JP5743418B2 - Novel pyrazole compound, its production method and pest control agent - Google Patents

Description

  The present invention relates to a novel pyrazole compound, a production method thereof, and a pest control agent.

  Conventionally, in the field of agriculture and horticulture, insecticides and acaricides for the purpose of controlling various pests have been developed and put to practical use. However, the emergence of pests that have acquired drug resistance has become a problem, and the control of those pests has become difficult year by year.

  In addition, there are insecticides and acaricides (for example, organic halogenated pesticides such as DDT and BHC, chlorinated cyclic diene pesticides such as aldrin and dieldrin, etc.) for which pests have not yet acquired resistance. There is a problem from the viewpoint of contamination. Therefore, development of a novel insecticide / acaricide which is effective against various resistant pests and has been considered with respect to toxicity and environmental aspects is eagerly desired.

  The compound in which the pyrazole ring 1-position of the present invention is substituted with a heterocycle at the 1-position and a sulfonate group at the 5-position has very few reported examples, and synthetic intermediates and pyrazoles described in pharmaceutical-related patents (see Patent Documents 1 to 3) It is only a report of the compound described in the literature (refer nonpatent literature 1-3) regarding the spectrum analysis and structure determination of a derivative, and the report regarding a pest control agent (insecticide and acaricide) is not known at all.

WO2008 / 121861 Publication WO2008 / 047198 Publication WO2009 / 041705 Publication

Kemiai Kozlemenyek, 54 (2-3), 313-320 (1980) Journal of Heterocyclic Chemistry, 17 (4), 781-783 (1980) Journal of Molecular Structure, 60, 43-48 (1980)

  An object of the present invention is to provide a novel pyrazole compound capable of expressing excellent biological activity not only against spider mites but also nematodes.

  As a result of intensive studies to solve the above problems, the present inventors have succeeded in synthesizing a novel pyrazole compound having a nitrogen-containing heterocycle at the 1-position of the pyrazole ring and a sulfonate group at the 5-position. It has been found that it exhibits excellent biological activity against nematodes as well as spider mites. The present invention has been completed based on such findings.

The present invention provides a pyrazole compound, a production method thereof, and a pest control agent described in Items 1 to 8 below.
Item 1. General formula (1)

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, or a C _2-6 haloalkenyl group. , C _2-6 alkynyl group, C _2-6 haloalkynyl group, formyl group, nitro group, cyano group, benzyl group or phenyl group (on the phenyl ring, a halogen atom, a C _1-4 alkyl group and C _1- 1 or more of at least one substituent selected from the group consisting of ₄ haloalkyl groups may be substituted).

R ² is a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, a C _2-6 alkynyl group, C _{2 -6} haloalkynyl group, heterocyclic group (on the heterocyclic ring, at least one substituent selected from the group consisting of a halogen atom, a C _1-4 alkyl group and a C _1-4 haloalkyl group is substituted. Benzyl group or phenyl group (on the phenyl ring, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 Alkylcal Alkenyl group, C _1-4 alkylthio, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, at least one substituent selected from the group consisting of a nitro group and a cyano group substituted with one or more May be).

R is pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, pyrazin-2-yl Group, pyridazin-2-yl group, pyridazin-3-yl group, triazin-2-yl group, thiazol-2-yl group, thiazol-4-yl group, oxazol-2-yl group, oxazol-4-yl group Benzothiazol-2-yl group, quinolin-2-yl group, isoquinolin-2-yl group or quinoxalin-2-yl group, and each nitrogen-containing heterocyclic ring has a halogen atom, C _1-4 alkyl Group, C _1-4 haloalkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _{1- 4} A Kokishi _{group, C 1-4 haloalkoxy, C 1-4} alkoxycarbonyl _{group, C 1-4 alkylcarbonyl, C 1-4 alkylthio, C 1-4} alkylsulfinyl _{group, C 1-4} alkylsulfonyl group, One or more substituents selected from the group consisting of a nitro group and a cyano group may be substituted.

Q is a hydrogen atom, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-6. Alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, mono- or di (C _1-6 alkyl) aminocarbonyl group, C _{1 -4} alkylthio group, _C1-4 alkylsulfinyl group, nitro group, cyano group, phenyl group or heterocyclic group.

On the phenyl ring of Q, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-18 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 haloalkoxycarbonyl group, C _1-4 Alkylcarbonyl group, C _1-4 haloalkylcarbonyl group, group —C (R ³ ) ═NO (R ⁴ ), C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, nitro One or more substituents selected from the group consisting of a group, a cyano group, an amino group and a heterocyclic group may be substituted. In addition, when a C _1-12 alkyl group is substituted on two adjacent carbon atoms on the phenyl ring, these alkyl groups may be bonded to each other to form a saturated 5- or 6-membered ring. .

Here, R ³ represents a C _1-6 alkyl group, a C _1-6 haloalkyl group or a phenyl group (on the phenyl ring, a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _{1- And} at least one substituent selected from the group consisting of ₄ alkoxy groups and C _1-4 haloalkoxy groups may be substituted, and R ⁴ represents a C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group or benzyl group (of benzyl group) On the phenyl ring, a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 haloalkoxy group, a C _1-4 alkoxycarbonyl group, a mono or di ( C _1-6 alkyl) aminocarbonyl group, C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, at least one substituent selected from the group consisting of nitro group and cyano group may be substituted by one or more. Good).

On the heterocyclic ring of Q, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-18 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 alkylcarbonyl group, group —C (R ³ ) = NO (R ⁴ ), C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, nitro group, cyano group, amino group and heterocyclic group Further, at least one substituent may be substituted by one or more. Here, R ³ and R ⁴ are the same as described above. ] The pyrazole compound represented by these, and its N-oxide.
Item 2. Item 2. The pyrazole compound according to Item 1, wherein the pyrazole compound is a compound in which R represents a pyridin-2-yl group, a pyrazin-2-yl group, or a thiazol-2-yl group in the general formula (1), and an N-oxide thereof. .
Item 3. Item 3. The pyrazole compound according to Item 1 or 2, wherein the pyrazole compound is a compound in which R ¹ represents a hydrogen atom or a halogen atom in General Formula (1), and an N-oxide thereof.
Item 4. Item 4. The pyrazole compound according to any one of Items 1 to 3, and the N-oxide thereof, wherein the pyrazole compound is a compound in which R ² represents a C _1-4 alkyl group in the general formula (1).
Item 5. The pyrazole compound is represented by the general formula (1), wherein Q is a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _3-8 cycloalkyl group, a mono- or di (C _1-6 alkyl) aminocarbonyl group, Item 5. The pyrazole compound according to any one of Items 1 to 4, which is a cyano group, a phenyl group, or a heterocyclic group, and an N-oxide thereof.
Item 6. General formula (1)

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, or a C _2-6 haloalkenyl group. , C _2-6 alkynyl group, C _2-6 haloalkynyl group, formyl group, nitro group, cyano group, benzyl group or phenyl group (on the phenyl ring, a halogen atom, a C _1-4 alkyl group and C _1- 1 or more of at least one substituent selected from the group consisting of ₄ haloalkyl groups may be substituted).

R ² is a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, a C _2-6 alkynyl group, C _{2 -6} haloalkynyl group, heterocyclic group (on the heterocyclic ring, at least one substituent selected from the group consisting of a halogen atom, a C _1-4 alkyl group and a C _1-4 haloalkyl group is substituted. Benzyl group or phenyl group (on the phenyl ring, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 Alkylcal Alkenyl group, C _1-4 alkylthio, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, at least one substituent selected from the group consisting of a nitro group and a cyano group substituted with one or more May be).

R is pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, pyrazin-2-yl Group, pyridazin-2-yl group, pyridazin-3-yl group, triazin-2-yl group, thiazol-2-yl group, thiazol-4-yl group, oxazol-2-yl group, oxazol-4-yl group Benzothiazol-2-yl group, quinolin-2-yl group, isoquinolin-2-yl group or quinoxalin-2-yl group, and each nitrogen-containing heterocyclic ring has a halogen atom, C _1-4 alkyl Group, C _1-4 haloalkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _{1- 4} A Kokishi _{group, C 1-4 haloalkoxy, C 1-4} alkoxycarbonyl _{group, C 1-4 alkylcarbonyl, C 1-4 alkylthio, C 1-4} alkylsulfinyl _{group, C 1-4} alkylsulfonyl group, One or more substituents selected from the group consisting of a nitro group and a cyano group may be substituted.

Q is a hydrogen atom, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-6. Alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, mono- or di (C _1-6 alkyl) aminocarbonyl group, C _{1 -4} alkylthio group, _C1-4 alkylsulfinyl group, nitro group, cyano group, phenyl group or heterocyclic group.
On the phenyl ring of Q, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-18 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 haloalkoxycarbonyl group, C _1-4 Alkylcarbonyl group, C _1-4 haloalkylcarbonyl group, group —C (R ³ ) ═NO (R ⁴ ), C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, nitro One or more substituents selected from the group consisting of a group, a cyano group, an amino group and a heterocyclic group may be substituted. In addition, when a C _1-12 alkyl group is substituted on two adjacent carbon atoms on the phenyl ring, these alkyl groups may be bonded to each other to form a saturated 5- or 6-membered ring. .

Here, R ³ represents a C _1-6 alkyl group, a C _1-6 haloalkyl group or a phenyl group (on the phenyl ring, a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _{1- And} at least one substituent selected from the group consisting of ₄ alkoxy groups and C _1-4 haloalkoxy groups may be substituted, and R ⁴ represents a C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group or benzyl group (of benzyl group) On the phenyl ring, a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 haloalkoxy group, a C _1-4 alkoxycarbonyl group, a mono or di ( C _1-6 alkyl) aminocarbonyl group, C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, at least one substituent selected from the group consisting of nitro group and cyano group may be substituted by one or more. Good).

On the heterocyclic ring of Q, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-18 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 alkylcarbonyl group, group —C (R ³ ) = NO (R ⁴ ), C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, nitro group, cyano group, amino group and heterocyclic group Further, at least one substituent may be substituted by one or more. Here, R ³ and R ⁴ are the same as described above. ] The pyrazole compound represented by these, and its manufacturing method of N-oxide, Comprising: General formula (2)

[Wherein R, R ¹ and Q are as defined above] and a general formula (3)

[Wherein R ² is the same as defined above. X represents a halogen atom. ] A sulfonyl halide represented by the general formula (4)

[Wherein R ² is the same as defined above. ] The manufacturing method of the pyrazole compound and its N-oxide which are made to react with the sulfonic acid anhydride represented by these.
Item 7. Item 6. A pest control agent comprising the pyrazole compound according to any one of Items 1 to 5 and an N-oxide thereof.
Item 8. Item 6. An acaricide containing the pyrazole compound according to any one of Items 1 to 5 and an N-oxide thereof.
Specific examples of each group shown in the present specification include the following.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

Examples of the _C1-4 alkyl group include C1-C4 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. A linear or branched alkyl group is mentioned.

Examples of the C _1-6 alkyl group include carbons such as n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, and isohexyl group, in addition to the groups exemplified as the C _1-4 alkyl group. The linear or branched alkyl group of number 1-6 is mentioned.

As the C _1-12 alkyl group, in addition to the groups exemplified for the C _1-6 alkyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n- C1-C12 linear or branched alkyl groups, such as a decyl group, an isodecyl group, n-undecyl group, an isoundecyl group, n-dodecyl group, isododecyl group, are mentioned.

Examples of the saturated 5- or 6-membered ring formed by substituting a C _1-12 alkyl group on two adjacent carbon atoms on the phenyl ring and bonding these alkyl groups to each other include a cyclopentane ring and cyclohexane. And a ring condensed with a phenyl ring to form an indane ring or a tetrahydronaphthalene ring, respectively.

Examples of the C _1-4 haloalkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a trifluoromethyl group, a chlorodifluoromethyl group, a bromodifluoromethyl group, a dichlorofluoromethyl group, 1 -Fluoroethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-iodoethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl 1-9 such as a group, 1-fluoroisopropyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-bromopropyl group, heptafluoropropyl group, 4-fluorobutyl group, 4-chlorobutyl, nonafluorobutyl group, etc. , Preferably 1 to 6 carbon atoms substituted with halogen atoms 1-4 linear or branched alkyl groups are mentioned.

As the C _1-6 haloalkyl group, in addition to the groups exemplified for the C _1-4 haloalkyl group, a 5,5,5-trifluoropentyl group, a 5-chloropentyl group, an undecafluoropentyl group, 6,6 , 6-trifluorohexyl group, 6-chlorohexyl group, tridecafluorohexyl group, etc. 1-13, preferably 1-9 linear or branched, substituted with 1 to 9 halogen atoms A chain alkyl group is mentioned.

As the C _1-12 haloalkyl group, in addition to the groups exemplified for the C _1-6 haloalkyl group, a 1-fluoroheptyl group, a 1-fluorooctyl group, a 1-fluoroundecyl group, a 1-fluorododecyl group, etc. Examples thereof include a linear haloalkyl group having 1 to 12 carbon atoms and substituted with 1 to 13, preferably 1 to 9 halogen atoms.

