups such as pentenyloxy group and butenyloxy group; C1-C6 haloalkyl groups such as trifluoromethyl group and pentafluoroethyl group; C1-C6 haloalkoxy groups such as trifluoromethoxy group and pentafluoroethoxy group; C2-C6 haloalkenyloxy groups such as chloropropenyloxy group and chlorobutenyloxy group; C1-C6 alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group (alkoxycarbonyl having 1 to 6 carbon atoms in the alkoxy moiety) Meaning the group. The same applies hereinafter.); Phenyl group optionally having substituents such as phenyl group, 4-methylphenyl group, 2-chlorophenyl group; and the like.

R ₃ and R ₄ are each independently a hydrogen atom; a C1 to C12 alkyl group such as a methyl group or an ethyl group; a C1 to C12 haloalkyl group such as a trifluoromethyl group or a pentafluoroethyl group; a cyclopropyl group or a cyclopentyl group. C3-C12 cycloalkyl group such as cyclohexyl group; C2-C12 alkenyl group such as vinyl group and allyl group; C2-C12 haloalkenyl group such as 3-chloroallyl group; C2-C12 such as propargyl group and 3-butynyl group Alkynyl group; C2-C12 haloalkynyl group such as 2-chloroethynyl group, 2-bromoethynyl group, 3,3,3-trifluoro-1-propynyl group; C1-C12 alkylthio group such as methylthio group, ethylthio group; Hydroxyl group; C1-C12 alkoxy group such as methoxy group and ethoxy group; amino group; methylamino Mono-C1-C6 alkylamino groups such as ethylamino group; di-C1-C6 alkylamino groups such as dimethylamino group and diethylamino group; acylamino groups such as acetylamino group and benzoylamino group; phenylamino group, 4-methylphenyl Phenylamino group optionally having substituents such as amino group; phenyl optionally having substituents such as phenyl group, 4-methylphenyl group, 2-chlorophenyl group, 2,4-difluorophenyl group Or a heterocyclic group which may have a substituent similar to those exemplified as the heterocyclic group which may have a substituent of Y;

R ₅ , R ₆ and R ₇ are each independently a hydrogen atom; a C1-C12 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group; A C1-C12 haloalkyl group such as a methyl group or a pentafluoroethyl group; or a phenyl group which may have a substituent such as a phenyl group or a 4-methylphenyl group.

  n represents an integer of 0 to 4. When n is 2 or more, the plurality of Y may be the same as or different from each other.

When two Ys are adjacent to each other, the two Ys are bonded together to form —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH. ₂ O—, —CH ₂ CH ₂ S—, —CH ₂ SCH ₂ , —SCH ₂ S—, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ O—, —CH ₂ CH _{2 OCH 2 -, - CH 2 OCH} 2 O -, - OCH 2 CH 2 O -, - OCH 2 CH 2 S -, - SCH 2 CH 2 S -, - OCH = N -, - forming a SCH = N-like By doing so, you may form a 5-membered ring or a 6-membered ring with the carbon atom to which each of two Y couple | bonds.

  At this time, the hydrogen atom bonded to each carbon atom forming the ring may be substituted by a substituent T. Further, when simultaneously substituted by two or more T, each T is the same as each other Or they may be different.

  Here, T is a cyano group, nitro group, formyl group, halogen atom, C1-C6 alkyl group, C1-C6 alkoxy group, C3-C8 cycloalkyl group, C3-C8 cycloalkyloxy group, C3-C8 cycloalkyl. C1-C6 alkyl group, C3-C8 cycloalkyl C1-C6 alkoxy group, C2-C6 alkenyloxy group, C1-C6 haloalkyl group, C1-C6 haloalkoxy group, C2-C6 haloalkenyloxy group, C1-C6 alkoxycarbonyl Group, phenyl group optionally having substituent (s); and the like. Specific examples thereof are the same as those exemplified as the substituent for the heterocyclic group of Y.

A dotted line represents a single bond or a double bond. However, one of the two bonds represented by the dotted line is a single bond, and the other represents a double bond.
X represents a group represented by CH, CH ₂ or N (Q).
Q is a hydrogen atom, a C1-C12 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxycarbonyl group, an optionally substituted phenyl group, Or represents the heterocyclic group which may have a substituent.

Q, a C1-C12 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxycarbonyl group, an optionally substituted phenyl group, or a substituent Examples of the heterocyclic group optionally having R ₃ include R ₃ , R ₄ , and the same as the examples of r described later.

  Z represents a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. Specific examples of these are the same as those listed above as specific examples of the phenyl group which may have a substituent and the heterocyclic group which may have a substituent. The following (Z-1) to (Z-32) are preferable.

  In the above formula, r is a halogen atom such as fluorine atom, chlorine atom or bromine atom; cyano group; nitro group; C1-C6 alkyl group such as methyl group or ethyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. C3-C8 cycloalkyl group; C2-C6 alkenyl group such as vinyl group and propenyl group; C2-C6 alkynyl group such as ethynyl group and propargyl group; hydroxyl group; C1-C6 alkoxy such as methoxy group, ethoxy group and isopropoxy group A phenoxy group optionally having a substituent such as a phenoxy group or a 4-methylphenoxy group; a mercapto group; a C1-C6 alkylthio group such as a methylthio group or an ethylthio group; a C1 such as a methylsulfinyl group or an ethylsulfinyl group; -C6 alkylsulfinyl group; C1 such as methylsulfonyl group and ethylsulfonyl group C6 alkylsulfonyl group; phenylthio group optionally having substituents such as phenylthio group and 4-chlorophenylthio group; phenylsulfonyl optionally having substituents such as phenylsulfonyl group and 4-methylphenylsulfonyl group Group: C1-C6 alkylsulfonyloxy group such as methylsulfonyloxy group and ethylsulfonyloxy group; phenylsulfonyloxy group optionally having substituent such as phenylsulfonyloxy group and 2-chlorophenylsulfonyloxy group; methoxycarbonyl Group, ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group and the like C1-C6 alkoxycarbonyl group (C1-C6 represents the number of carbon atoms of the alkoxy group of the alkoxycarbonyl group; the same applies hereinafter); Represents.

