JPH09169736A - Pyrazole derivative and pest controlling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new pyrazole derivative, capable of manifesting excellent insecticidal and acaricidal activities against agricultural insect pests and tetranychids in a low dose and useful as a pest controlling agent hardly adversely affecting mammals, fishes and useful insects. SOLUTION: This compound of formula I A and B are each R<3> (R<3> is H, a halogen, etc.) or formula II [W is N or CR<6> (R<6> is a halogen, nitro, etc.); R<4> and R<5> are each R<6> ], with the proviso that B is formula II when A is R<3> and B is R<3> when A is formula II; R<1> is H, a 1-6C alkyl, etc.; R<2> is H, cyano, etc.} or its salt, e.g. 5-(3-chloro-5-trifluoromethylpyridin-2-yl)-1-methyl-3- trifluoromethyl-1H-pyrazole. The compound is obtained by reacting a compound of formula III (M is preferably tributylstannyl or zinc monochloride) with a compound of the formula G-L<1> (L<1> is an eliminative group such as chlorine atom; G is formula II) in the presence of a base and a transition metallic catalyst in an inert solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel pyrazole derivative or a salt thereof and a pest control agent containing these derivatives as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, 2-position, 4-position and 6-position on a benzene ring have been known.
Regarding the phenylpyrazole derivative having a substituent at the position, Indian Journal of Chemistry, Section B (Indian J. Chem., Sect. B 28B, 150-3 (198
9)) describes 3-phenylpyrazole derivatives and 5-phenylpyrazole derivatives, wherein the substituents on the benzene ring are a methyl group and a methoxy group, and at the 3-position on the pyrazole ring, a phenyl group or 4 It is only a compound having an aminosulfonylphenylazo group at the position. Moreover, although this document shows activity against microorganisms, it does not show insecticidal activity.

[0003]

With the long-term use of pest control agents, pests have acquired resistance in recent years, making it difficult to control them with conventional pest control agents. Some pesticides are highly toxic, and some are disturbing the ecosystem due to persistence. Therefore, the development of new pest control agents with low toxicity and low residue is always expected.

[0004]

Means for Solving the Problems As a result of intensive studies on the pyrazole derivative, the present inventors have found that the novel pyrazole derivative and a salt thereof exhibit excellent pest control activity at a low dose, and a mammal. The present inventors have completed the present invention by finding that they are extremely useful compounds with almost no adverse effects on fish and beneficial insects.

The present invention relates to a compound of the general formula (I)

[0006]

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[Wherein A and B are R ³ or G (provided that A and B
Is R ³ , B means G, and when A is G, B means R ³ ), and G is

[0008]

Embedded image

Where W is a nitrogen atom or CR ⁶ and R is
¹ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a formyl group, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 haloalkyl group, C _{2 -6} alkoxyalkyl group, C _2-6 cyanoalkyl group, C _2-6 alkylcarbonyl group, C _2-6 alkoxycarbonyl group, C _2-6 haloalkylcarbonyl group, C _1-6 alkylthio group, C _1-6 alkyl Sulfinyl group, C _1-6 alkylsulfonyl group, C
_1-6 haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, R ⁸ OC (O) N (R ⁹ ) S-
Group, R ⁹ (R ¹⁰⁾ NS- group, (R ⁷⁾ a phenyl group optionally substituted by _q, (R ⁷⁾ may be substituted by _q phenylthio group, substituted by (R ⁷⁾ _q Optionally represents a phenylsulfinyl group or a phenylsulfonyl group optionally substituted by (R ⁷ ) _q , R ² and R ⁷ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group , A C _1-6 alkyl group, a C _1-6 haloalkyl group,
C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 haloalkylthio group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, C _2-6 An alkoxycarbonyl group, an amino group or a di C _1-6 alkylamino group is shown, and R ³ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a formyl group, an SCN group, a trimethylsilyl group, R ¹¹ or OR ¹¹ , S (O) _p R ¹¹ groups, OS (O) ₂ R ¹¹ groups, OC (O) R
¹¹ groups, C (O) R ¹¹ groups, CO ₂ R ¹¹ groups, C (O) N (R ¹¹ ) R ¹² groups, SO ₂ N (R
¹¹ ) R ¹² group, NHC (O) R ¹¹ group or N (R ¹¹ ) R ¹² group, R ⁴ and R ⁵
And R ⁶ are each independently a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C _1-6 alkyl group, a C _1-6 haloalkyl group,
C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _1-6 alkoxy group, C
_1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 haloalkylthio group, C _1-6 alkylsulfinyl group, C _1-6 haloalkylsulfinyl group, C _1-6 alkylsulfonyl group, C _{1 -6} Haloalkylsulfonyl group, C _2-6 alkoxycarbonyl group, C _2-6 haloalkoxycarbonyl group, amino group, C _1-6 alkylamino group, C _1-6 haloalkylamino group or di C _1-6 alkylamino group , R ⁸ , R ⁹ and R
^10, each independently represents a C _1-6 alkyl group, (R ⁷⁾ a phenyl group optionally substituted by _q or (R ⁷⁾ a benzyl group which may be substituted by _q, R ¹¹ is C _1-6 alkyl group, C _1-6 haloalkyl group, C _2-6 alkenyl group, C _2-6
Haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _3-6 cycloalkyl group, C _3-6 halocycloalkyl group, C _4-7 cycloalkylalkyl group, C _2-6 alkoxy An alkyl group, a C _2-6 alkylthioalkyl group, a C _3-6 alkoxycarbonylalkyl group, a C _2-6 cyanoalkyl group, R ¹² represents a hydrogen atom or a C _1-6 alkyl group, p
Represents an integer of 0 to 2, q represents an integer of 0 to 5 (provided that when q is 2 to 5, R ⁷ may be the same or different), and r represents 0 to An integer of 4 (where r is 2
In the case of ~ 4, R ⁷ may be the same or different). ] The present invention relates to a pyrazole derivative represented by the following formula or a salt thereof, and a pest control agent containing one or more of these derivatives as an active ingredient.

Examples of each substituent shown in the present specification are shown below. The carbon chain of each substituent may be linear, branched or cyclic. Hereinafter, n- is normal, i
-Is iso, sec- is secondary, t- is tertiary, and c- is cyclo.

Examples of the C _1-6 alkyl group are methyl group, ethyl group, n-propyl group, i-propyl group, c-propyl group, n-butyl group, i-butyl group, sec-butyl group,
Examples thereof include t-butyl group, c-butyl group, n-pentyl group, c-pentyl group, n-hexyl group and c-hexyl group.

As the C _2-6 alkenyl group, an ethenyl group,
2-propenyl group, 2-methyl-2-propenyl group, 2
A butenyl group and the like.

As the C _2-6 alkynyl group, an ethynyl group,
Examples include 2-propynyl group and 2-butynyl group.

Examples of the C _2-6 alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group and a 1-methoxyethyl group.

The C _2-6 alkylcarbonyl group is a methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, c-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group. , Sec-butylcarbonyl group, t-butylcarbonyl group, c-butylcarbonyl group and the like.

The C _2-6 alkoxycarbonyl group is a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, c
Examples include-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, c-butoxycarbonyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halo notation also represents a halogen atom.

R ¹ is hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, formyl group, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 Haloalkyl group, C _2-6 haloalkenyl group, C _2-6 haloalkynyl group, C _2-6 alkoxyalkyl group, C _2-6 cyanoalkyl group, C _2-6 alkylcarbonyl group, C _2-6 alkoxycarbonyl group , C _2-6 haloalkylcarbonyl group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _{1 -6} haloalkylsulfonyl group, R ⁸
OC (O) N (R ⁹ ) S- group, R ⁹ (R ¹⁰ ) NS-group, phenyl group optionally substituted by (R ⁷ ) _q , optionally substituted by (R ⁷ ) _q Examples thereof include a phenylthio group, a phenylsulfinyl group optionally substituted by (R ⁷ ) _q , and a phenylsulfonyl group optionally substituted by (R ⁷ ) _q .

