WO2020246329A1 - METHOD FOR PRODUCING β-KETOSULFONE COMPOUND - Google Patents

METHOD FOR PRODUCING β-KETOSULFONE COMPOUND Download PDF

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WO2020246329A1
WO2020246329A1 PCT/JP2020/020859 JP2020020859W WO2020246329A1 WO 2020246329 A1 WO2020246329 A1 WO 2020246329A1 JP 2020020859 W JP2020020859 W JP 2020020859W WO 2020246329 A1 WO2020246329 A1 WO 2020246329A1
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halogen atoms
atom
substituted
formula
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裕美 林
俊之 木地
博美 貝瀬
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/16—Halogen atoms; Nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/18—Oxygen or sulfur atoms

Definitions

  • the present invention relates to a method for producing a ⁇ -ketosulfone compound.
  • ⁇ -ketosulfone compounds are an important group of compounds as intermediates and final products for the production of pharmaceuticals and pesticides.
  • Patent Document 1 describes that a ⁇ -ketosulfone compound is useful as a compound having anticancer activity against warm-blooded animals including humans.
  • a method for producing a ⁇ -ketosulfone compound an addition reaction of an alkylsulfone compound with a nitrile compound described in Patent Document 2 and Non-Patent Document 1 is known.
  • strong bases such as alkyllithium and sodium alkoxide are required, and industrial control of the reaction may be difficult, or the substrate may be damaged under basic conditions.
  • An object of the present invention is to provide an efficient method for producing a ⁇ -ketosulfone compound.
  • the present inventors As a result of investigating a method for producing a ⁇ -ketosulfone compound, the present inventors have obtained an ⁇ -sulfonyl ⁇ -ketoenamine compound by reacting a nitrile compound with a ⁇ -carbonyl sulfone compound in the presence of a metal salt and a base. Found to be generated. Then, it was found that the ⁇ -ketosulfone compound can be efficiently produced by reacting the compound with water in the presence of an acid. That is, the present invention is as follows.
  • X 1 represents CR 3 or a nitrogen atom
  • R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms.
  • R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms.
  • the benzene ring ⁇ the benzene ring may be substituted with one or more substituents selected from group A. ⁇ Is formed.
  • Group A Halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, even if substituted with one or more halogen atoms A group consisting of a good heteroaryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms.
  • Compound represented by and formula (2) [In the formula, X represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms.
  • R 1 represents a C1-C6 alkyl group that may be substituted with one or more halogen atoms.
  • the compound represented by (4) is reacted in the presence of a metal salt and a base to formulate (4).
  • X, X 1 , R 1 , R 2 , R 4 and R 5 have the same meanings as described above.
  • Step of obtaining the compound represented by: A method for producing a compound represented by the formula (4), which comprises.
  • R 2 may be substituted with a hydrogen atom, a halogen atom, one or more halogen atoms, an aryl group, or one or more halogen atoms, or a C1-C6 alkoxy group.
  • ⁇ The production method according to any one of [1] to [3].
  • [5] The production method according to any one of [1] to [4], wherein X 1 is a nitrogen atom in the formula (1).
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom
  • R 4 is a hydrogen atom
  • R 5 is a hydrogen atom, a halogen atom, or three OCH 2 CF 2 CF groups.
  • [7] The production method according to any one of [1] to [6], wherein X is a methyl group in the formula (2).
  • [8] The production method according to any one of [1] to [7], wherein R 1 is an ethyl group in the formula (2).
  • the base is an inorganic base or an amine-based base.
  • Equation (4) in the presence of acid
  • X, X 1 , R 1 , R 2 , R 4 and R 5 have the same meanings as described above.
  • Equation (4) [During the ceremony, X represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms.
  • R 1 represents a C1-C6 alkyl group that may be substituted with one or more halogen atoms.
  • X 1 represents CR 3 or nitrogen atom
  • R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms.
  • R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms.
  • the benzene ring ⁇ the benzene ring may be substituted with one or more substituents selected from group A. ⁇ Is formed.
  • Group A Halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, even if substituted with one or more halogen atoms A group consisting of a good heteroaryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms.
  • R 2 may be substituted with a hydrogen atom, a halogen atom, one or more halogen atoms, an aryl group, or one or more halogen atoms, or a C1-C6 alkoxy group.
  • a benzene ring may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of good aryl groups or C1-C6 alkoxy groups which may be substituted with one or more halogen atoms.
  • substituents selected from the group consisting of good aryl groups or C1-C6 alkoxy groups which may be substituted with one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom
  • R 4 is a hydrogen atom
  • R 5 is a hydrogen atom, a halogen atom, or three OCH 2 CF 2 CF groups.
  • [19] The compound according to any one of [13] to [18], wherein X is a methyl group in the formula (4).
  • [20] The compound according to any one of [13] to [19], wherein R 1 is an ethyl group in the formula (4).
  • a ⁇ -ketosulfone compound can be efficiently produced.
  • halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a butyl group, and a tert-butyl group. Examples include a pentyl group and a hexyl group.
  • C1-C6 alkyl group optionally substituted with one or more halogen atoms examples include a difluoromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and 2-.
  • aryl group include a phenyl group and a naphthyl group.
  • aryl group optionally substituted with one or more halogen atoms examples include a 2-bromophenyl group, a 3-iodophenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, and a 2,4-dichlorophenyl group.
  • heteroaryl group examples include pyrrolyl group, furyl group, thienyl group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, oxazolyl group, isooxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group and pyridyl group.
  • heteroaryl group examples include pyrrolyl group, furyl group, thienyl group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, oxazolyl group, isooxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group and pyridyl group.
  • examples thereof include a pyridazinyl group, a pyrimidinyl group, and a pyr
  • heteroaryl group optionally substituted with one or more halogen atoms examples include a 5-chloro-2-thienyl group, a 4-chloro-2-thienyl group, a 4-bromo-2-thienyl group, and 5 -Chloro-3-thienyl group, 5-chloro-2-pyrrrolyl group, 4-chloro-2-pyrrrolyl group, 4-bromo-2-pyrrrolyl group, 4-chloro-1-pyrrrolyl group, 5-chloro-2- Frill group, 4-chloro-2-furyl group, 5-fluoro-3-furyl group, 3-chloro-1-pyrazolyl group, 2-chloro-1-imidazolyl group, 4-bromo-1-imidazolyl group, 4- Fluoro-1,2,3-triazolyl group, 3-chloro-1,2,4-triazolyl group, 5-bromo-1,2,4-triazolyl group, 5-bromo-1,2,4-tri
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a 1,1-dimethylpropoxy group, a 1,2-dimethylpropoxy group, a 1-ethylpropoxy group, a butoxy group, and a tert-butoxy group. , Pentyloxy group, hexyloxy group and the like.
  • alkoxy group optionally substituted with one or more halogen atoms include a difluoromethoxy group, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group and a 2-bromo-1 group.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ac represents an acetyl group
  • THF represents tetrahydrofuran.
  • the compounds described herein may have, for example, the tautomers shown below.
  • the compound in the present invention may have one or more stereoisomers.
  • Stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • the present invention includes each stereoisomer and a mixture of stereoisomers in any ratio.
  • any stereoisomer or a mixture of stereoisomers contained in an arbitrary isomer ratio can be used as a compound represented by the formulas (2), (3) and (4), and is a geometric isomer. Since is not specified, the coupling is indicated by a wavy line.
  • Examples of the mode of the compound represented by the formula (1) include the following compounds.
  • X 1 is CR 3 or a nitrogen atom
  • R 3 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, and one or more halogen atoms.
  • R 2 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, 1 or more.
  • R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with one or more halogen atoms, and one or more halogen atoms.
  • Aryl groups may be represented, heteroaryl groups may be substituted with one or more halogen atoms, or C1-C6 alkoxy groups may be substituted with one or more halogen atoms, or they are attached.
  • a benzene ring together with a carbon atom ⁇ the benzene ring may be substituted with one or more substituents selected from Group A.
  • X 1 is CR 3 or a nitrogen atom, and R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, respectively.
  • -C6 alkyl group aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms, or C1 optionally substituted with one or more halogen atoms -C6 alkoxy group in which R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with one or more halogen atoms, and one or more halogen atoms.
  • X 1 is CR 3 or a nitrogen atom
  • R 2 , R 3 , R 4 , and R 5 are independently substituted with hydrogen atom, halogen atom, or one or more halogen atoms.
  • C1-C6 alkyl group which may be substituted, an aryl group which may be substituted with one or more halogen atoms, a heteroaryl group which may be substituted with one or more halogen atoms, or a halogen atom substituted with one or more atoms.
  • benzene ring may be substituted with a halogen atom, one or more halogen atoms C1 -C6 alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms, or C1 optionally substituted with one or more halogen atoms -C6 alkoxy group, R 4 and R 5 together with the carbon atom to which they are bonded, benzene ring ⁇ The benzene ring may be substituted with a halogen atom, one or more halogen atoms C1 -C6 alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms, or C1 optionally substituted with one or more halogen atoms -It may be substituted with one or more substituents selected from the group consisting of C6 alkoxy groups.
  • X 1 is CR 3 and R 2 , R 3 , R 4 , and R 5 are independently substituted with hydrogen atom, halogen atom, and one or more halogen atoms.
  • a compound that is a good C1-C6 alkoxy group In formula (1), X 1 is CR 3 , and R 2 and R 3 are C1-C6 alkyl groups which may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. An aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms.
  • a benzene ring ⁇ the benzene ring is a C1-C6 alkyl group that may be substituted with a halogen atom, one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 , R 4 , and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, C1-.
  • X 1 is a nitrogen atom and R 2 is substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms.
  • An aryl group which may be an aryl group, a heteroaryl group which may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, and R 4 and R 5
  • the benzene ring ⁇ the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 , and R 5 are independent hydrogen atoms, halogen atoms, C1-C6 alkyl groups, and one or more halogen atoms.
  • X 1 is CR 3 and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or one or more halogen atoms.
  • a benzene ring ⁇ the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group, an aryl group optionally substituted with one or more halogen atoms, and one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of heteroaryl groups which may be present, or C1-C6 alkoxy groups which may be substituted with one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 , R 4 , and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group, and one or more halogen atoms.
  • Aryl group which may be an aryl group, a heteroaryl group which may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms;
  • X 1 is a nitrogen atom and R 2 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, an aryl group which may be substituted with one or more halogen atoms, and one or more halogen atoms.
  • the benzene ring ⁇ the benzene ring is a halogen atom, a C1-C6 alkyl group, an aryl group that may be substituted with one or more halogen atoms, a heteroaryl group that may be substituted with one or more halogen atoms, or It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with one or more halogen atoms.
  • the benzene ring ⁇ the benzene ring is an aryl group optionally substituted with one or more halogen atoms, or a heteroaryl group optionally substituted with one or more halogen atoms, or one or more It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with a halogen atom.
  • X 1 is a nitrogen atom
  • R 2 , R 4 , and R 5 are aryl groups that may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • R 2 is an aryl group that may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or one or more halogen atoms.
  • the benzene ring may be substituted with a halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups.
  • X 1 is a nitrogen atom
  • R 2 , R 4 , and R 5 are independently substituted with a hydrogen atom, a halogen atom, and one or more halogen atoms.
  • a heteroaryl group, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms;
  • X 1 is a nitrogen atom and R 2 is an aryl group, a heteroaryl group, or one or more halogen atoms which may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 , R 4 , and R 5 are independently substituted with a hydrogen atom, a halogen atom, and one or more halogen atoms.
  • R 2 is substituted with a hydrogen atom, a halogen atom, an aryl group optionally substituted with one or more halogen atoms, or one or more halogen atoms.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 , and R 5 are each independently substituted with a hydrogen atom, a halogen atom, an aryl group, or one or more halogen atoms.
  • X 1 is CR 3
  • R 2 and R 3 may each be independently substituted with a hydrogen atom, a halogen atom, an aryl group, or one or more halogen atoms.
  • benzene ring ⁇ the benzene ring is substituted with a halogen atom, an aryl group, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups.
  • X 1 is a nitrogen atom
  • R 2 , R 4 , and R 5 are each independently substituted with a hydrogen atom, a halogen atom, an aryl group, or one or more halogen atoms.
  • a compound that is a good C1-C6 alkoxy group In formula (1), X 1 is a nitrogen atom and R 2 is a C1-C6 alkoxy group optionally substituted with a hydrogen atom, a halogen atom, an aryl group, or one or more halogen atoms, and R 4 , And R 5 together with the carbon atom to which they are attached, from the benzene ring ⁇ the benzene ring is from a C1-C6 alkoxy group that may be substituted with a halogen atom, an aryl group, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group. ⁇ The compound forming;
  • X 1 is CR 3
  • R 2 , R 3 , R 4 , and R 5 are each independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • X 1 is CR 3
  • R 2 and R 3 may each be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, C1-C6 alkoxy.
  • C1-C6 which is a group and R 4 and R 5 together with the carbon atom to which they are bonded are substituted with a benzene ring
  • the benzene ring may be substituted with a halogen atom or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of alkoxy groups.
  • X 1 is a nitrogen atom
  • R 2 , R 4 , and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, respectively.
  • X 1 is a nitrogen atom and R 2 is a C1-C6 alkoxy group optionally substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms
  • R 4 and R. 5 is selected from the group consisting of a benzene ring ⁇ the benzene ring is a halogen atom, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, together with the carbon atom to which they are bonded 1 It may be substituted with the above substituents.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 , and R 5 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, and methoxy group.
  • Ethoxy group, propoxy group isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy Group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2, Compounds that are 2,3,4,5,4-hexafluorobutoxy groups;
  • X 1 is CR 3
  • R 2 and R 3 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group and propoxy group.
  • X 1 is a nitrogen atom
  • R 2 , R 4 , and R 5 are independent hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, methoxy groups, and ethoxy groups.
  • X 1 is a nitrogen atom and R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, 1,1-.
  • R 4 and R 5 are combined with the carbon atom to which they are attached to form a benzene ring ⁇ the benzene ring is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, Isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, With 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2,2,3,4,5,4-hexafluorobutoxy group Yes, R 4 and R 5 are combined with the carbon atom to which they are attached to form a benzene ring ⁇ the benzene ring is a flu
  • X 1 is CR 3
  • R 2 , R 3 , and R 4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, and R 5
  • hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy Group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1 , 1,2,3,3,3-hexafluoropropoxy group, or 2,2,3,4,5,4-hexafluorobutoxy group;
  • X 1 is CR 3
  • R 2 and R 3 are independently hydrogen atoms, fluorine
  • X 1 is a nitrogen atom
  • R 2 and R 4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms
  • R 5 is hydrogen.
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
  • R 4 and R 5 are carbon atoms to which they are bonded.
  • the benzene ring may be substituted with one or more substituents selected from the group consisting of fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
  • substituents selected from the group consisting of fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
  • R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a 1,1-dimethylpropoxy group, a 1,2-dimethylpropoxy group.
  • X 1 is CR 3
  • R 2 is a hydrogen atom
  • R 3 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
  • R 4 and R 5 are.
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom
  • R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
  • R 5 is a hydrogen atom.
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom
  • R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring.
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom
  • R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
  • R 5 is a hydrogen atom.
  • X 1 is a nitrogen atom
  • R 2 and R 4 are hydrogen atoms
  • R 5 is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, 2, 2 , 3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2,2,3,4,5,4-hexafluorobutoxy group
  • X 1 is a nitrogen atom
  • R 2 and R 4 are hydrogen atoms
  • R 5 is a fluorine atom
  • a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a fluorine atom; In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a chlorine atom; In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a bromine atom; In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is an iodine atom; In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a methoxy group; In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is an ethoxy group; In formula (1), X 1 is a
  • Examples of the mode of the compound represented by the formula (2) include the following compounds.
  • formula (2) a compound in which R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
  • formula (2) the compound in which R 1 is a C1-C6 alkyl group;
  • the compound in which R 1 is a methyl group, an ethyl group, or a propyl group;
  • formula (2) the compound in which R 1 is an ethyl group;
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms, or an aryl group optionally substituted with one or more halogen atoms;
  • the compound in which X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
  • the compound in which X is an aryl group optionally substituted with one or more halogen atoms;
  • formula (2) the compound in which X
  • the compound in which X is a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group;
  • the compound in which X is a methyl group;
  • R 1 is a C1-C6 alkyl group, and X is substituted with a C1-C6 alkyl group that may be substituted with one or more halogen atoms, or one or more halogen atoms.
  • R 1 is a C1-C6 alkyl group and X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
  • R 1 is a C1-C6 alkyl group and X is an aryl group optionally substituted with one or more halogen atoms;
  • R 1 is a methyl group, an ethyl group, or a propyl group, and X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a hexafluoroethyl group, 2,2,2-.
  • R 1 is a methyl group, an ethyl group, or a propyl group
  • X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group, or a 4-chlorophenyl group.
  • R 1 is a methyl group, an ethyl group, or a propyl group
  • X is a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group
  • a compound in which R 1 is an ethyl group and X is a methyl group.
  • Examples of the mode of the compound represented by the formula (4) include the following compounds.
  • X 1 is CR 3 or a nitrogen atom
  • R 3 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom, 1 or more halogen atoms, and 1 or more halogen atoms.
  • R 2 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, 1 or more.
  • R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with one or more halogen atoms, and one or more halogen atoms. It represents an aryl group which may be an aryl group, a heteroaryl group which may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, or they are bonded.
  • a benzene ring ⁇ the benzene ring may be a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl optionally substituted with one or more halogen atoms.
  • the group is substituted with one or more substituents selected from the group consisting of a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. You may.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms
  • R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogens.
  • X 1 is CR 3 or a nitrogen atom, and R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms C1-C6.
  • the groups, R 4 and R 5, are each independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with one or more halogen atoms, and one or more halogen atoms.
  • the benzene ring is a C1-C6 alkyl group optionally substituted with one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, Even if it is substituted with one or more substituents selected from the group consisting of a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. Good.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogen atoms.
  • X 1 is CR 3 or a nitrogen atom, and R 2 , R 3 , R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom and one or more halogen atoms.
  • a C1-C6 alkyl group which may be substituted by one or more halogen atoms, an aryl group which may be substituted by one or more halogen atoms, a heteroaryl group which may be substituted by one or more halogen atoms, or one or more halogen atoms.
  • X is a C1-C6 alkyl group which may be substituted with one or more halogen atoms or an aryl group which may be substituted with one or more halogen atoms
  • R 1 is A compound that is a C1-C6 alkyl group that may be substituted with one or more halogen atoms
  • X 1 is CR 3 or a nitrogen atom
  • R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms C1-C6.
  • Alkyl group aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1-C6 alkoxy optionally substituted with one or more halogen atoms C1-C6 alkyl which is a group and R 4 and R 5 together with the carbon atom to which they are bonded, are substituted with a benzene ring ⁇ the benzene ring may be substituted with a halogen atom, one or more halogen atoms.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • C1-C6 Alkyl group aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1 optionally substituted with one or more halogen atoms -C6 alkoxy group
  • X is a C1-C6 alkyl group which may be substituted with 1 or more halogen atoms or an aryl group which may be substituted with 1 or more halogen atoms
  • R 1 is 1 or more.
  • X 1 is CR 3
  • R 2 and R 3 are C1-C6 alkyl groups, which may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • a benzene ring ⁇ the benzene ring is a C1-C6 alkyl group, which may be substituted with one or more halogen atoms, 1 A group consisting of an aryl group optionally substituted with the above halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. It may be substituted with one or more substituents selected from.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogen atoms.
  • X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms C1-C6.
  • Alkyl group aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1-C6 alkoxy optionally substituted with one or more halogen atoms
  • X 1 is a nitrogen atom and R 2 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom, 1 or more halogen atoms, and 1 or more halogen atoms.
  • the aryl group may be a heteroaryl group which may be substituted with one or more halogen atoms or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, and R 4 and R 5 are them.
  • the benzene ring ⁇ the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms.
  • a halogen atom a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogen atoms.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • C1-C6 alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1 optionally substituted with one or more halogen atoms -C1-C6 is a C1-C6 alkyl group or aryl group that represents a C6 alkoxy group and in which X may be substituted with one or more halogen atoms and R 1 may be substituted with one or more halogen atoms.
  • X 1 is CR 3
  • R 2 and R 3 are C1-C6 alkyl groups, which may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • a benzene ring ⁇ the benzene ring is a C1-C6 alkyl group, which may be substituted with one or more halogen atoms, 1 A group consisting of an aryl group optionally substituted with the above halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. It may be substituted with one or more substituents selected from.
  • Alkyl group aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1-C6 alkoxy optionally substituted with one or more halogen atoms
  • X 1 is a nitrogen atom and R 2 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom, 1 or more halogen atoms, and 1 or more halogen atoms.
  • the aryl group may be a heteroaryl group which may be substituted with one or more halogen atoms or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, and R 4 and R 5 are them.
  • the benzene ring ⁇ the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms.
  • a halogen atom a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms.
  • X 1 is CR 3
  • R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or one or more halogen atoms.
  • aryl group a heteroaryl group that may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, where R 4 and R 5 are attached.
  • the benzene ring ⁇ the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group, an aryl group optionally substituted with one or more halogen atoms, and one or more halogen atoms.
  • ⁇ Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 , R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group and one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, an aryl group that may be substituted with one or more halogen atoms, and one or more halogen atoms.
  • Ring ⁇ The benzene ring is a halogen atom, a C1-C6 alkyl group, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or one or more heteroaryl groups. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with a halogen atom.
  • Aryl group represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, where X is substituted with one or more halogen atoms.
  • X 1 is CR 3
  • R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, and one or more aryl groups.
  • a heteroaryl group that may be substituted with a halogen atom or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, with R 4 and R 5 combined with the carbon atom to which they are attached.
  • the benzene ring ⁇ the benzene ring is a halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted.
  • X 1 is a nitrogen atom and R 2 may be substituted with a hydrogen atom, a halogen atom, an aryl group that may be substituted with one or more halogen atoms, or one or more halogen atoms.
  • a C1-C6 alkoxy group that may be substituted with a heteroaryl group or one or more halogen atoms, with R 4 and R 5 combined with the carbon atom to which they are attached, the benzene ring ⁇ the benzene ring is , Halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or C1-C6 optionally substituted with one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of alkoxy groups.
  • X 1 is CR 3
  • R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or an aryl group or a heteroaryl group.
  • it is a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, and R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring ⁇ the benzene ring is a halogen atom.
  • X is a C1-C6 alkyl group or aryl group that may be substituted with one or more halogen atoms
  • X 1 is a nitrogen atom and R 2 is substituted with a hydrogen atom, a halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group or one or more halogen atoms.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 and R 5 may be independently substituted with hydrogen atom, halogen atom, or one or more halogen atoms.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms, R.
  • a compound in which 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
  • X 1 is CR 3
  • R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or an aryl group or a heteroaryl group.
  • it is a C1-C6 alkoxy group that may be substituted with one or more halogen atoms
  • R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring ⁇ the benzene ring is a halogen atom.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms and R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 , R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom and one or more halogen atoms, respectively.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms
  • R 1 is 1.
  • X 1 is a nitrogen atom and R 2 is substituted with a hydrogen atom, a halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group or one or more halogen atoms.
  • It is a C1-C6 alkoxy group that may be present, in which R 4 and R 5 , together with the carbon atom to which they are bonded, are substituted with a benzene ring ⁇ the benzene ring is replaced with a halogen atom, one or more halogen atoms.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms and R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms.
  • R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 and R 5 may be independently substituted with hydrogen atom, halogen atom, or one or more halogen atoms.
  • X is a C1-C6 alkyl group that may be substituted with one or more halogen atoms
  • R 1 is 1 or more.
  • X 1 is CR 3
  • R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or an aryl group or one or more.
