JPWO2016208554A1 - Iron complex compound and method for producing organosilicon compound using the same - Google Patents
Iron complex compound and method for producing organosilicon compound using the same Download PDFInfo
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- JPWO2016208554A1 JPWO2016208554A1 JP2017524904A JP2017524904A JPWO2016208554A1 JP WO2016208554 A1 JPWO2016208554 A1 JP WO2016208554A1 JP 2017524904 A JP2017524904 A JP 2017524904A JP 2017524904 A JP2017524904 A JP 2017524904A JP WO2016208554 A1 JPWO2016208554 A1 JP WO2016208554A1
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- Prior art keywords
- reaction
- mmol
- iron complex
- complex compound
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- Prior art date
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- -1 Iron complex compound Chemical class 0.000 title claims abstract description 237
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 150000003961 organosilicon compounds Chemical class 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 319
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 86
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 48
- 125000005843 halogen group Chemical group 0.000 claims abstract description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 40
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 17
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 150000004678 hydrides Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 125000004434 sulfur atom Chemical group 0.000 claims description 14
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 5
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 13
- 150000004698 iron complex Chemical class 0.000 description 94
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 84
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 66
- 230000015572 biosynthetic process Effects 0.000 description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 229940125904 compound 1 Drugs 0.000 description 52
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 238000003756 stirring Methods 0.000 description 51
- 238000003786 synthesis reaction Methods 0.000 description 49
- 239000007795 chemical reaction product Substances 0.000 description 44
- 238000001035 drying Methods 0.000 description 44
- 239000002002 slurry Substances 0.000 description 44
- 230000008859 change Effects 0.000 description 43
- 239000012456 homogeneous solution Substances 0.000 description 43
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 42
- 238000011088 calibration curve Methods 0.000 description 40
- 229910001873 dinitrogen Inorganic materials 0.000 description 40
- 238000004128 high performance liquid chromatography Methods 0.000 description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 29
- 239000002904 solvent Substances 0.000 description 25
- QRLBICHXRCOJDU-UHFFFAOYSA-N methyl(phenyl)silane Chemical compound C[SiH2]C1=CC=CC=C1 QRLBICHXRCOJDU-UHFFFAOYSA-N 0.000 description 24
- 229940125782 compound 2 Drugs 0.000 description 23
- 239000000843 powder Substances 0.000 description 23
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- FULSRCPEOUATID-UHFFFAOYSA-N methyl(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](C)C1=CC=CC=C1 FULSRCPEOUATID-UHFFFAOYSA-N 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 15
- 238000000023 Kugelrohr distillation Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000012043 crude product Substances 0.000 description 13
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 10
- OVRWOJSJXRBZJI-UHFFFAOYSA-N dioctyl(phenyl)silane Chemical compound CCCCCCCC[SiH](CCCCCCCC)C1=CC=CC=C1 OVRWOJSJXRBZJI-UHFFFAOYSA-N 0.000 description 10
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000001309 chloro group Chemical group Cl* 0.000 description 8
- 229940125898 compound 5 Drugs 0.000 description 8
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 8
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 7
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 6
- ZHIFOTWXGZPWDH-UHFFFAOYSA-N 1-(6-pyridin-2-ylpyridin-2-yl)ethanone Chemical compound CC(=O)C1=CC=CC(C=2N=CC=CC=2)=N1 ZHIFOTWXGZPWDH-UHFFFAOYSA-N 0.000 description 6
- BLMIXWDJHNJWDT-UHFFFAOYSA-N 6-chlorohex-1-ene Chemical compound ClCCCCC=C BLMIXWDJHNJWDT-UHFFFAOYSA-N 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- QIJVDMJQEWBRJO-UHFFFAOYSA-N octyl(phenyl)silane Chemical compound C(CCCCCCC)[SiH2]C1=CC=CC=C1 QIJVDMJQEWBRJO-UHFFFAOYSA-N 0.000 description 6
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 5
- TVHJQJDMMBNPPQ-UHFFFAOYSA-N 2-pyridin-2-yl-4h-pyridin-3-imine Chemical class N=C1CC=CN=C1C1=CC=CC=N1 TVHJQJDMMBNPPQ-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- HEAXGLZBOUYDFV-UHFFFAOYSA-L dibromoiron 1-(6-pyridin-2-ylpyridin-2-yl)-N-(2,4,6-trimethylphenyl)ethanimine Chemical compound [Fe](Br)Br.N1=C(C=CC=C1C(C)=NC1=C(C=C(C=C1C)C)C)C1=NC=CC=C1 HEAXGLZBOUYDFV-UHFFFAOYSA-L 0.000 description 5
- QBXSGVBOANRTDZ-UHFFFAOYSA-N dioctyl(diphenyl)silane Chemical compound C(CCCCCCC)[Si](C1=CC=CC=C1)(C1=CC=CC=C1)CCCCCCCC QBXSGVBOANRTDZ-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- NCRIDSGPLISUEU-UHFFFAOYSA-N 2-bromo-6-pyridin-2-ylpyridine Chemical compound BrC1=CC=CC(C=2N=CC=CC=2)=N1 NCRIDSGPLISUEU-UHFFFAOYSA-N 0.000 description 4
- QWFHFNGMCPMOCD-UHFFFAOYSA-N 6-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=CC(C=O)=N1 QWFHFNGMCPMOCD-UHFFFAOYSA-N 0.000 description 4
- PJROSBIRSKZRRR-UHFFFAOYSA-N C1=CC=C(C2=CC=CC(C(=O)C(F)(F)F)=N2)N=C1 Chemical compound C1=CC=C(C2=CC=CC(C(=O)C(F)(F)F)=N2)N=C1 PJROSBIRSKZRRR-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229940125773 compound 10 Drugs 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- XGVXKJKTISMIOW-ZDUSSCGKSA-N simurosertib Chemical compound N1N=CC(C=2SC=3C(=O)NC(=NC=3C=2)[C@H]2N3CCC(CC3)C2)=C1C XGVXKJKTISMIOW-ZDUSSCGKSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- GYUURHMITDQTRU-UHFFFAOYSA-N tributyl(pyridin-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CC=N1 GYUURHMITDQTRU-UHFFFAOYSA-N 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CAGNPARUGYVPNR-UHFFFAOYSA-N C(C)(C)(C)C(=O)C1=CC=CC(=N1)C1=NC=CC=C1 Chemical compound C(C)(C)(C)C(=O)C1=CC=CC(=N1)C1=NC=CC=C1 CAGNPARUGYVPNR-UHFFFAOYSA-N 0.000 description 3
- CRIFYTMAKNESLJ-UHFFFAOYSA-N C1=CC=CC=C1[Si](C)(CCCCCCCC)CCCCCCCC Chemical compound C1=CC=CC=C1[Si](C)(CCCCCCCC)CCCCCCCC CRIFYTMAKNESLJ-UHFFFAOYSA-N 0.000 description 3
- IVYOOQJQKHZRPW-UHFFFAOYSA-N C1CCCCC1[SiH2]C1=CC=CC=C1 Chemical compound C1CCCCC1[SiH2]C1=CC=CC=C1 IVYOOQJQKHZRPW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ZISUALSZTAEPJH-UHFFFAOYSA-N dimethyl(phenyl)silane Chemical compound C[SiH](C)C1=CC=CC=C1 ZISUALSZTAEPJH-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- USKQYZHWJZDNCM-UHFFFAOYSA-N tributyl-(6-methylpyridin-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CC(C)=N1 USKQYZHWJZDNCM-UHFFFAOYSA-N 0.000 description 3
- IAWUBQHOGZFDFX-UHFFFAOYSA-N 1-(6-pyridin-2-ylpyridin-2-yl)-N-(2,4,6-trimethylphenyl)ethanimine Chemical compound N1=C(C=CC=C1C(C)=NC1=C(C=C(C=C1C)C)C)C1=NC=CC=C1 IAWUBQHOGZFDFX-UHFFFAOYSA-N 0.000 description 2
- UQSLWVWTOIHTQE-UHFFFAOYSA-N 1-(6-pyridin-2-ylpyridin-2-yl)-N-(2,4,6-trimethylphenyl)methanimine Chemical compound CC1=CC(=C(C(=C1)C)N=CC2=CC=CC(=N2)C3=CC=CC=N3)C UQSLWVWTOIHTQE-UHFFFAOYSA-N 0.000 description 2
- RUFWYZCIHQMLHP-UHFFFAOYSA-N 1-[6-(6-methylpyridin-2-yl)pyridin-2-yl]-N-phenylmethanimine Chemical compound CC1=CC=CC(=N1)C2=NC(=CC=C2)C=NC3=CC=CC=C3 RUFWYZCIHQMLHP-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- SOHDPICLICFSOP-UHFFFAOYSA-N 2-bromo-6-methylpyridine Chemical compound CC1=CC=CC(Br)=N1 SOHDPICLICFSOP-UHFFFAOYSA-N 0.000 description 2
- HCDMJFOHIXMBOV-UHFFFAOYSA-N 3-(2,6-difluoro-3,5-dimethoxyphenyl)-1-ethyl-8-(morpholin-4-ylmethyl)-4,7-dihydropyrrolo[4,5]pyrido[1,2-d]pyrimidin-2-one Chemical compound C=1C2=C3N(CC)C(=O)N(C=4C(=C(OC)C=C(OC)C=4F)F)CC3=CN=C2NC=1CN1CCOCC1 HCDMJFOHIXMBOV-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007866 imination reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- QGNRLAFFKKBSIM-UHFFFAOYSA-N prop-2-enylsulfanylbenzene Chemical compound C=CCSC1=CC=CC=C1 QGNRLAFFKKBSIM-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- VCGRFBXVSFAGGA-UHFFFAOYSA-N (1,1-dioxo-1,4-thiazinan-4-yl)-[6-[[3-(4-fluorophenyl)-5-methyl-1,2-oxazol-4-yl]methoxy]pyridin-3-yl]methanone Chemical compound CC=1ON=C(C=2C=CC(F)=CC=2)C=1COC(N=C1)=CC=C1C(=O)N1CCS(=O)(=O)CC1 VCGRFBXVSFAGGA-UHFFFAOYSA-N 0.000 description 1
- UURSXESKOOOTOV-MDZDMXLPSA-N (e)-dec-5-ene Chemical compound CCCC\C=C\CCCC UURSXESKOOOTOV-MDZDMXLPSA-N 0.000 description 1
- IRUCBBFNLDIMIK-FPLPWBNLSA-N (z)-oct-4-ene Chemical compound CCC\C=C/CCC IRUCBBFNLDIMIK-FPLPWBNLSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ABDDQTDRAHXHOC-QMMMGPOBSA-N 1-[(7s)-5,7-dihydro-4h-thieno[2,3-c]pyran-7-yl]-n-methylmethanamine Chemical compound CNC[C@@H]1OCCC2=C1SC=C2 ABDDQTDRAHXHOC-QMMMGPOBSA-N 0.000 description 1
- BVASRSXIIXNITN-UHFFFAOYSA-N 1-[6-(6-methylpyridin-2-yl)pyridin-2-yl]-N-(2,4,6-trimethylphenyl)methanimine Chemical compound CC1=CC=CC(=N1)C2=NC(=CC=C2)C=NC3=C(C=C(C=C3C)C)C BVASRSXIIXNITN-UHFFFAOYSA-N 0.000 description 1
- WXBWKMLIVXELSF-UHFFFAOYSA-N 2,2,2-trifluoro-n,n-dimethylacetamide Chemical compound CN(C)C(=O)C(F)(F)F WXBWKMLIVXELSF-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- LLCYXFYLGPOKQO-UHFFFAOYSA-N 2-methyl-6-pyridin-2-ylpyridine Chemical compound CC1=CC=CC(C=2N=CC=CC=2)=N1 LLCYXFYLGPOKQO-UHFFFAOYSA-N 0.000 description 1
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 1
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 1
- KVCQTKNUUQOELD-UHFFFAOYSA-N 4-amino-n-[1-(3-chloro-2-fluoroanilino)-6-methylisoquinolin-5-yl]thieno[3,2-d]pyrimidine-7-carboxamide Chemical compound N=1C=CC2=C(NC(=O)C=3C4=NC=NC(N)=C4SC=3)C(C)=CC=C2C=1NC1=CC=CC(Cl)=C1F KVCQTKNUUQOELD-UHFFFAOYSA-N 0.000 description 1
- JUQRLACJJQXBDE-UHFFFAOYSA-N 6,6-dimethylhept-1-ene Chemical compound CC(C)(C)CCCC=C JUQRLACJJQXBDE-UHFFFAOYSA-N 0.000 description 1
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- SZUZOYIUYVPYGX-UHFFFAOYSA-N C(C)[SiH](CCCCCCCC)CC Chemical compound C(C)[SiH](CCCCCCCC)CC SZUZOYIUYVPYGX-UHFFFAOYSA-N 0.000 description 1
- UQSLWVWTOIHTQE-LPYMAVHISA-N Cc(cc1C)cc(C)c1/N=C/c1cccc(-c2ccccn2)n1 Chemical compound Cc(cc1C)cc(C)c1/N=C/c1cccc(-c2ccccn2)n1 UQSLWVWTOIHTQE-LPYMAVHISA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- AYCPARAPKDAOEN-LJQANCHMSA-N N-[(1S)-2-(dimethylamino)-1-phenylethyl]-6,6-dimethyl-3-[(2-methyl-4-thieno[3,2-d]pyrimidinyl)amino]-1,4-dihydropyrrolo[3,4-c]pyrazole-5-carboxamide Chemical compound C1([C@H](NC(=O)N2C(C=3NN=C(NC=4C=5SC=CC=5N=C(C)N=4)C=3C2)(C)C)CN(C)C)=CC=CC=C1 AYCPARAPKDAOEN-LJQANCHMSA-N 0.000 description 1
- WDUCYGSEOIQGGN-UHFFFAOYSA-N N-[2,6-di(propan-2-yl)phenyl]-1-(6-pyridin-2-ylpyridin-2-yl)methanimine Chemical compound N1=C(C=CC=C1C=NC1=C(C=CC=C1C(C)C)C(C)C)C1=NC=CC=C1 WDUCYGSEOIQGGN-UHFFFAOYSA-N 0.000 description 1
