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WO1996028401A1 - Process for producing unsaturated organic compounds - Google Patents

Process for producing unsaturated organic compounds Download PDF

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WO1996028401A1
WO1996028401A1 PCT/JP1996/000570 JP9600570W WO9628401A1 WO 1996028401 A1 WO1996028401 A1 WO 1996028401A1 JP 9600570 W JP9600570 W JP 9600570W WO 9628401 A1 WO9628401 A1 WO 9628401A1
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ethyl acetate
silane
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Japanese (ja)
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Yasuo Hatanaka
Emiko Hagiwara
Ken-Ichi Gouda
Tamejiro Hiyama
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Sagami Chemical Research Institute
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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
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • 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
    • C07D213/26—Radicals substituted by halogen atoms or nitro 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
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine

Definitions

  • the present invention relates to the use of organic halosilanes and organic halides in the presence of functional organic materials such as liquid crystals, and organic compounds such as biaryls and alkenylarenes useful as pharmaceuticals or agricultural chemicals in the presence of a Group 10 transition metal catalyst. And a method for producing by reacting Background art
  • biaryls are used as liquid crystals and intermediates thereof ["Basic Liquid Crystal", Baifukan (1985) p232] or as intermediates for synthesis of medicinal and agricultural chemicals ["The Organic Chemistry of Drug Synthesis” Vols. 1-3, Wiley-Interscience, New York (1977-1984).
  • the 1,3-alkadienes and alkenylarenes obtained by the present invention are industrially important compounds as raw materials for synthetic polymers ["The Chemistry of Alkene, Vol. 2, p411, Wiley, New York” (1970) o Therefore, their simple and economical production methods are of great industrial importance.
  • the methods for producing biaryls from aryl halides as raw materials include: (1) a method in which an aryl grignard reactant is reacted with aryl chloride in the presence of a transition metal catalyst: J. Organomet. Chem., 118, 349 (1976 ;; J. Chem. Soc., Chem. Commun., 1984, 511 Synthesis, 1990, 147.) 2Reaction between aryl borane compound and aryl chloride in the presence of a transition metal catalyst. , 32, 2273 (1991)], and 3 a method of reacting aryl bromide with aryl chloride in the presence of a nickel complex [Tetrahedron Lett., 29, 545 (1988)].
  • Methods for producing alkenyl arenes using aryl halides include 4 a method of reacting an alkenyl Grignard reagent with aryl chloride in the presence of a transition metal catalyst [Tetrahedron Lett., 1975, 1719], etc. There is.
  • a method for producing biaryls using an organic gayne compound a method of reacting a aryl (no-opening) silane with a halogenated aryl in the presence of a fluoride salt and a palladium catalyst [Japanese Patent Application Laid-Open No. HEI 9-284207]. 6-239766] is known.
  • alkenyl (haguchi) silane and aryl halide are prepared in the presence of a fluoride salt and a palladium catalyst.
  • a reaction method Japanese Patent Laid-Open No. 1-26831] is known.
  • the method (1) has the disadvantages that the yield of the reaction with aryl chloride is generally low at 30% or less, and that symmetric biaryls derived from the homocoupling reaction are by-produced.
  • the method (2) has a low yield of 30% or less.
  • the method (3) requires a stoichiometric amount of nickel, which is a heavy metal, and has the disadvantage that a large amount of symmetric biaryls are by-produced.
  • Method (2) has a low yield of 20% or less.
  • a stoichiometric amount of expensive fluoride salt is required, and satisfactory results are not always obtained when aryl chloride is used as a raw material. Disclosure of the invention
  • An object of the present invention is to provide a simple and economical method for producing an unsaturated organic compound which does not have such a problem.
  • organic halosilanes include a Group 10 transition metal catalyst and sodium hydroxide. By reacting with an organic halide in the presence of a base, an unsaturated organic compound can be obtained in one step and in a good yield.Organohalosilanes are specified.Group 10 transition metal catalyst having a phosphine ligand The present inventors have found that an unsaturated organic compound can be obtained in one step and in a good yield by reacting with an organic halide in the presence of a fluoride salt.
  • R 2 is the same as R 1 , or a lower alkyl group X represents a halogen atom, and m represents an integer from 0 to 2. However, when is an alkyl group, m is 0.) and an organic halosilane represented by the following general formula: Formula [H]
  • R 3 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted 1-alkenyl group, or a substituted or unsubstituted 2-alkenyl group
  • Y ′ represents a halogen atom.
  • R 1 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkyl group.
  • R 2 is the same as R 1 , or lower.
  • X represents a halogen atom
  • 01 represents an integer from 0 to 2.
  • R 1 is an alkyl group
  • m is 0.
  • R 3 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted 1-alkenyl group, or a substituted or unsubstituted 2-alkenyl group.
  • Y 2 represents a chlorine atom or a bromine atom. Characterized by reacting with an organic chloride represented by the following in the presence of a Group 10 transition metal catalyst having a trialkylphosphine ligand and a fluoride salt,
  • X represents a halogen atom, especially a fluorine atom and a chlorine atom
  • a chlorine atom is preferably used, and a chlorine atom is more preferable in that it is inexpensive.
  • aryl (halo) silane having a substituted or unsubstituted aryl group as R ′ and Z or R 2 is an aromatic metal compound and In addition to being easily synthesized by a method of reacting with chlorosilane [Synthesis, 841 (1979)], various types are easily available industrially.
  • the substituted or unsubstituted aryl group also includes a heteroaryl group. Examples of the substituent of the aryl group include an alkyl group, a cycloalkyl group, and an alkoxy group which may be substituted with a fluorine atom.
  • alkoxycarbonyl group an acyl group, and an aryl group; one or more groups selected from a cyano group, a formyl group, a nitro group, a tri (lower alkynole) silyl group, and a fluorine atom; Those that can be further substituted, for example, with the above substituents.
  • Examples of the substituted or unsubstituted aryl group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentyl phenyl, 4-hexyl phenyl, 4-heptyl phenyl, 4-octyl phenyl, 2-methoxy phenyl, 3-methoxy phenyl, 4-methoxy phenyl, 4-methoxy phenyl, 4 -Propoxyphenyl, 4-butoxyphenyl, 4-pentyloxyphenyl, 3-cyanophenyl, 4-cyanophenyl, 3-dimethoxy, 4-nitrophenyl, 4-formylphenyl, 4-methyl Toxylcarbonyl, 4-ethoxycarbonyl, 4-acetylphenyl, 4-fluorophenyl, 3,4-difluorophenyl Zinyl, 2-flu
  • aryl (c) silane examples include, for example, chloro (dimethyl) (phenyl) silane, dichloro (methyl) (phenyl) silane, dichloro (ethyl) (phenyl) silane, trichloro (phenyl) silane, dichloro (Diphenyl) silane, chloro (methyl) (diphenyl) silane, dichloro (ethyl) (2-methylphenyl) silane, dichloro (ethyl) (3-methylphenyl) silane, dichlorodi (3-methylphenyl) silane, Dichloro (ethyl) (4-methylphenyl) silane, dichlorodi (4-methylphenyl) silane, chloro (dimethyl) (4-pentylphenyl) silane, dichloro (methyl) (4-pentylphenyl) silane, dichloro (ethyl) (4 -Pentylphenyl) silane, e
  • R 1 and Z or R 2 represent an alkenyl (haguchi) silane having a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkyl group
  • the substituted or unsubstituted alkenyl group for R 1 or R 2 in the general formula: I] also includes a cycloalkenyl group, and specifically includes an ethenyl group, a 1-propenyl group, a 1-butenyl group, -Pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 1-octenyl group, 5-octenyl group, 2-phenylenyl group, 1-cyclohexenyl group, and the like.
  • substituent include those described above.
  • alkenyl (c) silane examples include, for example, dichloro (ethenyl) (methyl) silane, chloro (ethenyl) (dimethyl) silane, dichloro (methyl) (1-propenyl) silane, chloro (dimethyl) (1 -Propenyl) silane, (butenyl) (dichloro) (methyl) silane, (1-butenyl) (chloro) (dimethyl) silane, dichloro (methyl) (1-pentenyl) silane, chloro Methyl (dimethyl) (1-pentenyl) silane, Dixco (1-hexenyl) (methyl) silane, Chloro (1-hexenyl) (dimethyl) silane, Chloro (2-hexenyl) (dimethyl) silane, Dichloro (1-heptenyl) (methyl) silane, Clo (1-heptenyl) (dimethyl) silane, Dichloro (1-oc
  • alkenyl (c) silanes having a substituted or unsubstituted alkenyl group as R 1 the alkenyl (a, c) silane having a tri- or 2-alkenyl group is preferred in view of the reaction efficiency.
  • examples of the substituted or unsubstituted alkyl group include a linear or branched alkyl group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, Examples include ethyl group, propyl group, butyl group, isobutyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, and decyl group. That place Examples of the substituent include those described above.
  • alkyl (c) silanes include trichloro (methyl) silane, trichloro (ethyl) silane, trichloro (propyl) silane, butyl (triclo) silane, and trichloro (isobutyl silane, trichloro ( Pentyl) silane, trichloro (hexyl) silane, trichloro (cyanobutyl) silane, trichloro (2-phenylethyl) silane and the like can be exemplified.
  • the lower alkyl group of R 2 in the general formula [I] means a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, Isobutyl group, pentyl group, neopentyl group, hexyl group, etc.
  • the other starting material an organic halide represented by the above general formula [ ⁇ ] is a compound that can be easily synthesized and is industrially easily available.
  • Y 1 is a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom.
  • R 3 is a substituted or unsubstituted aryl group or a 1- or 2-alkenyl group.
  • the aryl group also includes a heteroaryl group, and includes a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group, a furyl group, a chenyl group, a pyrrolyl group, and the like.
  • Examples of the substituent a linear or branched alkyl Le group or alkoxy group having 1 to 10 carbon atoms, di-lower alkylamino group, Shiano group, lower halogen atom of atomic number than Y 1, Ashiru group, Ashiruamino group And an amino group, an aryl group, a carbonyl group, a carboxyl group, a nitrogen atom group, a cycloalkyl group and a cycloalkoxy group.
  • those that can be substituted may be further substituted with a halogen atom, an alkyl group, or the like having an atomic number smaller than Y ′.
  • reel group examples include 3-methylphenyl group, 4-methylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 4-octylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, and 4-pentyl.
  • the 1- or 2-alkenyl group also includes a cycloalkenyl group, such as an ethenyl group, a toppropenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2-pentenyl group.
  • a cycloalkenyl group such as an ethenyl group, a toppropenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2-pentenyl group.
  • -Pentenyl group 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 1-octenyl group, tricyclohexenyl group, 2-cyclohexenyl group and the like.
  • the substituents which may be present in these are the same as those described above.
  • organic halide represented by the above general formula: ⁇ having a substituted or unsubstituted aryl group as R 3 in the formula include:
  • 1-odo-4-octylbenzene 1-odo-4- (trifluoromethyl) benzene, 1-odo-4- (trifluoromethyloxy) benzene, 4-methyl methylbenzoate, 4 -Ethyl benzoate, 4-iodobenzo-2-trinole, 4-iodoacetophenone, 4-oxyfluorobenzene, 4-hydroxychlorobenzene, 2-iodobenzaldehyde, 3-iodobenzo Aldehyde, 4-odobenzaldehyde, 2-odopyridine, 3-odopyridine, 4-odopyridine, 2-odopyrimidine, 4-iodobiphenyl, 4-odo-4'-pentylbiphenyl , 1-odonaphthalene, 2-odonaphthalene, 3-odofuran, 2-odothiophene and the like.
  • Specific examples of the compound having a substituted or unsubstituted 1- or 2-alkenyl group as R 3 include 1-odo-1-propene, bromo-1-proben, 2-bromo-1-propene, and toluene- Tobutene, 1-odo-1-pentene, 1-odo-1-hexene, 1-odo-1-heptene, 1-odo-1-octene, 1-odo-tricyclohexene , / 3-odostyrene, 2-butane styrene, 2-odo-1-propene, 2-odo-1-butene, 1-bromo-1-pentene, tribromo-1-hexene, 1- Bromo-1-heptene, 1-bromo-1-octene, torodo-1-cyclohexene, 2-odo-1-hexene and the like can be mentioned.
  • Y 2 is a chlorine atom or a bromine atom. In this case, even if Y 2 is a chlorine atom, it is a feature of the second method of the present invention that the desired product is obtained with a high yield.
  • R 3 is the same as above, but the halogen atom as a substituent is limited to those having an atomic number smaller than Y 1 . Accordingly, specific examples of the organic halide represented by the above general formula [ ⁇ ] include benzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotolusolene, 2-chloroacetophenone, and 3-chloroacetophenone.
  • organic halide in which 3 is an alkenyl group examples include compounds in which an iodine atom is replaced with a bromine atom or a chlorine atom in the specific examples of the compound represented by the above general formula [ ⁇ ].
  • Examples of the Group 10 transition metal catalyst used in the first method of the present invention include Pd such as palladium tetrakis (triphenylphosphine), palladium benzalacetone complex, and palladium benzalacetone chloroform complex.
  • (0) complex aryl palladium chloride dimer, palladium chloride [1,2-bis (dicyclohexylphosphino) ethane: palladium chloride [bis (trisopropylphosphine)], palladium chloride: bis (t Licyclohexyl phosphine)], Pd (n) complexes such as phenyl palladium iodide bis (triphenyl phosphine palladium acetate), tetrakis (triphenyl phosphine) platinum and platinum chloride bis (triphenyl phosphine) Platinum complex such as, or tetrakis (triphenylphosphine) nickel, nickel chloride bis ( And a nickel complex such as refinylphosphine.
  • phosphine ligands include triphenylphosphine, tri-0-tolylphosphine, tris (2-furisole) phosphine, tributylphosphine, triethylphosphine, tricyclohexylphosphine, and 1,2-bis (dicyclophosphine).
  • Hexylphosphino) ethane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, triisopropylphosphine and the like can be used. It is preferable to use these Group 10 transition metal catalysts in an amount of from 0.2 to 5.0 mol per mol of the organic halide represented by the general formula [I].
  • the second method of the present invention is directed to a method having a trialkylphosphine ligand.
  • trialkylphosphine means phosphine trisubstituted with an arbitrary group selected from an alkyl group and a cycloalkyl group. However, these substituents may be the same or different.
  • alkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms, such as an ethyl group, an isopropyl group, a butyl group and a hexyl group. May be substituted.
  • cycloalkyl group examples include those having 3 to 8 carbon atoms, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. These may be substituted with the above-mentioned alkyl group.
  • two phosphorus atoms are bonded to the tri (cyclo) alkylphosphine ligand via a polymethylene group such as an ethylene group such as 1,2-bis (dicyclohexylphosphino) ethane. Diphosphine ligands are also included.
  • Tri (alkyl and ⁇ or cycloalkyl) phosphine ligands Group 10 transition metal catalysts containing palladium chloride [bis (triethylphosphine)], palladium chloride [bis (tripropylpropylphosphine)], palladium chloride [bis (tricyclohexylphosphine)], palladium chloride Pd (n) complexes such as [1,2-bis (dicyclohexylphosphino) ethane], platinum complexes such as platinum chloride [1,2-bis (dicyclohexylphosphino) ethane], or nickel chloride: 1,2-bis Nickel complexes such as (dicyclohexylphosphino) ethane] can be used.
  • an aryl chloride palladium dimer or palladium benzalacetone complex or the like can be used as a catalyst in combination with a tri (alkyl and Z or cycloalkyl) phosphine ligand.
  • the amount of the phosphine ligand used is about 1 to 5 times the molar amount of the transition metal catalyst.
  • the phosphine ligand triisopropyl phosphine, triethyl phosphine, tricyclohexyl phosphine, tributyl phosphine, 1,2-bis (dicyclohexyl phosphino) ethane and the like can be used.
  • Group 10 transition metal catalysts in an amount of from 0.2 to 5.0 mol% based on the organic halide represented by the general formula: W].
  • Examples of the base used in the first method of the present invention include sodium hydroxide, metal hydroxides such as a hydrating power, sodium carbonate, potassium carbonate, carbonates such as ammonium carbonate, ammonium hydroxide, and the like.
  • a hydroxide such as tetrabutylammonium hydroxide can be used, but an alkali metal hydroxide is preferred in terms of reaction efficiency, and sodium hydroxide is more preferred in terms of reaction efficiency and cost.
  • the amount used is in the range of an equivalent amount or an excess amount based on the organohalosilane represented by the general formula: I]. Although it can be used in a box, it is preferable to use a molar amount of 3.0 to 10 times.
  • fluoride salt used in the second method of the present invention examples include tris (ethylamino) sulfonium difluoro trimethylsilyl tris, tris (dimethylamino) sulfonium difluoro dimethyl trimethyl silicate, and tetrabutyl fluoride
  • fluoride salts such as ammonium and benzyltrimethylammonium fluoride
  • metal fluoride salts such as cesium fluoride and potassium fluoride.
  • the amount of the fluoride salt used can be a catalytic amount or an excess amount with respect to the stoichiometric amount, but it is 0.8 to 6.0 times the amount of the organohalosilane represented by the general formula [I]. It is preferred to use molar.
  • a solvent for example, tetrahydrofuran, dioxane, ether, benzene, toluene, acetone, ⁇ , ⁇ ′-dimethylformamide, dimethylsulfoxide, ⁇ -methylpyrrolidone, Hexamethylphosphoric acid triamide, acetate nitrile, ', ⁇ -dimethylimidazolidinone and the like can be used alone or in combination.
  • the reaction is preferably carried out in the range of 0 to 200 ° C, more preferably from room temperature to 150 ° C, which is convenient for the operation, and further preferably heated to 50 ° C or more from the viewpoint of reaction efficiency.
  • the method of the present invention is preferably performed in an inert gas atmosphere such as nitrogen or argon, and more preferably, the inside of the reaction system is replaced with an inert gas.
  • Example 1 Example 1
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration.
  • the aqueous layer was extracted with ethyl acetate (5 mix 2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate.
  • the aqueous layer was extracted with ethyl acetate (5 ml ⁇ 3), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate.
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml ⁇ 3), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate.
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration.
  • the aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate.
  • reaction solution is cooled to room temperature, and water (5 ml) And ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml ⁇ 3), the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate.
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml ⁇ 2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate.
  • the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration.
  • the aqueous layer was extracted with ethyl acetate (5nilx2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure.
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration.
  • the solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, the catalyst was filtered by celite filtration, the aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined.
  • reaction solution was cooled to room temperature, and under an argon atmosphere, 2-bromo-3-nitropyridine (78.6 mg, 0.39 mmol) and palladium chloride as a catalyst [bis (trihexylhexylphosphine)] (7.1 mg, lO ⁇ mol, 2.5 mol%), and the mixture was heated and stirred at 120 for 24 hours.
  • the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration.
  • the N-dimethylformamide suspension (1.4 ml) was cooled to 0 ° C, and dichloro (diphenyl) silane (165.Omg, 0.65mniol) was added dropwise, followed by stirring at 60 ° C for 3 hours.
  • the reaction solution was cooled to room temperature, and under an argon atmosphere, 2-chloro-3-dinitropyridine (86.7 mg, 0.55 mmol) and palladium chloride [bis (trisopropylphosphine)] (6.8 mg, U / i ol, 2.5 mol%), and the mixture was heated with stirring at 120 for 24 hours.
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate.
  • Example 40 Under an argon atmosphere, a suspension of potassium fluoride powder (140.5 mg, 2.42 fflinoO in N, N-dimethylformamide (1.0 ml)) was cooled to 0 ° C, and dichloro ( After diphenyl) silane (122.2 mg, 0.48 mrao 1) was added dropwise, the mixture was stirred at 60 ° C. for 3 hours. The reaction solution was cooled to room temperature, and under argon atmosphere, 4-chlorobiphenyl (76.
  • the ⁇ -dimethylformamide suspension (1.4 ml) was cooled to 0 ° C, and dichloro (diphenyl) silane (165.Omg, 0.65mmol) was added dropwise, followed by stirring at 60 ° C for 3 hours.
  • the reaction solution is cooled to room temperature, and under an argon atmosphere, 4-bromobiphenyl (124.9 mg, 0.54 raol) and palladium chloride [bis (tricyclohexylphosphine)] (9.9 mg, 13 mol, 2.5 mol! 3 ⁇ 4) as a catalyst.
  • the mixture was heated and stirred at 120 for 24 hours.
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml ⁇ 2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate.
  • potassium fluoride powder (203.5mg, 3.50 ol)
  • potassium fluoride powder (252.0mg, 4.34mniol) ⁇ '
  • the ⁇ -dimethylformamide suspension (1.8 ml) was cooled to 0, and dichloro (diphenyl) silane (220 ⁇ Omg, 0.87 marl) was added dropwise, followed by stirring at 60 for 3 hours.
  • the reaction solution was cooled to room temperature, and under an argon atmosphere, 3-acetoamide-2-chloropyridine (123.3 mg, 0.72 mmol) and palladium chloride [bis (triisopropylphosphine)] (18. Omg, 36 mol , 5.0 mol 53 ⁇ 4), and the mixture was heated with stirring at 120 for 90 hours.
  • the N-dimethylformamide suspension (1.5 ml) was cooled to 0 ° C, and dichlorodi (4-trifluoromethylphenyl) silane (276.lmg, 0.71 nmol) was added dropwise. Stirred for hours.
  • the reaction solution was cooled to room temperature, and under argon atmosphere, 2-chloro-3-dinitropyridine (94.Omg, 0.59 marl) and palladium chloride [bis (triisopropylphosphine)] (7.4 mg, 15 mg) as a catalyst. // ⁇ 1,2.5 ⁇ 1%), and heated and stirred at 120 for 60 hours.
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml ⁇ 2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate.
  • reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate.
  • the reaction solution was cooled to room temperature, and under an argon atmosphere, 2-bromopyridine (91.lmg, 0.58 mol) and palladium chloride [bis (trisopropylphosphine)] as a catalyst (15.4 mg, 31jumol, 5.4 mol%), and the mixture was heated and stirred at 120 to 60 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration.

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Abstract

A process whereby organic compounds, such as biaryls or alkenylallenes, which are useful as functional organic materials such as liquid crystals, drugs or pesticides can be efficiently synthesized in a short step. This process comprises reacting organic halosilanes with organic halides in the presence of a base or in the presence of a catalyst of a transition metal of the group (10) having a trialkylphosphine ligand and a fluoride to thereby give unsaturated organic compounds represented by the following general formula: R1-R3, wherein R1 represents optionally substituted aryl, optionally substituted alkenyl or optionally substituted alkyl; and R2 represents optionally substituted aryl, optionally substituted 1-alkenyl or optionally substituted 2-alkenyl.

Description

明 細 書 不飽和有機化合物の製造方法 技術分野  Description Method for producing unsaturated organic compounds

本発明は液晶などの機能性有機材料、 医薬または農薬等として有 用なビアリール類およびアルケニルァレーン類などの有機化合物を- 第 10族遷移金属触媒存在下に、 有機ハロシラン類と有機ハロゲン化 物とを反応させて製造する方法に関する。 背景技術  The present invention relates to the use of organic halosilanes and organic halides in the presence of functional organic materials such as liquid crystals, and organic compounds such as biaryls and alkenylarenes useful as pharmaceuticals or agricultural chemicals in the presence of a Group 10 transition metal catalyst. And a method for producing by reacting Background art

本発明によって得られる有機化合物のうち、 ビアリール類は液晶 およびその中間体として ["液晶 基礎編"培風館（1985)p232]または 医農薬の合成中間体として [ "The Organic Chemistry of Drug Synthesis"Vols. 1 -3, Wi ley- Intersc ience, New York( 1977- 1984) . 有用な化合物である。 また、 本発明により得られる 1, 3-アルカジエ ン類およびアルケニルアレーン類は合成高分子の原料として工業的 に重要な化合物である ["The Chemistry of Alkene, Vol. 2, p411, Wiley, New York( 1970) o したがって、 それらの簡便かつ経済的な 製造法は工業的に極めて重要である。 Among the organic compounds obtained by the present invention, biaryls are used as liquid crystals and intermediates thereof ["Basic Liquid Crystal", Baifukan (1985) p232] or as intermediates for synthesis of medicinal and agricultural chemicals ["The Organic Chemistry of Drug Synthesis" Vols. 1-3, Wiley-Interscience, New York (1977-1984). The 1,3-alkadienes and alkenylarenes obtained by the present invention are industrially important compounds as raw materials for synthetic polymers ["The Chemistry of Alkene, Vol. 2, p411, Wiley, New York" (1970) o Therefore, their simple and economical production methods are of great industrial importance.

ハロゲン化ァリ一ルを原料としてビアリ一ル類を製造する方法と しては、 ①遷移金属触媒存在下、 ァリールグリニャール反応剤を塩 化ァリールと反応させる方法： J. Organomet. Chem. , 118, 349( 1976；; J. Chem. Soc. , Chem. Commun. , 1984, 511 Synthesis, 1990, 147. 、 ②遷 移金属触媒存在下、 ァリールホウ素化合物と塩化ァリールを反応さ せる方法 [Tetrahedron Lett. , 32, 2273( 1991 ) ]、 ③ニッケル錯体存 在下、 臭化ァリールと塩化ァリールを反応させる方法 [Tetrahedron Lett.， 29, 545 ( 1988) ]が知られている。 The methods for producing biaryls from aryl halides as raw materials include: (1) a method in which an aryl grignard reactant is reacted with aryl chloride in the presence of a transition metal catalyst: J. Organomet. Chem., 118, 349 (1976 ;; J. Chem. Soc., Chem. Commun., 1984, 511 Synthesis, 1990, 147.) ②Reaction between aryl borane compound and aryl chloride in the presence of a transition metal catalyst. , 32, 2273 (1991)], and ③ a method of reacting aryl bromide with aryl chloride in the presence of a nickel complex [Tetrahedron Lett., 29, 545 (1988)].

また、 ハロゲン化ァリ一ルを用いてアルケニルアレーンを製造す る方法としては、 ④遷移金属触媒存在下、 アルケニルグリニャール 反応剤を塩化ァリールと反応させる方法 [Tetrahedron Let t.， 1975, 1719 ] などがある。  Methods for producing alkenyl arenes using aryl halides include ④ a method of reacting an alkenyl Grignard reagent with aryl chloride in the presence of a transition metal catalyst [Tetrahedron Lett., 1975, 1719], etc. There is.

さらに、 本発明と同様に有機ゲイ素化合物を用いたビアリール類 の製造法として、 ⑤ァリール（ノヽ口）シランとハロゲン化ァリールを フッ化物塩およびパラジウム触媒の存在下、 反応させる方法 [特開 平 6-239766 ]が知られている。 また、 有機ゲイ素化合物を用いた 1， 3 -アルカジエン誘導体およびアルケニルアレーン類の製造法として、 ⑥アルケニル（ハ口）シランとハロゲン化ァリ一ルをフッ化物塩およ びパラジウム触媒の存在下、 反応させる方法〔特開平 1 - 226831 ]が知 られている。  Further, in the same manner as in the present invention, as a method for producing biaryls using an organic gayne compound, a method of reacting a aryl (no-opening) silane with a halogenated aryl in the presence of a fluoride salt and a palladium catalyst [Japanese Patent Application Laid-Open No. HEI 9-284207]. 6-239766] is known. In addition, as a method for producing 1,3-alkadiene derivatives and alkenylarenes using an organic gayne compound, alkenyl (haguchi) silane and aryl halide are prepared in the presence of a fluoride salt and a palladium catalyst. A reaction method [Japanese Patent Laid-Open No. 1-26831] is known.

これらの方法のうち、 ①の方法は、 一般に、 塩化ァリールとの反 応の収率が 30 %以下と低いうえ、 ホモカツプリング反応に由来する 対称ビアリール類が副生するという欠点がある。 ②の方法は収率が 低く、 30 %以下である。 ③の方法は重金属であるニッケルを化学量 論量必要とするうえ、 対称ビアリール類が大量に副生するという欠 点がある。 ④の方法は収率が 20 %以下と低い。 ⑤および⑥の方法で は高価なフッ化物塩を化学量論量必要とするほか、 塩化ァリールを 原料として用いた場合、 必ずしも満足すべき結果が得られない。 発明の開示 Of these methods, the method (1) has the disadvantages that the yield of the reaction with aryl chloride is generally low at 30% or less, and that symmetric biaryls derived from the homocoupling reaction are by-produced. The method (2) has a low yield of 30% or less. The method (3) requires a stoichiometric amount of nickel, which is a heavy metal, and has the disadvantage that a large amount of symmetric biaryls are by-produced. Method (2) has a low yield of 20% or less. In the methods (1) and (2), a stoichiometric amount of expensive fluoride salt is required, and satisfactory results are not always obtained when aryl chloride is used as a raw material. Disclosure of the invention

本発明はかかる問題を有しない、 不飽和有機化合物の簡便かつ経 済的な製造法を提供することを目的とする。  An object of the present invention is to provide a simple and economical method for producing an unsaturated organic compound which does not have such a problem.

本発明者らは不飽和有機化合物の効率的かつ工業的に適用可能な 製造法につき検討を加えた結果、 有機ハロシラン類を第 10族遷移金 属触媒および水酸化ナ卜リゥ厶をはじめとする塩基の存在下で有機 ハロゲン化物と反応させることにより、 不飽和有機化合物がー段階 かつ良好な収率で得られること、 および、 有機ハロシラン類を特定 ホスフィン配位子をもつ第 10族遷移金属触媒およびフッ化物塩の存 在下で有機ハロゲン化物と反応させることにより、 不飽和有機化合 物が一段階かつ良好な収率で得られることを見いだし本発明を完成 した。  The present inventors have studied an efficient and industrially applicable method for producing unsaturated organic compounds, and as a result, have found that organic halosilanes include a Group 10 transition metal catalyst and sodium hydroxide. By reacting with an organic halide in the presence of a base, an unsaturated organic compound can be obtained in one step and in a good yield.Organohalosilanes are specified.Group 10 transition metal catalyst having a phosphine ligand The present inventors have found that an unsaturated organic compound can be obtained in one step and in a good yield by reacting with an organic halide in the presence of a fluoride salt.

すなわち本発明は、 下記一般式 [ I ]  That is, the present invention provides the following general formula [I]

R'-S i R2 mX3-m [ I ] R'-S i R 2 m X 3 - m [I]

(式中、 は、 置換もしくは未置換のァリール基、 置換もしくは未 置換のアルケニル基、 または置換もしくは未置換のアルキル基を表 す。 R2は、 R1と同一であるか、 または低級アルキル基を表す。 Xは ハロゲン原子を表し、 mは 0から 2までの整数を表す。 ただし、 が アルキル基である場合には mは 0である。 ）で表される有機ハロシラ ン類と、 下記一般式〔H ] (In the formula, represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkyl group. R 2 is the same as R 1 , or a lower alkyl group X represents a halogen atom, and m represents an integer from 0 to 2. However, when is an alkyl group, m is 0.) and an organic halosilane represented by the following general formula: Formula [H]

R3-Y， [ H ] R 3 -Y, [H]

(式中、 R3は、 置換もしくは未置換のァリール基、 置換もしくは未 置換の 1 -アルケニル基、 または置換もしくは未置換の 2-アルケニル 基を表し、 Y'はハロゲン原子を表す。 ）で表される有機ハロゲン化 物とを、 第 10族遷移金属触媒および塩基の存在下に反応させること を特徴とする、 下記一般式 [n] (Wherein, R 3 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted 1-alkenyl group, or a substituted or unsubstituted 2-alkenyl group, and Y ′ represents a halogen atom.) Reacting with a halogenated organic halide in the presence of a Group 10 transition metal catalyst and a base. The following general formula [n]

R，-R3 [I] R, -R 3 [I]

(式中、 および R3は前記と同一の意味を表す。 ）で表される不飽和 有機化合物の製造方法に関する。 (Wherein, and R 3 have the same meanings as described above.)