  • X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms and R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • X is a C1-C6 alkyl group that may be substituted with 1 or more halogen atoms
  • R 1 is 1 or more halogen atoms.
  • X 1 is a nitrogen atom and R 2 may be substituted with a hydrogen atom, a halogen atom, an aryl group which may be substituted with one or more halogen atoms, or one or more halogen atoms. It is a C1-C6 alkoxy group, and R 4 and R 5 are combined with the carbon atom to which they are bonded, and the benzene ring ⁇ the benzene ring may be substituted with a halogen atom and one or more halogen atoms.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • X 1 is CR 3
  • R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or an aryl group or one or more.
  • X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
  • X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms.
  • a compound representing a C1-C6 alkoxy group that may be substituted with one or more halogen atoms where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
  • X 1 is a nitrogen atom and R 2 may be substituted with a hydrogen atom, a halogen atom, an aryl group which may be substituted with one or more halogen atoms, or one or more halogen atoms.
  • R 4 and R 5 are combined with the carbon atom to which they are bonded, and the benzene ring ⁇ the benzene ring may be substituted with a halogen atom and one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of an aryl group or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms.
  • X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
  • X 1 is CR 3
  • R 2 , R 3 , R 4 and R 5 are each independently substituted with a hydrogen atom, a halogen atom, an aryl group or one or more halogen atoms.
  • X 1 is CR 3
  • R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, an aryl group or one or more halogen atoms, C1-C6. It is an alkoxy group
  • R 4 and R 5 together with the carbon atom to which they are bonded, a benzene ring ⁇ the benzene ring may be substituted with a halogen atom, an aryl group or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups.
  • X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
  • X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, an aryl group or one or more halogen atoms.
  • a compound representing a C1-C6 alkoxy group where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
  • X 1 is a nitrogen atom and R 2 is a C1-C6 alkoxy group optionally substituted with a hydrogen atom, a halogen atom, an aryl group or one or more halogen atoms
  • R 4 and R 5 is a benzene ring together with the carbon atom to which they are attached ⁇ from the group consisting of a halogen atom, an aryl group or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms.
  • X 1 is CR 3
  • R 2 , R 3 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom or one or more halogen atoms.
  • a compound representing a C1-C6 alkoxy group where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
  • X 1 is CR 3
  • R 2 and R 3 are C1-C6 alkoxy groups that may be independently substituted with hydrogen atoms, halogen atoms, or one or more halogen atoms.
  • R 4 and R 5 together with the carbon atom to which they are attached, from the benzene ring ⁇ the benzene ring is from a C1-C6 alkoxy group that may be substituted with a halogen atom or one or more halogen atoms.
  • X 1 is a nitrogen atom
  • R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom or one or more halogen atoms C1-C6.
  • a compound representing an alkoxy group where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
  • X 1 is a nitrogen atom
  • R 2 is a C1-C6 alkoxy group optionally substituted with a hydrogen atom, a halogen atom or one or more halogen atoms
  • R 4 and R 5 are: Together with the carbon atom to which they are attached, the benzene ring ⁇ the benzene ring is one or more substitutions selected from the group consisting of C1-C6 alkoxy groups optionally substituted with one or more halogen atoms. It may be substituted with a group.
  • X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
  • X 1 is CR 3
  • R 2 , R 3 , R 4 and R 5 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom and methoxy group.
  • Ethoxy group, propoxy group isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group , 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2 3,4,4,4-hexafluorobutoxy group,
  • X is methyl group, ethyl group, propyl group, trifluoromethyl group, phenyl group or 4-chlorophenyl group
  • R 1 is methyl group, ethyl group, Compounds that are propyl or isopropyl groups;
  • X 1 is CR 3
  • R 2 and R 3 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, me
  • Ethoxy group, propoxy group isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy Group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2 , 3, 4, 4, 4-Hexafluorobutoxy groups may be substituted with one or more substituents selected from the group.
  • X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group or a 4-chlorophenyl group
  • R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group
  • X 1 is a nitrogen atom
  • R 2 , R 4 and R 5 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group and ethoxy group.
  • Propyl group isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2, 2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3,4 , 4,4-Hexafluorobutoxy group, X is methyl group, ethyl group, propyl group, trifluoromethyl group, phenyl group or 4-chlorophenyl group, R 1 is methyl group, ethyl group, propyl group or Compounds that are isopropyl groups; In formula (4), X 1 is a nitrogen atom and R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • Dimethylpropoxy group 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group.
  • a benzene ring ⁇ the benzene ring is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy.
  • X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group or a 4-chlorophenyl group
  • R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group
  • X 1 is CR 3 , R 2 , R 3 and R 4 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom, and R 5 is.
  • X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group or a 4-chlorophenyl group
  • R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group
  • X 1 is a nitrogen atom
  • R 2 and R 4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms
  • R 5 is a hydrogen atom.
  • the benzene ring ⁇ the benzene ring may be substituted with one or more substituents selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • substituents selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group or a 4-chlorophenyl group
  • R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group;
  • X 1 is CR 3 , R 2 , R 3 and R 4 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom, and R 5 is. Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, Butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1 , 2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, X is methyl group, ethyl group or propyl group, R 1 is methyl Compounds that are groups
  • X 1 is a nitrogen atom
  • R 2 and R 4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms
  • R 5 is a hydrogen atom.
  • X is methyl group, ethyl group or propyl group
  • R 1 is methyl group, ethyl Compounds that are groups or propyl groups;
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iod
  • the benzene ring ⁇ the benzene ring may be substituted with one or more substituents selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • substituents selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • R 5 is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1- Ethyl propoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group , 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, X is a methyl group, an ethyl group or a propyl group.
  • X 1 is CR 3
  • R 2 is a hydrogen atom
  • R 3 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
  • R 4 and R 5 are them.
  • a compound that forms a benzene ring together with the carbon atom to which it is attached where X is a methyl, ethyl or propyl group and R 1 is a methyl, ethyl or propyl group;
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom
  • R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
  • R 5 is a hydrogen atom and a fluorine atom.
  • X is methyl group, ethyl group or propyl group
  • R 1 is methyl group, ethyl group or Compounds that are propyl groups;
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom
  • R 4 and R 5 together with the carbon atom to which they are bonded form a benzene ring
  • X 1 is a nitrogen atom
  • R 2 is a hydrogen atom
  • R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
  • R 5 is a hydrogen atom and a fluorine atom.
  • X is a methyl group, an ethyl group or a propyl group
  • R 1 is a methyl group, Compounds that are ethyl or propyl groups
  • X 1 is a nitrogen atom
  • R 2 and R 4 are hydrogen atoms
  • R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, and a propoxy.
  • X is a methyl group, an ethyl group or a propyl group
  • R 1 is a methyl group, an ethyl group or a propyl group
  • X 1 is a nitrogen atom
  • R 2 and R 4 are hydrogen atoms
  • R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, and a propoxy.
  • R 1 is an ethyl group
  • X 1 is a nitrogen atom
  • R 2 and R 4 are hydrogen atoms
  • R 5 is a 1,1,2,3,3,3-hexafluoropropoxy group
  • X is a methyl.
  • a compound that is a group and R 1 is an ethyl group
  • X 1 is a nitrogen atom
  • R 2 and R 4 are hydrogen atoms
  • R 5 is a 2,2,3,4,5,4-hexafluorobutoxy group
  • X is a methyl.
  • a compound that is a group and R 1 is an ethyl group.
  • X is preferably a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group, or a 4-chlorophenyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group.
  • R 1 is preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and more preferably a methyl group, an ethyl group, or a propyl group.
  • R 2 is a C1-C6 alkyl group which may be substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, an aryl group which may be substituted with one or more halogen atoms, or one or more.
  • Heteroaryl groups that may be substituted with halogen atoms or C1-C6 alkoxy groups that may be substituted with one or more halogen atoms are preferred, and are substituted with hydrogen atoms, halogen atoms, or one or more halogen atoms.
  • R 3 is a C1-C6 alkyl group which may be substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, an aryl group which may be substituted with one or more halogen atoms, or one or more.
  • Heteroaryl groups that may be substituted with halogen atoms or C1-C6 alkoxy groups that may be substituted with one or more halogen atoms are preferred, and are substituted with hydrogen atoms, halogen atoms, or one or more halogen atoms. More preferably, a C1-C6 alkyl group which may be substituted, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms.
  • R 4 and R 5 are a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom and one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms.
  • a heteroaryl group that may be substituted with one or more halogen atoms, a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, or a carbon atom to which R 4 and R 5 are bonded.
  • a benzene ring and a C1-C6 alkyl group which may be substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, and a C1-C6 which may be substituted with one or more halogen atoms. It is more preferable to form a benzene ring together with an alkoxy group or a carbon atom to which R 4 and R 5 are bonded.
  • X 1 is preferably a nitrogen atom.
  • the symbols have the same meaning as above.
  • Compound (1) is a commercially available compound or can be produced according to a known method.
  • Compound (2) is a commercially available compound or can be produced according to a known method.
  • the amount of the compound (2) to be used is usually 0.5 to 10 mol, preferably 0.8 to 5 mol, per 1 mol of the compound (1).
  • the metal salt include a zinc metal salt and a silver metal salt.
  • Preferred zinc salts include zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc trifluoromethanesulfonate, zinc nitrate, zinc perchlorate, zinc thiocyanate, zinc phosphate, diphosphate.
  • Examples thereof include zinc, zinc borate, zinc carbonate, zinc acetate, zinc propionate, zinc 2-ethylhexanate, zinc laurate, zinc stearate, zinc naphthenate, zinc acetylacetonate, zinc oxide and zinc sulfide. More preferably, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc trifluoromethanesulfonate, zinc nitrate, zinc perchlorate, zinc thiocyanate, zinc carbonate, zinc acetate, zinc propionate and Examples thereof include zinc 2-ethylhexanoate.
  • Preferred silver salts include silver fluoride, silver chloride, silver bromide, silver sulfate, silver trifluoromethanesulfonate, silver p-toluenesulfonate, silver methanesulfonate, silver carbonate, silver acetate, silver trifluoroacetate, Silver citrate, silver lactate, silver benzoate, silver nitrate, silver nitrite, silver diethylthiocarbamate, silver thiocyanate, silver phosphate, silver hexafluoroantimonate (V), silver tetrafluoroborate, silver oxide and silver sulfide Etc., more preferably silver fluoride, silver chloride, silver bromide, silver sulfate, silver trifluoromethanesulfonate, silver p-toluenesulfonate, silver methanesulfonate, silver carbonate, silver acetate, trifluoroacetic acid.
  • Examples thereof include silver, silver citrate, silver lactate, silver benzoate, silver nitrate, silver nitrite, silver thiocyanate, silver phosphate and silver tetrafluoroborate.
  • the amount of the metal salt used is usually 0.01 to 10 mol, preferably 0.01 to 5 mol, more preferably 0.05 to 3 mol, per 1 mol of compound (1). is there.
  • Bases include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydride, potassium hydride, etc .; trimethylamine, triethylamine, tributylamine, dimethyl Octylamine, trioctylamine, N, N-dimethylbenzylamine, N, N-diisopropylethylamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 4-methylmorpholin, 4-ethylmorpholin, N-methylpyrrolidin, N-ethyl Amine-based bases such as pyrrolidine, 1-methylpiperidin, 1-azabicyclo [2.2.2] octane, 1,4-diazabicyclo [2.2.2] octane, hexamethylenetetramine; 1,8-diazabicyclo [5] .4.0] Undeca-7-ene
  • Amidin-based bases that may be substituted with one or more active substituents; aniline-based bases such as N, N-dimethylaniline, N, N-diethylaniline; pyridine, 2-methylpyridine, 3-methylpyridine, 4 -Methylpyridine, 2-ethylpyridine, 2-propylpyridine, 2,4-lutidine, 3,4-lutidine, 2,6-lutidine, 3,5-lutidine, 2-methyl-5-ethylpyridine, 2,4 , 6-trimethylpyridine, 2,3,5-trimethylpyridine, 4- (dimethylamino) pyridine, 4-pyrrolidinopyridine, 2,2'-bipyridyl, etc.
  • aniline-based bases such as N, N-dimethylaniline, N, N-diethylaniline
  • aniline-based bases such as N, N-dimethylaniline, N, N-diethylaniline
  • pyridine 2-methylpyridine, 3-methylpyridine, 4
  • Pyridine-based bases which may be used; quinoline-based bases such as quinoline, 2-methylquinoline, and isoquinoline are mentioned, and inorganic substances such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydride, and sodium hydride are preferable.
  • Bases Amine-based bases such as trimethylamine, triethylamine, N, N-diisopropylethylamine, 4-methylmorpholin; pyridine-based bases such as pyridine, 2,6-lutidine, 4- (dimethylamino) pyridine; quinoline, 2-methylquinoline , Isoquinolin and other quinoline bases and the like.
  • the amount of the base used is usually 0.1 to 10 mol, preferably 0.1 to 5 mol, per 1 mol of compound (1).
  • the reaction is usually carried out in a solvent.
  • the solvent include ether solvents such as diethyl ether, tetrahydrofuran, methyl t-butyl ether, cyclopentyl methyl ether and ethylene glycol dimethyl ether; alkyl nitrile solvents such as acetonitrile and propionitrile; N, N-dimethylformamide and N-methyl-2.
  • -Amid solvent such as pyrrolidone; aromatic solvents such as toluene, xylene, monochlorobenzene and mixed solvents thereof are mentioned, and ethers such as diethyl ether, tetrahydrofuran, methyl t-butyl ether, cyclopentyl methyl ether and ethylene glycol dimethyl ether are preferable. Solvents can be mentioned.
  • the amount of the solvent used is usually 1 to 10 times the weight, preferably 1 to 5 times the weight of the compound (1).
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C., preferably in the range of 20 to 80 ° C.
  • the reaction time is usually in the range of 0.5 to 48 hours, preferably 3 to 48 hours.
  • the reaction mixture After completion of the reaction, the reaction mixture is concentrated; the reaction mixture is mixed with neutral or weakly basic water and then extracted with an organic solvent to dry or concentrate the obtained organic layer; the reaction mixture and alkali.
  • metal hydroxide, alkali metal carbonate or alkali metal hydrogen carbonate for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.
  • metal hydroxide, alkali metal carbonate or alkali metal hydrogen carbonate for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.
  • the insoluble material is filtered off, the filtrate is extracted with an organic solvent, and the obtained organic layer is dried or concentrated; the compound (4) is obtained by performing a post-treatment operation such as. Can be isolated. Further, the isolated compound (4) can be further purified by a method such as recrystallization, chromatography, or salting out. Further, the reaction mixture containing the compound (4) can be subjected to the next step (B) without isolating the compound (4) to produce the compound (3).
  • step (B) of obtaining the compound (3) from the compound (4) will be described.
  • the step proceeds by reacting compound (4) with water in the presence of an acid.
  • the theoretical amount of water used is usually 2 mol per 1 mol of compound (4), but an excess amount can be used.
  • the acid include carboxylic acids such as acetic acid, formic acid, citric acid, oxalic acid, 3-phenylacrylic acid, benzoic acid, 4-chlorobenzoic acid, terephthalic acid, isophthalic acid, 1-naphthalenecarboxylic acid; phosphoric acid; Nitrate; sulfonic acid such as sulfuric acid, methanesulfonic acid, 4-toluenesulfonic acid monohydrate; hydrogen halide such as hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen fluoride; and the like, preferably acetic acid.
  • carboxylic acids such as acetic acid, formic acid, citric acid, oxalic acid, 3-phenylacrylic acid, benzoic acid, 4-chlorobenz
  • Carboxylic acids such as formic acid and citric acid; phosphoric acid; nitric acid; sulfuric acid; hydrogen chloride and the like.
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C., preferably in the range of 0 to 70 ° C.
  • the reaction time is usually in the range of 0.5 to 48 hours.
  • the step can also be carried out in a solvent, such as an ether solvent such as diethyl ether, tetrahydrofuran, methyl t-butyl ether, cyclopentyl methyl ether, ethylene glycol dimethyl ether; an alkylnitrile solvent such as acetonitrile and propionitrile.
  • Amid solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; aromatic solvents such as toluene, xylene and monochlorobenzene and mixed solvents thereof are mentioned, preferably diethyl ether, tetrahydrofuran and methyl t.
  • ether solvents such as butyl ether, cyclopentyl methyl ether and ethylene glycol dimethyl ether.
  • an aqueous solution of carbonate or alkali metal hydrogen carbonate for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.
  • extraction is performed with an organic solvent, and the obtained organic layer is dried.
  • an aqueous solution of alkali metal hydroxide, alkali metal carbonate or alkali metal hydrogen carbonate eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.
  • the insoluble matter is filtered off, the filtrate is extracted with an organic solvent, and the obtained organic layer is dried or concentrated;
  • the compound (3) can be isolated by performing a post-treatment operation such as. Further, the isolated compound (3) can be further purified by a method such as recrystallization, chromatography, or salting out.
  • a compound having an excellent control effect on harmful arthropods can be produced by the production method described in International Publication No. 2017/065228.
  • Example 1 7.8 g of zinc chloride, 2.3 g of triethylamine, 3.9 g of the compound represented by the formula (2-1) and 10 g of THF were mixed at 25 ° C. for 30 minutes. 2.0 g of the compound represented by the formula (1-1) was added to the mixture, mixed, heated to 50 ° C., and stirred for 20 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-1) was produced with an area percentage value of 86%. After cooling the reaction solution to 0 ° C., 30 g of water was added and the insoluble matter was filtered off.
  • Example 2 120 mg of zinc chloride, 150 mg of triethylamine, 130 mg of the compound represented by the formula (2-1) and 500 mg of toluene were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-1) was added to the mixture, mixed, heated to 50 ° C. for 5 hours at 25 ° C., and stirred for 5 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-1) was produced with an area percentage value of 31%.
  • Example 3 120 mg of zinc chloride, 150 mg of triethylamine, 130 mg of the compound represented by the formula (2-1) and 500 mg of methyl t-butyl ether were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-1) was added to the mixture, mixed, heated to 50 ° C. for 5 hours at 25 ° C., and stirred for 5 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-1) was produced with an area percentage value of 27%.
  • Example 4 6.0 mg of silver acetate, 40 mg of triethylamine, 70 mg of the compound represented by the formula (2-1) and 300 ⁇ L of THF were mixed at 25 ° C. for 20 minutes. 50 mg of the compound represented by the formula (1-2) was added to the mixture, mixed, heated to 50 ° C., and stirred for 6 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-2) was produced with an area percentage value of 40%.
  • Example 5 0.10 g of zinc chloride, 50 mg of sodium hydride (purity 60%), 0.10 g of the compound represented by the formula (2-1) and 0.20 g of THF were mixed at 25 ° C. for 1 hour. To the mixture, 0.10 g of the compound represented by the formula (1-2) was added and mixed, the temperature was raised to 65 ° C., and the mixture was stirred for 8 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-2) was produced with an area percentage value of 48%.
  • Example 6 11 mg of silver trifluoromethanesulfonate, 70 ⁇ L of diisopropylethylamine, 70 mg of the compound represented by the formula (2-1) and 300 ⁇ L of THF were mixed at 25 ° C. for 20 minutes. 50 mg of the compound represented by the formula (1-2) was added to the mixture, mixed, heated to 50 ° C., and stirred for 6 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-2) was produced with an area percentage value of 73%.
  • Example 7 After dissolving 11 mg of silver trifluoromethanesulfonate, 55 ⁇ L of triethylamine, and 74 mg of the compound represented by the formula (2-1) in 570 ⁇ L of THF, the mixture was stirred at 20 ° C. for 20 minutes. To the obtained mixed solution, 0.10 g of the compound represented by the formula (1-3) was added and mixed, the temperature was raised to 50 ° C., and the mixture was stirred for 6 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-3) was produced with an area percentage value of 58%.
  • Example 8 2.9 g of zinc chloride, 1.4 mL of triethylamine, 1.7 g of the compound represented by the formula (2-1) and 5 mL of THF were mixed at 25 ° C. for 1 hour. 1.0 g of the compound represented by the formula (1-5) was added to the mixture, mixed, heated to 45 ° C., and stirred for 20 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-5) was produced with an area percentage value of 20%. The reaction mixture was cooled to 25 ° C., water was added, and the mixture was extracted with 50 mL of ethyl acetate.
  • Example 9 150 mg of the compound represented by the formula (4-5) obtained by purification in Example 8 and 14 mL of 4N hydrochloric acid were mixed at 20 ° C. and stirred for 15 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-5) was produced with an area percentage value of 20%.
  • Example 10 15 g of zinc chloride, 16 mL of triethylamine, 9.0 g of the compound represented by the formula (2-1) and 70 mL of THF were mixed at 20 ° C. for 1 hour. 7.0 g of the compound represented by the formula (1-4) was added to the mixture and mixed, the temperature was raised to 50 ° C., and the mixture was stirred for 19 hours. The obtained reaction solution was cooled to 20 ° C., 23 mL of 20% hydrochloric acid was added, and the mixture was stirred at 20 ° C. for 16 hours.
  • Example 11 570 mg of zinc chloride, 0.19 g of triethylamine, 0.34 g of the compound represented by the formula (2-1) and 1 g of THF were mixed at 25 ° C. for 30 minutes. 200 mg of the compound represented by the formula (1-1) was added to the mixture, mixed, heated to 50 ° C., and stirred for 18 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-1) was produced with an area percentage value of 83%. After cooling the reaction solution to 0 ° C., 0.40 g of 35% hydrochloric acid was added, the temperature was raised to 25 ° C., and the mixture was stirred for 16 hours.
  • the obtained mixed solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-1) was produced with an area percentage value of 57%.
  • Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 ⁇ m, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
  • Example 12 220 mg of zinc chloride, 70 mg of triethylamine, 130 mg of the compound represented by the formula (2-1) and 500 mg of THF were mixed at 25 ° C. for 1 hour. To the mixture, 100 mg of the compound represented by the formula (1-2) was added and mixed, the temperature was raised to 50 ° C. for 19 hours at 25 ° C., and the mixture was stirred for 10 hours. The obtained reaction solution was cooled to 20 ° C., 220 mg of 35% hydrochloric acid and 200 mg of water were added, and the mixture was stirred at 20 ° C. for 12 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-2) was produced with an area percentage value of 79%.
  • Example 13 After dissolving 320 mg of zinc trifluoromethanesulfonate, 55 ⁇ L of triethylamine, and 73 mg of the compound represented by the formula (2-1) in 720 ⁇ L of THF, the mixture was stirred at 20 ° C. for 20 minutes. To the obtained mixed solution, 100 mg of the compound represented by the formula (1-3) was added and mixed, the temperature was raised to 50 ° C., and the mixture was stirred for 6 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-3) was produced with an area percentage value of 78%.
  • Example 14 500 mg of zinc trifluoromethanesulfonate, 0.1 mL of triethylamine, 100 mg of the compound represented by the formula (2-1) and 3.0 mL of THF were mixed at 25 ° C. for 1 hour. 0.1 g of the compound represented by the formula (1-6) was added to the mixture, mixed, the temperature was raised to 50 ° C., and the mixture was stirred for 20 hours. After cooling the obtained reaction solution to 20 ° C., 1 mL of 4N hydrochloric acid was added dropwise, and the mixture was stirred at 20 ° C. for 14 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-6) was produced with an area percentage value of 77%.
  • Example 15 500 mg of zinc trifluoromethanesulfonate, 50 mg of pyridine, 100 mg of the compound represented by the formula (2-1) and 3.0 mL of THF were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-6) was added to the mixture, mixed, heated to 45 ° C., and stirred for 30 hours. After cooling the obtained reaction solution to 20 ° C., 1 mL of 4N hydrochloric acid was added dropwise, and the mixture was stirred at 20 ° C. for 24 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-6) was produced with an area percentage value of 35%.
  • Example 16 500 mg of zinc trifluoromethanesulfonate, 0.1 mL of DBU, 100 mg of the compound represented by the formula (2-1) and 3.0 mL of THF were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-6) was added to the mixture, mixed, heated to 45 ° C., and stirred for 30 hours. After cooling the obtained reaction solution to 20 ° C., 1 mL of 4N hydrochloric acid was added dropwise, and the mixture was stirred at 20 ° C. for 24 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-6) was produced with an area percentage value of 51%.
  • Example 17 500 mg of zinc trifluoromethanesulfonate, 70 mg of sodium carbonate, 100 mg of the compound represented by the formula (2-1) and 3.0 mL of THF were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-6) was added to the mixture, mixed, heated to 45 ° C., and stirred for 30 hours. After cooling the obtained reaction solution to 20 ° C., 1 mL of 4N hydrochloric acid was added dropwise, and the mixture was stirred at 20 ° C. for 24 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-6) was produced with an area percentage value of 49%.
  • Comparative Example 1 11 mg of silver trifluoromethanesulfonate, 74 mg of the compound represented by the formula (2-1), and 300 ⁇ L of THF were mixed at 20 ° C. for 30 minutes. 50 mg of the compound represented by the formula (1-2) was added to the mixture, mixed, heated to 50 ° C., and stirred for 6 hours. The obtained mixture was cooled to 20 ° C. and analyzed by high performance liquid chromatography, and the area percentage value of the compound represented by the formula (4-2) was 0%. After adding 55 ⁇ L of triethylamine to the mixture, the mixture was stirred at 50 ° C. for 5 hours.
  • reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-2) was produced with an area percentage value of 67%.
  • Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 ⁇ m, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
  • Comparative Example 2 1.6 g of the compound represented by the formula (5) (hereinafter, also referred to as compound (5)) was dissolved in 2 g of THF, cooled to 5 ° C., and 5.4 mL of a 2.6 M butyllithium hexane solution was added dropwise. After completion of the dropping, the temperature of the mixed solution was raised to 20 ° C. and the mixture was stirred for 1 hour to obtain a compound (5) butyllithium reaction solution. After dissolving 1 g of the compound represented by the formula (1-1) in 2 g of THF, the mixture was cooled to ⁇ 5 ° C.
  • Comparative Example 3 In Comparative Example 2, an attempt was made to synthesize the compound represented by the formula (6) from the compound represented by the formula (1-1) by the same method except that t-butoxypotassium was used instead of the 2.6M butyllithium hexane solution. It was. When the obtained reaction solution was analyzed by high performance liquid chromatography, the area percentage value of the compound represented by the formula (1-1) was 4%, and the area percentage value of the compound represented by the formula (6) was 0%. It was.
  • Example 1 Comparative Example 4, Comparative Example 5, Comparative Example 6 and Example 1
  • Q represents a hydrogen atom, a methoxy group or a nitro group.
  • the compound represented by the formula (1-7) is used in the same manner as in Example 1 except that the compound represented by the formula (1-7) is used instead of the compound represented by the formula (1-1).
  • Area percentage value of the compound represented by the formula (4-7) hereinafter, also referred to as the compound (4-7)
  • the compound represented by the formula (2-1) when the compound represented by the formula (2-1), the metal salt and the base are reacted. was 0%.
  • a ⁇ -ketosulfone compound can be efficiently produced.