- PGQQYZUBRBCACJ-UHFFFAOYSA-N N-[2,6-di(propan-2-yl)phenyl]-1-[6-(6-methylpyridin-2-yl)pyridin-2-yl]methanimine Chemical compound CC1=CC=CC(=N1)C2=NC(=CC=C2)C=NC3=C(C=CC=C3C(C)C)C(C)C PGQQYZUBRBCACJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- JEDZLBFUGJTJGQ-UHFFFAOYSA-N [Na].COCCO[AlH]OCCOC Chemical compound [Na].COCCO[AlH]OCCOC JEDZLBFUGJTJGQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- UGVKNKATEGDKDY-UHFFFAOYSA-L dibromoiron 1-(6-pyridin-2-ylpyridin-2-yl)-N-(2,4,6-trimethylphenyl)methanimine Chemical compound [Fe](Br)Br.N1=C(C=CC=C1C=NC1=C(C=C(C=C1C)C)C)C1=NC=CC=C1 UGVKNKATEGDKDY-UHFFFAOYSA-L 0.000 description 1
- XOTCRBYGSDNMFM-UHFFFAOYSA-L dibromoiron N-[2,6-di(propan-2-yl)phenyl]-1-(6-pyridin-2-ylpyridin-2-yl)methanimine Chemical compound [Fe](Br)Br.N1=C(C=CC=C1C=NC1=C(C=CC=C1C(C)C)C(C)C)C1=NC=CC=C1 XOTCRBYGSDNMFM-UHFFFAOYSA-L 0.000 description 1
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 1
- MAFHCSBBTZYXDW-UHFFFAOYSA-N diethyl(dioctyl)silane Chemical compound CCCCCCCC[Si](CC)(CC)CCCCCCCC MAFHCSBBTZYXDW-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- OKHRRIGNGQFVEE-UHFFFAOYSA-N methyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C)C1=CC=CC=C1 OKHRRIGNGQFVEE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SZRMOYPJGSZDRA-UHFFFAOYSA-N n-[2,6-di(propan-2-yl)phenyl]-1-(6-pyridin-2-ylpyridin-2-yl)ethanimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C(C)C1=CC=CC(C=2N=CC=CC=2)=N1 SZRMOYPJGSZDRA-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- GZTNBKQTTZSQNS-UHFFFAOYSA-N oct-4-yne Chemical compound CCCC#CCCC GZTNBKQTTZSQNS-UHFFFAOYSA-N 0.000 description 1
- XDXCLOWYWRFTOS-UHFFFAOYSA-N octyl(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](CCCCCCCC)C1=CC=CC=C1 XDXCLOWYWRFTOS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical compound CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012419 sodium bis(2-methoxyethoxy)aluminum hydride Substances 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- XVKXMTGNOIVVLP-UHFFFAOYSA-N triethyl(octyl)silane Chemical compound CCCCCCCC[Si](CC)(CC)CC XVKXMTGNOIVVLP-UHFFFAOYSA-N 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
ヒドロシリル化反応における触媒を改良し、効率良く有機ケイ素化合物を製造することができる方法を提供することを目的とする。アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる反応工程を含む有機ケイ素化合物の製造方法において、触媒として、下記式（Ａ）で表される鉄錯体化合物とヒドリド還元剤を使用することにより、効率良く有機ケイ素化合物を製造することができる。（式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、Ｘはハロゲン原子を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）An object of the present invention is to provide a method capable of improving the catalyst in the hydrosilylation reaction and efficiently producing an organosilicon compound. In the method for producing an organosilicon compound including a reaction step in which an alkene and / or alkyne and hydrosilane are reacted in the presence of a catalyst, an iron complex compound represented by the following formula (A) and a hydride reducing agent are used as a catalyst. By using it, an organosilicon compound can be produced efficiently. (In formula (A), R1 and R2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, R3 represents a hydrocarbon group having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom, R4 represents a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, X represents a halogen atom, m represents an integer of 0 to 4, and n represents an integer of 0 to 3, provided that m is 2 to 4. The hydrocarbon groups of R1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon groups of R2 are linked to form a cyclic structure. May be.)
Description
本発明は、鉄錯体化合物及び有機ケイ素化合物の製造方法に関し、より詳しくはコモンメタルである鉄を中心金属とする錯体とそれをヒドロシリル化反応の触媒として利用した有機ケイ素化合物の製造方法に関する。 The present invention relates to a method for producing an iron complex compound and an organosilicon compound, and more particularly to a complex having iron as a central metal as a common metal and a method for producing an organosilicon compound using the complex as a catalyst for a hydrosilylation reaction.
分子内にケイ素−炭素結合を有する有機ケイ素化合物は、電子材料、シリコーンオイル、シリコーン樹脂、シリコーンゴム等の原料として用いられており、その利用範囲は多岐にわたる有用な化合物である。しかし、有機ケイ素化合物は天然には存在しないため、人工的に化学合成する必要があり、合成方法の１つである炭素−炭素多重結合へのヒドロシリル化反応は公知の技術である。
ヒドロシリル化反応には、主に遷移金属触媒が用いられているが、工業的にはＳｐｅｉｅｒ触媒（特許文献１参照）やＫａｒｓｔｅｄｔ触媒（特許文献２参照）等の白金触媒に依存しているのが現状である。Organosilicon compounds having a silicon-carbon bond in the molecule are used as raw materials for electronic materials, silicone oils, silicone resins, silicone rubbers, and the like, and are widely useful compounds. However, since an organosilicon compound does not exist in nature, it must be artificially chemically synthesized, and hydrosilylation to a carbon-carbon multiple bond, which is one of the synthesis methods, is a known technique.
Transition metal catalysts are mainly used in the hydrosilylation reaction, but industrially, it depends on platinum catalysts such as Speier catalysts (see Patent Document 1) and Karstedt catalysts (see Patent Document 2). Currently.
前述のようにヒドロシリル化反応には、希少金属である白金触媒等が利用されているため、コスト等の観点で改善の余地を残すものであった。
本発明は、ヒドロシリル化反応における触媒を改良し、効率良く有機ケイ素化合物を製造することができる方法を提供することを目的とする。As described above, a platinum catalyst, which is a rare metal, is used for the hydrosilylation reaction, so that there remains room for improvement in terms of cost and the like.
An object of the present invention is to provide a method capable of improving the catalyst in the hydrosilylation reaction and efficiently producing an organosilicon compound.
本発明者らは、上記の課題を解決すべく鋭意検討を重ねた結果、イミノビピリジン誘導体を配位子とする特定の鉄錯体とヒドリド還元剤を触媒として使用することにより、効率良く有機ケイ素化合物を製造することができることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have efficiently used an organosilicon compound by using a specific iron complex having an iminobipyridine derivative as a ligand and a hydride reducing agent as a catalyst. The present invention has been completed.
即ち、本発明は以下の通りである。
＜１＞ アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる反応工程を含む有機ケイ素化合物の製造方法であって、
前記反応工程が、触媒として下記式（Ａ）で表される鉄錯体化合物とヒドリド還元剤を使用する工程であることを特徴とする、有機ケイ素化合物の製造方法。
（式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、Ｘはそれぞれ独立してハロゲン原子を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）
＜２＞ 下記式（Ｉ−１）〜（Ｉ−９）及び（ＩＩ−１）〜（ＩＩ−３０）で表される化合物からなる群より選択される少なくとも１種の化合物を製造する方法である、＜１＞に記載の有機ケイ素化合物の製造方法。
（式（Ｉ−１）〜（Ｉ−９）及び式（ＩＩ−１）〜（ＩＩ−３０）中、Ｒ５〜Ｒ８はそれぞれ独立して水素原子、ハロゲン原子、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を、Ｒ９はそれぞれ独立して水素原子、ハロゲン原子、シロキシ基、ケイ素数１〜５０のポリシロキシ基、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表す。但し、Ｒ５〜Ｒ８の２個以上が炭化水素基である場合、その２個以上の炭化水素基が連結して環状構造を形成していてもよい。）
＜３＞ 下記式（ａ）で表されるイミノビピリジン化合物。
（式（ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）
＜４＞ 下記式（Ａ）で表される鉄錯体化合物。
（式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、Ｘはそれぞれ独立してハロゲン原子を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）That is, the present invention is as follows.
<1> A method for producing an organosilicon compound comprising a reaction step of reacting alkenes and / or alkynes with hydrosilanes in the presence of a catalyst,
The method for producing an organosilicon compound, wherein the reaction step is a step of using an iron complex compound represented by the following formula (A) and a hydride reducing agent as a catalyst.
(In Formula (A), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, X is independently a halogen atom, m is an integer of 0 to 4, and n is an integer of 0 to 3. However, when m is an integer of 2 to 4, the hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon group of R 2 They may be linked together to form an annular structure.)
<2> A method for producing at least one compound selected from the group consisting of compounds represented by the following formulas (I-1) to (I-9) and (II-1) to (II-30). The manufacturing method of the organosilicon compound as described in <1>.
(In formulas (I-1) to (I-9) and formulas (II-1) to (II-30), R 5 to R 8 are each independently a hydrogen atom, a halogen atom, a nitrogen atom, or an oxygen atom. A hydrocarbon group having 1 to 20 carbon atoms which may contain at least one selected from the group consisting of a silicon atom, a sulfur atom, and a halogen atom, R 9 is independently a hydrogen atom, a halogen atom, 1 to 50 carbon atoms which may contain at least one selected from the group consisting of a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, oxygen atom, silicon atom, sulfur atom and halogen atom Represents a hydrocarbon group, provided that when two or more of R 5 to R 8 are hydrocarbon groups, the two or more hydrocarbon groups may be linked to form a cyclic structure.)
<3> An iminobipyridine compound represented by the following formula (a).
(In formula (a), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, m is an integer of 0 to 4, and n is an integer of 0 to 3, provided that m is an integer of 2 to 4. The hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon groups of R 2 are linked to form a cyclic structure. May be.)
<4> An iron complex compound represented by the following formula (A).
(In Formula (A), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, X is independently a halogen atom, m is an integer of 0 to 4, and n is an integer of 0 to 3. However, when m is an integer of 2 to 4, the hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon group of R 2 They may be linked together to form an annular structure.)
本発明によれば、効率良く有機ケイ素化合物を製造することができる。 According to the present invention, an organosilicon compound can be produced efficiently.
本発明を説明するに当たり、具体例を挙げて説明するが、本発明の趣旨を逸脱しない限り以下の内容に限定されるものではなく、適宜変更して実施することができる。 In describing the present invention, specific examples will be described. However, the present invention is not limited to the following contents without departing from the gist of the present invention, and can be implemented with appropriate modifications.
＜有機ケイ素化合物の製造方法＞
本発明の一態様である有機ケイ素化合物の製造方法（以下、「本発明の製造方法」と略す場合がある。）は、アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる反応工程（以下、「反応工程」と略す場合がある。）を含む方法であり、反応工程が触媒として下記式（Ａ）で表される鉄錯体化合物とヒドリド還元剤を使用することを特徴とする。
（式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、Ｘはそれぞれ独立してハロゲン原子を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）
遷移金属触媒を用いたヒドロシリル化反応の反応機構には、（Ｍｏｄｉｆｉｅｄ）Ｃｈａｌｋ−Ｈａｒｒｏｄ機構（非特許文献１〜３参照）とＧｌａｓｅｒ−Ｔｉｌｌｙ機構（非特許文献４、５参照）が知られている。Ｇｌａｓｅｒ−Ｔｉｌｌｙ機構の場合、反応中間体としてシリレン錯体を経由することから、反応に適用できるヒドロシランは第１級シランのみとなり、白金触媒のように幅広いヒドロシランに触媒活性を示すためには、（Ｍｏｄｉｆｉｅｄ）Ｃｈａｌｋ−Ｈａｒｒｏｄ機構を考慮して触媒設計を行う必要がある。この場合、触媒サイクル中で炭素−炭素不飽和結合のπ配位とヒドロシランの酸化的付加で４電子増加し、形式酸化数が＋２増加となることから、鉄錯体においては触媒活性種が０価で価電子総数が１４電子以下となる錯体が好ましいと考えられる。
本発明者らは、式（Ａ）で表される鉄錯体とヒドリド還元剤を反応系中に添加することによって容易に活性種を誘導することができ、これがヒドロシリル化反応において高い触媒活性を示して、効率良く有機ケイ素化合物を製造することができることを見出したのである。また、かかる触媒は、第１級シランや第２級シランに含まれる複数のケイ素−水素結合（Ｓｉ−Ｈ）を活性化して、複数の炭素−ケイ素結合（Ｃ−Ｓｉ）を形成することができる特長を有しており、幅広い有機ケイ素化合物の製造に利用することできる。さらに式（Ａ）で表される鉄錯体は、比較的簡易的に合成することができる化合物であり、さらに空気中で安定であるため、取扱いが容易で、実用性に富んだ触媒となるのである。
なお、「アルケン類」とは炭素−炭素二重結合を少なくとも１つ有する有機化合物を、「アルキン類」とは炭素−炭素三重結合を少なくとも１つ有する有機化合物を、「ヒドロシラン類」とはケイ素−水素結合（Ｓｉ−Ｈ）を少なくとも１つ有する化合物を、「有機ケイ素化合物」とは炭素−ケイ素結合（Ｃ−Ｓｉ）を少なくとも１つ有する有機化合物を意味するものとする。従って、「アルケン類及び／又はアルキン類」と「ヒドロシラン類」の反応として、例えば下記の反応式で示されるような反応が挙げられる（「アルケン類」が「１−オクテン」であり、「ヒドロシラン類」がジフェニルメチルシランである。）。
The method for producing an organosilicon compound which is one embodiment of the present invention (hereinafter sometimes abbreviated as “the production method of the present invention”) reacts alkenes and / or alkynes with hydrosilanes in the presence of a catalyst. A method comprising a reaction step (hereinafter sometimes abbreviated as “reaction step”), wherein the reaction step uses an iron complex compound represented by the following formula (A) as a catalyst and a hydride reducing agent. To do.