また、 本発明は下記一般式 [ I ] Further, the present invention provides the following general formula [I]

Figure imgf000006_0001
Figure imgf000006_0001

(式中、 R 1は、 置換もしくは未置換のァリール基、 置換もしくは未 置換のアルケニル基、 または置換もしくは未置換のアルキル基を表 す。 R2は、 R1と同一であるか、 または低級アルキル基を表す。 Xは ハロゲン原子を表し、 01は 0から 2までの整数を表す。 ただし、 R 1が ァルキル基である場合には mは 0である。 ）で表される有機ハロシラ ン類と、 下記一般式 [IV ](Wherein, R 1 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkyl group. R 2 is the same as R 1 , or lower. Represents an alkyl group, X represents a halogen atom, and 01 represents an integer from 0 to 2. However, when R 1 is an alkyl group, m is 0.) And the following general formula [IV]

Figure imgf000006_0002
Figure imgf000006_0002

(式中、 R3は、 置換もしくは未置換のァリール基、 置換もしくは未 置換の 1 -アルケニル基、 または置換もしくは未置換の 2-アルケニル 基を表す。 Y2は、 塩素原子、 または臭素原子を表す。 で表される 有機塩化物とを、 トリアルキルホスフィン配位子をもつ第 10族遷移 金属触媒およびフッ化物塩の存在下に反応させることを特徴とする, 下記一般式 [ = (Wherein, R 3 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted 1-alkenyl group, or a substituted or unsubstituted 2-alkenyl group. Y 2 represents a chlorine atom or a bromine atom. Characterized by reacting with an organic chloride represented by the following in the presence of a Group 10 transition metal catalyst having a trialkylphosphine ligand and a fluoride salt,

R，-R3 [ 1； R, -R 3 [1;

(式中、 R 1および は前記と同一の意味を表す。 〕で表される不飽和 有機化合物の製造方法に関する。 本発明における前記一般式： I ]で表される有機ハロシラン類にお いて、 Xはハロゲン原子を表すが、 とくにフッ素原子および塩素原 子が好適に用いられ、 塩素原子が安価な点でより好ましい。 (Wherein, R 1 and have the same meanings as described above.) A method for producing an unsaturated organic compound represented by the formula: In the present invention, the organic halosilanes represented by the general formula: I] X represents a halogen atom, especially a fluorine atom and a chlorine atom A chlorine atom is preferably used, and a chlorine atom is more preferable in that it is inexpensive.

前記一般式 [ I ]で表される有機ハロシラン類のうち、 R'および Z または R2として置換もしくは未置換のァリ一ル基をもつァリ一ル（ ハロ）シランは芳香族金属化合物とクロロシランとを反応させる方 法 [Synthesis, 841(1979) ]により容易に合成できる上に、 種々のも のが工業的に入手容易である。 この置換もしくは未置換のァリ一ル 基とはへテロァリ一ル基をも包含し、 ァリール基の置換基としては、 例えばフッ原子で置換されていてもよいアルキル基、 シクロアルキ ル基、 アルコキシ基、 アルコキシカルボニル基、 ァシル基、 および ァリール基； シァノ基、 ホルミル基、 ニトロ基、 トリ（低級アルキ ノレ）シリル基、 ならびにフッ素原子等から選ばれる 1個以上の基であ り、 これらのうち置換しうるものについては、 さらに例えば上記の 置換基で置換されていてもよい。 Among the organic halosilanes represented by the general formula [I], aryl (halo) silane having a substituted or unsubstituted aryl group as R ′ and Z or R 2 is an aromatic metal compound and In addition to being easily synthesized by a method of reacting with chlorosilane [Synthesis, 841 (1979)], various types are easily available industrially. The substituted or unsubstituted aryl group also includes a heteroaryl group. Examples of the substituent of the aryl group include an alkyl group, a cycloalkyl group, and an alkoxy group which may be substituted with a fluorine atom. , An alkoxycarbonyl group, an acyl group, and an aryl group; one or more groups selected from a cyano group, a formyl group, a nitro group, a tri (lower alkynole) silyl group, and a fluorine atom; Those that can be further substituted, for example, with the above substituents.

置換もしくは未置換のァリール基として、 具体的には、 フヱニル 基、 2-メチルフヱニル基、 3-メチルフ ニル基、 4-メチルフヱニル 基、 4-ェチルフヱニル基、 4-プロピルフヱニル基、 4-ブチルフエ二 ル基、 4-ペンチルフヱニル基、 4-へキシルフヱニル基、 4-ヘプチル フエニル基、 4-ォクチルフヱニル基、 2-メ トキシフ丄ニル基、 3-メ トキシフヱニル基、 4-メ トキシフヱニル基、 4-ェ卜キシフヱニル基、 4-プロポキシフヱニル基、 4-ブトキシフヱニル基、 4-ペンチルォキ シフヱニル基、 3-シァノフヱニル基、 4-シァノフエ二ル基、 3-二卜 ロフヱニル基、 4-ニトロフヱニル基、 4-ホルミルフヱニル基、 4-メ トキシカルボニルフヱニル基、 4-ェトキシカルボニルフヱニル基、 4-ァセチルフエニル基、 4-フルオロフヱニル基、 3, 4-ジフルオロフ ヱニル基、 2-フルォ口- 4-メチルフヱニル基、 2-フルォロ -4-ペンチ ルフヱニル基、 3-フルォロ- 4-ペンチルフヱニル基、 2-フルォロ -4- (4-ペンチルシク口へキシル）フヱニル基、 3-フルォ口- 4- (4-ペンチ ルシクロへキシル）フエニル基 、 4 -トリフルォロメチルフヱニル基、 3， 4-ジトリフルォロメチルフヱニル基、 4-ペン夕フルォロェチルフ ヱニル基、 4-卜リフルォロメチルォキシフヱニル基、 4-ペンタフル ォロェチルォキシフヱニル基、 4-シクロへキシルフヱニル基、 4-(4 -シク口へキシルシク口へキシル）フヱニル基、 4-(4-プロピルシク 口へキシル）フヱニル基、 4- (4-ペンチルシク口へキシル）フヱニル 基、 4-(4-プロビルシクロへキシル）シクロへキシルフヱニル基、 4- (4-ペンチルシクロへキシル）シクロへキシルフヱニル基、 ビフエ二 ル基、 3' -メチルビフエニル基、 4' -メチルビフヱニル基、 4' -ペン チルビフヱニル基、 3' -フルォロビフエ二ル基、 4' -フルォロビフエ ニル基、 3' , 4' -ジフルォロビフヱニル基、 2-フルォロ -4' -ペンチル ビフヱニル基、 3-フルォロ -4' -ペンチルビフヱニル基、 4-(4-プロ ビルシクロへキシル）ビフヱニル基、 ナフチル基、 4-メチルナフチ ル基、 6-ペンチルナフチル基、 6-シクロペンチルナフチル基、 2-ピ リジル基、 3-ピリジル基、 4-へキシル -2-ピリジル基、 2-ピリ ミジ ル基、 2-フリル基、 5-ペンチル- 3-フリル基、 2-チェ二ル基等を例 示することができる。 Examples of the substituted or unsubstituted aryl group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentyl phenyl, 4-hexyl phenyl, 4-heptyl phenyl, 4-octyl phenyl, 2-methoxy phenyl, 3-methoxy phenyl, 4-methoxy phenyl, 4-methoxy phenyl, 4 -Propoxyphenyl, 4-butoxyphenyl, 4-pentyloxyphenyl, 3-cyanophenyl, 4-cyanophenyl, 3-dimethoxy, 4-nitrophenyl, 4-formylphenyl, 4-methyl Toxylcarbonyl, 4-ethoxycarbonyl, 4-acetylphenyl, 4-fluorophenyl, 3,4-difluorophenyl Zinyl, 2-fluoro-4-methylphenyl, 2-fluoro-4-pent Fluorinyl, 3-fluoro-4-pentylphenyl, 2-fluoro-4- (4-pentylcyclohexyl) phenyl, 3-fluoro-4- (4-pentylcyclohexyl) phenyl, 4-trifuryl Fluoromethylphenyl group, 3,4-ditrifluoromethylphenyl group, 4-pentafluoromethylphenyl group, 4-trifluoromethyloxyphenyl group, 4-pentafluoroethyl Oxyphenyl, 4-cyclohexylphenyl, 4- (4-hexylhexylhexyl) phenyl, 4- (4-propylcyclohexyl) phenyl, 4- (4-pentylcyclyl) Hexyl) phenyl group, 4- (4-propylcyclohexyl) cyclohexylphenyl group, 4- (4-pentylcyclohexyl) cyclohexylphenyl group, biphenyl group, 3'-methylbiphenyl group, 4 ' -Methylbiphenyl group, 4'-pe 3'-Fluorobiphenyl, 3 ', 4'-Difluorobiphenyl, 2-Fluoro-4'-pentylbiphenyl, 3-Fluoro-4' -Pentylbiphenyl, 4- (4-propylcyclohexyl) biphenyl, naphthyl, 4-methylnaphthyl, 6-pentylnaphthyl, 6-cyclopentylnaphthyl, 2-pyridyl, 3-pyridyl Groups, 4-hexyl-2-pyridyl group, 2-pyrimidyl group, 2-furyl group, 5-pentyl-3-furyl group, 2-phenyl group and the like.

上記ァリール（ハ口）シランの具体例としては、 たとえばクロ口（ ジメチル）（フヱニル）シラン、 ジクロロ（メチル）（フエニル）シラン、 ジクロロ（ェチル）（フエニル）シラン、 トリクロ口（フエニル）シラン、 ジクロロ（ジフエニル）シラン、 クロロ（メチル）（ジフエニル）シラン、 ジクロロ（ェチル）（2-メチルフエニル）シラン、 ジクロロ（ェチル）（3 -メチルフエニル）シラン、 ジクロロジ（3-メチルフヱニル）シラン、 ジクロロ（ェチル）（4-メチルフヱニル）シラン、 ジクロロジ（4-メチ ルフヱニル）シラン、 クロロ（ジメチル）（4-ペンチルフヱニル）シラ ン、 ジクロロ（メチル）（4-ペンチルフヱニル）シラン、 ジクロロ（ェ チル）（4-ペンチルフヱニル）シラン、 ェチル（ジフルォロ）（4-ペンチ ルフヱニル）シラン、 フルォロ（ジメチル）（4-ペンチルフヱニル）シ ラン、 ジフルォロ（メチル）（4-ペンチルフヱニル）シラン、 トリクロ 口（4-ペンチルフヱニル）シラン、 クロロ（ジメチル）（4-プロピルフ ェニル）シラン、 ジクロロ（メチル）（4-プロピルフヱニル）シラン、 ジクロロ（ェチル）（4-プロピルフヱニル）シラン、 ェチル（ジフルォ 口）（4-プロピルフエニル）シラン、 フルォロ（ジメチル）（4-プロピル フエニル）シラン、 ジフルォロ（メチル）（4-プロピルフヱニル）シラ ン、 ジクロロ（メチル）（4-ォクチルフヱニル）シラン、 クロ口（ジメ チル）（4-ォクチルフエニル）シラン、 ジクロロ（ェチル）（4-ォクチル フエニル）シラン、 ジクロロ（ェチル）（2-メ トキシフヱニル）シラン、 ジクロロ（ェチル）（3-メ 卜キシフヱニル）シラン、 ジクロロジ（3-メ トキシフヱニル）シラン、 ジクロロ（ェチル）（4-メ トキシフヱ二ル） シラン、 ジクロロジ（4-メ トキシフエニル）シラン、 ジクロロジ（3- フルオロフヱニル）シラン、 ジクロロジ（2-フルォロ- 4-メチルフェ ニル）シラン、 クロ口（ジメチル） [3-フルォ口- 4-(4-ペンチルシクロ へキシル）フヱニル]シラン、 ジクロロ（メチル） [3-フルォロ -4-(4- ペンチルシク口へキシル）フヱニノ シラン、 ジクロロ（ェチル） [3- フルォ口- 4- (4-ペンチルシク口へキシル）フヱニル]シラン、 ジクロ 口ジ（4-卜リフルォロメチルフヱニル）シラン、 クロロ（ジメチル J :4 -(4-プロピルシク口へキシル）フヱニル]シラン、 ジクロロ（ェチル） :4- (4-プロビルシクロへキシル）フヱニル：シラン、 ジクロロ（メチ ル） [4- (4-ペンチルシク口へキシル）フエニル]シラン、 4-クロ口（ジ メチル）シリル- 4' -ペンチルビフエニル、 4-ジクロロ〔メチル）シリ ル -4' -ペンチルビフヱニル、 4-ジクロロ（ェチル）シリル -4' -ペンチ ルビフエニル、 4-ジクロロ（ェチル）シリル- 2-フルォロ -4' -ペンチ ノレビフヱニル、 4-クロ口（ジメチル）シリノレ- 2-フルォロ -4' -ペンチ ルビフヱニル、 4-ジクロロ（ェチル）シリノレ- 3-フルォロ -4' -ペンチ ルビフヱニル、 ジクロロ（メチル） [4- (4-ペンチルシク口へキシル） シク口へキシルフヱニル]シラン、 ジクロロ（ェチル^ 4- (4-ペンチ ルシク口へキシル）シク口へキシノレフヱニル]シラン、 クロ口（ジメ チル） [4- (4-ペンチルシク口へキシル）シク口へキシルフヱニル]シ ラン等を挙げることができる。 Specific examples of the above aryl (c) silane include, for example, chloro (dimethyl) (phenyl) silane, dichloro (methyl) (phenyl) silane, dichloro (ethyl) (phenyl) silane, trichloro (phenyl) silane, dichloro (Diphenyl) silane, chloro (methyl) (diphenyl) silane, dichloro (ethyl) (2-methylphenyl) silane, dichloro (ethyl) (3-methylphenyl) silane, dichlorodi (3-methylphenyl) silane, Dichloro (ethyl) (4-methylphenyl) silane, dichlorodi (4-methylphenyl) silane, chloro (dimethyl) (4-pentylphenyl) silane, dichloro (methyl) (4-pentylphenyl) silane, dichloro (ethyl) (4 -Pentylphenyl) silane, ethyl (difluoro) (4-pentylphenyl) silane, fluoro (dimethyl) (4-pentylphenyl) silane, difluoro (methyl) (4-pentylphenyl) silane, trichloro (4-pentylphenyl) silane, chloro (Dimethyl) (4-propylphenyl) silane, dichloro (methyl) (4-propylphenyl) silane, dichloro (ethyl) (4-propylphenyl) silane, ethyl (difluoro mouth) (4-propylphenyl) silane, fluoro (dimethyl) ) (4-Propylphenyl) silane Difluoro (methyl) (4-propylphenyl) silane, dichloro (methyl) (4-octylphenyl) silane, chloro (dimethyl) (4-octylphenyl) silane, dichloro (ethyl) (4-octylphenyl) silane, dichloro ( Ethyl) (2-methoxyphenyl) silane, dichloro (ethyl) (3-methoxyphenyl) silane, dichlorodi (3-methoxyphenyl) silane, dichloro (ethyl) (4-methoxyphenyl) silane, dichlorodi (4- Methoxyphenyl) silane, dichlorodi (3-fluorophenyl) silane, dichlorodi (2-fluoro-4-methylphenyl) silane, chloro (dimethyl) [3-fluoro-4- (4-pentylcyclohexyl) phenyl] silane , Dichloro (methyl) [3-fluoro-4- (4-pentylcyclylhexyl) phenylinosilane, Chloro (ethyl) [3-fluoro-4- (4-pentylcyclyl hexyl) phenyl] silane, dichloro di (4-trifluoromethylphenyl) silane, chloro (dimethyl J: 4--(4 -Propylcyclohexyl) phenyl] silane, dichloro (ethyl): 4- (4-propylcyclohexyl) phenyl: silane, dichloro (methyl) ) [4- (4-pentylcyclylhexyl) phenyl] silane, 4-chloro (dimethyl) silyl-4'-pentylbiphenyl, 4-dichloro [methyl] silyl-4'-pentylbiphenyl 4-dichloro (ethyl) silyl-4'-pentylbiphenyl, 4-dichloro (ethyl) silyl-2-fluoro-4'-pentylnorebifnil, 4-chloro (dimethyl) silinole-2-fluoro-4'-pentyl Rubiphenyl, 4-dichloro (ethyl) silinole-3-fluoro-4'-pentylbiphenyl, dichloro (methyl) [4- (4-pentylcyclohexyl) cyclohexylphenyl] silane, dichloro (ethyl ^ 4- (4 -Pentyl hexyl) hexyl hexinolephenyl] silane, and black (dimethyl) [4- (4-pentyl hexyl) hexyl hexyl phenyl] silane.

前記一般式 [ I ]で表される有機ハロシラン類のうち、 R1および Z または R2として、 置換もしくは未置換のアルケニル基をもつアルケ ニル（ハ口）シラン、 および置換もしくは未置換のアルキル基をもつ アルキル（ハ口）シランは、 白金触媒を用いるアルキン類またはアル ゲン類のヒ ドロシリル化反応 [Organometal lics, 1, 355( 1982) ]をは じめとする種々の ¾法 LS. Paulenko, "Organosilicon Chemistry , Walter de Gruyter, New York( 1986)〕により容易に合成できるほか、 工業的にも種々の構造のものが入手容易である。 Among the organic halosilanes represented by the general formula [I], R 1 and Z or R 2 represent an alkenyl (haguchi) silane having a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkyl group Alkyl (haguchi) silanes with various methods, including a platinum-catalyzed hydrosilylation reaction of alkynes or argens [Organometallics, 1, 355 (1982)], can be used in various methods LS. Paulenko, "Organosilicon Chemistry, Walter de Gruyter, New York (1986)], and those having various structures are easily available industrially.

一般式： I ]の R1または R2の置換もしくは未置換のアルケニル基は シクロアルケ二ル基をも包含し、 具体的には、 ェテニル基、 1 -プロ ぺニル基、 1 -ブテニル基、 1 -ペンテニル基、 1 -へキセニル基、 2-へ キセニル基、 1 -ヘプテニル基、 1 -ォクテニル基、 5-ォクテニル基、 2 -フエニルェテニル基、 1 -シク口へキセニル基等を挙げることがで きる。 その置換基としては、 上記のものが挙げられる。 アルケニル（ハ口）シランの具体例としては、 たとえばジクロロ（ ェテニル）（メチル）シラン、 クロロ（ェテニル）（ジメチル）シラン、 ジクロロ（メチル）（1-プロぺニル）シラン、 クロロ（ジメチル）（1-プ ロぺニル）シラン、 （卜ブテニル）（ジクロ口）（メチル）シラン、 （1-ブ テニル）（クロ口）（ジメチル）シラン、 ジクロロ（メチル）（1-ペンテ二 ル）シラン、 クロ口（ジメチル）（1-ペンテニル）シラン、 ジクコ口（1- へキセニル）（メチル）シラン、 クロロ（1-へキセニル）（ジメチル）シ ラン、 クロ口（2-へキセニル）（ジメチル）シラン、 ジクロロ（1-ヘプ テニル）（メチル）シラン、 クロ口（1-ヘプテニル）（ジメチル）シラン、 ジクロロ（1-ォクテニル）（メチル）シラン、 ジクロロ（5-ォクテン- 1- ィル）（メチル）シラン、 クロロ（1-ォクテニル）（ジメチル）シラン、 ジクロロ（メチル）（2-フヱニルェテニル）シラン、 ジクロロ（メチル） (2-フヱニルェテニル）シラン、 クロロ（ジメチル）（2-フヱニルェテ ニル）シラン、 ジクロロ（1-シクロへキセニル）（メチル）シラン、 ジ フルォロ（メチル）（卜プロぺニル）シラン、 フルォロ（ジメチル）（1- プロぺニル）シラン、 （1-ブテニル）（ジフルォロ）（メチル）シラン、 （ 1-ブテニル）（フルォロ）（ジメチル）シラン等を挙げることができる。 The substituted or unsubstituted alkenyl group for R 1 or R 2 in the general formula: I] also includes a cycloalkenyl group, and specifically includes an ethenyl group, a 1-propenyl group, a 1-butenyl group, -Pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 1-octenyl group, 5-octenyl group, 2-phenylenyl group, 1-cyclohexenyl group, and the like. . Examples of the substituent include those described above. Specific examples of alkenyl (c) silane include, for example, dichloro (ethenyl) (methyl) silane, chloro (ethenyl) (dimethyl) silane, dichloro (methyl) (1-propenyl) silane, chloro (dimethyl) (1 -Propenyl) silane, (butenyl) (dichloro) (methyl) silane, (1-butenyl) (chloro) (dimethyl) silane, dichloro (methyl) (1-pentenyl) silane, chloro Methyl (dimethyl) (1-pentenyl) silane, Dixco (1-hexenyl) (methyl) silane, Chloro (1-hexenyl) (dimethyl) silane, Chloro (2-hexenyl) (dimethyl) silane, Dichloro (1-heptenyl) (methyl) silane, Clo (1-heptenyl) (dimethyl) silane, Dichloro (1-octenyl) (methyl) silane, Dichloro (5-octene-1-y) ) (Methyl) silane, chloro (1-octenyl) (dimethyl) silane, dichloro (methyl) (2-phenylethenyl) silane, dichloro (methyl) (2-phenylethenyl) silane, chloro (dimethyl) (2-phenylethenyl) silane , Dichloro (1-cyclohexenyl) (methyl) silane, difluoro (methyl) (topropropenyl) silane, fluoro (dimethyl) (1-propenyl) silane, (1-butenyl) (difluoro) (methyl ) Silane, (1-butenyl) (fluoro) (dimethyl) silane and the like.

R1として置換もしくは未置換のアルケニル基を有するアルケニル (ハ口）シランのうち、 卜もしくは 2-アルケニル基をもつアルケニル ( 、口）シランが反応効率の点で好ましい。 Of the alkenyl (c) silanes having a substituted or unsubstituted alkenyl group as R 1 , the alkenyl (a, c) silane having a tri- or 2-alkenyl group is preferred in view of the reaction efficiency.

一般式 [ I ]の R'のうち、 置換もしぐは未置換のアルキル基として は、 炭素数 1〜10の直鎖状もしくは分岐状のアルキル基が挙げられ、 その具体例として、 メチル基、 ェチル基、 プロピル基、 ブチル基、 イソブチル基、 ペンチル基、 ネオペンチル基、 へキシル基、 ォクチ ル基、 ノニル基、 およびデシル基等を挙げることができる。 その置 換基としては、 上記のものが挙げられる。 Among R ′ in the general formula [I], examples of the substituted or unsubstituted alkyl group include a linear or branched alkyl group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, Examples include ethyl group, propyl group, butyl group, isobutyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, and decyl group. That place Examples of the substituent include those described above.

アルキル（ハ口）シランの具体例としてはトリクロ口（メチル）シラ ン、 トリクロ口（ェチル）シラン、 トリクロ口（プロピル）シラン、 ブ チル（トリクロ口）シラン、 トリクロ口（イソブチル シラン、 トリク ロロ（ペンチル）シラン、 卜リクロロ（へキシル）シラン、 トリクロ口 (シァノブチル）シラン、 トリクロロ（2-フヱニルェチル）シラン等を 例示することができる。  Specific examples of alkyl (c) silanes include trichloro (methyl) silane, trichloro (ethyl) silane, trichloro (propyl) silane, butyl (triclo) silane, and trichloro (isobutyl silane, trichloro ( Pentyl) silane, trichloro (hexyl) silane, trichloro (cyanobutyl) silane, trichloro (2-phenylethyl) silane and the like can be exemplified.

また、 一般式 [ I ]の R2の低級アルキル基とは、 炭素数 1 ~ 6の直鎖 状もしくは分岐状のアルキル基を意味し、 メチル基、 ェチル基、 プ 口ピル基、 ブチル基、 イソブチル基、 ペンチル基、 ネオペンチル基、 へキシル基等を挙げられる Further, the lower alkyl group of R 2 in the general formula [I] means a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, Isobutyl group, pentyl group, neopentyl group, hexyl group, etc.

他方の原料である前記一般式 [ Π ]で表される有機ハロゲン化物は 容易に合成でき、 かつ工業的に入手容易な化合物である。 式中、 Y 1 はハロゲン原子であり、 塩素原子、 臭素原子、 ヨウ素原子が望まし い。 R3は置換もしくは未置換のァリール基または 1 -もしくは 2-アル ケニル基である。 ァリ一ル基としてはへテロァリ一ル基をも包含し、 フエニル基、 ビフヱニル基、 ナフチル基、 ピリジル基、 ピリ ミジル 基、 フリル基、 チェニル基、 ピロリル基等を挙げることができ、 そ の置換基としては、 炭素数 1〜10の直鎖状もしくは分岐状のアルキ ル基もしくはアルコキシ基、 ジ低級アルキルアミノ基、 シァノ基、 Y 1よりも原子番号の小さいハロゲン原子、 ァシル基、 ァシルァミノ 基、 アミ ノ基、 ァリール基、 カルボニル基、 カルボキシル基、 二卜 口基、 シクロアルキル基、 シクロアルコキシ基等が挙げられる。 こ れらのうち置換しうるものについては、 Y 'よりも原子番号の小さい ハロゲン原子、 アルキル基等がさらに置換していてもよい。 置換ァ リール基の具体例として、 3-メチルフヱニル基、 4-メチルフヱニル 基、 3-ェチルフヱニル基、 4-ェチルフエ二ル基、 4-ォクチルフエ二 ル基、 4-メ トキシフヱニル基、 4-エトキシフヱニル基、 4-ペンチル ォキシフエニル基、 4-ジメチルァミノフエニル基、 4-シァノフエ二 ル基、 3 -ニトロフエ二ル基、 4-フルオロフヱニル基、 4-クロ口フエ ニル基、 4- (トリフルォロメチル）フヱニル基、 3，4-ジフルオロフヱ ニル基、 2-ァセチルフエニル基、 3-ァセチルフヱニル基、 4-ァセチ ルフヱニル基、 4-カルボキシルフ Iニル基、 4-〔エトキシカルボ二 ル）フヱニル基、 4- (ペンチルシクロへキシル）フヱニル基、 4-ペン チルビフヱニル基、 4' -シクロへキシルビフヱニル基、 3-メチル -2- フルォロビフヱニル基、 3-ニトロ- 2-ピリジル基、 5-メチル -3-ピリ ジル基、 3-ァセ卜アミ ド -2-ピリジル基、 3-ホルムアミ ド -2-ピリジ ル基、 2-シァノ -4-ピリジル基、 4-フルォロ- 2-ピリ ミジル基、 4-二 トロ- 3-フリル基、 5-シァノ -2-チェ二ル基等を例示することができ る。 The other starting material, an organic halide represented by the above general formula [Π], is a compound that can be easily synthesized and is industrially easily available. In the formula, Y 1 is a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom. R 3 is a substituted or unsubstituted aryl group or a 1- or 2-alkenyl group. The aryl group also includes a heteroaryl group, and includes a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group, a furyl group, a chenyl group, a pyrrolyl group, and the like. Examples of the substituent, a linear or branched alkyl Le group or alkoxy group having 1 to 10 carbon atoms, di-lower alkylamino group, Shiano group, lower halogen atom of atomic number than Y 1, Ashiru group, Ashiruamino group And an amino group, an aryl group, a carbonyl group, a carboxyl group, a nitrogen atom group, a cycloalkyl group and a cycloalkoxy group. Of these, those that can be substituted may be further substituted with a halogen atom, an alkyl group, or the like having an atomic number smaller than Y ′. Replacement Specific examples of the reel group include 3-methylphenyl group, 4-methylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 4-octylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, and 4-pentyl. Oxyphenyl group, 4-dimethylaminophenyl group, 4-cyanophenyl group, 3-nitrophenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4- (trifluoromethyl) phenyl group, 3 , 4-difluorophenyl group, 2-acetylphenyl group, 3-acetylphenyl group, 4-acetylphenyl group, 4-carboxyphenyl group, 4- [ethoxycarboxy] phenyl group, 4- (pentylcyclohexyl) Phenyl, 4-pentylbiphenyl, 4'-cyclohexylbiphenyl, 3-methyl-2-fluorobiphenyl, 3-nitro-2-pyridyl, 5-methyl-3- Lysyl group, 3-acetamido-2-pyridyl group, 3-formamido-2-pyridyl group, 2-cyano-4-pyridyl group, 4-fluoro-2-pyrimidyl group, 4-2 Toro-3-furyl group, 5-cyano-2-phenyl group and the like can be exemplified.

1 -または 2-アルケニル基としてはシクロアルケ二ル基をも包含し、 ェテニル基、 卜プロぺニル基、 2-プロぺニル基、 1 -ブテニル基、 2- ブテニル基、 1 -ペンテニル基、 2-ペンテニル基、 1-へキセニル基、 2-へキセニル基、 1 -ヘプテニル基、 1 -ォクテニル基、 卜シクロへキ セニル基、 2-シクロへキセニル基等を挙げることができる。 これら に存在しうる置換基としては上記のものを同様に挙げることができ る。  The 1- or 2-alkenyl group also includes a cycloalkenyl group, such as an ethenyl group, a toppropenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2-pentenyl group. -Pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 1-octenyl group, tricyclohexenyl group, 2-cyclohexenyl group and the like. The substituents which may be present in these are the same as those described above.