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Abstract

A method for producing a compound represented by formula (4), said method including a step for reacting a compound represented by formula (1) [In formula (1), X1 represents CR3 or a nitrogen atom, R2 and R3 each independently represent a hydrogen atom, a halogen atom, a C1-6 alkyl group which may be substituted with one or more halogen atoms, or the like, and R4 and R5 each independently represent a hydrogen atom, a halogen atom, a C1-6 alkyl group which may be substituted with one or more halogen atoms, or the like.] and a compound represented by formula (2) [In formula (2), X represents a C1-6 alkyl group which may be substituted with one or more halogen atoms, or the like, and R1 represents a C1-6 alkyl group which may be substituted with one or more halogen atoms.] in the presence of a metal salt or a base to obtain the compound represented by formula (4) [In formula (4), X, X1, R1, R2, R4, and R5 represent the same groups as described above.].

Description

β－ケトスルホン化合物の製造方法Method for producing β-ketosulfone compound
　本発明は、β－ケトスルホン化合物を製造する方法に関する。 The present invention relates to a method for producing a β-ketosulfone compound.
　β－ケトスルホン化合物は、医薬、及び農薬の製造中間体及び最終製品として重要な化合物群である。例えば、特許文献１には、β－ケトスルホン化合物が、ヒトを含む温血動物に対する、抗癌活性を有する化合物として有用であることが記載されている。
β－ケトスルホン化合物の製造方法としては、特許文献２及び非特許文献１に記載の、ニトリル化合物に対するアルキルスルホン化合物の付加反応が知られている。しかしながら、アルキルリチウム、ナトリウムアルコキシド等の強塩基を必要とし、反応の工業的な制御が困難な場合や、基質が塩基性条件下で損壊する場合がある。 β-ketosulfone compounds are an important group of compounds as intermediates and final products for the production of pharmaceuticals and pesticides. For example, Patent Document 1 describes that a β-ketosulfone compound is useful as a compound having anticancer activity against warm-blooded animals including humans.
As a method for producing a β-ketosulfone compound, an addition reaction of an alkylsulfone compound with a nitrile compound described in Patent Document 2 and Non-Patent Document 1 is known. However, strong bases such as alkyllithium and sodium alkoxide are required, and industrial control of the reaction may be difficult, or the substrate may be damaged under basic conditions.
国際公開第１９９５／０９１５８号International Publication No. 1995/09158 ＵＳ２０１３／０２１７９１８US2013 / 0217918
　本発明は、効率的なβ－ケトスルホン化合物の製造方法を提供することを課題とする。 An object of the present invention is to provide an efficient method for producing a β-ketosulfone compound.
　本発明者らは、β－ケトスルホン化合物を製造する方法について検討した結果、金属塩及び塩基の存在下、ニトリル化合物とβ－カルボニルスルホン化合物とを反応させることにより、α－スルホニルβ－ケトエナミン化合物が生成されることを見出した。ついで、酸の存在下、該化合物と水とを反応させることによりβ－ケトスルホン化合物を効率よく製造できることを見出した。
　すなわち、本発明は以下の通りである。
［１］　工程（Ａ）：式（１）
Figure JPOXMLDOC01-appb-I000007
［式中、Ｘ1はＣＲ3又は窒素原子を表し、
Ｒ2及びＲ3は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、
Ｒ4及びＲ5は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は群Ａより選ばれる１以上の置換基で置換されていてもよい。｝を形成する。
群Ａ：ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群。］
で表される化合物と、式（２）
Figure JPOXMLDOC01-appb-I000008
［式中、Ｘは、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基を表し、
Ｒ1は、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基を表す。］
で表される化合物とを、金属塩および塩基の存在下で反応させて、式（４）
Figure JPOXMLDOC01-appb-I000009
［式中、Ｘ、Ｘ1、Ｒ1、Ｒ2、Ｒ4及びＲ5は前記と同じ意味を表す。］
で表される化合物を得る工程：
を含む、式（４）で表される化合物の製造方法。
［２］　式（１）において、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である、［１］に記載の製造方法。
［３］　式（１）において、Ｘ1がＣＲ3又は窒素原子であり、Ｘ1がＣＲ3である場合に、Ｒ3が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である、［１］又は［２］に記載の製造方法。
［４］　式（１）において、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基及び１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成する、［１］～［３］のいずれかに記載の製造方法。
［５］　式（１）において、Ｘ1が窒素原子である、［１］～［４］のいずれかに記載の製造方法。
［６］　式（１）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4が水素原子であり、Ｒ5が水素原子、ハロゲン原子又はＯＣＨ2ＣＦ2ＣＦ3基である、［１］～［５］のいずれかに記載の製造方法。
［７］　式（２）において、Ｘがメチル基である、［１］～［６］のいずれかに記載の製造方法。
［８］　式（２）において、Ｒ1がエチル基である、［１］～［７］のいずれかに記載の製造方法。
［９］　塩基が、無機塩基又はアミン系塩基である、［１］～［８］のいずれかに記載の製造方法。
［１０］　金属塩が、亜鉛又は銀の塩である、［１］～［９］のいずれかに記載の製造方法。
［１１］　金属塩が、ＺｎＣｌ2、Ｚｎ（ＯＳ（Ｏ）2ＣＦ3）2、ＡｇＯＳ（Ｏ）2ＣＦ3又はＡｇＯＣ（Ｏ）ＣＨ3である、［１］～［１０］のいずれかに記載の製造方法。
［１２］　［１］～［１１］のいずれかに記載の工程（Ａ）にさらに下記工程（Ｂ）を含む、式（３）
Figure JPOXMLDOC01-appb-I000010
［式中、Ｘ1、Ｒ1、Ｒ2、Ｒ4及びＲ5は前記と同じ意味を表す。］
で表される化合物の製造方法。
工程（Ｂ）：
酸の存在下、式（４）
Figure JPOXMLDOC01-appb-I000011
［式中、Ｘ、Ｘ1、Ｒ1、Ｒ2、Ｒ4及びＲ5は前記と同じ意味を表す。］
で表される化合物と水とを反応させ、式（３）で示される化合物を得る工程。
［１３］　式（４）
Figure JPOXMLDOC01-appb-I000012
［式中、
Ｘは、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基を表し、
Ｒ1は、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基を表し、
Ｘ1はＣＲ3又は窒素原子を表し、
Ｒ2及びＲ3は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、
Ｒ4及びＲ5は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は群Ａより選ばれる１以上の置換基で置換されていてもよい。｝を形成する。
群Ａ：ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群。］
で表される化合物。
［１４］　式（４）において、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である、［１３］に記載の化合物。
［１５］　式（４）において、Ｘ1がＣＲ3又は窒素原子であり、Ｘ1がＣＲ3である場合に、Ｒ3が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である、［１３］又は［１４］に記載の化合物。
［１６］　式（４）において、Ｒ4及びＲ5が各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であるか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成する［１３］～［１５］のいずれかに記載の化合物。
［１７］　式（４）において、Ｘ1が窒素原子である、［１３］～［１６］のいずれかに記載の化合物。
［１８］　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4が水素原子であり、Ｒ5が水素原子、ハロゲン原子又はＯＣＨ2ＣＦ2ＣＦ3基である、［１３］～［１７］のいずれかに記載の化合物。
［１９］　式（４）において、Ｘがメチル基である、［１３］～［１８］のいずれかに記載の化合物。
［２０］　式（４）において、Ｒ1がエチル基である、［１３］～［１９］のいずれかに記載の化合物。 As a result of investigating a method for producing a β-ketosulfone compound, the present inventors have obtained an α-sulfonyl β-ketoenamine compound by reacting a nitrile compound with a β-carbonyl sulfone compound in the presence of a metal salt and a base. Found to be generated. Then, it was found that the β-ketosulfone compound can be efficiently produced by reacting the compound with water in the presence of an acid.
That is, the present invention is as follows.
[1] Step (A): Formula (1)
Figure JPOXMLDOC01-appb-I000007
[In the formula, X 1 represents CR 3 or a nitrogen atom,
R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. Represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms.
R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. Represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, or combined with a carbon atom to which they are attached. The benzene ring {the benzene ring may be substituted with one or more substituents selected from group A. } Is formed.
Group A: Halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, even if substituted with one or more halogen atoms A group consisting of a good heteroaryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. ]
Compound represented by and formula (2)
Figure JPOXMLDOC01-appb-I000008
[In the formula, X represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms.
R 1 represents a C1-C6 alkyl group that may be substituted with one or more halogen atoms. ]
The compound represented by (4) is reacted in the presence of a metal salt and a base to formulate (4).
Figure JPOXMLDOC01-appb-I000009
[In the formula, X, X 1 , R 1 , R 2 , R 4 and R 5 have the same meanings as described above. ]
Step of obtaining the compound represented by:
A method for producing a compound represented by the formula (4), which comprises.
[2] In the formula (1), R 2 may be substituted with a hydrogen atom, a halogen atom, one or more halogen atoms, an aryl group, or one or more halogen atoms, or a C1-C6 alkoxy group. The production method according to [1].
[3] In the formula (1), when X 1 is CR 3 or a nitrogen atom and X 1 is CR 3 , even if R 3 is substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. The production method according to [1] or [2], which is a good aryl group or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms.
[4] In the formula (1), R 4 and R 5 are independently substituted with an aryl group or one or more halogen atoms which may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. Represents a C1-C6 alkoxy group that may be present, or together with the carbon atom to which they are attached, a benzene ring {the benzene ring may be substituted with a halogen atom, one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of a group and a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. }, The production method according to any one of [1] to [3].
[5] The production method according to any one of [1] to [4], wherein X 1 is a nitrogen atom in the formula (1).
[6] In the formula (1), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 is a hydrogen atom, and R 5 is a hydrogen atom, a halogen atom, or three OCH 2 CF 2 CF groups. The production method according to any one of [1] to [5].
[7] The production method according to any one of [1] to [6], wherein X is a methyl group in the formula (2).
[8] The production method according to any one of [1] to [7], wherein R 1 is an ethyl group in the formula (2).
[9] The production method according to any one of [1] to [8], wherein the base is an inorganic base or an amine-based base.
[10] The production method according to any one of [1] to [9], wherein the metal salt is a zinc or silver salt.
[11] The metal salt is ZnCl 2 , Zn (OS (O) 2 CF 3 ) 2 , AgOS (O) 2 CF 3, or AgOC (O) CH 3 , any of [1] to [10]. The manufacturing method described.
[12] Formula (3), wherein the step (A) according to any one of [1] to [11] further includes the following step (B).
Figure JPOXMLDOC01-appb-I000010
[In the formula, X 1 , R 1 , R 2 , R 4 and R 5 have the same meanings as described above. ]
A method for producing a compound represented by.
Process (B):
Equation (4) in the presence of acid
Figure JPOXMLDOC01-appb-I000011
[In the formula, X, X 1 , R 1 , R 2 , R 4 and R 5 have the same meanings as described above. ]
A step of reacting a compound represented by (3) with water to obtain a compound represented by the formula (3).
[13] Equation (4)
Figure JPOXMLDOC01-appb-I000012
[During the ceremony,
X represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms.
R 1 represents a C1-C6 alkyl group that may be substituted with one or more halogen atoms.
X 1 represents CR 3 or nitrogen atom
R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. Represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms.
R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. Represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, or combined with a carbon atom to which they are attached. The benzene ring {the benzene ring may be substituted with one or more substituents selected from group A. } Is formed.
Group A: Halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, even if substituted with one or more halogen atoms A group consisting of a good heteroaryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. ]
The compound represented by.
[14] In the formula (4), R 2 may be substituted with a hydrogen atom, a halogen atom, one or more halogen atoms, an aryl group, or one or more halogen atoms, or a C1-C6 alkoxy group. The compound according to [13].
[15] In the formula (4), when X 1 is a CR 3 or a nitrogen atom and X 1 is a CR 3 , even if R 3 is substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. The compound according to [13] or [14], which is a good aryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms.
[16] In the formula (4), R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, an aryl group which may be substituted with one or more halogen atoms, or one or more halogen atoms. It may be a C1-C6 alkoxy group, or together with the carbon atom to which they are attached, a benzene ring {the benzene ring may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of good aryl groups or C1-C6 alkoxy groups which may be substituted with one or more halogen atoms. } The compound according to any one of [13] to [15].
[17] The compound according to any one of [13] to [16], wherein X 1 is a nitrogen atom in the formula (4).
[18] In equation (4), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 is a hydrogen atom, and R 5 is a hydrogen atom, a halogen atom, or three OCH 2 CF 2 CF groups. A compound according to any one of [13] to [17].
[19] The compound according to any one of [13] to [18], wherein X is a methyl group in the formula (4).
[20] The compound according to any one of [13] to [19], wherein R 1 is an ethyl group in the formula (4).
　本発明により、β－ケトスルホン化合物を効率よく製造できる。 According to the present invention, a β-ketosulfone compound can be efficiently produced.
　以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明における置換基について説明する。
　「置換されていてもよい」とは、置換されているか、又は置換されていないことを意味する。２以上の置換基で置換されている場合、それらの置換基は互いに同一でも異なっていてもよい。
「ハロゲン原子で置換されていてもよい」とは、ハロゲン原子を有しているか、又は有していないことを意味する。２以上のハロゲン原子を有している場合、それらのハロゲン原子は互いに同一でも異なっていてもよい。
　本明細書における「ＣＹ－ＣＺ」との表記は、炭素原子数がＹ乃至Ｚであることを意味する。例えば「Ｃ１－Ｃ６」の表記は、炭素原子数が１乃至６であることを意味する。
　本明細書中「ハロゲン原子」とは、フッ素原子、塩素原子、臭素原子、又はヨウ素原子を表す。
　「アルキル基」としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、１，１－ジメチルプロピル基、１，２－ジメチルプロピル基、１－エチルプロピル基、ブチル基、ｔｅｒｔ－ブチル基、ペンチル基及びヘキシル基等が挙げられる。
「１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基」としては、例えば、ジフルオロメチル基、トリクロロメチル基、トリフルオロメチル基、２，２，２－トリフルオロエチル基、２－ブロモ－１，１，２，２－テトラフルオロエチル基、２，２，３，３－テトラフルオロプロピル基、２，２，３，３，３－ペンタフルオロプロピル基、１，１，２，３，３，３－ヘキサフルオロプロピル基、１－メチル－２，２，３，３－テトラフルオロプロピル基、２，２，３，４，４，４－ヘキサフルオロブチル基及びペルフルオロヘキシル基等が挙げられる。
　「アリール基」としては、フェニル基、及びナフチル基等が挙げられる。
「１以上のハロゲン原子で置換されていてもよいアリール基」としては、例えば、２－ブロモフェニル基、３－ヨードフェニル基、４－クロロフェニル基、４－フルオロフェニル基、２，４－ジクロロフェニル基、３－ブロモ－５－ヨードフェニル基、２，３，４－トリクロロフェニル基、２，４，６－トリフルオロフェニル基、４－ブロモ－２，６－ジクロロフェニル基、２，３，４，５，６－ペンタブロモフェニル基、２－クロロ－１－ナフチル基、３－ブロモ－１－ナフチル基、４－ヨード－１－ナフチル基、５－フルオロ－１－ナフチル基、６－クロロ－１－ナフチル基、７－ブロモ－１－ナフチル基、８－クロロ－１－ナフチル基、４，５－ジクロロ－１－ナフチル基、６－ブロモ－８－クロロ－１－ナフチル基、１－クロロ－２－ナフチル基、３－ブロモ－２－ナフチル基、２，４，５－トリクロロ－１－ナフチル基、４－ヨード－２－ナフチル基、５－フルオロ－２－ナフチル基、６－クロロ－２－ナフチル基、７－ブロモ－２－ナフチル基、８－クロロ－２－ナフチル基、４，５－ジクロロ－２－ナフチル基、６－ブロモ－８－クロロ－２－ナフチル基及び１，４，５－トリクロロ－２－ナフチル基等が挙げられる。
　「ヘテロアリール基」としては、ピロリル基、フリル基、チエニル基、ピラゾリル基、イミダゾリル基、トリアゾリル基、テトラゾリル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、ピリジル基、ピリダジニル基、ピリミジニル基、及びピラジニル基等が挙げられる。
「１以上のハロゲン原子で置換されていてもよいヘテロアリール基」としては、例えば、５－クロロ－２－チエニル基、４－クロロ－２－チエニル基、４－ブロモ－２－チエニル基、５－クロロ－３－チエニル基、５－クロロ－２－ピロリル基、４－クロロ－２－ピロリル基、４－ブロモ－２－ピロリル基、４－クロロ－１－ピロリル基、５－クロロ－２－フリル基、４－クロロ－２－フリル基、５－フルオロ－３－フリル基、３－クロロ－１－ピラゾリル基、２－クロロ－１－イミダゾリル基、４－ブロモ－１－イミダゾリル基、４－フルオロ－１，２，３－トリアゾリル基、３－クロロ－１，２，４－トリアゾリル基、５－ブロモ－１，２，４－トリアゾリル基、５－ブロモ－１－テトラゾリル基、５－クロロ－２－オキサゾリル基、４，５－ジクロロ－２－オキサゾリル基、２－フルオロ－５－オキサゾリル基、３－ヨード－４－イソオキサゾリル基、５－ヨード－４－イソオキサゾリル基、４－ヨード－３－イソオキサゾリル基、４－ヨード－５－イソオキサゾリル基、５－クロロ－２－チアゾリル基、４－クロロ－２－チアゾリル基、２－クロロ－５－チアゾリル基、３－ヨード－４－イソチアゾリル基、５－ヨード－４－イソチアゾリル基、４－ヨード－３－イソチアゾリル基、４－ヨード－５－イソチアゾリル基、３－クロロ－１，２，４－オキサジアゾリル基、５－クロロ－１，２，４－オキサジアゾリル基、３－クロロ－１，２，４－チアジアゾリル基、５－クロロ－１，２，４－チアジアゾリル基、６－ブロモ－２－ピリジル基、４－ブロモ－６－クロロ－２－ピリジル基、５－クロロ－３－ピリジル基、２，６－ジクロロ－４－ピリジル基、５－クロロ－３－ピリダジニル基、５－クロロ－６－ブロモ－３－ピリダジニル基、３－クロロ－４－ピリダジニル基、３－クロロ－６－ブロモ－４－ピリダジニル基、５－クロロ－２－ピリミジニル基、４－クロロ－５－ブロモ－２－ピリミジニル基、２－クロロ－４－ピリミジニル基、２－ヨード－５－ピリミジニル基、３－クロロ－２－ピラジニル基、５－クロロ－２－ピラジニル基、６－フルオロ－２－ピラジニル基、５，６－ジフルオロ－２－ピラジニル基等が挙げられる。
　「アルコキシ基」としては、例えばメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、ペンチルオキシ基及びヘキシルオキシ基等が挙げられる。
「１以上のハロゲン原子で置換されていてもよいアルコキシ基」としては、例えば、ジフルオロメトキシ基、トリクロロメトキシ基、トリフルオロメトキシ基、２，２，２－トリフルオロエトキシ基、２－ブロモ－１，１，２，２－テトラフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、１－メチル－２，２，３，３－テトラフルオロプロポキシ基、２，２，３，４，４，４－ヘキサフルオロブトキシ基及びペルフルオロヘキシロキシ基等が挙げられる。
本明細書中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ａｃはアセチル基を表し、ＴＨＦはテトラヒドロフランを表す。 The substituent in the present invention will be described.
"May be replaced" means that it has been replaced or has not been replaced. When substituted with two or more substituents, those substituents may be the same or different from each other.
"May be substituted with a halogen atom" means having or not having a halogen atom. When it has two or more halogen atoms, those halogen atoms may be the same or different from each other.
The notation "CY-CZ" in the present specification means that the number of carbon atoms is Y to Z. For example, the notation "C1-C6" means that the number of carbon atoms is 1 to 6.
As used herein, the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
Examples of the "alkyl group" include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a butyl group, and a tert-butyl group. Examples include a pentyl group and a hexyl group.
Examples of the "C1-C6 alkyl group optionally substituted with one or more halogen atoms" include a difluoromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and 2-. Bromo-1,1,2,2-tetrafluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,3 , 3,3-Hexafluoropropyl group, 1-methyl-2,2,3,3-tetrafluoropropyl group, 2,2,3,4,5,4-hexafluorobutyl group, perfluorohexyl group and the like. Be done.
Examples of the "aryl group" include a phenyl group and a naphthyl group.
Examples of the "aryl group optionally substituted with one or more halogen atoms" include a 2-bromophenyl group, a 3-iodophenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, and a 2,4-dichlorophenyl group. , 3-Bromo-5-iodophenyl group, 2,3,4-trichlorophenyl group, 2,4,6-trifluorophenyl group, 4-bromo-2,6-dichlorophenyl group, 2,3,4,5 , 6-Pentabromophenyl group, 2-chloro-1-naphthyl group, 3-bromo-1-naphthyl group, 4-iodo-1-naphthyl group, 5-fluoro-1-naphthyl group, 6-chloro-1- Phenyl group, 7-bromo-1-naphthyl group, 8-chloro-1-naphthyl group, 4,5-dichloro-1-naphthyl group, 6-bromo-8-chloro-1-naphthyl group, 1-chloro-2 -Naphenyl group, 3-bromo-2-naphthyl group, 2,4,5-trichloro-1-naphthyl group, 4-iodo-2-naphthyl group, 5-fluoro-2-naphthyl group, 6-chloro-2- Phenyl group, 7-bromo-2-naphthyl group, 8-chloro-2-naphthyl group, 4,5-dichloro-2-naphthyl group, 6-bromo-8-chloro-2-naphthyl group and 1,4,5 -Trichloro-2-naphthyl group and the like can be mentioned.
Examples of the "heteroaryl group" include pyrrolyl group, furyl group, thienyl group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, oxazolyl group, isooxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group and pyridyl group. Examples thereof include a pyridazinyl group, a pyrimidinyl group, and a pyrazinyl group.
Examples of the "heteroaryl group optionally substituted with one or more halogen atoms" include a 5-chloro-2-thienyl group, a 4-chloro-2-thienyl group, a 4-bromo-2-thienyl group, and 5 -Chloro-3-thienyl group, 5-chloro-2-pyrrrolyl group, 4-chloro-2-pyrrrolyl group, 4-bromo-2-pyrrrolyl group, 4-chloro-1-pyrrrolyl group, 5-chloro-2- Frill group, 4-chloro-2-furyl group, 5-fluoro-3-furyl group, 3-chloro-1-pyrazolyl group, 2-chloro-1-imidazolyl group, 4-bromo-1-imidazolyl group, 4- Fluoro-1,2,3-triazolyl group, 3-chloro-1,2,4-triazolyl group, 5-bromo-1,2,4-triazolyl group, 5-bromo-1-tetrazolyl group, 5-chloro- 2-Oxazolyl group, 4,5-dichloro-2-oxazolyl group, 2-fluoro-5-oxazolyl group, 3-iodo-4-isooxazolyl group, 5-iodo-4-isooxazolyl group, 4-iodo-3-isooxazolyl Group, 4-iodo-5-isooxazolyl group, 5-chloro-2-thiazolyl group, 4-chloro-2-thiazolyl group, 2-chloro-5-thiazolyl group, 3-iodo-4-isothiazolyl group, 5-iodine -4-isothiazolic group, 4-iodo-3-isothiazolic group, 4-iodo-5-isothiazolic group, 3-chloro-1,2,4-oxadiazolyl group, 5-chloro-1,2,4-oxadiazolyl group, 3-Chloro-1,2,4-thiadiazolyl group, 5-chloro-1,2,4-thiadiazolyl group, 6-bromo-2-pyridyl group, 4-bromo-6-chloro-2-pyridyl group, 5- Chloro-3-pyridyl group, 2,6-dichloro-4-pyridyl group, 5-chloro-3-pyridazinyl group, 5-chloro-6-bromo-3-pyridazinyl group, 3-chloro-4-pyridazinyl group, 3 -Chloro-6-bromo-4-pyridazinyl group, 5-chloro-2-pyrimidinyl group, 4-chloro-5-bromo-2-pyrimidinyl group, 2-chloro-4-pyrimidinyl group, 2-iodo-5-pyrimidinyl Examples thereof include a group, 3-chloro-2-pyrazinyl group, 5-chloro-2-pyrazinyl group, 6-fluoro-2-pyrazinyl group, 5,6-difluoro-2-pyrazinyl group and the like.
Examples of the "alkoxy group" include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a 1,1-dimethylpropoxy group, a 1,2-dimethylpropoxy group, a 1-ethylpropoxy group, a butoxy group, and a tert-butoxy group. , Pentyloxy group, hexyloxy group and the like.
Examples of the "alkoxy group optionally substituted with one or more halogen atoms" include a difluoromethoxy group, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group and a 2-bromo-1 group. , 1,2,2-tetrafluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3 Examples thereof include 3-hexafluoropropoxy group, 1-methyl-2,2,3,3-tetrafluoropropoxy group, 2,2,3,4,5,4-hexafluorobutoxy group and perfluorohexyloxy group.
In the present specification, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Ac represents an acetyl group, and THF represents tetrahydrofuran.
　本明細書中に記載する化合物は、例えば以下に示す互変異性体が存在する場合がある。
Figure JPOXMLDOC01-appb-I000013