m represents an integer of 0 to 5, m1 represents an integer of 0 to 4, m2 represents an integer of 0 to 3, m3 represents an integer of 0 to 2, and m4 represents 0 or 1. When m and m1 to m3 are each 2 or more, a plurality of r may be the same as or different from each other.
r ′ represents a hydrogen atom; a C1-C6 alkyl group such as a methyl group or an ethyl group; a phenyl group optionally having a substituent such as a phenyl group or a 4-methylphenyl group;

R ₁ and R ₂ are each independently substituted with a hydrogen atom, a cyano group, or G (C1-C12 alkyl group, C3-C12 cycloalkyl group, C2-C12 alkenyl group, C3-C12 cycloalkenyl group). Group, C2-C12 alkynyl group), mercapto group, C1-C6 alkylthio group, C1-C6 alkylsulfonyl group, phenylthio group optionally having substituent, phenylsulfonyl group optionally having substituent, _{-SN (R 8) (R 9} ), - S (O) 2 N (R 8) (R 9), - OR 8, -N (R 8) (R 9), - N = C (R 8) _{(R 9), - C (} = O) R 8, -C (= O) N (R 8) (R 9), - C (= S) R 8, -C (= S) N (R 8) _{(R 9), - C (} = NR 8) R 9, -C (= NR 8) N (R 9 (R _10), represents an optionally substituted phenyl group, or an optionally substituted heterocyclic group.

R ₈ , R ₉ and R ₁₀ are each independently the same as R ₃ and R ₄ , hydrogen atom, C1-C12 alkyl group, C1-C12 haloalkyl group, C3-C12 cycloalkyl group, C2-C12 alkenyl. Group, C2-C12 haloalkenyl group, C2-C12 alkynyl group, C2-C12 haloalkynyl group, C1-C12 alkylthio group, hydroxyl group, C1-C12 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1- A C6 alkylamino group, an acylamino group, a phenylamino group which may have a substituent, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.

Wherein _{R 1} and _{R 2,} as the C1~C12 alkyl group substituted C1~C12 may alkyl group by G, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, t -Butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group and the like can be mentioned.

  Examples of the C3-C12 cycloalkyl group of the C3-C12 cycloalkyl group optionally substituted by G include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like.

  Examples of the C2-C12 alkenyl group of the C2-C12 alkenyl group optionally substituted by G include a vinyl group, an n-propenyl group, a 2-butenyl group, a 3-butenyl group, a 2-pentenyl group, a 3-pentenyl group, 4-pentenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like can be mentioned.

  Examples of the C3-C12 cycloalkenyl group of the C3-C12 cycloalkenyl group optionally substituted by G include a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, and the like.

  Examples of the C2-C12 alkynyl group of the C2-C12 alkynyl group optionally substituted by G include an ethynyl group, a propargyl group, a 2-butynyl group, and a 2-pentynyl group.

G is a halogen atom, a cyano group, a C3-C8 cycloalkyl group, a C3-C8 halocycloalkyl group, a C1-C6 alkylsulfonyloxy group, an optionally substituted phenylsulfonyloxy group, a mercapto group, C1 -C6 alkylthio group, C1-C6 alkylsulfenyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylthio group, C1-C6 haloalkylsulfenyl group, C1-C6 haloalkylsulfonyl group, may have a substituent A good phenylthio group, a phenylsulfenyl group which may have a substituent, a phenylsulfonyl group which may have a substituent, an amino group, —OR ₁₁ , —N (R ₁₁ ) (R ₁₂ ), — N = C (R ₁₁ ) (R ₁₂ ), —C (═O) R ₁₁ , —C (═O) N (R ₁₁ ) (R ₁₂ ) _{, -C (= S) R 11} , -C (= S) N (R 11) (R 12), - C (= NR 11) R 12, -C (= NR 11) N (R 12) (R _{13), - Si (R 14} ) (R 15) (R 16), represents an optionally substituted phenyl group, or an optionally substituted heterocyclic group.

Here, R ₁₁ , R ₁₂ and R ₁₃ are each independently the same as R ₃ and R ₄ , hydrogen atom, C1-C12 alkyl group, C1-C12 haloalkyl group, C3-C12 cycloalkyl group, C2 -C12 alkenyl group, C2-C12 haloalkenyl group, C2-C12 alkynyl group, C2-C12 haloalkynyl group, C1-C12 alkylthio group, hydroxyl group, C1-C12 alkoxy group, amino group, mono C1-C6 alkylamino group, It represents a di-C1-C6 alkylamino group, an acylamino group, a phenylamino group which may have a substituent, or a phenyl group which may have a substituent.

R ₁₄ , R ₁₅ and R ₁₆ may each independently have a hydrogen atom, a C1 to C12 alkyl group, a C1 to C12 haloalkyl group, or a substituent, similar to R _{5 to} R _7. Represents a good phenyl group.

  Specific examples of the heterocyclic group which may have a substituent of G include those similar to those listed as specific examples of the heterocyclic group which may have a substituent of Y. .

R ₁ and R ₂ , a C1-C6 alkylthio group, a C1-C6 alkylsulfonyl group, an optionally substituted phenylthio group, an optionally substituted phenylsulfonyl group, mono C1-C6 An alkylamino group, a di-C1-C6 alkylamino group, an acylamino group, a phenylamino group which may have a substituent, a phenyl group which may have a substituent, and a substituent. Specific examples of the heterocyclic group include those similar to some of those listed in Y above.

R ₁ and R ₂ are bonded together to form a group represented by ═C (R ₈ ) (R ₉ ) (R ₈ and R ₉ have the same meaning as described above). Alternatively, R ₁ and R ₂ may be bonded together to form a 3- to 8-membered ring.