Examples of the C _3-8 cycloalkyl group include cyclic alkyl groups having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the C _2-6 alkenyl group include a vinyl group, 1-propenyl group, allyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 1,3-butadienyl. Group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1,1-dimethyl-2-propenyl group, 1-ethyl-2-propenyl group, 1-methyl-2-butenyl group 1-methyl-3-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1,1-dimethyl-2-butenyl group, 1,1- Examples thereof include a C2-C6 linear or branched alkenyl group having at least one double bond at an arbitrary position such as a dimethyl-3-butenyl group.

Examples of the C _2-6 haloalkenyl group include 2,2-dichlorovinyl group, 2,2-dibromovinyl group, 3-chloro-2-propenyl group, 3,3-difluoro-2-allyl group, 3, 3-dichloro-2-allyl group, 4-chloro-2-butenyl group, 4,4,4-trifluoro-2-butenyl group, 4,4,4-trichloro-3-butenyl group, 5-chloro-3 A linear or branched alkenyl group having 2 to 6 carbon atoms and having at least one double bond at an arbitrary position such as a pentenyl group, 6-fluoro-2-hexenyl group, etc., 1 to 13, An alkenyl group substituted with 1 to 7 halogen atoms is preferable.

Examples of the C _2-6 alkynyl group include ethynyl group, 2-propynyl group, 1-methyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-butynyl group, 2-butynyl group, 3 -Butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 1-methyl-3-butynyl group, 1,1-dimethyl-2- 2 to 6 carbon atoms having at least one triple bond at any position such as butynyl group, 1,1-dimethyl-3-butynyl group, 1-methyl-3-pentynyl group, 1-methyl-4-pentynyl group, etc. A linear or branched alkynyl group is mentioned.

Examples of the C _2-18 alkynyl group include 1-heptynyl group, 1-octynyl group, 2-cyclopentynyl group, 2-cyclohexynyl group, 1-decanyl in addition to the groups exemplified for the C _2-6 alkynyl group. A linear, cyclic or branched alkynyl group having 2 to 18 carbon atoms having at least one triple bond at an arbitrary position such as a group, 1-octadodenyl group, 1-octadecanyl group and the like.

C _2-6 haloalkynyl group includes 2-fluoroethynyl group, 2-bromoethynyl group, 2-chloroethynyl group, 2-iodoethynyl group, 3-chloro-1-propynyl group, 1-chloro-2-propynyl group Group, 3-chloro-1-methyl-2-propynyl group, 4-chloro-1-butynyl group, 4-chloro-2-butynyl group, 4-chloro-3-butynyl group, 3-chloro-1-pentynyl group 5,5,5-trifluoro-3-pentynyl group, 1-methyl-2-butynyl group, 4-chloro-1-methyl-2-butynyl group, 1,1-dimethyl-4-chloro-2-butynyl Group having at least one triple bond at any position such as a group, 1-methyl-5-chloro-3-pentynyl group, 1-methyl-5,5,5-trifluoro-2-pentynyl group and the like. Linear or minute A chain alkynyl groups, one to nine, and preferably an alkenyl group substituted with 1-5 halogen atoms.

Examples of the heterocyclic group include thienyl, furyl, tetrahydrofuryl, dioxolanyl, dioxanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl, isoxazolinyl, thiazolyl, isothiazolyl, thiazolinyl, thiazolidinyl, isothiazolinyl, pyrazolyl, pyrazolyl, , Imidazolinyl, imidazolidinyl, oxadiazolyl, oxadiazolinyl, thiadiazolinyl, triazolyl, triazolinyl, triazolidinyl, tetrazolyl, tetrazolinyl, pyridyl, dihydropyridyl, tetrahydropyridyl, piperidyl, oxazinyl, dihydrooxazinyl, morpholino, thiazinyl, thiazinyl, thiazinyl , Pyridazini Dihydropyridazinyl, tetrahydropyridazinyl, hexahydropyridazinyl, oxadiazinyl, dihydrooxadiazinyl, tetrahydrooxadiazinyl, thiadiazolyl, thiadiazinyl, dihydrothiadiazinyl, tetrahydrothiadiazinyl, pyrimidinyl, Dihydropyrimidinyl, tetrahydropyrimidinyl, hexahydropyrimidinyl, pyrazinyl, dihydropyrazinyl, tetrahydropyrazinyl, piperazinyl, triazinyl, dihydrotriazinyl, tetrahydrotriazinyl, hexahydrotriazinyl, tetrazinyl, dihydrotetrazinyl, indolyl , Indolinyl, isoindolyl, indazolyl, quinazolinyl, dihydroquinazolyl, tetrahydroquinazolyl, carbazolyl, benzoxazolyl, Nzooxazolinyl, benzisoxazolyl, benzoisoxazolinyl, benzothiazolyl, benzisothiazolyl, benzisothiazolinyl, benzimidazolyl, indazolinyl, quinolinyl, dihydroquinolinyl, tetrahydroquinolinyl, isoquinolinyl, dihydro Isoquinolinyl, tetrahydroisoquinolinyl, pyridoindolyl, dihydrobenzoxazinyl, cinnolinyl, dihydrocinnolinyl, tetrahydrocinnolyl, phthalazinyl, dihydrophthalazinyl, tetrahydrophthalazinyl, quinoxalinyl, dihydroquinoxalin Nyl, tetrahydroquinoxalinyl, purinyl, dihydrobenzotriazinyl, dihydrobenzotetrazinyl, phenothiazinylfuranyl, benzofuranyl, chromanyl, benzothienyl, etc. Can be mentioned. These heterocyclic groups may include those in the form of an oxo form or thioketone form at any substitutable position, and these heterocyclic groups may have an appropriate substituent such as a halogen atom at any substitutable position. , A C _1-4 alkyl group, a C _1-4 haloalkyl group, a heterocyclic group having a substituent (specifically, a 3-chloropyridin-2-yl group, a 5-trifluoromethylpyridin-2-yl group, 4-methyl-1,3-thiazole group etc.) may be substituted by 1 to 5 (preferably 1 to 3).

  Among these heterocycles, thienyl, furanyl, chromanyl, pyridyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, isoxazolinyl, pyrimidinyl, pyrazinyl and pyridazinyl are preferred, and thienyl, chromanyl, pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, and isoxazolyl, Isoxazolinyl is particularly preferred.

Examples of the C _1-4 alkoxy group include carbon number 1 such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropyloxy group, n-butoxy group, sec-butoxy group, and tert-butoxy group. -4 linear or branched alkoxy groups.

Examples of the C _1-4 haloalkoxy group include a fluoromethoxy group, a chloromethoxy group, a bromomethoxy group, an iodomethoxy group, a dichloromethoxy group, a trichloromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a chlorodifluoromethoxy group, Bromodifluoromethoxy group, dichlorofluoromethoxy group, 1-fluoroethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 2-iodoethoxy group, 2,2,2-trifluoroethoxy group 2,2,2-trichloroethoxy group, pentafluoroethoxy group, 1-fluoroisopropoxy group, 3-fluoropropoxy group, 3-chloropropoxy group, 3-bromopropoxy group, 4-fluorobutoxy group, 4-chloro 1-9 such as butoxy groups, preferred Or a linear or branched alkoxy group having 1 to 4 carbon atoms substituted with 1 to 5 halogen atoms.

The C _1-4 alkoxycarbonyl group is, for example, a group in which a linear or branched alkoxy group having 1 to 4 carbon atoms and a carbonyl group are bonded, specifically, a methoxycarbonyl group, ethoxycarbonyl, or the like. Group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group and the like are included.

Examples of the C _1-4 alkylcarbonyl group include a methylcarbonyl group (acetyl group), an ethylcarbonyl group (propionyl group), an n-propylcarbonyl group (butyryl group), an isopropylcarbonyl group (isobutyryl group), and n-butylcarbonyl. Examples thereof include a linear or branched alkylcarbonyl group having 1 to 4 carbon atoms such as a group (valeryl group), an isobutylcarbonyl group (isovaleryl group), a sec-butylcarbonyl group, and a tert-butylcarbonyl group.

Examples of the C _1-4 haloalkoxycarbonyl group include a fluoromethoxycarbonyl group, a chloromethoxycarbonyl group, a bromomethoxycarbonyl group, an iodomethoxycarbonyl group, a dichloromethoxycarbonyl group, a trichloromethoxycarbonyl group, a difluoromethoxycarbonyl group, and trifluoro. Methoxycarbonyl group, chlorodifluoromethoxycarbonyl group, bromodifluoromethoxycarbonyl group, dichlorofluoromethoxycarbonyl group, 1-fluoroethoxycarbonyl group, 2-fluoroethoxycarbonyl group, 2-chloroethoxycarbonyl group, 2-bromoethoxycarbonyl group, 2-iodoethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, pen Tafluoroethoxycarbonyl group, 1-fluoroisopropyloxycarbonyl group, 3-fluoropropyloxycarbonyl group, 3-chloropropyloxycarbonyl group, 3-bromopropyloxycarbonyl group, 4-fluorobutyloxycarbonyl group, 4-chlorobutyl Examples thereof include linear or branched alkoxycarbonyl groups having 1 to 4 carbon atoms and substituted with 1 to 9, preferably 1 to 5, halogen atoms such as an oxycarbonyl group.

Examples of the C _1-4 alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, a cyclopropylthio group, an n-butylthio group, a sec-butylthio group, and a tert-butylthio group. -4 linear or branched alkylthio groups are mentioned.

Examples of the C _1-4 alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, an n-propylsulfinyl group, an isoprosulfinyl group, a cyclopropylsulfinyl group, an n-butylsulfinyl group, a sec-butylsulfinyl group, and a tert-butyl. C1-C4 linear or branched alkyl sulfinyl groups, such as a sulfinyl group, are mentioned.

Examples of the C _1-4 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an isoprosulfonyl group, a cyclopropylsulfonyl group, an n-butylsulfonyl group, a sec-butylsulfonyl group, and a tert-butyl. C1-C4 linear or branched alkylsulfonyl groups, such as a sulfonyl group, are mentioned.

Examples of the C _1-4 haloalkylcarbonyl group include a fluoromethylcarbonyl group, a chloromethylcarbonyl group, a bromomethylcarbonyl group, an iodomethylcarbonyl group, a dichloromethylcarbonyl group, a trichloromethylcarbonyl group, a difluoromethylcarbonyl group, and trifluoromethyl. Carbonyl group, chlorodifluoromethylcarbonyl group, bromodifluoromethylcarbonyl group, dichlorofluoromethylcarbonyl group, 1-fluoroethylcarbonyl group, 2-fluoroethylcarbonyl group, 2-chloroethylcarbonyl group, 2-bromoethylcarbonyl group, 2 -Iodoethylcarbonyl group, 2,2,2-trifluoroethylcarbonyl group, 2,2,2-trichloroethylcarbonyl group, pentafluoroethylcarbonyl group, 1-fur 1 to 9, such as oroisopropylcarbonyl group, 3-fluoropropylcarbonyl group, 3-chloropropylcarbonyl group, 3-bromopropylcarbonyl group, 4-fluorobutylcarbonyl group, 4-chlorobutylcarbonyl group, preferably 1 to Examples thereof include a linear or branched alkylcarbonyl group having 1 to 4 carbon atoms, which is substituted with 5 halogen atoms.

Examples of the mono or di (C _1-6 alkyl) aminocarbonyl group include an N-methylaminocarbonyl group, an N, N-dimethylaminocarbonyl group, an N-ethylaminocarbonyl group, an N, N-diethylaminocarbonyl group, an N , N-dipropylaminocarbonyl group, N, N-dibutylaminocarbonyl group, N, N-dihexylaminocarbonyl group, etc., and a linear or branched alkyl group having 1 to 6 carbon atoms.

Pyrazole Compound The pyrazole compound represented by the general formula (1) of the present invention is a novel compound in terms of structure having a sulfonate group at the 5-position of the pyrazole ring.

[Wherein, R ¹ , R ² , R and Q are the same as above. ]

Among the pyrazole compounds represented by the general formula (1) of the present invention, R ¹ is a hydrogen atom, a halogen atom, a C _1-3 alkyl group or a benzoyl group (1 to 5 halogen atoms are substituted on the phenyl ring) And a compound in which R ¹ represents a hydrogen atom is particularly preferable.

Among the pyrazole compounds represented by the general formula (1) of the present invention, R ² is a C _1-10 alkyl group, a C _1-6 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a mono Or a di (C _1-6 alkyl) aminocarbonyl group, a heterocyclic group (on the heterocyclic ring, at least one selected from the group consisting of a halogen atom, a C _1-4 alkyl group and a C _1-4 haloalkyl group) 1 or more substituents may be substituted) or a phenyl group (on the phenyl ring, a halogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _3-8 cycloalkyl group, a C _{2- At} least one selected from the group consisting of a ₆ alkenyl group, a C _2-6 haloalkenyl group, a C _2-6 alkynyl group, a C _2-6 haloalkynyl group, a C _1-6 alkoxy group and a C _1-4 haloalkoxy group Species substituent Is preferably a compound that shows a good) be substituted with one or more, _{furthermore, C 1-10 alkyl, C 1-6} haloalkyl _group, a compound showing a _{C 3-8} cycloalkyl group or a _{C 2-6} alkenyl group Particularly preferred.