式中の R3として置換もしくは未置換のァリ一ル基をもつ上記一般 式：Π :で表される有機ハロゲン化物の具体例としては、 Specific examples of the organic halide represented by the above general formula: Π having a substituted or unsubstituted aryl group as R 3 in the formula include:

2-クロ口 トルエン、 3 -クロ口 トルエン、 4-クロ口 トルエン、 2-クロ ロアセトフエノン、 3-クロロアセトフエノン、 4-クロロアセトフエ ノン、 1 -クロ口- 4- (トリフルォロメチル）ベンゼン、 4-クロ口ベン ゾニトリノレ、 2-クロ口ピリジン、 3-クロ口ピリジン、 4-クロ口ピリ ジン、 3-ァミノ- 2-クロ口ピリジン、 3-ァセトアミ ド -2-クロ口ピリ ジン、 2-クロ口- 3-ニトロピリジン、 2-ブロモトルエン、 3-ブロモ トルエン、 4-ブロモトルエン、 2-ブロモアセトフヱノン、 3-ブロモ ァセトフエノ ン、 4-ブロモアセトフヱノン、 卜ブロモ -4-ペンチル ベンゼン、 1 -ブロモ -4- (ペンチルォキシ）ベンゼン、 1 -ブロモ -4- (4 -ペンチルシク口へキシル）ベンゼン、 1 -ブロモ -4-ォクチルベンゼ ン、 1 -ブロモ -4- (トリフルォロメチル）ベンゼン、 1 -ブロモ -4- (卜 リフルォロメチルォキシ）ベンゼン、 4-ブロモ安息香酸メチル、 4- ブロモ安息香酸ェチル、 4-ブロモフルォロベンゼン、 4-ブロモク口 口ベンゼン、 4-ブロモベンゾニトリル、 2-ブロモピリジン、 3-ブロ モピリジン、 4-ブロモピリジン、 3-アミ ノ -2-ブロモピリジン、 3- ァセトアミ ド -2 -ブロモピリジン、 2-プロモ -3-二トロピリジン、 2- ブロモピリ ミジン、 4-ブロモビフヱニル、 4-ブロモ -4' -ペンチルビ フエニル、 2-ブロモベンズアルデヒ ド、 3-ブロモベンズアルデヒ ド 、 4-ブロモベンズアルデヒ ド、 1 -ブロモナフタレン、 2-ブロモナフ タレン、 1 -ョー ド -4-ペンチルベンゼン、 卜ョー ド -4- (ペンチルォ キシ）ベンゼン、 1 -ョ一 ド- 4- (4-ペンチルシクロへキシル）ベンゼン、2-black mouth Toluene, 3-black mouth Toluene, 4-black mouth Toluene, 2-black mouth Loacetophenone, 3-Chloroacetophenone, 4-Chloroacetophenone, 1-Chloro-4- (trifluoromethyl) benzene, 4-Chlorobenzonitrinole, 2-Chloropyridine, 3-Chloropyridine, 3-Chloropyridine 4-chloropyridine, 3-amino-2-chloropyridine, 3-acetamido-2-cyclopyridine, 2-chloro-3-nitropyridine, 2-bromotoluene, 3-bromotoluene, 4 -Bromotoluene, 2-bromoacetophenone, 3-bromoacetophenone, 4-bromoacetophenone, tribromo-4-pentylbenzene, 1-bromo-4- (pentyloxy) benzene, 1-bromo-4 -(4-pentylcyclohexyl) benzene, 1-bromo-4-octylbenzene, 1-bromo-4- (trifluoromethyl) benzene, 1-bromo-4- (trifluoromethyloxy) benzene , 4-bromobenzoic acid methyl , 4-bromoethylbenzene, 4-bromofluorobenzene, 4-bromobenzo-benzene, 4-bromobenzonitrile, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 3-amino-2 -Bromopyridine, 3-acetamido -2-bromopyridine, 2-bromo-3-ditropyridine, 2-bromopyrimidine, 4-bromobiphenyl, 4-bromo-4'-pentylbiphenyl, 2-bromobenzaldehyde, 3 -Bromobenzaldehyde, 4-bromobenzaldehyde, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodo-4-pentylbenzene, torodo-4- (pentyloxy) benzene, 1-iodo -4- (4-pentylcyclohexyl) benzene,

1 -ョー ド -4-ォクチルベンゼン、 1 -ョ一 ド -4- (トリフルォロメチル） ベンゼン、 1 -ョード- 4- (卜リフルォロメチルォキシ）ベンゼン、 4 - ョード安息香酸メチル、 4-ョード安息香酸ェチル、 4-ョー ドベンゾ 二卜リノレ、 4-ョー ドアセトフヱノン、 4-ョ一ドフルォロベンゼン、 4-ョ一 ドクロロベンゼン、 2-ョー ドベンズアルデヒ ド、 3-ョ一 ドベ ンズアルデヒ ド、 4-ョードベンズアルデヒ ド、 2-ョードピリジン、 3-ョー ドピリジン、 4-ョー ドピリジン、 2-ョー ドピリ ミジン、 4-ョ 一ドビフヱニル、 4-ョー ド- 4' -ペンチルビフヱニル、 1-ョー ドナフ タレン、 2-ョードナフタレン、 3-ョードフラン、 2-ョ一 ドチオフェ ン等を挙げることができる。 1-odo-4-octylbenzene, 1-odo-4- (trifluoromethyl) benzene, 1-odo-4- (trifluoromethyloxy) benzene, 4-methyl methylbenzoate, 4 -Ethyl benzoate, 4-iodobenzo-2-trinole, 4-iodoacetophenone, 4-oxyfluorobenzene, 4-hydroxychlorobenzene, 2-iodobenzaldehyde, 3-iodobenzo Aldehyde, 4-odobenzaldehyde, 2-odopyridine, 3-odopyridine, 4-odopyridine, 2-odopyrimidine, 4-iodobiphenyl, 4-odo-4'-pentylbiphenyl , 1-odonaphthalene, 2-odonaphthalene, 3-odofuran, 2-odothiophene and the like.

R3として置換もしくは未置換の 1-もしくは 2-アルケニル基をもつ ものの具体例としては、 1-ョード -1-プロペン、 ブロモ -1-プロべ ン、 2-ブロモ -1-プロペン、 卜ョード -卜ブテン、 1-ョ一ド -1-ペン テン、 1-ョ一ド -1-へキセン、 1-ョー ド -1-ヘプテン、 1-ョード -1- ォクテン、 1-ョード -卜シクロへキセン、 /3-ョー ドスチレン、 2-ブ 口モスチレン、 2-ョード -1-プロペン、 2-ョ一ド -1-ブテン、 1-ブロ モ- 1-ペンテン、 卜ブロモ -1-へキセン、 1-ブロモ -1-ヘプテン、 1- ブロモ -1-ォクテン、 卜ョード -1-シクロへキセン、 2-ョード -1-へ キセン等を挙げることができる。 Specific examples of the compound having a substituted or unsubstituted 1- or 2-alkenyl group as R 3 include 1-odo-1-propene, bromo-1-proben, 2-bromo-1-propene, and toluene- Tobutene, 1-odo-1-pentene, 1-odo-1-hexene, 1-odo-1-heptene, 1-odo-1-octene, 1-odo-tricyclohexene , / 3-odostyrene, 2-butane styrene, 2-odo-1-propene, 2-odo-1-butene, 1-bromo-1-pentene, tribromo-1-hexene, 1- Bromo-1-heptene, 1-bromo-1-octene, torodo-1-cyclohexene, 2-odo-1-hexene and the like can be mentioned.

また、 前記一般式 [W]で表される有機ハロゲン化物においては、 Further, in the organic halide represented by the general formula [W],

Y2は塩素原子または臭素原子であり、 この場合、 Y2が塩素原子であ つても、 収率良く 目的物を得ることが、 上記本発明の第二の方法の 特徴である。 Y 2 is a chlorine atom or a bromine atom. In this case, even if Y 2 is a chlorine atom, it is a feature of the second method of the present invention that the desired product is obtained with a high yield.

R3は上記と同様であるが、 置換基としてのハロゲン原子は Y1より も原子番号の小さいものに限られる。 従って上記一般式 [ΙΠで表さ れる有機ハロゲン化物の具体例としては、 クロ口ベンゼン、 2-クロ 口 トルエン、 3-クロ口 トルエン、 4-クロ口 卜ゾレエン、 2-クロロアセ トフェノ ン、 3-クロロアセ トフエノ ン、 4-クロロアセ トフエノ ン、 1-クロ口- 4- (トリフルォロメチル）ベンゼン、 1-クロ口- 4- (トリフ ルォロメチルォキシ）ベンゼン、 1-クロ口- 4-ペンチルベンゼン、 卜 クロロ- 4- (ペンチルォキシ）ベンゼン、 ：! -クロ口- 4- (4-ペンチルシ クロへキシノレ）ベンゼン、 1 -クロ口- 4-ォクチノレベンゼン、 4-クロ口 安息香酸メチル、 4-クロ口安息香酸ェチル、 4-クロ口べンゾニトリ ル、 2-クロ口フルォロベンゼン、 3-クロ口フルォロベンゼン、 4-ク ロロフルォロベンゼン、 卜クロ口- 2， 3-ジフルォロベンゼン、 レク ロロ- 4-シクロへキシルベンゼン、 3-ァミノ- 2-クロ口ピリジン、 3- ァセトァミ ド -2-クロロピリジン、 2-クロ口ピリジン、 3-クロ口ピ リジン、 4-クロ口ピリジン、 2-クロ口- 3-二卜口ピリジン、 3-クロ 口- 5-シァノピリジン、 2-クロ口ピリ ミジン、 2-クロ口フラン、 3- クロ口フラン、 2-クロ口- 3-ニトロフラン、 2-クロロチォフェン、 4 -クロ口ビフヱニル、 4-クロ口- 4' -ペンチルビフヱニル、 2-クロ口 ベンズアルデヒド、 3-クロ口べンズアルデヒ ド、 4-クロ口べンズァ ルデヒ ド、 1 -クロロナフタレン、 2-クロロナフタレン、 ブロモベン ゼン、 2-ブロモトルエン、 3-ブロモトルエン、 4-ブロモトルエン、 2-ブロモアセトフヱノン、 3-ブロモアセ卜フエノン、 4-ブロモアセ トフヱノン、 1 -ブロモ -4 -(トリフルォロメチル）ベンゼン、 1-ブロ モ -4- (トリフルォロメチルォキシ）ベンゼン、 1-ブロモ -4-ペンチル ベンゼン、 1 -ブロモ -4- (ペンチルォキシ）ベンゼン、 1-ブロモ - 4-(4 -ペンチルシク口へキシル）ベンゼン、 ブロモ -4-ォクチルベンゼ ン、 4-ブロモ安息香酸メチル、 4-ブロモ安息香酸ェチル、 4-ブロモ ベンゾニトリル、 2-ブロモフルォロベンゼン、 3-ブロモフルォ口べ ンゼン、 4-ブロモフルォロベンゼン、 1 -ブロモ -2, 3-ジフルォ口べ ンゼン、 卜ブロモ -4-シクロへキシルベンゼン、 3-ァミノ - 2-ブロモ ピリジン、 3-ァセトアミ ド- 2-ブロモピリジン、 2-ブロモピリジン、 3-ブロモピリジン、 4-ブロモピリジン、 2-ブロモ -3-ニトロピリジ ン、 3-ブロモ -5-シァノピリジン、 2-ブロモピリ ミジン、 2-ブロモ フラン、 3-ブロモフラン、 2-ブロモ -3-ニトロフラン、 2-ブロモチ ォフェン、 4-ブロモビフエニル、 4-ブロモ -4· -ペンチルビフヱニル、 2-ブロモベンズアルデヒ ド、 3-ブロモベンズアルデヒ ド、 4-ブロモ ベンズアルデヒ ド、 1 -ブロモナフタレン、 2-ブロモナフタレン等を 挙げることができる。 R 3 is the same as above, but the halogen atom as a substituent is limited to those having an atomic number smaller than Y 1 . Accordingly, specific examples of the organic halide represented by the above general formula [ΙΠ] include benzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotolusolene, 2-chloroacetophenone, and 3-chloroacetophenone. Chloroacetophenone, 4-Chloroacetophenone, 1-Chloro-4- (trifluoromethyl) benzene, 1-Chloro-4- (trifluoromethyloxy) benzene, 1-Chloro-4-pentyl Benzene, benzene Chloro-4- (pentyloxy) benzene,:!-Black mouth-4- (4-pentylcyclohexynole) benzene, 1-Black mouth-4-octynolebenzene, 4-Chloromethyl benzoate, 4-Chloro Ethyl mouth benzoate, 4-chloro benzonitrile, 2-chloro fluorobenzene, 3-chloro fluorobenzene, 4-chlorofluorobenzene, cyclochloro-2,3-difluorobenzene, rechloro- 4-cyclohexylbenzene, 3-amino-2-chloropyridine, 3-acetamido-2-chloropyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-chloropyridine -3-nitropyridine, 3-chloro-5-cyanopyridine, 2-chloropyrimidine, 2-chlorofuran, 3-chlorofuran, 2-chloro-3-nitrofuran, 2-chlorothio Fen, 4-clo mouth biphenyl, 4-clo mouth-4'-pentyl biphenyl, 2-k B benzaldehyde, 3-chlorobenzene aldehyde, 4-chlorobenzylaldehyde, 1-chloronaphthalene, 2-chloronaphthalene, bromobenzene, 2-bromotoluene, 3-bromotoluene, 4-bromotoluene, 2 -Bromoacetophenone, 3-bromoacetophenone, 4-bromoacetophenone, 1-bromo-4- (trifluoromethyl) benzene, 1-bromo-4- (trifluoromethyloxy) benzene, 1 -Bromo-4-pentylbenzene, 1-bromo-4- (pentyloxy) benzene, 1-bromo-4- (4-pentylcyclohexyl) benzene, bromo-4-octylbenzene, methyl 4-bromobenzoate, 4 -Ethyl-bromobenzoate, 4-bromobenzonitrile, 2-bromofluorobenzene, 3-bromofluorobenzene, 4-bromofluorobenzene, 1-bromo-2,3-diph Benzene, tribromo-4-cyclohexylbenzene, 3-amino-2-bromopyridine, 3-acetamido-2-bromopyridine, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 2 -Bromo-3-nitropyrid , 3-bromo-5-cyanopyridine, 2-bromopyrimidine, 2-bromofuran, 3-bromofuran, 2-bromo-3-nitrofuran, 2-bromothiophene, 4-bromobiphenyl, 4-bromo-4-pentyl Biphenyl, 2-bromobenzaldehyde, 3-bromobenzaldehyde, 4-bromobenzaldehyde, 1-bromonaphthalene, 2-bromonaphthalene and the like can be mentioned.

また、 I？3がアルケニル基である有機ハロゲン化物としては、 前記 一般式 [ ΙΠで表される化合物の具体例において、 沃素原子を臭素原 子もしくは塩素原子に置換した化合物を挙げることができる。 Also I? Examples of the organic halide in which 3 is an alkenyl group include compounds in which an iodine atom is replaced with a bromine atom or a chlorine atom in the specific examples of the compound represented by the above general formula [ΙΠ].

上記の化合物において、 アルケニル基が反応に関与擦る場合、 一 般に、 その立体化学は保持されてカツプリ ング反応が進行する。 本発明の第一の方法において用いられる第 10族遷移金属触媒とし ては、 パラジウムテトラキス（トリフヱニルホスフィ ン）、 パラジゥ ムベンザルァセトン錯体、 パラジゥ厶ベンザルァセトンクロロホル ム錯体等の Pd(0)錯体、 ァリル塩化パラジウム 2量体、 塩化パラジゥ 厶 [ 1, 2-ビス（ジシクロへキシルホスフィノ）エタン：、 塩化パラジゥ ム [ビス（トリィソプロピルホスフィ ン）]、 塩化パラジゥム：ビス（ト リシクロへキシルホスフィ ン）]、 ヨウ化フヱニルパラジウムビス（ トリフヱニルホスフィ ン 酢酸パラジウムなどの Pd( n )錯体、 テ トラキス（トリフエニルホスフィ ン）白金や塩化白金ビス（トリフエ ニルホスフィ ン）などの白金錯体、 またはテトラキス（トリフヱニル ホスフィ ン）ニッケル、 塩化ニッケルビス（トリフエニルホスフィ ン )などのニッケル錯体などを挙げることができる。 これらの第 10族 遷移金属触媒のうち、 ホスフィ ン配位子を持たないものは、 ホスフ イ ン配位子と共に用いることもできる。 使用量は遷移金属触媒の 1 ~5倍モル量でよい。 ホスフィ ン配位子としては、 トリフエニルホ スフイ ン、 ト リ - 0- 卜リルホスフィ ン、 ト リス（2-フリゾレ）ホスフィ ン、 トリブチルホスフィン、 トリェチルホスフィン、 トリシクロへ キシルホスフィ ン、 1，2-ビス（ジシクロへキシルホスフィノ）エタン、 1，2-ビス（ジフエニルホスフイノ）ェタン、 1， 3-ビス（ジフエニルホ スフイノ）プロパン、 卜リイソプロピルホスフィンなどを用いるこ とができる。 これらの第 10族遷移金属触媒を前記一般式 [ I ]で表さ れる有機ハロゲン化物に対して、 0· 2〜5, 0モル ί¾用いることが好ま しい。 In the above compounds, when an alkenyl group participates in the reaction, the stereochemistry is generally maintained and the coupling reaction proceeds. Examples of the Group 10 transition metal catalyst used in the first method of the present invention include Pd such as palladium tetrakis (triphenylphosphine), palladium benzalacetone complex, and palladium benzalacetone chloroform complex. (0) complex, aryl palladium chloride dimer, palladium chloride [1,2-bis (dicyclohexylphosphino) ethane: palladium chloride [bis (trisopropylphosphine)], palladium chloride: bis (t Licyclohexyl phosphine)], Pd (n) complexes such as phenyl palladium iodide bis (triphenyl phosphine palladium acetate), tetrakis (triphenyl phosphine) platinum and platinum chloride bis (triphenyl phosphine) Platinum complex such as, or tetrakis (triphenylphosphine) nickel, nickel chloride bis ( And a nickel complex such as refinylphosphine. Among these Group 10 transition metal catalysts, those having no phosphine ligand can be used together with the phosphine ligand. The amount used is 1 of the transition metal catalyst It may be up to 5 times the molar amount. Examples of phosphine ligands include triphenylphosphine, tri-0-tolylphosphine, tris (2-furisole) phosphine, tributylphosphine, triethylphosphine, tricyclohexylphosphine, and 1,2-bis (dicyclophosphine). Hexylphosphino) ethane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, triisopropylphosphine and the like can be used. It is preferable to use these Group 10 transition metal catalysts in an amount of from 0.2 to 5.0 mol per mol of the organic halide represented by the general formula [I].

本発明の第二の方法は、 トリアルキルホスフィ ン配位子をもつ第 The second method of the present invention is directed to a method having a trialkylphosphine ligand.

10族遷移金属触媒の存在下に反応させるものであり、 本発明におい て卜リアルキルホスフィ ンとは、 アルキル基およびシクロアルキル 基から選ばれる任意の基で三置換されたホスフィ ンを意味し、 これ らの置換基は同一でも異なっていてもよい。 アルキル基としては、 炭素数 1 ~ 6の直鎖状もしくは分岐状のアルキル基、 例えばェチル基、 イソプロピル基、 ブチル基、 へキシル基等を挙げることができ、 こ れらは下記のシクロアルキル基で置換されていてもよい。 また、 シ クロアルキル基としては、 炭素数 3〜8のもの、 例えばシクロプロピ ル基、 シクロペンチル基、 シクロへキシル基等を挙げることができ、 これらは上記のアルキル基で置換されていてもよい。 なお、 トリ（ シクロ）アルキルホスフィ ン配位子には、 例えば 1，2-ビス（ジシクロ へキシルホスフィノ）エタンのような、 ェチレン基等のポリメチレ ン基を介して二つのリ ン原子が結合したジホスフィン配位子も包含 される。 The reaction is carried out in the presence of a Group 10 transition metal catalyst. In the present invention, trialkylphosphine means phosphine trisubstituted with an arbitrary group selected from an alkyl group and a cycloalkyl group. However, these substituents may be the same or different. Examples of the alkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms, such as an ethyl group, an isopropyl group, a butyl group and a hexyl group. May be substituted. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. These may be substituted with the above-mentioned alkyl group. In addition, two phosphorus atoms are bonded to the tri (cyclo) alkylphosphine ligand via a polymethylene group such as an ethylene group such as 1,2-bis (dicyclohexylphosphino) ethane. Diphosphine ligands are also included.

トリ（アルキルおよび Ζまたはシクロアルキル）ホスフィ ン配位子 をもつ第 10族遷移金属触媒としては、 塩化パラジウム [ビス（トリェ チルホスフィ ン）]、 塩化パラジウム [ビス（トリィソプロピルホスフ ィン）]、 塩化パラジウム [ビス（トリシクロへキシルホスフィン）]、 塩化パラジウム [ 1, 2-ビス（ジシクロへキシルホスフィノ）エタン]な どの Pd( n )錯体、 塩化白金 [ 1, 2-ビス（ジシクロへキシルホスフイノ )ェタン]などの白金錯体、 または塩化ニッケル： 1 , 2 -ビス（ジシクロ へキシルホスフィノ）エタン]などのニッケル錯体などを用いること ができる。 Tri (alkyl and Ζ or cycloalkyl) phosphine ligands Group 10 transition metal catalysts containing palladium chloride [bis (triethylphosphine)], palladium chloride [bis (tripropylpropylphosphine)], palladium chloride [bis (tricyclohexylphosphine)], palladium chloride Pd (n) complexes such as [1,2-bis (dicyclohexylphosphino) ethane], platinum complexes such as platinum chloride [1,2-bis (dicyclohexylphosphino) ethane], or nickel chloride: 1,2-bis Nickel complexes such as (dicyclohexylphosphino) ethane] can be used.

または、 ァリル塩化パラジゥムニ量体やパラジゥムベンザルァセ 卜ン錯体などを、 トリ（アルキルおよび Zまたはシクロアルキル）ホ スフィン配位子と組み合わせて触媒として用いることができる。 こ のホスフィン配位子の使用量は遷移金属触媒の 1 ~5倍モル量程度で ある。 ホスフィン配位子としては、 トリイソプロピルホスフィ ン、 トリェチルホスフィン、 卜リシクロへキシルホスフィ ン、 トリブチ ルホスフィン、 1, 2-ビス（ジシクロへキシルホスフイノ）ェタンなど を用いることができる。  Alternatively, an aryl chloride palladium dimer or palladium benzalacetone complex or the like can be used as a catalyst in combination with a tri (alkyl and Z or cycloalkyl) phosphine ligand. The amount of the phosphine ligand used is about 1 to 5 times the molar amount of the transition metal catalyst. As the phosphine ligand, triisopropyl phosphine, triethyl phosphine, tricyclohexyl phosphine, tributyl phosphine, 1,2-bis (dicyclohexyl phosphino) ethane and the like can be used.

これらの第 10族遷移金属触媒を前記一般式:: W]で表される有機ハ ロゲン化物に対して、 0. 2〜5. 0モル％用ぃることが好ましい。 本発明の第一の方法において使用される、 塩基としては水酸化ナ トリゥム、 水酸化力リゥム等の金属水酸化物、 炭酸ナトリゥム、 炭 酸カリウム、 炭酸アンモニゥム等の炭酸塩、 水酸化アンモニゥ厶、 水酸化テトラプチルアンモニゥ厶等の水酸化物を使用できるが、 反 応効率の点でアル力リ金属水酸化物が好ましく、 水酸化ナトリウム が反応効率およびコス卜の点でより好ましい。 使用量は前記一般式 ： I〕で表される有機ハロシラン類に対し、 当量ないしは過剰量の範 囲で使用できるが、 3. 0〜10倍モル量使用することが好ましい。 It is preferable to use these Group 10 transition metal catalysts in an amount of from 0.2 to 5.0 mol% based on the organic halide represented by the general formula: W]. Examples of the base used in the first method of the present invention include sodium hydroxide, metal hydroxides such as a hydrating power, sodium carbonate, potassium carbonate, carbonates such as ammonium carbonate, ammonium hydroxide, and the like. A hydroxide such as tetrabutylammonium hydroxide can be used, but an alkali metal hydroxide is preferred in terms of reaction efficiency, and sodium hydroxide is more preferred in terms of reaction efficiency and cost. The amount used is in the range of an equivalent amount or an excess amount based on the organohalosilane represented by the general formula: I]. Although it can be used in a box, it is preferable to use a molar amount of 3.0 to 10 times.

本発明の第二の方法において使用される、 フッ化物塩としては、 トリス（ジェチルァミノ）スルホ二ゥ厶ジフルォロ トリメチルシリ力 一卜、 トリス（ジメチルァミノ）スルホ二ゥ厶ジフルォロ トリメチル シリカー ト、 フッ化テトラブチルアンモニゥ厶、 フッ化ベンジルト リメチルアンモニゥムなどのフッ化ォニゥム塩、 またはフッ化セシ ゥ厶、 フッ化カリウ厶等の金属フッ化物塩を例示することができる。 フッ化物塩の使用量は化学量論量に対し、 触媒量ないしは過剰量の 範囲で使用できるが、 前記一般式 [ I ]で表される有機ハロシラン類 に対して 0. 8〜6. 0倍モル使用することが好ましい。  Examples of the fluoride salt used in the second method of the present invention include tris (ethylamino) sulfonium difluoro trimethylsilyl tris, tris (dimethylamino) sulfonium difluoro dimethyl trimethyl silicate, and tetrabutyl fluoride Examples thereof include ammonium fluoride salts such as ammonium and benzyltrimethylammonium fluoride, and metal fluoride salts such as cesium fluoride and potassium fluoride. The amount of the fluoride salt used can be a catalytic amount or an excess amount with respect to the stoichiometric amount, but it is 0.8 to 6.0 times the amount of the organohalosilane represented by the general formula [I]. It is preferred to use molar.

本発明のいずれの方法も溶媒中で行なうことが好ましく、 例えば、 テ卜ラヒ ドロフラン、 ジォキサン、 エーテル、 ベンゼン、 トルエン、 アセトン、 Ν, Ν'-ジメチルホル厶アミ ド、 ジメチルスルホキシド、 Ν- メチルピロリ ドン、 へキサメチルリ ン酸トリアミ ド、 ァセ卜ニトリ ル、 ', Ν-ジメチルイ ミダゾリジノン等を単独あるいは 混合して用 いることができる。 反応は通常、 0〜200°Cの範囲で行なうことが好 ましく、 操作の簡便な室温〜 150°Cがより好ましく、 反応効率の点 で 50°C以上に加熱することがさらに好ましい。  It is preferable to carry out any of the methods of the present invention in a solvent, for example, tetrahydrofuran, dioxane, ether, benzene, toluene, acetone, Ν, Ν′-dimethylformamide, dimethylsulfoxide, Ν-methylpyrrolidone, Hexamethylphosphoric acid triamide, acetate nitrile, ', Ν-dimethylimidazolidinone and the like can be used alone or in combination. Usually, the reaction is preferably carried out in the range of 0 to 200 ° C, more preferably from room temperature to 150 ° C, which is convenient for the operation, and further preferably heated to 50 ° C or more from the viewpoint of reaction efficiency.

本発明の方法の実施にあたっては、 窒素やアルゴン等の不活性ガ ス雰囲気下で行うことが好ましく、 反応系内を不活性ガスで置換す ることがより好ましい。 発明を実施するための最良の形態  The method of the present invention is preferably performed in an inert gas atmosphere such as nitrogen or argon, and more preferably, the inside of the reaction system is replaced with an inert gas. BEST MODE FOR CARRYING OUT THE INVENTION

以下、 実施例および参考例により本発明をさらに詳細に説明する。 ただし、 本発明はこれらの実施例により限定されるものではない。 実施例 1

Figure imgf000021_0001
Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples. However, the present invention is not limited by these examples. Example 1
Figure imgf000021_0001

アルゴン雰囲気下、 水酸化ナトリウム粉末（371mg, 9.3匪 ol)のテ トラヒドロフラン懸濁液（2ml)を 0°Cに冷却し、 ジクロロ（ェチル）（4 -メ トキシフヱニル）シラン（1.9mmol)のテトラヒ ドロフラン溶液（0. 74ml)を滴下した後、 室温で 3時間撹拌した。 別の反応容器中、 酢酸 パラジウム（1.8mg, 8 mol， 1.5mol%)およびトリフエニルホスフィン (4. Omg, 15 mol，2.9mol«のテトラヒ ドロフラン溶液（0.4ml)を室温 で 40分間撹拌して触媒を調製した。 反応溶液に、 1-ブロモ -3,4-ジ フルォロベンゼン（100.7mg, 0.52mmol)および調製したパラジゥム触 媒のテトラヒドロフラン溶液を加え、 60 で 14時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml)および酢酸ェチ ル（5ml)を加え、 セライ ト濾過により触媒を除去した。 水層を酢酸 ェチル（5ml X2)で抽出し、 有機層と合わせ、 水および飽和食塩水に より洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去した 後、 減圧下で溶媒を留去し、 得られた粗生成物を薄層クロマトグラ フィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分離精製したところ、 3,4-ジフルォ口- 4' -メ 卜キシビフエニル（108mg, 0.49mmol，94%)を白 色針状結晶として得た。  Under an argon atmosphere, a suspension of sodium hydroxide powder (371 mg, 9.3 mol) in tetrahydrofuran (2 ml) was cooled to 0 ° C, and dichloro (ethyl) (4-methoxyphenyl) silane (1.9 mmol) was added. After dropwise addition of a tetrahydrofuran solution (0.74 ml), the mixture was stirred at room temperature for 3 hours. In a separate reaction vessel, stir palladium acetate (1.8 mg, 8 mol, 1.5 mol%) and triphenylphosphine (4. Omg, 15 mol, 2.9 mol «tetrahydrofuran solution (0.4 ml) at room temperature for 40 minutes. To the reaction solution, 1-bromo-3,4-difluorobenzene (100.7 mg, 0.52 mmol) and a prepared solution of palladium catalyst in tetrahydrofuran were added, and the mixture was heated and stirred at 60 for 14 hours. The reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration.The aqueous layer was extracted with ethyl acetate (5 ml × 2), and the organic layer was combined. After washing with water and a saturated saline solution and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure after removing the desiccant, and the obtained crude product was subjected to thin-layer chromatography (developing solvent: acetic acid). Ethyl: hexane = 1: 7) When the 3,4 Jifuruo port - 4 '- give main Bok Kishibifueniru (108mg, 0.49mmol, 94%) as a white Irohari like crystal.

'H- R(400 Hz, CDC13): δ 3.85(s, 3H, 0CH3), 6.97(d, J=8.9Hz, 2H， HC (3' , 5' )), 7.18(ddd, J = 8.3' 8.3 and 10.0Hz, 1H, HC(5)), 7.23(m， 1H' H C(6))， 7.32(ddd, J=2.1， 7.6 and 11.7Hz, 1H， HC(2 ， 7.44(d, J=8.9Hz , 2H, HC(2',6' )). IR(KBr):1600, 1500, 1245, 1230, 1180, 1020, 820cm—'. 実施例 2 'H- R (400 Hz, CDC1 3): δ 3.85 (s, 3H, 0CH 3), 6.97 (d, J = 8.9Hz, 2H, HC (3', 5 ')), 7.18 (ddd, J = 8.3 '8.3 and 10.0Hz, 1H, HC (5)), 7.23 (m, 1H' HC (6)), 7.32 (ddd, J = 2.1, 7.6 and 11.7Hz, 1H, HC (2, 7.44 (d, J = 8.9Hz, 2H, HC (2 ', 6')). IR (KBr): 1600, 1500, 1245, 1230, 1180, 1020, 820cm— '. Example 2

n-C3H7

Figure imgf000022_0001
nC 3 H 7
Figure imgf000022_0001

アルゴン雰囲気下、 水酸化ナトリウム粉末（327mg,8.2腿 ol)のべ ンゼン懸濁液（3ml)を 0°Cに冷却し、 ジクロロ（ェチル） [4-(4-トラン ス -n-プロピルシク口へキシル）フエニル]シラン（538mg， 1.6ππηο1)を 滴下した後、 室温で 3時間撹拌した。 別の反応容器中、 酢酸パラジ ゥム（1.8mg, 8^mol, 0.8mol%)およびトリフヱニルホスフィ ン（4.2mg , 16^mol, 1.6mol%)のベンゼン溶液（0.5ml)を室温で 1時間撹拌して 触媒を調製した。 反応溶液に、 1-ブロモ -3,4-ジフルォロベンゼン（ 190mg, 0.98mmol)および調製したパラジウム触媒のベンゼン溶液を 加え、 80°Cで 62時間加熱撹拌した。 反応終了後、 反応溶液を室温ま で冷却し、 水（5ml)および酢酸ェチル（5ml)を加え、 セライ ト濾過に より触媒を除去した。 水層を酢酸ェチル（5πι1χ2)で抽出し、 有機層 と合わせ、 水および飽和食塩水により洗浄後、 無水硫酸マグネシゥ ムで乾燥した。 乾燥剤を除去した後、 減圧下で溶媒を留去し、 得ら れた粗生成物を薄層クロマ卜グラフィ一（展開溶媒；へキサン）で分 離精製したところ、 3, 4-ジフルォロ- 4' -：1-(4-卜ランス- n-プロピ ルシクロへキシル）〕ビフエニル（274mg, 0.87龍 ol， 89%〕を白色針状結 晶として得た。  Under an argon atmosphere, a benzene suspension (3 ml) of sodium hydroxide powder (327 mg, 8.2 mol) was cooled to 0 ° C, and dichloro (ethyl) [4- (4-trans-n-propyl cycle) was added. After [xyl) phenyl] silane (538 mg, 1.6ππηο1) was added dropwise, the mixture was stirred at room temperature for 3 hours. In a separate reaction vessel, a benzene solution (0.5 ml) of palladium acetate (1.8 mg, 8 ^ mol, 0.8 mol%) and triphenylphosphine (4.2 mg, 16 ^ mol, 1.6 mol%) was added at room temperature. For 1 hour to prepare a catalyst. To the reaction solution, 1-bromo-3,4-difluorobenzene (190 mg, 0.98 mmol) and a benzene solution of the prepared palladium catalyst were added, and the mixture was heated with stirring at 80 ° C for 62 hours. After the reaction was completed, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5πι1χ2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the drying agent, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: hexane) to give 3,4-difluoro- 4′-: 1- (4-Trans-n-propylcyclohexyl)] biphenyl (274 mg, 0.87 dragonol, 89%) was obtained as white needles.