R ¹ is preferably cyano group, formyl group, C _1-6 alkyl group, C _1-6 haloalkyl group, C _2-6 haloalkenyl group, C _2-6 haloalkynyl group, C _1-6 alkoxy. groups, C _{1 -6} haloalkoxy group, C _1-6 alkylthio group, C _1-6
Haloalkylthio group, C _1-6 alkylsulfinyl group, C
_1-6 haloalkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, C _2-6 alkoxycarbonyl group, C _2-6 haloalkoxycarbonyl group, C
Examples thereof include a _2-6 alkylcarbonyl group and a C _2-6 haloalkylcarbonyl group. More preferable examples of R ¹ include a hydrogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 alkoxyalkyl group, a C _2-6 alkylcarbonyl group and a cyano group.

R ² is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy group or a C _1-6 haloalkoxy group. , C _{1 -6} alkylthio groups, C _1-6 haloalkylthio groups, C
_1-6 alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, C _2-6 alkoxycarbonyl group, amino group and di-C
_1-6 alkylamino group is mentioned.

R ² is preferably a hydrogen atom, a halogen atom, a C _1-6 alkyl group or an amino group.

R ³ is a halogen atom, hydroxyl group, cyano group, nitro group, formyl group, SCN group, trimethylsilyl group, C _1-6 alkyl group, C _1-6 haloalkyl group, C _2-6 alkenyl group, C 3 _2-6 haloalkenyl group, C _2-6 alkynyl group,
C _2-6 haloalkynyl group, C _3-6 cycloalkyl group, C _3-6 halocycloalkyl group, C _4-7 cycloalkyl group,
C _2-6 alkoxyalkyl group, C _2-6 alkylthioalkyl group, C _3-6 alkoxycarbonylalkyl group, C _2-6 cyanoalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _{2 -6} alkenyloxy group, C _2-6 haloalkenyloxy group, C _2-6 alkynyloxy group, C _2-6 haloalkynyloxy group, C _3-6 cycloalkyloxy group, C _{3 -6} halocycloalkyloxy group , C _4-7 cycloalkylalkyloxy group, C _2-6 alkoxyalkyloxy group, C _2-6 alkylthioalkyloxy group, C _3-6 alkoxycarbonylalkyloxy group, C _2-6 cyanoalkyloxy group, C _{1 -6} alkylthio group, C _1-6 haloalkylthio group, C _2-6 alkenylthio group, C _2-6 haloalkenylthio group, C _2-6 alkynylthio group, C _2-6 haloalkynylthio group, C _{3- 6} cycloalkylthio group, C _3-6 halo cycloalkylthio group C _4-7 cycloalkylalkyl thio group, C _2-6 alkoxyalkyl thio group,
C _2-6 alkylthioalkylthio group, C _3-6 alkoxycarbonylalkylthio group, C _2-6 cyanoalkylthio group, C
_1-6 alkylsulfinyl group, C _1-6 haloalkylsulfinyl group, C _2-6 alkenylsulfinyl group, C _2-6 haloalkenylsulfinyl group, C _2-6 alkynylsulfinyl group, C _2-6 haloalkynylsulfinyl group, C _3-6 cycloalkylsulfinyl group, C _3-6 halocycloalkyl alkylsulfinyl group, C _4-7 cycloalkyl alkylsulfinyl group, C _{2 -6} alkoxyalkyl alkylsulfinyl group, C _2-6 alkyl thio alkylsulfinyl group, C _1-6 Alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, C _2-6 alkenylsulfonyl group, C _2-6 haloalkenylsulfonyl group, C
_2-6 alkynylsulfonyl group, C _2-6 haloalkynylsulfonyl group, C _3-6 cycloalkylsulfonyl group, C _3-6 halocycloalkylsulfonyl group, C _4-7 cycloalkylalkylsulfonyl group, C _2-6 alkoxy Alkylsulfonyl group, C _2-6 alkylthioalkylsulfonyl group, C _3-6 alkoxycarbonylalkylsulfonyl group, C _2-6 cyanoalkylsulfonyl group, C _1-6 alkylsulfonyloxy group, C _1-6 haloalkylsulfonyloxy group, C _3-6 cycloalkylsulfonyloxy group, C _3-6 halocycloalkylsulfonyloxy group, C _2-6 cyanoalkylsulfonyloxy group, C _2-7 alkylcarbonyloxy group, C _2-7 haloalkylcarbonyloxy group, C _4-7 cycloalkylcarbonyl group, C _4-7 halocycloalkyl carbonyl group, C _3-7 cyanoalkyl carbonylation Oxy group, C _2-7 alkylcarbonyl group, C _2-7 haloalkylcarbonyl group,
C _4-7 cycloalkylcarbonyl group, C _4-7 halocycloalkylcarbonyl group, C _3-7 cyanoalkylcarbonyl group,
C _2-7 alkoxycarbonyl group, C _2-7 haloalkoxycarbonyl group, C _4-7 cycloalkyloxycarbonyl group, C
_4-7 halocycloalkyl oxycarbonyl group, C _3-7 cyanoalkyl oxycarbonyl group, mono C _{1 -6} alkylaminocarbonyl group, a mono C _1-6 halo alkylaminocarbonyl group, di C _1-6 alkylaminocarbonyl group, Di C _1-6 haloalkylaminocarbonyl group, mono C _1-6 alkylaminosulfonyl group, mono C _1-6 haloalkylaminosulfonyl group, di C _1-6 alkylaminosulfonyl group, di C _1-6 haloalkylaminosulfonyl group, aminocarbonyl group, aminosulfonyl group, formylamino group, C _2-7 alkylcarbonylamino group, C _2-7 haloalkylcarbonyl group, an amino group, mono C _{1 -6} alkylamino group, mono-C _1-6 haloalkyl amino group , Di-C _1-6 alkylamino group, di-C _1-6
Haloalkylamino group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted phenylsulfinyl group, optionally substituted phenylsulfonyl group An optionally substituted phenylsulfonyloxy group, an optionally substituted phenylcarbonyloxy group, an optionally substituted phenylcarbonyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted phenyl Aminocarbonyl group, optionally substituted phenylsulfonylamino group, optionally substituted phenylcarbonylamino group, optionally substituted phenylamino group, optionally substituted benzyl group, optionally substituted Good benzyloxy group, optionally substituted Dilthio group, optionally substituted benzylsulfinyl group, optionally substituted benzylsulfonyl group, optionally substituted benzylsulfonyloxy group, optionally substituted benzylcarbonyloxy group, optionally substituted Good benzylcarbonyl group, optionally substituted benzyloxycarbonyl group, optionally substituted benzylaminocarbonyl group, optionally substituted benzylsulfonylamino group, optionally substituted benzylcarbonylamino group, substituted Optionally substituted benzylamino group, optionally substituted pyridyl group, optionally substituted pyridyloxy group, optionally substituted pyridylthio group, optionally substituted pyridylsulfinyl group, substituted May be pyridylsulfonyl group, substituted Optionally pyridylsulfonyloxy group, optionally substituted pyridylcarbonyloxy group, optionally substituted pyridylcarbonyl group, optionally substituted pyridyloxycarbonyl group, optionally substituted pyridylaminocarbonyl group , An optionally substituted pyridylsulfonylamino group, an optionally substituted pyridylcarbonylamino group or an optionally substituted pyridylamino group (however, the optionally substituted substituent is a halogen atom, a hydroxyl group, or a cyano group). Group, nitro group, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkylthio group, C _1-6 haloalkylthio group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, Examples thereof include a C _2-6 alkoxycarbonyl group, an amino group and a di C _1-6 alkylamino group. ).

R ³ is preferably a halogen atom, a cyano group, a nitro group, a formyl group, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 haloalkenyl group, a C _2-6 haloalkynyl group. , C _1-6 alkoxy group, C _1-6 haloalkoxy group, C
_1-6 alkylthio group, C _1-6 haloalkylthio group, C _1-6 alkylsulfinyl group, C _1-6 haloalkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, C _2-6 Alkoxycarbonyl group, C _2-6 haloalkoxycarbonyl group, C _2-6 alkylcarbonyl group, C _2-6
A haloalkylcarbonyl group is mentioned.