Specific examples of the group represented by ═C (R ₈ ) (R ₉ ) include ═CH ₂ , ═CH (CH ₃ ), ═C (CH ₃ ) ₂ , ═CH (C ₆ H ₅ ), ═C (C ₆ H ₅ ) _{2 and the} like, but are not limited thereto.

Specific examples of the 3-8 membered ring and _{R 1} and _{R 2} are formed by bonding together, _{R 1} and _{R 2} and is - to form a C2~C7 alkylene chain turned cord And a 3- to 8-membered ring constituted with a nitrogen atom to be bonded.

  At this time, the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and is a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy (C1-C6) alkyl group, It may be substituted by a C1-C6 alkoxy group, a formyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, or a C1-C6 alkoxycarbonyl group.

Among these, as R ₁ and R ₂ , R ₁ is a hydrogen atom, R ₂ is an aromatic heterocyclic group which may have a substituent, or C1-C12 alkyl optionally substituted by G. A group is preferred.

  As the nitrogen-containing heterocyclic compound of the present invention, the following formula (I-1)

(Wherein, A _{1 to} A ₄ , Y, n, R ₁ , R ₂ , D, W, and Z represent the same meaning as described above), and are preferably nitrogen-containing heterocyclic compounds represented by Formula (Ia)

(Wherein, D, W, Z, R ₁ and R ₂ represent the same meaning as described above, and Y ₁ represents a C1-C6 haloalkyl group). Preferably, the formula (Ib)

(Wherein R ₁ , R ₂ , Y ₁ , r, m and D represent the same meaning as described above), and more preferably a nitrogen-containing heterocyclic compound represented by:
The nitrogen-containing heterocyclic compound of the present invention includes a compound represented by the formula (Ic)

The compound represented by the formula is particularly preferred.
The compound represented by the formula (I) can be produced, for example, by the method shown below.
(Production method 1)

(In the formula, A _{1 to} A ₄ , R ₁ , R ₂ , D, X, Y, Z, n, and W represent the same meaning as described above. L represents a halogen atom, a C1 to C6 alkoxy group, a phenoxy group, It represents a leaving group such as a C1-C6 alkylcarbonyloxy group, a C1-C6 alkoxycarbonyloxy group, a 1-imidazolyl group, a 1-pyrazolyl group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyl group. )

  That is, a compound represented by formula (4) (hereinafter referred to as “compound (4)”) and a compound represented by formula (3) (hereinafter referred to as “compound (3)”) are converted into a condensing agent. The compound represented by the formula (I) (hereinafter referred to as “compound (I)”) can be obtained by reacting in the presence of a base if desired.

  As the condensing agent used in this reaction, 2-chloro-N-methylpyridinium iodide (Mukayama reagent), 1,3-dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI), carbonyldiimidazole, dimethylpropynylsulfonium bromide, propargyl triphenylphosphonium bromide, diethyl cyanophosphate and the like.

  Examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate and potassium carbonate; metal alkoxides such as sodium methoxide, potassium t-butoxide and magnesium ethoxide; n-butyl Organic metals such as lithium and lithium diisopropylamide (LDA); metal hydrides such as sodium hydride and potassium hydride; organic bases such as triethylamine, diisopropylethylamine, pyridine and N, N-dimethylaminopyridine; and the like.

The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene; dichloromethane, 1,2-dichloroethane, chloroform, tetrachloride Halogen solvents such as carbon; nitrile solvents such as acetonitrile and propionitrile; ether solvents such as diethyl ether, dioxane and tetrahydrofuran; aprotic such as N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) Polar solvents; and mixed solvents in which two or more of these solvents are mixed; and the like.
The reaction temperature is usually in the temperature range from −78 ° C. to the boiling point of the solvent used.

  Further, a compound represented by the formula (2) (hereinafter referred to as “compound (2)”) is obtained from the compound (4), and this is reacted with the compound (3) in the presence of a base, if desired. To give compound (I).

  As a method for obtaining compound (2) from compound (4), for example, compound (4) is reacted with a chlorinating agent such as thionyl chloride or oxalyl chloride; compound (4), pivaloyl chloride, Examples thereof include a method of reacting an organic halogen compound such as ethyl acid in the presence of a base if desired; a method of reacting compound (4) with carbonylimidazole; and the like.

Examples of the base and solvent that can be used in the reaction for obtaining the compound (I) from the compound (2) include those exemplified as the base and solvent that can be used in the reaction for obtaining the compound (I) from the compound (4). The same thing is mentioned.
The reaction temperature is usually in the temperature range from −78 ° C. to the boiling point of the solvent used.

Compound (4) can be produced, for example, by the following production methods 2 to 5.
(Production method 2)

(In the formula, A _{1 to} A ₄ , D, Y, Z, n, and W represent the same meaning as described above, and R ′ represents a C1 to C6 alkyl group.)
That is, a compound represented by formula (5) (hereinafter referred to as “compound (5)”) and a compound represented by formula (6) (hereinafter referred to as “compound (6)”) are described in the literature. Known methods, for example, J. Org. Org. Chem. , 36, 3316 (1971) and the like, a compound represented by formula (7) (hereinafter referred to as “compound (7)”) is obtained. This is then subjected to a general ester hydrolysis reaction described in the literature, e.g. Am. Chem. Soc. 51, 1865 (1929); Angew. Chem. , 63, 329 (1950) and the like, the compound (4a) in which X is a methylene group can be obtained from the compound (4). At the same time, the isomerization reaction of the pyrroline ring also proceeds.
(Production method 3)

_{(Wherein, A 1 ~A 4, D,} Y, L, Z, n, R ' and W are as defined above.)
That is, the compound represented by the formula (9) (hereinafter referred to as “compound (9)”) and the compound (6) are converted into known methods described in the literature, for example, J. Org. Org. Chem. , 36, 3316 (1971) and the like, to obtain a compound represented by the formula (10). Then, this is combined with known methods described in the literature, for example, J. Org. Org. Chem. , 39, 3318 (1974), etc., the compound (7) can be obtained by reacting under a reaction condition according to a CO insertion reaction using a transition metal catalyst such as palladium.