即： 105〜107°C Ή-ΝΜΚ(200ΜΗζ, CDC13): 5 0.91(t, J=7.0Hz, 3H, CH3)， 1.00〜： 1.60(m, 9H), 1.80〜2.00(m, 4H), 2.50(tt, J=3.1 and 12.1Hz, 1H)， 7.17(dt, J = 9.7 and 8.3Hz， 1H, HC(5))， 7.23〜7.30(m, 1H, HC(6)), 7.27(d, J=8.2H z, 2H, HC(3' , 5，））, 7.35(m, 1H, HC(2))， 7.43(d, J=8.2Hz, 2H, HC(2' , 6' )). IRCKBr):2970, 2930, 2850, 1600, 1530, 1500, 1120， 810, 780cm-1. 実施例 3

Figure imgf000023_0001
Immediately: 105-107 ° C Ή-ΝΜΚ (200ΜΗζ, CDC1 3 ): 5 0.91 (t, J = 7.0Hz, 3H, CH 3), 1.00~: 1.60 (m, 9H), 1.80~2.00 (m, 4H), 2.50 (tt, J = 3.1 and 12.1Hz, 1H), 7.17 (dt, J = 9.7 and 8.3Hz, 1H, HC (5)), 7.23-7.30 (m, 1H, HC (6)), 7.27 (d, J = 8.2H z, 2H, HC (3 ', 5,)), 7.35 (m, 1H, HC (2)), 7.43 (d, J = 8.2Hz, 2H, HC (2', 6 ')). IRCKBr): 2970, 2930, 2850, 1600, 1530, 1500, 1120, 810, 780cm- 1 .
Figure imgf000023_0001

アルゴン雰囲気下、 水酸化ナトリウム粉末（278mg,6.9匪 ol)のテ トラヒ ドロフラン懸濁液（3ml)を 0 に冷却し、 ジクロロ（ェチル）（4 -メチルフヱニル）シラン（304mg, 1.4mniol)を滴下した後、 室温で 3時 間撹拌した。 別の反応容器中、 酢酸パラジウム（1.5mg,7 mol， 1.2m ol%)およびトリフヱニルホスフィ ン（3.5mg, 13^mol, 2.4niol%)のテ トラヒ ドロフラン溶液（0.3ml)を室温で 40分間撹拌して触媒を調製 した。 反応溶液に、 1-ブロモ -3,4-ジフルォロベンゼン（lllnig，0.58 蘭 ol)および調製したパラジウム触媒のテ卜ラヒ ドロフラン溶液を 加え、 60°Cで 15時間加熱撹拌した。 反応終了後、 反応溶液を室温ま で冷却し、 水（5ml)および酢酸ェチル（5πιυを加え、 セライ 卜濾過に より触媒を除去した。 水層を酢酸ェチル（5ml Χ2)で抽出し、 有機層 と合わせ、 水および飽和食塩水により洗浄後、 無水硫酸マグネシゥ ムで乾燥した。 乾燥剤を除去した後、 減圧下で溶媒を留去し、 得ら れた粗生成物を薄層ク口マトグラフィー（展開溶媒；酢酸ェチル：へ キサン = 1:10)で分離精製したところ、 3, 4-ジフルォロ- 4' -メチルビ フ ニル（80mg, 0.40mmol, 68!¾)を白色針状結晶として得た。 Under an argon atmosphere, a suspension of sodium hydroxide powder (278 mg, 6.9 mg ol) in tetrahydrofuran (3 ml) was cooled to 0, and dichloro (ethyl) (4-methylphenyl) silane (304 mg, 1.4 mniol) was added dropwise. Thereafter, the mixture was stirred at room temperature for 3 hours. In a separate reaction vessel, add a solution of palladium acetate (1.5 mg, 7 mol, 1.2 mol%) and triphenylphosphine (3.5 mg, 13 ^ mol, 2.4 niol%) in tetrahydrofuran (0.3 ml) to room temperature. The mixture was stirred for 40 minutes to prepare a catalyst. To the reaction solution were added 1-bromo-3,4-difluorobenzene (llnnig, 0.58 orol) and a solution of the prepared palladium catalyst in tetrahydrofuran, and the mixture was heated and stirred at 60 ° C for 15 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5πιυ) were added, and the catalyst was removed by cerite filtration.The aqueous layer was extracted with ethyl acetate (5 mlml2), and the organic layer was extracted. After removing the desiccant, the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to thin-layer mouth chromatography. (Developing solvent: ethyl acetate: hexane = 1:10) and purified with 3,4-difluoro-4'-methylbi. Phenyl (80 mg, 0.40 mmol, 68! ¾) was obtained as white needles.

ni :47.5-48.0て ni: 47.5-48.0

'H-N R(400 Hz,CDCl3): δ 2.38(s, 3H, CH3), 7.18(ddd, J=8.3, 8.3 an d 10.2Hz, IH, HC(5)), 7.23(d, J = 8.2Hz， 2H， HC(3'， 5， )), 7.25(m, 1H, HC (6)), 7.35(ddd, J=2.2， 7.6 and 11.7Hz, IH, HC(2))， 7.40(d, J=8.2Hz, 2H, HC(2',6' ·)')· 'HN R (400 Hz, CDCl 3 ): δ 2.38 (s, 3H, CH 3 ), 7.18 (ddd, J = 8.3, 8.3 and 10.2Hz, IH, HC (5)), 7.23 (d, J = 8.2Hz, 2H, HC (3 ', 5,)), 7.25 (m, 1H, HC (6)), 7.35 (ddd, J = 2.2, 7.6 and 11.7Hz, IH, HC (2)), 7.40 ( d, J = 8.2Hz, 2H, HC (2 ', 6') ')'

Mass m/z:204(100¾, M+), 183(26), 151(7), 91(9). Mass m / z: 204 (100¾, M + ), 183 (26), 151 (7), 91 (9).

IR(KBr):2950, 1600, 1530, 1500, 1310, 1275, 1180, 1120, 1030, 1005, 81 IR (KBr): 2950, 1600, 1530, 1500, 1310, 1275, 1180, 1120, 1030, 1005, 81

0,780cm-1. 実施例 4 n-

Figure imgf000024_0001
0,780cm- 1. EXAMPLE 4 n-
Figure imgf000024_0001

アルゴン雰囲気下、 水酸化ナトリウム粉末（147mg, 3.7mmol)のテ トラヒ ドロフラン懸濁液（lml)を 0°Cに冷却し、 ジクロロ（（E)- 1-へ キセニル）（メチル）シラン（145mg, 0.74隨 ol)を滴下した後、 室温で 1 時間撹拌した。 反応溶液に、 3-ブロモトルエン（104mg, 0.61ππηο1)お よび触媒として酢酸パラジウム（3.4mg, 15 ηιο1、 2.5mol¾)のテトラ ヒ ドロフラン溶液（0.4ml)を加え、 60°Cで 5時間加熱撹拌した。 反応 終了後、 反応溶液を室温に冷却し、 水（5ml)および酢酸ェチル（5ml) を加え、 セライ ト濾過により触媒を除去した。 水層を酢酸ェチル（5 mix 2)で抽出し、 有機層と合わせ、 水および飽和食塩水により洗浄 後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去した後、 減圧 下で溶媒を留去し、 得られた粗生成物を薄層クロマトグラフィー（ 展開溶媒；へキサン）で分離精製したところ、 （E)-l- (3-メチルフエ 二ル）- 1-へキセン（81mg, 0.47匪 ol, 77%)を無色油状物として得た。 1H-NMR(200MHz, CDC13): δ 0.92(t, J = 6.8Hz, 3H), 1.17〜1.54(m, 4H), 2.20(dt, J=6.5 and 6.8Hz, 2H), 2.32(s， 3H), 6.19(dt, J = 15.8 and 6. 5Hz, 1H)， 6.35(d, J = 15.8Hz, 1H)， 6.95〜7.24(m， 4H). Under an argon atmosphere, a suspension of sodium hydroxide powder (147 mg, 3.7 mmol) in tetrahydrofuran (1 ml) was cooled to 0 ° C, and dichloro ((E) -1-hexenyl) (methyl) silane (145 mg, After dropwise addition of 0.74 mol), the mixture was stirred at room temperature for 1 hour. To the reaction solution, add 3-bromotoluene (104 mg, 0.61ππηο1) and palladium acetate (3.4 mg, 15 ηιο1, 2.5 mol%) as a catalyst in tetrahydrofuran (0.4 ml), and heat and stir at 60 ° C for 5 hours. did. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5 mix 2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to thin layer chromatography ( Separation and purification with a developing solvent (hexane) gave (E) -l- (3-methylphenyl) -1-hexene (81 mg, 0.47 marl, 77%) as a colorless oil. 1 H-NMR (200MHz, CDC1 3): δ 0.92 (t, J = 6.8Hz, 3H), 1.17~1.54 (m, 4H), 2.20 (dt, J = 6.5 and 6.8Hz, 2H), 2.32 (s , 3H), 6.19 (dt, J = 15.8 and 6.5 Hz, 1H), 6.35 (d, J = 15.8 Hz, 1H), 6.95 to 7.24 (m, 4H).

IR(neat) :3025， 2950, 2925, 2850, 1600, 1460, 1450， 960, 770, 690cm"1. 実施例 5 IR (neat): 3025, 2950, 2925, 2850, 1600, 1460, 1450, 960, 770, 690cm " 1. Example 5

COMe  COMe

n-C^H n-C ^ H

Si(Me)CI2 + Si (Me) CI 2 +

n-C4 COMe

Figure imgf000025_0001
nC 4 COMe
Figure imgf000025_0001

アルゴン雰囲気下、 水酸化ナ卜リゥム粉末（136mg，3.4匪 ol)のテ トラヒ ドロフラン懸濁液（lml)を 0°Cに冷却し、 ジクロロ（（E)-卜へ キセニル）（メチル）シラン（144mg， 0.68mmol)を滴下した後、 室温で 1 時間撹拌した。 反応溶液に、 3-プロモアセトフヱノン（113mg, 0.57m mol)および触媒として酢酸パラジゥム（3.2mg, 14 mol， 2.5mol%)の テ卜ラヒ ドロフラン溶液（0.4ml)を加え、 60 で 5時間加熱撹拌した c 反応終了後、 反応溶液を室温に冷却し、 水（5ml)および酢酸ェチル（ 5ml)を加え、 セライ 卜濾過により触媒を除去した。 水層を酢酸ェチ ル（5ml X2)で抽出し、 有機層と合わせ、 水および飽和食塩水にて洗 浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去した後、 減 圧下で溶媒を留去し、 得られた粗生成物を薄層クロマトグラフィ ー (展開溶媒；酢酸ェチル：へキサン = 1:7〕で分離精製したところ、 （E)- レ（3-ァセチルフヱ二ル）-トへキセン（90mg， 0.45随 ol， 79ύを無色油 状物として得た。 Under an argon atmosphere, a suspension of sodium hydroxide powder (136 mg, 3.4 bandol) in tetrahydrofuran (1 ml) was cooled to 0 ° C, and dichloro ((E) -hexenyl) (methyl) silane ( (144 mg, 0.68 mmol) was added dropwise, followed by stirring at room temperature for 1 hour. To the reaction solution was added 3-bromoacetophenone (113 mg, 0.57 mmol) and a solution of palladium acetate (3.2 mg, 14 mol, 2.5 mol%) in tetrahydrofuran (0.4 ml) as a catalyst. After completion of the reaction by heating and stirring for c , the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by filtration through celite. The aqueous layer was extracted with ethyl acetate (5 ml X2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the drying agent, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7). -Re (3-acetylphenyl) -tohexene (90mg, 0.45 ol, 79%) as colorless oil Obtained as a solid.

1H-NMR(200MHz,CDCl3): δ 0.93(t( J=7. OHz, 3H), 1.28〜1.56(m( 4H), 2.23(dt, J=6.3 and 6.8Hz, 2H), 2.60(s, 3H), 6.30(dt, J = 16.0 and 6. 3Hz, IH), 6.43(d, J = 16. OHz, IH), 7.37(t, J=7.7Hz, IH), 7.53(d, J = 7.7H z, IH), 7.76(d, J=7.7Hz, IH), 7.92(s, IH). 1 H-NMR (200 MHz, CDCl 3 ): δ 0.93 (t ( J = 7.OHz, 3H), 1.28 to 1.56 (m ( 4H), 2.23 (dt, J = 6.3 and 6.8 Hz, 2H), 2.60 ( s, 3H), 6.30 (dt, J = 16.0 and 6.3Hz, IH), 6.43 (d, J = 16.OHz, IH), 7.37 (t, J = 7.7Hz, IH), 7.53 (d, J = 7.7Hz, IH), 7.76 (d, J = 7.7Hz, IH), 7.92 (s, IH).

I (neat) :2950, 2920, 2860, 1610, 1325, 1160, 1120, 1105, 1065, 1010,9 65cm" '. 実施例 6  I (neat): 2950, 2920, 2860, 1610, 1325, 1160, 1120, 1105, 1065, 1010, 9 65cm "'. Example 6

n-C*H n-C * H

Si(Me)CI B

Figure imgf000026_0001
Si (Me) CI B
Figure imgf000026_0001

アルゴン雰囲気下、 水酸化ナトリゥム粉末（140mg，3.5niinol)のテ トラヒドロフラン懸濁液（lml)を 0^に冷却し、 ジクロロ（（E)-l-へ キセニル）（メチル）シラン（ Omg, 0.71 O1)を滴下した後、 室温で 1 時間撹拌した。 この反応溶液に、 4-ブロモ（トリフルォロメチル）ベ ンゼン（130mg, 0.58龍 ol)および触媒として酢酸パラジゥム（3.3mg, 1 5^ιηο1，2.5mol%)のテトラヒドロフラン溶液（0.4ml)を加え、 60°Cで 5時間加熱撹拌した。 反応終了後、 反応溶液を室温に冷却し、 水（5m 1)および酢酸ェチル（5ml)を加え、 セライ ト濾過により触媒を除去 した。 瀘液は、 酢酸ェチル（5ml X2)で抽出し、 有機層を合わせ、 水 および飽和食塩水にて洗浄後、 無水硫酸マグネシゥムで乾燥した。 乾燥剤を除去した後、 減圧下で溶媒を留去し、 得られた粗生成物を 薄層クロマトグラフィー（展開溶媒；へキサン）で分離精製したとこ ろ、 （E)-ト [(4-卜リフルォロメチル）フヱニル] -1-へキセン（114mg, 0.50議 ol, 86%)を無色油状物として得た。 Under an argon atmosphere, a suspension of sodium hydroxide powder (140 mg, 3.5 niinol) in tetrahydrofuran (lml) was cooled to 0 ^, and dichloro ((E) -l-hexenyl) (methyl) silane (Omg, After dropwise addition of 0.71 O1), the mixture was stirred at room temperature for 1 hour. To this reaction solution was added 4-bromo (trifluoromethyl) benzene (130 mg, 0.58 dragonol) and a solution of palladium acetate (3.3 mg, 15 ^ ιηο1, 2.5 mol%) in tetrahydrofuran (0.4 ml) as a catalyst. The mixture was heated and stirred at 60 ° C for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The filtrate was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by thin-layer chromatography (developing solvent: hexane). Then, (E) -to [(4-trifluoromethyl) phenyl] -1-hexene (114 mg, 0.50 mol, 86%) was obtained as a colorless oil.

1H-NMR(200MHz,CDCl3): <5 0.93(t, J=7. OHz, 3H), 1.28- 1.57(m, 4H), 2.23(dt， J=5.8 and 6.9Hz， 2H)， 6.31(dt, J = 15.9 and 5.8Hz， 1H)， 6.4 2(d， J = 15.9Hz, 1H), 7.40(d, J=8.4Hz, 2H)， 7.53(d， J=8.4Hz, 2H). 1 H-NMR (200 MHz, CDCl 3 ): <5 0.93 (t, J = 7. OHz, 3H), 1.28-1.57 (m, 4H), 2.23 (dt, J = 5.8 and 6.9 Hz, 2H), 6.31 (dt, J = 15.9 and 5.8Hz, 1H), 6.42 (d, J = 15.9Hz, 1H), 7.40 (d, J = 8.4Hz, 2H), 7.53 (d, J = 8.4Hz, 2H).

IR(neat) :2950, 2920, 2860, 1610, 1325, 1160, 1120， 1105, 1065， 1010, 9 65cm" 実施例 7 IR (neat): 2950, 2920, 2860, 1610, 1325, 1160, 1120, 1105, 1065, 1010, 965cm "Example 7

n-C4H nC 4 H

Si(Me)CI CN

Figure imgf000027_0001
Si (Me) CI CN
Figure imgf000027_0001

アルゴン雰囲気下、 水酸化ナトリゥム粉末（52mg, 1.3mniol)のテト ラヒドロフラン懸濁液（lml)を 0°Cに冷却し、 ジクロロ（（E)-l-へキ セニル）（メチル）シラン（51mg， 0.73minol)を滴下した後、 室温で 1時 間撹拌した。 この反応溶液に、 4-ョ一 ドベンゾニトリル（46mg， 0.58 蘭 ol)および触媒として酢酸パラジゥム（2.2mg， lOit mol, 5.0mol )を 加え、 室温で 4.5時間撹拌した。 反応終了後、 反応溶液に水（5ml)お よび酢酸ェチル（5ml)を加え、 セライ 卜濾過により触媒を除去した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層と合わせ、 水および飽 和食塩水にて洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を 除去した後、 減圧下で溶媒を留去し、 得られた粗生成物を薄層クロ マトグラフィ一（展開溶媒；酢酸ェチル：へキサン = 1:5)で分離精製し たところ、 （E)-l- (4-シァノフエニル） -1-へキセン（30mg， 0.24匪 ol, 82%)を無色油状物として得た。 Under an argon atmosphere, a suspension of sodium hydroxide powder (52 mg, 1.3mniol) in tetrahydrofuran (1 ml) was cooled to 0 ° C, and dichloro ((E) -l-hexenyl) (methyl) silane (51 mg, (0.73 minol) was added dropwise, followed by stirring at room temperature for 1 hour. To this reaction solution, 4-chlorinated benzonitrile (46 mg, 0.58 orchid ol) and palladium acetate (2.2 mg, lOit mol, 5.0 mol) as a catalyst were added, and the mixture was stirred at room temperature for 4.5 hours. After completion of the reaction, water (5 ml) and ethyl acetate (5 ml) were added to the reaction solution, and the catalyst was removed by filtration through celite. The aqueous layer was extracted with ethyl acetate (5 ml X2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 5). E) -l- (4-Cyanophenyl) -1-hexene (30mg, 0.24 maraudal ol, 82%) as a colorless oil.

1H-NMR(200MHz,CDCl3): δ 0.92(t， J=7.1Hz, 3H), 1.20〜1.57(m, 4H), 2.18〜2.34(m, 2H), 6.33-6.43(m, 2H)， 7.38(d, J = 8.4Hz, 2H), 7.56(d， J=8.4Hz, 2H). 1 H-NMR (200 MHz, CDCl 3 ): δ 0.92 (t, J = 7.1 Hz, 3H), 1.20 to 1.57 (m, 4H), 2.18 to 2.34 (m, 2H), 6.33 to 6.43 (m, 2H) , 7.38 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H).

IR(neat) :2959, 2930, 2858, 2226, 1649, 1664, 1062, 968, 856, 831, 719cIR (neat): 2959, 2930, 2858, 2226, 1649, 1664, 1062, 968, 856, 831, 719c

HI" 1. 実施例 8 ^^Si(Me)CI2 + ^^Ph Ph アルゴン雰囲気下、 水酸化ナトリゥム粉末（52mg, 1.3mmol)のテ卜 ラヒドロフラン懸濁液（lml)を 0°Cに冷却し、 ジクロロ（（E)-l-へキ セニル）（メチル）シラン（137mg, 0.70龍 ol)を滴下した後、 室温で 1時 間撹拌した。 この反応溶液に、 （E)-^-ョードスチレン（138mg,0.60 顏 ol)および触媒として酢酸パラジゥ厶（2.2mg, ΙΟ^ιποΙ, 5. Omol%)を 加え、 室温で 4.5時間撹拌した。 反応終了後、 反応溶液に水（5ml )お よび酢酸ェチル（5ml)を加え、 セライ 卜濾過により触媒を除去した。 瀘液は、 酢酸ェチル (5ralx2)で抽出し、 有機層を合わせ、 水および 飽和食塩水にて洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤 を除去した後、 減圧下で溶媒を留去し、 得られた粗生成物を薄層ク ロマ卜グラフィー（展開溶媒；へキサン）で分離精製したところ、 （1E ， 3E)-1 -フエニル - 1， 3-ォクタジェン（65mg, 0.35画 1, 58¾)を無色油 状物として得た。 HI " 1. Example 8 ^^ Si (Me) CI 2 + ^^ Ph Ph A suspension of sodium hydroxide powder (52 mg, 1.3 mmol) in tetrahydrofuran (lml) was cooled to 0 ° C under an argon atmosphere. Then, dichloro ((E) -l-hexenyl) (methyl) silane (137 mg, 0.70 dragonol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. (138 mg, 0.60 mol) and palladium acetate (2.2 mg, ΙΟ ^ ιποΙ, 5. Omol%) as a catalyst were added, and the mixture was stirred at room temperature for 4.5 hours.After the reaction was completed, water (5 ml) and acetic acid were added to the reaction solution. The filtrate was extracted with ethyl acetate (5ralx2), the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to thin-layer chromatography (developing solvent; (1E, 3E) -1-phenyl-1,3-octadiene (65 mg, 0.35 fraction, 1,58¾) was obtained as a colorless oil.

'H-NMR(200 Hz, CDC13): δ 0.92(ΐ, J=7.3Hz, 3Η), 1.10〜1.71(m, 4Η), 1.9δ~2.40(m, 2Η)， 5.72(dt, J = 15.5 and 7.2Hz, 1H , 6.14(dd， J = 15.5 and 9.8Hz, 1H), 6.33(d, J = 15.5Hz, 1H), 6.66(dd, J = 15.5 and 9.8Hz, 1H). 'H-NMR (200 Hz, CDC1 3): δ 0.92 (ΐ, J = 7.3Hz, 3Η), 1.10~1.71 (m, 4Η), 1.9δ ~ 2.40 (m, 2Η), 5.72 (dt, J = 15.5 and 7.2Hz, 1H, 6.14 (dd, J = 15.5 and 9.8Hz, 1H), 6.33 (d, J = 15.5Hz, 1H), 6.66 (dd, J = 15.5 and 9.8Hz, 1H).

IR(neat):1645, 1595, 990cm-1. 実施例 9 IR (neat):. 1645, 1595, 990cm- 1 Example 9

n- H

Figure imgf000029_0001
アルゴン雰囲気下、 水酸化ナトリゥム粉末（52mg， 1.3mmol)のベン ゼン懸濁液（lml)を 0 に冷却し、 ジクロロ（（E)-l-へキセニル）（メ チル）シラン（51mg， 0.26IMO1)を滴下した後、 室温で 1時間撹拌した。 凍結脱気を 4回行った後、 この反応溶液に、 4-クロ口べンゾニトリ ル（27mg， 0.20iMol)および触媒として塩化パラジゥム [1, 2 _ビス（ジ シク口へキシルホスフィノ）エタン:;（5. Omg, 8^mol, 4.0mol%)を加え、 80 で 5時間加熱撹拌した。 反応終了後、 反応溶液に水（5ml)および 酢酸ェチル (5ml)を加え、 セライ ト濾過により触媒を除去した。 水 層を酢酸ェチル (5mlx2)で抽出し、 有機層と合わせ、 水および飽和 食塩水にて洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除 去した後、 減圧下で溶媒を留去し、 得られた粗生成物を薄層クロマ トグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:5)で分離精製した ところ、 （E)-l-(4-シァノフヱ二ル）- 1-へキセン（32mg, 0· 17mmol,86 %)を無色油状物として得た。 このもののスぺク トルデータは実施例 7で得たもののデータと一致した。 実施例 1 o n- H
Figure imgf000029_0001
Under an argon atmosphere, a benzene suspension (lml) of sodium hydroxide powder (52mg, 1.3mmol) was cooled to 0, and dichloro ((E) -l-hexenyl) (methyl) silane (51mg, 0.26IMO1 ) Was added dropwise, followed by stirring at room temperature for 1 hour. After four freeze degassing cycles, the reaction solution was added to 4-chlorobenzonitrile (27 mg, 0.20 iMol) and palladium chloride [1,2_bis (dicyclohexylphosphino) ethane] as a catalyst:; ( 5. Omg, 8 ^ mol, 4.0mol%), and the mixture was heated and stirred at 80 for 5 hours. After completion of the reaction, water (5 ml) and ethyl acetate (5 ml) were added to the reaction solution, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 2), combined with the organic layer, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 5). E) -l- (4-Cyanophenyl) -1-hexene (32 mg, 0.17 mmol, 86%) was obtained as a colorless oil. The spectral data of this was consistent with the data obtained in Example 7. Example 1 o

Figure imgf000030_0001
Figure imgf000030_0001

アルゴン雰囲気下、 水酸化ナ卜リウム粉末（210.3mg,5.26mniol)の ベンゼン懸濁液（lml)を 0てに冷却し、 ジクロロ（（E)-l-へキセニル） (メチル）シラン（207, 6nig, 1.05mmol)を滴下した後、 室温で 1時間撹 拌した。 この反応溶液に、 4-クロ口（トリフルォロメチル）ベンゼン (155.3mg, 0.86mmol)および触媒として塩化パラジゥム [1, 2 -ビス（ジ シク口へキシルホスフィノ）エタン] (12.9mg, 22 mol, 2.5mol¾)のべ ンゼン溶液（0.4ml) を加え、 80てで 12時間加熱撹拌した。 反応終了 後、 反応溶液を室温に冷却し、 水（5ml)および酢酸ェチル（5ml)を加 え、 セライ 卜濾過により触媒を除去した。 水層を酢酸ェチル（5ml X 2)で抽出し、 有機層と合わせ、 水および飽和食塩水にて洗浄後、 無 水硫酸マグネシウムで乾燥した。 乾燥剤を除去した後、 減圧下で溶 媒を留去し、 得られた粗生成物を薄層クロマトグラフィー（展開溶 媒；へキサン）で分離精製したところ、 目的の（E)- [(4-トリフルォ Dメチル）フヱニル] -1-へキセン（152mg， 0.67ramol, 785 を無色油状 物で得た。 このもののスペク トルデータは実施例 6で得たもののデ —タと一致した。 実施例 1 1  Under an argon atmosphere, a benzene suspension (1ml) of sodium hydroxide powder (210.3mg, 5.26mniol) was cooled to 0, and dichloro ((E) -l-hexenyl) (methyl) silane (207, (6nig, 1.05 mmol) was added dropwise, followed by stirring at room temperature for 1 hour. To this reaction solution, 4-chloro (trifluoromethyl) benzene (155.3 mg, 0.86 mmol) and palladium chloride [1,2-bis (dicyclohexylphosphino) ethane] (12.9 mg, 22 mol, A 2.5 mol%) benzene solution (0.4 ml) was added, and the mixture was heated with stirring at 80 rpm for 12 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by filtration through celite. The aqueous layer was extracted with ethyl acetate (5 ml × 2), combined with the organic layer, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; hexane) to obtain the desired (E)-[( 4-Trifluoro-D-methyl) phenyl] -1-hexene (152 mg, 0.67 ramol, 785) was obtained as a colorless oil. The spectral data of this compound were consistent with those obtained in Example 6. 1 1

n-C4H CI nC 4 H CI

Si(Me)CU + Si (Me) CU +

Figure imgf000030_0002
アルゴン雰囲気下、 水酸化ナ卜リゥム粉末（n5mg，4.4inmol)のべ ンゼン懸濁液（lffll)を 0 に冷却し、 ジクロロ（（E)-l-へキセニル）（ メチル）シラン（177mg, 0.88minol)を滴下した後、 室温で 1時間撹拌し た。 この反応溶液に、 2-クロ口ピリジン（90mg, 0.73mmol)および触 媒として塩化パラジウム [1,2-ビス（ジシクロへキシルホスフィノ） エタ ](llmg, 18^mol, 2.5mol!¾)のベンゼン溶液（0.4ml)を加え、 80 °Cで 12時間加熱撹拌した。 反応終了後、 反応溶液を室温に冷却し、 水（5ml)および酢酸ェチル（5ml)を加え、 セライ ト濾過により触媒を 除去した。 瀘液を酢酸ェチル (5ml X2)で抽出し、 有機層を合わせ、 水および飽和食塩水にて洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去した後、 減圧下で溶媒を留去し、 得られた粗生成物を 薄層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分 離精製したところ、 （E)-l-(2-ピリジル） - 1-へキセン（86mg，0.53隨 0 1， 73%)を無色油状物として得た。
Figure imgf000030_0002
Under an argon atmosphere, a benzene suspension (lffll) of sodium hydroxide powder (n5 mg, 4.4 inmol) was cooled to 0, and dichloro ((E) -l-hexenyl) (methyl) silane (177 mg, 0.88 minol), and the mixture was stirred at room temperature for 1 hour. To this reaction solution, a benzene solution of 2-chloropyridine (90 mg, 0.73 mmol) and palladium chloride [1,2-bis (dicyclohexylphosphino) eta] (llmg, 18 ^ mol, 2.5 mol! Mol) as a catalyst (0.4 ml), and the mixture was heated and stirred at 80 ° C for 12 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The filtrate was extracted with ethyl acetate (5 ml X2), the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7). ) -l- (2-Pyridyl) -l-hexene (86 mg, 0.53; 01, 73%) was obtained as a colorless oil.

'H-N R(200MHz,CDCl3): <5 0.92(t, J:7. OHz, 3H)， 1.30〜1.61(DI, 4H)， 2.26(dt, J = 6.7 and 6.8Hz, 2H)， 6.47(d, J = 15.7Hz, 1H), 6.74(dt, J = 15 .7 and 6.8Hz, 1H), 7.06(dd, J=4.9 and 7.7Hz， 1H), 7.22(d, J=7.7Hz, 1H), 7.58(dt, J = l.7 and 7.7Hz, 1H), 8.52(d， J=4.9Hz， 1H). 'HNR (200 MHz, CDCl 3 ): <5 0.92 (t, J: 7.OHz, 3H), 1.30 to 1.61 (DI, 4H), 2.26 (dt, J = 6.7 and 6.8 Hz, 2H), 6.47 ( d, J = 15.7Hz, 1H), 6.74 (dt, J = 15.7 and 6.8Hz, 1H), 7.06 (dd, J = 4.9 and 7.7Hz, 1H), 7.22 (d, J = 7.7Hz, 1H ), 7.58 (dt, J = l.7 and 7.7Hz, 1H), 8.52 (d, J = 4.9Hz, 1H).

IR(neat) :3000, 2950， 2910, 2850, 1650, 1580， 1560, 1465, 1425, 1150, 9 70,760, 740cm-1. IR (neat): 3000, 2950, 2910, 2850, 1650, 1580, 1560, 1465, 1425, 1150, 9 70,760, 740cm- 1 .