(In Formula (A), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, X is independently a halogen atom, m is an integer of 0 to 4, and n is an integer of 0 to 3. However, when m is an integer of 2 to 4, the hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon group of R 2 They may be linked together to form an annular structure.)
As a reaction mechanism of a hydrosilylation reaction using a transition metal catalyst, a (Modified) Chalk-Harrod mechanism (see Non-Patent Documents 1 to 3) and a Glaser-Tilly mechanism (see Non-Patent Documents 4 and 5) are known. . In the case of the Glaser-Tilly mechanism, since a silylene complex is used as a reaction intermediate, the only hydrosilane that can be applied to the reaction is a primary silane. ) It is necessary to design the catalyst in consideration of the Chalk-Harrod mechanism. In this case, π-coordination of the carbon-carbon unsaturated bond and hydrosilane oxidative addition increase 4 electrons in the catalyst cycle, and the formal oxidation number increases by +2. It is considered that a complex having a total number of valence electrons of 14 or less is preferable.
The present inventors can easily induce active species by adding an iron complex represented by the formula (A) and a hydride reducing agent to the reaction system, and this shows high catalytic activity in the hydrosilylation reaction. Thus, it has been found that an organosilicon compound can be produced efficiently. Further, such a catalyst may activate a plurality of silicon-hydrogen bonds (Si—H) contained in the primary silane or the secondary silane to form a plurality of carbon-silicon bonds (C—Si). It can be used for the production of a wide range of organosilicon compounds. Furthermore, the iron complex represented by the formula (A) is a compound that can be synthesized relatively easily, and is stable in the air, so that it is easy to handle and has a practical utility. is there.
“Alkenes” means an organic compound having at least one carbon-carbon double bond, “alkynes” means an organic compound having at least one carbon-carbon triple bond, and “hydrosilanes” means silicon. -A compound having at least one hydrogen bond (Si-H), and an "organosilicon compound" means an organic compound having at least one carbon-silicon bond (C-Si). Therefore, the reaction of “alkenes and / or alkynes” and “hydrosilanes” includes, for example, the reaction represented by the following reaction formula (“alkenes” is “1-octene”, “hydrosilane” Class "is diphenylmethylsilane).
反応工程は、触媒として下記式（Ａ）で表される鉄錯体化合物（以下、「鉄錯体化合物」と略す場合がある。）を使用することを特徴とするが、式（Ａ）で表される鉄錯体化合物の具体的種類は特に限定されず、目的に応じて適宜選択することができる。
（式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、Ｘはそれぞれ独立してハロゲン原子を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）
Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を表しているが、「炭化水素基」は、直鎖状の飽和炭化水素基に限られず、分岐構造、環状構造、炭素−炭素不飽和結合のそれぞれを有していてもよいものとする（分岐構造、環状構造、及び炭素−炭素不飽和結合からなる群より選択される少なくとも１種を有していてもよい。）。
Ｒ１の炭化水素基の炭素数としては、好ましくは４以下、より好ましくは３以下、さらに好ましくは２以下である。
Ｒ２の炭化水素基の炭素数としては、好ましくは４以下、より好ましくは３以下、さらに好ましくは２以下である。
Ｒ１としては、メチル基（−ＣＨ３）、エチル基（−ＣＨ２ＣＨ３）、ｎ−プロピル基（−ＣＨ２ＣＨ２ＣＨ３）、ｉ−プロピル基（−ＣＨ（ＣＨ２）ＣＨ３）、ｎ−ブチル基（−ＣＨ２ＣＨ２ＣＨ２ＣＨ３）、ｔ−ブチル基（−Ｃ（ＣＨ３）３）等が挙げられる。
Ｒ２としては、メチル基（−ＣＨ３）、エチル基（−ＣＨ２ＣＨ３）、ｎ−プロピル基（−ＣＨ２ＣＨ２ＣＨ３）、ｉ−プロピル基（−ＣＨ（ＣＨ２）ＣＨ３）、ｎ−ブチル基（−ＣＨ２ＣＨ２ＣＨ２ＣＨ３）、ｔ−ブチル基（−Ｃ（ＣＨ３）３）等が挙げられる。
また、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよいが、炭化水素基同士が連結して環状構造を形成している構造として、下記式で表されるものが挙げられる。
(In Formula (A), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, X is independently a halogen atom, m is an integer of 0 to 4, and n is an integer of 0 to 3. However, when m is an integer of 2 to 4, the hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon group of R 2 They may be linked together to form an annular structure.)
R 1 and R 2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, but the “hydrocarbon group” is not limited to a linear saturated hydrocarbon group, but a branched structure, a cyclic structure, Each of the carbon-carbon unsaturated bonds may have (at least one selected from the group consisting of a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond may be included. ).
The number of carbon atoms of the hydrocarbon group for R 1 is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less.
The number of carbon atoms of the hydrocarbon group for R 2 is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less.
R 1 includes a methyl group (—CH 3 ), an ethyl group (—CH 2 CH 3 ), an n-propyl group (—CH 2 CH 2 CH 3 ), an i-propyl group (—CH (CH 2 ) CH 3. ), N-butyl group (—CH 2 CH 2 CH 2 CH 3 ), t-butyl group (—C (CH 3 ) 3 ) and the like.
R 2 includes a methyl group (—CH 3 ), an ethyl group (—CH 2 CH 3 ), an n-propyl group (—CH 2 CH 2 CH 3 ), and an i-propyl group (—CH (CH 2 ) CH 3. ), N-butyl group (—CH 2 CH 2 CH 2 CH 3 ), t-butyl group (—C (CH 3 ) 3 ) and the like.
In addition, when m is an integer of 2 to 4, the hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon groups of R 2 are May be linked to form a cyclic structure, but examples of structures in which hydrocarbon groups are linked to form a cyclic structure include those represented by the following formula.
Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を表しているが、「炭化水素基」はＲ１等の場合と同義である。
Ｒ３の炭化水素基の炭素数としては、好ましくは６以下、より好ましくは４以下、さらに好ましくは３以下である。
Ｒ３としては、水素原子（−Ｈ）、メチル基（−ＣＨ３）、トリフルオロメチル基（−ＣＦ３）、エチル基（−ＣＨ２ＣＨ３）、ｎ−プロピル基（−ＣＨ２ＣＨ２ＣＨ３）、ｉ−プロピル基（−ＣＨ（ＣＨ２）ＣＨ３）、ｎ−ブチル基（−ＣＨ２ＣＨ２ＣＨ２ＣＨ３）、ｔ−ブチル基（−Ｃ（ＣＨ３）３）等が挙げられるが、水素原子、メチル基（−ＣＨ３）、トリフルオロメチル基（−ＣＦ３）、ｔ−ブチル基（−Ｃ（ＣＨ３）３）が好ましい。R 3 represents a hydrocarbon group having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom, and the “hydrocarbon group” has the same meaning as in R 1 and the like.
The number of carbon atoms of the hydrocarbon group for R 3 is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
As R 3 , a hydrogen atom (—H), a methyl group (—CH 3 ), a trifluoromethyl group (—CF 3 ), an ethyl group (—CH 2 CH 3 ), an n-propyl group (—CH 2 CH 2). CH 3 ), i-propyl group (—CH (CH 2 ) CH 3 ), n-butyl group (—CH 2 CH 2 CH 2 CH 3 ), t-butyl group (—C (CH 3 ) 3 ) and the like. Examples thereof include a hydrogen atom, a methyl group (—CH 3 ), a trifluoromethyl group (—CF 3 ), and a t-butyl group (—C (CH 3 ) 3 ).
Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を表しているが、「芳香族炭化水素基」には、フェニル基のような芳香族性を有する単環の芳香族炭化水素基が含まれるほか、ナフチル基のような芳香族性を有する多環の芳香族炭化水素基も含まれるものとする。
Ｒ４の炭化水素基の炭素数としては、好ましくは１８以下、より好ましくは１６以下、さらに好ましくは１４以下である。
Ｒ４としては、下記式に挙げられるような水素原子、フェニル基、２，６−ジメチルフェニル基、２，４−ジメチルフェニル基、２，４，６−トリメチルフェニル基、２，６−ジイソプロピルフェニル基等が挙げられる。
The number of carbon atoms of the hydrocarbon group for R 4 is preferably 18 or less, more preferably 16 or less, and still more preferably 14 or less.
R 4 includes a hydrogen atom, a phenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group, and 2,6-diisopropylphenyl, as listed in the following formula. Groups and the like.
Ｘはそれぞれ独立してハロゲン原子を表しているが、塩素原子（−Ｃｌ）、臭素原子（−Ｂｒ）、ヨウ素原子（−Ｉ）が好ましく、臭素原子が特に好ましい。臭素原子であると、有機ケイ素化合物をより収率良く製造することができる。 X each independently represents a halogen atom, preferably a chlorine atom (—Cl), a bromine atom (—Br), or an iodine atom (—I), and particularly preferably a bromine atom. When it is a bromine atom, an organosilicon compound can be produced with higher yield.
鉄錯体化合物は、イミノビピリジン誘導体を配位子とする錯体であるが、イミノビピリジン誘導体としては、下記式で表されるものが挙げられる。
鉄錯体化合物としては、下記式で表されるものが挙げられる。
反応工程における鉄錯体化合物の使用量は、目的に応じて適宜選択することができるが、ヒドロシラン類の使用量に対して、物質量（［ｍｏｌ］）で、通常０．００００５倍以上、好ましくは０．００１倍以上、より好ましくは０．０１倍以上であり、通常１倍以下、好ましくは０．１倍以下、より好ましくは０．０１倍以下である。上記範囲内であると、有機ケイ素化合物をより収率良く製造することができる。 The amount of the iron complex compound used in the reaction step can be appropriately selected according to the purpose. However, the amount of the substance ([mol]) relative to the amount of hydrosilane used is usually 0.00005 times or more, preferably It is 0.001 times or more, more preferably 0.01 times or more, usually 1 time or less, preferably 0.1 times or less, more preferably 0.01 times or less. Within the above range, the organosilicon compound can be produced with higher yield.
（ヒドリド還元剤）
反応工程は、ヒドリド還元剤を使用することを特徴とするが、ヒドリド還元剤の具体的種類は特に限定されず、公知のものを目的に応じて適宜選択することができる。
ヒドリド還元剤としては、水素化ホウ素リチウム（ＬｉＢＨ４）、水素化ホウ素ナトリウム（ＮａＢＨ４）、シアノ水素化ホウ素ナトリウム（ＮａＢＨ３ＣＮ）、水素化トリエチルホウ素リチウム（ＬｉＢＨＥｔ３）、水素化トリエチルホウ素ナトリウム（ＮａＢＨＥｔ３）、水素化トリ（ｓｅｃ−ブチル）ホウ素リチウム（ＬｉＢＨ（ｓｅｃ−Ｂｕ）３）、水素化トリ（ｓｅｃ−ブチル）ホウ素カリウム（ＫＢＨ（ｓｅｃ−Ｂｕ）３）等の水素化ホウ素酸塩；水素化アルミニウムリチウム（ＬｉＡｌＨ４）、水素化ビス（２−メトキシエトキシ）アルミニウムナトリウム（ＮａＡｌＨ２（ＯＣ２Ｈ４ＯＣＨ３）２）等のアルミニウムのヒドリド錯体等が挙げられる。
これらの中でも、水素化トリエチルホウ素ナトリウム（ＮａＢＨＥｔ３）が特に好ましい。(Hydride reducing agent)
The reaction step is characterized by using a hydride reducing agent, but the specific type of the hydride reducing agent is not particularly limited, and a known one can be appropriately selected according to the purpose.
Examples of the hydride reducing agent include lithium borohydride (LiBH 4 ), sodium borohydride (NaBH 4 ), sodium cyanoborohydride (NaBH 3 CN), lithium triethylborohydride (LiBHEt 3 ), sodium triethylborohydride. Boron acid such as (NaBHEt 3 ), lithium tri (sec-butyl) borohydride (LiBH (sec-Bu) 3 ), potassium tri (sec-butyl) borohydride (KBH (sec-Bu) 3 ), etc. Salts; aluminum hydride complexes such as lithium aluminum hydride (LiAlH 4 ), sodium bis (2-methoxyethoxy) aluminum hydride (NaAlH 2 (OC 2 H 4 OCH 3 ) 2 ), and the like.
Among these, sodium triethylborohydride (NaBHEt 3 ) is particularly preferable.