  Compound (9) can be obtained by a known method. Specifically, it can be obtained as follows.

(In the formula, A _{1 to} A ₄ , Y, n and L have the same meaning as described above.)
That is, the compound represented by the formula (a) is reacted with a reducing agent such as lithium aluminum hydride in an organic solvent to obtain a compound represented by the formula (b), and then reacted with a formate ester. A compound represented by the formula (c) is obtained. Next, compound (9) can be obtained by allowing triphosgene to act on this compound in the presence of a base such as triethylamine.
(Production Method 4)

(In the formula, A _{1 to} A ₄ , Q, D, Y, Z, n, R ′ and W represent the same meaning as described above, and L ₁ represents a halogen atom.)

That is, the compound represented by the formula (11) and the compound (6) are converted into known methods described in literatures, for example, Chem. Ber. , 117, 1194 (1984) and the like, to obtain a compound represented by the formula (12). This is then subjected to a general ester hydrolysis reaction described in the literature, e.g. Am. Chem. Soc. 51, 1865 (1929); Angew. Chem. , 63, 329 (1950), etc., the compound (4b) in which X is a group represented by N (Q) can be obtained from the compound (4) by hydrolysis. it can.
(Production method 5)

(In the formula, A _{1 to} A ₄ , D, Y, Z, n, R ′ and W represent the same meaning as described above.)
That is, the compound represented by the formula (14) and the compound (6) are converted into known methods described in literatures, for example, J. Org. Med. Chem. , 27, 1516 (1984) and the like, to obtain a compound represented by the formula (15). This is then subjected to a general ester hydrolysis reaction described in the literature, e.g. Am. Chem. Soc. 51, 1865 (1929); Angew. Chem. , 63, 329 (1950), etc., the compound (4c) in which X is NH among the compounds (4) can be obtained by hydrolysis.

  The salt of compound (I) is not particularly limited as long as it is agriculturally and horologically acceptable. 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 by a conventionally known production method, for example, a method in which an inorganic acid or organic acid is allowed to act on compound (I).

  In any reaction, after completion of the reaction, if purification of the product is necessary after the usual post-treatment operation, it is purified by a known and conventional purification means such as distillation, recrystallization or column chromatography. The target product can be isolated.

  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.

2) Pest Control Agent The pest control agent of the present invention contains one or more compounds (I) and salts thereof (hereinafter referred to as “the present compound”) as active ingredients.
Since the compound of the present invention has an insecticidal, larvicidal, larvicidal and ovicidal action, it can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests and the like. Typical examples include the following.

  Lepidopterous pests, for example, Spodoptera litura, Coleoptera, Tamanayaga, Aomushi, Tamanaginuwaba, Koga, Chanoko Kakumon Hamaki, Chahamaki, Momosinkiga, Nashihime Shinkii, Citrus Harmiga, Chanohosoga, Giant Pomera , Sugimadama, Heliotis, Helicoberpa, Agrotis, 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 acaricides has developed in many pests such as Japanese pests, leafhoppers, leafhoppers, and aphids, resulting in insufficient efficacy of these drugs. Also effective drugs are desired. The compound of the present invention is an agent having an insecticidal and acaricidal effect which is excellent not only for susceptible strains but also for pests resistant to organophosphates, carbamates and pyrethroids, and mites that are resistant to acaricides.

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

  Some compounds of the present invention exhibit bactericidal activity, herbicidal activity, and planting action. Some intermediate compounds of the compounds of the present invention exhibit insecticidal / miticidal activity.

  When the compound of the present invention is actually applied, it can be used as it is without adding other components. Usually, however, it is further mixed with a solid carrier, liquid carrier, gaseous carrier, or impregnated with a base such as a porous ceramic plate or nonwoven fabric. In addition, if necessary, surfactants and other adjuvants may be added to form a general agricultural chemical for use as an agricultural chemical, that is, a wettable powder, granule, powder, emulsion, aqueous solvent, suspension. , Granulated wettable powder, flowable, aerosol, fumes, heat transpiration, smoke, poison bait, microcapsule, etc.

  Additives and carriers include solid powders, vegetable powders such as soybean grains and wheat flour, mineral powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay, benzoic Organic and inorganic compounds such as acid 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, LG, dimethyl ether and carbon dioxide gas can be used.

  Examples of the bait base include bait ingredients such as cereal flour, vegetable oil, sugar, 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.

  In order to obtain a uniform and stable form in these preparations, a surfactant may 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.

  When the compound of the present invention is used as an agricultural pest control agent, the amount of the active ingredient in the preparation is 0.01 to 90% by weight, particularly preferably 0.05 to 85% by weight. Emulsions, suspensions, flowables, aqueous solvents, and granule wettable powders are diluted with water to a predetermined concentration. As a solution, suspension, or emulsion, powders and granules are directly applied to plants or soil. Used in a spraying method.

  In addition, when the compound of the present invention is used as a pest control agent for prevention of epidemics, emulsions, wettable powders, flowables and the like are diluted with water to a predetermined concentration before application, oils, aerosols, fumes, poison baits. Apply it as it is about anti-tick sheets.

  When the compound of the present invention is used as a pest control agent for controlling animal ectoparasites of domestic animals such as cattle and pigs, and pets such as dogs and cats, the formulation of the compound of the present invention is usually known in veterinary medicine. Use this method. As the method, for example, for the purpose of systemic control, administration is performed by tablets, capsules, immersion liquid, feed mixture, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), etc. In the case of aiming at 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 is usually used at a ratio of 0.01 to 1000 mg per 1 kg of the host animal.

  It goes without saying that the compound of the present invention is sufficiently effective by itself, but other pesticides, fungicides, insecticides / acaricides, herbicides, plant regulators, synergists, fertilizers, soil improvers, animals It can also be used in combination or in combination with one or more feeds such as feeds.