Figure JPOXMLDOC01-appb-I000014

Figure JPOXMLDOC01-appb-I000015
The compounds described herein may have, for example, the tautomers shown below.
Figure JPOXMLDOC01-appb-I000013

Figure JPOXMLDOC01-appb-I000014

Figure JPOXMLDOC01-appb-I000015
　本発明における化合物は一つ以上の立体異性体が存在する場合がある。立体異性体としては、エナンチオマー、ジアステレオマー、アトロプ異性体及び幾何異性体が挙げられる。本発明には各立体異性体及び任意の比率の立体異性体混合物が含まれる。
　本発明ではいずれかの立体異性体又は任意の異性体比で含有する立体異性体混合物を式（２）、式（３）及び式（４）で示される化合物として用いることができ、幾何異性体が特定されるものではないことから、結合を波線により表記する。 The compound in the present invention may have one or more stereoisomers. Stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. The present invention includes each stereoisomer and a mixture of stereoisomers in any ratio.
In the present invention, any stereoisomer or a mixture of stereoisomers contained in an arbitrary isomer ratio can be used as a compound represented by the formulas (2), (3) and (4), and is a geometric isomer. Since is not specified, the coupling is indicated by a wavy line.
　式（１）で示される化合物の態様としては、例えば、以下の化合物が挙げられる。 
　式（１）において、Ｘ1がＣＲ3、又は窒素原子であり、Ｒ3が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
式（１）において、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は群Ａより選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3、又は窒素原子であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は群Ａより選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3、又は窒素原子であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3、又は窒素原子であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物； Examples of the mode of the compound represented by the formula (1) include the following compounds.
In formula (1), X 1 is CR 3 or a nitrogen atom, and R 3 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, and one or more halogen atoms. A compound that is an aryl group that may be substituted with, a heteroaryl group that may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms;
In formula (1), R 2 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, 1 or more. A compound that is a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms;
In formula (1), R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with one or more halogen atoms, and one or more halogen atoms. Aryl groups may be represented, heteroaryl groups may be substituted with one or more halogen atoms, or C1-C6 alkoxy groups may be substituted with one or more halogen atoms, or they are attached. A benzene ring together with a carbon atom {the benzene ring may be substituted with one or more substituents selected from Group A. } The compound forming;
In formula (1), X 1 is CR 3 or a nitrogen atom, and R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, respectively. -C6 alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms, or C1 optionally substituted with one or more halogen atoms -C6 alkoxy group in which R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with one or more halogen atoms, and one or more halogen atoms. It represents an aryl group which may be substituted, a heteroaryl group which may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, or they are bonded. A benzene ring {the benzene ring may be substituted with one or more substituents selected from Group A. } The compound forming;
In formula (1), X 1 is CR 3 or a nitrogen atom, and R 2 , R 3 , R 4 , and R 5 are independently substituted with hydrogen atom, halogen atom, or one or more halogen atoms. C1-C6 alkyl group which may be substituted, an aryl group which may be substituted with one or more halogen atoms, a heteroaryl group which may be substituted with one or more halogen atoms, or a halogen atom substituted with one or more atoms. Compounds that are C1-C6 alkoxy groups that may be used;
In formula (1), X 1 is CR 3 or a nitrogen atom, and R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, respectively. -C6 alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms, or C1 optionally substituted with one or more halogen atoms -C6 alkoxy group, R 4 and R 5 together with the carbon atom to which they are bonded, benzene ring {The benzene ring may be substituted with a halogen atom, one or more halogen atoms C1 -C6 alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms, or C1 optionally substituted with one or more halogen atoms -It may be substituted with one or more substituents selected from the group consisting of C6 alkoxy groups. } The compound forming;
式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4、及びＲ5は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物； In formula (1), even if X 1 is CR 3 and R 2 , R 3 , R 4 , and R 5 are independently substituted with hydrogen atom, halogen atom, and one or more halogen atoms. A good C1-C6 alkyl group, an aryl group that may be substituted with one or more halogen atoms, a heteroaryl group that may be substituted with one or more halogen atoms, or a heteroaryl group that may be substituted with one or more halogen atoms. A compound that is a good C1-C6 alkoxy group;
In formula (1), X 1 is CR 3 , and R 2 and R 3 are C1-C6 alkyl groups which may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. An aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. And R 4 and R 5 together with the carbon atom to which they are bonded, a benzene ring {the benzene ring is a C1-C6 alkyl group that may be substituted with a halogen atom, one or more halogen atoms. An aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of. } The compound forming;
In formula (1), X 1 is a nitrogen atom, and R 2 , R 4 , and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, C1-. C6 alkyl group, aryl group which may be substituted with one or more halogen atoms, heteroaryl group which may be substituted with one or more halogen atoms, or C1- which may be substituted with one or more halogen atoms. Compounds that are C6 alkoxy groups;
In formula (1), X 1 is a nitrogen atom and R 2 is substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms. An aryl group which may be an aryl group, a heteroaryl group which may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, and R 4 and R 5 However, together with the carbon atom to which they are bonded, the benzene ring {the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms. One or more selected from the group consisting of an aryl group which may be used, a heteroaryl group which may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. It may be substituted with a substituent. } The compound forming;
In formula (1), X 1 is CR 3 , and R 2 , R 3 , R 4 , and R 5 are independent hydrogen atoms, halogen atoms, C1-C6 alkyl groups, and one or more halogen atoms. A compound that is an aryl group optionally substituted with, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms;
In formula (1), even if X 1 is CR 3 and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or one or more halogen atoms. A good aryl group, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, wherein R 4 and R 5 are them. A benzene ring {the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group, an aryl group optionally substituted with one or more halogen atoms, and one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of heteroaryl groups which may be present, or C1-C6 alkoxy groups which may be substituted with one or more halogen atoms. } The compound forming;
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物； In formula (1), X 1 is a nitrogen atom, and R 2 , R 4 , and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group, and one or more halogen atoms. Aryl group which may be an aryl group, a heteroaryl group which may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms;
In formula (1), X 1 is a nitrogen atom and R 2 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, an aryl group which may be substituted with one or more halogen atoms, and one or more halogen atoms. A heteroaryl group optionally substituted with, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, with R 4 and R 5 combined with the carbon atom to which they are attached. The benzene ring {the benzene ring is a halogen atom, a C1-C6 alkyl group, an aryl group that may be substituted with one or more halogen atoms, a heteroaryl group that may be substituted with one or more halogen atoms, or It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with one or more halogen atoms. } The compound forming;
In formula (1), even if X 1 is CR 3 and R 2 , R 3 , R 4 , and R 5 are independently substituted with hydrogen atom, halogen atom, and one or more halogen atoms. A good aryl group, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms;
In formula (1), X 1 is CR 3 , and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, and one or more aryl groups. A heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, where R 4 and R 5 are the carbon atoms to which they are bonded. Together, the benzene ring {the benzene ring is an aryl group optionally substituted with one or more halogen atoms, or a heteroaryl group optionally substituted with one or more halogen atoms, or one or more It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with a halogen atom. } The compound forming;
In formula (1), X 1 is a nitrogen atom, and R 2 , R 4 , and R 5 are aryl groups that may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. Compounds that are heteroaryl groups that may be substituted with one or more halogen atoms, or C1-C6 alkoxy groups that may be substituted with one or more halogen atoms;
In formula (1), even if X 1 is a nitrogen atom and R 2 is an aryl group that may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or one or more halogen atoms. A good heteroaryl group, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, in which R 4 and R 5 are combined with the carbon atom to which they are attached to form a benzene ring. The benzene ring may be substituted with a halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups. } The compound forming;
In formula (1), even if X 1 is CR 3 and R 2 , R 3 , R 4 , and R 5 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. A compound that is a good aryl group, a heteroaryl group, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms;
In formula (1), X 1 is CR 3 , and R 2 and R 3 are each independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, an aryl group or a heteroaryl. A C1-C6 alkoxy group that may be substituted with a group or one or more halogen atoms, with R 4 and R 5 combined with the carbon atom to which they are attached, the benzene ring {the benzene ring is One or more substitutions selected from the group consisting of halogen atoms, aryl groups optionally substituted with one or more halogen atoms, heteroaryl groups, or C1-C6 alkoxy groups optionally substituted with one or more halogen atoms. It may be substituted with a group. } The compound forming;
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5がそれらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、アリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、アリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、アリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、アリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、ハロゲン原子、アリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、アリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物； In formula (1), X 1 is a nitrogen atom, and R 2 , R 4 , and R 5 are independently substituted with a hydrogen atom, a halogen atom, and one or more halogen atoms. , A heteroaryl group, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms;
In formula (1), X 1 is a nitrogen atom and R 2 is an aryl group, a heteroaryl group, or one or more halogen atoms which may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. It is a C1-C6 alkoxy group that may be substituted, and R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring {the benzene ring is a halogen atom, one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of an aryl group which may be substituted, a heteroaryl group, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. } The compound forming;
In formula (1), even if X 1 is CR 3 and R 2 , R 3 , R 4 , and R 5 are independently substituted with hydrogen atom, halogen atom, and one or more halogen atoms. A compound that is a good aryl group or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms;
In formula (1), X 1 is CR 3 , and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or 1 It is a C1-C6 alkoxy group that may be substituted with the above halogen atoms, and R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring {the benzene ring is a halogen atom, 1 It may be substituted with one or more substituents selected from the group consisting of an aryl group optionally substituted with the above halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. .. } The compound forming;
In formula (1), X 1 is a nitrogen atom, and R 2 , R 4 , and R 5 are independently substituted with a hydrogen atom, a halogen atom, and one or more halogen atoms. , Or a compound that is a C1-C6 alkoxy group optionally substituted with one or more halogen atoms;
In formula (1), X 1 is a nitrogen atom and R 2 is substituted with a hydrogen atom, a halogen atom, an aryl group optionally substituted with one or more halogen atoms, or one or more halogen atoms. It is also a good C1-C6 alkoxy group, with R 4 and R 5 together with the carbon atom to which they are attached, and a benzene ring {even if the benzene ring is substituted with a halogen atom, one or more halogen atoms. It may be substituted with a good aryl group or one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with one or more halogen atoms. } The compound forming;
In formula (1), X 1 is CR 3 , and R 2 , R 3 , R 4 , and R 5 are each independently substituted with a hydrogen atom, a halogen atom, an aryl group, or one or more halogen atoms. Compounds that are C1-C6 alkoxy groups that may be used;
In formula (1), X 1 is CR 3 , and R 2 and R 3 may each be independently substituted with a hydrogen atom, a halogen atom, an aryl group, or one or more halogen atoms. -C6 alkoxy group, R 4 and R 5 , together with the carbon atom to which they are attached, benzene ring {the benzene ring is substituted with a halogen atom, an aryl group, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups. } The compound forming;
In formula (1), X 1 is a nitrogen atom, and R 2 , R 4 , and R 5 are each independently substituted with a hydrogen atom, a halogen atom, an aryl group, or one or more halogen atoms. A compound that is a good C1-C6 alkoxy group;
In formula (1), X 1 is a nitrogen atom and R 2 is a C1-C6 alkoxy group optionally substituted with a hydrogen atom, a halogen atom, an aryl group, or one or more halogen atoms, and R 4 , And R 5 together with the carbon atom to which they are attached, from the benzene ring {the benzene ring is from a C1-C6 alkoxy group that may be substituted with a halogen atom, an aryl group, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group. } The compound forming;
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、ハロゲン原子、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4、及びＲ5が、各々独立して、水素原子、ハロゲン原子、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、ハロゲン原子、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4、及びＲ5が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4、及びＲ5が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物； In formula (1), X 1 is CR 3 , and R 2 , R 3 , R 4 , and R 5 are each independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. A compound that is a good C1-C6 alkoxy group;
In formula (1), X 1 is CR 3 , and R 2 and R 3 may each be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, C1-C6 alkoxy. C1-C6 which is a group and R 4 and R 5 together with the carbon atom to which they are bonded are substituted with a benzene ring {the benzene ring may be substituted with a halogen atom or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of alkoxy groups. } The compound forming;
In formula (1), X 1 is a nitrogen atom, and R 2 , R 4 , and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, respectively. -A compound that is a C6 alkoxy group;
In formula (1), X 1 is a nitrogen atom and R 2 is a C1-C6 alkoxy group optionally substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, R 4 and R. 5 is selected from the group consisting of a benzene ring {the benzene ring is a halogen atom, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, together with the carbon atom to which they are bonded 1 It may be substituted with the above substituents. } The compound forming;
In formula (1), X 1 is CR 3 , and R 2 , R 3 , R 4 , and R 5 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, and methoxy group. , Ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy Group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2, Compounds that are 2,3,4,5,4-hexafluorobutoxy groups;
In the formula (1), X 1 is CR 3 , and R 2 and R 3 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group and propoxy group. , Isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2 3,3-Tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2,2,3,4 It is a 4,4-hexafluorobutoxy group, and R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring {the benzene ring is a fluorine atom, chlorine atom, bromine atom, iodine atom, Methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-tri Fluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or It may be substituted with one or more substituents selected from the group consisting of 2,2,3,4,5,4-hexafluorobutoxy groups. } The compound forming;
In formula (1), X 1 is a nitrogen atom, and R 2 , R 4 , and R 5 are independent hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, methoxy groups, and ethoxy groups. , Propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2 , 2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2,2,3 , 4, 4,4-Hexafluorobutoxy group;
In formula (1), X 1 is a nitrogen atom and R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, 1,1-. Dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, With 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2,2,3,4,5,4-hexafluorobutoxy group Yes, R 4 and R 5 are combined with the carbon atom to which they are attached to form a benzene ring {the benzene ring is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, Isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3 , 3-Tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2,2,3,4,4 , 4-Hexafluorobutoxy group may be substituted with one or more substituents selected from the group. } The compound forming;
式（１）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、及びＲ4が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2、及びＲ3が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子、及びヨウ素原子からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2、及びＲ4が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、フッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子、及びヨウ素原子からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成している化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2が水素原子であり、Ｒ3、及びＲ4が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物；
　式（１）において、Ｘ1がＣＲ3であり、Ｒ2が水素原子であり、Ｒ3が水素原子、フッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4が水素原子、フッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環を形成している化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4が水素原子、フッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基、又は２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、又は２，２，３，３，３－ペンタフルオロプロポキシ基である化合物； In formula (1), X 1 is CR 3 , and R 2 , R 3 , and R 4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, and R 5 However, hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy Group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1 , 1,2,3,3,3-hexafluoropropoxy group, or 2,2,3,4,5,4-hexafluorobutoxy group;
In formula (1), X 1 is CR 3 , R 2 and R 3 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, R 4 and R. 5 is substituted with a benzene ring {the benzene ring is substituted with one or more substituents selected from the group consisting of fluorine, chlorine, bromine, and iodine atoms, together with the carbon atoms to which they are attached. May be good. } The compound forming;
In formula (1), X 1 is a nitrogen atom, R 2 and R 4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, and R 5 is hydrogen. Atomic, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy Group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1, Compounds that are 2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group;
In formula (1), X 1 is a nitrogen atom, R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and R 4 and R 5 are carbon atoms to which they are bonded. Together with the benzene ring {the benzene ring may be substituted with one or more substituents selected from the group consisting of fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. } The compound forming;
In formula (1), X 1 is CR 3 , R 2 is a hydrogen atom, and R 3 and R 4 are independent hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms. R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a 1,1-dimethylpropoxy group, a 1,2-dimethylpropoxy group. , 1-ethyl propoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-penta Compounds that are fluoropropoxy groups, 1,1,2,3,3,3-hexafluoropropoxy groups, or 2,2,3,4,5,4-hexafluorobutoxy groups;
In formula (1), X 1 is CR 3 , R 2 is a hydrogen atom, R 3 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and R 4 and R 5 are. , Compounds that form a benzene ring together with the carbon atoms to which they are attached;
In formula (1), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and R 5 is a hydrogen atom. Fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2, Compounds that are 3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group;
In formula (1), X 1 is a nitrogen atom, R 2 is a hydrogen atom, and R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring. ;
In formula (1), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and R 5 is a hydrogen atom. Fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, Or a compound that is a 2,2,3,4,5,4-hexafluorobutoxy group;
In formula (1), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, 2, 2 , 3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, or 2,2,3,4,5,4-hexafluorobutoxy group;
In formula (1), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, or 2, Compounds that are 2,3,3,3-pentafluoropropoxy groups;
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、フッ素原子である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、塩素原子である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、臭素原子である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、ヨウ素原子である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、メトキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、エトキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、２，２，３，３，３－ペンタフルオロプロポキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、１，１，２，３，３，３－ヘキサフルオロプロポキシ基である化合物；
　式（１）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が、２，２，３，４，４，４－ヘキサフルオロブトキシ基である化合物。 In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a fluorine atom;
In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a chlorine atom;
In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a bromine atom;
In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is an iodine atom;
In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a methoxy group;
In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is an ethoxy group;
In formula (1), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a 2,2,3,3,3-pentafluoropropoxy group;
In formula (1), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a 1,1,2,3,3,3-hexafluoropropoxy group;
In formula (1), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a 2,2,3,4,5,4-hexafluorobutoxy group.
式（２）で示される化合物の態様としては、例えば、以下の化合物が挙げられる。
　式（２）において、Ｒ1が、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（２）において、Ｒ1が、Ｃ１－Ｃ６アルキル基である化合物；
　式（２）において、Ｒ1が、メチル基、エチル基、又はプロピル基である化合物；
　式（２）において、Ｒ1が、エチル基である化合物；
　式（２）において、Ｘが、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、又は１以上のハロゲン原子で置換されていてもよいアリール基である化合物；
　式（２）において、Ｘが、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
式（２）において、Ｘが、１以上のハロゲン原子で置換されていてもよいアリール基である化合物；
式（２）において、Ｘが、Ｃ１－Ｃ６アルキル基である化合物；
式（２）において、Ｘが、アリール基である化合物；
式（２）において、Ｘが、メチル基、エチル基、プロピル基、トリフルオロメチル基、ヘキサフルオロエチル基、２，２，２－トリフルオロエチル基、２，２，３，３－テトラフルオロプロピル基、２，２，３，３，３－ペンタフルオロプロピル基、フェニル基、４－クロロフェニル基、４－フルオロフェニル基、又は２，４－ジクロロフェニル基である化合物；
式（２）において、Ｘが、メチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基、又は４－クロロフェニル基である化合物；
式（２）において、Ｘが、メチル基、エチル基、プロピル基、又はトリフルオロメチル基である化合物；
式（２）において、Ｘが、メチル基である化合物；
式（２）において、Ｒ1が、Ｃ１－Ｃ６アルキル基であり、Ｘが、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、又は１以上のハロゲン原子で置換されていてもよいアリール基である化合物；
式（２）において、Ｒ1が、Ｃ１－Ｃ６アルキル基であり、Ｘが、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
式（２）において、Ｒ1が、Ｃ１－Ｃ６アルキル基であり、Ｘが、１以上のハロゲン原子で置換されていてもよいアリール基である化合物；
式（２）において、Ｒ1が、メチル基、エチル基、又はプロピル基であり、Ｘが、メチル基、エチル基、プロピル基、トリフルオロメチル基、ヘキサフルオロエチル基、２，２，２－トリフルオロエチル基、２，２，３，３－テトラフルオロプロピル基、２，２，３，３，３－ペンタフルオロプロピル基、フェニル基、４－クロロフェニル基、４－フルオロフェニル基、又は２，４－ジクロロフェニル基である化合物；
式（２）において、Ｒ1が、メチル基、エチル基、又はプロピル基であり、Ｘが、メチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基、又は４－クロロフェニル基である化合物；
式（２）において、Ｒ1が、メチル基、エチル基、又はプロピル基であり、Ｘが、メチル基、エチル基、プロピル基、又はトリフルオロメチル基である化合物；
　式（２）において、Ｒ1が、エチル基であり、Ｘが、メチル基である化合物。 Examples of the mode of the compound represented by the formula (2) include the following compounds.
In formula (2), a compound in which R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
In formula (2), the compound in which R 1 is a C1-C6 alkyl group;
In formula (2), the compound in which R 1 is a methyl group, an ethyl group, or a propyl group;
In formula (2), the compound in which R 1 is an ethyl group;
In formula (2), X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms, or an aryl group optionally substituted with one or more halogen atoms;
In formula (2), the compound in which X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
In formula (2), the compound in which X is an aryl group optionally substituted with one or more halogen atoms;
In formula (2), the compound in which X is a C1-C6 alkyl group;
In formula (2), the compound in which X is an aryl group;
In formula (2), X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a hexafluoroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group. A compound that is a group, 2,2,3,3,3-pentafluoropropyl group, phenyl group, 4-chlorophenyl group, 4-fluorophenyl group, or 2,4-dichlorophenyl group;
In formula (2), a compound in which X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group, or a 4-chlorophenyl group;
In formula (2), the compound in which X is a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group;
In formula (2), the compound in which X is a methyl group;
In formula (2), R 1 is a C1-C6 alkyl group, and X is substituted with a C1-C6 alkyl group that may be substituted with one or more halogen atoms, or one or more halogen atoms. Compounds that are also good aryl groups;
In formula (2), R 1 is a C1-C6 alkyl group and X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
In formula (2), R 1 is a C1-C6 alkyl group and X is an aryl group optionally substituted with one or more halogen atoms;
In formula (2), R 1 is a methyl group, an ethyl group, or a propyl group, and X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a hexafluoroethyl group, 2,2,2-. Trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, phenyl group, 4-chlorophenyl group, 4-fluorophenyl group, or 2, Compounds that are 4-dichlorophenyl groups;
In formula (2), R 1 is a methyl group, an ethyl group, or a propyl group, and X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group, or a 4-chlorophenyl group. ;
In formula (2), R 1 is a methyl group, an ethyl group, or a propyl group, and X is a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group;
In formula (2), a compound in which R 1 is an ethyl group and X is a methyl group.
　式（４）で示される化合物の態様としては、例えば、以下の化合物が挙げられる。 
　式（４）において、Ｘ1がＣＲ3又は窒素原子であり、Ｒ3が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
　式（４）において、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である化合物；
式（４）において、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成する化合物；
　式（４）において、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基である化合物；
式（４）において、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3又は窒素原子であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3又は窒素原子であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3又は窒素原子であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物； Examples of the mode of the compound represented by the formula (4) include the following compounds.
In formula (4), X 1 is CR 3 or a nitrogen atom, and R 3 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom, 1 or more halogen atoms, and 1 or more halogen atoms. A compound that is an aryl group that may be substituted, a heteroaryl group that may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms;
In formula (4), R 2 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, 1 or more. A compound that is a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms;
In formula (4), R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with one or more halogen atoms, and one or more halogen atoms. It represents an aryl group which may be an aryl group, a heteroaryl group which may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, or they are bonded. Along with the carbon atom, a benzene ring {the benzene ring may be a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl optionally substituted with one or more halogen atoms. The group is substituted with one or more substituents selected from the group consisting of a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. You may. } Forming compounds;
In formula (4), a compound in which X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms;
In formula (4), a compound in which R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
In formula (4), X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogens. A compound that is a C1-C6 alkyl group that may be substituted with an atom;
In formula (4), X 1 is CR 3 or a nitrogen atom, and R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms C1-C6. Alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1-C6 alkoxy optionally substituted with one or more halogen atoms The groups, R 4 and R 5, are each independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with one or more halogen atoms, and one or more halogen atoms. May represent an aryl group, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, or a carbon atom to which they are attached. Together with the benzene ring {the benzene ring is a C1-C6 alkyl group optionally substituted with one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, Even if it is substituted with one or more substituents selected from the group consisting of a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. Good. }, And X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogen atoms. A compound that is a C1-C6 alkyl group that may be substituted with;
In formula (4), X 1 is CR 3 or a nitrogen atom, and R 2 , R 3 , R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom and one or more halogen atoms. A C1-C6 alkyl group which may be substituted by one or more halogen atoms, an aryl group which may be substituted by one or more halogen atoms, a heteroaryl group which may be substituted by one or more halogen atoms, or one or more halogen atoms. It represents a good C1-C6 alkoxy group, and X is a C1-C6 alkyl group which may be substituted with one or more halogen atoms or an aryl group which may be substituted with one or more halogen atoms, and R 1 is A compound that is a C1-C6 alkyl group that may be substituted with one or more halogen atoms;
In formula (4), X 1 is CR 3 or a nitrogen atom, and R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms C1-C6. Alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1-C6 alkoxy optionally substituted with one or more halogen atoms C1-C6 alkyl which is a group and R 4 and R 5 together with the carbon atom to which they are bonded, are substituted with a benzene ring {the benzene ring may be substituted with a halogen atom, one or more halogen atoms. A group, an aryl group that may be substituted with one or more halogen atoms, a heteroaryl group that may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of. }, And X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogen atoms. A compound that is a C1-C6 alkyl group that may be substituted with;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. C1-C6 Alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1 optionally substituted with one or more halogen atoms -C6 alkoxy group, X is a C1-C6 alkyl group which may be substituted with 1 or more halogen atoms or an aryl group which may be substituted with 1 or more halogen atoms, and R 1 is 1 or more. A compound that is a C1-C6 alkyl group that may be substituted with a halogen atom;
式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物； In formula (4), X 1 is CR 3 , and R 2 and R 3 are C1-C6 alkyl groups, which may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. An aryl group that may be substituted with one or more halogen atoms, a heteroaryl group that may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms. , R 4 and R 5 together with the carbon atom to which they are bonded, a benzene ring {the benzene ring is a C1-C6 alkyl group, which may be substituted with one or more halogen atoms, 1 A group consisting of an aryl group optionally substituted with the above halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. It may be substituted with one or more substituents selected from. }, And X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogen atoms. A compound that is a C1-C6 alkyl group that may be substituted with;
In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms C1-C6. Alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1-C6 alkoxy optionally substituted with one or more halogen atoms A C1-C6 alkyl group in which X may be substituted with one or more halogen atoms or an aryl group in which X may be substituted with one or more halogen atoms, and R 1 is one or more halogen atoms. Compounds that are C1-C6 alkyl groups that may be substituted;
In formula (4), X 1 is a nitrogen atom and R 2 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom, 1 or more halogen atoms, and 1 or more halogen atoms. The aryl group may be a heteroaryl group which may be substituted with one or more halogen atoms or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, and R 4 and R 5 are them. Along with the carbon atom to which is bonded, the benzene ring {the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms. May be an aryl group, a heteroaryl group optionally substituted with one or more halogen atoms, or one or more substituents selected from the group consisting of C1-C6 alkoxy groups optionally substituted with one or more halogen atoms. It may be replaced. }, And X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms, and R 1 is one or more halogen atoms. A compound that is a C1-C6 alkyl group that may be substituted with;
式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物； In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. C1-C6 alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1 optionally substituted with one or more halogen atoms -C1-C6 is a C1-C6 alkyl group or aryl group that represents a C6 alkoxy group and in which X may be substituted with one or more halogen atoms and R 1 may be substituted with one or more halogen atoms. Compounds that are alkyl groups;
In formula (4), X 1 is CR 3 , and R 2 and R 3 are C1-C6 alkyl groups, which may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. An aryl group that may be substituted with one or more halogen atoms, a heteroaryl group that may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms. , R 4 and R 5 together with the carbon atom to which they are bonded, a benzene ring {the benzene ring is a C1-C6 alkyl group, which may be substituted with one or more halogen atoms, 1 A group consisting of an aryl group optionally substituted with the above halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. It may be substituted with one or more substituents selected from. } Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms. Compounds;
In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms C1-C6. Alkyl group, aryl group optionally substituted with one or more halogen atoms, heteroaryl group optionally substituted with one or more halogen atoms or C1-C6 alkoxy optionally substituted with one or more halogen atoms A C1-C6 alkyl group or an aryl group representing a group, in which X may be substituted with one or more halogen atoms, and R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms. A compound;
In formula (4), X 1 is a nitrogen atom and R 2 is a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom, 1 or more halogen atoms, and 1 or more halogen atoms. The aryl group may be a heteroaryl group which may be substituted with one or more halogen atoms or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, and R 4 and R 5 are them. Along with the carbon atom to which is bonded, the benzene ring {the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and one or more halogen atoms. May be an aryl group, a heteroaryl group optionally substituted with one or more halogen atoms, or one or more substituents selected from the group consisting of C1-C6 alkoxy groups optionally substituted with one or more halogen atoms. It may be replaced. } Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms. Compounds;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 are independently hydrogen atoms, halogen atoms, C1-C6 alkyl groups, and one or more halogen atoms. It represents an aryl group that may be substituted, a heteroaryl group that may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, and X is 1 or more. A compound which is a C1-C6 alkyl group or an aryl group which may be substituted with a halogen atom and whose R 1 is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;
In formula (4), X 1 is CR 3 , and R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or one or more halogen atoms. An aryl group, a heteroaryl group that may be substituted with one or more halogen atoms, or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, where R 4 and R 5 are attached. Along with the carbon atom, the benzene ring {the benzene ring is substituted with a halogen atom, a C1-C6 alkyl group, an aryl group optionally substituted with one or more halogen atoms, and one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of a heteroaryl group, which may be substituted, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. } Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms. Compounds;
式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、Ｃ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物； In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom, a C1-C6 alkyl group and one or more halogen atoms. May represent an aryl group, a heteroaryl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, where X is one or more halogen atoms. A compound that is a C1-C6 alkyl group or an aryl group that may be substituted, and is a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms;
In formula (4), X 1 is a nitrogen atom, R 2 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, an aryl group that may be substituted with one or more halogen atoms, and one or more halogen atoms. A heteroaryl group that may be substituted or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, with R 4 and R 5 combined with the carbon atom to which they are attached, benzene. Ring {The benzene ring is a halogen atom, a C1-C6 alkyl group, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or one or more heteroaryl groups. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with a halogen atom. } Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms. Compounds;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 may be independently substituted with hydrogen atom, halogen atom, or one or more halogen atoms. Aryl group represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, where X is substituted with one or more halogen atoms. A compound which is a C1-C6 alkyl group or an aryl group and is a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms;
In formula (4), X 1 is CR 3 , and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, and one or more aryl groups. A heteroaryl group that may be substituted with a halogen atom or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, with R 4 and R 5 combined with the carbon atom to which they are attached. The benzene ring {the benzene ring is a halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted. } Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms. Compounds;
In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom and one or more halogen atoms, respectively. It represents a heteroaryl group that may be substituted with one or more halogen atoms or a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, and X may be substituted with one or more halogen atoms. A compound that is a C1-C6 alkyl group or an aryl group and is a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms;
式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又はアリール基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物； In formula (4), X 1 is a nitrogen atom and R 2 may be substituted with a hydrogen atom, a halogen atom, an aryl group that may be substituted with one or more halogen atoms, or one or more halogen atoms. A C1-C6 alkoxy group that may be substituted with a heteroaryl group or one or more halogen atoms, with R 4 and R 5 combined with the carbon atom to which they are attached, the benzene ring {the benzene ring is , Halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group optionally substituted with one or more halogen atoms, or C1-C6 optionally substituted with one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of alkoxy groups. } Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms. Compounds;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 may be independently substituted with hydrogen atom, halogen atom, or one or more halogen atoms. Represents a C1-C6 alkoxy group that may be substituted with an aryl group, a heteroaryl group or one or more halogen atoms, and a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms. A compound in which R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