R ³ is particularly preferably C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 haloalkylthio group and
C _1-6 haloalkylsulfinyl group can be mentioned.

[0025] R ^4, as the R ⁵ and R ^6, each a halogen atom, a hydroxyl group, a cyano group, a nitro groups, C _{1 -6} alkyl groups, C
_1-6 haloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group,
C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 haloalkylthio group, C _1-6 alkylsulfinyl group, C _1-6 haloalkylsulfinyl group, C _1-6 Alkylsulfonyl group, C _1-6 haloalkylsulfonyl group,
Examples thereof include a C _2-6 alkoxycarbonyl group, a C _2-6 haloalkoxycarbonyl group, an amino group, a C _1-6 alkylamino group, a C _1-6 haloalkylamino group and a di C _1-6 alkylamino group.

[0026] Preferably the R ^4, R ⁵ and R ⁶ are each a halogen atom, C _1-6 haloalkyl groups include C _{1 -6} haloalkoxy group and a cyano group.

Particularly preferably, R ⁴ , R ⁵ and R ⁶ are a halogen atom and a C _1-6 haloalkyl group, respectively.

The preferred compounds of the present invention include the following compounds.

(1) R ¹ is cyano group, formyl group, C _1-6
Alkyl group, C _1-6 haloalkyl group, C _2-6 haloalkenyl group, C _2-6 haloalkynyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _{1 -6} haloalkylthio group, C _1-6 alkylsulfinyl group, C _1-6 haloalkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6
A haloalkylsulfonyl group, a C _2-6 alkoxycarbonyl group, a C _2-6 haloalkoxycarbonyl group, a C _2-6 alkylcarbonyl group, a C _2-6 haloalkylcarbonyl group, R ³
Is a halogen atom, cyano group, nitro group, formyl group,
C _1-6 alkyl groups, C _{1 -6} haloalkyl groups, C _2-6 haloalkenyl groups, C _2-6 haloalkynyl group, C _1-6 alkoxy groups, C
_1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 haloalkylthio group, C _1-6 alkylsulfinyl group, C _1-6 haloalkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 A pyrazole derivative represented by the formula (I) or a haloalkylsulfonyl group, a C _2-6 alkoxycarbonyl group, a C _2-6 haloalkoxycarbonyl group, a C _2-6 alkylcarbonyl group or a C _2-6 haloalkylcarbonyl group salt

(2) R ⁴ , R ⁵ and R ⁶ are each independently a halogen atom, cyano group, nitro group, C _1-6 alkyl group, C _1-6
The pyrazole derivative or a salt thereof according to (1) above, which represents a haloalkyl group, a C _2-6 alkoxycarbonyl group or a C _2-6 haloalkoxycarbonyl group.

(3) A pyrazole derivative or a salt thereof according to the above (2), in which A represents G and B represents R ³ .

(4) A pyrazole derivative or a salt thereof according to the above (2), wherein A represents R ³ and B represents G.

(5) The pyrazole derivative or salt thereof according to the above (3), wherein W represents CR ⁶ .

(6) The pyrazole derivative or salt thereof according to the above (3), wherein W represents a nitrogen atom.

(7) The pyrazole derivative or salt thereof according to the above (4), wherein W represents CR ⁶ .

(8) The pyrazole derivative or salt thereof according to the above (4), wherein W represents a nitrogen atom.

[0037] (9) R ³ is, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 haloalkylthio group, C _1-6 (5) showing a haloalkylsulfinyl group pyrazole derivative according or Its salt.

[0038] (10) R ³ is, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 haloalkylthio group, C _1-6 above (6) showing a haloalkylsulfinyl group pyrazole derivative according or Its salt.

[0039] (11) R ³ is, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 haloalkylthio group, C _1-6 (7) showing a haloalkylsulfinyl group pyrazole derivative according or Its salt.

[0040] (12) R ³ is, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 haloalkylthio group, C _1-6 (8) showing a haloalkylsulfinyl group pyrazole derivative according or Its salt.

(13) R ⁴ , R ⁵ and R ⁶ are each independently
The above (9) showing a halogen atom or a C _1-6 haloalkyl group.
The pyrazole derivative or salt thereof described.

(14) The pyrazole derivative or salt thereof according to (10) above, wherein R ⁴ and R ⁵ each independently represent a halogen atom or a C _1-6 haloalkyl group.

(15) R ⁴ , R ⁵ and R ⁶ are each independently
The above (1) showing a halogen atom or a C _1-6 haloalkyl group.
1) The pyrazole derivative described above or a salt thereof.

(16) The pyrazole derivative or the salt thereof according to the above (12), wherein R ⁴ and R ⁵ each independently represent a halogen atom or a C _1-6 haloalkyl group.

The compounds included in the present invention include pyrazole derivatives in which the 3-position on the ring is substituted with G and the 5-position is substituted with R ³ , and the 3-position on the ring is substituted with R ^3. 5th place is G
Although there are two structural isomers of the pyrazole derivative substituted with, the present invention includes these isomers alone or a mixture containing the two isomers in any ratio. Further, in the case of a compound having an asymmetric carbon atom, R form and S form are included. Furthermore, the compound of the present invention can form a salt with an acid, and examples of such a salt include salts with a mineral acid such as hydrochloric acid, sulfuric acid and phosphoric acid, and salts with an organic acid such as acetic acid. .

In the present invention, the pest control agent means especially a pest control agent. The compounds of the present invention are effective against various harmful pests at extremely low drug concentrations. Examples of the pests include leafhoppers, brown planthoppers, green peach aphids, pearl oysters, green agar beetles, pearl oyster moths, diamondback moths, cabbage moths, cabbage moths, chanocokakumon hamakis, chahamakis, tobacco bad worms, european corns. Agricultural pests such as, Corn Earworm, Southern Corn Rootworm, Northern Corn Rootworm, Western Corn Rootworm,
Spider mites such as scabbard mites, mandarin mites, kanzawa mites, mosquitoes, house flies, German cockroaches, ants,
Flea, sanitary pests such as lice, weevil, stag beetle, stored grain pests such as striped moth, house pests such as termites, livestock pests such as mites, fleas, lice, indoor dust mites such as mites, leopard mites, tick mites, Examples include molluscs such as slugs and snails. That is, the compound of the present invention, Orthoptera, hemiptera, Lepidoptera, Coleoptera,
It can effectively control pests of Hymenoptera, Diptera, Termites, and mites and lice at low concentrations. On the other hand, it was found that the compound of the present invention is a very useful compound having almost no adverse effect on mammals, fish, crustaceans and beneficial insects, and completed the present invention.

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION

Next, a method for producing the compound of the present invention will be described. The compound of the present invention is a novel pyrazole derivative,
A typical manufacturing method will be specifically described below.

[0049] The compounds of the present invention, 3-position and 5-position is substituted by G on the ring 3-position and 5-position is substituted with R ³ on the pyrazole derivatives and ring substituted with R ³ is substituted by G And two structural isomers of the pyrazole derivative are included. These two pyrazole derivatives are simultaneously produced during the reaction, and when they are a mixture, they can be directly used in the next reaction, or at any stage of the reaction route. It is possible to separate structural isomers. As the separation method, known separation methods in synthetic organic chemistry such as recrystallization, column chromatography, thin layer chromatography, liquid chromatography and gas chromatography can be used.

The pyrazole derivative in which the 3-position on the ring is substituted with R ³ and the 5-position is substituted with G is given as an example, and the production method thereof will be specifically described below.