反応工程におけるヒドリド還元剤の使用量は、目的に応じて適宜選択することができるが、鉄錯体化合物の使用量に対して、物質量（［ｍｏｌ］）で、通常２倍以上、好ましくは４倍以上、より好ましくは８倍以上であり、通常５０倍以下、好ましくは３０倍以下、より好ましくは２０倍以下である。上記範囲内であると、有機ケイ素化合物をより収率良く製造することができる。 The amount of hydride reducing agent used in the reaction step can be appropriately selected according to the purpose, but it is usually at least twice as much as the amount of the iron complex compound ([mol]), preferably 4 It is twice or more, more preferably 8 times or more, usually 50 times or less, preferably 30 times or less, more preferably 20 times or less. Within the above range, the organosilicon compound can be produced with higher yield.
（有機ケイ素化合物）
本発明の製造方法によって製造される有機ケイ素化合物は、前述のように炭素−ケイ素結合（Ｃ−Ｓｉ）を少なくとも有する有機化合物であれば、具体的な構造は特に限定されず、幅広い有機ケイ素化合物に適用することができる。
具体的には、下記式（Ｉ−１）〜（Ｉ−９）及び（ＩＩ−１）〜（ＩＩ−３０）で表される化合物が挙げられる。(Organic silicon compound)
As long as the organosilicon compound produced by the production method of the present invention is an organic compound having at least a carbon-silicon bond (C—Si) as described above, the specific structure is not particularly limited, and a wide variety of organosilicon compounds. Can be applied to.
Specific examples include compounds represented by the following formulas (I-1) to (I-9) and (II-1) to (II-30).
（式（Ｉ−１）〜（Ｉ−９）及び式（ＩＩ−１）〜（ＩＩ−３０）中、Ｒ５〜Ｒ８はそれぞれ独立して水素原子、ハロゲン原子、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を、Ｒ９はそれぞれ独立して水素原子、ハロゲン原子、シロキシ基、ケイ素数１〜５０のポリシロキシ基、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表す。但し、Ｒ５〜Ｒ８の２個以上が炭化水素基である場合、その２個以上の炭化水素基が連結して環状構造を形成していてもよい。）
なお、式（Ｉ−１）〜（Ｉ−９）で表される化合物は、アルケン類とヒドロシラン類との反応によって得られる有機ケイ素化合物であり、式（ＩＩ−１）〜（ＩＩ−３０）で表される化合物は、アルキン類とヒドロシラン類との反応によって得られる有機ケイ素化合物である。また、ＳｉＲ９ ３基が付加する位置は特に限定されず、さらにアルキン類とヒドロシラン類との反応によって得られる有機ケイ素化合物は、Ｚ体、Ｅ体、Ｚ体とＥ体の混合物の何れであってもよいことを表している。さらに式（Ｉ−３）〜（Ｉ−５）で表される化合物と式（ＩＩ−５）〜（ＩＩ−１４）で表される化合物は、ヒドロシラン類の２つのケイ素−水素結合（Ｓｉ−Ｈ）を活性化して、２つの炭素−ケイ素結合（Ｃ−Ｓｉ）を形成した化合物を、式（Ｉ−６）〜（Ｉ−９）で表される化合物と式（ＩＩ−１５）〜（ＩＩ−３０）で表される化合物は、ヒドロシラン類の３つのケイ素−水素結合（Ｓｉ−Ｈ）を活性化して、３つの炭素−ケイ素結合（Ｃ−Ｓｉ）を形成した化合物を表しており、幅広い有機ケイ素化合物の製造に利用することできるのである。
(In formulas (I-1) to (I-9) and formulas (II-1) to (II-30), R 5 to R 8 are each independently a hydrogen atom, a halogen atom, a nitrogen atom, or an oxygen atom. A hydrocarbon group having 1 to 20 carbon atoms which may contain at least one selected from the group consisting of a silicon atom, a sulfur atom, and a halogen atom, R 9 is independently a hydrogen atom, a halogen atom, 1 to 50 carbon atoms which may contain at least one selected from the group consisting of a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, oxygen atom, silicon atom, sulfur atom and halogen atom Represents a hydrocarbon group, provided that when two or more of R 5 to R 8 are hydrocarbon groups, the two or more hydrocarbon groups may be linked to form a cyclic structure.)
The compounds represented by formulas (I-1) to (I-9) are organosilicon compounds obtained by the reaction of alkenes and hydrosilanes, and are represented by formulas (II-1) to (II-30). The compound represented by is an organosilicon compound obtained by reaction of alkynes and hydrosilanes. The position where SiR 9 3 group is added is not particularly limited, further organosilicon compounds obtained by the reaction of alkynes and hydrosilane is either a Z isomer, E-isomer, a mixture of Z-form and E form It represents that it may be. Furthermore, the compounds represented by the formulas (I-3) to (I-5) and the compounds represented by the formulas (II-5) to (II-14) include two silicon-hydrogen bonds (Si— H) is activated to form two carbon-silicon bonds (C—Si), and the compounds represented by formulas (I-6) to (I-9) and formulas (II-15) to (II) The compound represented by II-30) represents a compound in which three silicon-hydrogen bonds (Si-H) of hydrosilanes are activated to form three carbon-silicon bonds (C-Si). It can be used for the production of a wide range of organosilicon compounds.
Ｒ５〜Ｒ８はそれぞれ独立に水素原子、ハロゲン原子、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表しているが、「窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい」とは、クロロ基（−Ｃｌ）、フルオロ基（−Ｆ）、アミノ基（−ＮＨ２）、ニトロ基（−ＮＯ２）、エポキシ基、ヒドロキシル基（−ＯＨ）、カルボニル基（−Ｃ（＝Ｏ）−）、ｔｅｒｔ−ブチルジメチルシリル基（−ＳｉＢｕＭｅ２）、アジ基（−Ｎ３）等の窒素原子、酸素原子、ケイ素原子、硫黄原子、又はハロゲン原子を含む官能基を含んでいてもよいことを意味するほか、エーテル基（−Ｏ−）、チオエーテル基（−Ｓ−）等の窒素原子、酸素原子、ケイ素原子、硫黄原子、又はハロゲン原子を含む連結基を炭素骨格の内部又は末端に含んでいてもよいことを意味する。
Ｒ５〜Ｒ８が炭化水素基である場合の炭素数は、好ましくは２以上、より好ましくは３以上、さらに好ましくは４以上であり、好ましくは１９以下、より好ましくは１７以下、さらに好ましくは１５以下である。なお、Ｒ５〜Ｒ８の２個以上が炭化水素基である場合、その２個以上の炭化水素基が連結して環状構造を形成していてもよいが、例えばＲ５とＲ６が連結してシクロヘプタン構造、シクロヘプテン構造、シクロヘキサン構造、シクロヘキセン構造等を形成していることが挙げられる。
Ｒ５〜Ｒ８が炭化水素基である場合の炭化水素基に含まれる官能基は、クロロ基（−Ｃｌ）、フルオロ基（−Ｆ）、アミノ基（−ＮＨ２）、ジメチルアミノ基（−Ｎ（ＣＨ３）２）、ニトロ基（−ＮＯ２）、エポキシ基、ヒドロキシル基（−ＯＨ）、カルボニル基（−Ｃ（＝Ｏ）−）、チオエーテル基（−Ｓ−）、ｔｅｒｔ−ブチルジメチルシリル基（−ＳｉＢｕＭｅ２）、アジ基（−Ｎ３）等が挙げられる。
また、Ｒ５〜Ｒ８が炭化水素基である場合、直鎖状の飽和炭化水素基に限られず、分岐構造、環状構造、炭素−炭素不飽和結合のそれぞれを有していてもよい（分岐構造、環状構造、及び炭素−炭素不飽和結合からなる群より選択される少なくとも１種を有していてもよい。）。
Ｒ５〜Ｒ８としては、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ｎ−へキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、メチルプロピル基、メチルブチル基、メチルペンチル基、メチルへキシル基、メチルヘプチル基、ジメチルプロピル基、ジメチルブチル基、ジメチルペンチル基、ジメチルへキシル基、ジメチルヘプチル基、フェニルエチル基、フェニルプロピル基、フェニルブチル基、フェニルペンチル基、フェニルへキシル基、フェニルヘプチル基、１−クロロプロピル基、１−クロロブチル基、１−クロロペンチル基、１−クロロへキシル基、１−クロロヘプチル基、ジメチルアミノメチル基、フェニルスルファニルメチル基等が挙げられる。R 5 to R 8 may each independently contain at least one selected from the group consisting of a hydrogen atom, a halogen atom, or a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. Represents a hydrocarbon group of ˜20, but “may contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom” means a chloro group (—Cl), fluoro group (—F), amino group (—NH 2 ), nitro group (—NO 2 ), epoxy group, hydroxyl group (—OH), carbonyl group (—C (═O) —), tert- butyldimethylsilyl group (-SiBuMe 2), meaning the nitrogen atom such as azide group (-N 3), an oxygen atom, a silicon atom, a sulfur atom, or that may contain a functional group containing a halogen atom In addition, a linking group containing a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, or a halogen atom such as an ether group (—O—) or a thioether group (—S—) is contained in the carbon skeleton or at the terminal. Means good.
The number of carbons in the case where R 5 to R 8 are hydrocarbon groups is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 19 or less, more preferably 17 or less, and still more preferably 15 or less. When two or more of R 5 to R 8 are hydrocarbon groups, the two or more hydrocarbon groups may be linked to form a cyclic structure. For example, R 5 and R 6 are linked. Thus, a cycloheptane structure, a cycloheptene structure, a cyclohexane structure, a cyclohexene structure and the like are formed.
The functional groups contained in the hydrocarbon group when R 5 to R 8 are hydrocarbon groups are a chloro group (—Cl), a fluoro group (—F), an amino group (—NH 2 ), a dimethylamino group (— N (CH 3 ) 2 ), nitro group (—NO 2 ), epoxy group, hydroxyl group (—OH), carbonyl group (—C (═O) —), thioether group (—S—), tert-butyldimethyl a silyl group (-SiBuMe 2), and the like azide group (-N 3) is.
Further, when R 5 to R 8 is a hydrocarbon group, not limited to a saturated hydrocarbon group having a linear, branched structure, cyclic structure, carbon - which may have a respective carbon unsaturated bond (branch It may have at least one selected from the group consisting of a structure, a cyclic structure, and a carbon-carbon unsaturated bond.
R 5 to R 8 include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a methylpropyl group, and a methylbutyl group. , Methylpentyl group, methylhexyl group, methylheptyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group , Phenylhexyl group, phenylheptyl group, 1-chloropropyl group, 1-chlorobutyl group, 1-chloropentyl group, 1-chlorohexyl group, 1-chloroheptyl group, dimethylaminomethyl group, phenylsulfanylmethyl group, etc. Is mentioned.
Ｒ９はそれぞれ独立に水素原子、ハロゲン原子、シロキシ基、ケイ素数１〜５０のポリシロキシ基、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表しているが、「窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい」については、Ｒ５〜Ｒ８の場合と同義である。
Ｒ９が炭化水素基である場合の炭素数は、好ましくは２以上、より好ましくは３以上、さらに好ましくは４以上であり、好ましくは１９以下、より好ましくは１７以下、さらに好ましくは１５以下である。
Ｒ９がポリシロキシ基である場合のケイ素数は、好ましくは２以上、より好ましくは３以上、さらに好ましくは４以上であり、好ましくは４８以下、より好ましくは４６以下、さらに好ましくは４５以下である。
また、Ｒ９が炭化水素基である場合、直鎖状の飽和炭化水素基に限られず、分岐構造、環状構造、炭素−炭素不飽和結合のそれぞれを有していてもよい（分岐構造、環状構造、及び炭素−炭素不飽和結合からなる群より選択される少なくとも１種を有していてもよい。）。
Ｒ９としては、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、フェニル基、メトキシ基、エトキシ基、ポリメチルシロキシ基等が挙げられる。この中でも、水素原子が好ましい。R 9 is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain “at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. "It may be present" has the same meaning as in the case of R 5 to R 8 .
When R 9 is a hydrocarbon group, the carbon number is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 19 or less, more preferably 17 or less, and still more preferably 15 or less. is there.
When R 9 is a polysiloxy group, the number of silicon is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 48 or less, more preferably 46 or less, and even more preferably 45 or less. .
When R 9 is a hydrocarbon group, it is not limited to a linear saturated hydrocarbon group, and may have a branched structure, a cyclic structure, or a carbon-carbon unsaturated bond (branched structure, cyclic It may have at least one selected from the group consisting of a structure and a carbon-carbon unsaturated bond).
Examples of R 9 include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group, a methoxy group, an ethoxy group, and a polymethylsiloxy group. It is done. Among these, a hydrogen atom is preferable.