Figure imgf000031_0001
アルゴン雰囲気下、 水酸化ナトリウム粉末（52mg， 1.3 01)のテト ラヒドロフラン懸濁液（lml)を 0 に冷却し、 トリクロ口（2-フエ二 ルェチル）シラン（191mg，0.80蘭 ol)を滴下した後、 室温で 1時間撹拌 した。 この反応溶液に、 4-ョードアセトフヱノン（146mg, 0.60mmol) および触媒として酢酸パラジゥム（2.2mg, 10 inol，5. Omol¾)を加え、 60てで 5時間加熱撹拌した。 反応終了後、 反応溶液に水（5ml)および 酢酸ェチル (5ml)を加え、 セライ ト滤過により触媒を除去した。 水 層を酢酸ェチル（5ml x2)で抽出し、 有機層と合わせ、 水および飽和 食塩水にて洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除 去した後、 減圧下で溶媒を留去し、 得られた粗生成物を薄層クロマ トグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:10)で分離精製し たところ、 1-(4-ァセチルフヱニル） -2-フヱニルエタン（76mg, 0.34m mol, 57¾ を無色油状物として得た。
Figure imgf000031_0001
Under an argon atmosphere, a suspension of sodium hydroxide powder (52 mg, 1.301) in tetrahydrofuran (1 ml) was cooled to 0, and trichloro- (2-phenylethyl) silane (191 mg, 0.80 ol) was added dropwise. The mixture was stirred at room temperature for 1 hour. To this reaction solution were added 4-iodoacetophenone (146 mg, 0.60 mmol) and palladium acetate (2.2 mg, 10 inol, 5. Omol) as a catalyst, and the mixture was heated with stirring at 60 rpm for 5 hours. After completion of the reaction, water (5 ml) and ethyl acetate (5 ml) were added to the reaction solution, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 2), combined with the organic layer, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 10). 1- (4-Acetylphenyl) -2-phenylethane (76 mg, 0.34 mmol, 57%) was obtained as a colorless oil.

•H-N ROOMHz, CDC13): δ 2.55(s， 3H)， 2.95(s, 4H), 7.05〜7.40(m, 7H ),7.86(d, J=8.4Hz,2H). • HN ROOMHz, CDC1 3): δ 2.55 (s, 3H), 2.95 (s, 4H), 7.05~7.40 (m, 7H), 7.86 (d, J = 8.4Hz, 2H).

IR(neat):1680, 1608, 1360, 1265,820,750,700cm-1. 実施例 13 IR (neat):. 1680, 1608, 1360, 1265,820,750,700cm- 1 Example 13

Me Q~Si(Me)CI2 + r- ) ~ >Me Q ~ Si (Me) CI 2 + r-) ~>

Figure imgf000032_0001
Figure imgf000032_0001

アルゴン雰囲気下、 水酸化ナトリゥ厶粉末（588. Omg, 14.7minol)の テトラヒドロフラン懸濁液（5ml)を 0°Cに冷却し、 ジクロロ（メチル） (4-メチルフヱニル）シラン（600mg， 3.94ππηο1)を滴下した後、 室温で 3時間撹拌した。 別の反応容器中、 酢酸パラジウム（1.8mg，8 inol,0 · 8mol¾ )及びトリフヱニルホスフィ ン（4.3mg, 15 imol, 1.6mol%)の テトラヒ ドロフラン溶液（lml)を室温で 40分間撹拌して触媒を調製 した。 反応溶液に、 2-ブロモピリジン（162.4mg， 1.03ramol)及び調製 したパラジウム触媒のテトラヒ ドロフラン溶液を加え、 60 で 15時 間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml )及び酢酸ェチル (5ml)を加え、 セライ ト濾過により触媒を濾過した。 水層を酢酸ェチル (5ml X2)で抽出し、 有機層を合わせ、 水及び飽和 食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去 し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層クロマ卜グラ フィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分離精製し、 目的の 2- (4-メチルフヱニル）ピリジン（167. Omg, 0.99mmol,収率 95.8%)を無 色油状物として得た。 Under an argon atmosphere, a suspension of sodium hydroxide powder (588.Omg, 14.7minol) in tetrahydrofuran (5ml) was cooled to 0 ° C, and dichloro (methyl) (4-methylphenyl) silane (600mg, 3.94ππηο1) was added. After the dropwise addition, the mixture was stirred at room temperature for 3 hours. In a separate reaction vessel, palladium acetate (1.8 mg, 8 inol, 0.8 mol%) and triphenylphosphine (4.3 mg, 15 imol, 1.6 mol%) The catalyst was prepared by stirring the tetrahydrofuran solution (lml) at room temperature for 40 minutes. To the reaction solution were added 2-bromopyridine (162.4 mg, 1.03 ramol) and a solution of the prepared palladium catalyst in tetrahydrofuran, and the mixture was heated with stirring at 60 for 15 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7) to obtain the desired compound. -(4-Methylphenyl) pyridine (167. Omg, 0.99 mmol, yield 95.8%) was obtained as a colorless oil.

,H-NMRC200MHz,CDCl3): 5 2.40(s, 3H, CH3), 7.18(dd, J=3.9 and 5.2 Hz, 1H, HC(5)), 7.28(d, J=8.2Hz, 2H), 7.68-7.79(m, 2H， HC(3, 4)), 7.8 9(d, J=8.2Hz， 2H), 8.67(d, J=3.9Hz, 1H, HC(6)). , H-NMRC200MHz, CDCl 3 ): 5 2.40 (s, 3H, CH 3 ), 7.18 (dd, J = 3.9 and 5.2 Hz, 1H, HC (5)), 7.28 (d, J = 8.2 Hz, 2H) , 7.68-7.79 (m, 2H, HC (3, 4)), 7.89 (d, J = 8.2Hz, 2H), 8.67 (d, J = 3.9Hz, 1H, HC (6)).

Mass m/z:169(100¾,M+), 154(8), 91(7). Mass m / z: 169 (100 °, M + ), 154 (8), 91 (7).

IR(neat):3070, 3025, 2940, 2880, 1620, 1595， 1570, 1520， 1470， 1440, 8 35,780,750cm-'. 実施例 1 4

Figure imgf000033_0001
IR (neat): 3070, 3025, 2940, 2880, 1620, 1595, 1570, 1520, 1470, 1440, 8 35,780,750cm- '.
Figure imgf000033_0001

アルゴン雰囲気下、 水酸化ナ卜リウム粉末（377. Omg, 9.43匪 ol)の テトラヒ ドロフラン懸濁液（5ml)を 0°Cに冷却し、 ジクロロ（メチル） (フエニル）シラン（359.9mg, 1.90mmol)を滴下した後、 室温で 3時間 撹拌した。 別の反応容器中、 酢酸パラジウム（1.8mg, 8 mol,0.5niol %)及び卜リフヱニルホスフィン（4. lmg, 15 imol, l.Omo )のテトラ ヒドロフラン溶液（lml)を室温で 40分間撹拌して触媒を調製した。 反応溶液に、 4-プロモアセトフヱノン（313mg， 1.57mmol)及び調製し たパラジウム触媒のテトラヒドロフラン溶液を加え、 60°Cで 39時間 加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml) 及び酢酸ェチル (5ml)を加え、 セライ ト濾過により触媒を濾過した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層を合わせ、 水及び飽和 食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去 し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層クロマトグラ フィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分離精製し、 目的の 4-ァセチルビフエニル（274.6mg, 1.40mmol，収率 89.1%)を白色固体と して得た。 Under an argon atmosphere, a suspension of sodium hydroxide powder (377. Omg, 9.43 bandol) in tetrahydrofuran (5 ml) was cooled to 0 ° C, and dichloro (methyl) (phenyl) silane (359.9 mg, 1.90 mmol) was added. ) Was added dropwise, followed by stirring at room temperature for 3 hours. In another reaction vessel, palladium acetate (1.8 mg, 8 mol, 0.5 niol %) And triflunylphosphine (4.1 mg, 15 imol, l. Omo) in tetrahydrofuran (1 ml) were stirred at room temperature for 40 minutes to prepare a catalyst. To the reaction solution, 4-bromoacetophenone (313 mg, 1.57 mmol) and a prepared palladium catalyst in tetrahydrofuran solution were added, and the mixture was heated with stirring at 60 ° C for 39 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7) to obtain the desired 4- Acetylbiphenyl (274.6 mg, 1.40 mmol, 89.1% yield) was obtained as a white solid.

mp:121.5〜122.0て mp: 121.5 ~ 122.0

lH-NMR(200 Hz, CDC13): δ 2.64(s, 3H, C0CH3), 7.39〜7.50(m, 3H), 7. 57〜7.68(m, 2H), 7.69(d, J = 8.4Hz, 2H， HC(2， 6)), 8.04(d, J=8.4Hz, 2H， HC(3,5)). lH-NMR (200 Hz, CDC1 3): δ 2.64 (s, 3H, C0CH 3), 7.39~7.50 (m, 3H), 7. 57~7.68 (m, 2H), 7.69 (d, J = 8.4Hz , 2H, HC (2, 6)), 8.04 (d, J = 8.4Hz, 2H, HC (3,5)).

Mass m/z:196(51¾,M+), 181(100), 152(45), 76(10). Mass m / z: 196 (51 °, M + ), 181 (100), 152 (45), 76 (10).

IR( Br):3080, 3050, 3020, 1865, 1610, 1410， 1365, 1270, 840, 770, 700, IR (Br): 3080, 3050, 3020, 1865, 1610, 1410, 1365, 1270, 840, 770, 700,

600cm-1. 実施例 15

Figure imgf000034_0001
600cm- 1. Example 15
Figure imgf000034_0001

アルゴン雰囲気下、 水酸化ナトリゥ厶粉末（506.5mg, 12.7minol)の テトラヒ ドロフラン懸濁液（5ml)を 0°Cに冷却し、 ジクロロ（メチル） (4-メチルフヱニル）シラン（519.6mg,2.53imnol)を滴下した後、 室温 で 3時間撹拌した。 別の反応容器中、 酢酸パラジウム（2.4mg, ll mo 1， 0.5mo )及びトリフエニルホスフィ ン（5.5mg, 21 ^mol, 1. Omol¾) のテトラヒドロフラン溶液（0.3ml)を室温で 40分間撹拌して触媒を 調製した。 反応溶液に、 1-ブロモ -3， 5-ジトリフルォロメチルベン ゼン（580. Omg, 1.98ππηο1)及び調製したパラジウム触媒のテトラヒ ド 口フラン溶液を加え、 60てで 39時間加熱撹拌した。 反応終了後、 反 応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5πι1)を加え、 セ ライ ト濾過により触媒を濾過した。 水層を酢酸ェチル（5ml Χ3)で抽 出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネ シゥムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得ら れた粗生成物を薄層クロマ卜グラフィー（展開溶媒；酢酸ェチル：へ キサン = 1:19)で分離精製し、 目的の 3,5-ジ卜リフルォロメチル- 4'- メチルビフエニル（514. Omg, 1.69mmol,収率 85.45 を無色油状物とし て得た。 Under argon atmosphere, sodium hydroxide powder (506.5mg, 12.7minol) The tetrahydrofuran suspension (5 ml) was cooled to 0 ° C, and dichloro (methyl) (4-methylphenyl) silane (519.6 mg, 2.53 imnol) was added dropwise, followed by stirring at room temperature for 3 hours. In a separate reaction vessel, stir a solution of palladium acetate (2.4 mg, llmo 1, 0.5 mol) and triphenylphosphine (5.5 mg, 21 ^ mol, 1. Omol¾) in tetrahydrofuran (0.3 ml) at room temperature for 40 minutes. Thus, a catalyst was prepared. To the reaction solution were added 1-bromo-3,5-ditrifluoromethylbenzene (580.Omg, 1.98ππηο1) and a prepared furan solution of a palladium catalyst in a tetrahydrofuran, and the mixture was heated and stirred at 60 ° C for 39 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5πι1) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 mlΧ3), the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 19) to obtain the desired product. , 5-Ditrifluoromethyl-4'-methylbiphenyl (514.Omg, 1.69mmol, yield 85.45) as a colorless oil.

,H-NMR(200MHz)CDCl3): δ 2.40(s， 3H， CH3), 7.29(d, J=8.1Hz, 2H, HC( 3'， 5' )， 7.48(d, J = 8.1Hz, 2H， HC(2' , 6' )， 7.82(s, 1H, HC(4))， 7.98(s， 2 H， HC(2，6)). , H-NMR (200MHz ) CDCl 3 ): δ 2.40 (s, 3H, CH 3 ), 7.29 (d, J = 8.1Hz, 2H, HC (3 ′, 5 ′), 7.48 (d, J = 8.1Hz) , 2H, HC (2 ', 6'), 7.82 (s, 1H, HC (4)), 7.98 (s, 2H, HC (2,6)).

Mass m/z:304( +, 100%)， 285(13), 235(24), 215(9), 165(22). Mass m / z: 304 ( + , 100%), 285 (13), 235 (24), 215 (9), 165 (22).

IR(neat):1385, 1280, 1180, 1135, 1060, 900, 820, 685cm"1. 実施例 1 6

Figure imgf000036_0001
IR (neat): 1385, 1280, 1180, 1135, 1060, 900, 820, 685cm " 1 . Example 16
Figure imgf000036_0001

アルゴン雰囲気下、 水酸化ナトリウム粉末（264.0mg，6.60mmol)の テトラヒドロフラン懸濁液（2ml)を 0°Cに冷却し、 ジクロロ（ェチル） ((Z)-l-ォクチル）シラン（315.2mg， 1.32匪 ol)を滴下した後、 室温で 1時間撹拌した。 反応溶液に、 3 -プロモアセトフヱノ ン（217.5mg, 1. 09mmol)及び触媒として酢酸パラジゥム（6.2mg, 28 mol, 2.5mol%)の テトラヒドロフラン溶液（2ml)を加え、 60てで 12時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（ 5ml)を加え、 セライ 卜濾過により触媒を濾過した。 水層を酢酸ェチ ル (5ml X 3)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下 に留去し、 得られた粗生成物を薄層クロマトグラフィー（展開溶媒； 酢酸ェチル：へキサン = 1:7)で分離精製し、 目的の（Z)-l-(3-ァセチ ルフエ二ル）- 1-ォクテン（175. Omg, 0.76画 1，収率 69.7¾)を無色油状 物として得た。 Under an argon atmosphere, a suspension of sodium hydroxide powder (264.0 mg, 6.60 mmol) in tetrahydrofuran (2 ml) was cooled to 0 ° C, and dichloro (ethyl) ((Z) -l-octyl) silane (315.2 mg, 1.32 mg) was added. After dropping ol (ol), the mixture was stirred at room temperature for 1 hour. To the reaction solution was added 3-bromoacetophenone (217.5 mg , 1.09 mmol) and a solution of palladium acetate (6.2 mg, 28 mol, 2.5 mol%) in tetrahydrofuran (2 ml) as a catalyst. The mixture was heated and stirred for an hour. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 3), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7) to obtain the desired (Z). -l- (3-Acetylphenyl) -1-octene (175.Omg, 0.76 fraction 1, yield 69.7¾) was obtained as a colorless oil.

1H-NMR(200Mz, CDC13): δ 0.87(ΐ, J=6.9Hz, 3H, CH3), 1.20〜1.51(m， 8 H), 2.27〜2.40(m, 2H), 2.60(s, 3H, C0CH3), 5.75(dt, J = ll.7 and 7.3H z, 1H), 6.44(d, J = ll.7Hz, 1H), 7.41(dd, J=7.5 and 7.5Hz, 1H,HC(5)), 7.43(d, J=7.5Hz， 1H, HC(4)), 7.81(d, J=7.5Hz， 1H， HC(6))， 7.85(s( 1H( HC(2)). 1 H-NMR (200Mz, CDC1 3): δ 0.87 (ΐ, J = 6.9Hz, 3H, CH 3), 1.20~1.51 (m, 8 H), 2.27~2.40 (m, 2H), 2.60 (s, 3H, C0CH 3 ), 5.75 (dt, J = ll.7 and 7.3H z, 1H), 6.44 (d, J = ll.7Hz, 1H), 7.41 (dd, J = 7.5 and 7.5Hz, 1H, HC (5)), 7.43 (d, J = 7.5Hz, 1H, HC (4)), 7.81 (d, J = 7.5Hz, 1H, HC (6)), 7.85 (s ( 1H ( HC (2)) .

Mass m/z:230( +, 29¾), 146(37), 131(41), 43(100). Mass m / z: 230 ( + , 29¾), 146 (37), 131 (41), 43 (100).

IR(neat) :2950, 2930, 2850, 1690, 1360, 1260,810,695cm-'. Anal. Calcd for CI6H220: C, 83.43; H, 9.63. IR (neat): 2950, 2930, 2850, 1690, 1360, 1260,810,695cm- '. Anal.Calcd for C I6 H 22 0: C, 83.43; H, 9.63.

Found: C, 83.58; H, 9.63. 実施例 1 7Found: C, 83.58; H, 9.63. Example 17

Figure imgf000037_0001
Figure imgf000037_0001

アルゴン雰囲気下、 水酸化ナ卜リウ厶粉末（133.6mg, 3.34腿 ol)の テトラヒドロフラン懸濁液（2ml)を 0 に冷却し、 ジクロロ（ェチル） ((Z)-l-ォクチル）シラン（157.6mg, 0.66mmol)を滴下した後、 室温で Under an argon atmosphere, a suspension of sodium hydroxide powder (133.6 mg, 3.34 mol) in tetrahydrofuran (2 ml) was cooled to 0, and dichloro (ethyl) ((Z) -l-octyl) silane (157.6 mg) was added. , 0.66 mmol) at room temperature

1時間撹拌した。 反応溶液に、 1-ブロモ -3,5-ジトリフルォロメチル ベンゼン（163. Omg, 0.56mniol)及び触媒として酢酸パラジゥム（3. Img , 14 raol, 2.5moll¾)のテトラヒ ドロフラン溶液（lml)を加え、 60てで 12時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水 (5ml)及び酢酸ェチル（5nil)を加え、 セライ ト濾過により触媒を濾過 した。 水層を酢酸ェチル (5ml Χ3)で抽出し、 有機層を合わせ、 水及 び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤 を除去し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層クロマ トグラフィー（展開溶媒;齚酸ェチル：へキサン = 1:7)で分離精製し、 目的の（Z)-卜（3， 5-ジトリフルォロメチルフエニル） -1-ォクテン（14 2. Img, 0.44画 1，収率 66.4%)を無色油状物として得た。 Stir for 1 hour. To the reaction solution was added 1-bromo-3,5-ditrifluoromethylbenzene (163.Omg, 0.56mniol) and a solution of palladium acetate (3.Img, 14 raol, 2.5moll) in tetrahydrofuran (lml) as a catalyst. In addition, the mixture was heated and stirred at 60 ° for 12 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5nil) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 mlΧ3), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7) to obtain the desired ( Z)-(3,5-Ditrifluoromethylphenyl) -1-octene (142. Img, 0.44 fraction 1, yield 66.4%) was obtained as a colorless oil.

'H- MR(200MHz, CDC13): ( 0.88(t, J = 6.0Hz, 3H， CH3), 1.20〜1.60(m, 8H), 2.29(dt， J=7.4 and 7.5Hz, 2H), 5.89(td, J=7.4 and 11.5Hz)， 6. 45(d, J = ll.5Hz, 1H)， 7.69(s, 2H, HC(2, 6))， 7.74(s, 1H, HC(4)). 'H- MR (200MHz, CDC1 3 ): (0.88 (t, J = 6.0Hz, 3H, CH 3), 1.20~1.60 (m, 8H), 2.29 (dt, J = 7.4 and 7.5Hz, 2H), 5.89 (td, J = 7.4 and 11.5Hz), 6.45 (d, J = ll.5Hz, 1H), 7.69 (s, 2H, HC (2, 6)), 7.74 (s, 1H, HC (4 )).

Mass m/z:324(M+, 10¾), 305(3), 293(2), 279(1), 267(1), 253(8), 240( 100). Mass m / z: 324 (M + , 10¾), 305 (3), 293 (2), 279 (1), 267 (1), 253 (8), 240 ( 100).

IR(neat) :2950, 2930, 2850, 1365, 1280, 1175, 1140, 895, 690cm- 1. Anal. Calcd for Cl t(H1 8F6 : C, 59. 26 ; H, 5. 59. IR (neat): 2950, 2930 , 2850, 1365, 1280, 1175, 1140, 895, 690cm- 1 Anal Calcd for C lt (H 1 8 F 6:.. C, 59. 26; H, 5. 59.

Found: C, 59. 23; H, 5. 64. 実施例 1 8

Figure imgf000038_0001
Found: C, 59. 23; H, 5.64. Example 18
Figure imgf000038_0001

アルゴン雰囲気下、 水酸化ナトリウム粉末（469. 4mg， 11. 7mmol)の テトラヒドロフラン懸濁液（5ml )を 0 に冷却し、 1-ジクロロ（メチ ル）シリル -2- ト リメチルシリル-（E)-ビニレン（500. 5mg， 2. 35mmol) を滴下した後、 室温で 1時間撹拌した。 反応溶液に、 3-プロモアセ トフヱノン（390, Omg, 1. 96mmol)及び触媒として酢酸パラジゥム（11. 0 ，49 11101, 2. 511101!¾)を加ぇ、 60°Cで 12時間加熱撹拌した。 反応終 了後、 反応溶液を室温まで冷却し、 水（5ml )及び酢酸ェチル（5ml)を 加え、 セライ ト濾過により触媒を濾過した。 水層を酢酸ェチル（5ml X 3)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水 硫酸マグネシウムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留 去し、 得られた粗生成物を薄層クロマトグラフィー（展開溶媒；酢酸 ェチル：へキサン = 1 : 19)で分離精製し、 目的の 3- (2-トリメチルシリ ル -(E)-レエチニル）ァセ トフエノン（265. Omg, 1. 21画 1，収率 62. 0¾) を無色油状物として得た。  Under an argon atmosphere, a suspension of sodium hydroxide powder (469.4 mg, 11.7 mmol) in tetrahydrofuran (5 ml) was cooled to 0, and 1-dichloro (methyl) silyl-2-trimethylsilyl- (E) -vinylene was cooled. (50.5 mg, 2.35 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. To the reaction solution, 3-promosetphenone (390, Omg, 1.96 mmol) and palladium acetate (11.0, 49 11101, 2.511101!) As a catalyst were added, and the mixture was heated with stirring at 60 ° C. for 12 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 3), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 19) to give the desired 3- ( 2-Trimethylsilyl- (E) -retinyl) acetophenone (265.Omg, 1.21 fraction 1, yield 62.0¾) was obtained as a colorless oil.

Ή-ΝΜΚ(200ΜΗζ, CDC13) : δ 0. 25(s, 9H， CH3), 2. 70(s, 3H, C0CH3), 6. 65 (d, J = 19. 2Hz, 1H), 7. 00(d, J = 19. 2Hz, 1H)， 7. 50(t, J=7. 7Hz, 1H, HC(5) ) , 7.72(d, J=7.7Hz, IH, HC(4))， 7.91(d, J=7.7Hz, IH, HC(6)), 8.09(s, IH ,HC(2)). Ή-ΝΜΚ (200ΜΗζ, CDC1 3 ): δ 0. 25 (s, 9H, CH 3), 2. 70 (s, 3H, C0CH 3), 6. 65 (d, J = 19. 2Hz, 1H), 7.00 (d, J = 19.2 Hz, 1H), 7.50 (t, J = 7.7 Hz, 1H, HC (5)) , 7.72 (d, J = 7.7Hz, IH, HC (4)), 7.91 (d, J = 7.7Hz, IH, HC (6)), 8.09 (s, IH, HC (2)).

Mass m/z:218(42¾,M+), 203(61), 186(100), 159(16), 145(10), 129(9) ,115(8). Mass m / z: 218 (42 °, M + ), 203 (61), 186 (100), 159 (16), 145 (10), 129 (9), 115 (8).

IR(neat):2970, 2910, 1690, 1430, 1380, 1270, 1250, 990， 870, 845, 790, 690cm-1. IR (neat): 2970, 2910, 1690, 1430, 1380, 1270, 1250, 990, 870, 845, 790, 690cm- 1 .

Anal. Calcd for C13H180Si: C71.50; H, 8.31. Anal.Calcd for C 13 H 18 0Si: C71.50; H, 8.31.

Found: C, 71.44; H, 8.31. 実施例 1 9Found: C, 71.44; H, 8.31.

Figure imgf000039_0001
Figure imgf000039_0001

アルゴン雰囲気下、 水酸化ナ卜リゥム粉末（221.3mg, 5.53mmol)の テトラヒドロフラン懸濁液（5ml)を 0°Cに冷却し、 1-ジクロロ（メチ ル）シリル -2-トリメチルシリル- (E)-ビニレン（237.4ng, 1. llmmol) を滴下した後、 室温で 1時間撹拌した。 反応溶液に、 1-ブロモ -3,5- ジトリフルォロメチルベンゼン（266.2mg， 0.91mmol)及び触媒として 醜パラジゥ厶（5. l g, 23 imol, 2.5mol¾)を加え、 60°Cで 36時間加 熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml)及 び酢酸ェチル（5ml)を加え、 セライ 卜濾過により触媒を濾過した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層を合わせ、 水及び飽和 食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去 し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層クロマトグラ フィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分離精製し、 目的の 3, 5 -ジトリフルォロメチル- 1- (2-卜リメチルシリノレ- (E)-l-ェチニ ル）ベンゼン（210.5mg， 0.67minol,収率 74.1%)を白色固体として得た。 即：57.0〜58.0 Under an argon atmosphere, a suspension of sodium hydroxide powder (221.3 mg, 5.53 mmol) in tetrahydrofuran (5 ml) was cooled to 0 ° C, and 1-dichloro (methyl) silyl-2-trimethylsilyl- (E)- After vinylene (237.4 ng, 1. llmmol) was added dropwise, the mixture was stirred at room temperature for 1 hour. To the reaction solution, 1-bromo-3,5-ditrifluoromethylbenzene (266.2 mg, 0.91 mmol) and palladium as a catalyst (5. lg, 23 imol, 2.5 mol%) were added, and the mixture was added at 60 ° C. Heated and stirred for hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 7), and the desired product was purified. 3,5-Ditrifluoromethyl-1- (2-trimethylsilinole- (E) -l-ethynyl) benzene (210.5 mg, 0.67 minol, yield 74.1%) was obtained as a white solid. Immediately: 57.0-58.0

,H-NMR(200MHz,CDCl3): δ 0.22(s， 9H,CH3)， 6.71(d, J = 19.1Hz, 1H),6 .95(d, J = 19. lHz， 1H), 7.77(s, 1H, HC(4))， 7.87(s, 2H, HC(2, 6)). , H-NMR (200 MHz, CDCl 3 ): δ 0.22 (s, 9H, CH 3 ), 6.71 (d, J = 19.1 Hz, 1H), 6.95 (d, J = 19. lHz, 1H), 7.77 (s, 1H, HC (4)), 7.87 (s, 2H, HC (2, 6)).

Mass m/z:312(2.3¾, +), 297(91), 216(92), 201(7), 182(8), 169(9), 1 51(15), 77(68), 59(100). Mass m / z: 312 (2.3¾, + ), 297 (91), 216 (92), 201 (7), 182 (8), 169 (9), 151 (15), 77 (68), 59 (100).

IR( Br):2950,2900, 1375, 1280, 1250, 1170, 1140, 985， 840cm—  IR (Br): 2950, 2900, 1375, 1280, 1250, 1170, 1140, 985, 840cm—

Anal. Calcd for C13H14F6Si: C, 50.00; H, 4.52, Anal.Calcd for C 13 H 14 F 6 Si: C, 50.00; H, 4.52,

Found: C, 50.18; H, 4.66. 実施例 2 0 n-C.Hi W Si(Et)CI2 +

Figure imgf000040_0001
Found: C, 50.18; H, 4.66. Example 20 nC.Hi W Si (Et) CI 2 +
Figure imgf000040_0001

アルゴン雰囲気下、 水酸化ナトリゥム粉末（478.8mg, 11.9mmol)の ベンゼン懸濁液（3ml)を 0 に冷却し、 ジクロロ（ェチル）（（Z)-l-ォ クチル）シラン（374.3mg, 1.56imnol)を滴下した後、 室温で 1時間撹拌 した。 反応溶液に、 4-クロ口（トリフルォロメチル）ベンゼン（236.3 mg, 1.31mniol)及び触媒として塩化パラジウム [1，2-ビス（ジシクロへ キシルホスフィノ；)エタン] (19.6mg, 33 mol, 2.5mol¾)を加え、 80て で 12時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過により触媒を濾 過した。 水層を 酢酸ェチル（5ml X3)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾 燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層ク 口マトグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:19)で分離精 製し、 目的の（Z)- 1-(4-トリフルォロメチルフヱ二ル）- 1-ォクテン（ 185. Omg, 0.722画 1，収率 55.1%)を無色油状物として得た。 Under an argon atmosphere, a suspension of sodium hydroxide powder (478.8 mg, 11.9 mmol) in benzene (3 ml) was cooled to 0, and dichloro (ethyl) ((Z) -l-octyl) silane (374.3 mg, 1.56 imnol ) Was added dropwise, followed by stirring at room temperature for 1 hour. To the reaction solution, 4-chloro (trifluoromethyl) benzene (236.3 mg, 1.31mniol) and palladium chloride [1,2-bis (dicyclohexylphosphino;) ethane] as a catalyst (19.6 mg, 33 mol, 2.5 mol¾) ), And the mixture was heated and stirred at 80 ° C. for 12 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered off by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X3), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. Dry The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 19), (Z) -1- (4-Trifluoromethylphenyl) -1-octene (185.Omg, 0.722 fraction 1, yield 55.1%) was obtained as a colorless oil.

,H-NMR(200MHz,CDCl3): δ 0.87(t, J=6.5Hz, 3H, CH3), 1.17-1.56(m, 8H), 2. Π〜2.36(m, 2H), 5.77(dt, J = ll.7 and 7.3Hz, 1H), 6.41(d， J =l 1.7Hz, 1H), 7.36(d, J=8.3Hz, 2H, HC(3, 5)), 7.57(d, J=8.3Hz, 2H, HC(2, 6)). , H-NMR (200 MHz, CDCl 3 ): δ 0.87 (t, J = 6.5 Hz, 3H, CH 3 ), 1.17-1.56 (m, 8H), 2.Π-2.36 (m, 2H), 5.77 (dt , J = ll.7 and 7.3Hz, 1H), 6.41 (d, J = l 1.7Hz, 1H), 7.36 (d, J = 8.3Hz, 2H, HC (3, 5)), 7.57 (d, J = 8.3Hz, 2H, HC (2, 6)).

Mass m/z:256(15¾, M+), 237(4), 185(19), 172(100). Mass m / z: 256 (15 °, M + ), 237 (4), 185 (19), 172 (100).

IR(neat) :2950, 2930, 2850, 1615, 1330, 1165, 1130, 1070,850cm—1. Anal. Calcd for C15H19F3 ： C, 70.29; H, 7.47. IR (neat): 2950, 2930, 2850, 1615, 1330, 1165, 1130, 1070,850cm- 1 . Anal. Calcd for C 15 H 19 F 3 : C, 70.29; H, 7.47.