Method A

[0052]

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The compound (II) is reacted with the compound (III) in the presence or absence of a base in an inert solvent in the presence or absence of a transition metal catalyst to give the compound (I) of the present invention. Can be obtained. In the formula, as M, trialkylstannyl such as trimethylstannyl, triethylstannyl, tributylstannyl, tripentylstannyl and trihexylstannyl, dihydroboranyl, dimethoxyboranyl, diethoxyboranyl, dipropoxy. Dialkoxyboranyl such as boranyl, diisopropoxyboranyl, dibutoxyboranyl and isomers thereof or alkyleneoxyboranyl such as ethylenedioxyboranyl and 1,3-propylenedioxyboranyl, zinc monochloride ,
Examples thereof include zinc halides such as zinc monobromide and zinc monoiodide, and magnesium halides such as magnesium monochloride, magnesium monobromide and magnesium monoiodide. Tributylstannyl and zinc monochloride are generally preferred.

Examples of the transition metal catalyst used include palladium chloride, palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (dibenzylideneacetone) palladium and tris (dibenzalacetone) palladium. Palladium compounds, bis (triphenylphosphine) nickel chloride, tetrakis (triphenylphosphine) nickel, 1,2-bis (diphenylphosphino) ethane nickel chloride and 1,3-bis (diphenylphosphino) propane nickel chloride Nickel compounds are mentioned. Generally, tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium are preferred.
Further, as a ligand that can be used in combination with these transition metal catalysts, triphenylphosphine, tri (o-tolyl) phosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenyl) Examples thereof include compounds containing a phosphorus atom such as phosphino) propane and 1,1′-bis (diphenyl) ferrocene, compounds containing an arsenic metal such as triphenylarsine and ethylenebis (diphenylarsine), and the like. When there is no ligand such as palladium acetate, a good effect can be obtained by performing a reaction in combination with these ligands. Further, the amount of the catalyst used can be used in the range of 0.01 to 20 mol%, but it is preferably used in the range of 0.1 to 10 mol%. Generally, it is preferable to use 5 mol%.

Examples of the base used in this method include alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate, alkali metal hydrides such as sodium hydride and potassium hydride, organic bases such as triethylamine and pyridine. Can be mentioned.

Any solvent may be used as long as it does not hinder the progress of the reaction. For example, aromatic hydrocarbons such as benzene and toluene, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane. And the like, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, amides such as dimethylformamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, water and the like.
These inert solvents may be used alone or in a mixture. Generally as a base,
It is preferable to use an organic base such as triethylamine and pyridine, and use aromatic hydrocarbons such as benzene and toluene or ethers such as tetrahydrofuran and diethyl ether as a solvent.

The reaction temperature can be set to any temperature from -60 ° C to the reflux temperature of the reaction mixture, but it is preferably carried out from room temperature to the reflux temperature of the reaction mixture.

Method B

[0059]

[Chemical 6]

The compound (I) of the present invention (R ¹ ≠ H) can be obtained by reacting the compound (I) of the present invention with the compound (IV) in the presence or absence of a base in an inert solvent. it can.

Examples of the base used in this method include alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate, alkali metal hydrides such as sodium hydride and potassium hydride, organic bases such as triethylamine and pyridine. Can be mentioned.

Any solvent may be used as long as it does not hinder the progress of the reaction. For example, aromatic hydrocarbons such as benzene and toluene, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane. And the like, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, amides such as dimethylformamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, water and the like.
These inert solvents may be used alone or in a mixture.

The reaction temperature can be set at any temperature from -60 ° C to the reflux temperature of the reaction mixture, but is 0 ° C.
It is preferable to carry out at a temperature of up to 120 ° C.

Method C

[0065]

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The compound (I) of the present invention (R ² ≠ H) can be obtained by reacting the compound (I) of the present invention with a halogenating agent or a nitrating agent in an inert solvent or without a solvent.

As the halogenating agent, chlorination is chlorine,
Sulfuryl chloride or N-chlorosuccinimide,
Bromine, sulfuryl bromide, or N-bromosuccinimide is preferably used for bromination, and iodine or iodine monochloride is preferably used for iodination. As the solvent, acetic acid or a halogenated hydrocarbon such as dichloromethane or carbon tetrachloride is preferably used. The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but is preferably 20 ° C to the reflux temperature of the reaction mixture. Moreover, the reaction can be smoothed by using an additive such as sodium acetate. In the case of chlorination, it is generally preferable to carry out the reaction in acetic acid in the presence of N-chlorosuccinimide and sodium acetate.

As the nitrating agent, nitric acid or a mixture of nitric acid and sulfuric acid is preferably used. As the solvent, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane or acetic acid are preferable, but the solvent may not be used.
The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but it is preferably carried out at 0 ° C to 90 ° C.

Method D

[0070]

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The compound (I) of the present invention can be obtained by reacting the compound (I) of the present invention with the compound (V) or a perfluoroalkylating agent in the presence of a base in an inert solvent.

Examples of the perfluoroalkylating agent include S- (trifluoromethyl) dibenzothiophenium trifluoromethylmethanesulfonate, S- (trifluoromethyl) dibenzothiophenium-3-sulfonate and S- (tri Fluoromethyl) -3,7-dinitrodibenzothiophenium trifluoromethanesulfonate, Se- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate, S- (perfluoroethyl) dibenzophenium trifluoromethanesulfonate, S- (n -Perfluorobutyl) dibenzothiophenium trifluoromethanesulfonate and S- (n-perfluorooctyl) dibenzothiophenium trifluoromethanesulfonate.
In the case of trifluoromethylation, it is generally preferred to use S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate.

Examples of the base used in this method include alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate, alkali metal hydrides such as sodium hydride and potassium hydride, organic bases such as triethylamine and pyridine. Can be mentioned.

Any solvent may be used as long as it does not hinder the progress of the reaction. For example, aromatic hydrocarbons such as benzene and toluene, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane. And the like, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, amides such as dimethylformamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, water and the like.
These inert solvents may be used alone or in a mixture.

The reaction temperature can be set at any temperature from -60 ° C to the reflux temperature of the reaction mixture, but is 0 ° C.
It is preferable to carry out at a temperature of from 50 to 50 ° C.

Method E

[0077]

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By reacting the compound (I) of the present invention with an oxidizing agent in an inert solvent, the compound (I) of the present invention (n)
≠ 0) can be obtained. Examples of the oxidizing agent include hydrogen peroxide, peracetic acid, performic acid, perbenzoic acid and metachloroperbenzoic acid. Metachloroperbenzoic acid is generally preferred. As the solvent used, the same solvent as used in Method A can be used. Generally, it is preferable to use methylene chloride.

In each method (method A to method E), G, M,
R ¹ , R ² , R ³ , R ¹¹ and n have the same meanings as described above, and L ¹ , L
² and L ³ represent good leaving groups such as chlorine atom, bromine atom, iodine atom, alkyl sulfonate group or aryl sulfonate group.

In each method, the molar ratio of each reactant is not particularly limited, but it is advantageous to carry out the reaction in an equimolar ratio or a ratio close thereto.

When the compound of the present invention needs to be purified, it can be separated and purified by any purification method such as recrystallization, column chromatography, thin layer chromatography and the like.

In applying the compound of the present invention as a pest control agent, generally, a suitable carrier, for example, a solid carrier such as clay, talc, bentonite, diatomaceous earth, white carbon or water, alcohols (isopropanol, butanol, benzyl alcohol) is used. , Furfuryl alcohol etc.), aromatic hydrocarbons (toluene, xylene etc.), ethers (anisole etc.), ketones (cyclohexanone, isophorone etc.), esters (butyl acetate etc.), acid amides (N-methyl) (Pyrrolidone etc.) or halogenated hydrocarbons (chlorobenzene etc.) and the like can be mixed and applied, and if desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners, Antifreeze agents, anti-caking agents, stabilizers, etc. are added, and liquid agents, emulsions,
It can be put to practical use in any dosage form such as wettable powders, dry flowables, flowables, powders, granules and the like.