In formula (4), X 1 is CR 3 , and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or an aryl group or a heteroaryl group. Alternatively, it is a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, and R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring {the benzene ring is a halogen atom. Substituted with one or more substituents selected from the group consisting of an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. It may have been. } Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms. Compounds;
In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom and one or more halogen atoms, respectively. Represents a C1-C6 alkoxy group that may be substituted with a heteroaryl group or one or more halogen atoms, and X is a C1-C6 alkyl group or aryl group that may be substituted with one or more halogen atoms, and R A compound in which 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
In formula (4), X 1 is a nitrogen atom and R 2 is substituted with a hydrogen atom, a halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group or one or more halogen atoms. It is a C1-C6 alkoxy group that may be present, in which R 4 and R 5 , together with the carbon atom to which they are bonded, are substituted with a benzene ring {the benzene ring is replaced with a halogen atom, one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of an aryl group, a heteroaryl group, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. } Is a C1-C6 alkyl group or aryl group in which X may be substituted with one or more halogen atoms, and a C1-C6 alkyl group in which R 1 may be substituted with one or more halogen atoms. Compounds;
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基、ヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物； In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 may be independently substituted with hydrogen atom, halogen atom, or one or more halogen atoms. Represents a C1-C6 alkoxy group that may be substituted with an aryl group, a heteroaryl group or one or more halogen atoms, and X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms, R. A compound in which 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms;
In formula (4), X 1 is CR 3 , and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or an aryl group or a heteroaryl group. Alternatively, it is a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, and R 4 and R 5 are combined with the carbon atom to which they are bonded to form a benzene ring {the benzene ring is a halogen atom. Substituted with one or more substituents selected from the group consisting of an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. It may have been. }, Where X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms and R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms. ;
In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 are independently substituted with a hydrogen atom, a halogen atom and one or more halogen atoms, respectively. Represents a C1-C6 alkoxy group that may be substituted with a heteroaryl group or one or more halogen atoms, X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and R 1 is 1. A compound that is a C1-C6 alkyl group that may be substituted with the above halogen atoms;
In formula (4), X 1 is a nitrogen atom and R 2 is substituted with a hydrogen atom, a halogen atom, an aryl group optionally substituted with one or more halogen atoms, a heteroaryl group or one or more halogen atoms. It is a C1-C6 alkoxy group that may be present, in which R 4 and R 5 , together with the carbon atom to which they are bonded, are substituted with a benzene ring {the benzene ring is replaced with a halogen atom, one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of an aryl group, a heteroaryl group, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. }, Where X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms and R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms. ;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 may be independently substituted with hydrogen atom, halogen atom, or one or more halogen atoms. Represents a C1-C6 alkoxy group that may be substituted with an aryl group or one or more halogen atoms, X is a C1-C6 alkyl group that may be substituted with one or more halogen atoms, and R 1 is 1 or more. A compound that is a C1-C6 alkyl group optionally substituted with a halogen atom of;
In formula (4), X 1 is CR 3 , and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or an aryl group or one or more. It is a C1-C6 alkoxy group that may be substituted with a halogen atom, and R 4 and R 5 together with a carbon atom to which they are bonded, a benzene ring {the benzene ring is a halogen atom, one or more. It may be substituted with one or more substituents selected from the group consisting of an aryl group optionally substituted with a halogen atom or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. }, Where X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms and R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms. ;
式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘが１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基であり、Ｒ1が１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、アリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物； In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. Represents a C1-C6 alkoxy group that may be substituted with 1 or more halogen atoms, X is a C1-C6 alkyl group that may be substituted with 1 or more halogen atoms, and R 1 is 1 or more halogen atoms. A compound that is a C1-C6 alkyl group that may be substituted with;
In formula (4), X 1 is a nitrogen atom and R 2 may be substituted with a hydrogen atom, a halogen atom, an aryl group which may be substituted with one or more halogen atoms, or one or more halogen atoms. It is a C1-C6 alkoxy group, and R 4 and R 5 are combined with the carbon atom to which they are bonded, and the benzene ring {the benzene ring may be substituted with a halogen atom and one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of an aryl group or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. }, Where X is a C1-C6 alkyl group optionally substituted with one or more halogen atoms and R 1 is a C1-C6 alkyl group optionally substituted with one or more halogen atoms. ;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. A compound representing a C1-C6 alkoxy group optionally substituted with an aryl group or one or more halogen atoms, where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is CR 3 , and R 2 and R 3 are independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, or an aryl group or one or more. It is a C1-C6 alkoxy group that may be substituted with a halogen atom, and R 4 and R 5 together with a carbon atom to which they are bonded, a benzene ring {the benzene ring is a halogen atom, one or more. It may be substituted with one or more substituents selected from the group consisting of an aryl group optionally substituted with a halogen atom or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. }, Where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. A compound representing a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is a nitrogen atom and R 2 may be substituted with a hydrogen atom, a halogen atom, an aryl group which may be substituted with one or more halogen atoms, or one or more halogen atoms. It is a C1-C6 alkoxy group, and R 4 and R 5 are combined with the carbon atom to which they are bonded, and the benzene ring {the benzene ring may be substituted with a halogen atom and one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of an aryl group or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. }, Where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 are each independently substituted with a hydrogen atom, a halogen atom, an aryl group or one or more halogen atoms. A compound in which X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group, which represents a optionally C1-C6 alkoxy group;
式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子、アリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、アリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、アリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子、アリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子、アリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、ハロゲン原子又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、ハロゲン原子又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は、ハロゲン原子又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、ＸがＣ１－Ｃ６アルキル基であり、Ｒ1がＣ１－Ｃ６アルキル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3、Ｒ4及びＲ5が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基又は４－クロロフェニル基であり、Ｒ1がメチル基、エチル基、プロピル基又はイソプロピル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｒ4、及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘがメチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基又は４－クロロフェニル基であり、Ｒ1がメチル基、エチル基、プロピル基又はイソプロピル基である化合物； In formula (4), X 1 is CR 3 , and R 2 and R 3 may be independently substituted with a hydrogen atom, a halogen atom, an aryl group or one or more halogen atoms, C1-C6. It is an alkoxy group, and R 4 and R 5 together with the carbon atom to which they are bonded, a benzene ring {the benzene ring may be substituted with a halogen atom, an aryl group or one or more halogen atoms. It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups. }, Where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, an aryl group or one or more halogen atoms. A compound representing a C1-C6 alkoxy group, where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is a nitrogen atom and R 2 is a C1-C6 alkoxy group optionally substituted with a hydrogen atom, a halogen atom, an aryl group or one or more halogen atoms, and R 4 and R 5 is a benzene ring together with the carbon atom to which they are attached {from the group consisting of a halogen atom, an aryl group or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms. It may be substituted with one or more substituents of choice. }, Where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom or one or more halogen atoms. A compound representing a C1-C6 alkoxy group, where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is CR 3 , and R 2 and R 3 are C1-C6 alkoxy groups that may be independently substituted with hydrogen atoms, halogen atoms, or one or more halogen atoms. Yes, R 4 and R 5 together with the carbon atom to which they are attached, from the benzene ring {the benzene ring is from a C1-C6 alkoxy group that may be substituted with a halogen atom or one or more halogen atoms. It may be substituted with one or more substituents selected from the group. }, Where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom or one or more halogen atoms C1-C6. A compound representing an alkoxy group, where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is a nitrogen atom, R 2 is a C1-C6 alkoxy group optionally substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, and R 4 and R 5 are: Together with the carbon atom to which they are attached, the benzene ring {the benzene ring is one or more substitutions selected from the group consisting of C1-C6 alkoxy groups optionally substituted with one or more halogen atoms. It may be substituted with a group. }, Where X is a C1-C6 alkyl group and R 1 is a C1-C6 alkyl group;
In formula (4), X 1 is CR 3 , and R 2 , R 3 , R 4 and R 5 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom and methoxy group. Ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group , 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2 3,4,4,4-hexafluorobutoxy group, X is methyl group, ethyl group, propyl group, trifluoromethyl group, phenyl group or 4-chlorophenyl group, R 1 is methyl group, ethyl group, Compounds that are propyl or isopropyl groups;
In the formula (4), X 1 is CR 3 , and R 2 and R 3 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group and propoxy group. Isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3 , 3-Tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3,4,4 It is a 4-hexafluorobutoxy group, and R 4 and R 5 together with the carbon atom to which they are bonded, are a benzene ring {the benzene ring is a fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group. , Ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy Group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2 , 3, 4, 4, 4-Hexafluorobutoxy groups may be substituted with one or more substituents selected from the group. }, Where X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group or a 4-chlorophenyl group, and R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group;
式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基又は４－クロロフェニル基であり、Ｒ1がメチル基、エチル基、プロピル基又はイソプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘがメチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基又は４－クロロフェニル基であり、Ｒ1がメチル基、エチル基、プロピル基又はイソプロピル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3及びＲ4が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基又は４－クロロフェニル基であり、Ｒ1がメチル基、エチル基、プロピル基又はイソプロピル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子及びヨウ素原子からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘがメチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基又は４－クロロフェニル基であり、Ｒ1がメチル基、エチル基、プロピル基又はイソプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基又は４－クロロフェニル基であり、Ｒ1がメチル基、エチル基、プロピル基又はイソプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子及びヨウ素原子からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘがメチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基又は４－クロロフェニル基であり、Ｒ1がメチル基、エチル基、プロピル基又はイソプロピル基である化合物； In formula (4), X 1 is a nitrogen atom, and R 2 , R 4 and R 5 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group and ethoxy group. Propyl group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2, 2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3,4 , 4,4-Hexafluorobutoxy group, X is methyl group, ethyl group, propyl group, trifluoromethyl group, phenyl group or 4-chlorophenyl group, R 1 is methyl group, ethyl group, propyl group or Compounds that are isopropyl groups;
In formula (4), X 1 is a nitrogen atom and R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, 1,1-. Dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group. , R 4 and R 5 together with the carbon atom to which they are bonded, a benzene ring {the benzene ring is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy. Group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3 -Tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4- It may be substituted with one or more substituents selected from the group consisting of hexafluorobutoxy groups. }, Where X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group or a 4-chlorophenyl group, and R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group;
In formula (4), X 1 is CR 3 , R 2 , R 3 and R 4 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom, and R 5 is. Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, Butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1 , 2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, where X is methyl group, ethyl group, propyl group, trifluoromethyl group, phenyl A compound that is a group or 4-chlorophenyl group and R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group;
In formula (4), X 1 is CR 3 , R 2 and R 3 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms, and R 4 and R 5 are Together with the carbon atom to which they are bonded, the benzene ring {the benzene ring may be substituted with one or more substituents selected from the group consisting of fluorine, chlorine, bromine and iodine atoms. }, Where X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group or a 4-chlorophenyl group, and R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms, and R 5 is a hydrogen atom. Fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2, 3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, where X is methyl group, ethyl group, propyl group, trifluoromethyl group, phenyl group or 4 -A compound that is a chlorophenyl group and R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group;
In formula (4), X 1 is a nitrogen atom, R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R 4 and R 5 are together with the carbon atom to which they are bonded. Then, the benzene ring {the benzene ring may be substituted with one or more substituents selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. }, Where X is a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group or a 4-chlorophenyl group, and R 1 is a methyl group, an ethyl group, a propyl group or an isopropyl group;
式（４）において、Ｘ1がＣＲ3であり、Ｒ2、Ｒ3及びＲ4が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2及びＲ3が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子及びヨウ素原子からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ5が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はフッ素原子、塩素原子、臭素原子及びヨウ素原子からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成し、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1がＣＲ3であり、Ｒ2が水素原子であり、Ｒ3及びＲ4が、各々独立して、水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ5が水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物； In formula (4), X 1 is CR 3 , R 2 , R 3 and R 4 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom, and R 5 is. Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, Butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1 , 2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, X is methyl group, ethyl group or propyl group, R 1 is methyl Compounds that are groups, ethyl groups or propyl groups;
In formula (4), X 1 is CR 3 , R 2 and R 3 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms, and R 4 and R 5 are Together with the carbon atom to which they are bonded, the benzene ring {the benzene ring may be substituted with one or more substituents selected from the group consisting of fluorine, chlorine, bromine and iodine atoms. }, Where X is a methyl, ethyl or propyl group and R 1 is a methyl, ethyl or propyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms or iodine atoms, and R 5 is a hydrogen atom. Fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2, 3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, X is methyl group, ethyl group or propyl group, R 1 is methyl group, ethyl Compounds that are groups or propyl groups;
In formula (4), X 1 is a nitrogen atom, R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R 4 and R 5 are together with the carbon atom to which they are bonded. Then, the benzene ring {the benzene ring may be substituted with one or more substituents selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. }, Where X is a methyl, ethyl or propyl group and R 1 is a methyl, ethyl or propyl group;
In formula (4), X 1 is CR 3 , R 2 is a hydrogen atom, and R 3 and R 4 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom. , R 5 is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1- Ethyl propoxy group, butoxy group, tert-butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group , 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, X is a methyl group, an ethyl group or a propyl group. Compounds in which R 1 is a methyl group, an ethyl group or a propyl group;
式（４）において、Ｘ1がＣＲ3であり、Ｒ2が水素原子であり、Ｒ3が水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環を形成し、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4が水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ5が水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、１，１－ジメチルプロポキシ基、１，２－ジメチルプロポキシ基、１－エチルプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３－テトラフルオロプロポキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4及びＲ5が、それらが結合する炭素原子と一緒になって、ベンゼン環を形成し、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4が水素原子、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、Ｒ5が水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基、エチル基又はプロピル基であり、Ｒ1がメチル基、エチル基又はプロピル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基、プロポキシ基、２，２，２－トリフルオロエトキシ基、２，２，３，３，３－ペンタフルオロプロポキシ基、１，１，２，３，３，３－ヘキサフルオロプロポキシ基又は２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、エトキシ基又は２，２，３，３，３－ペンタフルオロプロポキシ基であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
式（４）において、Ｘ1が窒素原子であり、Ｒ2、Ｒ4及びＲ5が水素原子であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5がフッ素原子であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が塩素原子であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が臭素原子であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5がヨウ素原子であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5がメトキシ基であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5がエトキシ基であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が２，２，３，３，３－ペンタフルオロプロポキシ基であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が１，１，２，３，３，３－ヘキサフルオロプロポキシ基であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物；
　式（４）において、Ｘ1が窒素原子であり、Ｒ2及びＲ4が水素原子であり、Ｒ5が２，２，３，４，４，４－ヘキサフルオロブトキシ基であり、Ｘがメチル基であり、Ｒ1がエチル基である化合物。 In formula (4), X 1 is CR 3 , R 2 is a hydrogen atom, R 3 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R 4 and R 5 are them. A compound that forms a benzene ring together with the carbon atom to which it is attached, where X is a methyl, ethyl or propyl group and R 1 is a methyl, ethyl or propyl group;
In formula (4), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R 5 is a hydrogen atom and a fluorine atom. , Chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, butoxy group, tert- Butoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3 3,3-Hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, X is methyl group, ethyl group or propyl group, R 1 is methyl group, ethyl group or Compounds that are propyl groups;
In formula (4), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 and R 5 together with the carbon atom to which they are bonded form a benzene ring, and X is methyl. A compound which is a group, an ethyl group or a propyl group, and R 1 is a methyl group, an ethyl group or a propyl group;
In formula (4), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R 5 is a hydrogen atom and a fluorine atom. , Chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2 , 3,3,3-hexafluoropropoxy group or 2,2,3,4,5,4-hexafluorobutoxy group, X is a methyl group, an ethyl group or a propyl group, R 1 is a methyl group, Compounds that are ethyl or propyl groups;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, and a propoxy. Group, 2,2,2-trifluoroethoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3 , 4,4,4-Hexafluorobutoxy group, X is a methyl group, an ethyl group or a propyl group, and R 1 is a methyl group, an ethyl group or a propyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, and a propoxy. Group, 2,2,2-trifluoroethoxy group, 2,2,3,3,3-pentafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group or 2,2,3 , 4,4,4-Hexafluorobutoxy group, X is a methyl group, R 1 is an ethyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, and R 5 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group or 2 , 2,3,3,3-Pentafluoropropoxy group, X is a methyl group, R 1 is an ethyl group;
In formula (4), a compound in which X 1 is a nitrogen atom, R 2 , R 4 and R 5 are hydrogen atoms, X is a methyl group, and R 1 is an ethyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is a fluorine atom, X is a methyl group, and R 1 is an ethyl group;
In formula (4), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is a chlorine atom, X is a methyl group, and R 1 is an ethyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is a bromine atom, X is a methyl group, and R 1 is an ethyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is an iodine atom, X is a methyl group, and R 1 is an ethyl group;
In formula (4), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is a methoxy group, X is a methyl group, and R 1 is an ethyl group;
In formula (4), a compound in which X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is an ethoxy group, X is a methyl group, and R 1 is an ethyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is a 2,2,3,3,3-pentafluoropropoxy group, and X is a methyl group. Yes, a compound in which R 1 is an ethyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is a 1,1,2,3,3,3-hexafluoropropoxy group, and X is a methyl. A compound that is a group and R 1 is an ethyl group;
In formula (4), X 1 is a nitrogen atom, R 2 and R 4 are hydrogen atoms, R 5 is a 2,2,3,4,5,4-hexafluorobutoxy group, and X is a methyl. A compound that is a group and R 1 is an ethyl group.
　本発明において、Ｘは、メチル基、エチル基、プロピル基、トリフルオロメチル基、フェニル基、又は４－クロロフェニル基が好ましく、メチル基、エチル基、プロピル基、又はトリフルオロメチル基がより好ましい。
本発明において、Ｒ1は、メチル基、エチル基、プロピル基、又はイソプロピル基が好ましく、メチル基、エチル基、又はプロピル基がより好ましい。
本発明において、Ｒ2は、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基が好ましく、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基がより好ましい。
本発明において、Ｒ3は、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基が好ましく、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基がより好ましい。
本発明において、Ｒ4、及びＲ5は、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基、又はＲ4及びＲ5が結合する炭素原子と一緒になって、ベンゼン環を形成することが好ましく、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基、又はＲ4及びＲ5が結合する炭素原子と一緒になって、ベンゼン環を形成することがより好ましい。
　本発明において、Ｘ1は窒素原子が好ましい。 In the present invention, X is preferably a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, a phenyl group, or a 4-chlorophenyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group.
In the present invention, R 1 is preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and more preferably a methyl group, an ethyl group, or a propyl group.
In the present invention, R 2 is a C1-C6 alkyl group which may be substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, an aryl group which may be substituted with one or more halogen atoms, or one or more. Heteroaryl groups that may be substituted with halogen atoms or C1-C6 alkoxy groups that may be substituted with one or more halogen atoms are preferred, and are substituted with hydrogen atoms, halogen atoms, or one or more halogen atoms. More preferably, a C1-C6 alkyl group which may be substituted, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms.
In the present invention, R 3 is a C1-C6 alkyl group which may be substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, an aryl group which may be substituted with one or more halogen atoms, or one or more. Heteroaryl groups that may be substituted with halogen atoms or C1-C6 alkoxy groups that may be substituted with one or more halogen atoms are preferred, and are substituted with hydrogen atoms, halogen atoms, or one or more halogen atoms. More preferably, a C1-C6 alkyl group which may be substituted, or a C1-C6 alkoxy group which may be substituted with one or more halogen atoms.
In the present invention, R 4 and R 5 are a C1-C6 alkyl group optionally substituted with a hydrogen atom, a halogen atom and one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. A heteroaryl group that may be substituted with one or more halogen atoms, a C1-C6 alkoxy group that may be substituted with one or more halogen atoms, or a carbon atom to which R 4 and R 5 are bonded. It is preferable to form a benzene ring, and a C1-C6 alkyl group which may be substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, and a C1-C6 which may be substituted with one or more halogen atoms. It is more preferable to form a benzene ring together with an alkoxy group or a carbon atom to which R 4 and R 5 are bonded.
In the present invention, X 1 is preferably a nitrogen atom.
　以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明では、
１）式（１）で示される化合物（以下、化合物（１）とも記す。）と、式（２）で示される化合物（以下、化合物（２）とも記す。）とを、金属塩および塩基の存在下で反応させて、式（４）で示される化合物（以下、化合物（４）とも記す。）を得る工程（Ａ）；及び
　２）前記工程（Ａ）で得られた化合物を、必要に応じて酸性水溶液の存在下で水と反応させる工程（Ｂ）；
により、式（３）で示される化合物（以下、化合物（３）とも記す。）を製造する。
Figure JPOXMLDOC01-appb-I000016
[式中、記号は前記と同じ意味を示す。] In the present invention
1) The compound represented by the formula (1) (hereinafter, also referred to as compound (1)) and the compound represented by the formula (2) (hereinafter, also referred to as compound (2)) are the metal salts and bases. Step (A) to obtain the compound represented by the formula (4) (hereinafter, also referred to as compound (4)) by reacting in the presence; and 2) The compound obtained in the above step (A) is required. The step (B) of reacting with water in the presence of an acidic aqueous solution accordingly;
To produce the compound represented by the formula (3) (hereinafter, also referred to as compound (3)).
Figure JPOXMLDOC01-appb-I000016
[In the formula, the symbols have the same meaning as above. ]
　まず、化合物（１）及び化合物（２）から化合物（４）を得る工程（Ａ）について説明する。
　化合物（１）は、市販の化合物であるか、又は公知の方法に準じて製造することができる。
　化合物（２）は、市販の化合物であるか、又は公知の方法に準じて製造することができる。 First, the step (A) of obtaining the compound (4) from the compound (1) and the compound (2) will be described.
Compound (1) is a commercially available compound or can be produced according to a known method.
Compound (2) is a commercially available compound or can be produced according to a known method.
　化合物（２）の使用量は、化合物（１）１モルに対して通常０．５～１０モルの割合、好ましくは０．８～５モルの割合である。
　金属塩としては、亜鉛の金属塩及び銀の金属塩が挙げられる。
好ましい亜鉛の塩としては、フッ化亜鉛、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛、硫酸亜鉛、トリフルオロメタンスルホン酸亜鉛、硝酸亜鉛、過塩素酸亜鉛、チオシアン酸亜鉛、リン酸亜鉛、二リン酸亜鉛、ホウ酸亜鉛、炭酸亜鉛、酢酸亜鉛、プロピオン酸亜鉛、２－エチルヘキサン酸亜鉛、ラウリン酸亜鉛、ステアリン酸亜鉛、ナフテン酸亜鉛、亜鉛アセチルアセトナート、酸化亜鉛及び硫化亜鉛等が挙げられ、さらに好ましくは、フッ化亜鉛、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛、硫酸亜鉛、トリフルオロメタンスルホン酸亜鉛、硝酸亜鉛、過塩素酸亜鉛、チオシアン酸亜鉛、炭酸亜鉛、酢酸亜鉛、プロピオン酸亜鉛及び２－エチルヘキサン酸亜鉛等が挙げられる。
好ましい銀の塩としては、フッ化銀、塩化銀、臭化銀、硫酸銀、トリフルオロメタンスルホン酸銀、ｐ－トルエンスルホン酸銀、メタンスルホン酸銀、炭酸銀、酢酸銀、トリフルオロ酢酸銀、クエン酸銀、乳酸銀、安息香酸銀、硝酸銀、亜硝酸銀、ジエチルチオカルバミン酸銀、チオシアン酸銀、リン酸銀、ヘキサフルオロアンチモン(V)酸銀、テトラフルオロホウ酸銀、酸化銀及び硫化銀等が挙げられ、さらに好ましくは、フッ化銀、塩化銀、臭化銀、硫酸銀、トリフルオロメタンスルホン酸銀、ｐ－トルエンスルホン酸銀、メタンスルホン酸銀、炭酸銀、酢酸銀、トリフルオロ酢酸銀、クエン酸銀、乳酸銀、安息香酸銀、硝酸銀、亜硝酸銀、チオシアン酸銀、リン酸銀及びテトラフルオロホウ酸銀等が挙げられる。
　金属塩の使用量は、化合物（１）１モルに対して通常０．０１～１０モルの割合、好ましくは０．０１～５モルの割合、さらに好ましくは、０．０５～３モルの割合である。 The amount of the compound (2) to be used is usually 0.5 to 10 mol, preferably 0.8 to 5 mol, per 1 mol of the compound (1).
Examples of the metal salt include a zinc metal salt and a silver metal salt.
Preferred zinc salts include zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc trifluoromethanesulfonate, zinc nitrate, zinc perchlorate, zinc thiocyanate, zinc phosphate, diphosphate. Examples thereof include zinc, zinc borate, zinc carbonate, zinc acetate, zinc propionate, zinc 2-ethylhexanate, zinc laurate, zinc stearate, zinc naphthenate, zinc acetylacetonate, zinc oxide and zinc sulfide. More preferably, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc trifluoromethanesulfonate, zinc nitrate, zinc perchlorate, zinc thiocyanate, zinc carbonate, zinc acetate, zinc propionate and Examples thereof include zinc 2-ethylhexanoate.
Preferred silver salts include silver fluoride, silver chloride, silver bromide, silver sulfate, silver trifluoromethanesulfonate, silver p-toluenesulfonate, silver methanesulfonate, silver carbonate, silver acetate, silver trifluoroacetate, Silver citrate, silver lactate, silver benzoate, silver nitrate, silver nitrite, silver diethylthiocarbamate, silver thiocyanate, silver phosphate, silver hexafluoroantimonate (V), silver tetrafluoroborate, silver oxide and silver sulfide Etc., more preferably silver fluoride, silver chloride, silver bromide, silver sulfate, silver trifluoromethanesulfonate, silver p-toluenesulfonate, silver methanesulfonate, silver carbonate, silver acetate, trifluoroacetic acid. Examples thereof include silver, silver citrate, silver lactate, silver benzoate, silver nitrate, silver nitrite, silver thiocyanate, silver phosphate and silver tetrafluoroborate.
The amount of the metal salt used is usually 0.01 to 10 mol, preferably 0.01 to 5 mol, more preferably 0.05 to 3 mol, per 1 mol of compound (1). is there.
塩基としては、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化バリウム、水素化ナトリウム、水素化カリウム等の無機塩基；トリメチルアミン、トリエチルアミン、トリブチルアミン、ジメチルオクチルアミン、トリオクチルアミン、Ｎ，Ｎ－ジメチルベンジルアミン、Ｎ，Ｎ－ジイソプロピルエチルアミン、テトラメチルエチレンジアミン、テトラメチルヘキサメチレンジアミン、４－メチルモルホリン、４－エチルモルホリン、Ｎ－メチルピロリジン、Ｎ－エチルピロリジン、１－メチルピぺリジン、１－アザビシクロ［２．２．２］オクタン、１，４－ジアザビシクロ［２．２．２］オクタン、ヘキサメチレンテトラミン等のアミン系塩基；１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン（以下、ＤＢＵとも記す。）、１，５－ジアザビシクロ［４．３．０］ノナ－５－エン（以下、ＤＢＮとも記す。）等の付加反応に不活性な１以上の置換基で置換されていてもよいアミジン系塩基；Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジエチルアニリン等のアニリン系塩基；ピリジン、２－メチルピリジン、３－メチルピリジン、４－メチルピリジン、２－エチルピリジン、２－プロピルピリジン、２，４－ルチジン、３，４－ルチジン、２，６－ルチジン、３，５－ルチジン、２－メチル－５－エチルピリジン、２，４，６－トリメチルピリジン、２，３，５－トリメチルピリジン、４－（ジメチルアミノ）ピリジン、４―ピロリジノピリジン、２，２‘－ビピリジル等の付加反応に不活性な１以上の置換基で置換されていてもよいピリジン系塩基；キノリン、２-メチルキノリン、イソキノリン等のキノリン系塩基等が挙げられ、好ましくは、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、水素化ナトリウム、水素化ナトリウム等の無機塩基；トリメチルアミン、トリエチルアミン、Ｎ，Ｎ－ジイソプロピルエチルアミン、４－メチルモルホリン等のアミン系塩基；ピリジン、２，６－ルチジン、４－（ジメチルアミノ）ピリジン等のピリジン系塩基；キノリン、２-メチルキノリン、イソキノリン等のキノリン系塩基等が挙げられる。
　塩基の使用量は、化合物（１）１モルに対して通常０．１～１０モルの割合、好ましくは０．１～５モルの割合である。
　反応は、通常溶媒中で行われる。
　溶媒としては、例えばジエチルエーテル、テトラヒドロフラン、メチルｔ－ブチルエーテル、シクロペンチルメチルエーテル、エチレングリコールジメチルエーテル等のエーテル溶媒；アセトニトリル、プロピオニトリル等のアルキルニトリル溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン等のアミド溶媒；トルエン、キシレン、モノクロロベンゼン等の芳香族溶媒及びこれらの混合溶媒等が挙げられ、好ましくはジエチルエーテル、テトラヒドロフラン、メチルｔ－ブチルエーテル、シクロペンチルメチルエーテル、エチレングリコールジメチルエーテル等のエーテル溶媒が挙げられる。　　　
溶媒の使用量は、化合物（１）の重量に対し、通常１～１０倍の重量であり、好ましくは１～５倍の重量である。
　反応温度は、通常－２０～１００℃の範囲内、好ましくは２０～８０℃の範囲内である。
反応時間は、通常０．５～４８時間、好ましくは３～４８時間の範囲内である。 Bases include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydride, potassium hydride, etc .; trimethylamine, triethylamine, tributylamine, dimethyl Octylamine, trioctylamine, N, N-dimethylbenzylamine, N, N-diisopropylethylamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 4-methylmorpholin, 4-ethylmorpholin, N-methylpyrrolidin, N-ethyl Amine-based bases such as pyrrolidine, 1-methylpiperidin, 1-azabicyclo [2.2.2] octane, 1,4-diazabicyclo [2.2.2] octane, hexamethylenetetramine; 1,8-diazabicyclo [5] .4.0] Undeca-7-ene (hereinafter, also referred to as DBU), 1,5-diazabicyclo [4.3.0] nona-5-ene (hereinafter, also referred to as DBN), etc. Amidin-based bases that may be substituted with one or more active substituents; aniline-based bases such as N, N-dimethylaniline, N, N-diethylaniline; pyridine, 2-methylpyridine, 3-methylpyridine, 4 -Methylpyridine, 2-ethylpyridine, 2-propylpyridine, 2,4-lutidine, 3,4-lutidine, 2,6-lutidine, 3,5-lutidine, 2-methyl-5-ethylpyridine, 2,4 , 6-trimethylpyridine, 2,3,5-trimethylpyridine, 4- (dimethylamino) pyridine, 4-pyrrolidinopyridine, 2,2'-bipyridyl, etc. Substituted with one or more substituents inert to the addition reaction. Pyridine-based bases which may be used; quinoline-based bases such as quinoline, 2-methylquinoline, and isoquinoline are mentioned, and inorganic substances such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydride, and sodium hydride are preferable. Bases: Amine-based bases such as trimethylamine, triethylamine, N, N-diisopropylethylamine, 4-methylmorpholin; pyridine-based bases such as pyridine, 2,6-lutidine, 4- (dimethylamino) pyridine; quinoline, 2-methylquinoline , Isoquinolin and other quinoline bases and the like.
The amount of the base used is usually 0.1 to 10 mol, preferably 0.1 to 5 mol, per 1 mol of compound (1).
The reaction is usually carried out in a solvent.
Examples of the solvent include ether solvents such as diethyl ether, tetrahydrofuran, methyl t-butyl ether, cyclopentyl methyl ether and ethylene glycol dimethyl ether; alkyl nitrile solvents such as acetonitrile and propionitrile; N, N-dimethylformamide and N-methyl-2. -Amid solvent such as pyrrolidone; aromatic solvents such as toluene, xylene, monochlorobenzene and mixed solvents thereof are mentioned, and ethers such as diethyl ether, tetrahydrofuran, methyl t-butyl ether, cyclopentyl methyl ether and ethylene glycol dimethyl ether are preferable. Solvents can be mentioned.
The amount of the solvent used is usually 1 to 10 times the weight, preferably 1 to 5 times the weight of the compound (1).
The reaction temperature is usually in the range of −20 to 100 ° C., preferably in the range of 20 to 80 ° C.
The reaction time is usually in the range of 0.5 to 48 hours, preferably 3 to 48 hours.
反応終了後は、反応混合物を濃縮する；反応混合物と中性又は弱塩基性の水とを混合した後、有機溶媒で抽出を行い、得られた有機層を乾燥又は濃縮する；反応混合物及びアルカリ金属水酸化物、アルカリ金属炭酸塩あるいはアルカリ金属炭酸水素塩（例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム等）の水溶液を混合した後、有機溶媒で抽出し、得られた有機層を乾燥又は濃縮する；反応混合物及びアルカリ金属水酸化物、アルカリ金属炭酸塩あるいはアルカリ金属炭酸水素塩（例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム等）の水溶液を混合した後、不溶物を濾別し、濾液を有機溶媒で抽出し、得られた有機層を乾燥又は濃縮する；等の後処理操作を行うことにより、化合物（４）を単離することができる。
また単離した化合物（４）をさらに再結晶、クロマトグラフィー、又は塩析等の方法により精製することもできる。
また、化合物（４）を単離せずに、化合物（４）を含む反応混合物を次の工程（Ｂ）に供し、化合物（３）を製造することができる。 After completion of the reaction, the reaction mixture is concentrated; the reaction mixture is mixed with neutral or weakly basic water and then extracted with an organic solvent to dry or concentrate the obtained organic layer; the reaction mixture and alkali. After mixing an aqueous solution of metal hydroxide, alkali metal carbonate or alkali metal hydrogen carbonate (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.), it is extracted with an organic solvent. The resulting organic layer is dried or concentrated; the reaction mixture and alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate). Etc.), then the insoluble material is filtered off, the filtrate is extracted with an organic solvent, and the obtained organic layer is dried or concentrated; the compound (4) is obtained by performing a post-treatment operation such as. Can be isolated.
Further, the isolated compound (4) can be further purified by a method such as recrystallization, chromatography, or salting out.
Further, the reaction mixture containing the compound (4) can be subjected to the next step (B) without isolating the compound (4) to produce the compound (3).
　次に、化合物（４）から化合物（３）を得る工程（Ｂ）について説明する。 Next, the step (B) of obtaining the compound (3) from the compound (4) will be described.
　該工程は、酸の存在下、化合物（４）と水とを反応させることにより進行する。水の使用量の理論量は、化合物（４）１モルに対して通常２モルの割合であるが、過剰量用いることができる。
　　酸としては、例えば、酢酸、ギ酸、クエン酸、シュウ酸、３－フェニルアクリル酸、安息香酸、４－クロロ安息香酸、テレフタル酸、イソフタル酸、１－ナフタレンカルボン酸等のカルボン酸；リン酸；硝酸；硫酸、メタンスルホン酸、４－トルエンスルホン酸一水和物等のスルホン酸；塩化水素、臭化水素、ヨウ化水素、フッ化水素等のハロゲン化水素；等が挙げられ、好ましくは酢酸、ギ酸、クエン酸等のカルボン酸；リン酸；硝酸；硫酸；塩化水素等が挙げられる。
　反応温度は、通常－２０～１００℃の範囲内、好ましくは０～７０℃の範囲内である。
反応時間は、通常０．５～４８時間の範囲内である。
　該工程は、溶媒中で行うこともでき、かかる溶媒としては、例えばジエチルエーテル、テトラヒドロフラン、メチルｔ－ブチルエーテル、シクロペンチルメチルエーテル、エチレングリコールジメチルエーテル等のエーテル溶媒；アセトニトリル、プロピオニトリル等のアルキルニトリル溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン等のアミド溶媒；トルエン、キシレン、モノクロロベンゼン等の芳香族溶媒及びこれらの混合溶媒等が挙げられ、好ましくはジエチルエーテル、テトラヒドロフラン、メチルｔ－ブチルエーテル、シクロペンチルメチルエーテル、エチレングリコールジメチルエーテル等のエーテル溶媒が挙げられる。
反応終了後は、反応混合物を濃縮する；反応混合物と水とを混合した後、有機溶媒で抽出を行い、得られた有機層を乾燥又は濃縮する；反応混合物及びアルカリ金属水酸化物、アルカリ金属炭酸塩あるいはアルカリ金属炭酸水素塩（例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム等）の水溶液を混合した後、有機溶媒で抽出し、得られた有機層を乾燥又は濃縮する；反応混合物及びアルカリ金属水酸化物、アルカリ金属炭酸塩あるいはアルカリ金属炭酸水素塩（例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム等）の水溶液を混合した後、不溶物を濾別し、濾液を有機溶媒で抽出し、得られた有機層を乾燥又は濃縮する；等の後処理操作を行うことにより、化合物（３）を単離することができる。
また単離した化合物（３）をさらに再結晶、クロマトグラフィー、又は塩析等の方法により精製することもできる。 The step proceeds by reacting compound (4) with water in the presence of an acid. The theoretical amount of water used is usually 2 mol per 1 mol of compound (4), but an excess amount can be used.
Examples of the acid include carboxylic acids such as acetic acid, formic acid, citric acid, oxalic acid, 3-phenylacrylic acid, benzoic acid, 4-chlorobenzoic acid, terephthalic acid, isophthalic acid, 1-naphthalenecarboxylic acid; phosphoric acid; Nitrate; sulfonic acid such as sulfuric acid, methanesulfonic acid, 4-toluenesulfonic acid monohydrate; hydrogen halide such as hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen fluoride; and the like, preferably acetic acid. , Carboxylic acids such as formic acid and citric acid; phosphoric acid; nitric acid; sulfuric acid; hydrogen chloride and the like.
The reaction temperature is usually in the range of −20 to 100 ° C., preferably in the range of 0 to 70 ° C.
The reaction time is usually in the range of 0.5 to 48 hours.
The step can also be carried out in a solvent, such as an ether solvent such as diethyl ether, tetrahydrofuran, methyl t-butyl ether, cyclopentyl methyl ether, ethylene glycol dimethyl ether; an alkylnitrile solvent such as acetonitrile and propionitrile. Amid solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; aromatic solvents such as toluene, xylene and monochlorobenzene and mixed solvents thereof are mentioned, preferably diethyl ether, tetrahydrofuran and methyl t. -Examples include ether solvents such as butyl ether, cyclopentyl methyl ether and ethylene glycol dimethyl ether.
After completion of the reaction, the reaction mixture is concentrated; the reaction mixture is mixed with water and then extracted with an organic solvent, and the obtained organic layer is dried or concentrated; the reaction mixture and alkali metal hydroxide, alkali metal. After mixing an aqueous solution of carbonate or alkali metal hydrogen carbonate (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.), extraction is performed with an organic solvent, and the obtained organic layer is dried. Or concentrate; the reaction mixture and an aqueous solution of alkali metal hydroxide, alkali metal carbonate or alkali metal hydrogen carbonate (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.) were mixed. After that, the insoluble matter is filtered off, the filtrate is extracted with an organic solvent, and the obtained organic layer is dried or concentrated; the compound (3) can be isolated by performing a post-treatment operation such as.
Further, the isolated compound (3) can be further purified by a method such as recrystallization, chromatography, or salting out.
本発明により製造できる化合物（３）から、国際公開第２０１７／０６５２２８号に記載の製造方法により、有害節足動物に対して優れた防除効力を有する化合物を製造することができる。 From the compound (3) that can be produced according to the present invention, a compound having an excellent control effect on harmful arthropods can be produced by the production method described in International Publication No. 2017/065228.
　以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらの例のみに限定されるものではない。
［ＬＣ－ＭＳ条件］
［ＬＣ条件］
カラム：Zorbax Extend C18 (寸法4.6 x 50 mm, 粒子径５μｍ, 80Å、Agilent)
ＵＶ測定波長：２６０ｎｍ
移動相：Ａ液：10mM酢酸アンモニウム水溶液、Ｂ液：アセトニトリル
流速：１．２ｍＬ／分
グラジエント条件：［表ＬＣ１］に記載の濃度勾配で送液する。
［表ＬＣ１］
Figure JPOXMLDOC01-appb-I000017