Found: C, 70.11; H, 7.69. 実施例 2 1 Found: C, 70.11; H, 7.69. Example 2 1

n- H9ゝ 八 n-H 9ゝ 8

Si( e)CI2 + Cl-C CF3 Si (e) CI 2 + Cl-C CF 3

n-

Figure imgf000041_0001
アルゴン雰囲気下、 水酸化ナトリウ厶粉末（236.7mg，5.92mmol)の ベンゼン懸濁液（3ml)を 0 に冷却し、 ジクロロ（（E)-l-へキセニル） (メチル）シラン（233.6mg, 1.18mmol)を滴下した後、 室温で 1時間撹 拌した。 反応溶液に、 4-クロ口（トリフルォロメチル）ベンゼン（175 .5mg, 0·97ΜΙΟ1)及び触媒として塩化パラジウム [ビス（トリイソプロ ピルホスフィン）] (12. lmg,
Figure imgf000041_0002
2.5mol%)を加え、 80。Cで 12時間 加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml) 及び酢酸ェチル（5ml)を加え、 セライ 卜濾過により触媒を濾過した。 水層を酢酸ェチル（5ml x3)で抽出し、 有機層を合わせ、 水及び飽和 食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去 し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層クロマトグラ フィー（展開溶媒；酢酸ェチル：へキサン = 1:19)で分離精製し、 目的 の（E)-l-[(4-卜リフルォロメチル）フヱニル] -1-へキセン（211. lmg, 0.925mmol,収率 95.3 )を無色油状物として得た。 このもののスぺク トルデータは実施例 6で得たもののデータと一致した。 実施例 22 n-
Figure imgf000041_0001
Under an argon atmosphere, a suspension (3 ml) of sodium hydroxide powder (236.7 mg, 5.92 mmol) in benzene was cooled to 0, and dichloro ((E) -l-hexenyl) (methyl) silane (233.6 mg, 1.18 mmol) was added. (mmol) was added dropwise, followed by stirring at room temperature for 1 hour. To the reaction solution, 4-chloro (trifluoromethyl) benzene (175.5 mg, 0.971) and palladium chloride [bis (triisopropylpropylphosphine)] (12.lmg,
Figure imgf000041_0002
2.5 mol%). The mixture was heated and stirred at C for 12 hours. After completion of the reaction, the reaction solution is cooled to room temperature, and water (5 ml) And ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 3), the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 19) to obtain the desired (E) ) -l-[(4-Trifluoromethyl) phenyl] -1-hexene (211.1 mg, 0.925 mmol, yield 95.3) was obtained as a colorless oil. The spectral data of this was consistent with the data obtained in Example 6. Example 22

n- H9 n- H 9

Figure imgf000042_0001
Figure imgf000042_0001

アルゴン雰囲気下、 水酸化ナトリゥム粉末（141.4mg, 3.54mmol)の ベンゼン懸濁液（3ml)を 0。Cに冷却し、 ジクロロ（（E)-l-へキセニル） (メチル）シラン（140. lmg, 0.71DIIBO1)を滴下した後、 室温で 1時間撹 拌した。 反応溶液に、 2-クロ口ピリジン（66.6mg, 0.59關01)及び触 媒として塩化パラジゥム [ビス（トリィソプロピルホスフィン）] (7.3 mg, 15 mol， 2.5mol¾)を加え、 80 で 12時間加熱撹拌した。 反応終 了後、 反応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を 加え、 セライ ト濾過により触媒を濾過した。 水層を酢酸ェチル（5ml x2)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水 硫酸マグネシウムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留 去し、 得られた粗生成物を薄層クロマ卜グラフィー（展開溶媒；酢酸 ェチル：へキサン =1:7)で分離精製し、 目的の（E)-卜（2-ピリジル） -1 -へキセン（75. Omg, 0.465mmol,収率 78.8¾)を無色油状物として得た。 このもののスぺク トルデータは実施例 1 1で得たもののデータと一 致した。 実施例 2 3 Under an argon atmosphere, a benzene suspension (3 ml) of sodium hydroxide powder (141.4 mg, 3.54 mmol) was added. After cooling to C, dichloro ((E) -1-hexenyl) (methyl) silane (140.lmg, 0.71DIIBO1) was added dropwise, and the mixture was stirred at room temperature for 1 hour. To the reaction solution were added 2-chloropyridine (66.6 mg, 0.59) and palladium chloride [bis (trisopropylphosphine)] (7.3 mg, 15 mol, 2.5 mol) as a catalyst, and heated at 80 for 12 hours. Stirred. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7) to obtain the desired (E) ) -Toluene (2-pyridyl) -1-hexene (75. Omg, 0.465 mmol, yield 78.8¾) was obtained as a colorless oil. The spectrum data of this sample was consistent with the data obtained in Example 11. Example 2 3

Πーレ 4Π9Pale 4Π9

Figure imgf000043_0001
Figure imgf000043_0001

アルゴン雰囲気下、 水酸化ナトリゥ厶粉末（198.6mg,4.97minol)の ベンゼン懸濁液（3ml)を 0°Cに冷却し、 ジクロロ（（E)- 1-へキセニル） (メチル）シラン（197.2mg, 0· 99ramol)を滴下した後、 室温で 1時間撹 拌した。 反応溶液に、 3-クロ口トルエン（107. Omg, 0.845mmol)及び 触媒として塩化パラジウム [ビス（卜リイソプロピルホスフィン）] (1 0.3mg,21 mol, 2.5mol%)を加え、 80 で 12時間加熱撹拌した。 反応 終了後、 反応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル (5ml) を加え、 セライ ト濾過により触媒を濾過した。 水層を酢酸ェチル (5 mix 3)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無 水硫酸マグネシウムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に 留去し、 得られた粗生成物を薄層クロマ卜グラフィ ー（展開溶媒；酢 酸ェチル：へキサン = 1:19)で分離精製し、 目的の（E)-l-(3-メチルフ ェニル） -卜へキセン（133. Omg, 0.736丽 ol，収率 91.0¾)を無色油状物 として得た。 このもののスぺク トルデータは実施例 4で得たものの データと一致した。 実施例 24

Figure imgf000044_0001
Under an argon atmosphere, a benzene suspension (3 ml) of sodium hydroxide powder (198.6 mg, 4.97 minol) was cooled to 0 ° C, and dichloro ((E) -1-hexenyl) (methyl) silane (197.2 mg , 0.99ramol) was added dropwise, followed by stirring at room temperature for 1 hour. To the reaction solution, 3-chlorotoluene toluene (107. Omg, 0.845 mmol) and palladium chloride [bis (triisopropylphosphine)] (1 0.3 mg, 21 mol, 2.5 mol%) as a catalyst were added, and the mixture was stirred at 80 for 12 hours. The mixture was heated and stirred. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 mix 3), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 19). (E) -l- (3-Methylphenyl) -trihexene (133.Omg, 0.736 丽 ol, yield 91.0¾) was obtained as a colorless oil. The spectral data of this was consistent with the data obtained in Example 4. Example 24
Figure imgf000044_0001

アルゴン雰囲気下、 水酸化ナトリウム粉末（343.8mg，8.60mraol)の ベンゼン懸濁液（3ml)を 0 に冷却し、 ジクロロ（（E)-l-へキセニル） (メチル）シラン（342.5mg， 1.74ramol)を滴下した後、 室温で 1時間撹 拌した。 反応溶液に、 3-クロロアセトフヱノン（222. Orag, 1.44miDol) 及び触媒として塩化パラジウム [ビス（トリイソプロピルホスフィン

Figure imgf000044_0002
36 11101,2.511101¾)を加ぇ、 80てで 12時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（ 5ml)を加え、 セライ ト濾過により触媒を濾過した。 水層を酢酸ェチ ル（5mlx3)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下 に留去し、 得られた粗生成物を薄層クロマトグラフィー（展開溶媒； 酢酸ェチル：へキサン = 1:19)で分離精製し、 目的の（E)-l-(3-ァセチ ルフヱニル） -1-へキセン（190. Omg, 0.94mmol,収率 65.25 を無色油状 物として得た。 このもののスぺク トルデータは実施例 5で得たもの のデータと一致した。 実施例 25
Figure imgf000044_0003
Under an argon atmosphere, a benzene suspension (33.8 mg) of sodium hydroxide powder (343.8 mg, 8.60 mraol) was cooled to 0, and dichloro ((E) -l-hexenyl) (methyl) silane (342.5 mg, 1.74 ramol) was added. ) Was added dropwise, followed by stirring at room temperature for 1 hour. Add 3-chloroacetophenone (222.Orag, 1.44miDol) and palladium chloride [bis (triisopropylphosphine)
Figure imgf000044_0002
36 11101, 2.511101¾), and the mixture was heated and stirred at 80 ° C. for 12 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 3), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 19) to obtain the desired compound (E). -l- (3-Acetylphenyl) -1-hexene (190. Omg, 0.94 mmol, yield 65.25) was obtained as a colorless oil, and the spectrum data of this was obtained in Example 5. Example 25
Figure imgf000044_0003

アルゴン雰囲気下、 フッ化力リゥム（358mg, 6.2隱 ol)の Ν,Ν-ジメ チルホルムアミ ド懸濁液（3ml)を 0°Cに冷却し、 ジクロロ（ェチル）（4 -メ トキシフヱニル）シラン（289mg, 1.2mmol)を滴下した後、 60 で 3 時間撹拌した。 冷却後、 反応溶液に、 4-クロ口べンゾニトリル（135 rag, 0.98mmol)およびパラジウム触媒として塩化パラジウム [ビス（ト リイソプロピルホスフィン）] (2.6mg,5 mol)を加え、 120°Cで 20時 間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml )および酢酸ェチル (5ml)を加え、 セライ ト濾過により触媒を除去し た。 水層を酢酸ェチル (5ml X2)で抽出し、 有機層と合わせ、 水およ び飽和食塩水により洗浄後、 無水硫酸マグネシウムで乾燥した。 乾 燥剤を除去した後、 減圧下で溶媒を留去し、 得られた粗生成物を薄 層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサン- 1:5)で分離 精製したところ、 4-シァノ _4'-メ トキシビフヱニル（195mg, 0.93隱 0 1,95¾ を白色針状結晶として得た。 Under an argon atmosphere, a suspension of fluorinated realm (358 mg, 6.2 mmol) in Ν, Ν-dimethylformamide (3 ml) was cooled to 0 ° C, and dichloro (ethyl) (4 After addition of-(methoxyphenyl) silane (289 mg, 1.2 mmol), the mixture was stirred at 60 for 3 hours. After cooling, benzonitrile 4-chloro (135 rag, 0.98 mmol) and palladium chloride [bis (triisopropylphosphine)] (2.6 mg, 5 mol) as a palladium catalyst were added to the reaction solution. The mixture was heated and stirred for hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), combined with the organic layer, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the drying agent, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane-1: 5). Cyano_4'-methoxybiphenyl (195 mg, 0.93 concealed 0,95%) was obtained as white needle crystals.

'H-NMROOMHz, CDC13): δ 3.86(s， 3H), 7.01(d, J = 9, 0Hz, 2H)， 7.55(d， J=9.0Hz,2H),7.66(s，4H) 'H-NMROOMHz, CDC1 3) : δ 3.86 (s, 3H), 7.01 (d, J = 9, 0Hz, 2H), 7.55 (d, J = 9.0Hz, 2H), 7.66 (s, 4H)

IR(KBr):2200, 1600， 1490, 1235, 820， 816, 562, 532cm—1. 実施例 26IR (KBr): 2200, 1600, 1490, 1235, 820, 816, 562, 532cm— 1 .

Figure imgf000045_0001
Figure imgf000045_0001

アルゴン雰囲気下、 フッ化カリゥム（251mg,4.3mniol)の Ν,Ν-ジメ チルホル厶アミ ド懸濁液（3ml)を 0°Cに冷却し、 ジクロロ（ェチル）（4 -メ トキシフヱニル）シラン（202nig， 0.86 01)を滴下した後、 60°Cで 3時間撹拌した。 冷却後、 反応溶液に、 4-クロロアセトフエノン（11 lmg, 0.72mmol)およびノ ラジウム触媒として塩化ノ、。ラジウム [ビス（ トリイソプロピルホスフィノ）ェタン] (3.6mg,7 mol)を加え、 120 で 62時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml)および酢酸ェチル（5ml)を加え、 セライ ト濾過により触媒を 除去した。 水層を齚酸ェチル (5ml X2)で抽出し、 有機層と合わせ、 水および飽和食塩水により洗浄後、 無水硫酸マグネシウムで乾燥し た。 乾燥剤を除去した後、 減圧下で溶媒を留去し、 得られた粗生成 物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:5) で分雜精製したところ、 4-ァセチル -4'-メ トキシビフヱニル（115mg , 0.51mmol, 71X)を白色針状結晶として得た。 Under an argon atmosphere, a suspension of potassium fluoride (251 mg, 4.3mniol) in Ν, Ν-dimethylformamide (3 ml) was cooled to 0 ° C., and dichloro (ethyl) (4-methoxyphenyl) silane (202 nig) was added. , 0.86 01) was added dropwise, and the mixture was stirred at 60 ° C for 3 hours. After cooling, the reaction solution was charged with 4-chloroacetophenone (11 lmg, 0.72 mmol) and chloride as a nordium catalyst. Radium [bis ( [Triisopropylphosphino) ethane] (3.6 mg, 7 mol), and the mixture was heated with stirring at 120 for 62 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), combined with the organic layer, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the drying agent, the solvent was distilled off under reduced pressure. The resulting crude product was purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 5). Acetyl-4'-methoxybiphenyl (115 mg, 0.51 mmol, 71X) was obtained as white needles.

'H-NM OOMHz.CDCla): δ 2.62(s, 3H), 3.86(s, 3H), 7.00(d, J=8.8Hz, 2H)， 7.58(d, J=8.8Hz， 2H), 7.64(d, J = 8.4Hz, 2H), 8.01(d, J=8.4Hz, 2H). I ( Br):1680, 1600, 1200,820cm-1. 実施例 2 7'H-NM OOMHz.CDCla): δ 2.62 (s, 3H), 3.86 (s, 3H), 7.00 (d, J = 8.8Hz, 2H), 7.58 (d, J = 8.8Hz, 2H), 7.64 ( d, J = 8.4Hz, 2H), 8.01 (d, J = 8.4Hz, 2H). I (Br): 1680, 1600, 1200, 820cm- 1 .

Figure imgf000046_0001
Figure imgf000046_0001

アルゴン雰囲気下、 フッ化カリゥム（183mg, 3.14mmol)の N，N-ジメ チルホルムアミ ド懸濁液（3ml)を O^Cに冷却し、 ジクロロ（ェチル）（4 -メチルフヱニル）シラン（137mg， 0.62 O1)を滴下した後、 60 で 3 時間撹拌した。 冷却後、 反応溶液に、 4-クロ口（ トリフルォロメチ ル）ベンゼン（54mg, 0.30mniol)およびパラジウム触媒として塩化パラ ジゥム [ビス（トリイソプロピルホスフィン）: (3.6mg, を加え、 Under an argon atmosphere, a suspension of potassium fluoride (183 mg, 3.14 mmol) in N, N-dimethylformamide (3 ml) was cooled to O ^ C, and dichloro (ethyl) (4-methylphenyl) silane (137 mg, 0.62 O1 ) Was added dropwise, followed by stirring at 60 for 3 hours. After cooling, 4-chloro (trifluoromethyl) benzene (54 mg, 0.30 mniol) and palladium chloride [bis (triisopropylphosphine): (3.6 mg,) as a palladium catalyst were added to the reaction solution.

120°Cで 20時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷 却し、 水（5ml)および酢酸ェチル（5ml)を加え、 セライ ト濾過により 触媒を除去した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層と合 わせ、 水および飽和食塩水により洗浄後、 無水硫酸マグネシウムで 乾燥した。 乾燥剤を除去した後、 減圧下で溶媒を留去し、 得られた 粗生成物を薄層クロマトグラフィー（展開溶媒：酢酸ェチル：へキサ ン = 1:5)で分離精製したところ、 4-卜リフルォロメチル -4' -メチル ビフエ二ル（62mg, 0.26mmol, 87%)を白色針状結晶として得た。 The mixture was heated and stirred at 120 ° C for 20 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2) and combined with the organic layer. The mixture was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5). Trifluoromethyl-4'-methylbiphenyl (62 mg, 0.26 mmol, 87%) was obtained as white needles.

mp:102.0-103.0°C  mp: 102.0-103.0 ° C

1H-N R(200MHz, CDC13): (5 2.40(s, 3H, CH3), 7.26(d, J=8.1Hz, 2H, HC( 3' ' 5' )), 7.49(d, J=8.1Hz, 2H, HC(2' ,6* )),7.66(s, 4H, HC(2, 3, 5, 6)). Mass in/z:236(100¾, M+)， 217(7), 167(34), 152(7), 91(8). 1 HN R (200MHz, CDC1 3 ): (5 2.40 (s, 3H, CH 3), 7.26 (d, J = 8.1Hz, 2H, HC (3 '' 5 ')), 7.49 (d, J = 8.1 Hz, 2H, HC (2 ', 6 *)), 7.66 (s, 4H, HC (2, 3, 5, 6)). Mass in / z: 236 (100¾, M +), 217 (7), 167 (34), 152 (7), 91 (8).

lR( Br):1300, 1140, 1120, 1080, 820cm-1. 実施例 2 8

Figure imgf000047_0001
lR (Br): 1300, 1140, 1120, 1080, 820cm- 1 .
Figure imgf000047_0001

アルゴン雰囲気下、 フッ化カリゥ厶（312mg， 5.37mmol)の N，N-ジメ チルホルムアミ ド懸濁液（3ml)を 0°Cに冷却し、 ジクロロ（メチル）（4 -メチルフェニル）シラン（221mg, 1.1漏 ol)を滴下した後、 60°Cで 3時 間撹拌した。 冷却後、 この反応溶液を液体窒素により冷却し、 減圧 脱気を 3回行った。 反応溶液に、 アルゴン雰囲気下、 1-クロ口- 3,4- ジフルォロベンゼン（80mg， 0.54蘭 ol)およびパラジゥ厶触媒として 塩化パラジウム:：ビス（卜リイソプロピルホスフィ ン）: (13.4ing，27 mol)を加え、 120°Cで 85時間加熱撹拌した。 反応終了後、 反応溶液 を室温まで冷却し、 水（5ml)および酢酸ェチル（5ml)を加え、 セライ ト濾過により触媒を除去した。 水層を酢酸ェチル（5ml X2)で抽出し- 有機層と合わせ、 水および飽和食塩水により洗浄後、 無水硫酸マグ ネシゥムで乾燥した。 乾燥剤を除去した後、 減圧下で溶媒を留去し、 得られた粗生成物を薄層クロマトグラフィ一（展開溶媒；酢酸ェチル ：へキサン = 1:5)で分離精製したところ、 3， 4-ジフルォ口- 4' -メチル ビフヱニル（71mg, 0.35ramol, 65%)を白色針状結晶として得た。 この もののスぺク トルデータは実施例 3で得たもののデータと一致した。 実施例 29 Under an argon atmosphere, a suspension of potassium fluoride (312 mg, 5.37 mmol) in N, N-dimethylformamide (3 ml) was cooled to 0 ° C, and dichloro (methyl) (4-methylphenyl) silane (221 mg, After 1.1 drops ol) were added dropwise, the mixture was stirred at 60 ° C for 3 hours. After cooling, the reaction solution was cooled with liquid nitrogen, and degassed under reduced pressure three times. Under an argon atmosphere, 1-chloro-3,4-difluorobenzene (80 mg, 0.54 ol) and palladium chloride as a palladium catalyst: bis (triisopropylphosphine): (13.4ing , 27 mol), and the mixture was heated and stirred at 120 ° C for 85 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. Extract the aqueous layer with ethyl acetate (5 ml X2) The organic layer was combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 5). -Difluo-4'-methylbiphenyl (71 mg, 0.35 ramol, 65%) was obtained as white needles. The spectrum data of this was in agreement with the data obtained in Example 3. Example 29

Figure imgf000048_0001
Figure imgf000048_0001

アルゴン雰囲気下、 フッ化カリゥ厶（312ing， 5.37mmol)の Ν,Ν-ジメ チルホルムアミ ド懸濁液（3ml)を 0 に冷却し、 ジクロロ（ェチル） [4 -(4-トランス -n-プロピルシク口へキシル）フヱニル]シラン（362mg， 1. lnnnol)を滴下した後、 60てで 3時間撹拌した。 冷却後、 反応溶液 に、 1 -クロ口- 3, 4 -ジフルォ口べンゼン（80mg, 0.54匪 ol )およびノヽ。ラ ジゥム触媒として塩化パラジウム [ビス（トリイソプロピルホスフィ ン）] (13.4mg,27 ^ol)を加え、 150^で 85時間加熱撹拌した。 反応 終了後、 反応溶液を室温まで冷却し、 水（5ml)および酢酸ェチル（5m 1)を加え、 セライ ト濾過により触媒を除去した。 水層を酢酸ェチル (5ml X2)で抽出し、 有機層と合わせ、 水および飽和食塩水により洗 浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去した後、 減 圧下で溶媒を留去し、 得られた粗生成物を薄層クロマトグラフィ一 (展開溶媒：酢酸ェチル：へキサン = 1:5)で分離精製したところ、 3,4- ジフルォ口- 4' -[1-(4-トランス- n-プロピルシク口へキシル）]ビフ ェニル（274mg，0.87mmol，8950を白色針状結晶として得た。 このもの のスぺク トルデータは実施例 2で得たもののデータと一致した。 実施例 30 Under an argon atmosphere, a suspension of potassium fluoride (312 in, 5.37 mmol) in Ν, Ν-dimethylformamide (3 ml) was cooled to 0, and dichloro (ethyl) [4- (4-trans-n-propylcycline) was added. [Hexyl) phenyl] silane (362 mg, 1. Innnol) was added dropwise, and the mixture was stirred at 60 rpm for 3 hours. After cooling, 1-chloro-3,4-difluobenzene (80 mg, 0.54 ol) and phenol were added to the reaction solution. Palladium chloride [bis (triisopropylphosphine)] (13.4 mg, 27 ^ ol) was added as a radium catalyst, and the mixture was heated and stirred at 150 ^ for 85 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the drying agent, the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5). - Difluoro-4 '-[1- (4-trans-n-propylcyclohexyl)] biphenyl (274 mg, 0.87 mmol, 8950) was obtained as white needles. The spectral data of this compound were obtained. This was consistent with the data obtained in Example 2. Example 30

Me0-(v /)-Si(Et)CI2 + CIMe0- (v /)-Si (Et) CI 2 + CI

Figure imgf000049_0001
Figure imgf000049_0001

アルゴン雰囲気下、 フッ化カリゥム（260mg,4.48mmol)の Ν, Ν-ジメ チルホルムアミ ド懸濁液（3ml)を 0 に冷却し、 ジクロロ（ェチル）（4 -メ トキシフヱニル）シラン（210mg, 0.90mmol)を滴下した後、 60 で 3時間撹拌した。 反応溶液を液体窒素下、 凍結脱気（3回）を行ない脱 酸素した。 この反応溶液に、 3-クロロアセ卜フヱノン（70mg, 0.45 ol)およびパラジウム触媒として塩化パラジウム [ビス（卜リイソプ 口ピルホスフィン）] (llmg，22 mol)を加え、 120 で 109時間加熱撹 拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml)および 酢酸ェチル (5ml)を加え、 セライ ト濾過により触媒を除去した。 水 層を酢酸ェチル (5nilx2)で抽出し、 有機層と合わせ、 水および飽和 食塩水により洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を 除去した後、 減圧下で溶媒を留去し、 得られた粗生成物を薄層クロ マトグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:5)で分離精製し たところ、 3-ァセチル -4'-メ 卜キシビフエニル（63mg, 0.28匪 ol, 62% )を白色針状結晶として得た。  Under an argon atmosphere, a suspension of potassium fluoride (260 mg, 4.48 mmol) in Ν, Ν-dimethylformamide (3 ml) was cooled to 0, and dichloro (ethyl) (4-methoxyphenyl) silane (210 mg, 0.90 mmol). Was added dropwise, followed by stirring at 60 for 3 hours. The reaction solution was deaerated by freezing and deaeration (three times) under liquid nitrogen. To this reaction solution were added 3-chloroacetophenone (70 mg, 0.45 ol) and palladium chloride [bis (triisopropoxypyrphosphine)] (ll mg, 22 mol) as a palladium catalyst, and the mixture was heated and stirred at 120 at 109 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5nilx2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5). -Acetyl-4'-methoxybiphenyl (63 mg, 0.28 ol, 62%) was obtained as white needles.

mp:48~49.0°C mp: 48 ~ 49.0 ° C

,H-NMR(200MHz, CDC13): δ 2.63(s, 3H, C0CH3), 3.84(s, 3H, 0CH3), 6.9 9(d， J=8.7Hz, 2H, HC(3， ,5')), 7.49(t, J=7.7Hz, IH, HC(5))， 7.55(d, J = 8.7Hz, 2H, HCC2' , 6' ))， 7.73(dd, J = l.7 and 7.7Hz, IH, HC(6))， 7.88(d d, J = l.7 and 7.7Hz, IH, HC(4))， 8.13(t, J = l.7Hz， IH, HC(2)). , H-NMR (200MHz, CDC1 3): δ 2.63 (s, 3H, C0CH 3), 3.84 (s, 3H, 0CH 3), 6.9 9 (d, J = 8.7Hz, 2H, HC (3,, 5 ')), 7.49 (t, J = 7.7Hz, IH, HC (5)), 7.55 (d, J = 8.7Hz, 2H, HCC2 ', 6')), 7.73 (dd, J = l.7 and 7.7Hz, IH, HC (6)), 7.88 (dd, J = l.7 and 7.7Hz, IH, HC (4)), 8.13 (t, J = l.7Hz, IH, HC (2)).

Mass ni/z: 226(100 M+), 211(64), 183(34入 168(19), 152(11). Mass ni / z: 226 (100 M + ), 211 (64), 183 (34 in 168 (19), 152 (11).

IR( Br)： 1680, 1250, 840, 800, 690cm-1. IR (Br): 1680, 1250, 840, 800, 690cm- 1 .

実施例 3 1 Example 3 1

n-C4H nC 4 H

Si(Me)CI2 + Cl^ VCN

Figure imgf000050_0001
Si (Me) CI 2 + Cl ^ VCN
Figure imgf000050_0001

アルゴン雰囲気下、 フッ化テトラプチルアンモニゥムのテトラヒ ドロフラン溶液（2.0ml, 2. Ommol)に、 4-クロ口べンゾニトリル（69mg ， 0.50mmol)およびパラジウム触媒として塩化パラジウム [ビス（トリ ェチルホスフィン）] (5.4mg， 13 mol)を加えた後、 液体窒素により 冷却し減圧脱気を 3回行った。 0 にてこの溶液にジクロロ（（E)-l- へキセニル）（メチル）シラン（118mg, 0.60πππο1)を加え、 30分間室温 で撹拌後、 90てで 20時間撹拌した。 反応終了後、 反応溶液を室温ま で冷却し、 水（5ml)および酢酸ェチル（5ml)を加え、 セライ ト濾過に より触媒を除去した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層 と合わせ、 水および飽和食塩水により洗浄後、 無水硫酸マグネシゥ ムで乾燥した。 乾燥剤を除去した後、 減圧下で溶媒を留去し、 得ら れた粗生成物を薄層クロマトグラフィ一（展開溶媒；酢酸ェチル：へ キサン = 1:5)で分離精製したところ、 （E)-l-(4-シァノフエニル） -1- へキセン（76mg， 0.41随 ol, 83%)を白色針状結晶として得た。 このも ののスぺク トルデータは実施例 7で得たもののデータと一致した。 実施例 3 2

Figure imgf000051_0001
Under an argon atmosphere, a tetrachlorofuran solution of tetrabutylammonium fluoride (2.0 ml, 2.0 mmol) was added with 4-chlorobenzonitrile (69 mg, 0.50 mmol) and palladium chloride [bis (triethylphosphine) as a palladium catalyst. )] (5.4 mg, 13 mol), cooled with liquid nitrogen, and degassed under reduced pressure three times. At 0, dichloro ((E) -l-hexenyl) (methyl) silane (118 mg, 0.60πππο1) was added to this solution, and the mixture was stirred at room temperature for 30 minutes, and further stirred at 90 ° for 20 hours. After the reaction was completed, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was removed by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), combined with the organic layer, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 5). ) -l- (4-Cyanophenyl) -1-hexene (76 mg, 0.41 ol, 83%) was obtained as white needles. This one The spectral data of the sample coincided with the data obtained in Example 7. Example 3 2
Figure imgf000051_0001

アルゴン雰囲気下、 フッ化カリゥム粉末（257.8mg, 4.44mmol)の N， N-ジメチルホルムアミ ド懸濁液（3ml)を 0°Cに冷却し、 ジクロロ（ェ チル）（4-メ トキシフエ二ル）シラン（209.2mg, 0.89mmol)を滴下した 後、 60 で 3時間撹拌した。 この反応溶液を液体窒素下、 凍結脱気（ 3回）を行ない脱酸素した。 反応溶液に、 アルゴン雰囲気下、 4-クロ ロアセトフヱノン（69. Omg, 0.45mmol)及び触媒として塩化パラジゥ ム [1,2-ビス（ジシクロへキシルホスフィノ）エタン] (5.4mg, 9 mol， 2.0fflol%)を加え、 120 で 48時間加熱撹拌した。 反応終了後、 反応 溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セラ ィ 卜濾過により触媒を濾過した。 水層を酢酸ェチル (5ml X2)で抽出 し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネ シゥムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得ら れた粗生成物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル:へ キサン = 1:5、 2回）で分離精製し、 目的の 4-ァセチル -4'-メ 卜キシビ フエニル（98. lmg, 0.433mmol，収率 97.1%)を白色固体として得た。 即：154.0〜155.0  Under an argon atmosphere, a suspension of potassium fluoride (257.8 mg, 4.44 mmol) in N, N-dimethylformamide (3 ml) was cooled to 0 ° C, and dichloro (ethyl) (4-methoxyphenyl) was added. ) Silane (209.2 mg, 0.89 mmol) was added dropwise, followed by stirring at 60 for 3 hours. The reaction solution was deaerated by freeze degassing (3 times) under liquid nitrogen. Under an argon atmosphere, 4-chloroacetophenone (69. Omg, 0.45 mmol) and palladium chloride [1,2-bis (dicyclohexylphosphino) ethane] as a catalyst (5.4 mg, 9 mol, 2.0fflol%) were added to the reaction solution under an argon atmosphere. Was added and the mixture was heated and stirred at 120 for 48 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by cerite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 5, twice). Of 4-acetyl-4'-methoxybiphenyl (98.lmg, 0.433mmol, 97.1% yield) was obtained as a white solid. Immediately: 154.0 to 155.0

1H-NMR(200 Hz, CDC13): δ 2.62(s, 3H， C0CH3), 3.85(s, 3H, 0CH3), 6.9 9(d, J=8.8Hz, 2H, HCC3' , 5' )), 7.57(d, J=8.8Hz, 2H， HC(2'， 6' )), 7.63( d, J=8.4Hz, 2H, HC(2, 6)), 8.00(d, J=8.4Hz, 2H， HC(3, 5)). Mass m/z:226(75¾,M+), 211(100), 183(12), 168(18). 1 H-NMR (200 Hz, CDC1 3): δ 2.62 (s, 3H, C0CH 3), 3.85 (s, 3H, 0CH 3), 6.9 9 (d, J = 8.8Hz, 2H, HCC3 ', 5' )), 7.57 (d, J = 8.8Hz, 2H, HC (2 ', 6')), 7.63 (d, J = 8.4Hz, 2H, HC (2, 6)), 8.00 (d, J = 8.4 Hz, 2H, HC (3, 5)). Mass m / z: 226 (75 °, M + ), 211 (100), 183 (12), 168 (18).