  Representative examples of active ingredients such as bactericides, insecticides, acaricides, plant growth regulators and the like that can be used in combination with or in combination with the compounds 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, quinomethionate, carpropamide, etc.

Insecticides and acaricides:
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.
Acaricide:
Chlorbenzilate, phenisobromolate, dicofol, amitraz, BPPS, benzomate, hexithiazox, fenbutazin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentedin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad, thiomidibene Dienochlor, fluacrylpyrim, acequinosyl, bifenazate, etoxazole, spirodiclofen, phenazaquin and the like.

Plant growth regulator:
Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA and the like.

  Next, an Example is given and this invention is demonstrated further in detail. However, the present invention is not limited by the examples.

(Example 1)
4- [4- (3,5-dichlorophenyl) -4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl] -2-methyl-N-pyridin-2-ylmethylbenzamide (Compound No. 1-1) Production step 1: Production of 4-bromo-3-methylbenzylamine

  To a suspension of 2.4 g of lithium aluminum hydride in 100 ml of diethyl ether, 10 g of 4-bromo-3-methylbenzonitrile was added dropwise under ice cooling, and after completion of the addition, the reaction solution was further heated to reflux for 3 hours. The reaction solution was ice-cooled, 5 ml of water was added and stirred for 30 minutes, and then the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 6.8 g of the target compound. Yield 67%

¹ H-NMR (CDCl ₃ , δ ppm) 2.39 (s, 3H), 3.80 (s, 2H), 7.00 (d, 1H), 7.19 (s, 1H), 7.47 ( d, 1H)

Step 2: Production of N- (4-bromo-3-methylbenzyl) formamide

  6.8 g of 4-bromo-3-methylbenzylamine was dissolved in 30 ml of methyl formate and the solution was heated to reflux overnight. The solvent was distilled off from the reaction mixture under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/2 (volume ratio)) to obtain 3.9 g of the target compound. It was. Yield 50%

¹ H-NMR (CDCl ₃ , δ ppm) 2.39 (s, 3H), 4.42 (d, 2H) 5.76 (m, 1H), 6.98 (d, 1H), 7.16 (s , 1H), 7.51 (d, 1H), 8.28 (s, 1H)

Step 3: Production of 1-bromo-4-isocyanomethyl-2-methylbenzene

  4.1 g of triethylamine was added to a solution of 3.9 g of N- (4-bromo-3-methylbenzyl) formamide in 40 ml of dichloromethane. Thereto, a solution of 1.9 g of triphosgene in 17 ml of dichloromethane was added dropwise over 30 minutes under ice cooling. The reaction was returned to room temperature and stirred overnight. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain 3.6 g of the desired compound. Yield 100%

¹ H-NMR (CDCl ₃ , δ ppm) 2.42 (s, 3H), 4.57 (s, 2H), 7.03 (d, 1H), 7.16 (s, 1H), 7.56 ( d, 1H)

Step 4: Preparation of 2- (4-bromo-3-methylphenyl) -4- (3,5-dichlorophenyl) -4-trifluoromethyl-3,4-dihydro-2H-pyrrole

  3.6 g of 1-bromo-4-isocyanomethyl-2-methylbenzene and 5 g of 3,5-dichloro-1- (1-trifluoromethylethenyl) benzene are dissolved in 50 ml of toluene, and copper oxide is added to this solution. (I) 0.12 g was added and heated to reflux overnight. The solvent was distilled off from the reaction mixture under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9 (volume ratio)) to obtain 4 g of the target compound. Yield 53%

¹ H-NMR (CDCl ₃ , δ ppm) 2.04-2.44 (m, 1H), 2.37 and 2.40 (s, 3H), 2.79 and 3.21 (dd, 1H), 5.01 and 5.36 (Td, 1H), 6.85-7.53 (m, 6H), 7.98-8.01 (m, 1H)

Step 5: Preparation of ethyl 4- [4- (3,5-dichlorophenyl) -4-trifluoromethyl-3,4-dihydro-2H-pyrrol-2-yl] -2-methylbenzoate

  In a metal autoclave, 2- (4-bromo-3-methylphenyl) -4- (3,5-dichlorophenyl) -4-trifluoromethyl-3,4-dihydro-2H-pyrrole in 30 ml of ethanol, acetic acid 0.89 g of sodium, 0.5 g of 1,1′-bis (diphenylphosphino) ferrocene, and 0.1 g of palladium (II) acetate were added, and the total volume was 5 at 110 ° C. under a carbon monoxide atmosphere of 1.0 MPa. Stir for hours.

  The solvent was distilled off from the reaction mixture under reduced pressure, followed by extraction with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9 (volume ratio)) to obtain 1.7 g of the objective compound. Yield 43%

¹ H-NMR (CDCl ₃ , δ ppm) 1.35 to 1.42 (m, 3H), 2.05-2.39 (m, 1H) 2.57 and 2.61 (s, 3H), 2.82 and 3. 21 (dd, 1H), 4.30-4.40 (m, 2H), 5.09 and 5.44 (td, 1H), 7.05-7.43 (m, 5H), 7.89- 8.04 (m, 2H)

Step 6: Preparation of 4- [4- (3,5-dichlorophenyl) -4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl] -2-methylbenzoic acid

  1.7 g of ethyl 4- [4- (3,5-dichlorophenyl) -4-trifluoromethyl-3,4-dihydro-2H-pyrrol-2-yl] -2-methylbenzoate, 20 ml of ethanol and 5 ml of water To the suspension, 0.31 g of sodium hydroxide was added and heated to reflux for 1 hour. After the solvent was distilled off under reduced pressure, the reaction solution was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure to obtain 1.6 g of the target compound. Yield 100%

¹ H-NMR (CDCl ₃ , δ ppm) 2.70 (s, 3H), 3.53 (d, 1H), 3.86 (d, 1H), 4.50 (d, 1H), 4.95 ( d, 1H), 7.18-7.40 (m, 3H) 7.76-7.81 (m, 2H), 8.11 (d, 1H)

Step 7: 4- [4- (3,5-dichlorophenyl) -4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl] -2-methyl-N-pyridin-2-ylmethyl-benzamide Production of (Compound No. 1-1)

  To a suspension of 0.69 g of 4- [4- (3,5-dichlorophenyl) -4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl] -2-methylbenzoic acid in 10 ml of dichloromethane, Add 0.36 g of 2-picolylamine, 0.42 g of 4- (dimethylamino) pyridine, and 0.65 g of 1- [3- (diethylamino) propyl] -3-ethylcarbodiimide hydrochloride and stir overnight at room temperature. .