In addition, the compound of the present invention may be used as a herbicide of other species, various insecticides, acaricides, nematicides, fungicides, plant growth regulators, synergists, fertilizers during formulation or spraying, if necessary. Alternatively, it may be mixed with a soil conditioner and applied.

Particularly when mixed with other pesticides or plant hormones, application can be expected to reduce costs by reducing the amount of application, to expand the insecticidal spectrum due to the synergistic action of the mixed agents, and to have a higher pest control effect. On this occasion,
It is also possible to combine a plurality of known pesticides at the same time. Examples of the kind of pesticide to be used in mixture with the compound of the present invention include, for example, Farm Chemicals Handbook (Farm Chemi
cals Handbook) Compounds described in the 1994 edition.

The application dose of the compound of the present invention varies depending on the application scene, application time, application method, cultivated crop, etc., but is generally 0.005 per hectare (ha) as an active ingredient amount.
Approximately 50 kg is suitable.

Next, formulation examples of the preparations using the compounds of the present invention will be shown concretely. However, the composition examples of the present invention are not limited to these. In the following formulation examples, "part" means part by weight.

[Wettable powder] Compound of the present invention: 5 to 80 parts Solid carrier: 10 to 85 parts Surfactant: 1 to 10 parts ........ 1 to 5 parts Other examples include anti-caking agents.

[Emulsion] Compound of the present invention: 1 to 30 parts Liquid carrier: 30 to 95 parts Surfactant: 5 to 15 parts

[Flowable agent] Compound of the present invention: 5 to 70 parts Liquid carrier: 15 to 65 parts Surfactant: 5 to 12 parts Others: ..... 5 to 30 parts Other examples include antifreezing agents and thickeners.

[Granular wettable powder (dry flowable agent)] Compound of the present invention: 20 to 90 parts Solid carrier: 10 to 60 parts Surfactant:・ 1 to 20 copies

[Granule] Compound of the present invention: 0.1 to 10 parts Solid carrier: 90 to 99.99 parts Others: 1 to 5 parts

[Powder] Compound of the present invention: 0.01 to 30 parts Solid carrier: 67 to 99.5 parts Other :: 0 to 3 parts

[0093]

【Example】

Examples (Synthesis Examples, Formulation Examples, Test Examples) Hereinafter, the present invention will be described in detail with reference to Examples (synthesis examples, preparation examples, test examples).

[Synthesis Example] The compounds included in the present invention are
Although it can be produced or can be produced based on the synthetic examples shown below, the present invention is not limited to these compounds.

Synthesis Example 1 5- (3-chloro-5-trifluoromethylpyridine-
2-yl) -1-methyl-3-trifluoromethyl-1
H-pyrazole (invention compound No. 1-2) A solution of 0.4 g of diisopropylamine and 5 ml of tetrahydrofuran was cooled to -78 ° C, and 2.5 ml of 1.62M n-butyllithium hexane solution was added dropwise. Fifteen
After stirring for 1 minute, 0.5 g of 1-methyl-3-trifluoromethyl-1H-pyrazole and tetrahydrofuran 2
ml solution was added and stirring was continued for another 1.5 hours. 1
4 ml of M zinc chloride diethyl ether solution was added, and the temperature was raised to room temperature and stirred for 1 hour, and then 2,3-dichloro-5-
A solution of 0.75 g of trifluoromethylpyridine, 0.2 g of tetrakis (triphenylphosphine) palladium and 5 ml of tetrahydrofuran was added dropwise, and the reaction was carried out at room temperature overnight. After the reaction, ethyl acetate was added, washed with dilute hydrochloric acid, successively with water and brine, dried and the solvent was distilled off. Silica gel preparative thin layer chromatography of the residue (benzene)
The title compound (0.25 g) was obtained as an oil.
n _D ^21.1 = 1.4874

Synthesis Example 2 5- (3-chloro-5-trifluoromethylpyridine-
2-yl) -1-methyl-3-trifluoromethyl-1
H-pyrazole (invention compound No. 1-2) 1-methyl-3-trifluoromethyl-5-tributylstannyl-1H-pyrazole 150 mg, 2,3-dichloro-5-trifluoromethylpyridine 81 mg and tetrahydrofuran 3 ml 2.2 mg of dichlorobis (triphenylphosphine) palladium was added to the solution of and the mixture was stirred overnight under reflux. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was separated by preparative liquid chromatography (acetonitrile / water = 4/1),
63 mg of the title compound was obtained.

Reference Example 1 Synthesis of 1-methyl-3-trifluoromethyl-5-tributylstannyl-1H-pyrazole A solution of 4.0 g of diisopropylamine and 50 ml of tetrahydrofuran was cooled to -78 ° C and 1.62 M n-
Add 24.7 ml of butyllithium hexane solution, and add 1
Stir for 5 minutes. A solution of 5.0 g of 1-methyl-3-trifluoromethylpyrazole and 30 ml of tetrahydrofuran was added dropwise to the reaction mixture, and after stirring for 30 minutes, a solution of 13.0 g of tributyltin chloride and 30 ml of tetrahydrofuran was added dropwise. After stirring at −78 ° C. for 3 hours,
Stirred overnight at room temperature. The reaction mixture was poured into water, extracted with ethyl acetate, and then washed with saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over anhydrous sodium sulfate and the solvent was evaporated to give the title compound (9.2 g) as an oil.

Synthesis Example 3 4-chloro-5- (3-chloro-5-trifluoromethylpyridin-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole (invention compound No. 1
-3) 5- (3-chloro-5-trifluoromethyl-pyridin-2-yl) -1-methyl-5-trifluoromethyl-
A solution of 230 mg of 1H-pyrazole and 3 ml of acetic acid was added with N.
Add 220mg CS, 120mg sodium acetate, 1
The mixture was stirred at 30 ° C for 6 hours. After allowing to cool, the reaction mixture was extracted with ethyl acetate, the organic layer was washed with water, and dried over anhydrous sodium sulfate. The solvent was evaporated, and the obtained residue was separated by preparative liquid chromatography (acetonitrile / water = 4/1) to give 63 mg of the title compound as an oil. ¹ H-NMR (CDCl ₃ ) δ: 3.62 (3H, s), 8.10-8.18 (1H, m), 8.
62-8.73 (1H, m).

Synthesis Example 4 5- (3-chloro-5-trifluoromethylpyridine-
2-yl) -1-methoxymethyl-3-trifluoromethyl-1H-pyrazole (present compound No. 1-
4) 10.0 g of 1-methoxymethyl-3-trifluoromethyl-5-tributylstannyl-1H-pyrazole, 2,
3-Dichloro-5-trifluoromethylpyridine 5.1
g and tetrahydrofuran 50 ml, dichlorobis (triphenylphosphine) palladium 0.75 g was added, and the mixture was stirred overnight under reflux. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was evaporated, and the obtained residue was separated by preparative liquid chromatography (acetonitrile / water = 4/1) to give the title compound (3.8 g) as a solid. mp =
48-50 ° C

Synthesis Example 5 5- (3-chloro-5-trifluoromethylpyridine-
2-yl) -3-trifluoromethyl-1H-pyrazole (inventive compound No. 1-1) 5- (3-chloro-5-trifluoromethylpyridine-
2-yl) -1-methoxymethyl-3-trifluoromethyl-1H-pyrazole 2.0 g and methanol 10 m
Two drops of concentrated hydrochloric acid were added to the solution of 1 and the mixture was stirred under reflux for 5 hours.
Methanol was distilled off, ethyl acetate was added to the residue, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 1.5 g of the title compound.