  Among the pyrazole compounds represented by the general formula (1) of the present invention, R is a pyridin-2-yl group, a pyridin-3-yl group, a pyridin-4-yl group, a pyrimidin-2-yl group, and a pyrimidine-4. A compound showing -yl group, pyrimidin-5-yl group, pyrazin-2-yl group, thiazol-2-yl group or triazolyl group is preferred, and further pyridin-2-yl group, pyrimidin-2-yl group or A compound showing a pyrazin-2-yl group is particularly preferred.

Among the pyrazole compounds represented by the general formula (1) of the present invention, Q is a halogen atom, a C _1-10 alkyl group, a C _1-6 haloalkyl group, a C _3-8 cycloalkyl group, mono- or di (C _{1 -6} alkyl) aminocarbonyl group, a nitro group, a cyano group, on the phenyl group [the phenyl ring, a halogen _{atom, C 1-6 alkyl, C 1-4} haloalkyl _{group, C 3-8} cycloalkyl group, _{C 2 -6} alkenyl group, C _2-6 haloalkenyl group, C _2-12 alkynyl group, C _1-4 alkoxy group, C _1-4 alkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl _{group, C 1-4 alkylcarbonyl, C 1-4} haloalkylcarbonyl group, ^{group, -C (R 3) = NO} (R 4) {R 3 _{are, C 1-6} alkyl groups, C _-6 haloalkyl group, ^{R 4} _{is, C 1-6 alkyl, C 1-6} haloalkyl _{group, C 3-8} cycloalkyl _{group, C 2-6 alkenyl, C 2-6 haloalkenyl, C 3-6} An alkynyl group, a C _3-6 haloalkynyl group, a phenyl group (on the phenyl ring, at least one substituent selected from the group consisting of a halogen atom, a C _1-4 alkyl group and a C _1-4 haloalkyl group is One or more may be substituted), a benzyl group (on the phenyl ring of the benzyl group, selected from the group consisting of a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, and a C _1-4 alkoxy group) at least one substituent may be substituted one or _{more)}, C 1-4 alkylthio, C 1-4} alkylsulfinyl _{group, C 1-4} alkylsulfonyl group, a nitro group, a cyano group was, Ami Groups, on the Hajime Tamaki (heterocyclic, halogen _{atom, C 1-10} alkyl _group, at least one substituent selected from _{C 1-6} haloalkyl group and a _{C 3-8} group consisting cycloalkyl group 1 or more may be substituted.)] Or a heterocyclic group (on the heterocyclic ring, a group consisting of a halogen atom, a C _1-10 alkyl group, a C _1-6 haloalkyl group, and a C _3-8 cycloalkyl group). A compound in which at least one selected substituent may be substituted by 1 or more.), A C _1-6 haloalkyl group, a cyano group, a phenyl group [on the phenyl ring, a halogen atom; , C _1-6 alkyl group, C _1-4 haloalkyl group, C _2-6 alkenyl group, C _2-12 alkynyl group, C _1-4 alkoxy C _1-4 alkynyl group, —C (R ³ ) ═NO ( R ⁴ ) {R ³ is C _{1 -3} alkyl group, C _1-3 haloalkyl group, R ⁴ is a C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, phenyl group (phenyl ring Above, at least one substituent selected from the group consisting of a halogen atom, a C _1-4 alkyl group and a C _1-4 haloalkyl group may be substituted one or more) benzyl group (phenyl of benzyl group) At least one substituent selected from the group consisting of a halogen atom, a C _1-4 alkyl group and a C _1-4 haloalkyl group may be substituted on the ring)}, C _1-4 An alkylthio group, a C _1-4 alkylsulfinyl group, a nitro group, a cyano group, and a heterocyclic group (a compound showing an isoxazolyl group or a pyrazolyl group is preferable. On the heterocyclic ring, at least one substituent selected from the group consisting of a halogen atom, a C _1-10 alkyl group, a C _1-6 haloalkyl group, and a C _3-8 cycloalkyl group is substituted. Also good. 1 or more may be substituted with at least one substituent selected from the group consisting of: ], A heterocyclic group (a compound showing a pyrazolyl group, a thienyl group, a furyl group, an oxadiazolyl group, a triazolyl group or a thiazolyl group. On the heterocyclic ring, a halogen atom, a C _1-10 alkyl group, a C _1-6 haloalkyl is preferable. And at least one substituent selected from the group consisting of a group and a C _3-8 cycloalkyl group may be substituted by one or more.) Is particularly preferred.

The manufacturing method of a pyrazole compound The pyrazole compound represented by General formula (1) of this invention is manufactured by the method shown to following Reaction Formula-1, for example.
Reaction Formula-1

[Wherein R ¹ , R ² , R and Q are the same as above]

  In the method shown in Reaction Formula-1, the pyrazole compound represented by the general formula (1) is represented by the pyrazole compound represented by the general formula (2) and the general formula (3) or the general formula (4). It is produced by reacting a sulfonyl compound in a solvent.

  As the solvent used in the reaction of the compound of the general formula (2) with the compound of the general formula (3) or the general formula (4), a known solvent is widely used as long as it is an inert solvent for the reaction. be able to. For example, aliphatic or alicyclic hydrocarbon solvents such as hexane, cyclohexane, heptane, aromatic hydrocarbon solvents such as benzene, chlorobenzene, toluene, xylene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride Halogenated hydrocarbon solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, etc., ester solvents such as methyl acetate and ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, N, N-dimethyl Examples thereof include amide solvents such as formamide, nitrile solvents such as acetonitrile and propionitrile, and aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone and N, N′-dimethylimidazolinone. These solvents can be used alone or in combination of two or more as required.

  These solvents are generally used in an amount of about 1 to 500 parts by weight, preferably about 5 to 100 parts by weight per 1 part by weight of the pyrazole compound represented by the general formula (2).

  The reaction between the compound of general formula (2) and the compound of general formula (3) or general formula (4) is preferably carried out in the presence of a base. As the base used, known inorganic bases and organic bases can be used. Examples of the inorganic base include alkali metals such as sodium and potassium, alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium hydride, Examples thereof include alkali metal hydrides such as potassium hydride. Examples of the organic base include alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, amines such as triethylamine, diisopropylamine and pyridine. These bases are used individually by 1 type or in mixture of 2 or more types.

  Such a base is usually 0.1 to 100 equivalents, preferably 0.5 to 5 equivalents, more preferably 1 to 2 equivalents with respect to the pyrazole compound represented by the general formula (2). Used in.

  The proportion of the pyrazole compound represented by the general formula (2) and the sulfonyl compound represented by the general formula (3) or the general formula (4) can be appropriately selected from a wide range. On the other hand, the latter is preferably used in an amount of 0.5 mol or more, more preferably 1 to 2 mol.

  The reaction can usually be carried out within a range from −78 ° C. to the boiling temperature of the solvent used. The reaction is preferably performed at 0 ° C. to the boiling temperature of the solvent used, and more preferably at room temperature.

  The reaction time varies depending on the reaction temperature and cannot be generally specified, but the reaction is usually completed in about 0.5 to 24 hours.

  The pyrazole compound represented by the general formula (2) used as a starting material in the above reaction formula-1 is a known compound or a novel compound, and is produced, for example, according to the method shown in the following reaction formula-2.

  Reaction formula-2

[Wherein R ¹ , R and Q are the same as above]

  In the method shown in Reaction Formula-2, the pyrazole compound represented by the general formula (2) comprises a β-ketoester compound represented by the general formula (5) and a hydrazine compound represented by the general formula (6). It is produced by reacting in a solvent.

  As the solvent used in the reaction of the compound of the general formula (5) and the compound of the general formula (6), known solvents can be widely used as long as they are inert to the reaction. For example, any solvent used in the reaction represented by Reaction Scheme-1 can be used. These solvents can be used alone or in combination of two or more as required.

  These solvents are generally used in an amount of about 1 to 500 parts by weight, preferably about 5 to 100 parts by weight, based on 1 part by weight of the β-ketoester compound represented by the general formula (5).

  The ratio of the β-ketoester compound represented by the general formula (5) and the hydrazine compound represented by the general formula (6) can be appropriately selected from a wide range, but with respect to 1 mol of the former, The latter is preferably used in an amount of 0.5 mol or more, more preferably 1 to 2 mol.

  The reaction can usually be carried out within a range from −78 ° C. to the boiling temperature of the solvent used. The reaction is preferably performed at 0 ° C. to the boiling point of the solvent to be used, and more preferably the reaction is performed under heating and reflux.

  The reaction time varies depending on the reaction temperature and cannot be generally specified, but the reaction is usually completed in about 0.5 to 24 hours.

  Each target compound obtained in each of the above reactions is easily isolated from the reaction mixture by a commonly used isolation means such as organic solvent extraction, chromatography, recrystallization, distillation, etc. Purified by conventional purification means.

  The pyrazole compound represented by the general formula (1) of the present invention can be used for controlling agricultural pests, for example, pests such as Lepidoptera, Hemiptera, Thripidae, Coleoptera, and mites. It can be preferably applied.

  The pyrazole compound represented by the general formula (1) of the present invention exhibits an excellent control effect against mites at a low dose. Examples of the mites include plant parasitic mites in various agricultural and horticultural fields, for example, spider mites, citrus mites, kanzawa spider mites, apple spider mites, etc .; Rust mites such as: dust mites such as mite dust mite and cyclamen dust mites; mite mites such as mite mite and robin mite.

Acaricide The pest control agent of the present invention will be described taking an acaricide as an example.

  When the pyrazole compound represented by the general formula (1) of the present invention is used as an acaricide, it may be used as it is without adding other components, but is usually liquid, solid, gaseous, etc. Mix with various carriers, and add surfactants and other formulation adjuvants as necessary. Oils, emulsions, wettable powders, dry flowables, flowables, aqueous solvents, granules, fine granules, granules It can be used in various preparation forms such as an agent, powder, coating agent, spray preparation, aerosol preparation, microcapsule preparation, fumigation preparation, and smoke preparation.

  In these preparations, the content of the pyrazole compound of the general formula (1) can be appropriately selected from a wide range according to various conditions such as the form of preparation and use place, but is usually about 0.01 to 95% by weight, preferably It may be about 0.1 to 50% by weight.

  Examples of solid carriers used in preparing these preparations include clays such as kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay, talc, ceramic, celite, quartz, sulfur, activated carbon, silica carbonate, hydrated silica Inorganic minerals such as, fine powders such as chemical fertilizers, and granular materials.

  Examples of liquid carriers include water; alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; aliphatic or alicyclic hydrocarbons such as n-hexane, cyclohexane, kerosene, and light oil; benzene, toluene, xylene, naphthalene, and the like. Aromatic hydrocarbons; Esters such as ethyl acetate and butyl acetate; Nitriles such as acetonitrile and isobutyronitrile; Ethers such as diisopropyl ether and dioxane; N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl Examples include acid amides such as pyrrolidone and N, N′-dimethylimidazolinone; halogenated hydrocarbons such as dichloromethane, trichloroethane, and carbon tetrachloride; vegetable oils such as dimethyl sulfoxide, soybean oil, and cottonseed oil.

  The gaseous carrier is generally used as a propellant, and examples thereof include butane gas, liquefied petroleum gas, dimethyl ether, and carbon dioxide gas.

  Examples of the surfactant include nonionic surfactants and anionic surfactants.

More specifically, nonionic surfactants include, for example, sugar ester type nonionic surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters; fatty acid ester type nonionic surfactants such as polyoxyethylene fatty acid esters. Agents; vegetable oil type nonionic surfactants such as polyoxyethylene castor oil; alcohol type nonionic surfactants such as polyoxyethylene alkyl ether; polyoxyethylene alkyl (C _8-12 ) phenyl ether / formalin condensate Alkylphenol type nonionic surfactant; Polyoxyethylene / polyoxypropylene block polymer type nonionic surfactant such as polyoxyethylene / polyoxypropylene block polymer; Polyaromatic ring type nonionic surfactant such as phenylphenyl ether And the like.

  More specifically, anionic surfactants include, for example, sulfonate type anionic surfactants such as alkylbenzene sulfonate, alkyl sulfosuccinate, and allyl sulfonate; sulfate type anionic interfaces such as alkyl sulfate and polyoxyethylene alkyl sulfate. Activators; lignin sulfites and the like.

  Examples of the formulation adjuvant include a fixing agent, a dispersing agent, a thickener, a preservative, an antifreezing agent, a stabilizer, and an adjuvant.

  Examples of the fixing agent and dispersant include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic). Acid, etc.).

  Examples of the thickener include water-soluble polymer compounds such as xanthan gum and carboxymethyl cellulose, high-purity bentonite, and white carbon.

  Examples of the preservative include sodium benzoate and parahydroxybenzoic acid ester.

  Examples of the antifreezing agent include ethylene glycol and diethylene glycol.

  Examples of the stabilizer include PAP (isopropyl acid isopropyl), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol and 3-tert- And mixtures thereof with butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof.

  Examples of the adjuvant include vegetable oils such as soybean oil and corn oil, machine oil, glycerin, polyethylene glycol and the like.

  These preparations may be colored using organic or inorganic dyes.

  In addition, the compound of the present invention is mixed in advance with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists (such as piperonyl butoxide), soil improvers and the like. May be formulated. Or you may use together the acaricide of this invention and said each agent in the case of use.