IR( Br):1680, 1600, 1200, 820cm-1. 実施例 33 ^Si(Me)2CI + CI-^>-CN . IR (Br): 1680, 1600, 1200, 820cm- 1 Example 33 ^ Si (Me) 2 CI + CI - ^> - CN

n-C

Figure imgf000052_0001
アルゴン雰囲気下、 4-クロ口べンゾニトリル（68.9mg, 0.50minol) 及び触媒として塩化パラジウム [ビス（トリエチルホスフィン）] (5.5 mg, 12 mol,2.4mol? を加え、 次いでフッ化テトラブチルアンモニ ゥムのテトラヒドロフラン溶液（2.0ml， 2. Ommol)を加えた。 この溶 液を液体窒素下、 凍結脱気（3回）を行ない溶存酸素を除去した。 こ の反応溶液を 0 に冷却し、 クロ口（（E)- 1-へキセニル）（ジメチル） シラン（107mg，0.60mmol)を滴下した後、 室温で 30分間撹拌し、 更に 90 で 20時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却 し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過により触媒 を濾過した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾 燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層ク 口マトグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分離精製 し、 目的の（E)-l-(4-シァノフェニル）-1-へキセン（48.2mg, 0.26mmo 1,収率 52. O )を無色油状物として得た。 このもののスぺク トルデ一 タは実施例 7で得たもののデータと一致した。 実施例 34 nC
Figure imgf000052_0001
Under an argon atmosphere, 4-chlorobenzonitrile (68.9 mg, 0.50 minol) and palladium chloride [bis (triethylphosphine)] (5.5 mg, 12 mol, 2.4 mol?) As a catalyst were added, and then tetrabutylammonium fluoride was added. This solution was subjected to freeze degassing (3 times) under liquid nitrogen to remove dissolved oxygen under liquid nitrogen, and the reaction solution was cooled to 0, and then cooled. ((E) -1-Hexenyl) (dimethyl) silane (107 mg, 0.60 mmol) was added dropwise, and the mixture was stirred at room temperature for 30 minutes, and further heated and stirred at 90 for 20 hours. After cooling, water (5 ml) and ethyl acetate (5 ml) were added, the catalyst was filtered by celite filtration, the aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined and washed with water and saturated saline. Then, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 7) to give the desired (E)- l- (4-Cyanophenyl) -1-hexene (48.2 mg, 0.26 mmol, yield 52.O) was obtained as a colorless oil, and the spectral data was obtained as in Example 7. Data matched. Example 34

Figure imgf000053_0001
アルゴン雰囲気下、 4-クロ口べンゾニトリル（68.8mg, 0.50mmol) 及び触媒として塩化パラジウム [ビス（卜リエチルホスフィン）] (5.4 mg, 12 mol, 2.5mol%)を加え、 次いでフッ化テトラブチルアンモニ ゥムのテ卜ラヒドロフラン溶液（3. Oml, 3. Ommol)を加えた。 この溶 液を液体窒素下、 凍結脱気（3回）を行ない溶存酸素を除去した。 こ の反応溶液を 0 に冷却し、 トリクロロ（（E)- 1-へキセニル）シラン（ 130.8mg, 0.60iMol)を滴下した後、 室温で 30分間撹拌し、 更に 90て で 41時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過により触媒を濾 過した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層を合わせ、 水 及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥 剤を除去し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層クロ マ卜グラフィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分離精製し- 目的の（E)-l-(4-シァノフヱニル） -卜へキセン（83.3mg, 0.45腿 ol,収 率 89.9%)を無色油状物として得た。 このもののスぺク トルデータは 実施例 7で得たもののデータと一致した。 実施例 35
Figure imgf000054_0001
Figure imgf000053_0001
Under an argon atmosphere, benzonitrile 4-chloro (68.8 mg, 0.50 mmol) and palladium chloride [bis (triethylphosphine)] (5.4 mg, 12 mol, 2.5 mol%) as a catalyst were added. A solution of ammonium in tetrahydrofuran (3. Oml, 3. Ommol) was added. This solution was subjected to freeze degassing (three times) under liquid nitrogen to remove dissolved oxygen. The reaction solution was cooled to 0, and trichloro ((E) -1-hexenyl) silane (130.8 mg, 0.60 iMol) was added dropwise. The mixture was stirred at room temperature for 30 minutes, and further heated and stirred at 90 to 41 hours. . After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered off by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7). E) -l- (4-Cyanophenyl) -trihexene (83.3 mg, 0.45 mol, yield 89.9%) was obtained as a colorless oil. The spectrum data of this was consistent with the data obtained in Example 7. Example 35
Figure imgf000054_0001

アルゴン雰囲気下、 4-クロ口べンゾニトリル（68.8mg， 0.50匪 ol) 及び触媒として塩化パラジウム【ビス（卜リエチルホスフィン）] (5.4 mg, 13^mol, 2.5mol¾)を加え、 次いでフッ化テトラブチルァンモニ ゥムのテトラヒドロフラン溶液（2.0inl,2. Ommol)を加えた。 この溶 液を液体窒素下、 凍結脱気（3回）を行ない溶存酸素を除去した。 こ の反応溶液を 0 に冷却し、 ジクロロ（ェチル）（（Z) -】-ォクテニル） シラン（143.8mg, 0.60minol)を滴下した後、 室温で 90分間撹拌し、 更 に 90 で 36時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷 却し、 水（5ml)及び酢酸ェチル (5ml)を加え、 セライ ト滤過により触 媒を瀘過した。 水層を齚酸ェチル (5ml X2)で抽出し、 有機層を合わ せ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した c 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層 クロマ卜グラフィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分離精 製し、 目的の（Z)-l-(4-シァノフヱニル） -1-ォクテン（97. Omg, 0.46m mol,収率 90.9%)を無色油状物として得た。 Under an argon atmosphere, 4-chlorobenzonitrile (68.8 mg, 0.50 mol ol) and palladium chloride [bis (triethylphosphine)] (5.4 mg, 13 ^ mol, 2.5 mol%) as a catalyst were added. A solution of butylammonium in tetrahydrofuran (2.0 inl, 2.0 mmol) was added. This solution was subjected to freeze degassing (three times) under liquid nitrogen to remove dissolved oxygen. After the reaction solution was cooled to 0, dichloro (ethyl) ((Z)-]-octenyl) silane (143.8 mg, 0.60 minol) was added dropwise, and the mixture was stirred at room temperature for 90 minutes and further heated at 90 at 36 hours. Stirred. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with齚酸Echiru (5 ml X2), move the organic layer was washed with water and brine to remove the c desiccant and dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure The obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 7) to obtain the desired (Z) -l- (4-cyanophenyl) -1-octene. (97. Omg, 0.46 mmol, yield 90.9%) was obtained as a colorless oil.

1H-NMR(200 Hz,CDCl3): δ 0.87(t, J = 6.5Hz, 3H, CH3), 1.20-1.55(m, 8H), 2.19-2.36(m, 2H), 5.82(td, J=7.4 and 11.5Hz， 1H), 6.40(d， J =l 1.5Hz, 1H)， 7.35Cd, J=8.3Hz， 2H， HC(3, 5)), 7.61(d, J=8.3Hz, 2H, HC(2, 6)). 1H-NMR (200 Hz, CDCl 3 ): δ 0.87 (t, J = 6.5 Hz, 3H, CH 3 ), 1.20-1.55 (m, 8H), 2.19-2.36 (m, 2H), 5.82 (td, J = 7.4 and 11.5Hz, 1H), 6.40 (d, J = 1.5Hz, 1H), 7.35Cd, J = 8.3Hz, 2H, HC (3, 5)), 7.61 (d, J = 8.3Hz, 2H , HC (2, 6)).

Mass m/z:213(13¾,M+), 154(2), 142(23), 129(100), 116(15), 102(4). IR(neat):2950, 2930, 2850, 2250, 1605, 855cm—1, Anal. Calcd. for C15H19N: C, 84.46; H, 8.98; N, 6.57. Mass m / z: 213 (13¾, M + ), 154 (2), 142 (23), 129 (100), 116 (15), 102 (4) .IR (neat): 2950, 2930, 2850, 2250 , 1605, 855cm— 1 , Anal.Calcd. For C 15 H 19 N: C, 84.46; H, 8.98; N, 6.57.

Found: C, 84.27; H, 8.87; N, 6.30. 実施例 36

Figure imgf000055_0001
Found: C, 84.27; H, 8.87; N, 6.30. Example 36
Figure imgf000055_0001

アルゴン雰囲気下、 4-クロ口（トリクロロメチル）ベンゼン（90.7m g, 0.50minol)及び触媒として塩化パラジゥム [ビス（トリェチルホス フィン）] (5.4mg, 13^mol, 2.6mol¾ を加え、 次いでフッ化テトラブ チルアンモニゥムのテ卜ラヒドロフラン溶液（2.0ml, 2.0匪 ol)を加 えた。 この溶液を液体窒素下、 凍結脱気（3回）を行ない溶存酸素を除 去した。 この反応溶液を 0 に冷却し、 ジクロロ（ェチル）（（Z)-l- ォクテニル）シラン（143.8mg，0.60關 ol)を滴下した後、 室温で 30分 間撹拌し、 更に 90 で 12時間加熱撹拌した。 反応終了後、 反応溶液 を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト 濾過により触媒を濾過した。 水層を酢酸ェチル (5ml X 2)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシゥ 厶で乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた 粗生成物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサ ン = 1:19)で分離精製し、 目的の（Z)- （4-卜リフルォロメチルフヱ ニル） -1-ォクテン（74.3mg, 0.29画 1，収率 58.0%)を無色油状物とし て得た。 このもののスぺク トルデータは実施例 20で得たものの データと一致した。 実施例 37 Under an argon atmosphere, add 4-chloro (trichloromethyl) benzene (90.7 mg, 0.50 minol) and palladium chloride [bis (triethylphosphine)] (5.4 mg, 13 ^ mol, 2.6 mol%) as a catalyst, and then add tetrabutylammonium fluoride. This solution was subjected to freeze degassing (3 times) under liquid nitrogen to remove dissolved oxygen in liquid nitrogen. (Ethyl) ((Z) -l-octenyl) silane (143.8 mg, 0.60 ol) was added dropwise, and the mixture was stirred at room temperature for 30 minutes, and further heated and stirred at 90 at 12 hours. After cooling to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, the catalyst was filtered through celite filtration, the aqueous layer was extracted with ethyl acetate (5 ml × 2), the organic layers were combined, and water and saturated saline were added. After washing with water, anhydrous magnesium sulfate The drying agent was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 19). Of (Z)-(4-trifluoromethylphenyl) -1-octene (74.3 mg, 0.29 fraction 1, 58.0% yield) was obtained as a colorless oil. Was consistent with the data obtained in Example 20. Example 37

COMe  COMe

n- H! n- H!

Si(Me)CI ~ COMe Si (Me) CI ~ COMe

Figure imgf000056_0001
Figure imgf000056_0001

アルゴン雰囲気下、 3-クロロアセトフエノン（76.8mg, 0.50mmol) 及び触媒として塩化パラジウム [ビス（卜リエチルホスフィン）] (5.3 mg, 12 mol, 2.5mol5 を加え、 次いでフッ化テトラブチルアンモニ ゥムのテトラヒドロフラン溶液（2.0ml，2. Ommol)を加えた。 この溶 液を液体窒素下、 凍結脱気 (3回）を行ない溶存酸素を除去した。 こ の反応溶液を 0°Cに冷却し、 ジクロロ（（E)- 1-へキセニル）（メチル） シラン（118.3mg,0.60mniol)を滴下した後、 室温で 30分間撹拌し、 更 に 90 で 17時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷 却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過により触 媒を濾過した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層を合わ せ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した c 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層 クロマトグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:7)で分離精 製し、 目的の（E)-l-(3-ァセチルフエニル） -1-へキセン（83.9fflg, 0.4 2MIO1，収率 82.9¾ を無色油状物として得た。 このもののスぺク トル データは実施例 5で得たもののデータと一致した。 実施例 3 8

Figure imgf000057_0001
Under an argon atmosphere, 3-chloroacetophenone (76.8 mg, 0.50 mmol) and palladium chloride [bis (triethylphosphine)] (5.3 mg, 12 mol, 2.5 mol5) as a catalyst were added, followed by tetrabutylammonium fluoride. The solution was subjected to freeze degassing (3 times) under liquid nitrogen to remove dissolved oxygen, and the reaction solution was cooled to 0 ° C. After dropwise addition of dichloro ((E) -1-hexenyl) (methyl) silane (118.3 mg, 0.60 mniol), the mixture was stirred at room temperature for 30 minutes, and further heated and stirred at 90 at 17 hours. The solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, the catalyst was filtered by celite filtration, the aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined. after washing with water and brine, c desiccant and dried over anhydrous magnesium sulfate The crude product obtained was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 7) to give the desired (E) -l -(3-Acetylphenyl) -1-hexene (83.9fflg, 0.42 MIO1, yield 82.9%) was obtained as a colorless oil, and its spectral data were consistent with those obtained in Example 5. Example 3 8
Figure imgf000057_0001

アルゴン雰囲気下、 フッ化カリゥム粉末（135. Omg, 2.32蘭01)の N, N-ジメチルホルムアミ ド懸濁液（lml)を 0 に冷却し、 ジクロロ（ジ フエニル）シラン（116. lmg， 0.46匪 ol)を滴下した後、 60°Cで 3時間撹 拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 2-ブロモ -3 -ニトロピリジン（78.6mg, 0.39mmol)及び触媒として塩化パラジウム [ビス（卜リシク口へキシルホスフィ ン）] (7. lmg, lO^mol, 2.5mol¾) を加え、 120 で 24時間加熱撹拌した。 反応終了後、 反応溶液を室 温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ 卜濾過 により触媒を濾過した。 水層を酢酸ェチル (5ml X2)で抽出し、 有機 層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで 乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生 成物を薄層クロマ卜グラフィ一（展開溶媒；酢酸ェチル：へキサン =1: 5)で分離精製し、 目的の 3-二卜口- 2-フヱニルピリジン（68. Omg, 0.3 4mraol,収率 87.8¾)を無色油状物として得た。  Under an argon atmosphere, a suspension of potassium fluoride powder (135.Omg, 2.32 orchid 01) in N, N-dimethylformamide (lml) was cooled to 0, and dichloro (diphenyl) silane (116.lmg, 0.46mg) was added. After dropping ol (ol), the mixture was stirred at 60 ° C for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 2-bromo-3-nitropyridine (78.6 mg, 0.39 mmol) and palladium chloride as a catalyst [bis (trihexylhexylphosphine)] (7.1 mg, lO ^ mol, 2.5 mol%), and the mixture was heated and stirred at 120 for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 5). 3-Nitro-2--2-phenylpyridine (68.Omg, 0.34mraol, yield 87.8¾) was obtained as a colorless oil.

1H- MR(200MHz,CDCl3): δ 7.39(dd, J=4.8 and 8.1Hz, 1H, HC(5)),7. 43〜7.62(m, 5H)， 8.10(d， J=8. lHz， 1H， HC(4))， 8.82(d, J =4.8Hz, 1H， HC (6)). 1H-MR (200MHz, CDCl 3 ): δ 7.39 (dd, J = 4.8 and 8.1Hz, 1H, HC (5)), 7.43 to 7.62 (m, 5H), 8.10 (d, J = 8.lHz , 1H, HC (4)), 8.82 (d, J = 4.8Hz, 1H, HC (6)).

Mass m/z:200(63¾, +), 172(87), 153(36), 127(100). Mass m / z: 200 (63 °, + ), 172 (87), 153 (36), 127 (100).

IR(neat):3435, 3065, 2925, 2855, 1722, 1595, 1560, 1445, 1425, 1355, 1 290, 1250,860,750,700cm-1. 実施例 3 9 IR (neat): 3435, 3065, 2925, 2855, 1722, 1595, 1560, 1445, 1425, 1355, 1 290, 1250,860,750,700cm- 1 . Example 3 9

SiCISiCI

Figure imgf000058_0001
Figure imgf000058_0001

アルゴン雰囲気下、 フッ化カリウム粉末（191.0mg, 3.29mmol)の N, Under an argon atmosphere, potassium fluoride (191.0 mg, 3.29 mmol) N,

N-ジメチルホルムアミ ド懸濁液（1.4ml)を 0°Cに冷却し、 ジクロロ（ ジフヱニル）シラン（165. Omg, 0.65mniol)を滴下した後、 60°Cで 3時間 撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 2-クロ口 -3-二トロピリジン（86.7mg, 0.55mmol)及び触媒として塩化パラジゥ ム[ビス（トリィソプロピルホスフィン）] (6.8mg, U/i ol, 2.5mol%) を加え、 120 で 24時間加熱撹拌した。 反応終了後、 反応溶液を室 温まで冷却し、 水（5ml)及び酢酸ェチル (5ml)を加え、 セライ ト濾過 により触媒を濾過した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機 層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで 乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生 成物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサン =1: 5)で分離精製し、 目的の 3-ニトロ- 2-フヱニルピリジン（107.3mg,0. 54mmol,収率 98.0¾i)を無色油状物として得た。 このもののスぺク ト ルデータは実施例 38で得たもののデータと一致した。 実施例 4 0

Figure imgf000058_0002
アルゴン雰囲気下、 フッ化カリゥ厶粉末（140.5mg，2.42fflinoOの N, N-ジメチルホルムアミ ド懸濁液（1.0ml)を 0°Cに冷却し、 ジクロロ（ ジフエ二ル）シラン（ 122.2mg, 0.48mrao 1 )を滴下した後、 60°Cで 3時間 撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 4-クロ口 ビフヱニル（76. Omg, 0.40mmol)及び触媒として塩化パラジゥム [ビス (トリイソプロピルホスフィ ン）] (5, Omg, lO^mol, 2.5raol¾)を加え、 120 で 24時間加熱撹拌した。 反応終了後、 反応溶液を室温まで冷 却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過により触 媒を濾過した。 水層を酢酸ェチル（5ml X 2)で抽出し、 有機層を合わ せ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生成物を薄層 クロマトグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:19)で分離 精製し、 目的のテルフエニル（69. Omg, 0.30mmol,収率 74.3%)を白色 針状結晶として得た。 The N-dimethylformamide suspension (1.4 ml) was cooled to 0 ° C, and dichloro (diphenyl) silane (165.Omg, 0.65mniol) was added dropwise, followed by stirring at 60 ° C for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 2-chloro-3-dinitropyridine (86.7 mg, 0.55 mmol) and palladium chloride [bis (trisopropylphosphine)] (6.8 mg, U / i ol, 2.5 mol%), and the mixture was heated with stirring at 120 for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5) to give the desired 3- Nitro-2-phenylpyridine (107.3 mg, 0.54 mmol, yield 98.0¾i) was obtained as a colorless oil. The spectral data of this was consistent with the data obtained in Example 38. Example 40
Figure imgf000058_0002
Under an argon atmosphere, a suspension of potassium fluoride powder (140.5 mg, 2.42 fflinoO in N, N-dimethylformamide (1.0 ml)) was cooled to 0 ° C, and dichloro ( After diphenyl) silane (122.2 mg, 0.48 mrao 1) was added dropwise, the mixture was stirred at 60 ° C. for 3 hours. The reaction solution was cooled to room temperature, and under argon atmosphere, 4-chlorobiphenyl (76. Omg, 0.40 mmol) and palladium chloride [bis (triisopropylphosphine)] (5, Omg, lO ^ mol, 2.5 raol¾), and the mixture was heated and stirred at 120 for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 19) to obtain the desired terphenyl (69). Omg, 0.30 mmol, yield 74.3%) were obtained as white needle crystals.

!H-NMR(200MHz, CDC13): δ 7.33〜7· 50(m, 6Η)， 7.60〜7.70(m, 8Η). Mass m/z:230(100¾,M+), 152(5). ! H-NMR (200MHz, CDC1 3): δ 7.33~7 · 50 (m, 6Η), 7.60~7.70 (m, 8Η) Mass m / z:. 230 (100¾, M +), 152 (5).

IR(KBr) :3450， 3060, 3040， 1480, 1460, 1405,840,750, 690cm-1. 実施例 41 IR (KBr): 3450, 3060, 3040, 1480, 1460, 1405,840,750, 690cm- 1 . Example 41

(<Q¾sici2 + (<Q¾sici 2 +

Figure imgf000059_0001
→QQQ) アルゴン雰囲気下、 フッ化カリウム粉末（186.7fflg,3.21minol)の X，
Figure imgf000059_0001
→ QQQ) Under argon atmosphere, potassium fluoride powder (186.7fflg, 3.21minol) X,

Ν·-ジメチルホルムアミ ド懸濁液（1.4ml)を 0°Cに冷却し、 ジクロロ（ ジフヱニル）シラン（165. Omg, 0.65mmol)を滴下した後、 60°Cで 3時間 撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 4-ブロモ ビフエニル（124.9mg, 0.54raol)及び触媒として塩化パラジウム [ビ ス（トリシクロへキシルホスフィ ン）] (9.9mg， 13^mol, 2.5mol!¾)を加 え、 120 で 24時間加熱撹拌した。 反応終了後、 反応溶液を室温ま で冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過によ り触媒を爐過した。 水層を酢酸ェチル (5ffllx2)で抽出し、 有機層を 合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾燥 した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生成物 を薄層クロマトグラフィ一（展開溶媒：酢酸ェチル：へキサン = 1:19) で分離精製し、 目的のテルフヱニル（69. Omg, 0.30ramol,収率 55.9¾) を白色針状結晶として得た。 このもののスぺク トルデータは実施例 4 0で得たもののデータと一致した。 実施例 4 2

Figure imgf000060_0001
The Ν-dimethylformamide suspension (1.4 ml) was cooled to 0 ° C, and dichloro (diphenyl) silane (165.Omg, 0.65mmol) was added dropwise, followed by stirring at 60 ° C for 3 hours. The reaction solution is cooled to room temperature, and under an argon atmosphere, 4-bromobiphenyl (124.9 mg, 0.54 raol) and palladium chloride [bis (tricyclohexylphosphine)] (9.9 mg, 13 mol, 2.5 mol! ¾) as a catalyst. ) The mixture was heated and stirred at 120 for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5ffllx2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 19) to obtain the desired terphenyl (69%). Omg, 0.30 ramol, yield 55.9¾) was obtained as white needle crystals. The spectrum data of this sample coincided with the data obtained in Example 40. Example 4 2
Figure imgf000060_0001

アルゴン雰囲気下、 フッ化カリゥ厶粉末（137.8mg, 2.37mmol)の Ν·， Ν-ジメチルホルムアミ ド懸濁液（1.0ml)を 0 に冷却し、 ジクロロ（ ジフヱニル）シラン（122.2mg, 0.48随 ol)を滴下した後、 60てで 3時間 撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 3-ァミノ - 2-クロ口ピリジン（50.8mg, 0.40mmol)及び触媒として塩化パラジゥ 厶[ビス（トリィソプロピルホスフィン）] (4.9mg, 10 ίπιοΐ, 2.5mol¾) を加え、 120°Cで 24時間加熱撹拌した。 反応終了後、 反応溶液を室 温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過 により触媒を濾過した。 水層を酢酸ェチル (5mlx2)で抽出し、 有機 層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで 乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生 成物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサン =1: 1)で分離精製し、 目的の 3-アミノ- 2-フエニルピリジン（17. Omg，0.1 Ommol,収率 25.3¾)を白色針状結晶として得た。 In an argon atmosphere, a suspension of potassium fluoride powder (137.8 mg, 2.37 mmol) in Ν ·, Ν-dimethylformamide (1.0 ml) was cooled to 0, and dichloro (diphenyl) silane (122.2 mg, 0.48 ol) was added dropwise, followed by stirring at 60 ° C for 3 hours. The reaction solution was cooled to room temperature, and in an argon atmosphere, 3-amino-2-chloropyridine (50.8 mg, 0.40 mmol) and palladium chloride [bis (trisopropylphosphine)] (4.9 mg, 10ίπιοΐ, 2.5 mol¾), and the mixture was heated and stirred at 120 ° C for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, and the solvent was distilled off under reduced pressure. The product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 1), and the desired 3-amino-2-phenylpyridine (17. Omg, 0.1 Ommol, yield 25.3¾) Was obtained as white needle-like crystals.

IH-NMR(200MHz,CDCl3): <5 3.84(br s， 2H)， 7.03〜7.08(m， 2H, HC(4, 5 )), 7.34〜7.54(m, 3H, HC(3' , 4，， 5' ))， 7.67(d, J=6.6Hz, 2H, HC(2' , 6' ) ),8.13(d, J = 6.0Hz, 1H， HC(6)). IH-NMR (200 MHz, CDCl 3 ): <5 3.84 (br s, 2H), 7.03 to 7.08 (m, 2H, HC (4, 5)), 7.34 to 7.54 (m, 3H, HC (3 ′, 4 ,, 5 ')), 7.67 (d, J = 6.6Hz, 2H, HC (2', 6 ')), 8.13 (d, J = 6.0Hz, 1H, HC (6)).

Mass m/z:170(59¾,M+), 169(100), 115(3). Mass m / z: 170 (59 °, M + ), 169 (100), 115 (3).

IR( Br):3450, 3320, 3200, 3050, 1620, 1580, 1450, 1400, 1295, 1140, 10 70,800,750,700cm-1. 実施例 43

Figure imgf000061_0001
IR (Br):. 3450, 3320, 3200, 3050, 1620, 1580, 1450, 1400, 1295, 1140, 10 70,800,750,700cm- 1 Example 43
Figure imgf000061_0001

アルゴン雰囲気下、 フッ化カリゥム粉末（132.4mg,2.28mmol)の N1, N-ジメチルホルムアミ ド懸濁液（1.0ml)を 0°Cに冷却し、 ジクロロ（ ジフヱニル）シラン（116. lmg, 0.46難 ol)を滴下した後、 60てで 3時間 撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 4-ブロモ ァセ卜フヱノン（75.6mg, 0.38IMO1)及び触媒として塩化パラジウム [ ビス（トリシク口へキシルホスフィン）] (7. Omg, 10 /mol, 2.5mol50を 加え、 120°Cで 24時間加熱撹拌した。 反応終了後、 反応溶液を室温 まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ 卜濾過に より触媒を濾過した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機層 を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで乾 燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生成 物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサン = 1:1) で分離精製し、 目的の 4-ァセチルビフヱニル（71.5mg， 0.364mmol，収 率 95.95 を白色針状結晶として得た。 このもののスぺク トルデータ は実施例 1 4で得たもののデータと一致した。 実施例 44

Figure imgf000062_0001
Under an argon atmosphere, a suspension of potassium fluoride powder (132.4 mg, 2.28 mmol) in N 1 , N-dimethylformamide (1.0 ml) was cooled to 0 ° C, and dichloro (diphenyl) silane (116 lmg, After the dropwise addition of 0.46), the mixture was stirred at 60 ° C for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 4-bromoacetophenone (75.6 mg, 0.38 IMO1) and palladium chloride as a catalyst [bis (tris-hexylhexylphosphine)] (7. Omg, 10 / mol, 2.5 mol 50 was added, and the mixture was heated and stirred for 24 hours at 120 ° C. After the reaction was completed, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, dried over anhydrous magnesium sulfate, the desiccant was removed, and the solvent was distilled off under reduced pressure. The obtained crude product is subjected to thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 1). The desired 4-acetylbiphenyl (71.5 mg, 0.364 mmol, yield: 95.95) was obtained as white needle-like crystals. The spectrum data of this compound was obtained from Example 14. Example 44
Figure imgf000062_0001

アルゴン雰囲気下、 フッ化カリゥム粉末（226.3mg, 3.90 O1)の N, Ν-ジメチルホルムアミ ド懸濁液（1.6ml)を 0°Cに冷却し、 ジクロロ（ ジフヱニル）シラン（195.5mg, 0.77mmol)を滴下した後、 60°Cで 3時間 撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 1-クロ口 -3,4-ジフルォロベンゼン（94.7mg, 0.64mmol )及び触媒として塩化パ ラジウム [ビス（トリイソプロピルホスフィ ン）] (7.9mg, 16/ mol, 2.5 mol!¾)を加え、 120 で 24時間加熱撹拌した。 反応終了後、 反応溶液 を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ 卜 濾過により触媒を濾過した。 水層を酢酸ェチル (5ml X 2)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシゥ ムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた 粗生成物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサ ン = 1:20)で分離精製し、 目的の 3， 4-ジフルォロビフエニル（121.4mg ，0.64匪 ol，収率 100.0%)を白色固体として得た。  Under an argon atmosphere, a suspension of potassium fluoride powder (226.3 mg, 3.90 O1) in N, Ν-dimethylformamide (1.6 ml) was cooled to 0 ° C, and dichloro (diphenyl) silane (195.5 mg, 0.77 mmol) was added. ) Was added dropwise, followed by stirring at 60 ° C for 3 hours. The reaction solution was cooled to room temperature and 1-chloro-3,4-difluorobenzene (94.7 mg, 0.64 mmol) and palladium chloride [bis (triisopropylphosphine)] (7.9 mg, 16 / mol, 2.5 mol! ¾), and the mixture was heated with stirring at 120 for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 20) to obtain the desired 3,3 4-Difluorobiphenyl (121.4 mg, 0.64 ol, yield 100.0%) was obtained as a white solid.

1H-NMR(200MHz,CDCl3): δ 7.10〜7.6Km， 8Η). 1H-NMR (200 MHz, CDCl 3 ): δ 7.10 to 7.6 km, 8Η).

Mass m/z:190(100¾, +), 170(9), 154(5), 94(4). Mass m / z: 190 (100 °, + ), 170 (9), 154 (5), 94 (4).

IR(KBr):3450, 3070, 3050, 1610， 1530, 1490, 1410, 1310, 1280, 1180, 11 20,760cm-1. 実施例 45 (<Q¾SiCl2

Figure imgf000063_0001
QrQr IR (KBr): 3450, 3070, 3050, 1610, 1530, 1490, 1410, 1310, 1280, 1180, 11 20,760cm- 1. Example 45 (<Q¾ SiCl2
Figure imgf000063_0001
QrQr

アルゴン雰囲気下、 フッ化カリゥム粉末（223.7mg,3.85mmol)の N, N-ジメチルホルムアミ ド懸濁液（1.6ml)を 0 に冷却し、 ジクロロ（ ジフヱニル）シラン（195.5mg，0.77mmol)を滴下した後、 60°Cで 3時間 撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 4-ブロモ 安息香酸メチル（137.2mg, 0.64mmol)及び触媒として塩化パラジゥム [ビス（トリシクロへキシルホスフィン）] (11.8mg, 16^mol,2.5mol¾) を加え、 120てで 94時間加熱撹拌した。 反応終了後、 反応溶液を室 温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライト濾過 により触媒を濾過した。 水層を酢酸ェチル（5ml X2)で抽出し、 有機 層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで 乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生 成物を薄層クロマトグラフィ一（展開溶媒；酢酸ェチル：へキサン =1: 4)で分離精製し、 目的の 4-メ トキシカルボ二ルビフヱニル（124. lmg , 0.56匪 ol,収率 91.6%)を白色針状結晶として得た。  Under an argon atmosphere, a suspension of potassium fluoride powder (223.7 mg, 3.85 mmol) in N, N-dimethylformamide (1.6 ml) was cooled to 0, and dichloro (diphenyl) silane (195.5 mg, 0.77 mmol) was added. After the dropwise addition, the mixture was stirred at 60 ° C for 3 hours. The reaction solution is cooled to room temperature, and under an argon atmosphere, methyl 4-bromobenzoate (137.2 mg, 0.64 mmol) and palladium chloride [bis (tricyclohexylphosphine)] (11.8 mg, 16 ^ mol, 2.5 mol%) as a catalyst. Was added and the mixture was heated and stirred at 120 rpm for 94 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by Celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 4), Methoxycarbonylbiphenyl (124. lmg, 0.56 bandol, yield 91.6%) was obtained as white needles.

'H-NMR(200 Hz,CDCl3): δ 3.93(s, 3H), 7.37-7.50(m, 3H, HC(3' , 4' ,'H-NMR (200 Hz, CDCl 3 ): δ 3.93 (s, 3H), 7.37-7.50 (m, 3H, HC (3', 4 ',

5* )), 7.61(d， J=8.1Hz, 2H， HC(2' , 6' )), 7.64(d， J=8.4Hz, 2H, HC(2, 6)) ,8.10(d， J=8.4Hz, 2H, HC(3, 5)). 5 *)), 7.61 (d, J = 8.1Hz, 2H, HC (2 ', 6')), 7.64 (d, J = 8.4Hz, 2H, HC (2, 6)), 8.10 (d, J = 8.4Hz, 2H, HC (3, 5)).

Mass m/z:212(60¾,M+), 181(100), 152(44), 90(10), 76(21). Mass m / z: 212 (60 °, M + ), 181 (100), 152 (44), 90 (10), 76 (21).