［ＭＳ条件］
イオン化法：ＥＳＩ Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
[LC-MS conditions]
[LC condition]
Column: Zorbax Extend C18 (Dimensions 4.6 x 50 mm, Particle Diameter 5 μm, 80 Å, Agilent)
UV measurement wavelength: 260 nm
Mobile phase: Solution A: 10 mM ammonium acetate aqueous solution, Solution B: Acetonitrile Flow rate: 1.2 mL / min Gradient conditions: The solution is fed at the concentration gradient shown in [Table LC1].
[Table LC1]
Figure JPOXMLDOC01-appb-I000017

[MS condition]
Ionization method: ESI
実施例１
Figure JPOXMLDOC01-appb-I000018
　塩化亜鉛７．８ｇ、トリエチルアミン２．３ｇ、式（２－１）で示される化合物３．９ｇ及びＴＨＦ１０ｇを２５℃で３０分混合した。該混合物に対して式（１－１）で示される化合物２．０ｇを加えて混合し、５０℃に加熱して２０時間撹拌した。得られた反応液を高速液体クロマトグラフィーで分析し、式（４－１）で示される化合物が面積百分率値８６％で生成していることを確認した。
　該反応液を０℃に冷却した後、水３０ｇを加えて不溶物を濾別した。得られた濾液に対して２５℃で炭酸水素ナトリウム１．６ｇを加えて混合し、減圧濃縮した後、不溶物を濾別した。得られた濾液を酢酸エチルにて２回抽出し、有機層を合一した。該有機層を５％炭酸水素ナトリウム水溶液にて洗浄し、得られた有機層を硫酸ナトリウムにて脱水した。該有機層を濃縮乾固し、式（４－１）で示される化合物を含む粗生成物を３．１ｇ得た。該粗生成物を酢酸エチルにて洗浄し、減圧濃縮して、式（４－１）で示される化合物を含む固体を１．９ｇ得た。該固体を高速液体クロマトグラフィーで分析したところ、該固体中の式（４－１）で示される化合物は面積百分率値９９％であった。

式（４－１）で示される化合物
1H-NMR (CDCl3) δ(ppm): 11.51 (1H, br), 8.74 (1H, s), 8.67 (1H, s), 8.56 (1H, s), 5.98 (1H, br), 3.27 (2H, q, J = 7.2Hz), 2.61 (3H, s), 1.31 (3H, t, J = 7.2Hz)

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 1
Figure JPOXMLDOC01-appb-I000018
7.8 g of zinc chloride, 2.3 g of triethylamine, 3.9 g of the compound represented by the formula (2-1) and 10 g of THF were mixed at 25 ° C. for 30 minutes. 2.0 g of the compound represented by the formula (1-1) was added to the mixture, mixed, heated to 50 ° C., and stirred for 20 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-1) was produced with an area percentage value of 86%.
After cooling the reaction solution to 0 ° C., 30 g of water was added and the insoluble matter was filtered off. To the obtained filtrate, 1.6 g of sodium hydrogen carbonate was added at 25 ° C., mixed, concentrated under reduced pressure, and then the insoluble material was filtered off. The obtained filtrate was extracted twice with ethyl acetate, and the organic layers were combined. The organic layer was washed with a 5% aqueous sodium hydrogen carbonate solution, and the obtained organic layer was dehydrated with sodium sulfate. The organic layer was concentrated to dryness to obtain 3.1 g of a crude product containing the compound represented by the formula (4-1). The crude product was washed with ethyl acetate and concentrated under reduced pressure to obtain 1.9 g of a solid containing the compound represented by the formula (4-1). When the solid was analyzed by high performance liquid chromatography, the compound represented by the formula (4-1) in the solid had an area percentage value of 99%.