When the compound of the present invention is used as an agricultural and horticultural acaricide, the application amount is not particularly limited, and various forms such as formulation form, application method, application time, application place, type of applied crop, type of mite to be controlled, etc. It is appropriately selected from a wide range depending on the conditions, and is usually about 0.1 to 1000 g, preferably about 10 to 500 g per 100 m ² . Moreover, when using an emulsion, a wettable powder, a flowable agent etc. diluted with water, the application density | concentration is about 1-1000 ppm normally, Preferably it is about 10-500 ppm. Granules, powders and the like are applied as they are without dilution.

  The pyrazole compound represented by the general formula (1) is a completely new type of pest control agent that is not present in existing pest control agents, and can be particularly suitably used as an acaricide.

  The present invention will be further clarified by the following production examples, formulation examples and test examples of the compound of the present invention, but the present invention is not limited thereto.

Example of production Example 1
Synthesis of 1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-yl butane-1-sulfonate (compound number: A-4)

1-1. Synthesis of Compound (3) Dissolve 9.2 g of ethyl 4,4,4-trifluoro-3-oxobutanoate (1) and 5.5 g of 2-hydrazinopyridine (2) in 100 ml of toluene, and attach a Dean-Stark device The mixture was stirred for 14 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to give 1- (pyridin-2-yl) -3- (trifluoromethyl)- 11.0 g of 1H-pyrazole-5-ol (3) was obtained.

1-2. Synthesis of compound (A-4)
1- (Pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-ol (3) (230 mg) and triethylamine (140 mg) were dissolved in acetonitrile (50 ml) and stirred at 0 ° C. with 1- A solution of butanesulfonyl chloride 220 mg in acetonitrile 10 ml was added dropwise and stirred at room temperature for 14 hours. The reaction solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 7: 1) to give 1- (pyridin-2-yl) -3- (trifluoromethyl)- 310 mg of 1H-pyrazol-5-yl butane-1-sulfonate (A-4) was obtained.

Example 2
Synthesis of 4-methyl-1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-yl methanesulfonate (compound number: B-1)

2-1. Synthesis of Compound (7) To a solution of 10.0 g of ethyl 2,2,2-trifluoroacetate (4) in 15 ml of tetrahydrofuran was added 3.1 g of sodium hydride (60%) under ice cooling, and the mixture was stirred at room temperature. After 15 minutes, a solution of ethyl propionate (5) 7.9 g in tetrahydrofuran 10 ml was gradually added at 50 ° C., and the mixture was stirred at 60 ° C. for 3 hours. After completion of the reaction, the reaction solution was acidified with 1N dilute hydrochloric acid, and extracted twice with diethyl ether. The organic layers are combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a liquid containing ethyl 4,4,4-trifluoro-2-methyl-3-oxobutanoate (6) I got a thing. To the liquid, 150 ml of toluene and 7.0 g of 2-hydrazinopyridine were added, and the mixture was stirred for 15 hours while heating under reflux in a system equipped with a Dean-Stark apparatus. The reaction solution was concentrated under reduced pressure, suspended in a mixed solvent of 30 ml of hexane and 5 ml of diethyl ether, and filtered to give 4-methyl-1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole 6.4 g of -5-ol (7) was obtained.

2-2. Synthesis of compound (B-1)
4-methyl-1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-ol (7) (300 mg) and triethylamine (152 mg) were dissolved in 50 ml of acetonitrile and stirred at 0 ° C. A solution of 150 mg of methanesulfonyl chloride in 10 ml of acetonitrile was added dropwise, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 30 ml of hexane was added to the obtained residue and filtered to give 4-methyl-1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-yl methanesulfonate (B-1 ) 310 mg was obtained.

Example 3
Synthesis of 4-chloro-1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-yl ethanesulfonate (compound number: C-1)

3-1. Synthesis of Compound (8) 1- (Pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-ol (3) 1.2 g synthesized in Example-1 was dissolved in 50 ml of chloroform. While stirring at 0 ° C., a solution of 0.8 g of sulfuryl chloride in 10 ml of chloroform was added dropwise, and the mixture was stirred at 0 ° C. for 30 minutes. After completion of the reaction, the reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to give 4-chloro-1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole -5-ol (8) 130 mg was obtained.

3-2. Synthesis of compound (C-1)
4-Chloro-1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-ol (8) (120 mg) and triethylamine (58 mg) are dissolved in acetonitrile (10 ml) and stirred at room temperature with ethane. A solution of 54 mg of sulfonyl chloride in 10 ml of acetonitrile was added dropwise, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to give 4-chloro-1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole 155 mg of -5-yl ethanesulfonate (C-1) was obtained.

Example 4
Synthesis of 1- (pyridin-2-yl) -3- [4- (trifluoromethyl) phenyl] -1H-pyrazol-5-yl ethanesulfonate (Compound No. D-16)

4-1. Synthesis of Compound (11) 10.6 g of ethyl potassium malonate and 13.7 g of magnesium chloride were suspended in 300 ml of acetonitrile, and a solution of triethylamine 14.6 g in 15 ml of acetonitrile was added dropwise with stirring under ice cooling. The suspension was stirred at 50 ° C. for 5 hours, and then a solution of 4- (trifluoromethyl) benzoyl chloride (10.6 g) in acetonitrile (10 ml) was added dropwise with stirring under ice cooling, followed by stirring at room temperature for 12 hours. After completion of the reaction, 2N dilute hydrochloric acid (200 ml) was added, and the mixture was stirred for 10 minutes at room temperature and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to remove ethyl 3-oxo-3- [4- (trifluoromethyl) phenyl] propanoate (10) A liquid material containing was obtained. To the liquid were added 250 ml of toluene and 6.4 g of 2-hydrazinopyridine, and the mixture was stirred for 15 hours under heating and reflux in a system equipped with a Dean-Stark apparatus. The reaction solution was concentrated under reduced pressure, 1N diluted hydrochloric acid was added to the residue, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized with a mixed solvent of n-hexane and ethyl acetate, and 1- (pyridin-2-yl) -3- [4- (trifluoromethyl) phenyl] -1H-pyrazol-5-ol ( 11) 14.1 g was obtained.

4-2. Synthesis of compound (D-16)
Dissolve 0.4 g of 1- (pyridin-2-yl) -3- [4- (trifluoromethyl) phenyl] -1H-pyrazol-5-ol (11) and 0.16 g of triethylamine in 20 ml of acetonitrile and stir at room temperature. Then, a solution of ethanesulfonyl chloride 0.16 g in acetonitrile 10 ml was added dropwise and stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized with a mixed solvent of n-hexane and ethyl acetate to give 1- (pyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazol-5-yl ethanesulfonate (D-16). ) 0.49 g was obtained.

Example 5
Synthesis of 3- (2,4-dichlorobenzyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (compound number: E-7)

5-1. Synthesis of Compound (13) 1.8 g of (2,4-dichlorophenyl) acetic acid (12) and 5.2 g of thionyl chloride were dissolved in 100 ml of 1,2-dichloroethane and stirred for 15 hours while heating under reflux. After completion of the reaction, the reaction solution was concentrated under reduced pressure to obtain 1.8 g of (2,4-dichlorophenyl) acetyl chloride (13).

5-2. Synthesis of Compound (E-7) In the same manner as in Example-4, from 1.8 g of (2,4-dichlorophenyl) acetyl chloride (13), 3- (2,4-dichlorobenzyl) -1- (pyridine-2 -Il) -1H-pyrazol-5-yl ethanesulfonate (E-7) 0.24 g was obtained.

Example 6
Synthesis of 1,3-di (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (compound number: F-2)

6-1. Synthesis of Compound (15) 1.35 g of sodium ethoxide, 8.7 g of ethyl acetate and 0.05 g of ethanol were suspended in 100 ml of toluene. After stirring at room temperature for 1 hour, 1.5 g of ethyl picolinate (14) in 10 ml of toluene was added, and the mixture was stirred at 90 ° C. for 14 hours. After completion of the reaction, the mixture was poured into water and extracted twice with toluene. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to give 1.87 g of ethyl 3-oxo-3- (pyridin-2-yl) propionate (15). It was.

6-2. Synthesis of Compound (F-2) In the same manner as in Example 1, from 1.87 g of ethyl 3-oxo-3- (pyridin-2-yl) propionate (15), 1,3-di (pyridin-2-yl) ) -1H-pyrazol-5-yl ethanesulfonate (F-2) 2.08 g was obtained.

Example 7
1- (Pyridin-2-yl) -3- (3,5,5,6,8,8-hexamethyl-5,6,7,7,8,8-tetrahydronaphthalen-2-yl) 1H-pyrazole- Synthesis of 5-yl ethanesulfonate (G-1)

7-1. Synthesis of Compound (17) Sodium hydride (60%) (2.3 g) is suspended in tetrahydrofuran (50 ml), stirred for 10 minutes under ice-cooling, diethyl carbonate and 1- (3,5,5,6,8,8-hexamethyl) A solution of 1.5 g of -5,6,7,8-tetrahydronaphthalen-2-yl) ethanone (16) in 20 ml of tetrahydrofuran was added, and the mixture was stirred for 3 hours while heating under reflux. After completion of the reaction, the mixture was poured into 1N dilute hydrochloric acid and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 9: 1), and ethyl 3-oxo-3- (3,5,5,6,8,8-hexamethyl-5,6 , 7,8-tetrahydronaphthalen-2-yl) propionate (17) 8.31 g was obtained.

7-2. Synthesis of Compound (G-1) Ethyl 3-oxo-3- (3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene- 2-yl) propionate (17) from 8.31 g, 1- (pyridin-2-yl) -3- (3,5,5,6,8,8-hexamethyl-5,6,7,7,8,8 -Tetrahydronaphthalen-2-yl) 1H-pyrazol-5-yl ethanesulfonate (G-1) (3.02 g) was obtained.

Example 8
Synthesis of 4-[(4-chlorophenyl) carbonyl] -1- (pyridin-2-yl) -3- [4- (trifluoromethyl) phenyl] -1H-pyrazol-5-yl ethanesulfonate (H-4)

8-1. Synthesis of compound (19)
Dissolve 2.0 g of 1- (pyridin-2-yl) -3- [4- (trifluoroethyl) phenyl] -1H-pyrazol-5-ol (19) and 1.3 g of triethylamine in 50 ml of dichloromethane at 0 ° C. While stirring, a solution of 1.3 g of 4-chlorobenzoyl chloride in 10 ml of dichloromethane was added dropwise, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was poured into water and extracted with dichloromethane. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The precipitated crystals were washed with hexane and filtered, and 1- (pyridin-2-yl) -3- [4- (trifluoroethyl) phenyl] -1H-pyrazol-5-yl 4-chlorobenzoate (19) (2.8 g) was added. Obtained.

8-2. Synthesis of compound (20)
1- (Pyridin-2-yl) -3- [4- (trifluoroethyl) phenyl] -1H-pyrazol-5-yl 4-chlorobenzoate (19) 0.7 g and potassium carbonate 0.3 g in toluene / N, N -Dimethylformamide was added to 60 ml of a mixed solvent of 5/1. After stirring for 15 hours under reflux with heating, the reaction solution was poured into water and extracted twice with ethyl acetate. The organic layers were combined, washed twice with water and once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) and (4-chlorophenyl) {5-hydroxy-1- (pyridin-2-yl) -3- [4- (trifluoro 0.4 g of (methyl) phenyl] -1H-pyrazol-4-yl} methanone (20) was obtained.

8-3. Synthesis of Compound (H-4) (4-Chlorophenyl) {5-hydroxy-1- (pyridin-2-yl) -3- [4- (trifluoromethyl) phenyl] -1H-pyrazol-4-yl} methanone (20) 0.7 g of triethylamine and 0.5 g of triethylamine were dissolved in 50 ml of tetrahydrofuran, a solution of 0.6 g of ethanesulfonyl chloride in 10 ml of tetrahydrofuran was added dropwise with stirring at 0 ° C., and the mixture was stirred at room temperature for 14 hours. The reaction solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (ethyl acetate), and recrystallized from a mixed solvent of n-hexane and ethyl acetate to give 4-[(4-chlorophenyl) carbonyl]- 0.5 g of 1- (pyridin-2-yl) -3- [4- (trifluoromethyl) phenyl] -1H-pyrazol-5-yl ethanesulfonate (H-4) was obtained.

Example 9
Synthesis of 1- (pyridin-2-yl) -3- [3- (pyridin-3-yl) phenyl] -1H-pyrazol-5-yl ethanesulfonate (I-2)

9-1. Synthesis of compound (23)
0.4M sodium carbonate aqueous solution 20ml, 3-bromopyridine (21) 3.2g, 3-carboxyphenylboronic acid 3.3g, tetrakis (triphenylphosphine) palladium (0) 1.15g was added to acetonitrile 100ml, and 90 ° C for 14 hours Stir. After completion of the reaction, the mixture was filtered through celite, 1N diluted hydrochloric acid was added to the filtrate, and the mixture was extracted with ethyl acetate and washed with saturated brine. After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The precipitated crystals were washed with hexane and filtered to obtain a solid containing 3- (pyridin-3-yl) benzoic acid (22). To the solid, 50 ml of ethanol and 5 ml of concentrated sulfuric acid were added. After refluxing for 12 hours, the reaction solution was quenched by adding sodium hydrogen carbonate. After ethanol was distilled off under reduced pressure, an aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted 3 times with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to obtain 1.7 g of ethyl 3- (pyridin-3-yl) benzoate (23).