Synthesis Example 6 5- (3-chloro-5-trifluoromethylpyridine-
2-yl) -1-methoxycarbonyl-3-trifluoromethyl-1H-pyrazole (invention compound No. 1
-5) and 3- (3-chloro-5-trifluoromethylpyridin-2-yl) -5-trifluoromethyl-1-
Methoxycarbonyl-1H-pyrazole (inventive compound No. 2-1) 5- (3-chloro-5-trifluoromethylpyridine-
2.7 g of methyl chloroformate in a mixture of 0.60 g of 2-yl) -3-trifluoromethyl-1H-pyrazole, 0.32 g of potassium carbonate and 5 ml of dimethylformamide.
Was added dropwise, and the mixture was stirred at room temperature overnight. After stirring at 50 ° C. for 5 hours, ethyl acetate was added, washed with water and dried over anhydrous sodium sulfate. The solvent was evaporated and the residue was separated by preparative liquid chromatography (acetonitrile / water = 4/1) to give the title compound 5- (3-chloro-5-trifluoromethylpyridin-2-yl) -1-methoxycarbonyl. -3-
Trifluoromethyl-1H-pyrazole 0.37 g and 3
-(3-chloro-5-trifluoromethylpyridine-2
-Yl) -5-trifluoromethyl-1-methoxycarbonyl-1H-pyrazole 0.090 g was obtained.

Reference Example 2 1-Methoxymethyl-3-trifluoromethyl-1H-
Synthesis of pyrazole 19 g of 3-trifluoromethylpyrazole and 30 g of dimethylformamide were added to a suspension of 6.7 g of 60% sodium hydride and 100 ml of dimethylformamide in a water bath.
ml solution was added dropwise followed by methoxymethyl chloride 1
7 g was dropped. After stirring overnight at room temperature, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 7.5 g of the title compound as an oily substance. Reference Example 3 Synthesis of 1-methoxymethyl-3-trifluoromethyl-5-tributylstannyl-1H-pyrazole A solution of 1.5 g of diisopropylamine and 15 ml of tetrahydrofuran was cooled to -78 ° C, and 1.6M n-butyllithium was used. 9.0 ml of a hexane solution was added dropwise, and the mixture was stirred for 30 minutes. To this, a solution of 2.2 g of 1-methoxymethyl-3-trifluoromethyl-1H-pyrazole and 10 ml of tetrahydrofuran was added dropwise, and after stirring for 30 minutes, a solution of 4.7 g of tributyltin chloride and 10 ml of tetrahydrofuran was added dropwise. After stirring at −78 ° C. for 1 hour, the mixture was stirred at room temperature overnight. The reaction mixture was poured into water, extracted with ethyl acetate, and then washed with saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over anhydrous sodium sulfate and the solvent was evaporated to give the title compound (4.7 g) as an oil.

Synthesis Example 7 1-Methyl-3-methylthio-5- (2,4,6-trichlorophenyl) -1H-pyrazole (invention compound No. 2-4) 0.72 g of 55% sodium hydride and tetrahydrofuran In a 45 ml suspension, 3-methylthio-5- under ice cooling.
A solution of 4.15 g of (2,4,6-trichlorophenyl) -1H-pyrazole and 20 ml of tetrahydrofuran was added dropwise. The mixture was stirred at room temperature for 1.5 hours, and a solution of 2.53 g of methyl iodide and 15 ml of tetrahydrofuran was added under ice cooling. The reaction was carried out at room temperature for 2 hours, the reaction mixture was poured into ice water, washed with water and dried, and the solvent was distilled off. The residue was purified by silica gel column chromatography (chloroform) to give the title compound (3.53 g) as an oil.

Synthesis Example 8 1-Methyl-3-methylsulfinyl-5- (2,4,
6-Trichlorophenyl) -1H-pyrazole (Compound No. 2-5 of the present invention) 3.5 g of 1-methyl-3-methylthio-5- (2,4,6-trichlorophenyl) -1H-pyrazole and 30 ml of methylene chloride A solution of 2.07 g of metachloroperbenzoic acid and 25 ml of methylene chloride was added dropwise to the solution of 1. under ice cooling. After reacting for 3.5 hours at room temperature, the solvent was distilled off. Ethyl acetate was added to the residue, washed with an aqueous sodium bicarbonate solution, dried and the solvent was distilled off. The obtained crude oily substance was purified by silica gel column chromatography (benzene) to obtain 2.5 g of the title compound as an oily substance.

Reference Example 4 1-Methyl-3-mercapto-5- (2,4,6-trichlorophenyl) -1H-pyrazole 1-Methyl-3-methylsulfinyl-5- (2,4,4)
1.5 g of 6-trichlorophenyl) -1H-pyrazole
And a solution of trifluoroacetic anhydride 10 ml was refluxed for 1 hour. The solvent was distilled off, 10 ml of methanol and 10 ml of triethylamine were added, and the mixture was stirred at room temperature for 1 hour. The solvent was distilled off under reduced pressure, diethyl ether was added to the residue, the mixture was washed with an aqueous ammonium chloride solution, dried and the diethyl ether was distilled off to obtain a crude oily substance. Purified by silica gel column chromatography (chloroform) to give the title compound 0.
9 g was obtained as an oil.

Synthesis Example 9 1-Methyl-3-trifluoromethylthio-5- (2,
4,6-Trichlorophenyl) -1H-pyrazole
(Compound of the present invention No. 1-14) 1-Methyl-3-mercapto-5- (2,4,6-trichlorophenyl) was added to a suspension of 0.11 g of 55% sodium hydride and 10 ml of dimethylformamide under ice cooling. ) −
0.64 g of 1H-pyrazole and 6 ml of dimethylformamide were added, and stirring was continued for another 40 minutes at room temperature. 1.15 g of S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate and 5 ml of dimethylformamide were added dropwise under ice cooling, and the reaction was carried out at room temperature for 4.5 hours. The reaction mixture was poured into ice water, extracted with diethyl ether, washed with brine, dried and the solvent was evaporated. The residue was purified by silica gel preparative thin layer chromatography (hexane) to give the title compound (0.13 g) as an oil.

The compound of the present invention can be synthesized according to the above-mentioned production method and Examples. Examples of such compounds are shown in Tables 1 and 2. However, the present invention is not limited to these. In addition, Me in the table represents a methyl group.

Table 1

[0109]

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[0110]

[Table 1] ──────────────────────────── No. R ¹ R ² R ³ R ⁵ W Properties ─────── ────────────────────── 1-1-1 H H CF ₃ CF ₃ N 157-158 ℃ 1-2 Me H CF ₃ CF ₃ N Oily 1-3 Me Cl CF ₃ CF ₃ N oily 1- 4 CH ₂ OMe H CF ₃ CF ₃ N 48-50 ° C 1-5 CO ₂ Me H CF ₃ CF ₃ N oily 1-6 H H C ₂ F ₅ CF ₃ N 137.5 -139.0 ° C 1-7 Me H C ₂ F ₅ CF ₃ N Oily 1-8 CH ₂ OMe H C ₂ F ₅ CF ₃ N n _D ^20.0 = 1.4460 1-9 CH ₂ OMe H C ₂ F ₅ CF ₃ N 50 -52 ℃ 1-10 H H SCF ₃ CF ₃ N 1-11 Me H SCF ₃ CF ₃ N 1-12 H H SOCF ₃ CF ₃ N 1-13 Me H SOCF ₃ CF ₃ N 1-14 Me H SCF ₃ Cl C-Cl oily 1-15 Me H SCF ₃ CF ₃ C-Cl 1-16 H H SCF ₃ CF ₃ C-Cl 1-17 Me H SOCF ₃ CF ₃ C-Cl 1-18 H H SOCF ₃ CF ₃ C-Cl 1-19 CH ₂ Cl H SCF ₃ Cl C-Cl oil 1-20 Me Cl SCF ₃ Cl C-Cl oil 1-21 Me Cl SCF ₃ CF ₃ C-Cl 1-22 Me Cl SOCF ₃ CF ₃ C-Cl 1-23 Me Br SOCF ₃ CF ₃ C-Cl 1-24 Me H S C ₂ F ₅ Cl C-Cl oily ────────────────────────────