（アルケン類・アルキン類）
反応工程は、アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる工程であるが、アルケン類及び／又はアルキン類の種類は特に限定されず、製造目的である有機ケイ素化合物に基づいて適宜選択されるべきである。
基本的に製造目的である有機ケイ素化合物と共通する構造を有するアルケン類やアルキン類を選択すべきであり、例えば式（Ｉ−１）〜（Ｉ−９）及び（ＩＩ−１）〜（ＩＩ−３０）で表される化合物を製造目的とする場合、アルケン類としては下記式（ｉ）で表される化合物が、アルキン類としては下記式（ｉｉ）で表される化合物が挙げられる。
（式（ｉ）及び（ｉｉ）中、Ｒ５〜Ｒ８はそれぞれ独立に水素原子、ハロゲン原子、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表す。但し、Ｒ５〜Ｒ８の２個以上が炭化水素基である場合、その２個以上の炭化水素基が連結して環状構造を形成していてもよい。）
アルケン類としては、１−オクテン、１−デセン、ｃｉｓ−４−オクテン、ｔｒａｎｓ−５−デセン、４−フェニル−１−ブテン、６，６−ジメチル−１−ヘプテン、４，４−ジメチル−１−ヘキセン、スチレン、シクロヘキセン、６−クロロ−１−ヘキセン、３−（ジメチルアミノ）−１−プロペン、アリルフェニルスルフィド等が挙げられる。
また、アルキン類としては、ジフェニルアセチレン、１−フェニル−１−プロピン、４−オクチン、フェニルアセチレン等が挙げられる。(Alkenes and alkynes)
The reaction step is a step of reacting alkenes and / or alkynes with hydrosilanes in the presence of a catalyst. It should be selected as appropriate.
Alkenes and alkynes having a structure that is basically the same as the organosilicon compound that is the production purpose should be selected. For example, formulas (I-1) to (I-9) and (II-1) to (II) When the compound represented by −30) is intended for production, examples of the alkene include compounds represented by the following formula (i), and examples of the alkyne include compounds represented by the following formula (ii).
(In formulas (i) and (ii), R 5 to R 8 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, or a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain one kind, provided that when two or more of R 5 to R 8 are hydrocarbon groups, the two or more hydrocarbon groups are linked; To form a ring structure.)
Alkenes include 1-octene, 1-decene, cis-4-octene, trans-5-decene, 4-phenyl-1-butene, 6,6-dimethyl-1-heptene, 4,4-dimethyl-1 -Hexene, styrene, cyclohexene, 6-chloro-1-hexene, 3- (dimethylamino) -1-propene, allylphenyl sulfide and the like.
Examples of alkynes include diphenylacetylene, 1-phenyl-1-propyne, 4-octyne, and phenylacetylene.
（ヒドロシラン類）
反応工程は、アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる工程であるが、ヒドロシラン類の種類は特に限定されず、製造目的である有機ケイ素化合物に基づいて適宜選択されるべきである。
基本的に製造目的である有機ケイ素化合物と共通する構造を有するヒドロシラン類を選択すべきであり、例えば式（Ｉ−１）〜（Ｉ−９）及び（ＩＩ−１）〜（ＩＩ−３０）で表される化合物を製造目的とする場合、ヒドロシラン類としては下記式（ｓ）で表される化合物が挙げられる。
（式（ｓ）中、Ｒ９はそれぞれ独立に水素原子、ハロゲン原子、シロキシ基、ケイ素数１〜５０のポリシロキシ基、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表す。）
ヒドロシラン類としては、ジエチルシラン、フェニルシラン、ジフェニルシラン、フェニル（メチル）シラン、フェニルジ（メチル）シラン、トリエトキシシラン、トリエチルシラン、ジエトキシメチルシラン等が挙げられる。(Hydrosilanes)
The reaction step is a step of reacting alkenes and / or alkynes and hydrosilanes in the presence of a catalyst, but the type of hydrosilanes is not particularly limited and is appropriately selected based on the organosilicon compound that is the production purpose. Should be.
Basically, hydrosilanes having a structure in common with the organosilicon compound that is the object of production should be selected. For example, formulas (I-1) to (I-9) and (II-1) to (II-30) In the case where the compound represented by formula (1) is intended for production, hydrosilanes include compounds represented by the following formula (s).
(In formula (s), each R 9 is independently a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. Represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one selected from more.)
Examples of hydrosilanes include diethyl silane, phenyl silane, diphenyl silane, phenyl (methyl) silane, phenyl di (methyl) silane, triethoxy silane, triethyl silane, diethoxymethyl silane, and the like.
反応工程におけるアルケン類及び／又はアルキン類とヒドロシラン類の使用量は、目的に応じて適宜選択することができるが、アルケン類及び／又はアルキン類の使用量は、ヒドロシラン類の使用量に対して、物質量（［ｍｏｌ］）で、通常０．２倍以上、好ましくは０．５倍以上、より好ましくは１倍以上であり、通常５０倍以下、好ましくは２０倍以下、より好ましくは１０倍以下である。上記範囲内であると、有機ケイ素化合物をより収率良く製造することができる。 The amount of alkene and / or alkyne and hydrosilane used in the reaction step can be appropriately selected according to the purpose, but the amount of alkene and / or alkyne used is relative to the amount of hydrosilane used. The amount of substance ([mol]) is usually 0.2 times or more, preferably 0.5 times or more, more preferably 1 time or more, usually 50 times or less, preferably 20 times or less, more preferably 10 times. It is as follows. Within the above range, the organosilicon compound can be produced with higher yield.
（溶媒）
反応工程は、溶媒を使用しても、使用しなくてもよいが、溶媒を使用しない方が好ましい。また、溶媒を使用する場合、その溶媒の種類は特に限定されず、目的に応じて適宜選択することができるが、具体的にはヘキサン、ベンゼン、トルエン等の炭化水素系溶媒、ジエチルエーテル、１，４−ジオキサン、テトラヒドロフラン（ＴＨＦ）等のエーテル系溶媒、エタノール、エチレングリコール、グリセリン等のプロトン性極性溶媒、アセトン、ジメチルアセトアミド（ＤＭＡ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルスルホキシド（ＤＭＳＯ）等の非プロトン性極性溶媒等が挙げられる。この中でも炭化水素系溶媒、エーテル系溶媒が好ましく、トルエン、テトラヒドロフランが特に好ましい。(solvent)
The reaction step may or may not use a solvent, but it is preferable not to use a solvent. When a solvent is used, the type of the solvent is not particularly limited and can be appropriately selected according to the purpose. Specifically, hydrocarbon solvents such as hexane, benzene, toluene, diethyl ether, 1 Ether solvents such as 1,4-dioxane and tetrahydrofuran (THF), protic polar solvents such as ethanol, ethylene glycol and glycerol, acetone, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone Examples include aprotic polar solvents such as (NMP) and dimethyl sulfoxide (DMSO). Of these, hydrocarbon solvents and ether solvents are preferable, and toluene and tetrahydrofuran are particularly preferable.
（反応条件）
反応工程は、アルケン類及び／又はアルキン類とヒドロシラン類とを触媒存在下で反応させる工程であるが、反応温度、反応時間等の反応条件は特に限定されない。
反応工程の反応温度は、通常２０℃以上、好ましくは４０℃以上、より好ましくは６０℃以上であり、通常１５０℃以下、好ましくは１００℃以下、より好ましくは８０℃以下である。上記範囲内であれば、有機ケイ素化合物をより収率良く製造することができる。
反応工程の反応時間は、通常１時間以上、好ましくは２時間以上、より好ましくは１０時間以上であり、通常６０時間以下、好ましくは４８時間以下、より好ましくは２４時間以下である。
反応は、通常窒素、アルゴン等の不活性雰囲気下で行う。(Reaction conditions)
The reaction step is a step of reacting alkenes and / or alkynes with hydrosilanes in the presence of a catalyst, but the reaction conditions such as reaction temperature and reaction time are not particularly limited.
The reaction temperature in the reaction step is usually 20 ° C or higher, preferably 40 ° C or higher, more preferably 60 ° C or higher, and usually 150 ° C or lower, preferably 100 ° C or lower, more preferably 80 ° C or lower. If it is in the said range, an organosilicon compound can be manufactured with a sufficient yield.
The reaction time in the reaction step is usually 1 hour or longer, preferably 2 hours or longer, more preferably 10 hours or longer, and usually 60 hours or shorter, preferably 48 hours or shorter, more preferably 24 hours or shorter.
The reaction is usually carried out under an inert atmosphere such as nitrogen or argon.
＜イミノビピリジン誘導体＞
鉄錯体化合物は、イミノビピリジン誘導体を配位子とする錯体であるが、下記式（ａ）で表されるイミノビピリジン化合物（以下、「イミノビピリジン化合物」と略す場合がある。）も本発明の一態様である。
（式（ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）
なお、Ｒ１、Ｒ２、Ｒ３、Ｒ４等については、＜有機ケイ素化合物の製造方法＞において説明した内容と同様である。<Iminobipyridine derivative>
The iron complex compound is a complex having an iminobipyridine derivative as a ligand, but an iminobipyridine compound represented by the following formula (a) (hereinafter also abbreviated as “iminobipyridine compound”) may also be used in the present invention. It is one mode.
(In formula (a), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, m is an integer of 0 to 4, and n is an integer of 0 to 3, provided that m is an integer of 2 to 4. The hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon groups of R 2 are linked to form a cyclic structure. May be.)
Note that R 1 , R 2 , R 3 , R 4 and the like are the same as those described in <Method for producing organosilicon compound>.
イミノビピリジン化合物の製造方法は、特に限定されず、公知の有機合成法を適宜組み合せて製造することができるが、下記式で表される合成経路によって製造することが挙げられる。
なお、かかる合成経路の具体的反応条件等は、Ｈｉｃｋｓ，Ｒ．Ｇ．，Ｏｒｇ．Ｌｅｔｔ．２００４，６，１８８７．、Ｖｅｒｎｉｅｓｔ，Ｇ．，Ｊ．Ｏｒｇ．Ｃｈｅｍ．２０１０，７５，４２４．、Ｓｃｈｕｂｅｒｔ，Ｕ．，Ｏｒｇ．Ｌｅｔｔ．２０００，２，３３７３．、Ｃｈａｍｐｏｕｒｅｔ，Ｙ．Ｄ．Ｍ．，Ｎｅｗ Ｊ．Ｃｈｅｍ．，２００７，３１，７５．、Ｄｉａｚ−Ｖａｌｅｎｚｕｅｌａ，Ｍ．Ｂ．，Ｃｈｅｍ．Ｅｕｒ．Ｊ．，２００９，１５，１２２７．Ｒａｎｇｈｅａｒｄ，Ｃ．，Ｄａｌｔｏｎ Ｔｒａｎｓ．，２００９，７７０．Ｄａｉ，Ｘ．，Ａｄｖ．Ｓｙｎｔｈ．Ｃａｔａｌ．，２０１４，３５６，１３１７．等を参考にすることができる。
また、例えば下記式で表される化合物等は、市販されており、原料として利用して幅広いイミノビピリジン化合物を製造することが可能である。
The specific reaction conditions and the like for this synthetic route are described in Hicks, R. et al. G. Org. Lett. 2004, 6, 1887. Verniest, G .; , J .; Org. Chem. 2010, 75, 424. Schubert, U .; Org. Lett. 2000, 2, 3373. Champouret, Y .; D. M.M. , New J .; Chem. , 2007, 31, 75. Diaz-Valenzuela, M .; B. , Chem. Eur. J. et al. , 2009, 15, 1227. Ranghard, C.I. Dalton Trans. , 2009, 770. Dai, X .; , Adv. Synth. Catal. , 2014, 356, 1317. Etc. can be referred to.
In addition, for example, compounds represented by the following formula are commercially available, and a wide range of iminobipyridine compounds can be produced by using them as raw materials.
＜鉄錯体化合物＞
鉄錯体化合物は、ヒドリド還元剤と共に反応系中に添加することによって容易に活性種を誘導することができ、これがヒドロシリル化反応において高い触媒活性を示すことを前述したが、鉄錯体化合物もまた本発明の一態様である。
（式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、Ｘはそれぞれ独立してハロゲン原子を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）
なお、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｘ等については、＜有機ケイ素化合物の製造方法＞において説明した内容と同様である。<Iron complex compound>
As described above, the iron complex compound can be easily derived from the active species by adding it to the reaction system together with the hydride reducing agent, and this shows high catalytic activity in the hydrosilylation reaction. It is one embodiment of the invention.
(In Formula (A), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, X is independently a halogen atom, m is an integer of 0 to 4, and n is an integer of 0 to 3. However, when m is an integer of 2 to 4, the hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon group of R 2 They may be linked together to form an annular structure.)
Note that R 1 , R 2 , R 3 , R 4 , X, and the like are the same as those described in <Organic silicon compound production method>.
鉄錯体化合物の製造方法は、特に限定されないが、通常イミノビピリジン化合物と２価のハロゲン化鉄を反応させることが挙げられる。
以下に実施例及び比較例を挙げて本発明をさらに具体的に説明するが、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.