9-2. Synthesis of Compound (I-2) In the same manner as in Example 6, from 1.7 g of ethyl 3- (pyridin-3-yl) benzoate (23), 1- (pyridin-2-yl) -3- [3 -(Pyridin-3-yl) phenyl] -1H-pyrazol-5-yl ethanesulfonate (I-2) 2.05 g was obtained.

Example 10
Synthesis of (5-Methylthiophen-2-yl) phenyl] -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (J-16)

10-1. Synthesis of compound (26)
1.8 g of 3-iodobenzoic acid (24), 1.1 g of 5-methyl-2-thiopheneboronic acid (25) and 2.9 g of potassium carbonate were suspended in 50 ml of distilled water. To the suspension, 1 ml of an aqueous palladium (II) chloride-EDTA complex solution prepared by the method described in Tetrahedron Letters, vol. 49 (2005), 5751-5754 was added and stirred at 100 ° C. for 5 hours. After completion of the reaction, the mixture was filtered through celite using 1,2-dichloroethane and aqueous sodium hydrogen carbonate solution. The aqueous layer was acidified with 1N dilute hydrochloric acid, and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The precipitated crystals were washed and filtered using hexane to obtain 1.4 g of 3- (5-methylthiophen-2-yl) benzoic acid (26).

10-2. Synthesis of Compound (J-16) In the same manner as in Example-5, from 1.4 g of 3- (5-methylthiophen-2-yl) benzoic acid (26), 3- [3- (5-methylthiophene-2 -Il) phenyl] -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (J-16) (2.0 g) was obtained.

Example 11
Synthesis of 3- (4'-methoxybiphenyl-3-yl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (K-10)

11-1. Synthesis of compound (28)
Add 3.0 g of 3- (3-iodophenyl) -1- (pyridin-2-yl) -1H-pyrazol-5-ol (27), 2.3 g of benzyl chloride and 2.3 g of potassium carbonate to N, N-dimethylformamide And stirred at 100 ° C. for 5 minutes. After completion of the reaction, the reaction solution was poured into water and extracted twice with ethyl acetate. The organic layers were combined, washed twice with water and once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to give 5- (benzyloxy) -3- (4′-methoxybiphenyl-3-yl) -1- (pyridine- There were obtained 2.2 g of 2-yl) -1H-pyrazole (28).

11-2. Synthesis of compound (30)
To 100 ml of a mixed solvent of 1,2-dimethoxyethane / water = 3/1, 5- (benzyloxy) -3- (4′-methoxybiphenyl-3-yl) -1- (pyridin-2-yl) -1H— 1.0 g of pyrazole (28), 0.1 g of tetrakis (triphenylphosphine) palladium (0), 0.5 g of potassium carbonate and 0.5 g of 4-methoxyphenylboronic acid were added, and the mixture was stirred for 14 hours while heating under reflux. After completion of the reaction, it was poured into water and extracted twice with ethyl acetate. The organic layers were combined, washed twice with water and once with saturated brine, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to remove 5- (benzyloxy) -3- (4′-methoxybiphenyl). A viscous liquid containing -3-yl) -1- (pyridin-2-yl) -1H-pyrazole (29) was obtained. The viscous liquid was dissolved in 100 ml of ethanol, 0.1 g of palladium carbon (10%) was suspended, the inside of the system was replaced with hydrogen, and the mixture was stirred at 70 ° C. for 14 hours. After completion of the reaction, the reaction solution was filtered through celite, and the solvent was distilled off under reduced pressure. The precipitated crystals were recrystallized from a mixed solvent of ethyl acetate and n-hexane to give 3- (4'-methoxybiphenyl-3-yl) -1- (pyridin-2-yl) -1H-pyrazol-5-ol (30) 0.4g was obtained.

11-3. Synthesis of compound (K-10)
3- (4'-Methoxybiphenyl-3-yl) -1- (pyridin-2-yl) -1H-pyrazol-5-ol (30) 300 mg and triethylamine 200 mg are dissolved in tetrahydrofuran 30 ml and stirred at 0 ° C. While adding ethanesulfonyl chloride (250 mg) in tetrahydrofuran (5 ml) dropwise, the mixture was stirred at room temperature for 14 hours. The reaction solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to give 3- (4′-methoxybiphenyl-3-yl) -1- (pyridine -2-yl) -1H-pyrazol-5-yl ethanesulfonate (K-10) 300 mg was obtained.

Example 12
Synthesis of 3- {5- [N-methoxyethaneimidoyl] -2-methylphenyl} -1-methyl-1H-pyrazol-5-yl ethanesulfonate (L-3)

12-1. The inside of the synthesis system of compound (32) was replaced with nitrogen, and 2- [5- (benzyloxy) -3- (5-bromo-2-methylphenyl) 1H-pyrazol-1-yl] was added to 100 ml of tetrahydrofuran (dehydrated). After dissolving 3.0 g of pyridine (31) and cooling to −78 ° C., 5.4 ml of 1.6M n-butyllithium hexane solution was added dropwise and stirred at −78 ° C. for 30 minutes. Next, a tetrahydrofuran (dehydrated) 10 ml solution of 1.0 g of N-methoxy-N-methylacetamide was dropped, and the mixture was stirred at −78 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into 1N dilute hydrochloric acid and extracted twice with diethyl ether. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to give 1- {3- [5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole 0.9 g of -3-yl] -4-methylphenyl} ethanone (32) was obtained.

12-2. Synthesis of compound (33)
1- {3- [5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazol-3-yl] -4-methylphenyl} ethanone (32) 0.9 g was dissolved in 100 ml of ethyl acetate, 0.1 g of palladium carbon (10%) was suspended, the system was replaced with hydrogen, and the mixture was stirred at 70 ° C. for 14 hours. After completion of the reaction, the reaction solution was filtered through celite, and the solvent was distilled off under reduced pressure. The precipitated crystals were recrystallized from a mixed solvent of ethyl acetate and n-hexane to give 1- [3- (5-hydroxyl-1-phenyl-1H-pyrazol-3-yl) -4-methylphenyl] ethanone (33 ) 0.5g was obtained.

12-3. Synthesis of compound (L-1) 1- [3- (5-hydroxyl-1-phenyl-1H-pyrazol-3-yl) -4-methylphenyl] ethanone (33) 0.39 From g, 0.32 g of 3- (5-acetyl-2-methylphenyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (L-1) was obtained.

12-4. Synthesis of compound (L-3)
3- (5-acetyl-2-methylphenyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (L-1) 150 mg is dissolved in ethanol, pyridine 100 mg and O-methyl Hydroxylamine hydrochloride (100 mg) was added, and the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, ethanol was distilled off under reduced pressure, water was added, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 3: 1) to give 3- {5- [N-methoxyethaneimidoyl] -2-methylphenyl} -1- (pyridine- 120 mg of 2-yl) -1H-pyrazol-5-yl ethanesulfonate (L-3) was obtained.

Example 13
Synthesis of 3- (2,4-dichlorobenzyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (M-2)

13-1. Synthesis of Compound (35) 0.04 g of lithium aluminum hydride was suspended in 15 ml of tetrahydrofuran, and while stirring under ice cooling, 2,2,2-trifluoro-1- {3- [5-hydroxy-1- 10 ml of tetrahydrofuran (0.30 g) of (pyridin-2-yl) -1H-pyrazol-3-yl] -4-methylphenyl} ethanone (34) was added dropwise. The mixture was stirred at room temperature for 1 hour, poured into 1N dilute hydrochloric acid, and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Washed and filtered with hexane, 3- [2-methyl-5- (2,2,2-trifluoro-1-hydroxyethyl) phenyl] -1- (pyridin-2-yl) -1H-pyrazol-5-ol (35) 0.28 g was obtained.

13-2. Synthesis of compound (M-2) In the same manner as in Synthesis Example-4, 3- [2-methyl-5- (2,2,2-trifluoro-1-hydroxyethyl) phenyl] -1- (pyridine-2 -Yl) -1H-pyrazol-5-ol (35) from 0.28 g, 1- (pyridin-2-yl) -3- (2-methyl-5- {2,2,2-trifluoro-1- [ 0.18 g of (ethylsulfonyl) oxy] ethyl} phenyl) -1H-pyrazol-5-yl ethanesulfonate (M-2) was obtained.

Example 14
Synthesis of 3- (5-ethenyl-2-methylphenyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (M-3)

1- [3- (5-Hydroxy-1-phenyl-1H-pyrazol-3-yl) -4-methylphenyl was suspended in 30 ml of tetrahydrofuran while stirring 0.44 g of lithium aluminum hydride under ice cooling. ] 50 ml of tetrahydrofuran (2.73 g) of ethanone (33) was added dropwise. The mixture was stirred at room temperature for 1 hour, poured into 1N dilute hydrochloric acid, and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Subsequently, the obtained viscous liquid containing 3- [5- (1-hydroxyethyl) -2-methylphenyl] -1- (pyridin-2-yl) -1H-pyrazole (36) was dissolved in 400 ml of toluene. Then, 0.2 g of tosylic acid monohydrate was added, and the mixture was heated to reflux for 14 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, water was added, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting viscous liquid containing 3- (5-ethenyl-2-methylphenyl) -1- (pyridin-2-yl) -1H-pyrazol-5-ol (37) was dissolved in 100 ml of tetrahydrofuran, and triethylamine 1.00 g and ethanesulfonyl chloride (1.25 g) were added, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the reaction solution was poured into water and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to give 3- (5-ethenyl-2-methylphenyl) -1- (pyridin-2-yl) -1H— 0.20 g of pyrazol-5-yl ethanesulfonate (M-3) was obtained.

Example 15
Synthesis of 3- (5-ethyl-2-methylphenyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (M-4)

0.80 g of 3- [5- (1-hydroxyethyl) -2-methylphenyl] -1- (pyridin-2-yl) -1H-pyrazole (36) was dissolved in 100 ml of acetic acid, 0.1% palladium on carbon (10%) g was suspended, the inside of the system was replaced with hydrogen, and the mixture was stirred with heating under reflux for 14 hours. After completion of the reaction, the reaction solution was filtered through celite, and acetic acid was distilled off under reduced pressure. Water was added to the obtained residue (38), and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to give 3- (5-ethyl-2-methylphenyl) -1- (pyridin-2-yl) -1H- 0.21 g of pyrazol-5-yl ethanesulfonate (M-4) was obtained.

Example 16
Synthesis of 3- (4-Ethoxybiphenyl-3-yl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (N-4)

16-1. Synthesis of compound (40)
To 100 ml of N, N-dimethylformamide, 2.03 g of 60% sodium hydride was added and cooled to 0 ° C. Next, 5.0 g of 5-bromosalicylic acid (39) and 7.9 g of ethyl iodide were added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, water was added and extracted three times with ethyl acetate. The organic layers were combined and washed with saturated brine, and the organic layer was dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave 4.30 g of ethyl 5-bromo-2-ethoxybenzoate (40).

16-2. Synthesis of compound (41)
In 100 ml of a mixed solution of 1,2-dimethoxyethane / ethanol = 1/1, 2.7 g of ethyl 5-bromo-2-ethoxybenzoate (40), 1.3 g of phenylboronic acid, 0.4 g of triphenylphosphine, 3.2 g of cesium fluoride Then, 0.11 g of palladium (II) acetate was added, and the mixture was heated to reflux for 12 hours. The reaction solution was returned to room temperature, filtered through celite, and the filtrate was concentrated under reduced pressure. Water was added to the obtained residue, and the mixture was extracted 3 times with ethyl acetate. The organic layers were combined and washed with saturated brine, and the organic layer was dried over anhydrous magnesium sulfate. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 6: 1) to obtain 1.3 g of ethyl 4-ethoxybiphenyl-3-carboxylate (41).

16-3. Synthesis of compound (N-4) In the same manner as in Example-6, from 0.5 g of ethyl 4-ethoxybiphenyl-3-carboxylate (41), 3- (4-methoxybiphenyl-3-yl) -1- ( 0.35 g of pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (N-4) was obtained.

Example 17
Synthesis of 3- [2-Chloro-5- (cyclopropylethynyl) phenyl] -1-methyl-1H-pyrazol-5-yl methanesulfonate (O-21)

17-1. Synthesis of compound (43)
To a 150 ml ethanol solution was added 3.3 g of 5-iodo-2-chlorobenzoic acid, 0.11 g of concentrated hydrochloric acid, and the mixture was stirred with heating under reflux for 12 hours. The reaction solution was returned to room temperature, diluted with water, 1N aqueous sodium hydroxide solution was added, and the mixture was extracted 3 times with ethyl acetate. The organic layers were combined and washed with saturated brine, and the organic layer was dried over anhydrous magnesium sulfate. The filtrate was concentrated under reduced pressure to obtain 1.74 g of ethyl 5-iodo-2-chlorobenzoate (43).