In the table, the spectral data of each compound of Nos. 1-2, 1-3, 1-5, 1-7 and 1-14 are as follows. No.1-2 ¹ H-NMR (CDCl ₃ , δppm, TMS) 4.08 (3H, s), 7.07 (1H,
s), 8.03 (1H, s), 8.90 (1H, s) No. 1-3 ¹ H-NMR (CDCl ₃ , δppm, TMS) 3.62 (3H, s), 8.14 (1H, b
s), 8.67 (1H, bs) No.1-5 ¹ H-NMR (CDCl ₃ , δppm, TMS) 4.00 (3H, s), 6.94 (1H,
s), 7.98 (1H, bs), 8.74 (1H, bs) No. 1-7 ¹ H-NMR (CDCl ₃ , δppm, TMS) 4.08 (3H, s), 7.10 (1H,
s), 8.08 (1H, bs), 9.40 (1H, bs) No. 1-8 ¹ H-NMR (CDCl ₃ , δppm, TMS) 3.26 (3H, s), 5.83 (2H,
s), 7.20 (1H, s), 8.18 (1H, bs), 8.95 (1H, bs) No. 1-14 ¹ H-NMR (CDCl ₃ , δppm, TMS) 3.70 (3H, s), 6.56 (1H ,
s), 7.46 (2H, s) MS (FAB) 361 (M ⁺ +1)

Table 2

[0113]

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[0114]

[Table 2] ──────────────────────────── No. R ¹ R ² R ³ R ⁵ W Properties ─────── ────────────────────── 2-1 CO ₂ Me H CF ₃ CF ₃ N Oily 2 2 CO ₂ Me H C ₂ F ₅ CF ₃ N 44 -44.5 ℃ 2-3 CN H C ₂ F ₅ CF ₃ N 2-4 H H SMe Cl C-Cl 111-114 ℃ 2-5 H H SOMe Cl C-Cl 159-162 ℃ 2-6 H H SCF ₃ Cl C-Cl 2-7 H H SOCF ₃ Cl C-Cl 2-8 Me H SCF ₃ CF ₃ C-Cl Oily 2-9 Me H SCF ₃ CF ₃ C-Cl 2-10 CN H SCF ₃ CF ₃ C -Cl 2-11 Me H SOCF ₃ CF ₃ C-Cl 2-12 CN H SOCF ₃ CF ₃ C-Cl 2-13 Me Cl SCF ₃ Cl C-Cl 70-71.5 ° C 2-14 Me Cl SCF ₃ CF ₃ C-Cl 2-15 Me Cl SOCF ₃ CF ₃ C-Cl 2-16 CN Cl SOCF ₃ CF ₃ C-Cl 2-17 Me Br SCF ₃ Cl C-Cl 80.0-81.5 ° C 2-18 CN Br SOCF ₃ CF ₃ C-Cl 2-19 H H SC ₂ F ₅ CF ₃ C-Cl 2-20 Me H SC ₂ F ₅ Cl C-Cl Oily 2-21 CN H SC ₂ F ₅ CF ₃ C-Cl 2-22 CN H SOC ₂ F ₅ CF ₃ C-Cl ─────────────────────────── ─

In the table, the spectral data of each compound of Nos. 2-1, 2-8 and 2-20 are as follows. No.2-1 ¹ H-NMR (CDCl ₃ , δppm, TMS) 4.16 (3H, m), 7.44 (1H,
s), 8.09 (1H, bs), 8.92 (1H, bs) No. 2-8 ¹ H-NMR (CDCl ₃ , δppm, TMS) 4.19 (3H, s), 6.88 (1H,
s), 7.51 (2H, s) No. 2-20 ¹ H-NMR (CDCl ₃ , δppm, TMS) 4.08 (3H, s), 6.72 (1H,
s), 7.40 (2H, s)

Formulation Examples Next, formulation examples of pest control agents containing the compound of the present invention as an active ingredient are shown, but the present invention is not limited thereto. In the following formulation examples, "part" means part by weight.

[Formulation Example 1] Wettable powder Compound of the present invention: 50 parts Diklite PFP: 43 parts (Kaolin clay: Sikhlite Industry Co., Ltd.) Product name: Solpol 5050 ・ ・ ・ ・ ・ ・ ・ 2 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. product name) Lunox 1000 C ・ ・ ・ ・ ・ ・ ・ 3 parts (Anionic interface Activator: Toho Chemical Industry Co., Ltd. product name) Carplex # 80 (anti-caking agent) ... 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd. product name) Use as an agent.

[Formulation Example 2] Emulsion Compound of the present invention: 3 parts xylene: 76 parts Isophorone: 15 parts Solpol 3005X ..... 6 parts (mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) The above components are uniformly mixed to form an emulsion.

[Formulation Example 3] Flowable agent Compound of the present invention: 35 parts Agrisol S-711: 8 parts (Nonionic surfactant: Kao (stock) ) Trade name) Lunox 1000 C --- 0.5 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) 1% Rhodopol water --- 20 parts ( Thickener: Trade name of Lorne Poulin Co., Ltd. Ethylene glycol (anti-freezing agent) ... 8 parts Water ... 28.5 parts Mix the above uniformly to make a flowable agent.

[Formulation Example 4] Granular wettable powder (dry flowable agent) Compound of the present invention: 75 parts Isoban No. 1: 10 parts (anionic interface Activator: Trade name of Kuraray Isoprene Chemical Co., Ltd. Vanillex N ........ 5 parts (Anionic surfactant: Trade name of Sanyo Kokusaku Pulp Co., Ltd.) Carplex # 80 ... 10 parts (white carbon: trade name of Shionogi Seiyaku Co., Ltd.) The above components are uniformly mixed and pulverized to obtain a dry flowable agent.

[Formulation Example 5] Granules Compound of the present invention: 0.1 part Bentonite: 55.0 parts Talc: 44.9 parts After being uniformly mixed and pulverized, a small amount of water is added, and the mixture is kneaded with stirring, granulated by an extrusion granulator, and dried to give granules.

[Formulation Example 6] Powder Compound of the present invention: 3.0 parts Carplex # 80: 0.5 part (White carbon: Shionogi Pharmaceutical Co., Ltd. ) Product name) Clay ・ ・ ・ ・ ・ ・ 95 parts Diisopropyl phosphate ・ ・ ・ ・ ・ ・ ・ ・ 1.5 parts The above is uniformly mixed and pulverized to give a powder.

In use, the above-mentioned wettable powder, emulsion, flowable agent and granular wettable powder are diluted 50 to 20000 times with water to prepare an active ingredient in an amount of 0.005 to 5 per hectare (ha).
Sprinkle so that it weighs 0 kg.

TEST EXAMPLE Next, the usefulness of the compound of the present invention as a pest control agent will be specifically described in the following test examples.

Test Example 1 Insecticidal test against green leafhopper 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent to give 1000 ppm. Prepare a chemical solution of the concentration and add this chemical solution to 1 / 20,00
A sufficient amount was applied to the foliage of rice planted in a pot of 0 are. After air-drying, a cylinder was erected, and 10 second-instar larvae of the leafhopper leafhopper were released in each pot, and capped with a hole.
It was housed in a constant temperature chamber at ℃. The mortality rate after 6 days was calculated from the following formula. The test was conducted in a two-division system. Mortality rate (%) = (Number of dead insects / Number of released insects) x 100

As a result, the following compounds of the present invention showed a mortality rate of 1
It showed 00%. The compound of the present invention: 1-3, 1-4, 1-
5,1-6,1-7,1-8,1-9,1-14,1-
19, 1-20, 1-24, 2-1, 2-4, 2-5,
2-13, 2-20.

Test Example 2 Insecticidal test against pearl oyster ladybug A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent. Then, prepare a chemical solution with a concentration of 1000 ppm, soak the tomato leaves in this chemical solution for about 10 seconds, air-dry and place in a petri dish.
Ten of the insects were released, covered and placed in a thermostatic chamber at 25 ° C, and the mortality rate after 6 days was calculated from the following formula. The test is 2
It was done in a ward system. Mortality rate (%) = (Number of dead insects / Number of released insects) x 100

As a result, the following compounds of the present invention showed a mortality rate of 1
It showed 00%. . Inventive compound: No. 1-2,1-
4, 1-5, 1-6, 1-19, 1-20, 1-24,
2-1, 2-2, 2-4, 2-5, 2-8, 2-13,
2-17, 2-20.