  The reaction solution was poured into ice water and extracted with chloroform. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 4/1 (volume ratio)) to obtain 0.5 g of the target compound. Yield 58%

¹ H-NMR (CDCl ₃ , δ ppm) 2.53 (s, 3H), 3.46 (d, 1H), 3.80 (d, 1H), 4.45 (d, 1H), 4.80 ( d, 2H), 4.90 (d, 1H), 7.27-7.83 (m, 9H), 8.55 (d, 1H)

(Example 2)
4- [5- (3,5-dichlorophenyl) -1-methyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methyl-N-pyridin-2-ylmethyl- Production step 1 of benzamide (Compound No. 4-2): Production of methyl 2-methyl-4- (methyl-hydrazonomethyl) benzoate

  Methyl hydrazine 0.19 was added to a solution of 0.6 g of methyl 4-formyl-2-methylbenzoate in 10 ml of ethanol, and the mixture was heated to reflux for 2 hours. The solvent was distilled off under reduced pressure to obtain 0.7 g of the target compound. Yield 100%

¹ H-NMR (CDCl ₃ , δ ppm) 2.61 (s, 3H), 3.01 (s, 3H), 3.88 (s, 3H), 7.39-7.45 (s, 2H), 7.91 (d, 1H)

Step 2: Preparation of methyl 4- [5- (3,5-dichlorophenyl) -1-methyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoate

To a solution of 0.7 g of methyl 2-methyl-4- (methyl-hydrazonomethyl) benzoate in 10 ml of carbon tetrachloride was added 0.54 g of bromine under ice cooling. The reaction was returned to room temperature and stirred overnight. Precipitated crystals were collected from the reaction solution by filtration, and the obtained crystals were dried to obtain crude α-bromo-4-methoxycarbonyl-3-methylbenzaldehyde-methylhydrazone hydrobromide.
Next, 0.8 g of 3,5-dichloro-1- (1-trifluoromethylethenyl) benzene and 1 g of triethylamine were added to a 10 ml suspension of this product and heated under reflux for 3 hours.

  The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/5 (volume ratio)) to obtain 0.98 g of the target compound. Yield 65%

¹ H-NMR (CDCl ₃ , δ ppm) 2.62 (s, 3H), 3.11 (s, 3H), 3.37 (d, 1H), 3.90 (s, 3H) 3.91 (d , 1H), 7.38-7.45 (m, 5H), 7.93 (d, 1H)

Step 3: Preparation of 4- [5- (3,5-dichlorophenyl) -1-methyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoic acid

  0.98 g of methyl 4- [5- (3,5-dichlorophenyl) -1-methyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoate in ethanol To a mixed solvent suspension composed of 10 ml and 4 ml of water, 0.18 g of sodium hydroxide was added and heated to reflux for 1 hour. The solvent was distilled off from the reaction solution under reduced pressure, and the resulting residue was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure to obtain 0.94 g of the target compound. Yield 100%

¹ H-NMR (CDCl ₃ , δ ppm) 2.69 (s, 3H), 3.13 (s, 3H), 3.42 (d, 1H), 3.92 (s, 3H), 7.39- 7.48 (m, 5H), 7.97 (d, 1H)

Step 4: 4- [5- (3,5-Dichlorophenyl) -1-methyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methyl-N-pyridine-2 -Production of ylmethylbenzamide (Compound No. 4-2)

  4- [5- (3,5-dichlorophenyl) -1-methyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoic acid 0.5 g methylene chloride 10 ml Under ice cooling, a few drops of DMF and 0.21 g of oxalyl chloride were added to the suspension, and the mixture was returned to room temperature and stirred at the same temperature for 3 hours. The reaction solution was concentrated under reduced pressure to give 4- [5- (3,5-dichlorophenyl) -1-methyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoate. The acid chloride was obtained and subjected to the next reaction without further purification.

  To a solution of 0.14 g of 2-picolylamine and 0.19 g of pyridine in 10 ml of methylene chloride under ice-cooling, the 4- [5- (3,5-dichlorophenyl) -1-methyl-5-trimethyl compound obtained above was obtained. Fluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoic acid chloride was added, the temperature was returned to room temperature, and the mixture was stirred overnight at the same temperature. The reaction solution was poured into water and extracted with chloroform. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 4/1 (volume ratio)) to obtain 0.41 g of the objective compound. Yield 71%

¹ H-NMR (CDCl ₃ , δ ppm) 2.50 (s, 3H), 3.10 (s, 3H), 3.38 (d, 1H), 3.91 (d, 1H), 4.78 ( d, 2H) 7.28-7.53 (m, 8H), 7.76 (t, 1H), 8.55 (d, 1H)

(Example 3)
4- [5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methyl-N-pyridin-2-ylmethyl-benzamide (Compound No. 4-1) Production step 1: Production of methyl 4-hydrazonomethyl-2-methylbenzoate

  To a solution of 3.1 g of methyl 4-formyl-2-methylbenzoate in 30 ml of ethanol was added 1.04 g of hydrazine monohydrate and heated to reflux for 2 hours. The solvent was distilled off under reduced pressure to obtain 3.1 g of the target compound. Yield 100%

¹ H-NMR (CDCl ₃ , δ ppm) 2.61 (s, 3H), 3.88 (s, 3H), 7.40 (d, 1H), 7.70 (s, 1H), 7.90 ( d, 1H)

Step 2: Preparation of methyl 4- [5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoate

  In a solution of 3.1 g of methyl 4-hydrazonomethyl-2-methylbenzoate in 50 ml of diethyl ether, 4.8 g of mercury oxide (yellow) and 10 ml of 0.11 N potassium hydroxide (ethanol solution) were added under ice cooling, Stir at the same temperature for 1 hour. The reaction solution was filtered to obtain a crude methyl 4-diazomethyl-2-methylbenzoate solution. To this reaction solution, 3.8 g of 3,5-dichloro-1- (1-trifluoromethylethenyl) benzene was added and stirred overnight at room temperature.