17-2. Synthesis of compound (44)
To a reaction solution in which 30 ml of triethylamine was added to 1.74 g of ethyl 5-iodo-2-chlorobenzoate (43), 0.74 g of cyclopropylacetylene, 0.39 g of bis (triphenylphosphine) palladium (II) dichloride, 0.10 g of copper iodide And stirred at room temperature for 13 hours. After completion of the reaction, water was added to the reaction solution, extracted with chloroform, washed with saturated brine, and the organic layer was dried over anhydrous magnesium sulfate. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 20: 1) to obtain 1.26 g of ethyl 2-chloro-5- (cyclopropylethynyl) benzoate (44). It was.

17-3. Synthesis of Compound (45) Water: Ethanol = 1: 2 Mixed solvent 150ml Ethyl 2-chloro-5- (cyclopropylethynyl) benzoate (44) 1.26g Lithium hydroxide 0.24g The mixture was further stirred at room temperature for 15 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, diluted with water, and 1N dilute hydrochloric acid was added to precipitate a solid, which was filtered to give 2-chloro-5- (cyclopropylethynyl) benzoic acid (45) 1.05 g was obtained.

17-4. Synthesis of Compound (O-21) In the same manner as in Example-5, from 1.05 g of 2-chloro-5- (cyclopropylethynyl) benzoic acid (45), 3- [2-chloro-5- (cyclopropylethynyl) ) Phenyl] -1-methyl-1H-pyrazol-5-yl methanesulfonate (O-21) 0.40 g was synthesized.

Example 18
3- {2-Methyl-5- [3- (trifluoromethyl) -1,2-oxazol-5-yl] phenyl} -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate Synthesis of (P-1)

18-1. Synthesis of Compound (47) The inside of the system was replaced with nitrogen, 10.0 g of 5-bromo-2-methylbenzoic acid (46) was dissolved in 450 ml of tetrahydrofuran (dehydrated), cooled to −78 ° C., 1.6 M n 62.5 ml of -butyllithium hexane solution was added dropwise and stirred at -78 ° C for 30 minutes. Then, a 20 ml solution of 5.27 g of N-methoxy-N-methylacetamide in tetrahydrofuran (dehydrated) was added dropwise, and the mixture was stirred at −78 ° C. for 1 hour and at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into 1N dilute hydrochloric acid and extracted twice with diethyl ether. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized with a mixed solvent of n-hexane and ethyl acetate to obtain 4.42 g of 5-acetyl-2-methylbenzoic acid (47).

18-2. Synthesis of Compound (49) 1.24 g of sodium hydride (60%) was suspended in 150 ml of tetrahydrofuran, and a solution of 2.52 g of 5-acetyl-2-methylbenzoic acid (47) in 20 ml of tetrahydrofuran was added dropwise under ice cooling. After stirring as it was for 1 hour, a solution of 2.21 g of ethyl trifluoroacetate in 15 ml of tetrahydrofuran was added dropwise, and the temperature was gradually raised to room temperature over 1 hour with stirring. After completion of the reaction, the reaction solution was poured into 1N dilute hydrochloric acid and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid containing 2-methyl-5- (4,4,4-trifluoro-3-oxobutanoyl) benzoic acid (48) was dissolved in 70 ml of a mixed solvent of pyridine: ethanol = 1: 1, 0.70 g of hydroxylammonium chloride was added, and the mixture was stirred with heating under reflux for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 1N diluted hydrochloric acid was added, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized with a mixed solvent of n-hexane and ethyl acetate to give 1.98 g of 2-methyl-5- [4,4,4-trifluoro-3- (hydroxyamino) butanoyl] benzoic acid (49). Got.

18-3. Synthesis of compound (P-1)
2-methyl-5- [4,4,4-trifluoro-3- (hydroxyamino) butanoyl] benzoic acid (49) 0.5 g was dissolved in 200 ml of toluene, 0.1 g of tosylic acid monohydrate was added, and 14 Heated to reflux for hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, water was added, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. From a solid containing 2-methyl-5- [3- (trifluoromethyl) -1,2-oxazol-5-yl] benzoic acid (50), in the same manner as in Example-5, 3- {2-methyl -5- [3- (Trifluoromethyl) -1,2-oxazol-5-yl] phenyl} -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (P-1) 0.46 g was synthesized.

Example 19
3- [5- (1,3-dioxolan-2-yl) -2-methylphenyl] -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (Q-1), 3- Synthesis of (5-formyl-2-methylphenyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (Q-2)

19-1. The inside of the synthesis system of compound (51) was replaced with nitrogen, 15.0 g of 5-bromo-2-methylbenzoic acid (46) was dissolved in 500 ml of tetrahydrofuran (dehydrated), cooled to −78 ° C., and 1.6 M n -96 ml of -butyllithium hexane solution was added dropwise and stirred at -78 ° C for 30 minutes. Then, a solution of 6.37 g of N, N-dimethylformamide in 15 ml of tetrahydrofuran (dehydrated) was added dropwise, followed by stirring at −78 ° C. for 1 hour and at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into 1N dilute hydrochloric acid and extracted twice with diethyl ether. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized with a mixed solvent of n-hexane and ethyl acetate to obtain 3.33 g of 5-formyl-2-methylbenzoic acid (51).

19-2. Synthesis of Compound (53) In the same manner as in Example-5, from 3.33 g of 5-formyl-2-methylbenzoic acid (51) to ethyl 3- (5-formyl-2-methylphenyl) -3-oxopropionate (53) 1.81 g was obtained.

19-3. Synthesis of Compound (Q-1) 1.81 g of ethyl 3- (5-formyl-2-methylphenyl) -3-oxopropionate (53) was dissolved in 200 ml of toluene, 0.2 g of tosylic acid monohydrate and Ethylene glycol 0.54 g was added, and the mixture was stirred with heating under reflux for 14 hours (preparation of ethyl 3- (1,3-dioxolane) -2-methylphenyl-3-oxopropionate (54)). After completion of the reaction, the reaction solution was ice-cooled, 1.1 g of 2-hydrazinopyridine was added, a Dean-Stark apparatus was attached to the flask, and the mixture was stirred for 14 hours with heating under reflux. Concentrate under reduced pressure and contain 3- [5- (1,3-dioxolan-2-yl) -2-methylphenyl] -1- (pyridin-2-yl) -1H-pyrazol-5-ol (55) A liquid was obtained. To the viscous liquid was added 1N aqueous sodium hydrogen carbonate solution, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in 100 ml of tetrahydrofuran, and 1.5 g of triethylamine was added. While stirring at room temperature, a solution of ethanesulfonyl chloride (1.25 g) in tetrahydrofuran (10 ml) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, 1N aqueous sodium hydrogen carbonate solution was added to the reaction solution, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1 → 2: 1) to give 3- [5- (1,3-dioxolan-2-yl) -2-methylphenyl ] 0.53 g of -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (Q-1) was synthesized.

19-4. Synthesis of compound (Q-2)
3- [5- (1,3-Dioxolan-2-yl) -2-methylphenyl] -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (Q-1) 0.30 g It was dissolved in 50 ml of ethanol, 30 ml of 1N diluted hydrochloric acid was added, and the mixture was stirred at 70 ° C. for 1 hour. After completion of the reaction, the reaction solution was concentrated under reduced pressure. 1N diluted hydrochloric acid was added to the obtained residue, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to give 3- (5-formyl-2-methylphenyl) -1- (pyridin-2-yl) -1H— 0.16 g of pyrazol-5-yl ethanesulfonate (Q-2) was obtained.

Example 20
Synthesis of 3- (methylsulfanyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (R-1)

20-1. Synthesis of Compound (57) 15.14 g of sodium hydride (60%) was suspended in 200 ml of N, N-dimethylformamide (dehydrated), and 20 g of N, N-dimethylformamide (56) of dimethyl malonate (56) was added under ice cooling. Dehydration) 15 ml solution was added dropwise. After stirring for 15 minutes under ice cooling, a solution of 28.81 g of carbon disulfide in 15 ml of N, N-dimethylformamide (dehydrated) was added dropwise. The temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 1 hour. Thereafter, 64.46 g of methyl iodide in 15 ml of N, N-dimethylformamide (dehydrated) was added dropwise and stirred at room temperature for 14 hours. After completion of the reaction, the mixture was poured into water and extracted twice with diethyl ether. The organic layers were combined, washed 3 times with water and once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The precipitated crystals were washed and filtered using a mixed solvent of hexane and diethyl ether to obtain 26.92 g of dimethyl [bis (methylsulfanyl) methylidene] propionate (57).

20-2. Synthesis of Compound (58) 7.77 g of dimethyl [bis (methylsulfanyl) methylidene] propionate (57) was dissolved in 200 ml of ethanol, 4.31 g of 2-hydrazinopyridine was added, and the mixture was stirred for 14 hours while heating under reflux. After completion of the reaction, the reaction mixture was concentrated, and the precipitated crystals were washed with diethyl ether and filtered to give methyl 5-hydroxy-3- (methylsulfanyl) -1- (pyridin-2-yl) -1H-pyrazole-4-carboxyl 6.55 g of rate (58) was obtained.

20-3. Synthesis of Compound (R-1) 1.80 g of methyl 5-hydroxy-3- (methylsulfanyl) -1- (pyridin-2-yl) -1H-pyrazole-4-carboxylate (58) was dissolved in 100 ml of ethanol, Concentrated hydrochloric acid (30 ml) was added, and the mixture was stirred with heating under reflux for 5 hours. After completion of the reaction, the solvent was removed under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid of 3- (methylsulfanyl) -1- (pyridin-2-yl) -1H-pyrazol-5-ol (59) was dissolved in tetrahydrofuran, and 1.50 g of triethylamine and 1.75 g of ethane sulfonyl chloride were added, Stir at room temperature for 4 hours. After completion of the reaction, the reaction solution was poured into water and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to give 3- (methylsulfanyl) -1- (pyridin-2-yl) -1H-pyrazol-5-ylethane 0.93 g of sulfonate (R-1) was obtained.

Example 21
3- [5- (5,5-Dimethyl-4,5-dihydro-1,2-oxazol-3-yl) -2-methylphenyl] -1- (pyridin-2-yl) -1H-pyrazole-5 Of 2-Ileethanesulfonate (S-1)

21-1. Synthesis of compound (60)
2.85 g of 5-formyl-2-methylbenzoic acid (51) was dissolved in 250 ml of ethanol, 3 ml of concentrated sulfuric acid was added, and the mixture was stirred with heating under reflux for 15 hours. After completion of the reaction, the reaction solution was concentrated, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 4: 1) to obtain 1.73 g of ethyl 5-formyl-2-methylbenzoate (60).

21-2. Synthesis of compound (62)
Ethyl 5-formyl-2-methylbenzoate (60) (1.73 g) in ethanol (250 ml), hydroxylammonium chloride (0.94 g) and sodium acetate (1.11 g) dissolved in water: ethanol = 3: 2 mixed solvent (25 ml) were dissolved in ice. It was dripped under cooling. After stirring at room temperature for 2 hours, the reaction solution was concentrated. Water was added to the obtained residue, and the mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting viscous liquid containing ethyl 5-[(hydroxyimino) methyl] -2-methylbenzoate (61) was dissolved in 30 ml of N, N-dimethylformamide, and 2.0 g of N-chlorosuccinimide was added. Stir for hours. Next, 2.0 g of triethylamine was added, the inside of the system was replaced with isopropene, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction solution was poured into water and extracted twice with ethyl acetate. The organic layers were combined, washed 3 times with water and once with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 6: 1), and 5- (5,5-dimethyl-4,5-dihydro-1,2-oxazol-3-yl) 1.60 g of ethyl 2-methylbenzoate (62) was obtained.

21-3. Synthesis of Compound (S-1) In the same manner as in Synthesis Example-6, ethyl 5- (5,5-dimethyl-4,5-dihydro-1,2-oxazol-3-yl) -2-methylbenzoate ( 62) From 1.60 g, 3- [5- (5,5-dimethyl-4,5-dihydro-1,2-oxazol-3-yl) -2-methylphenyl] -1- (pyridin-2-yl) 0.35 g of -1H-pyrazol-5-yl ethanesulfonate (S-1) was obtained.

Example 22
3- [4- (Methylsulfanyl) biphenyl-3-yl] -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (T-1), 3- [4- (methylsulfinyl) Synthesis of biphenyl-3-yl] -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (T-2)

22-1. Synthesis of compound (64)
1,2-dimethoxyethane: ethanol = 1: 1 in 200 ml of mixed solvent 10.0 g of 5-bromo-2-fluorobenzonitrile (63), 7.32 g of phenylboronic acid, 1.97 g of triphenylphosphine, 15.9 g of cesium fluoride, acetic acid 0.56 g of palladium was added, and the mixture was heated and stirred for 12 hours. The reaction solution was returned to room temperature, filtered through celite, and the filtrate was concentrated under reduced pressure. Water was added to the obtained residue, and the mixture was extracted 3 times with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 9: 1) to obtain 5.4 g of 4-fluorobiphenyl-3-carbonitrile (64).

22-2. Synthesis of Compound (65) 1.98 g of methyl mercaptan sodium was added to a solution of 1.97 g of 4-fluorobiphenyl-3-carbonitrile (64) dissolved in 50 ml of tetrahydrofuran, and the mixture was heated to reflux for 12 hours. The reaction solution was concentrated under reduced pressure, 1N diluted hydrochloric acid was added, the mixture was extracted with dichloroethane, and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The precipitated solid was washed and filtered with hexane to obtain 2.15 g of 4- (methylsulfanyl) biphenyl-3-carbonitrile (65).