＜配位子の合成＞
（合成例１：６−ブロモピリジン−２−カルボキシアルデヒドの合成）
ｎ−ＢｕＬｉヘキサン溶液（２．６５Ｍ，１０３ｍＬ，２７３ｍｍｏｌ）を−３０℃下、ＴＨＦ（３９５ｍＬ）で希釈し、−８０℃に冷却した。温度を−８０℃に維持し、撹拌しながら、これに２，６−ジブロモピリジン（６０．０ｇ，２４８ｍｍｏｌ）のＴＨＦ（２１０ｍＬ）溶液を滴下した。−８０℃以下で３０分間撹拌を続けた後、過剰量の無水ＤＭＦ（２９．０ｍＬ，３７２ｍｍｏｌ）を１分間かけて滴下したところ、発熱反応が生じた。この反応液を−７０℃以下に冷却した後、室温に戻し、反応をメタノール（１８０ｍＬ）でクエンチして、飽和炭酸水素ナトリウム水溶液（６００ｍＬ）を加えた。この溶液をクロロホルム（６００ｍＬ×５）で抽出し、有機相を集めて溶媒を留去した。粗生成物をカラムクロマトグラフィー（シリカ，ＣＨＣｌ３，Ｒｆ＝０．７０）で精製し、白色粉体である６−ブロモピリジン−２−カルボキシアルデヒドを得た（収率：９３％）。
1H NMR (400 MHz, CDCl3): 7.71 (m, 2H), 7.93 (dd, 1H, J = 6.8, 1.8 Hz), 10.01 (s,1H).<Synthesis of ligand>
(Synthesis Example 1: Synthesis of 6-bromopyridine-2-carboxaldehyde)
An n-BuLi hexane solution (2.65 M, 103 mL, 273 mmol) was diluted with THF (395 mL) at −30 ° C. and cooled to −80 ° C. While maintaining the temperature at −80 ° C. and stirring, a solution of 2,6-dibromopyridine (60.0 g, 248 mmol) in THF (210 mL) was added dropwise thereto. After stirring for 30 minutes at −80 ° C. or lower, an excessive amount of anhydrous DMF (29.0 mL, 372 mmol) was added dropwise over 1 minute, and an exothermic reaction occurred. The reaction solution was cooled to −70 ° C. or lower and then returned to room temperature. The reaction was quenched with methanol (180 mL), and a saturated aqueous sodium hydrogen carbonate solution (600 mL) was added. This solution was extracted with chloroform (600 mL × 5), the organic phase was collected, and the solvent was distilled off. The crude product was purified by column chromatography (silica, CHCl 3 , Rf = 0.70) to obtain 6-bromopyridine-2-carboxaldehyde as a white powder (yield: 93%).
1 H NMR (400 MHz, CDCl 3 ): 7.71 (m, 2H), 7.93 (dd, 1H, J = 6.8, 1.8 Hz), 10.01 (s, 1H).
（合成例２：２−（トリブチルスタニル）ピリジンの合成）
ｎ−ＢｕＬｉヘキサン溶液（２．６５Ｍ，９５ｍＬ，２５１ｍｍｏｌ）を、２−ブロモピリジン（４０．０ｇ，２３３ｍｍｏｌ）のＴＨＦ（３６０ｍＬ）溶液に−７８℃下で滴下した。−７０℃下で３０分間撹拌した後、−７８℃下でトリブチルスズクロリド（９０．８ｇ，２７９ｍｍｏｌ）を加え、反応液を室温に戻した。反応をメタノール（３０．５ｍＬ）でクエンチし、溶媒を留去した。得られた分散液を酢酸エチル（２００ｍＬ）で希釈し、セライトで濾過した。濾液の溶媒を留去し、得られた油性成分を蒸留（１４０℃，１８０Ｐａ）して精製し、黄色の油性成分である２−（トリブチルスタニル）ピリジンを得た（収率７４％）。
1H NMR (400 MHz, CDCl3): 0.88 (t, 9H, J = 7.3 Hz), 1.12 (m, 6H), 1.32 (m, 6H), 1.56 (m, 6H), 7.11 (m, 1H), 7.39 (d, 1H, J = 7.3 Hz), 7.48 (m, 1H), 8.73 (d, 1H, J = 4.5 Hz).(Synthesis Example 2: Synthesis of 2- (tributylstannyl) pyridine)
n-BuLi hexane solution (2.65 M, 95 mL, 251 mmol) was added dropwise to a solution of 2-bromopyridine (40.0 g, 233 mmol) in THF (360 mL) at −78 ° C. After stirring at −70 ° C. for 30 minutes, tributyltin chloride (90.8 g, 279 mmol) was added at −78 ° C., and the reaction solution was returned to room temperature. The reaction was quenched with methanol (30.5 mL) and the solvent was distilled off. The resulting dispersion was diluted with ethyl acetate (200 mL) and filtered through celite. The solvent of the filtrate was distilled off, and the resulting oil component was purified by distillation (140 ° C., 180 Pa) to obtain 2- (tributylstannyl) pyridine as a yellow oil component (yield 74%).
1 H NMR (400 MHz, CDCl 3 ): 0.88 (t, 9H, J = 7.3 Hz), 1.12 (m, 6H), 1.32 (m, 6H), 1.56 (m, 6H), 7.11 (m, 1H) , 7.39 (d, 1H, J = 7.3 Hz), 7.48 (m, 1H), 8.73 (d, 1H, J = 4.5 Hz).
（合成例３：［２，２’］ビピリジン−６−カルボキシアルデヒドの合成）
６−ブロモピリジン−２−カルボキシアルデヒド（２０．４ｇ，１１０ｍｍｏｌ）、２−（トリブチルスタニル）ピリジン（４０．４ｇ，１１０ｍｍｏｌ）、及びテトラキス（トリフェニルホスフィン）パラジウム（６．３３ｇ，５．４８ｍｍｏｌ）のトルエン（２００ｍＬ）溶液を窒素下で一晩還流した。この反応液を水（１００ｍＬ）で洗浄し、溶媒を留去した。粗生成物をカラムクロマトグラフィー（シリカ，ＡｃＯＥｔ，Ｒｆ＝０．７０）で精製し、黄色粉体である［２，２’］ビピリジン−６−カルボキシアルデヒドを得た（収率：４３％）。
1H NMR (400 MHz, CDCl3): 7.36 (m, 1H), 7.86 (m, 1H), 7.98 (m, 2H), 8.54 (m, 1H),8.65 (m, 1H), 8.71 (m, 1H), 10.17 (d, 1H, J = 1.2).(Synthesis Example 3: Synthesis of [2,2 ′] bipyridine-6-carboxaldehyde)
6-bromopyridine-2-carboxaldehyde (20.4 g, 110 mmol), 2- (tributylstannyl) pyridine (40.4 g, 110 mmol), and tetrakis (triphenylphosphine) palladium (6.33 g, 5.48 mmol) Of toluene (200 mL) was refluxed overnight under nitrogen. The reaction solution was washed with water (100 mL), and the solvent was distilled off. The crude product was purified by column chromatography (silica, AcOEt, Rf = 0.70) to obtain [2,2 ′] bipyridine-6-carboxaldehyde as a yellow powder (yield: 43%).
1 H NMR (400 MHz, CDCl 3 ): 7.36 (m, 1H), 7.86 (m, 1H), 7.98 (m, 2H), 8.54 (m, 1H), 8.65 (m, 1H), 8.71 (m, 1H), 10.17 (d, 1H, J = 1.2).
（合成例４：Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４，６−トリメチルベンゼンアミンの合成）
２，４，６−トリメチルアニリン（１．１４ｇ，８．１４ｍｍｏｌ）及び［２，２’］ビピリジン−６−カルボキシアルデヒド（１．５０ｇ、８．１４ｍｍｏｌ）のメタノール（２０．０ｍＬ）溶液を還流温度で加熱し、室温まで戻した。減圧下で溶媒を留去後、粗生成物をクーゲルロール蒸留（２５０℃，１７０Ｐａ）を利用して精製し、黄色の油性成分であるＮ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４，６−トリメチルベンゼンアミンを得た（収率：８２％）。なお、生成物には不純物として少量の２，４，６−トリメチルアニリンが含まれている。
1H NMR (400 MHz, CDCl3): 2.17 (s, 6H), 2.31 (s, 3H), 6.92 (s, 2H), 7.34 (m, 1H),7.84 (m, 1H), 7.97 (t, 1H, J = 7.9 Hz), 8.32 (d, 1H, J = 7.8 Hz), 8.44 (s, 1H),8.51 (m, 2H), 8.71 (m, 1H).
13C{1H} NMR (100.4 MHz, CDCl3): 18.39, 20.88, 121.00, 121.32, 122.67, 124.03, 126.92, 128.90, 133.47, 137.07, 137.64, 148.11, 149.36, 154.23, 155.81, 156.11, 164.02.(Synthesis Example 4: Synthesis of N-([2,2′-bipyridine] -6-ylmethylene) -2,4,6-trimethylbenzenamine)
A solution of 2,4,6-trimethylaniline (1.14 g, 8.14 mmol) and [2,2 ′] bipyridine-6-carboxaldehyde (1.50 g, 8.14 mmol) in methanol (20.0 mL) was refluxed. And heated to room temperature. After distilling off the solvent under reduced pressure, the crude product was purified using Kugelrohr distillation (250 ° C., 170 Pa), and N-([2,2′-bipyridine] -6-ylmethylene, a yellow oily component. ) -2,4,6-trimethylbenzenamine was obtained (yield: 82%). The product contains a small amount of 2,4,6-trimethylaniline as an impurity.
1 H NMR (400 MHz, CDCl 3 ): 2.17 (s, 6H), 2.31 (s, 3H), 6.92 (s, 2H), 7.34 (m, 1H), 7.84 (m, 1H), 7.97 (t, 1H, J = 7.9 Hz), 8.32 (d, 1H, J = 7.8 Hz), 8.44 (s, 1H), 8.51 (m, 2H), 8.71 (m, 1H).
13 C { 1 H} NMR (100.4 MHz, CDCl 3 ): 18.39, 20.88, 121.00, 121.32, 122.67, 124.03, 126.92, 128.90, 133.47, 137.07, 137.64, 148.11, 149.36, 154.23, 155.81, 156.11, 164.02.
（合成例５：Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，６−ジイソプロピルベンゼンアミンの合成）
２，６−ジイソプロピルアニリン（１．４４ｇ，８．１４ｍｍｏｌ）及び［２，２’］ビピリジン−６−カルボキシアルデヒド（１．５０ｇ、８．１４ｍｍｏｌ）のメタノール（２０．０ｍＬ）溶液を還流温度で加熱し、室温まで戻した。減圧下で溶媒を留去後、粗生成物をクーゲルロール蒸留（２４０℃，１７０Ｐａ）を利用して精製し、黄色粉体であるＮ−（［２，２’−ビピリジン］−６−イルメチレン）−２，６−ジイソプロピルベンゼンアミンを得た（収率：５５％）。なお、生成物には不純物として少量の２，６−ジイソプロピルアニリンが含まれている。
1H NMR (400 MHz, CDCl3): 1.19 (d, 12H, J = 6.8 Hz), 3.01 (sept, 2H, J = 6.7 Hz),7.11-7.22 (m, 3H), 7.34 (m, 1H), 7.85 (m, 1H), 7.98 (t, 1H, J = 7.6 Hz), 8.32 (d, 1H, J = 7.7 Hz), 8.41 (s, 1H), 8.52 (m, 2H), 8.71 (m, 1H).
13C{1H} NMR (100.4MHz, CDCl3): 23.53, 28.08, 121.11, 121.36, 122.73, 123.14, 124.05, 124.51, 137.06, 137.35, 137.69, 148.63, 149.34, 154.05, 155.78, 156.19, 163.52.(Synthesis Example 5: Synthesis of N-([2,2′-bipyridine] -6-ylmethylene) -2,6-diisopropylbenzenamine)
A solution of 2,6-diisopropylaniline (1.44 g, 8.14 mmol) and [2,2 ′] bipyridine-6-carboxaldehyde (1.50 g, 8.14 mmol) in methanol (20.0 mL) was heated at reflux temperature. And returned to room temperature. After distilling off the solvent under reduced pressure, the crude product was purified using Kugelrohr distillation (240 ° C., 170 Pa), and N-([2,2′-bipyridin] -6-ylmethylene) as a yellow powder. -2,6-diisopropylbenzenamine was obtained (yield: 55%). The product contains a small amount of 2,6-diisopropylaniline as an impurity.
1 H NMR (400 MHz, CDCl 3 ): 1.19 (d, 12H, J = 6.8 Hz), 3.01 (sept, 2H, J = 6.7 Hz), 7.11-7.22 (m, 3H), 7.34 (m, 1H) , 7.85 (m, 1H), 7.98 (t, 1H, J = 7.6 Hz), 8.32 (d, 1H, J = 7.7 Hz), 8.41 (s, 1H), 8.52 (m, 2H), 8.71 (m, 1H).
13 C { 1 H} NMR (100.4MHz, CDCl 3 ): 23.53, 28.08, 121.11, 121.36, 122.73, 123.14, 124.05, 124.51, 137.06, 137.35, 137.69, 148.63, 149.34, 154.05, 155.78, 156.19, 163.52.
（合成例６：６−メチル−２−（トリブチルスタニル）ピリジンの合成）
ｎ−ＢｕＬｉヘキサン溶液（２．６５Ｍ，２８．０ｍＬ，７４．６ｍｍｏｌ）を、２−ブロモ−６−メチルピリジン（１１．９ｇ，６９．２ｍｍｏｌ）のＴＨＦ（１０７ｍＬ）溶液に−８０℃下で滴下した。−７０℃下で３０分間撹拌した後、−８０℃以下の温度でトリブチルスズクロリド（２７．０ｇ，８３．０ｍｍｏｌ）を加え、反応液を室温に戻した。反応をメタノール（１０．０ｍＬ）でクエンチし、溶媒を留去した。得られた分散液をクロロホルム（１００ｍＬ）で希釈し、セライトで濾過した。濾液の溶媒を留去し、得られた油性成分を蒸留（１５０℃，６０Ｐａ）して精製し、無色油性成分である６−メチル−２−（トリブチルスタニル）ピリジンを得た（収率６５％）。
1H NMR (400 MHz, CDCl3): 0.88 (t, 9H, J = 7.3 Hz), 1.10 (m, 6H), 1.32 (m, 6H), 1.56 (m, 6H), 2.54 (s, 3H), 6.95 (d, 1H, J = 7.6 Hz), 7.17 (d, 1H, J = 7.2 Hz), 7.36 (t, 1H, J = 7.6 Hz).(Synthesis Example 6: Synthesis of 6-methyl-2- (tributylstannyl) pyridine)
n-BuLi hexane solution (2.65 M, 28.0 mL, 74.6 mmol) was added dropwise to a solution of 2-bromo-6-methylpyridine (11.9 g, 69.2 mmol) in THF (107 mL) at −80 ° C. did. After stirring at −70 ° C. for 30 minutes, tributyltin chloride (27.0 g, 83.0 mmol) was added at a temperature of −80 ° C. or lower, and the reaction solution was returned to room temperature. The reaction was quenched with methanol (10.0 mL) and the solvent was distilled off. The resulting dispersion was diluted with chloroform (100 mL) and filtered through celite. The solvent of the filtrate was distilled off, and the resulting oil component was purified by distillation (150 ° C., 60 Pa) to obtain 6-methyl-2- (tributylstannyl) pyridine as a colorless oil component (yield 65 %).