[0129]

INDUSTRIAL APPLICABILITY The compound of the present invention has excellent insecticidal and acaricidal activity against many agricultural pests and spider mites, and has almost no adverse effect on mammals, fish and beneficial insects. Therefore, the compound of the present invention can provide a useful pest control agent.

Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C07D 231/22 C07D 231/22 A 401/04 231 401/04 231 (72) Inventor Yoichi Inoue Minami Saitama District, Saitama Prefecture 1470 Shiraoka, Shiraoka-machi, Institute of Biological Sciences, Nissan Chemical Industry Co., Ltd. (72) Inventor, Toshiro Miyake 1470, Shiraoka, Shirooka-cho, Minamisaitama-gun, Saitama Prefecture Institute of Biological Sciences, Nissan Chemical Industries, Ltd.

Claims (18)

[Claims] 1. A compound of the formula (I) [In the formula, A and B are R ³ or G (provided that A is R ³ , B
Means G, when A is G, B means R ³ ), and G is W represents a nitrogen atom or CR ⁶ , R ¹ represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a formyl group, a C _1-6 alkyl group, a C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 haloalkyl group, C _2-6 haloalkenyl, C _2-6 haloalkynyl group, C _2-6 alkoxyalkyl group, C _{2 -6} cyanoalkyl group, C _2-6 alkyl Carbonyl group, C _2-6 alkoxycarbonyl group, C _2-6 haloalkylcarbonyl group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylthio group, C _1-6 haloalkylsulfinyl group, C
_1-6 haloalkylsulfonyl group, R ⁸ OC (O) N (R ⁹ ) S- group, R
⁹ (R ¹⁰⁾ NS- group, (R ⁷⁾ a phenyl group optionally substituted by _q, (R ⁷⁾ may phenylthio group optionally substituted by _q, optionally substituted by (R ⁷⁾ _q A good phenylsulfinyl group or a phenylsulfonyl group optionally substituted by (R ⁷ ) _q , R ² and R ⁷ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, C _{1 -6} alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 haloalkylthio group, C
_1-6 alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, C _2-6 alkoxycarbonyl group, amino group or di-C
_{1-6 represents} an alkylamino group, R ³ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a formyl group, an SCN group, a trimethylsilyl group,
R ¹¹ , OR ¹¹ , S (O) _p R ¹¹ group, OS (O) ₂ R ¹¹ group, OC (O) R ¹¹ group, C
(O) R ¹¹ group, CO ₂ R ¹¹ group, C (O) N (R ¹¹ ) R ¹² group, SO ₂ N (R ¹¹ ) R ^{12 group}
A group, NHC (O) R ¹¹ group or N (R ¹¹ ) R ¹² group is shown, R ⁴ , R ⁵ and R ⁶ are each independently a halogen atom, a hydroxyl group,
Cyano group, nitro group, C _1-6 alkyl group, C _1-6 haloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6
Alkynyl group, C _2-6 haloalkynyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6
Haloalkylthio group, C _1-6 alkylsulfinyl group, C
_1-6 haloalkylsulfinyl group, C _1-6 alkylsulfonyl group, C _{1 -6} haloalkylsulfonyl group, C _2-6 alkoxycarbonyl group, C _2-6 haloalkoxycarbonyl group, amino group, C _1-6 alkylamino group , C _1-6 haloalkylamino group or di C _1-6 alkylamino group is shown, R ⁸ , R ⁹ and R ¹⁰ are each independently a C _1-6 alkyl group, (R ⁷ ) _q
Represents a phenyl group _optionally substituted by or a benzyl group optionally substituted by (R ⁷ ) _q , R ¹¹ represents a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 alkenyl group. Group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _3-6 cycloalkyl group, C
_3-6 halocycloalkyl group, C _4-7 cycloalkylalkyl group, C _2-6 alkoxyalkyl group, C _2-6 alkylthioalkyl group, C _3-6 alkoxycarbonylalkyl group, C _2-6
A cyanoalkyl group, R ¹² represents a hydrogen atom or a C _1-6 alkyl group, p represents an integer of 0 to 2, q represents an integer of 0 to 5 (provided that q is 2 to 5) R ⁷ may be the same or different), r is an integer of 0 to 4 (provided that R ⁷ is the same or different when r is 2 to 4). Indicates. ] The pyrazole derivative represented by these, or its salt. 2. R ¹ is a cyano group, a formyl group, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 haloalkenyl group,
C _2-6 haloalkynyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 haloalkylthio group, C _1-6 alkylsulfinyl group, C _1-6 Haloalkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, C _2-6 alkoxycarbonyl group,
C _2-6 haloalkoxycarbonyl group, C _2-6 alkylcarbonyl group, represents a C _2-6 haloalkylcarbonyl group, R ³ is a halogen atom, a cyano group, a nitro group, a formyl group, a C _1-6 alkyl group, C _{1 -6} haloalkyl group, C _2-6 haloalkenyl, C _2-6 haloalkynyl group, C _1-6 alkoxy, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6
Haloalkylthio group, C _1-6 alkylsulfinyl group, C
_1-6 haloalkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylsulfonyl group, C _2-6 alkoxycarbonyl group, C _2-6 haloalkoxycarbonyl group, C
_2-6 alkylcarbonyl group, C _2-6 pyrazole derivative or its salt according to claim 1 showing a haloalkylcarbonyl group 3. R ⁴ , R ⁵ and R ⁶ are each independently a halogen atom, a cyano group, a nitro group, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 alkoxycarbonyl group, The pyrazole derivative or salt thereof according to claim 2, which represents a C _2-6 haloalkoxycarbonyl group. 4. A pyrazole derivative or a salt thereof according to claim ³ , wherein A represents G and B represents R ³ . 5. The pyrazole derivative or a salt thereof according to claim ³ , wherein A represents R ³ and B represents G. 6. The pyrazole derivative or a salt thereof according to claim 4, wherein W represents CR ⁶ . 7. The pyrazole derivative or a salt thereof according to claim 4, wherein W represents a nitrogen atom. 8. The pyrazole derivative or a salt thereof according to claim 5, wherein W represents CR ⁶ . 9. The pyrazole derivative or a salt thereof according to claim 5, wherein W represents a nitrogen atom. It is 10. R ^3, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 haloalkylthio group, C _1-6 pyrazole derivative or its salt according to claim 6, wherein indicating the haloalkylsulfinyl groups . It is 11. R ^3, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 haloalkylthio group, C _1-6 pyrazole derivative or its salt according to claim 7, wherein indicating a haloalkylsulfinyl group . Is 12. R ^3, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 haloalkylthio group, C _1-6 pyrazole derivative or its salt according to claim 8, wherein showing the haloalkylsulfinyl groups . It is 13. R ^3, C _1-6 alkyl, C _1-6 haloalkyl group, C _1-6 haloalkylthio group, C _1-6 pyrazole derivative or its salt according to claim 9, wherein indicating a haloalkylsulfinyl group . 14. The pyrazole derivative or a salt thereof according to claim 10, wherein R ⁴ , R ⁵ and R ⁶ each independently represent a halogen atom or a C _1-6 haloalkyl group. 15. The pyrazole derivative or a salt thereof according to claim 11, wherein R ⁴ and R ⁵ each independently represent a halogen atom or a C _1-6 haloalkyl group. 16. The pyrazole derivative or a salt thereof according to claim 12, wherein R ⁴ , R ⁵ and R ⁶ each independently represent a halogen atom or a C _1-6 haloalkyl group. 17. The pyrazole derivative or a salt thereof according to claim 13, wherein R ⁴ and R ⁵ each independently represent a halogen atom or a C _1-6 haloalkyl group. 18. A pest control agent containing, as an active ingredient, one or more of the pyrazole derivative or the salt thereof according to claim 1.