Compound represented by formula (4-1)
1 1 H-NMR (CDCl 3 ) δ (ppm): 11.51 (1H, br), 8.74 (1H, s), 8.67 (1H, s), 8.56 (1H, s), 5.98 (1H, br), 3.27 ( 2H, q, J = 7.2Hz), 2.61 (3H, s), 1.31 (3H, t, J = 7.2Hz)

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例２
Figure JPOXMLDOC01-appb-I000019
　塩化亜鉛１２０ｍｇ、トリエチルアミン１５０ｍｇ、式（２－１）で示される化合物１３０ｍｇ及びトルエン５００ｍｇを２５℃で１時間混合した。該混合物に対して式（１－１）で示される化合物１００ｍｇを加えて混合し、２５℃で５時間、５０℃に加熱して５時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（４－１）で示される化合物が面積百分率値３１％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 2
Figure JPOXMLDOC01-appb-I000019
120 mg of zinc chloride, 150 mg of triethylamine, 130 mg of the compound represented by the formula (2-1) and 500 mg of toluene were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-1) was added to the mixture, mixed, heated to 50 ° C. for 5 hours at 25 ° C., and stirred for 5 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-1) was produced with an area percentage value of 31%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例３
Figure JPOXMLDOC01-appb-I000020
　塩化亜鉛１２０ｍｇ、トリエチルアミン１５０ｍｇ、式（２－１）で示される化合物１３０ｍｇ及びメチルｔ－ブチルエーテル５００ｍｇを２５℃で１時間混合した。該混合物に対して式（１－１）で示される化合物１００ｍｇを加えて混合し、２５℃で５時間、５０℃に加熱して５時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（４－１）で示される化合物が面積百分率値２７％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 3
Figure JPOXMLDOC01-appb-I000020
120 mg of zinc chloride, 150 mg of triethylamine, 130 mg of the compound represented by the formula (2-1) and 500 mg of methyl t-butyl ether were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-1) was added to the mixture, mixed, heated to 50 ° C. for 5 hours at 25 ° C., and stirred for 5 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-1) was produced with an area percentage value of 27%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例４
Figure JPOXMLDOC01-appb-I000021
　酢酸銀６．０ｍｇ、トリエチルアミン４０ｍｇ、式（２－１）で示される化合物７０ｍｇ及びＴＨＦ３００μＬを２５℃で２０分混合した。該混合物に対して式（１－２）で示される化合物５０ｍｇを加えて混合し、５０℃に昇温して６時間撹拌した。得られた反応液を高速液体クロマトグラフィーで分析し、式（４－２）で示される化合物が面積百分率値４０％で生成していることを確認した。
式（４－２）で示される化合物
1H-NMR ((CD3)2SO) δ(ppm): 1.16 (3H, t, J = 7.4 Hz), 1.99 (3H, br), 3.29 (2H, q, J = 7.4 Hz), 8.67 (1H, d, J = 0.8 Hz), 8.83 (1H, d, J = 0.8 Hz), 9.1 (1H, br), 10.9 (1H, br)

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 4
Figure JPOXMLDOC01-appb-I000021
6.0 mg of silver acetate, 40 mg of triethylamine, 70 mg of the compound represented by the formula (2-1) and 300 μL of THF were mixed at 25 ° C. for 20 minutes. 50 mg of the compound represented by the formula (1-2) was added to the mixture, mixed, heated to 50 ° C., and stirred for 6 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-2) was produced with an area percentage value of 40%.
Compound represented by formula (4-2)
1 H-NMR ((CD 3 ) 2 SO) δ (ppm): 1.16 (3H, t, J = 7.4 Hz), 1.99 (3H, br), 3.29 (2H, q, J = 7.4 Hz), 8.67 ( 1H, d, J = 0.8 Hz), 8.83 (1H, d, J = 0.8 Hz), 9.1 (1H, br), 10.9 (1H, br)

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例５
Figure JPOXMLDOC01-appb-I000022
　塩化亜鉛０．１０ｇ、水素化ナトリウム（純度６０％）５０ｍｇ、式（２－１）で示される化合物０．１０ｇ及びＴＨＦ０．２０ｇを２５℃で１時間混合した。該混合物に対して式（１－２）で示される化合物０．１０ｇを加えて混合し、６５℃に昇温して８時間撹拌した。得られた反応液を高速液体クロマトグラフィーで分析し、式（４－２）で示される化合物が面積百分率値４８％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 5
Figure JPOXMLDOC01-appb-I000022
0.10 g of zinc chloride, 50 mg of sodium hydride (purity 60%), 0.10 g of the compound represented by the formula (2-1) and 0.20 g of THF were mixed at 25 ° C. for 1 hour. To the mixture, 0.10 g of the compound represented by the formula (1-2) was added and mixed, the temperature was raised to 65 ° C., and the mixture was stirred for 8 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-2) was produced with an area percentage value of 48%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例６
Figure JPOXMLDOC01-appb-I000023
　トリフルオロメタンスルホン酸銀１１ｍｇ、ジイソプロピルエチルアミン７０μＬ、式（２－１）で示される化合物７０ｍｇ及びＴＨＦ３００μＬを２５℃で２０分混合した。該混合物に対して式（１－２）で示される化合物５０ｍｇを加えて混合し、５０℃に昇温して６時間撹拌した。得られた反応液を高速液体クロマトグラフィーで分析し、式（４－２）で示される化合物が面積百分率値７３％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 6
Figure JPOXMLDOC01-appb-I000023
11 mg of silver trifluoromethanesulfonate, 70 μL of diisopropylethylamine, 70 mg of the compound represented by the formula (2-1) and 300 μL of THF were mixed at 25 ° C. for 20 minutes. 50 mg of the compound represented by the formula (1-2) was added to the mixture, mixed, heated to 50 ° C., and stirred for 6 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-2) was produced with an area percentage value of 73%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例７
Figure JPOXMLDOC01-appb-I000024
トリフルオロメタンスルホン酸銀１１ｍｇ、トリエチルアミン５５μＬ、及び式（２－１）で示される化合物７４ｍｇをＴＨＦ５７０μＬに溶解させた後、２０℃で２０分撹拌した。得られた混合液に対して式（１－３）で示される化合物０．１０ｇを加えて混合し、５０℃に昇温して６時間撹拌した。得られた反応液を高速液体クロマトグラフィーで分析し、式（４－３）で示される化合物が面積百分率値５８％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 7
Figure JPOXMLDOC01-appb-I000024
After dissolving 11 mg of silver trifluoromethanesulfonate, 55 μL of triethylamine, and 74 mg of the compound represented by the formula (2-1) in 570 μL of THF, the mixture was stirred at 20 ° C. for 20 minutes. To the obtained mixed solution, 0.10 g of the compound represented by the formula (1-3) was added and mixed, the temperature was raised to 50 ° C., and the mixture was stirred for 6 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-3) was produced with an area percentage value of 58%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例８
Figure JPOXMLDOC01-appb-I000025
　塩化亜鉛２．９ｇ、トリエチルアミン１．４ｍＬ、式（２－１）で示される化合物１．７ｇ及びＴＨＦ５ｍＬを２５℃で１時間混合した。該混合物に対して式（１－５）で示される化合物１．０ｇを加えて混合し、４５℃に昇温して２０時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（４－５）で示される化合物が面積百分率値２０％で生成していることを確認した。該反応液を２５℃に冷却して水を加えた後、酢酸エチル５０ｍＬにて抽出した。該有機層を飽和食塩水にて洗浄した後、硫酸ナトリウムを加えて撹拌し、得られた泥漿を濾過して不溶物を除去した。得られた有機層を減圧濃縮して、粗生成物を得た。該粗生成物をシリカゲルカラムクロマトグラフィーにて精製し、式（４－５）で示される化合物１５０ｍｇを得た。
式（４－５）で示される化合物
1H-NMR ((CD3)2SO) δ(ppm): 10.24 (1H, br), 8.77 (1H, br), 8.58 (1H, d, J = 3.5 Hz), 7.62 (1H, dd, J = 7.0, 7.4 Hz), 7.52 (2H, m), 3.38 (2H, q, J = 7.4 Hz), 2.11 (3H, s), 1.18 (3H, t, J = 7.0 Hz)

高速液体クロマトグラフィーの分析条件
使用カラム：XTerra Shield RP18 カラム（寸法4.6mm x 250mm、粒子径５μｍ、Waters）、移動相：Ａ液：10mM酢酸アンモニウム水溶液、Ｂ液：アセトニトリル、流速：1.0mL/min、検出器：ＵＶ、２５０ｎｍ Example 8
Figure JPOXMLDOC01-appb-I000025
2.9 g of zinc chloride, 1.4 mL of triethylamine, 1.7 g of the compound represented by the formula (2-1) and 5 mL of THF were mixed at 25 ° C. for 1 hour. 1.0 g of the compound represented by the formula (1-5) was added to the mixture, mixed, heated to 45 ° C., and stirred for 20 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-5) was produced with an area percentage value of 20%. The reaction mixture was cooled to 25 ° C., water was added, and the mixture was extracted with 50 mL of ethyl acetate. After washing the organic layer with saturated brine, sodium sulfate was added and stirred, and the obtained slurry was filtered to remove insoluble matter. The obtained organic layer was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 150 mg of the compound represented by the formula (4-5).
Compound represented by formula (4-5)
1 1 H-NMR ((CD 3 ) 2 SO) δ (ppm): 10.24 (1H, br), 8.77 (1H, br), 8.58 (1H, d, J = 3.5 Hz), 7.62 (1H, dd, J = 7.0, 7.4 Hz), 7.52 (2H, m), 3.38 (2H, q, J = 7.4 Hz), 2.11 (3H, s), 1.18 (3H, t, J = 7.0 Hz)

Analytical conditions for high performance liquid chromatography Column used: XTerra Shield RP18 column (dimensions 4.6 mm x 250 mm, particle size 5 μm, Waters), mobile phase: solution A: 10 mM ammonium acetate aqueous solution, solution B: acetonitrile, flow rate: 1.0 mL / min , Detector: UV, 250 nm
実施例９
Figure JPOXMLDOC01-appb-I000026
実施例８において精製して得た式（４－５）で示される化合物１５０ｍｇ及び４Ｎ塩酸１４ｍＬとを２０℃にて混合し、１５時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（３－５）で示される化合物が面積百分率値２０％で生成していることを確認した。
式（３－５）で示される化合物
ＬＣ－ＭＳ: 214 [M+H]+、RT＝2.22分

高速液体クロマトグラフィーの分析条件
使用カラム：XTerra Shield RP18 カラム（寸法4.6mm x 250mm、粒子径５μｍ、Waters）、移動相：Ａ液：10mM酢酸アンモニウム水溶液、Ｂ液：アセトニトリル、流速：1.0mL/min、検出器：ＵＶ、２５０ｎｍ Example 9
Figure JPOXMLDOC01-appb-I000026
150 mg of the compound represented by the formula (4-5) obtained by purification in Example 8 and 14 mL of 4N hydrochloric acid were mixed at 20 ° C. and stirred for 15 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-5) was produced with an area percentage value of 20%.
Compound LC-MS represented by formula (3-5): 214 [M + H] + , RT = 2.22 minutes

Analytical conditions for high performance liquid chromatography Column used: XTerra Shield RP18 column (dimensions 4.6 mm x 250 mm, particle size 5 μm, Waters), mobile phase: solution A: 10 mM ammonium acetate aqueous solution, solution B: acetonitrile, flow rate: 1.0 mL / min , Detector: UV, 250 nm
実施例１０
Figure JPOXMLDOC01-appb-I000027
　塩化亜鉛１５ｇ、トリエチルアミン１６ｍＬ、式（２－１）で示される化合物９．０ｇ及びＴＨＦ７０ｍＬを２０℃で１時間混合した。該混合物に対して式（１－４）で示される化合物７．０ｇを加えて混合し、５０℃に昇温して１９時間撹拌した。得られた反応液を２０℃に冷却した後、２０％塩酸２３ｍＬを加えて、２０℃で１６時間撹拌した。得られた反応液に対してトルエン５０ｍＬを加えた後、酢酸エチルにて抽出し、有機層を飽和食塩水にて洗浄後、硫酸ナトリウムを用いて脱水した。得られた泥漿を濾過し、濾液を濃縮乾固して粗生成物を得た。該粗生成物をシリカゲルカラムクロマトグラフィー（１５％酢酸エチル／石油エーテル）にて精製した後、メタノールを加え、得られた泥漿を濾過して不溶物を除去した。得られた濾液を濃縮乾固した後、シリカゲルカラムクロマトグラフィー（１５％酢酸エチル／石油エーテル）にて精製して、式（３－４）で示される化合物を１．４ｇ得た。

式（３－４）で示される化合物
1H-NMR ((CD3)2SO) δ(ppm): 8.14 (1H, dd, J = 7.5, 8.0 Hz), 8.06 (1H, dd, J = 0.5, 7.5 Hz), 7.90 (1H, dd, J = 0.5, 8.0 Hz), 5.08 (2H, s), 3.33 (2H, q, J = 7.5 Hz), 1.29 (3H, t, J = 7.5 Hz)

高速液体クロマトグラフィーの分析条件
使用カラム：ACQUITY UPLC BEH C18（寸法2.1mm x 50mm、粒子径1.7μｍ、Waters）、移動相：A 液：0.1%ギ酸、B 液：0.1％ギ酸／アセトニトリル溶液、流速：0.6mL/min、検出器：ＵＶ、２５４ｎｍ Example 10
Figure JPOXMLDOC01-appb-I000027
15 g of zinc chloride, 16 mL of triethylamine, 9.0 g of the compound represented by the formula (2-1) and 70 mL of THF were mixed at 20 ° C. for 1 hour. 7.0 g of the compound represented by the formula (1-4) was added to the mixture and mixed, the temperature was raised to 50 ° C., and the mixture was stirred for 19 hours. The obtained reaction solution was cooled to 20 ° C., 23 mL of 20% hydrochloric acid was added, and the mixture was stirred at 20 ° C. for 16 hours. Toluene (50 mL) was added to the obtained reaction solution, the mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, and dehydrated with sodium sulfate. The obtained slurry was filtered, and the filtrate was concentrated to dryness to obtain a crude product. The crude product was purified by silica gel column chromatography (15% ethyl acetate / petroleum ether), methanol was added, and the obtained slurry was filtered to remove insoluble matter. The obtained filtrate was concentrated to dryness and then purified by silica gel column chromatography (15% ethyl acetate / petroleum ether) to obtain 1.4 g of the compound represented by the formula (3-4).

Compound represented by formula (3-4)
1 H-NMR ((CD 3 ) 2 SO) δ (ppm): 8.14 (1H, dd, J = 7.5, 8.0 Hz), 8.06 (1H, dd, J = 0.5, 7.5 Hz), 7.90 (1H, dd) , J = 0.5, 8.0 Hz), 5.08 (2H, s), 3.33 (2H, q, J = 7.5 Hz), 1.29 (3H, t, J = 7.5 Hz)

Analysis conditions for high performance liquid chromatography Column used: ACQUITY UPLC BEH C18 (dimensions 2.1 mm x 50 mm, particle size 1.7 μm, Waters), mobile phase: solution A: 0.1% formic acid, solution B: 0.1% formic acid / acetonitrile solution, flow velocity : 0.6mL / min, Detector: UV, 254nm
実施例１１
Figure JPOXMLDOC01-appb-I000028
　塩化亜鉛５７０ｍｇ、トリエチルアミン０．１９ｇ、式（２－１）で示される化合物０．３４ｇ及びＴＨＦ１ｇを２５℃で３０分混合した。該混合物に対して式（１－１）で示される化合物２００ｍｇを加えて混合し、５０℃に加熱して１８時間撹拌した。得られた反応液を高速液体クロマトグラフィーで分析し、式（４－１）で示される化合物が面積百分率値８３％で生成していることを確認した。
該反応液を０℃に冷却した後、３５％塩酸０．４０ｇを加え、２５℃に昇温して１６時間撹拌した。得られた混合液を高速液体クロマトグラフィーで分析し、式（３－１）で示される化合物が面積百分率値５７％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 11
Figure JPOXMLDOC01-appb-I000028
570 mg of zinc chloride, 0.19 g of triethylamine, 0.34 g of the compound represented by the formula (2-1) and 1 g of THF were mixed at 25 ° C. for 30 minutes. 200 mg of the compound represented by the formula (1-1) was added to the mixture, mixed, heated to 50 ° C., and stirred for 18 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-1) was produced with an area percentage value of 83%.
After cooling the reaction solution to 0 ° C., 0.40 g of 35% hydrochloric acid was added, the temperature was raised to 25 ° C., and the mixture was stirred for 16 hours. The obtained mixed solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-1) was produced with an area percentage value of 57%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例１２
Figure JPOXMLDOC01-appb-I000029
　塩化亜鉛２２０ｍｇ、トリエチルアミン７０ｍｇ、式（２－１）で示される化合物１３０ｍｇ及びＴＨＦ５００ｍｇを２５℃で１時間混合した。該混合物に対して式（１－２）で示される化合物１００ｍｇを加えて混合し、２５℃で１９時間、５０℃に昇温して１０時間撹拌した。得られた反応液を２０℃に冷却した後、３５％塩酸２２０ｍｇ、及び水２００ｍｇを加え、２０℃で１２時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（３－２）で示される化合物が面積百分率値７９％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 12
Figure JPOXMLDOC01-appb-I000029
220 mg of zinc chloride, 70 mg of triethylamine, 130 mg of the compound represented by the formula (2-1) and 500 mg of THF were mixed at 25 ° C. for 1 hour. To the mixture, 100 mg of the compound represented by the formula (1-2) was added and mixed, the temperature was raised to 50 ° C. for 19 hours at 25 ° C., and the mixture was stirred for 10 hours. The obtained reaction solution was cooled to 20 ° C., 220 mg of 35% hydrochloric acid and 200 mg of water were added, and the mixture was stirred at 20 ° C. for 12 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-2) was produced with an area percentage value of 79%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例１３
Figure JPOXMLDOC01-appb-I000030
トリフルオロメタンスルホン酸亜鉛３２０ｍｇ、トリエチルアミン５５μＬ、及び式（２－１）で示される化合物７３ｍｇをＴＨＦ７２０μＬに溶解させた後、２０℃で２０分撹拌した。得られた混合液に対して式（１－３）で示される化合物１００ｍｇを加えて混合し、５０℃に昇温して６時間撹拌した。得られた反応液を高速液体クロマトグラフィーで分析し、式（４－３）で示される化合物が面積百分率値７８％で生成していることを確認した。
該反応液を２０℃に冷却した後、水０．１ｍＬ及び３５％塩酸０．２ｍＬを滴下し、２０℃で９時間撹拌した。得られた溶液を高速液体クロマトグラフィーで分析し、式（３－３）で示される化合物が面積百分率値７６％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Example 13
Figure JPOXMLDOC01-appb-I000030
After dissolving 320 mg of zinc trifluoromethanesulfonate, 55 μL of triethylamine, and 73 mg of the compound represented by the formula (2-1) in 720 μL of THF, the mixture was stirred at 20 ° C. for 20 minutes. To the obtained mixed solution, 100 mg of the compound represented by the formula (1-3) was added and mixed, the temperature was raised to 50 ° C., and the mixture was stirred for 6 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-3) was produced with an area percentage value of 78%.
After cooling the reaction solution to 20 ° C., 0.1 mL of water and 0.2 mL of 35% hydrochloric acid were added dropwise, and the mixture was stirred at 20 ° C. for 9 hours. The obtained solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-3) was produced with an area percentage value of 76%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
実施例１４
Figure JPOXMLDOC01-appb-I000031
　トリフルオロメタンスルホン酸亜鉛５００ｍｇ、トリエチルアミン０．１ｍＬ、式（２－１）で示される化合物１００ｍｇ及びＴＨＦ３．０ｍＬを２５℃で１時間混合した。該混合物に対して式（１－６）で示される化合物０．１ｇを加えて混合し、５０℃に昇温して２０時間撹拌した。得られた反応液を２０℃に冷却した後、４Ｎ塩酸１ｍＬを滴下し、２０℃で１４時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（３－６）で示される化合物が面積百分率値７７％で生成していることを確認した。

式（３－６）で示される化合物
1H-NMR ((CD3)2SO) δ(ppm): 8.64 (1H, d, J = 8.5 Hz), 8.25 (1H, d, J = 8.2 Hz), 8.14 (2H, d, J = 8.4 Hz), 7.94 (1H, dd, J = 7.0, 7.8 Hz), 7.82 (1H, dd, J = 7.2, 7.3 Hz), 5.34 (2H, s), 3.38 (2H, q, J = 7.5 Hz), 1.33 (3H, t, J = 7.5 Hz)

高速液体クロマトグラフィーの分析条件
使用カラム：ZORBAX Eclipse XDB C18（寸法4.6mm x 150mm、粒子径５μｍ、Agilent）、移動相：Ａ液：水、Ｂ液：アセトニトリル、流速：1.0mL/min、検出器：ＵＶ、２５０ｎｍ Example 14
Figure JPOXMLDOC01-appb-I000031
500 mg of zinc trifluoromethanesulfonate, 0.1 mL of triethylamine, 100 mg of the compound represented by the formula (2-1) and 3.0 mL of THF were mixed at 25 ° C. for 1 hour. 0.1 g of the compound represented by the formula (1-6) was added to the mixture, mixed, the temperature was raised to 50 ° C., and the mixture was stirred for 20 hours. After cooling the obtained reaction solution to 20 ° C., 1 mL of 4N hydrochloric acid was added dropwise, and the mixture was stirred at 20 ° C. for 14 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-6) was produced with an area percentage value of 77%.

Compound represented by formula (3-6)
1 H-NMR ((CD 3 ) 2 SO) δ (ppm): 8.64 (1H, d, J = 8.5 Hz), 8.25 (1H, d, J = 8.2 Hz), 8.14 (2H, d, J = 8.4) Hz), 7.94 (1H, dd, J = 7.0, 7.8 Hz), 7.82 (1H, dd, J = 7.2, 7.3 Hz), 5.34 (2H, s), 3.38 (2H, q, J = 7.5 Hz), 1.33 (3H, t, J = 7.5 Hz)

Analytical conditions for high performance liquid chromatography Column used: ZORBAX Eclipse XDB C18 (dimensions 4.6 mm x 150 mm, particle size 5 μm, Agilent), mobile phase: solution A: water, solution B: acetonitrile, flow rate: 1.0 mL / min, detector : UV, 250 nm
実施例１５
Figure JPOXMLDOC01-appb-I000032
　トリフルオロメタンスルホン酸亜鉛５００ｍｇ、ピリジン５０ｍｇ、式（２－１）で示される化合物１００ｍｇ及びＴＨＦ３．０ｍＬを２５℃で１時間混合した。該混合物に対して式（１－６）で示される化合物１００ｍｇを加えて混合し、４５℃に昇温して３０時間撹拌した。得られた反応液を２０℃に冷却した後、４Ｎ塩酸１ｍＬを滴下し、２０℃で２４時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（３－６）で示される化合物が面積百分率値３５％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：YMC TRIART C8（寸法4.6mm x 250mm、粒子径5μｍ、YMC）、移動相：Ａ液：10mM酢酸アンモニウム水溶液、Ｂ液：アセトニトリル、流速：1.0mL/min、検出器：ＵＶ、２５０ｎｍ Example 15
Figure JPOXMLDOC01-appb-I000032
500 mg of zinc trifluoromethanesulfonate, 50 mg of pyridine, 100 mg of the compound represented by the formula (2-1) and 3.0 mL of THF were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-6) was added to the mixture, mixed, heated to 45 ° C., and stirred for 30 hours. After cooling the obtained reaction solution to 20 ° C., 1 mL of 4N hydrochloric acid was added dropwise, and the mixture was stirred at 20 ° C. for 24 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-6) was produced with an area percentage value of 35%.