22-3. Synthesis of compound (66)
To 1.0 g of 4- (methylsulfanyl) biphenyl-3-carbonitrile (65) was added 100 ml of tetrahydrofuran (dehydrated), and the atmosphere was replaced with argon. The reaction solution was cooled to −78 ° C., 5.5 ml of 1.6M phenyl lithium was added, and the mixture was stirred for 2 hours. Next, 20 ml of 1N dilute hydrochloric acid was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, water was added, extracted with ethyl acetate, and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The precipitated solid was washed and filtered with hexane to obtain 0.91 g of 1- [4- (methylsulfanyl) biphenyl-3-yl] ethanone (66).

22-4. Synthesis of Compound (T-1) In the same manner as in Example 7, from 0.91 g of 1- [4- (methylsulfanyl) biphenyl-3-yl] ethanone (66), 3- [4- (methylsulfanyl) biphenyl -3-yl] -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (T-1) 0.45 g was obtained.

22-5. Synthesis of compound (T-2)
3- [4- (methylsulfanyl) biphenyl-3-yl] -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (T-1) 0.26 g was dissolved in dichloromethane 20 ml, 0.25 g of% metachloroperbenzoic acid was added and stirred for 1 hour. Sodium thiosulfate was added to the reaction solution, and the organic layer was collected. Sodium hydrogen carbonate was added to the organic layer and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to give 3- [4- (methylsulfinyl) biphenyl-3-yl] -1- (pyridin-2-yl) 0.18 g of -1H-pyrazol-5-yl ethanesulfonate (T-2) was obtained.

Example 23
Synthesis of ethyl 5-[(ethylsulfonyl) oxy] -1- (pyridin-2-yl) -1H-pyrazole-3-carboxylate (U-2)

23-1. Synthesis of Compound (68) Diethyl acetylenedicarboxylate (67) (6.0 g) was dissolved in ethanol (200 ml), 2-hydrazinopyridine (2) (4.61 g) and potassium carbonate (11.67 g) were added, and the mixture was stirred with heating under reflux for 14 hours. After completion of the reaction, the reaction solution was concentrated, acidified with 1N dilute hydrochloric acid, and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized with a mixed solvent of n-hexane and ethyl acetate to obtain 5.0 g of ethyl 5-hydroxy-1- (pyridin-2-yl) -1H-pyrazole-3-carboxylate (68). It was.

23-2. Synthesis of Compound (U-2) In the same manner as in Example-1 (2), from 0.3 g of ethyl 5-hydroxy-1- (pyridin-2-yl) -1H-pyrazole-3-carboxylate (68), 0.15 g of ethyl 5-[(ethylsulfonyl) oxy] -1- (pyridin-2-yl) -1H-pyrazole-3-carboxylate (U-2) was obtained.

Example 24
Synthesis of 3-cyano-1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (U-4)

24-1. Synthesis of Compound (69) 3.0 g of ethyl 5-hydroxy-1- (pyridin-2-yl) -1H-pyrazole-3-carboxylate (68) was dissolved in 200 ml of acetonitrile, 2.67 g of benzyl bromide, 2.42 g of potassium carbonate And stirred at room temperature for 14 hours. After completion of the reaction, water was added to the reaction solution and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 3: 1), and ethyl 5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole-3-carboxylate (69) 2.0 g was obtained.

24-2. Synthesis of Compound (70) 2.0 g of ethyl 5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole-3-carboxylate (69) was dissolved in 100 ml of ethanol, and 30 ml of 1N aqueous sodium hydroxide solution was dissolved. In addition, the mixture was stirred for 5 hours under heating to reflux. After completion of the reaction, the solvent was distilled off under reduced pressure, 100 ml of 1N diluted hydrochloric acid was added, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The precipitated crystals were washed and filtered with n-hexane to obtain 1.80 g of 5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole-3-carboxylic acid (70).

24-3. Synthesis of compound (71)
To 50 ml of 1,2-dichloroethane was added 6.5 g of 5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole-3-carboxylic acid (70) and 13.1 g of thionyl chloride, and the mixture was heated to reflux for 2 hours. . The reaction solution was concentrated under reduced pressure, 100 ml of tetrahydrofuran was added, 2M ammonia methanol solution was added dropwise under ice cooling, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, water was added, the mixture was extracted with ethyl acetate, and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (ethyl acetate) to give 5- (benzyloxy) -1- (pyridin-2-yl) ) -1H-pyrazole-3-carboxamide (71) 2.28 g was obtained.

24-4. Synthesis of Compound (72) To a solution of 2.0 g of 5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole-3-carboxamide (71) dissolved in 50 ml of chloroform, 4.2 g of phosphoryl chloride was added. The mixture was stirred at ° C for 15 minutes. The mixture was stirred at room temperature for 30 minutes, and then heated and stirred for 3 hours. After completion of the reaction, ice water was added and extracted three times with chloroform. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to give 5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole-3-carbonitrile (72) 0.66 g was obtained.

24-5. Synthesis of compound (73)
0.3 g of 5- (benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole-3-carbonitrile (72) was dissolved in 30 ml of ethyl acetate, and 0.02 g of palladium carbon (10%) was added. The system was replaced with hydrogen and stirred vigorously at room temperature for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, and the filtrate was concentrated under reduced pressure to obtain 0.09 g of 3-cyano-1- (pyridin-2-yl) -1H-pyrazol-5-ol (73). .

24-6. Synthesis of Compound (U-4) In the same manner as in Example 1 (2), from 0.09 g of 3-cyano-1- (pyridin-2-yl) -1H-pyrazol-5-ol (73), 0.08 g of cyano-1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (U-4) was obtained.

Example 25
3- (propan-2-ylcarbamoyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (U-6)

  5- (Benzyloxy) -1- (pyridin-2-yl) -1H-pyrazole-3-carboxylic acid (70) (0.52 g) is dissolved in chloroform (100 ml), thionyl chloride (0.64 ml) is added, and the mixture is stirred with heating under reflux for 4 hours. did. After completion of the reaction, the solvent was distilled off under reduced pressure, 100 ml of tetrahydrofuran was added to the residue, and a solution of 0.3 ml of isopropylamine in 10 ml of tetrahydrofuran was added dropwise under ice cooling.

  The mixture was stirred at room temperature for 1 hour, poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 0.57 g of 3- (propan-2-ylcarbamoyl) -1- (pyridin-2-yl) -1H-pyrazol-5-yl ethanesulfonate (U-6). .

Furthermore, the compounds shown in Table 1 below were produced in the same manner as in Examples 1 to 25 above. The ¹ H-NMR data is shown in Table 2 together with the results of Examples 1 to 25.

Formulation Example Formulation Example 1 Emulsion 10 parts of each of the compounds of the present invention were dissolved in 45 parts of Solvesso 150 and 35 parts of N-methylpyrrolidone, and 10 parts of an emulsifier (trade name: Solpol 3005X, manufactured by Toho Chemical Co., Ltd.). In addition, the mixture was stirred and mixed to obtain each 10% emulsion.

Formulation Example 2 Wetting Agent 20 parts of each of the compounds of the present invention were added to a mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of a synthetic silicon hydroxide fine powder and 54 parts of clay, and stirred with a mixer. Mix to give 20% wettable powder.

Formulation Example 3 Granules To 5 parts of each of the compounds of the present invention, 2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite and 83 parts of clay were added and mixed thoroughly. An application amount of water was added, further stirred, granulated with a granulator, and dried by ventilation to obtain 5% granules.

Formulation Example 4 Powder 1 part of each compound of the present invention is dissolved in an appropriate amount of acetone. To this, 5 parts of synthetic silicon hydroxide fine powder, 0.3 part of PAP (isopropyl acid phosphate) and 93.7 parts of clay are added. The mixture was stirred and mixed with a juice mixer, and acetone was removed by evaporation to obtain a 1% powder.

Formulation Example 5 Flowable Agent 20 parts of each of the compounds of the present invention and 1.5 parts of sorbitan triolate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol and pulverized with a sand grinder (particle size of 3 microns or less). Thereafter, 40 parts of an aqueous solution containing 0.05 part of chitansan gum and 0.1 part of aluminum magnesium silicate was added thereto, and further 10 parts of propylene glycol was added and stirred to obtain a 20% suspension in water.

Test Example Test Example 1 Insecticidal test against a spider mite Tap water was put into a plastic cup (KP-120, Tsugaike Plastic, Kamata), and a lid with a cut-in opening was made. A non-woven fabric (4.5 × 5.5 cm) having a 1 cm width and about 4 cm cut along the long side was placed on the lid and hung in the cup. A kidney bean leaf piece (about 3.5 × 4.5 cm) was placed on a non-woven fabric that had sufficiently absorbed water, and a spider mite (about 20 individuals) was infested on the non-woven fabric, and left in a constant temperature room (25 ± 2 ° C., 16L8D). The next day, an aqueous solution (100 ppm) of Solpol 355 (manufactured by Toho Chemical) is added to an acetone solution of the compound of the present invention to prepare a chemical solution (100 ppm) of the compound of the present invention, and 4 ml of the chemical solution is spray gun (PB-308 Peace Bonn (Olympus, Osaka)) 1 kgf / cm ² ). After air drying, it was allowed to stand in a temperature-controlled room, and after 2 days of treatment, the mortality rate of adult female spider mites was investigated.

  As a result, No. A-2, A-3, A-4, A-5, A-7, A-8, D-1, D-2, D-3, D-4, D-5, D -8, D-9, D-15, D-16, D-18, D-19, D-29, D-30, D-31, D-32, D-36, D-37, D-39 , D-40, D-42, D-44, D-45, D-49, D-50, D-52, D-54, D-55, D-57, D-59, D-62, D -63, D-64, D-66, D-68, E-1, E-5, E-7, E-9, E-12, E-13, E-15, E-16, E-18 , E-19, E-22, E-27, E-28, E-33, E-36, E-45, F-1, F-6, F-7, F-8, G-1, G -2, G-4, I-1, I-2, I-3, I-5, I-6, I-7, J-1, J-2, J-3, J-4, J-6 , J-7, J-8, J-9, J-10, J-11, J-12, J-15, J-16, J-17, J-18, J-20, J-22, J -23, J-24, J-25, J-26, J-27, J-28, J-29, J-30, J-37, J-40, J-41, K-2, K-3 , K-4, K-5, K-6, K-7, K-8, K-9, K-10, K-11, K-13, K-14, K-15, L-3, L -4, L-5, L-6, L-7, L-8, L-9, L-10, L-11, L-12, L-13, L-14, L-15, L-19 , L-20, L-22, L-23, L-24, L-25, M-3, N-1, N-2, N-3, N-4, O-1, O-2, O -3, O-4, O-5, O-6, O-7, O-10, O-11, O-18, O-19, O-20, O-21, O-22, O-23 , O-2 4, O-25, O-26, O-27, O-28, P-1, P-2, P-3, P-4, P-5, Q-1, S-1, T-1, The compounds of the present invention of U-3 and U-4 showed 100% mortality.

Test Example 2 Ovicidal test against a spider mite Tap water was placed in a plastic cup (KP-120, Tsugaike Plastic, Kamata), and a lid with a cut-in opening was made. A non-woven fabric (4.5 × 5.5 cm) having a 1 cm width and about 4 cm cut along the long side was placed on the lid and hung in the cup. Place a kidney bean leaf piece (about 3.5 x 4.5 cm) on a non-woven fabric that has sufficiently absorbed water, release a female adult spider mite (about 5) on it, and leave it in a thermostatic chamber (25 ± 2 ° C, 16L8D). did. On the next day, adult females were removed, and 4 ml of a chemical solution (100 ppm) of a test compound prepared according to Test Example 1 was sprayed with a spray gun (PB-308 Peace Bonn (Olympos, Osaka) 1 kgf / cm ² ). After air drying, it was allowed to stand in a thermostatic chamber, and after 6 days of treatment, the egg killing rate of the spider mite was investigated.

cv As a result, No. D-3, D-4, D-5, D-10, D-15, D-16, D-18, D-30, D-31, D-39, D-40, D-44, D-48, D-50, D-52, D-54, D-57, D-58, D-63, D-64, D-66, D-68, E-5, E- 7, E-9, E-12, E-13, E-15, E-16, E-18, E-27, E-33, E-45, F-1, F-7, G-1, G-2, I-1, I-5, I-6, J-2, J-4, J-6, J-8, J-9, J-11, J-12, J-16, J- 17, J-18, J-22, J-23, J-24, J-25, J-26, J-27, J-28, J-29, J-33, J-35, J-36, J-37, J-40, J-41, K-4, K-5, K-6, K-8, K-9, K-10, K-11, K-13, K-14, K- 15, L-3, L-5, L-6, L-7, L-8, L-9, L-10, L-11, L-12, L-14, L-15, L-18, L-19, L-20, L-21, L-22, L-23, L-24, N-1, N-2, O-1, O-2, O-3, O-4, O- 5, O-6, O-7, O-8, O-18, O-11, O-12, O-14, O-17, O-19, O-21, O-23, O-24, 100% of the compounds of the present invention of O-26, O-27, O-28, P-1, P-2, P-3, P-4, P-5, Q-1, S-1, U-4 Showed the egg-killing rate.