1 H NMR (400 MHz, CDCl 3 ): 0.88 (t, 9H, J = 7.3 Hz), 1.10 (m, 6H), 1.32 (m, 6H), 1.56 (m, 6H), 2.54 (s, 3H) , 6.95 (d, 1H, J = 7.6 Hz), 7.17 (d, 1H, J = 7.2 Hz), 7.36 (t, 1H, J = 7.6 Hz).
（合成例７：６’−メチル［２，２’］ビピリジン−６−カルボキシアルデヒドの合成）
６−ブロモピリジン−２−カルボキシアルデヒド（１．８９ｇ，１０．２ｍｍｏｌ）、６−メチル−２−（トリブチルスタニル）ピリジン（３．８８ｇ，１０．２ｍｍｏｌ）、及びテトラキス（トリフェニルホスフィン）パラジウム（１．１７ｇ，１．０２ｍｍｏｌ）のトルエン（１８．９ｍＬ）溶液を窒素下で一晩還流した。この反応液を水（１０．０ｍＬ）で洗浄し、溶媒を留去した。粗生成物をクーゲルロール蒸留（１２５℃，１９０Ｐａ）を利用して精製し、白色粉体である６’−メチル［２，２’］ビピリジン−６−カルボキシアルデヒドを得た（収率：７３％）。
1H NMR (400 MHz, CDCl3): 2.65 (s, 3H), 7.22 (d, 1H, J = 7.6 Hz), 7.33 (br, 1H), 7.75 (t, 1H, J = 7.8 Hz), 7.97 (m, 1H), 8.33 (d, 1H, J = 7.6 Hz), 8.67 (dd, 1H, J = 6.5, 2.3 Hz), 10.17 (s, 1H).(Synthesis Example 7: Synthesis of 6'-methyl [2,2 '] bipyridine-6-carboxaldehyde)
6-bromopyridine-2-carboxaldehyde (1.89 g, 10.2 mmol), 6-methyl-2- (tributylstannyl) pyridine (3.88 g, 10.2 mmol), and tetrakis (triphenylphosphine) palladium ( A solution of 1.17 g, 1.02 mmol) in toluene (18.9 mL) was refluxed overnight under nitrogen. This reaction solution was washed with water (10.0 mL), and the solvent was distilled off. The crude product was purified using Kugelrohr distillation (125 ° C., 190 Pa) to obtain 6′-methyl [2,2 ′] bipyridine-6-carboxaldehyde as a white powder (yield: 73%). ).
1 H NMR (400 MHz, CDCl 3 ): 2.65 (s, 3H), 7.22 (d, 1H, J = 7.6 Hz), 7.33 (br, 1H), 7.75 (t, 1H, J = 7.8 Hz), 7.97 (m, 1H), 8.33 (d, 1H, J = 7.6 Hz), 8.67 (dd, 1H, J = 6.5, 2.3 Hz), 10.17 (s, 1H).
（合成例８：Ｎ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−ベンゼンアミンの合成）
アニリン（０．１０ｇ，１．０７ｍｍｏｌ）及び６’−メチル［２，２’］ビピリジン−６−カルボキシアルデヒド（０．２１ｇ、１．０７ｍｍｏｌ）のメタノール（３．２ｍＬ）溶液を還流温度で加熱し、室温まで戻した。沈殿物を濾過で単離し、メタノール（０．３ｍＬ）で３回洗浄、真空乾燥させて、黄色粉体であるＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−ベンゼンアミンを得た（収率：２６％）。
1H NMR (400 MHz, CDCl3): 2.67 (s, 3H), 7.21 (d, 1H, J = 7.6 Hz), 7.24-7.35 (m, 3H), 7.43 (t, 2H, J = 7.6 Hz), 7.75 (t, 1H, J = 7.8 Hz), 7.94 (t, 1H, J = 7.8 Hz), 8.25 (d, 1H, J = 7.8 Hz), 8.29 (d, 1H, J = 7.8 Hz), 8.52 (d, 1H, J = 7.8 Hz), 8.71 (s, 1H).
13C{1H} NMR (100.4 MHz, CDCl3): 24.73, 118.44, 121.28, 121.38, 121.50, 122.82, 123.73, 129.36, 137.44, 137.64, 151.24, 154.30, 155.16, 158.16, 161.40, 193.96.
Anal. Calcd. for C18H15N3: C, 79.10; H, 5.53; N, 15.37. Found: C, 79.04; H, 5.62; N, 15.43.(Synthesis Example 8: Synthesis of N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) methylene] -benzeneamine)
A solution of aniline (0.10 g, 1.07 mmol) and 6′-methyl [2,2 ′] bipyridine-6-carboxaldehyde (0.21 g, 1.07 mmol) in methanol (3.2 mL) was heated at reflux temperature. , Returned to room temperature. The precipitate was isolated by filtration, washed three times with methanol (0.3 mL) and dried in vacuo to give a yellow powder N- [1- (6′-methyl [2,2′-bipyridine] -6- Yl) methylene] -benzeneamine was obtained (yield: 26%).
1 H NMR (400 MHz, CDCl 3 ): 2.67 (s, 3H), 7.21 (d, 1H, J = 7.6 Hz), 7.24-7.35 (m, 3H), 7.43 (t, 2H, J = 7.6 Hz) , 7.75 (t, 1H, J = 7.8 Hz), 7.94 (t, 1H, J = 7.8 Hz), 8.25 (d, 1H, J = 7.8 Hz), 8.29 (d, 1H, J = 7.8 Hz), 8.52 (d, 1H, J = 7.8 Hz), 8.71 (s, 1H).
13 C { 1 H} NMR (100.4 MHz, CDCl 3 ): 24.73, 118.44, 121.28, 121.38, 121.50, 122.82, 123.73, 129.36, 137.44, 137.64, 151.24, 154.30, 155.16, 158.16, 161.40, 193.96.
Anal.Calcd.for C 18 H 15 N 3 : C, 79.10; H, 5.53; N, 15.37.Found: C, 79.04; H, 5.62; N, 15.43.
（合成例９：Ｎ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，４，６−トリメチルベンゼンアミンの合成）
アニリンを２，４，６−トリメチルアニリンに変更した以外、合成例８と同様の方法を行って、黄色粉体であるＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，４，６−トリメチルベンゼンアミンを得た（収率：５５％）。
1H NMR (400 MHz, CDCl3): 2.16 (s, 6H), 2.30 (s, 3H), 2.66 (s, 3H), 6.91 (s, 2H),7.20 (d, 1H, J = 7.6 Hz), 7.72 (t, 1H, J = 7.8 Hz), 7.95 (t, 1H, J = 7.8 Hz), 8.26 (d, 1H, J = 7.8 Hz), 8.29 (d, 1H, J = 7.8 Hz), 8.42 (s, 1H), 8.52 (d, 1H, J =7.8 Hz).
13C{1H} NMR (100.4 MHz, CDCl3): 18.40, 20.89, 24.80, 118.33, 120.82, 122.77, 123.63, 126.95, 128.88, 133.45, 137.25, 137.57, 148.13, 154.17, 155.21, 156.44, 158.17, 164.16.
Anal. Calcd. for C21H21N3: C, 79.97; H, 6.71; N, 13.32. Found: C, 80.11; H, 6.85; N, 13.36.(Synthesis Example 9: Synthesis of N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) methylene] -2,4,6-trimethylbenzenamine)
A yellow powder N- [1- (6′-methyl [2,2′-bipyridine]-was obtained in the same manner as in Synthesis Example 8 except that aniline was changed to 2,4,6-trimethylaniline. 6-yl) methylene] -2,4,6-trimethylbenzenamine was obtained (yield: 55%).
1 H NMR (400 MHz, CDCl 3 ): 2.16 (s, 6H), 2.30 (s, 3H), 2.66 (s, 3H), 6.91 (s, 2H), 7.20 (d, 1H, J = 7.6 Hz) , 7.72 (t, 1H, J = 7.8 Hz), 7.95 (t, 1H, J = 7.8 Hz), 8.26 (d, 1H, J = 7.8 Hz), 8.29 (d, 1H, J = 7.8 Hz), 8.42 (s, 1H), 8.52 (d, 1H, J = 7.8 Hz).
13 C { 1 H} NMR (100.4 MHz, CDCl 3 ): 18.40, 20.89, 24.80, 118.33, 120.82, 122.77, 123.63, 126.95, 128.88, 133.45, 137.25, 137.57, 148.13, 154.17, 155.21, 156.44, 158.17, 164.16 .
Anal.Calcd.for C 21 H 21 N 3 : C, 79.97; H, 6.71; N, 13.32. Found: C, 80.11; H, 6.85; N, 13.36.
（合成例１０：Ｎ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，６−ジイソプロピルベンゼンアミンの合成）
アニリンを２，４，６−トリメチルアニリンに変更した以外、合成例８と同様の方法を行って、黄色粉体であるＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，６−ジイソプロピルベンゼンアミンを得た（収率：９６％）。
1H NMR (400 MHz, CDCl3): 1.19 (d, 12H, J = 6.8 Hz), 2.67 (s, 3H), 3.01 (sept, 2H, J = 6.8 Hz), 7.11-7.22 (m, 4H), 7.73 (t, 1H, J = 7.8 Hz), 7.97 (t, 1H, J = 7.8Hz), 8.29 (d, 2H, J = 7.5 Hz), 8.40 (s, 1H), 8.56 (d, 1H, J = 7.6 Hz).
13C{1H} NMR (100.4 MHz, CDCl3): 23.59, 24.80, 28.09, 118.37, 120.93, 122.83, 123.15, 123.64, 124.50, 137.23, 137.39, 137.61, 148.67, 154.02, 155.21, 156.55, 158.15, 163.65.
Anal. Calcd. for C24H24N3: C, 80.63; H, 7.61; N, 11.75. Found: C, 80.43; H,7.71; N, 11.70.(Synthesis Example 10: Synthesis of N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) methylene] -2,6-diisopropylbenzenamine)
A yellow powder N- [1- (6′-methyl [2,2′-bipyridine]-was obtained in the same manner as in Synthesis Example 8 except that aniline was changed to 2,4,6-trimethylaniline. 6-yl) methylene] -2,6-diisopropylbenzenamine was obtained (yield: 96%).
1 H NMR (400 MHz, CDCl 3 ): 1.19 (d, 12H, J = 6.8 Hz), 2.67 (s, 3H), 3.01 (sept, 2H, J = 6.8 Hz), 7.11-7.22 (m, 4H) , 7.73 (t, 1H, J = 7.8 Hz), 7.97 (t, 1H, J = 7.8 Hz), 8.29 (d, 2H, J = 7.5 Hz), 8.40 (s, 1H), 8.56 (d, 1H, J = 7.6 Hz).
13 C {1 H} NMR ( 100.4 MHz, CDCl 3): 23.59, 24.80, 28.09, 118.37, 120.93, 122.83, 123.15, 123.64, 124.50, 137.23, 137.39, 137.61, 148.67, 154.02, 155.21, 156.55, 158.15, 163.65 .
Anal.Calcd.for C 24 H 24 N 3 : C, 80.63; H, 7.61; N, 11.75. Found: C, 80.43; H, 7.71; N, 11.70.
＜式（Ａ）で表される鉄錯体化合物の調製＞
（実施例１：Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４,６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミドの調製）
乾燥した窒素雰囲気、室温下で激しく撹拌しながら、臭化鉄（ＩＩ）（１．２０ｇ，５．５５ｍｍｏｌ）を、Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４，６−トリメチルベンゼンアミン（１．６８ｇ，５．５７ｍｍｏｌ）のＴＨＦ（８４．０ｍＬ）溶液に加えた。沈殿物を濾過で単離し、ＴＨＦ（８．０ｍＬ）で３回洗浄、真空乾燥させて、暗緑色粉体であるＮ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物１」と略す場合がある。）を得た（収率：８９％）。
Anal. Calcd. for C20H19Br2FeN3: C, 46.46; H, 3.70; N, 8.13. Found: C, 46.00; H, 3.84; N, 7.96.<Preparation of iron complex compound represented by formula (A)>
Example 1: Preparation of N-([2,2′-bipyridin] -6-ylmethylene) -2,4,6-trimethylbenzenamine iron (II) bromide
With vigorous stirring under a dry nitrogen atmosphere at room temperature, iron (II) bromide (1.20 g, 5.55 mmol) was added to N-([2,2′-bipyridin] -6-ylmethylene) -2,4. , 6-trimethylbenzenamine (1.68 g, 5.57 mmol) in THF (84.0 mL). The precipitate was isolated by filtration, washed three times with THF (8.0 mL) and dried in vacuo to give N-([2,2′-bipyridin] -6-ylmethylene) -2,4 as a dark green powder. , 6-trimethylbenzeneamine iron (II) bromide (hereinafter sometimes abbreviated as “iron complex compound 1”) was obtained (yield: 89%).