Analysis conditions for high performance liquid chromatography Column used: YMC TRIART C8 (dimensions 4.6 mm x 250 mm, particle size 5 μm, YMC), mobile phase: solution A: 10 mM ammonium acetate aqueous solution, solution B: acetonitrile, flow rate: 1.0 mL / min, Detector: UV, 250 nm
実施例１６
Figure JPOXMLDOC01-appb-I000033
　トリフルオロメタンスルホン酸亜鉛５００ｍｇ、ＤＢＵ０．１ｍＬ、式（２－１）で示される化合物１００ｍｇ及びＴＨＦ３．０ｍＬを２５℃で１時間混合した。該混合物に対して式（１－６）で示される化合物１００ｍｇを加えて混合し、４５℃に昇温して３０時間撹拌した。得られた反応液を２０℃に冷却した後、４Ｎ塩酸１ｍＬを滴下し、２０℃で２４時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（３－６）で示される化合物が面積百分率値５１％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：YMC TRIART C8（寸法4.6mm x 250mm、粒子径5μｍ、YMC）、移動相：Ａ液：10mM酢酸アンモニウム水溶液、Ｂ液：アセトニトリル、流速：1.0mL/min、検出器：ＵＶ、２５０ｎｍ Example 16
Figure JPOXMLDOC01-appb-I000033
500 mg of zinc trifluoromethanesulfonate, 0.1 mL of DBU, 100 mg of the compound represented by the formula (2-1) and 3.0 mL of THF were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-6) was added to the mixture, mixed, heated to 45 ° C., and stirred for 30 hours. After cooling the obtained reaction solution to 20 ° C., 1 mL of 4N hydrochloric acid was added dropwise, and the mixture was stirred at 20 ° C. for 24 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-6) was produced with an area percentage value of 51%.

Analysis conditions for high performance liquid chromatography Column used: YMC TRIART C8 (dimensions 4.6 mm x 250 mm, particle size 5 μm, YMC), mobile phase: solution A: 10 mM ammonium acetate aqueous solution, solution B: acetonitrile, flow rate: 1.0 mL / min, Detector: UV, 250 nm
実施例１７
Figure JPOXMLDOC01-appb-I000034
　トリフルオロメタンスルホン酸亜鉛５００ｍｇ、炭酸ナトリウム７０ｍｇ、式（２－１）で示される化合物１００ｍｇ及びＴＨＦ３．０ｍＬを２５℃で１時間混合した。該混合物に対して式（１－６）で示される化合物１００ｍｇを加えて混合し、４５℃に昇温して３０時間撹拌した。得られた反応液を２０℃に冷却した後、４Ｎ塩酸１ｍＬを滴下し、２０℃で２４時間撹拌した。得られた混合物を高速液体クロマトグラフィーで分析し、式（３－６）で示される化合物が面積百分率値４９％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：YMC TRIART C8（寸法4.6mm x 250mm、粒子径5μｍ、YMC）、移動相：Ａ液：10mM酢酸アンモニウム水溶液、Ｂ液：アセトニトリル、流速：1.0mL/min、検出器：ＵＶ、２５０ｎｍ Example 17
Figure JPOXMLDOC01-appb-I000034
500 mg of zinc trifluoromethanesulfonate, 70 mg of sodium carbonate, 100 mg of the compound represented by the formula (2-1) and 3.0 mL of THF were mixed at 25 ° C. for 1 hour. 100 mg of the compound represented by the formula (1-6) was added to the mixture, mixed, heated to 45 ° C., and stirred for 30 hours. After cooling the obtained reaction solution to 20 ° C., 1 mL of 4N hydrochloric acid was added dropwise, and the mixture was stirred at 20 ° C. for 24 hours. The obtained mixture was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (3-6) was produced with an area percentage value of 49%.

Analysis conditions for high performance liquid chromatography Column used: YMC TRIART C8 (dimensions 4.6 mm x 250 mm, particle size 5 μm, YMC), mobile phase: solution A: 10 mM ammonium acetate aqueous solution, solution B: acetonitrile, flow rate: 1.0 mL / min, Detector: UV, 250 nm
参考例１
Figure JPOXMLDOC01-appb-I000035
　式（１－２）で示される化合物２．０ｇ及び２，２，３，３，３－ペンタフルオロプロパノール３．２ｇをＮ－メチルピロリドン６．０ｇに溶解させた後、２０℃で炭酸カリウム２．４ｇを加えた。該混合液を５０℃に昇温して２時間、次いで６０℃に昇温して２時間撹拌した。得られた反応液を２０℃に冷却した後、酢酸エチル４．０ｇ、ヘキサン１６ｇ及び水１８ｇを加えて分液した。該有機層を、水１８ｇをそれぞれ用いて３回洗浄した後、得られた有機層を硫酸ナトリウムで脱水した。該泥漿から不溶物を濾別した後、得られた濾液を濃縮して、式（１－３）で示される化合物３．４ｇを得た。

式（１－３）で示される化合物
1H-NMR (CDCl3) δ(ppm): 4.92 (2H, dt, J = 0.8, 12.4 Hz), 8.44 (1H, d, J = 1.2 Hz), 8.50 (1H, d, J = 1.2 Hz)

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Reference example 1
Figure JPOXMLDOC01-appb-I000035
After dissolving 2.0 g of the compound represented by the formula (1-2) and 3.2 g of 2,2,3,3,3-pentafluoropropanol in 6.0 g of N-methylpyrrolidone, potassium carbonate 2 at 20 ° C. .4 g was added. The mixture was heated to 50 ° C. for 2 hours, then heated to 60 ° C. and stirred for 2 hours. The obtained reaction solution was cooled to 20 ° C., and then 4.0 g of ethyl acetate, 16 g of hexane and 18 g of water were added to separate the solutions. The organic layer was washed 3 times with 18 g of water, and the obtained organic layer was dehydrated with sodium sulfate. After filtering the insoluble matter from the slurry, the obtained filtrate was concentrated to obtain 3.4 g of the compound represented by the formula (1-3).

Compound represented by formula (1-3)
1 1 H-NMR (CDCl 3 ) δ (ppm): 4.92 (2H, dt, J = 0.8, 12.4 Hz), 8.44 (1H, d, J = 1.2 Hz), 8.50 (1H, d, J = 1.2 Hz)

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
比較例１
Figure JPOXMLDOC01-appb-I000036
トリフルオロメタンスルホン酸銀１１ｍｇ、式（２－１）で示される化合物７４ｍｇ、及びＴＨＦ３００μＬを２０℃で３０分混合した。該混合物に対して式（１－２）で示される化合物５０ｍｇを加えて混合し、５０℃に昇温して６時間撹拌した。得られた混合物を２０℃に冷却し、高速液体クロマトグラフィーで分析し、式（４－２）で示される化合物の面積百分率値は０％であった。
該混合物に対してトリエチルアミン５５μＬを加えた後、５０℃で５時間撹拌した。得られた反応液を高速液体クロマトグラフィーで分析し、式（４－２）で示される化合物が面積百分率値６７％で生成していることを確認した。

高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ Comparative Example 1
Figure JPOXMLDOC01-appb-I000036
11 mg of silver trifluoromethanesulfonate, 74 mg of the compound represented by the formula (2-1), and 300 μL of THF were mixed at 20 ° C. for 30 minutes. 50 mg of the compound represented by the formula (1-2) was added to the mixture, mixed, heated to 50 ° C., and stirred for 6 hours. The obtained mixture was cooled to 20 ° C. and analyzed by high performance liquid chromatography, and the area percentage value of the compound represented by the formula (4-2) was 0%.
After adding 55 μL of triethylamine to the mixture, the mixture was stirred at 50 ° C. for 5 hours. The obtained reaction solution was analyzed by high performance liquid chromatography, and it was confirmed that the compound represented by the formula (4-2) was produced with an area percentage value of 67%.

Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
比較例２
Figure JPOXMLDOC01-appb-I000037
式（５）で示される化合物（以下、化合物（５）とも記す。）１．６ｇをＴＨＦ２ｇに溶解させた後、５℃に冷却し、２．６Ｍブチルリチウムヘキサン溶液５．４ｍＬを滴下した。滴下終了後、該混合液を２０℃に昇温して１時間撹拌し、化合物（５）ブチルリチウム反応液を得た。
式（１－１）で示される化合物１ｇをＴＨＦ２ｇに溶解させた後、－５℃に冷却した。該混合液に対し、化合物（５）ブチルリチウム反応液を－５℃で滴下した後、２０℃に昇温して４時間撹拌した。該反応液を高速液体クロマトグラフィーで分析したところ、式（１－１）で示される化合物の面積百分率値は２％、式（６）で示される化合物の面積百分率値は０％であった。

高速液体クロマトグラフィーの分析条件
使用カラム：SUMIPAX ODS Z CLUE（寸法4.6mm x 100mm、粒子径3μｍ、住化分析センター）、移動相：A 液：pH7 リン酸バッファー、B 液：アセトニトリル、流速：1.0mL/min、検出器：ＵＶ、２５４ｎｍ Comparative Example 2
Figure JPOXMLDOC01-appb-I000037
1.6 g of the compound represented by the formula (5) (hereinafter, also referred to as compound (5)) was dissolved in 2 g of THF, cooled to 5 ° C., and 5.4 mL of a 2.6 M butyllithium hexane solution was added dropwise. After completion of the dropping, the temperature of the mixed solution was raised to 20 ° C. and the mixture was stirred for 1 hour to obtain a compound (5) butyllithium reaction solution.
After dissolving 1 g of the compound represented by the formula (1-1) in 2 g of THF, the mixture was cooled to −5 ° C. The compound (5) butyllithium reaction solution was added dropwise to the mixed solution at −5 ° C., the temperature was raised to 20 ° C., and the mixture was stirred for 4 hours. When the reaction solution was analyzed by high performance liquid chromatography, the area percentage value of the compound represented by the formula (1-1) was 2%, and the area percentage value of the compound represented by the formula (6) was 0%.

Analysis conditions for high performance liquid chromatography Column used: SUMIPAX ODS Z CLUE (dimensions 4.6 mm x 100 mm, particle size 3 μm, Sumika Analysis Center), mobile phase: solution A: pH7 phosphate buffer, solution B: acetonitrile, flow velocity: 1.0 mL / min, detector: UV, 254 nm
比較例３
　比較例２において、２．６Ｍブチルリチウムヘキサン溶液に代えてｔ－ブトキシカリウムを用いる以外は同じ方法で、式（１－１）で示される化合物から式（６）で示される化合物の合成を試みた。得られた反応液を高速液体クロマトグラフィーで分析したところ、式（１－１）で示される化合物の面積百分率値は４％、式（６）で示される化合物の面積百分率値は０％であった。

高速液体クロマトグラフィーの分析条件
使用カラム：SUMIPAX ODS Z CLUE（寸法4.6mm x 100mm、粒子径3μｍ、住化分析センター）、移動相：A 液：pH7 リン酸バッファー、B 液：アセトニトリル、流速：1.0mL/min、検出器：ＵＶ、２５４ｎｍ Comparative Example 3
In Comparative Example 2, an attempt was made to synthesize the compound represented by the formula (6) from the compound represented by the formula (1-1) by the same method except that t-butoxypotassium was used instead of the 2.6M butyllithium hexane solution. It was. When the obtained reaction solution was analyzed by high performance liquid chromatography, the area percentage value of the compound represented by the formula (1-1) was 4%, and the area percentage value of the compound represented by the formula (6) was 0%. It was.

Analysis conditions for high performance liquid chromatography Column used: SUMIPAX ODS Z CLUE (dimensions 4.6 mm x 100 mm, particle size 3 μm, Sumika Analysis Center), mobile phase: solution A: pH7 phosphate buffer, solution B: acetonitrile, flow velocity: 1.0 mL / min, detector: UV, 254 nm
比較例４、比較例５、比較例６及び実施例１
Figure JPOXMLDOC01-appb-I000038
［式中、Ｑは、水素原子、メトキシ基又はニトロ基を示す。］
　実施例１において、式（１－１）で示される化合物に代えて式（１－７）で示される化合物を用いる以外は実施例１と同様にして、式（１－７）で示される化合物、式（２－１）で示される化合物、金属塩及び塩基を反応させた場合に、式（４－７）で示される化合物（以下、化合物（４－７）とも記す。）の面積百分率値は０％であった。 Comparative Example 4, Comparative Example 5, Comparative Example 6 and Example 1
Figure JPOXMLDOC01-appb-I000038
[In the formula, Q represents a hydrogen atom, a methoxy group or a nitro group. ]
In Example 1, the compound represented by the formula (1-7) is used in the same manner as in Example 1 except that the compound represented by the formula (1-7) is used instead of the compound represented by the formula (1-1). , Area percentage value of the compound represented by the formula (4-7) (hereinafter, also referred to as the compound (4-7)) when the compound represented by the formula (2-1), the metal salt and the base are reacted. Was 0%.
［表１］
Figure JPOXMLDOC01-appb-I000039



高速液体クロマトグラフィーの分析条件
使用カラム：Shim-pack XR-ODS（寸法3mm x 75mm、粒子径2.2μｍ、島津製作所）、移動相：A 液：0.1%リン酸、B 液：アセトニトリル、流速：0.9mL/min、検出器：ＵＶ、２５４ｎｍ [Table 1]
Figure JPOXMLDOC01-appb-I000039



Analytical conditions for high performance liquid chromatography Column used: Shim-pack XR-ODS (dimensions 3 mm x 75 mm, particle size 2.2 μm, Shimadzu Corporation), mobile phase: solution A: 0.1% phosphoric acid, solution B: acetonitrile, flow velocity: 0.9 mL / min, detector: UV, 254 nm
　本発明によればβ－ケトスルホン化合物を効率よく製造することができる。 According to the present invention, a β-ketosulfone compound can be efficiently produced.

Claims (20)

  1. 　工程（Ａ）：式（１）
    Figure JPOXMLDOC01-appb-I000001
    ［式中、Ｘ1はＣＲ3又は窒素原子を表し、
    Ｒ2及びＲ3は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、
    Ｒ4及びＲ5は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は群Ａより選ばれる１以上の置換基で置換されていてもよい。｝を形成する。
    群Ａ：ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群。］
    で表される化合物と、式（２）
    Figure JPOXMLDOC01-appb-I000002
    ［式中、Ｘは、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基を表し、
    Ｒ1は、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基を表す。］
    で表される化合物とを、金属塩および塩基の存在下で反応させて、式（４）
    Figure JPOXMLDOC01-appb-I000003
    ［式中、Ｘ、Ｘ1、Ｒ1、Ｒ2、Ｒ4及びＲ5は前記と同じ意味を表す。］
    で表される化合物を得る工程：
    を含む、式（４）で表される化合物の製造方法。     Step (A): Formula (1)
    Figure JPOXMLDOC01-appb-I000001
    [In the formula, X 1 represents CR 3 or a nitrogen atom,
    R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. Represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms.
    R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. Represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, or combined with a carbon atom to which they are attached. The benzene ring {the benzene ring may be substituted with one or more substituents selected from group A. } Is formed.
    Group A: Halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, even if substituted with one or more halogen atoms A group consisting of a good heteroaryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. ]
    Compound represented by and formula (2)
    Figure JPOXMLDOC01-appb-I000002
    [In the formula, X represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms.
    R 1 represents a C1-C6 alkyl group that may be substituted with one or more halogen atoms. ]
    The compound represented by (4) is reacted in the presence of a metal salt and a base to formulate (4).
    Figure JPOXMLDOC01-appb-I000003
    [In the formula, X, X 1 , R 1 , R 2 , R 4 and R 5 have the same meanings as described above. ]
    Step of obtaining the compound represented by:
    A method for producing a compound represented by the formula (4), which comprises.
  2. 式（１）において、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である、請求項１に記載の製造方法。 In formula (1), R 2 is an aryl group optionally substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. The manufacturing method according to claim 1.
  3. 式（１）において、Ｘ1がＣＲ3又は窒素原子であり、Ｘ1がＣＲ3である場合に、Ｒ3が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である、請求項１又は２に記載の製造方法。 In formula (1), when X 1 is CR 3 or a nitrogen atom and X 1 is CR 3 , R 3 may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. The production method according to claim 1 or 2, wherein the C1-C6 alkoxy group may be substituted with one or more halogen atoms.
  4. 式（１）において、Ｒ4及びＲ5が、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環はハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基及び１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成する、請求項１～３のいずれかに記載の製造方法。 In formula (1), R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, an aryl group which may be substituted with one or more halogen atoms, or one or more halogen atoms. A benzene ring {the benzene ring may be substituted with a halogen atom, one or more halogen atoms, and an aryl group representing a good C1-C6 alkoxy group or, together with a carbon atom to which they are attached It may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with the above halogen atoms. }. The production method according to any one of claims 1 to 3.
  5. 式（１）において、Ｘ1が窒素原子である、請求項１～４のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 4, wherein X 1 is a nitrogen atom in the formula (1).
  6. 式（１）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4が水素原子であり、Ｒ5が水素原子、ハロゲン原子又はＯＣＨ2ＣＦ2ＣＦ3基である、請求項１～５のいずれかに記載の製造方法。 In formula (1), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 is a hydrogen atom, and R 5 is a hydrogen atom, a halogen atom or three OCH 2 CF 2 CF groups. Item 8. The production method according to any one of Items 1 to 5.
  7. 式（２）において、Ｘがメチル基である、請求項１～６のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 6, wherein X is a methyl group in the formula (2).
  8. 式（２）において、Ｒ1がエチル基である、請求項１～７のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 7, wherein R 1 is an ethyl group in the formula (2).
  9. 　塩基が、無機塩基又はアミン系塩基である、請求項１～８のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 8, wherein the base is an inorganic base or an amine-based base.
  10. 金属塩が、亜鉛又は銀の塩である、請求項１～９のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 9, wherein the metal salt is a zinc or silver salt.
  11. 金属塩が、ＺｎＣｌ2、Ｚｎ（ＯＳ（Ｏ）2ＣＦ3）2、ＡｇＯＳ（Ｏ）2ＣＦ3又はＡｇＯＣ（Ｏ）ＣＨ3である、請求項１～１０のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 10, wherein the metal salt is ZnCl 2 , Zn (OS (O) 2 CF 3 ) 2 , AgOS (O) 2 CF 3, or AgOC (O) CH 3 .
  12. 請求項１～１１のいずれかに記載の工程（Ａ）に、さらに下記工程（Ｂ）を含む、式（３）
    Figure JPOXMLDOC01-appb-I000004
    ［式中、Ｘ1、Ｒ1、Ｒ2、Ｒ4及びＲ5は前記と同じ意味を表す。］
    で表される化合物の製造方法。
    工程（Ｂ）：
    酸の存在下、式（４）
    Figure JPOXMLDOC01-appb-I000005
    ［式中、Ｘ、Ｘ1、Ｒ1、Ｒ2、Ｒ4及びＲ5は前記と同じ意味を表す。］
    で表される化合物と水とを反応させ、式（３）で示される化合物を得る工程。     Formula (3), wherein the step (A) according to any one of claims 1 to 11 further includes the following step (B).
    Figure JPOXMLDOC01-appb-I000004
    [In the formula, X 1 , R 1 , R 2 , R 4 and R 5 have the same meanings as described above. ]
    A method for producing a compound represented by.
    Process (B):
    Equation (4) in the presence of acid
    Figure JPOXMLDOC01-appb-I000005
    [In the formula, X, X 1 , R 1 , R 2 , R 4 and R 5 have the same meanings as described above. ]
    A step of reacting a compound represented by (3) with water to obtain a compound represented by the formula (3).
  13. 式（４）
    Figure JPOXMLDOC01-appb-I000006
    ［式中、
    Ｘは、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基又は１以上のハロゲン原子で置換されていてもよいアリール基を表し、
    Ｒ1は、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基を表し、
    Ｘ1はＣＲ3又は窒素原子を表し、
    Ｒ2及びＲ3は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表し、
    Ｒ4及びＲ5は、各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基を表すか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は群Ａより選ばれる１以上の置換基で置換されていてもよい。｝を形成する。

    群Ａ：ハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルキル基、１以上のハロゲン原子で置換されていてもよいアリール基、１以上のハロゲン原子で置換されていてもよいヘテロアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群。］
    で表される化合物。     Equation (4)
    Figure JPOXMLDOC01-appb-I000006
    [During the ceremony,
    X represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms or an aryl group optionally substituted with one or more halogen atoms.
    R 1 represents a C1-C6 alkyl group that may be substituted with one or more halogen atoms.
    X 1 represents CR 3 or nitrogen atom
    R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. Represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms.
    R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and an aryl group optionally substituted with one or more halogen atoms. Represents a heteroaryl group optionally substituted with one or more halogen atoms or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, or combined with a carbon atom to which they are attached. The benzene ring {the benzene ring may be substituted with one or more substituents selected from group A. } Is formed.

    Group A: Halogen atom, a C1-C6 alkyl group optionally substituted with one or more halogen atoms, an aryl group optionally substituted with one or more halogen atoms, even if substituted with one or more halogen atoms A group consisting of a good heteroaryl group or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. ]
    The compound represented by.
  14. 式（４）において、Ｒ2が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である、請求項１３に記載の化合物。 In formula (4), R 2 is an aryl group optionally substituted with a hydrogen atom, a halogen atom or one or more halogen atoms, or a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. The compound according to claim 13.
  15. 式（４）において、Ｘ1がＣＲ3又は窒素原子であり、Ｘ1がＣＲ3である場合に、Ｒ3が水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基である、請求項１３又は１４に記載の化合物。 In formula (4), when X 1 is CR 3 or a nitrogen atom and X 1 is CR 3 , R 3 may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. The compound according to claim 13 or 14, which is a C1-C6 alkoxy group that may be substituted with one or more halogen atoms.
  16. 式（４）において、Ｒ4及びＲ5が各々独立して、水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基であるか、または、それらが結合する炭素原子と一緒になって、ベンゼン環｛該ベンゼン環は水素原子、ハロゲン原子、１以上のハロゲン原子で置換されていてもよいアリール基又は１以上のハロゲン原子で置換されていてもよいＣ１－Ｃ６アルコキシ基からなる群より選ばれる１以上の置換基で置換されていてもよい。｝を形成する請求項１３～１５のいずれかに記載の化合物。 In formula (4), R 4 and R 5 may be independently substituted with a hydrogen atom, a halogen atom, an aryl group which may be substituted with one or more halogen atoms, or one or more halogen atoms. A benzene ring {the benzene ring may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, either as a C1-C6 alkoxy group or together with a carbon atom to which they are attached. Alternatively, it may be substituted with one or more substituents selected from the group consisting of C1-C6 alkoxy groups which may be substituted with one or more halogen atoms. } The compound according to any one of claims 13 to 15.
  17. 式（４）において、Ｘ1が窒素原子である、請求項１３～１６のいずれかに記載の化合物。 The compound according to any one of claims 13 to 16, wherein X 1 is a nitrogen atom in the formula (4).
  18. 式（４）において、Ｘ1が窒素原子であり、Ｒ2が水素原子であり、Ｒ4が水素原子であり、Ｒ5が水素原子、ハロゲン原子又はＯＣＨ2ＣＦ2ＣＦ3基である、請求項１３～１７のいずれかに記載の化合物。 In formula (4), X 1 is a nitrogen atom, R 2 is a hydrogen atom, R 4 is a hydrogen atom, and R 5 is a hydrogen atom, a halogen atom or three OCH 2 CF 2 CF groups. Item 2. The compound according to any one of Items 13 to 17.
  19. 式（４）において、Ｘがメチル基である、請求項１３～１８のいずれかに記載の化合物。 The compound according to any one of claims 13 to 18, wherein X is a methyl group in the formula (4).
  20. 式（４）において、Ｒ1がエチル基である、請求項１３～１９のいずれかに記載の化合物。 The compound according to any one of claims 13 to 19, wherein R 1 is an ethyl group in the formula (4).
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WO2017150209A1 (en) * 2016-02-29 2017-09-08 住友化学株式会社 Heterocyclic compound
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