  The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/4 (volume ratio)) to obtain 1.36 g of the target compound. Yield 20%

¹ H-NMR (CDCl ₃ , δ ppm) 2.62 (s, 3H), 3.42 (d, 1H), 3.89 (d, 1H), 3.90 (s, 3H), 7.39- 7.9 (m, 6H)

Step 3: Preparation of 4- [5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoic acid

  1.36 g of methyl 4- [5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoate, 10 ml of ethanol and 5 ml of water 0.25 g of sodium hydroxide was added to the suspension of the mixed solvent consisting of and heated under reflux for 1 hour. The solvent was distilled off under reduced pressure, the reaction solution was poured into dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure to obtain 1.25 g of the target compound. Yield 95%

¹ H-NMR (CDCl ₃ , δ ppm) 2.65 (s, 3H), 3.42 (d, 1H), 3.92 (s, 3H), 7.39-7.97 (m, 6H)

Step 4: 4- [5- (3,5-Dichlorophenyl) -5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methyl-N- (2-pyridylmethyl) benzamide Production of (Compound No. 4-1)

  In a suspension of 0.28 g 4- [5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydro-1H-pyrazol-3-yl] -2-methylbenzoic acid in 10 ml dichloromethane To the mixture, 0.15 g of 2-picolylamine, 0.16 g of 4- (N, N-dimethylamino) pyridine and 0.26 g of 1- [3- (diethylamino) propyl] -3-ethylcarbodiimide hydrochloride And stirred overnight.

  The reaction solution was poured into ice water and extracted with chloroform. The organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 4/1 (volume ratio)) to obtain 0.1 g of the target compound. Yield 29%

¹ H-NMR (CDCl ₃ , δ ppm) 2.49 (s, 3H), 3.41 (d, 1H), 3.88 (d, 1H), 4.82 (d, 2H), 7.37- 7.57 (m, 8H), 7.89 (t, 1H), 8.57 (d, 1H)

The structural formulas and physical constants of the compounds of the present invention produced in the same manner as in Examples 1 to 3 are shown in Tables 1 to 4 including the compounds obtained in Examples 1 to 3. The ¹ H-NMR data is shown in Table 5. In the table, * represents a bonding position, and [] represents a melting point (° C.).

  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. Moreover, the part in a formulation Example shows a weight part.

Formulation Example 1 Wetting agent Compound of the present invention 40 parts Clay 48 parts Dioctylsulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts or more are uniformly mixed and finely pulverized, and 40% active ingredient wettable powder Get.

Formulation Example 2 Emulsion Compound of the present invention 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 The present compound 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 of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part After pulverizing and mixing well, adding water and kneading well, granulation drying As a result, granules containing 5% of the active ingredient are obtained.

Formulation Example 5 Suspension Compound of the present invention 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 The above is mixed and the particle size is 3 microns or less The suspension is wet-pulverized until a suspension of 10% active ingredient is obtained.

Formulation Example 6 Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Lignin sulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt 5 parts

  After mixing the above uniformly and finely grinding, 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 pest control agent of the present invention obtained as described above are shown below.
(Test Example 1) Efficacy Confirmation Test for Cotton Aphids Adult cotton aphids were inoculated into cucumbers that had been sown for 10 days after being sown in 3-inch pots. One day later, the adults were removed, and a chemical solution diluted with water so that the compound concentration was 125 ppm was sprayed on the cucumber infested with the larvae produced in accordance with the formulation of the emulsion shown in Formulation Example 2. It was placed in a thermostatic chamber at a temperature of 25 ° C. and a humidity of 65%. The test is duplicated. As a result, the following compounds showed 100% insecticidal rate.

Compound numbers: 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-11, 1-12, 1-13, 1-14 1-16, 1-19, 1-20, 1-21, 1-26, 1-27, 1-30, 1-32, 1-33
(Compound numbers correspond to the compound numbers in Tables 1 to 4. The same applies hereinafter.)
The insecticidal rate of Pirimi curve used as a control was 9%.

(Test Example 2) Efficacy Confirmation Test for Acacia Toyo In accordance with the prescription of wettable powder shown in Formulation Example 1 above, the compound concentration was diluted with water to 125 ppm. Corn leaves were immersed in the chemical solution for 30 seconds, air-dried, placed in a petri dish with filter paper, and 5 instar larvae were inoculated. The glass lid was put on and placed in a thermostatic chamber at a temperature of 25 ° C. and a humidity of 65%. After 5 days, the survival was examined and the insecticidal rate was determined. The test is duplicated. As a result, the following compounds showed 100% insecticidal rate.

Compound numbers: 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1 -25, 1-26, 1-27, 1-32, 1-33, 3-1, 4-1, 4-2, 4-3, 4-4, 4-6
The insecticide rate of chlordiform used as a control was 40%.

(Test Example 3) Efficacy Confirmation Test for Spider Mite After inoculating 17 adult female spider mites that are resistant to organophosphates on the first true leaf 7 to 10 days after germination of green beans seeded in 3 inch pots, According to the prescription of wettable powder shown in Example 1 of the drug, a drug solution diluted with water was sprayed so that the compound concentration was 125 ppm. It was placed in a temperature-controlled room with a temperature of 25 ° C. and a humidity of 65%. The test is duplicated. As a result, the following compounds showed 100% insecticidal rate.