IR(KBr):3450, 3040, 3000， 2950， 2850， 1720， 1605, 1440, 1290, 1270, 11 10,860,750,700cm-'. 実施例 46

Figure imgf000064_0001
IR (KBr): 3450, 3040, 3000, 2950, 2850, 1720, 1605, 1440, 1290, 1270, 11 10,860,750,700cm- '. Example 46
Figure imgf000064_0001

アルゴン雰囲気下、 フッ化カリウム粉末（203.5mg，3.50匪 ol)の Ν·， Under argon atmosphere, potassium fluoride powder (203.5mg, 3.50 ol)

Ν-ジメチルホルムアミ ド懸濁液（1.5ml)を 0てに冷却し、 ジクロロジ (3-メチルフエニル）シラン（196.0mg， 0.70mmol)を滴下した後、 60 で 3時間撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 4 -クロ口ビフヱニル（110. lmg, 0.58mmol)及び触媒として塩化パラジ ゥム [ビス（トリイソプロピルホスフィン）] (7.3mg, 15^mol, 2.5mol¾The suspension of Ν-dimethylformamide (1.5 ml) was cooled to 0, dichlorodi (3-methylphenyl) silane (196.0 mg, 0.70 mmol) was added dropwise, and the mixture was stirred at 60 for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 4-chlorobiphenyl (110.lmg, 0.58mmol) and palladium chloride [bis (triisopropylphosphine)] (7.3mg, 15 ^ mol, 2.5mol) as a catalyst.

)を加え、 120てで 24時間加熱撹拌した。 反応終了後、 反応溶液を室 温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過 により触媒を濾過した。 水層を酢酸ェチル (5ml X2)で抽出し、 有機 層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで 乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生 成物を薄層クロマトグラフィ一（展開溶媒；酢酸ェチル：へキサン =1: 15)で分離精製し、 目的の 3-メチル -1， 1' :4'， Γ' -テルフエニル（106 .6mg, 0.436動 1，収率 74.7%)を白色針状結晶として得た。 ), And the mixture was heated and stirred at 120 rpm for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 15) to obtain the desired product. Methyl-1, 1 ′: 4 ′, Γ′-terphenyl (106.6 mg, 0.436, yield 74.7%) was obtained as white needles.

1H-NMR(200MHz, CDC13): δ 2.44(s, 3H, CH3)， 7.18(d, J=T.5Hz, 1H), 7. 33-7.51(ni, 6H), 7.63~7.68(m, 6H). 1H-NMR (200MHz, CDC1 3 ): δ 2.44 (s, 3H, CH 3), 7.18 (d, J = T.5Hz, 1H), 7. 33-7.51 (ni, 6H), 7.63 ~ 7.68 (m , 6H).

Mass m/z:244(100¾, M+)， 228(5), 165(6), 122(4). Mass m / z: 244 (100¾, M + ), 228 (5), 165 (6), 122 (4).

IR(KBr):3450, 3060, 3040, 2930, 1605, 1480, 1400, 840， 790， 760， 690cm一1. 実施例 4 7 IR (KBr): 3450, 3060 , 3040, 2930, 1605, 1480, 1400, 840, 790, 760, 690cm one 1. Example 4 7

Figure imgf000065_0001
Figure imgf000065_0001

アルゴン雰囲気下、 フッ化カリゥム粉末（201.7mg，3.47mmol)の N， N-ジメチルホルムアミ ド懸濁液（1.5ml)を 0 に冷却し、 ジクロロジ (3-メチルフヱニル）シラン（196. Omg, 0.70mmol)を滴下した後、 60 で 3時間撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 2 -プロモピリジン（91. lmg, 0.58mmol)及び触媒として塩化パラジウム [ビス（トリシク口へキシルホスフィン）] (10.6mg, 14^mol,2.5mol¾) を加え、 120てで 24時間加熱撹拌した。 反応終了後、 反応溶液を室 温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライト濾過 により触媒を濾過した。 水層を酢酸ェチル (5ralx2)で抽出し、 有機 層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシウムで 乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた粗生 成物を薄層クロマ卜グラフィ一（展開溶媒；酢酸ェチル：へキサン =1: 15)で分離精製し、 目的の 2-(3-メチルフヱニル）ピリジン（40.5mg, 0 • 24mmol,収率 41.5%)を白色針状結晶として得た。  Under an argon atmosphere, a suspension of potassium fluoride (201.7 mg, 3.47 mmol) in N, N-dimethylformamide (1.5 ml) was cooled to 0, and dichlorodi (3-methylphenyl) silane (196.Omg, 0.70 (mmol) was added dropwise, followed by stirring at 60 for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 2-bromopyridine (91.lmg, 0.58mmol) and palladium chloride as a catalyst [bis (trihexylhexylphosphine)] (10.6mg, 14 ^ mol, 2.5mol¾) Was added, and the mixture was heated and stirred at 120 rpm for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by Celite filtration. The aqueous layer was extracted with ethyl acetate (5ralx2), the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 15). 2- (3-Methylphenyl) pyridine (40.5 mg, 0 • 24 mmol, yield 41.5%) was obtained as white needle crystals.

■H-NMRCCDCls.T S, ppm): δ 2.40(s, 3Η, CH3),7.18(dd, J = 3.9 and 5. 2Hz, 1H, HC(5)), 7.28(d, J=8.2Hz, 2H， HC(3， , 5' ))， 7.68〜7.79(m, 2H， H C(3， 4)), 7.89(d, J=8.2Hz, 2H, HC(2' , 6' ))， 8.67(d, J=3.9Hz， 1H, HC(6)). 実施例 48 H-NMRCCDCls.TS, ppm): δ 2.40 (s, 3Η, CH 3 ), 7.18 (dd, J = 3.9 and 5.2 Hz, 1H, HC (5)), 7.28 (d, J = 8.2 Hz, 2H, HC (3,, 5 ')), 7.68 to 7.79 (m, 2H, HC (3, 4)), 7.89 (d, J = 8.2Hz, 2H, HC (2', 6 ')), 8.67 (d, J = 3.9Hz, 1H, HC (6)). Example 48

Me ヽ

Figure imgf000066_0001
Me ヽ
Figure imgf000066_0001

アルゴン雰囲気下、 フッ化カリゥム粉末（240.9mg, 4.15mmol)の N, N-ジメチルホルムアミ ド懸濁液（1.7ml)を 0 に冷却し、 ジクロロジ (3-メチルフヱニル）シラン（231.7mg, 0.82mmol)を滴下した後、 60°C で 3時間撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 4-ブロモ安息香酸メチル（147.4mg, 0.69 O1)及び触媒として塩化パ ラジウム〔ビス（卜リシクロへキシルホスフィン）] (12.8mg, 17 mol, 2.5mol¾)を加え、 120 で 94時間加熱撹拌した。 反応終了後、 反応 溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セラ ィト濾過により触媒を濾過した。 水層を酢酸ェチル (5ml X2)で抽出 し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネ シゥムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られ た粗生成物を薄層クロマトグラフィー（展開溶媒：酢酸ェチル：へキ サン = 1:5)で分離精製し、 目的の 4-メ トキシカルボニル -4'-メチル ビフェニル（148.5mg, 0.656,01,収率 95.8%)を白色針状結晶として 得た。  In an argon atmosphere, a suspension of potassium fluoride powder (240.9 mg, 4.15 mmol) in N, N-dimethylformamide (1.7 ml) was cooled to 0, and dichlorodi (3-methylphenyl) silane (231.7 mg, 0.82 mmol) was added. ) Was added dropwise, and the mixture was stirred at 60 ° C for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, methyl 4-bromobenzoate (147.4 mg, 0.69 O1) and palladium chloride [bis (tricyclohexylphosphine)] (12.8 mg, 17 mol, 2.5 mol¾) as a catalyst. ) Was added and the mixture was heated and stirred at 120 at 94 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by cerite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 5), and the desired 4- Methoxycarbonyl-4'-methylbiphenyl (148.5 mg, 0.656,01, yield 95.8%) was obtained as white needle-like crystals.

1H-NMR(200MHz, CDC13): δ 2.43(s， 3H), 3.94(s, 3H)， 7.17〜7.44(m， 4 H)， 7.65(d, J = 8.4Hz, 2H, HC(2, 6)), 8.09(d， J = 8.4Hz, 2H, HC(3, 5)). Mass m/z:226(95¾, +), 195(100), 165(22), 152(27), 139(5), 28(46). IR(KBrJ:3450, 3040, 3000, 2950, 1720, 1610, 1440, 1400, 1280, 1210, 11 20,770,700cm-'. 実施例 49 1 H-NMR (200MHz, CDC1 3): δ 2.43 (s, 3H), 3.94 (s, 3H), 7.17~7.44 (m, 4 H), 7.65 (d, J = 8.4Hz, 2H, HC (2 , 6)), 8.09 (d, J = 8.4Hz, 2H, HC (3, 5)). Mass m / z: 226 (95¾, + ), 195 (100), 165 (22), 152 (27) , 139 (5), 28 (46) .IR (KBrJ: 3450, 3040, 3000, 2950, 1720, 1610, 1440, 1400, 1280, 1210, 11 20,770,700cm- '. Example 49

NHCOMe NHCOMe

Figure imgf000067_0001
NHCOMe NHCOMe
Figure imgf000067_0001

アルゴン雰囲気下、 フッ化カリウム粉末（252.0mg,4.34mniol)の Ν', Under argon atmosphere, potassium fluoride powder (252.0mg, 4.34mniol) Ν ',

Ν-ジメチルホルムアミ ド懸濁液（1.8ml)を 0 に冷却し、 ジクロロ（ ジフヱニル）シラン（220· Omg, 0.87匪 ol)を滴下した後、 60 で 3時間 撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 3-ァセト アミ ド -2-クロ口ピリジン（123.3mg, 0.72mmol)及び触媒として塩化 パラジウム [ビス（トリイソプロピルホスフィン）] (18. Omg, 36 mol, 5.0mol5¾)を加え、 120 で 90時間加熱撹拌した。 反応終了後、 反応 溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル (5ml)を加え、 セラ ィト濾過により触媒を濾過した。 水層を酢酸ェチル (5nilx2)で抽出 し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネ シゥムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得ら れた粗生成物を薄層ク口マトグラフィ ー（展開溶媒；酢酸ェチル：へ キサン = 1:1)で分離精製し、 目的の 3-ァセトアミ ド -2 -フエニルピリ ジン（115.5mg， 0.544雌 ol，収率 75.3%)を白色固体として得た。 The Ν-dimethylformamide suspension (1.8 ml) was cooled to 0, and dichloro (diphenyl) silane (220 · Omg, 0.87 marl) was added dropwise, followed by stirring at 60 for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 3-acetoamide-2-chloropyridine (123.3 mg, 0.72 mmol) and palladium chloride [bis (triisopropylphosphine)] (18. Omg, 36 mol , 5.0 mol 5¾), and the mixture was heated with stirring at 120 for 90 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5nilx2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer mouth chromatography (developing solvent: ethyl acetate: hexane = 1: 1), and the desired product was purified. 3-acetoamide-2-phenylpyridine (115.5 mg, 0.544 female ol, yield 75.3%) was obtained as a white solid.

'H-N R(200MHz,CDCl3): 5 2.04(s, 3H)， 7.27(dd, J=4.6 and 8.3Hz, 1 H， HC(5)), 7.43〜7.58(m, 6H, NH and benzenoid H), 8.38(d, J=4.6Hz, 1H， HC(4))， 8.56(d, J=8.3Hz， 1H, HC(6)). 'HNR (200 MHz, CDCl 3 ): 5 2.04 (s, 3H), 7.27 (dd, J = 4.6 and 8.3 Hz, 1 H, HC (5)), 7.43 to 7.58 (m, 6H, NH and benzenoid H ), 8.38 (d, J = 4.6Hz, 1H, HC (4)), 8.56 (d, J = 8.3Hz, 1H, HC (6)).

Mass m/z:212(49¾, +), 197(7), 181(5)， 169( 100), 77(4), 43(14), 28( 34). Mass m / z: 212 (49 °, + ), 197 (7), 181 (5), 169 (100), 77 (4), 43 (14), 28 (34).

IR(KBr):3250, 3200, 3180, 3000, 1690, 1530, 1440, 1425, 1370, 1300, 750, 740， 700cm-1. 実施例 5 0 IR (KBr): 3250, 3200, 3180, 3000, 1690, 1530, 1440, 1425, 1370, 1300, 750, 740, 700cm- 1 . Example 5 0

F3CF 3 C

Figure imgf000068_0001
Figure imgf000068_0001

アルゴン雰囲気下、 フッ化カリウム粉末（206.7mg，3.56minol)の N， Under argon atmosphere, potassium fluoride powder (206.7mg, 3.56minol) N,

N-ジメチルホルムアミ ド懸濁液（1.5ml)を 0°Cに冷却し、 ジクロロジ (4-トリフルォロメチルフエニル）シラン（276. lmg, 0.71nmiol)を滴下 した後、 60てで 3時間撹拌した。 反応溶液を室温に冷却し、 ァルゴ ン雰囲気下、 2-クロ口- 3-二トロピリジン（94. Omg, 0.59匪 ol)及び触 媒として塩化パラジウム [ビス（トリイソプロピルホスフィン）] (7.4 mg, 15//πιο1,2.5πιο1%)を加え、 120 で 60時間加熱撹拌した。 反応終 了後、 反応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を 加え、 セライ 卜濾過により触媒を濾過した。 水層を酢酸ェチル（5ml x2)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水 硫酸マグネシウムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留 去し、 得られた粗生成物を薄層クロマトグラフィー（展開溶媒；酢酸 ェチル：へキサン = 1:6)で分離精製し、 目的の 3-二トロ- 2-(4-トリフ ルォ口メチルフエニル）ピリジン（72.3mg, 0.273匪 ol,収率 46.0¾)を 淡黄色針状結晶として得た。 The N-dimethylformamide suspension (1.5 ml) was cooled to 0 ° C, and dichlorodi (4-trifluoromethylphenyl) silane (276.lmg, 0.71 nmol) was added dropwise. Stirred for hours. The reaction solution was cooled to room temperature, and under argon atmosphere, 2-chloro-3-dinitropyridine (94.Omg, 0.59 marl) and palladium chloride [bis (triisopropylphosphine)] (7.4 mg, 15 mg) as a catalyst. //πιο1,2.5πιο1%), and heated and stirred at 120 for 60 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 2), and the organic layers were combined, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 6) to give the desired 3- Toro-2- (4-trifluoromethylphenyl) pyridine (72.3 mg, 0.273 bandol, yield 46.0¾) was obtained as pale yellow needles.

,H-NMR(200 Hz,CDCl3): δ 7.51(dd, J:4.8 and 8.2Hz, 1H, HC(5)),7., H-NMR (200 Hz, CDCl 3 ): δ 7.51 (dd, J: 4.8 and 8.2 Hz, 1H, HC (5)), 7.

71(m, 4H),8.23(dd, J = 1.4 and 8.2Hz, 1H, HC(4)),8.89(dd,J = 1.4 and 4.8Hz, 1H,HC(6)). 71 (m, 4H), 8.23 (dd, J = 1.4 and 8.2Hz, 1H, HC (4)), 8.89 (dd, J = 1.4 and 4.8Hz, 1H, HC (6)).

Mass m/z:268(83¾, M + ), 240(88), 222(31), 202(98), 175(44λ 149(100). IR(KBr):3080, 1600, 1560, 1520, 1360, 1330, 1180, 1120， 1110, 1070,860, 850, 775CID-1. 実施例 5 1 Mass m / z: 268 (83¾, M + ), 240 (88), 222 (31), 202 (98), 175 (44λ 149 (100) .IR (KBr): 3080, 1600, 1560, 1520, 1360 , 1330, 1180, 1120, 1110, 1070,860, 850, 775CID- 1 . Example 5 1

N02 MeN0 2 Me

I I

Figure imgf000069_0001
Figure imgf000069_0001

アルゴン雰囲気下、 フッ化カリウム粉末（253.5mg,4.36minol)の Ν', Under argon atmosphere, potassium fluoride powder (253.5mg, 4.36minol) Ν ',

Ν-ジメチルホルムアミ ド懸濁液（1.8ml)を 0。Cに冷却し、 ジクロロジ (3-メチルフヱニル）シラン（243.5mg, 0.87minol)を滴下した後、 60 で 3時間撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 1 -クロ口- 3-ニトロピリジン（115.3mg, 0.73匪 ol)及び触媒として塩化 パラジウム [ビス（卜リイソプロピルホスフィ ン）] (9. lmg, 18^mol,2 .5mol!¾)を加え、 120°Cで 60時間加熱撹拌した。 反応終了後、 反応溶 液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト滹過により触媒を濾過した。 水層を酢酸ェチル (5ml X2)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシゥ ムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた 粗生成物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル：へキサ ン = 1:3)で分離精製し、 目的の 3-二卜口- 2-(3-メチルフヱニル）ピリ ジン（135· Omg, 0.630mmol,収率 86.7%)を黄色油状物として得た。 Ν-Dimethylformamide suspension (1.8 ml) was added. After cooling to C, dichlorodi (3-methylphenyl) silane (243.5 mg, 0.87 minol) was added dropwise, and the mixture was stirred at 60 for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 1-chloro-3-nitropyridine (115.3 mg, 0.73 bandol) and palladium chloride [bis (triisopropylphosphine)] (9.1 mg, 18 ^ mol, 2.5mol! ¾), and the mixture was heated and stirred at 120 ° C for 60 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl acetate: hexane = 1: 3) to obtain the desired 3- Nitroguchi-2- (3-methylphenyl) pyridine (135 · Omg, 0.630 mmol, yield 86.7%) was obtained as a yellow oil.

'H-NMR(200MHz, CDC13): <5 2.41(s, 3H, CH3), 7.25-7.47(m, 5H, HC(5, 2' , 4'， 5'， 6' )), 8.13(dd， J=l.4 and 8.1Hz, 1H, HC(4))， 8.85(dd, J = l. 4 and 4.6Hz, 1H，HC(6)). 'H-NMR (200MHz, CDC1 3): <5 2.41 (s, 3H, CH 3), 7.25-7.47 (m, 5H, HC (5, 2', 4 ', 5', 6 ')), 8.13 (dd, J = l.4 and 8.1Hz, 1H, HC (4)), 8.85 (dd, J = l. 4 and 4.6Hz, 1H, HC (6)).

IR(neat) :3430， 3070, 2940, 2880, 1600, 1565, 1530， 1450, 1360， 850， 765, 700cm-1. 実施例 52

Figure imgf000070_0001
IR (neat): 3430, 3070, 2940, 2880, 1600, 1565, 1530, 1450, 1360, 850, 765, 700cm- 1 . Example 52
Figure imgf000070_0001

アルゴン棼囲気下、 フッ化カリウム粉末（189.0mg，3.25mmol)の Ν, Under argon atmosphere, potassium fluoride powder (189.0mg, 3.25mmol)

Ν'-ジメチルホルムアミ ド懸濁液（1.3ml)を 0°Cに冷却し、 ジクロロジ (4-メ トキシフヱニル）シラン（202.4mg, 0.65匪 ol)を滴下した後、 60 で 3時間撹拌した。 反応溶液を室温に冷却し、 アルゴン雰囲気下、 2-クロ口- 3-二トロピリジン（86. Omg, 0.54mmol)及び触媒として塩化 パラジウム [ビス（トリイソプロピルホスフィ ン）] (6.8mg, 14 πιο1,2 .5mol¾)を加え、 120てで 24時間加熱撹拌した。 反応終了後、 反応溶 液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セライ ト濾過により触媒を濾過した。 水層を酢酸ェチル（5ml X 2)で抽出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグネシゥ ムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得られた 粗生成物を薄層クロマ卜ダラフィ一（展開溶媒；醉酸ェチル：へキサ ン = 1:1)で分雜精製し、 目的の 2-(4-メ トキシフヱニル） -3-ニトロピ リジン〔75.3mg, 0.327mmol,収率 60.3%)を黄色針状結晶として得た。 The suspension of Ν′-dimethylformamide (1.3 ml) was cooled to 0 ° C., and dichlorodi (4-methoxyphenyl) silane (202.4 mg, 0.65 dimethylol) was added dropwise, followed by stirring at 60 for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 2-chloro-3--3-nitropyridine (86. Omg, 0.54 mmol) and palladium chloride [bis (triisopropylphosphine)] (6.8 mg, 14πιο1 , 2.5 mol¾), and the mixture was heated and stirred at 120 rpm for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml × 2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by thin-layer chromatography (developing solvent: ethyl ethyl sulphate: hexane = 1: 1). The desired 2- (4-methoxyphenyl) -3-nitropyridine [75.3 mg, 0.327 mmol, yield 60.3%) was obtained as yellow needle crystals.

1H-NMR(200MHz, CDC13): δ 3.85(s, 3H， OMe), 6.98(d, J=8.8Hz, 2H, HC( 3'， 5' ))， 7.35(dd, J=4.7 and 8.1Hz, 1H， HC(5)), 7.54(d, J=8.8Hz, 2H， HC(2， , 6' )), 8.07(dd, J = l.5 and 8.1Hz, 1H， HC(4)), 8.80(dd, J = l.5 and 4.7Hz, 1H, HC(6)). 1H-NMR (200MHz, CDC1 3 ): δ 3.85 (s, 3H, OMe), 6.98 (d, J = 8.8Hz, 2H, HC (3 ', 5')), 7.35 (dd, J = 4.7 and 8.1 Hz, 1H, HC (5)), 7.54 (d, J = 8.8Hz, 2H, HC (2,, 6 ')), 8.07 (dd, J = l.5 and 8.1Hz, 1H, HC (4) ), 8.80 (dd, J = l.5 and 4.7Hz, 1H, HC (6)).

Mass m/z:230(100¾,M+), 200(18), 198(47), 185(26). Mass m / z: 230 (100 °, M + ), 200 (18), 198 (47), 185 (26).

IR( Br):3450, 3060, 2980, 2850, 1610, 1590, 1525, 1450， 1440, 1360, 13 10, 1255, 1180, 1020,860, 840cm-1. 実施例 5 3IR (Br): 3450, 3060, 2980, 2850, 1610, 1590, 1525, 1450, 1440, 1360, 13 10, 1255, 1180, 1020,860, 840cm- 1 . Example 5 3

Figure imgf000071_0001
Figure imgf000071_0001

アルゴン雰囲気下、 フッ化カリゥム粉末（217. Omg, 3.74mmol)の N, N-ジメチルホルムアミ ド懸濁液（1.6ml)を 0°Cに冷却し、 ジクロロ（ ェチル）（4-メ トキシフヱニル）シラン（n6.3mg,0.75minol)を滴下し た後、 60てで 3時間撹拌した。 反応溶液を室温に冷却し、 アルゴン 雰囲気下、 2-ブロモピリジン（91. lmg, 0.58腿 ol)及び触媒として塩 化パラジウム [ビス（トリィソプロピルホスフィ ン）] (15.4mg, 31jumo l,5.4mol%)を加え、 120てで 60時間加熱撹拌した。 反応終了後、 反 応溶液を室温まで冷却し、 水（5ml)及び酢酸ェチル（5ml)を加え、 セ ライ ト濾過により触媒を濾過した。 水層を酢酸ェチル（5ml X2)で抽 出し、 有機層を合わせ、 水及び飽和食塩水で洗浄後、 無水硫酸マグ ネシゥムで乾燥した。 乾燥剤を除去し、 溶媒を減圧下に留去し、 得 られた粗生成物を薄層クロマトグラフィー（展開溶媒；酢酸ェチル： へキサン = 1:4)で分離精製し、 目的の 2-(4-メ トキシフヱニル）ピリ ジン（81.5mg, 0.44mmol,収率 76.3¾)を白色固体として得た。 このも ののスぺク トルデータは参考例 1のもののデータと一致した。 参考例 1

Figure imgf000071_0002
Under an argon atmosphere, a suspension of potassium fluoride powder (217. Omg, 3.74 mmol) in N, N-dimethylformamide (1.6 ml) was cooled to 0 ° C and dichloro (ethyl) (4-methoxyphenyl) was added. After dropwise addition of silane (n6.3 mg, 0.75 minol), the mixture was stirred at 60 degrees for 3 hours. The reaction solution was cooled to room temperature, and under an argon atmosphere, 2-bromopyridine (91.lmg, 0.58 mol) and palladium chloride [bis (trisopropylphosphine)] as a catalyst (15.4 mg, 31jumol, 5.4 mol%), and the mixture was heated and stirred at 120 to 60 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, water (5 ml) and ethyl acetate (5 ml) were added, and the catalyst was filtered by celite filtration. The aqueous layer was extracted with ethyl acetate (5 ml X2), and the organic layers were combined, washed with water and saturated saline, and then dried over anhydrous magnesium sulfate. The desiccant was removed, the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by thin-layer chromatography (developing solvent; ethyl acetate: hexane = 1: 4) to obtain the desired 2- ( 4-Methoxyphenyl) pyridine (81.5 mg, 0.44 mmol, yield 76.3 7) was obtained as a white solid. The spectrum data of this was in agreement with the data of Reference Example 1. Reference example 1
Figure imgf000071_0002

アルゴン雰囲気下、 ェチル（ジクロ口）（4-メ トキシフヱニル）シラ ン 211mg(0.90薦 ol)、 2-ブロモピリジン 95nig(0.60匪 ol)およびフッ 化カリウム 241nig(4.5mmol)の Ν',Ν·-ジメチルホルムアミ ド溶液（lml) を 60 で 3時間撹拌した。 トリ- 0-トリルホスフィン 1. 82mg(6 mol) の Ν, Ν-ジメチルホルムアミ ド溶竦（lml)を加えた後、 反応混合物を 1 20 で 82時間撹拌した。 反応溶液を室温に冷却後、 炭酸ナトリウム 水溶液にそそぎ、 齚酸ェチルで抽出した。 抽出液を無水硫酸マグネ シゥムで乾燥後、 濾過、 溶媒留去により粗生成物を得た。 シリカゲ ルカラムクロマトグラフィー（へキサン：酢酸ェチル =5： 1 )により精 製し、 2-(4-メ トキシフエニル）ピリジン 26mg(0. 14蘭 ol,収率 23¾)を 得た。 Under an argon atmosphere, ethyl (dichloro mouth) (4-methoxyphenyl) silane 211 mg (0.90 recommended ol), 2-bromopyridine 95nig (0.60 bandol) and potassium fluoride 241nig (4.5 mmol) Ν ', Ν ·- Dimethylformamide solution (lml) Was stirred at 60 for 3 hours. After addition of 1.82 mg (6 mol) of 0, Ν-dimethylformamide solution (lml), the reaction mixture was stirred at 120 for 82 hours. After cooling the reaction solution to room temperature, it was poured into an aqueous solution of sodium carbonate and extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off to obtain a crude product. Purification was performed by silica gel column chromatography (hexane: ethyl acetate = 5: 1) to obtain 2- (4-methoxyphenyl) pyridine (26 mg, 0.14 orl, yield: 23¾).

mp:43〜45 mp: 43-45

•H-N RCCDC ) : δ 3. 85(s, 3H)， 7. 03(d, J=9. 0Hz, 2H), 7. 17(m( 1H), 7. 60〜7. 77(m, 2H), 7. 96(d, J = 9. 0Hz, 2H), 8. 65(d, J=5. 4Hz, 1H). HN RCCDC): δ 3.85 (s, 3H), 7.03 (d, J = 9.0 Hz, 2H), 7.17 (m ( 1H), 7.60 to 7.77 (m, 2H ), 7.96 (d, J = 9.0 Hz, 2H), 8.65 (d, J = 5.4 Hz, 1H).

IR(KBr) : 1610, 1590, 1245, 835, 780cm一1. 産業上の利用可能性 IR (KBr): 1610, 1590, 1245, 835, 780cm- 1 . Industrial applicability

本発明の方法により、 液晶などの機能性材料、 医薬および農薬と して有用なビアリール類ゃァルケニルァレーンおよびアルキルァレ ーン等の多官能性有機化合物を短工程かつ効率的に合成できる。  According to the method of the present invention, functional materials such as liquid crystals, and polyfunctional organic compounds such as biaryls alkenylarenes and alkylarenes useful as pharmaceuticals and agricultural chemicals can be efficiently synthesized in a short step.

Claims

請 求 の 範 囲 The scope of the claims 1. 下記一般式 [ I ] 1. The following general formula [I] R1-SiR2 mX3-m [ I ] R 1 -SiR 2 m X 3 - m [I] (式中、 R1は、 置換もしくは未置換のァリール基、 置換もしくは未 置換のアルケニル基、 または置換もしくは未置換のアルキル基を表 す。 R2は、 R'と同一であるか、 または低級アルキル基を表す。 Xは ハロゲン原子を表し、 mは 0から 2までの整数を表す。 ただし、 R1が アルキル基である場合には mは 0である。 ）で表される有機ハロシラ ン類と、 下記一般式 [H] (In the formula, R 1 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkyl group. R 2 is the same as R ′ or lower. Represents an alkyl group, X represents a halogen atom, m represents an integer from 0 to 2. However, when R 1 is an alkyl group, m is 0.) And the following general formula [H] R 1 [Π] R 1 [Π] (式中、 R3は、 置換もしくは未置換のァリール基、 置換もしくは未 置換の 1-アルケニル基、 または置換もしくは未置換の 2-アルケニル 基を表し、 Y1はハロゲン原子を表す。 ）で表される有機ハロゲン化 物とを、 第 10族遷移金属触媒および塩基の存在下に反応させること を特徴とする、 下記一般式： IE] (Wherein, R 3 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted 1-alkenyl group, or a substituted or unsubstituted 2-alkenyl group, and Y 1 represents a halogen atom.) Reacting with an organic halide to be used in the presence of a Group 10 transition metal catalyst and a base. The following general formula: IE] R'-R3 [I] R'-R 3 [I] (式中、 R1および R3は前記と同一の意味を表す。 ）で表される不飽和 有機化合物の製造方法。 (Wherein, R 1 and R 3 have the same meanings as described above.). 2. 下記一般式 [ 1〕 2. The following general formula [1]
Figure imgf000073_0001
Figure imgf000073_0001
 (式中、 R1は、 置換もしくは未置換のァリール基、 置換もしくは未 置換のアルケニル基、 または置換もしくは未置換のアルキル基を表 す。 R2は、 R1と同一であるか、 または低級アルキル基を表す。 Xは ハロゲン原子を表し、 mは 0から 2までの整数を表す。 ただし、 R1が アルキル基である場合には mは 0である。 ）で表される有機ハロシラ ン類と、 下記一般式 [IV ] (Wherein, R 1 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkyl group. R 2 is the same as R 1 , or lower. Represents an alkyl group, X represents a halogen atom, m represents an integer from 0 to 2, provided that R 1 is M is 0 when it is an alkyl group. ) And an organic halosilane represented by the following general formula [IV] R3-Y2 [IV] R 3 -Y 2 [IV] (式中、 R3は、 置換もしくは未置換のァリール基、 置換もしくは未 置換の 1 -アルケニル基、 または置換もしくは未置換の 2-アルケニル 基を表す。 Y2は、 塩素原子、 または臭素原子を表す。 ）で表される 有機塩化物とを、 トリアルキルホスフィン配位子をもつ第 10族遷移 金属触媒およびフッ化物塩の存在下に反応させることを特徵とする、 下記一般式 [皿] (Wherein, R 3 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted 1-alkenyl group, or a substituted or unsubstituted 2-alkenyl group. Y 2 represents a chlorine atom or a bromine atom. The organic compound represented by the following general formula [dish] is characterized by reacting with an organic chloride represented by) in the presence of a Group 10 transition metal catalyst having a trialkylphosphine ligand and a fluoride salt. R，-R3 [ 1 ] R, -R 3 [1] (式中、 R 1および R3は前記と同一の意味を表す。 ）で表される不飽和 有機化合物の製造方法。 (Wherein, R 1 and R 3 have the same meanings as described above.).
PCT/JP1996/000570 1995-03-10 1996-03-08 Process for producing unsaturated organic compounds Ceased WO1996028401A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0236132A (en) * 1988-04-29 1990-02-06 General Electric Co <Ge> Production of biaryl compound
JPH06239766A (en) * 1993-02-18 1994-08-30 Sagami Chem Res Center Production of biaryl compound

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0236132A (en) * 1988-04-29 1990-02-06 General Electric Co <Ge> Production of biaryl compound
JPH06239766A (en) * 1993-02-18 1994-08-30 Sagami Chem Res Center Production of biaryl compound

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