Test Example 3 Insecticidal test against spider mites of Kanzawa Tap water was put into a plastic cup (KP-120, Tsugaike Plastic, Kamata), and a lid with a cut-in opening was made. A non-woven fabric (4.5 × 5.5 cm) having a 1 cm width and about 4 cm cut along the long side was placed on the lid and hung in the cup. A 3.5 × 4.5 cm square kidney leaf was placed on the nonwoven fabric that had sufficiently absorbed water so that the back side was up. Thereafter, 20 adults / cups of adult female Kanzawa spider mites were released on the kidney leaf pieces. On the next day, 4 ml of a chemical solution (100 ppm) of a test compound prepared according to Test Example 1 was sprayed with a spray gun (PB-308 Peace Bonn (Olympos, Osaka) 1 kgf / cm ² ). After air-drying, it was allowed to stand in a temperature-controlled room (25 ± 2 ° C., 16L8D), and the mortality rate of adult female Kanzawa spider mite was investigated 2 days after spraying.

  As a result, No. A-1, A-2, A-3, A-10, D-1, D-5, D-9, D-16, D-18, D-19, D-29, D -30, D-39, D-40, D-48, D-63, E-9, E-12, E-16, E-18, E-36, E-37, F-6, F-8 , G-1, I-2, I-3, I-5, I-7, J-4, J-6, J-9, J-10, J-11, J-16, J-18, J -22, J-23, J-24, J-28, J-29, J-30, J-41, K-9, K-10, L-3, L-7, L-8, L-9 , L-11, L-12, L-18, N-3, O-1, O-2, O-7, U-4 showed 100% mortality.

Test Example 4 Ovicidal test for spider mite Kanzawa Spider mite female adults were released per 6 cups of green beans on a non-woven fabric so that water could be supplied from below, and left in a thermostatic chamber (25 ± 2 ° C., 16 L8D). The next day, after removal of adult spider mites, chemical solution (100 ppm) of the test compound prepared according to Test Example 1 was sprayed with a spray gun PB-308 Peace Bonn (Olympos, Osaka) 1 kgf / cm ² ), air-dried, and a constant temperature room (25 (± 2 ° C., 16 L8D). Seven days after spraying, the egg killing rate of Kanzawa spider mite was investigated.

  As a result, No. D-16, E-9, E-16, E-33, E-37, G-1, G-2, J-4, J-6, J-9, J-16, J -18, J-23, J-24, J-28, J-29, J-41, K-9, K-10, L-3, L-4, L-6, L-7, L-8 , L-9, L-10, L-11, L-12, L-14, L-18, L-22, O-1, O-2, O-6, O-7 % Oviposition rate.

Test Example 5 Insecticidal test against citrus red mite Tap water was put into a plastic cup (KP-120, Tsugaike Plastic, Kamata), and a lid with a cut-in opening was made. A non-woven fabric (4.5 × 5.5 cm) having a 1 cm width and about 4 cm cut along the long side was placed on the lid and hung in the cup. A filter paper (5 cm diameter, No. 2: Advantech Toyo) with a 3 × 3 cm square die-dye leaf on the top side and a 2.4 cm diameter hole for drying and prevention of tick escape on a nonwoven fabric that has sufficiently absorbed water ) And surrounded with tangles. Thereafter, 10 adults / cups of mandarin orange mite were released on Daidai leaf pieces. The next day, an aqueous solution (100 ppm) of Solpol 355 (manufactured by Toho Chemical) is added to an acetone solution of the compound of the present invention to prepare a chemical solution (100 ppm) of the compound of the present invention, and 4 ml of the chemical solution is spray gun (PB-308 Peace Bonn (Olympus, Osaka)) 1 kgf / cm ² ). After air-drying, it was allowed to stand in a thermostatic chamber (25 ± 2 ° C., 16L8D), and the mortality rate of adult mandarin mite was examined 2 days after spraying.

  As a result, D-62, E-33, G-2, G-4, I-5, J-9, J-16, J-18, J-28, K-14, L-3, L-4 , L-5, L-6, L-7, L-8, L-9, L-10, L-11, L-12, L-15, L-22, L-23, M-4, O -2, O-5, O-6, O-7, O-11, O-17, O-23, O-28, P-1, P-3, Q-1, S-1, U-3 The U-4 compound of the present invention showed 100% mortality.

Test Example 6 Insecticidal test against sweet potato nematode 8 g of river sand (passed through a 2 mm sieve) sterilized by dry heat at 180 ° C. for 2 hours in a vial (vessel tube V-5 Nippon Denka Glass) was prepared according to Test Example 1. The test compound drug solution (100 ppm) was irrigated at 1 ml / bottle. Next, sweet potato root nematode stage 2 larvae adjusted to 500 heads / ml were irrigated at 1 ml / bottle, capped with parafilm, and placed in a thermostatic chamber (25 ± 2 ° C., 16 L8D). The next day, a hole was made in the center of the parafilm (1-2 mm diameter), and a 1.2-leaf stage tomato cut out on the ground was inserted. The vial into which the tomato is inserted is placed in a plastic cup (KP-860M body, Kamoike Plastic), covered with a dozen holes (ventilation holes, 1 to 2 mm diameter), and temperature-controlled (25 ± 2 ° C) , 16L8D). Eleven days later, the control value was investigated from 0 (no galling) to 5 (an occurrence of wrinkles) to determine the control value. (Control value = {1− (average damage degree of test area / average damage degree of untreated area)} × 100)

  As a result, A-1, A-2, A-3, A-8, D-16, D-44, E-9, E-11, J-9, J-23, J-24, J-28 Of the present invention exhibited a control value of 50 or more.

Claims (9)

General formula (1)

[Wherein R ¹ represents a hydrogen atom or a halogen atom.
R ² represents a C _1-12 alkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, a C _2-6 alkynyl group, a C _2-6 haloalkynyl group, a complex A cyclic group (on the heterocycle, at least one substituent selected from the group consisting of a halogen atom, a C _1-4 alkyl group and a C _1-4 haloalkyl group may be substituted), benzyl Group or phenyl group (on the phenyl ring, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group) , C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 alkylcarbonyl group, C _{1- 4} alkyl O group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, a may) be substituted at least one substituent selected from the group consisting of a nitro group and a cyano group is 1 or more.
R is pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, pyrazin-2-yl Group, triazin-2-yl group, thiazol-2-yl group, thiazol-4-yl group, oxazol-2-yl group, oxazol-4-yl group, benzothiazol-2-yl group, quinolin-2-yl Group, isoquinolin-2-yl group or quinoxalin-2-yl group, each having a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, or a C _3-8 cyclo group on each nitrogen-containing heterocyclic ring. Alkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _{1 -4} At least one selected from the group consisting of an alkoxycarbonyl group, a _C1-4 alkylcarbonyl group, a _C1-4 alkylthio group, a _C1-4 alkylsulfinyl group, a _C1-4 alkylsulfonyl group, a nitro group, and a cyano group. One or more of these substituents may be substituted.
Q is a hydrogen atom, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-6. Alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, mono- or di (C _1-6 alkyl) aminocarbonyl group, C _{1 -4} alkylthio group, _C1-4 alkylsulfinyl group, nitro group, cyano group, phenyl group or heterocyclic group.
On the phenyl ring of Q, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-18 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 haloalkoxycarbonyl group, C _1-4 Alkylcarbonyl group, C _1-4 haloalkylcarbonyl group, group —C (R ³ ) ═NO (R ⁴ ), C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, nitro One or more substituents selected from the group consisting of a group, a cyano group, an amino group and a heterocyclic group may be substituted. In addition, when a C _1-12 alkyl group is substituted on two adjacent carbon atoms on the phenyl ring, these alkyl groups may be bonded to each other to form a saturated 5- or 6-membered ring. .
Here, R ³ represents a C _1-6 alkyl group, a C _1-6 haloalkyl group or a phenyl group (on the phenyl ring, a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _{1- And} at least one substituent selected from the group consisting of ₄ alkoxy groups and C _1-4 haloalkoxy groups may be substituted, and R ⁴ represents a C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group or benzyl group (of benzyl group) On the phenyl ring, a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 haloalkoxy group, a C _1-4 alkoxycarbonyl group, a mono or di ( C _1-6 alkyl) aminocarbonyl group, C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, at least one substituent selected from the group consisting of nitro group and cyano group may be substituted by one or more. Good).
On the heterocyclic ring of Q, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-18 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 alkylcarbonyl group, group —C (R ³ ) = NO (R ⁴ ), C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, nitro group, cyano group, amino group and heterocyclic group Further, at least one substituent may be substituted by one or more. Here, R ³ and R ⁴ are the same as described above. It represented Ru of compound in] or a N- oxide. In one general formula (1), compound or an N- oxide of claim 1 R is a compound showing a pyridin-2-yl group, pyrazin-2-yl group or a thiazol-2-yl group. In one general formula (1), compound or an N- oxide of claim 1 or 2 ^{R 2} is a compound that shows a _{C 1-4} alkyl group. In one general formula (1), Q _{is, C 1-4 alkyl, C 1-4} haloalkyl _{group, C 3-8} cycloalkyl, mono- or di _{(C 1-6} alkyl) aminocarbonyl group, a cyano group, compound or an N- oxide of according to any one of claims 1 to 3 is a phenyl group or a heterocyclic group. Compound represented by the general formula (1) is a compound of the following (J-12) or compound (E-10), compound or an N- oxide of claim 1.

General formula (1)

[Wherein R ¹ represents a hydrogen atom or a halogen atom.
R ² represents a C _1-12 alkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, a C _2-6 alkynyl group, a C _2-6 haloalkynyl group, a complex A cyclic group (on the heterocycle, at least one substituent selected from the group consisting of a halogen atom, a C _1-4 alkyl group and a C _1-4 haloalkyl group may be substituted), benzyl Group or phenyl group (on the phenyl ring, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group) , C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 alkylcarbonyl group, C _{1- 4} alkyl O group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, a may) be substituted at least one substituent selected from the group consisting of a nitro group and a cyano group is 1 or more.
R is pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, pyrazin-2-yl Group, triazin-2-yl group, thiazol-2-yl group, thiazol-4-yl group, oxazol-2-yl group, oxazol-4-yl group, benzothiazol-2-yl group, quinolin-2-yl Group, isoquinolin-2-yl group or quinoxalin-2-yl group, each having a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, or a C _3-8 cyclo group on each nitrogen-containing heterocyclic ring. Alkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _{1 -4} At least one selected from the group consisting of an alkoxycarbonyl group, a _C1-4 alkylcarbonyl group, a _C1-4 alkylthio group, a _C1-4 alkylsulfinyl group, a _C1-4 alkylsulfonyl group, a nitro group, and a cyano group. One or more of these substituents may be substituted.
Q is a hydrogen atom, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-6. Alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, mono- or di (C _1-6 alkyl) aminocarbonyl group, C _{1 -4} alkylthio group, _C1-4 alkylsulfinyl group, nitro group, cyano group, phenyl group or heterocyclic group.
On the phenyl ring of Q, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-18 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 haloalkoxycarbonyl group, C _1-4 Alkylcarbonyl group, C _1-4 haloalkylcarbonyl group, group —C (R ³ ) ═NO (R ⁴ ), C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, nitro One or more substituents selected from the group consisting of a group, a cyano group, an amino group and a heterocyclic group may be substituted. In addition, when a C _1-12 alkyl group is substituted on two adjacent carbon atoms on the phenyl ring, these alkyl groups may be bonded to each other to form a saturated 5- or 6-membered ring. .
Here, R ³ represents a C _1-6 alkyl group, a C _1-6 haloalkyl group or a phenyl group (on the phenyl ring, a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _{1- And} at least one substituent selected from the group consisting of ₄ alkoxy groups and C _1-4 haloalkoxy groups may be substituted, and R ⁴ represents a C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group or benzyl group (of benzyl group) On the phenyl ring, a halogen atom, a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 haloalkoxy group, a C _1-4 alkoxycarbonyl group, a mono or di ( C _1-6 alkyl) aminocarbonyl group, C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, at least one substituent selected from the group consisting of nitro group and cyano group may be substituted by one or more. Good).
On the heterocyclic ring of Q, a halogen atom, a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, C _2-18 alkynyl group, C _2-6 haloalkynyl group, C _1-4 alkoxy group, C _1-4 haloalkoxy group, C _1-4 alkoxycarbonyl group, C _1-4 alkylcarbonyl group, group —C (R ³ ) = NO (R ⁴ ), C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _1-4 alkylsulfonyl group, nitro group, cyano group, amino group and heterocyclic group Further, at least one substituent may be substituted by one or more. Here, R ³ and R ⁴ are the same as described above. ] Represented Ru of compounds or in a process for the preparation of the N- oxides of the general formula (2)

[Wherein R, R ¹ and Q are as defined above] and a general formula (3)

[Wherein R ² is the same as defined above. X represents a halogen atom. ] A sulfonyl halide represented by the general formula (4)

[Wherein R ² is the same as defined above. A sulfonic acid anhydride represented by] Ru reacted method. The manufacturing method of Claim 6 whose compound represented by General formula (1) is the following compound (J-12) or compound (E-10).

Compounds or pesticides containing the N- oxide of according to any one of claims 1 to 5. Compound or miticide containing the N- oxide of according to any one of claims 1 to 5.