Compound numbers: 1-1, 1-2, 1-3, 1-4, 1-7, 1-8, 1-11, 1-12, 1-13, 1-16, 1-17, 1-20 , 1-21, 1-22, 1-26, 1-27, 1-32, 1-33
The insecticide rate of chlordiform used as a control was 40%.

Claims (5)

Formula (I)

[In formula, a dotted line represents a single bond or a double bond. However, one of the two bonds represented by the dotted line is a single bond, and the other represents a double bond.
X represents a group represented by CH, CH ₂ or N (Q).
Q is a hydrogen atom, a C1-C12 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxycarbonyl group, an optionally substituted phenyl group, Or it represents the heterocyclic group which may have a substituent.
W represents an oxygen atom or a sulfur atom.
A ₁ , A ₂ , A ₃ and A ₄ each independently represents a carbon atom or a nitrogen atom.
Y represents a halogen atom, cyano group, nitro group, formyl group, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, C1-C6 haloalkyl group, C3-C8 cycloalkyl group, C3-C8 halo group. A cycloalkyl group, a hydroxyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylsulfonyloxy group, an optionally substituted phenylsulfonyloxy group, a mercapto group, a C1-C6 alkylthio group, C1-C6 alkylsulfenyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylthio group, C1-C6 haloalkylsulfenyl group, C1-C6 haloalkylsulfonyl group, optionally substituted phenylthio group, substituted Phenylsulfenyl group which may have a group, Which may be phenylsulfonyl group, an amino group, a mono C1~C6 alkylamino group, di-C1~C6 alkyl amino group, an acylamino group which may have a substituent phenylamino group, -N = C _{(R 3} ) (OR ₄ ), —CO ₂ R ₃ , —C (═O) N (R ₃ ) (R ₄ ), —C (═S) N (R ₃ ) (R ₄ ), —Si (R ₅ ) (R ₆ ) (R ₇ ), a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
R ₃ and R ₄ are each independently a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C2-C12 alkynyl group. Group, C2-C12 haloalkynyl group, C1-C12 alkylthio group, hydroxyl group, C1-C12 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, acylamino group, substituent It represents an optionally substituted phenylamino group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group.
R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, or an optionally substituted phenyl group.
n represents an integer of 0 to 4. When n is 2 or more, the plurality of Y may be the same as or different from each other.
When two Ys are adjacent to each other, the two Ys may be bonded together to form a 5-membered ring or a 6-membered ring.
R ₁ and R ₂ are each independently a hydrogen atom, a cyano group, a C1-C12 alkyl group optionally substituted by G, a C3-C12 cycloalkyl group optionally substituted by G, or a G-substituted group. An optionally substituted C2-C12 alkenyl group, a C3-C12 cycloalkenyl group optionally substituted by G, a C2-C12 alkynyl group optionally substituted by G, a mercapto group, a C1-C6 alkylthio group, a C1- C6 alkylsulfonyl group which may have a substituent phenylthio group, a substituted group may phenylsulfonyl group optionally _{having, -SN (R 8) (R} 9), - S (O) 2 N (R _{8) (R 9), -} OR 8, -N (R 8) (R 9), - N = C (R 8) (R 9), - C (= O) R 8, -C (= O) N _{(R 8 (R 9), - C (} = S) R 8, -C (= S) N (R 8) (R 9), - C (= NR 8) R 9, -C (= NR 8) N (R ₉ ) (R ₁₀ ) represents a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
R ₁ and R ₂ may be bonded together to form a group represented by ═C (R ₈ ) (R ₉ ), and R ₁ and R ₂ are combined together. It may combine to form a 3- to 8-membered ring.
R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, C2 -C12 alkynyl group, C2-C12 haloalkynyl group, C1-C12 alkylthio group, hydroxyl group, C1-C12 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, acylamino group, substituent Represents a phenylamino group which may have a phenyl group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
G is a halogen atom, a cyano group, a C3-C8 cycloalkyl group, a C3-C8 halocycloalkyl group, a C1-C6 alkylsulfonyloxy group, an optionally substituted phenylsulfonyloxy group, a mercapto group, C1 -C6 alkylthio group, C1-C6 alkylsulfenyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylthio group, C1-C6 haloalkylsulfenyl group, C1-C6 haloalkylsulfonyl group, may have a substituent A good phenylthio group, a phenylsulfenyl group which may have a substituent, a phenylsulfonyl group which may have a substituent, an amino group, —OR ₁₁ , —N (R ₁₁ ) (R ₁₂ ), — N = C (R ₁₁ ) (R ₁₂ ), —C (═O) R ₁₁ , —C (═O) N (R ₁₁ ) (R ₁₂ ) _{, -C (= S) R 11} , -C (= S) N (R 11) (R 12), - C (= NR 11) R 12, -C (= NR 11) N (R 12) (R _{13), - Si (R 14} ) (R 15) (R 16), represents an optionally substituted phenyl group or optionally substituted heterocyclic group.
R _{11 to} R ₁₃ are each independently a hydrogen atom, C1-C12 alkyl group, C1-C12 haloalkyl group, C3-C12 cycloalkyl group, C2-C12 alkenyl group, C2-C12 haloalkenyl group, C2-C12 alkynyl. Group, C2-C12 haloalkynyl group, C1-C12 alkylthio group, hydroxyl group, C1-C12 alkoxy group, amino group, mono C1-C6 alkylamino group, di-C1-C6 alkylamino group, acylamino group, substituent It represents an optionally substituted phenylamino group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group.
R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, or an optionally substituted phenyl group.
D represents a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, or an aryl group which may have a substituent.
Z represents a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. ]
Or a salt thereof. Formula (Ia)

(In the formula, D, Z, R ₁ , R ₂ and W represent the same meaning as described above, and Y ₁ represents a C1-C6 haloalkyl group. )
Or a salt thereof.   The pest control agent which contains at least 1 type of the nitrogen-containing heterocyclic compound of Claim 1 or 2 or its salt as an active ingredient.   The pest control agent according to claim 3, which is an insecticide.   The pest control agent according to claim 3, which is an acaricide.