Anal.Calcd.for C 20 H 19 Br 2 FeN 3 : C, 46.46; H, 3.70; N, 8.13. Found: C, 46.00; H, 3.84; N, 7.96.
（実施例２：Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，６−ジイソプロピルベンゼンアミン鉄（ＩＩ）ブロミドの調製）
Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４，６−トリメチルベンゼンアミンをＮ−（［２，２’−ビピリジン］−６−イルメチレン）−２，６−ジイソプロピルベンゼンアミンに変更した以外、実施例１と同様の方法を行って、青緑色粉体であるＮ−（［２，２’−ビピリジン］−６−イルメチレン）−２，６−ジイソプロピルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物２」と略す場合がある。）を得た（収率：５９％）。
Anal. Calcd. for C23H25Br2FeN3: C, 49.41; H, 4.51; N, 7.52. Found: C, 49.44; H, 4.68; N, 7.31.(Example 2: Preparation of N-([2,2'-bipyridin] -6-ylmethylene) -2,6-diisopropylbenzenamine iron (II) bromide)
N-([2,2′-bipyridin] -6-ylmethylene) -2,4,6-trimethylbenzenamine is converted to N-([2,2′-bipyridin] -6-ylmethylene) -2,6-diisopropylbenzene. N-([2,2′-bipyridin] -6-ylmethylene) -2,6-diisopropylbenzeneamine iron (II), which is a blue-green powder, was carried out in the same manner as in Example 1 except that the amine was changed. ) Bromide (hereinafter sometimes abbreviated as “iron complex compound 2”) was obtained (yield: 59%).
Anal.Calcd.for C 23 H 25 Br 2 FeN 3 : C, 49.41; H, 4.51; N, 7.52. Found: C, 49.44; H, 4.68; N, 7.31.
（実施例３：Ｎ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−ベンゼンアミン鉄（ＩＩ）ブロミドの調製）
Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４，６−トリメチルベンゼンアミンをＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−ベンゼンアミンに変更した以外、実施例１と同様の方法を行って、緑色粉体であるＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−ベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物３」と略す場合がある。）を得た（収率：９３％）。
Anal. Calcd. for C18H15Br2FeN3: C, 44.21; H, 3.09; N, 8.59. Found: C, 44.45; H, 3.41; N, 8.13.Example 3: Preparation of N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) methylene] -benzenamine iron (II) bromide
N-([2,2′-bipyridin] -6-ylmethylene) -2,4,6-trimethylbenzenamine is converted to N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) methylene, which is a green powder, was prepared in the same manner as in Example 1 except for changing to methylene] -benzeneamine. ] -Benzenamine iron (II) bromide (hereinafter sometimes abbreviated as “iron complex compound 3”) was obtained (yield: 93%).
Anal.Calcd.for C 18 H 15 Br 2 FeN 3 : C, 44.21; H, 3.09; N, 8.59.Found: C, 44.45; H, 3.41; N, 8.13.
（実施例４：Ｎ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミドの調製）
Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４，６−トリメチルベンゼンアミンをＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，４，６−トリメチルベンゼンアミンに変更した以外、実施例１と同様の方法を行って、青緑色粉体であるＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物４」と略す場合がある。）を得た（収率：８６％）。
Anal. Calcd. for C21H21Br2FeN3: C, 47.49; H, 3.99; N, 7.91. Found: C, 47.23; H, 4.03; N, 7.84.Example 4: Preparation of N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) methylene] -2,4,6-trimethylbenzenamine iron (II) bromide
N-([2,2′-bipyridin] -6-ylmethylene) -2,4,6-trimethylbenzenamine is converted to N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) N- [1- (6′-methyl [2,2′-], which is a blue-green powder, was carried out in the same manner as in Example 1 except for changing to methylene] -2,4,6-trimethylbenzenamine. Bipyridine] -6-yl) methylene] -2,4,6-trimethylbenzenamine iron (II) bromide (hereinafter sometimes abbreviated as “iron complex compound 4”) was obtained (yield: 86%). .
Anal.Calcd.for C 21 H 21 Br 2 FeN 3 : C, 47.49; H, 3.99; N, 7.91. Found: C, 47.23; H, 4.03; N, 7.84.
（実施例５：Ｎ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，６−ジイソプロピルベンゼンアミン鉄（ＩＩ）ブロミドの調製）
Ｎ−（［２，２’−ビピリジン］−６−イルメチレン）−２，４，６−トリメチルベンゼンアミンをＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，６−ジイソプロピルベンゼンアミンに変更した以外、実施例１と同様の方法を行って、青緑色粉体であるＮ−［１−（６’−メチル［２，２’−ビピリジン］−６−イル）メチレン］−２，６−ジイソプロピルメチルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物５」と略す場合がある。）を得た（収率：５９％）。
Anal. Calcd. for C24H24Br2FeN3: C, 50.29; H, 4.75; N, 7.33. Found: C, 50.41; H, 4.93; N, 7.06.Example 5: Preparation of N- [1- (6'-methyl [2,2'-bipyridin] -6-yl) methylene] -2,6-diisopropylbenzenamine iron (II) bromide
N-([2,2′-bipyridin] -6-ylmethylene) -2,4,6-trimethylbenzenamine is converted to N- [1- (6′-methyl [2,2′-bipyridin] -6-yl) N- [1- (6′-methyl [2,2′-bipyridine], a blue-green powder, was prepared in the same manner as in Example 1 except that it was changed to methylene] -2,6-diisopropylbenzeneamine. -6-yl) methylene] -2,6-diisopropylmethylbenzenamine iron (II) bromide (hereinafter sometimes abbreviated as “iron complex compound 5”) was obtained (yield: 59%).
Anal.Calcd.for C 24 H 24 Br 2 FeN 3 : C, 50.29; H, 4.75; N, 7.33. Found: C, 50.41; H, 4.93; N, 7.06.
＜有機ケイ素化合物の製造（ヒドロシリル化反応）＞
（実施例６）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０．７２ｍＬ，５．８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、ジオクチルフェニルシラン（変換率：８９％）の生成を確認した。結果を表１に示す。<Production of organosilicon compounds (hydrosilylation reaction)>
(Example 6)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (9.2 mL, 58 mmol), and start stirring at room temperature. did. Phenylsilane (0.72 mL, 5.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, formation of dioctylphenylsilane (conversion rate: 89%) was confirmed. The results are shown in Table 1.
（実施例７）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０．７２ｍＬ，５．８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。外温１００℃に設定して反応開始とし、２４時間後、室温まで冷却後、反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、ジオクチルフェニルシラン（変換率：９１％）の生成を確認した。結果を表１に示す。(Example 7)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (9.2 mL, 58 mmol), and start stirring at room temperature. did. Phenylsilane (0.72 mL, 5.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) The reaction was started by setting the external temperature to 100 ° C. After 24 hours and cooling to room temperature, the reaction solution was analyzed by high performance liquid chromatography (199 nm). When the reaction product was quantified by an absolute calibration curve method, formation of dioctylphenylsilane (conversion rate: 91%) was confirmed. The results are shown in Table 1.
（実施例８）
鉄錯体化合物１を鉄錯体化合物２に変更した以外、実施例６と同様の方法により反応を行った。結果を表１に示す。(Example 8)
The reaction was performed in the same manner as in Example 6 except that the iron complex compound 1 was changed to the iron complex compound 2. The results are shown in Table 1.
（実施例９）
鉄錯体化合物１を鉄錯体化合物２に変更した以外、実施例７と同様の方法により反応を行った。結果を表１に示す。Example 9
The reaction was performed in the same manner as in Example 7 except that the iron complex compound 1 was changed to the iron complex compound 2. The results are shown in Table 1.
（実施例１０）
鉄錯体化合物１を鉄錯体化合物３（０．０２１ｍｍｏｌ）に変更した以外、実施例７と同様の方法により反応を行った。結果を表１に示す。(Example 10)
The reaction was performed in the same manner as in Example 7 except that the iron complex compound 1 was changed to the iron complex compound 3 (0.021 mmol). The results are shown in Table 1.
（実施例１１）
フレームドライを行い、窒素を流入したシュレンク管に鉄錯体化合物４（３．０ｍｇ，０．００５６ｍｍｏｌ）を精密に量り取り、１−オクテン（８．９ｍＬ,５６．４９ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０．７０ｍＬ，５．６５ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニルシラン（変換率：７２％）及びジオクチルフェニルシラン（変換率：２６％)の生成を確認した。結果を表１に示す。(Example 11)
Perform flame drying, accurately weigh iron complex compound 4 (3.0 mg, 0.0056 mmol) into a Schlenk tube into which nitrogen has flowed, add 1-octene (8.9 mL, 56.49 mmol), and stir at room temperature. Started. Phenylsilane (0.70 mL, 5.65 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (if the iron complex compound remained undissolved visually, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, the production of octylphenylsilane (conversion rate: 72%) and dioctylphenylsilane (conversion rate: 26%) was confirmed. The results are shown in Table 1.
（実施例１２）
フレームドライを行い、窒素を流入したシュレンク管に鉄錯体化合物４（３．０ｍｇ，０．００５６ｍｍｏｌ）を精密に量り取り、１−オクテン（８．９ｍＬ,５６ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０．７０ｍＬ，５．７ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。外温１００℃に設定して反応開始とし、２４時間後、室温まで冷却後、反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニルシラン（変換率：５８％）及びジオクチルフェニルシラン（変換率：４０％）の生成を確認した。結果を表１に示す。(Example 12)
Flame-drying was performed, and iron complex compound 4 (3.0 mg, 0.0056 mmol) was accurately weighed into a Schlenk tube into which nitrogen was introduced, and 1-octene (8.9 mL, 56 mmol) was added, and stirring was started at room temperature. . Phenylsilane (0.70 mL, 5.7 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (if the iron complex compound remained undissolved visually, sodium triethylborohydride was added. And dissolve completely.) The reaction was started by setting the external temperature to 100 ° C. After 24 hours and cooling to room temperature, the reaction solution was analyzed by high performance liquid chromatography (199 nm). When the reaction product was quantified by an absolute calibration curve method, the production of octylphenylsilane (conversion rate: 58%) and dioctylphenylsilane (conversion rate: 40%) was confirmed. The results are shown in Table 1.
（実施例１３）
鉄錯体化合物４を鉄錯体化合物５に変更した以外、実施例１１と同様の方法により反応を行った。結果を表１に示す。(Example 13)
The reaction was performed in the same manner as in Example 11 except that the iron complex compound 4 was changed to the iron complex compound 5. The results are shown in Table 1.
（実施例１４）
鉄錯体化合物４を鉄錯体化合物５に変更した以外、実施例１２と同様の方法により反応を行った。結果を表１に示す。(Example 14)
The reaction was performed in the same manner as in Example 12 except that the iron complex compound 4 was changed to the iron complex compound 5. The results are shown in Table 1.
（実施例１５）
フェニルシランをジフェニルシランに変更した以外、実施例６と同様の方法により反応を行った。結果を表２に示す。(Example 15)
The reaction was performed in the same manner as in Example 6 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 2.
（実施例１６）
フェニルシランをジフェニルシランに変更した以外、実施例７と同様の方法により反応を行った。結果を表２に示す。(Example 16)
The reaction was performed in the same manner as in Example 7 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 2.
（実施例１７）
フェニルシランをジフェニルシランに変更した以外、実施例８と同様の方法により反応を行った。結果を表２に示す。(Example 17)
The reaction was conducted in the same manner as in Example 8 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 2.
（実施例１８）
フェニルシランをジフェニルシランに変更した以外、実施例９と同様の方法により反応を行った。結果を表２に示す。(Example 18)
The reaction was performed in the same manner as in Example 9 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 2.
（実施例１９）
フェニルシランをジフェニルシランに変更した以外、実施例１１と同様の方法により反応を行った。結果を表２に示す。(Example 19)
The reaction was performed in the same manner as in Example 11 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 2.
（実施例２０）
フェニルシランをジフェニルシランに変更した以外、実施例１２と同様の方法により反応を行った。結果を表２に示す。(Example 20)
The reaction was performed in the same manner as in Example 12 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 2.
（実施例２１）
フェニルシランをジフェニルシランに変更した以外、実施例１３と同様の方法により反応を行った。結果を表２に示す。(Example 21)
The reaction was performed in the same manner as in Example 13 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 2.
（実施例２２）
フェニルシランをジフェニルシランに変更した以外、実施例１４と同様の方法により反応を行った。結果を表２に示す。(Example 22)
The reaction was performed in the same manner as in Example 14 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 2.
（実施例２３）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例６と同様の方法により反応を行った。結果を表３に示す。(Example 23)
The reaction was performed in the same manner as in Example 6 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 3.
（実施例２４）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例７と同様の方法により反応を行った。結果を表３に示す。(Example 24)
The reaction was performed in the same manner as in Example 7 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 3.
（実施例２５）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例８と同様の方法により反応を行った。結果を表３に示す。(Example 25)
The reaction was performed in the same manner as in Example 8 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 3.
（実施例２６）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例９と同様の方法により反応を行った。結果を表３に示す。(Example 26)
The reaction was performed in the same manner as in Example 9 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 3.
（実施例２７）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例１１と同様の方法により反応を行った。結果を表３に示す。(Example 27)
The reaction was performed in the same manner as in Example 11 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 3.
（実施例２８）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例１２と同様の方法により反応を行った。結果を表３に示す。(Example 28)
The reaction was performed in the same manner as in Example 12 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 3.
（実施例２９）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例１３と同様の方法により反応を行った。結果を表３に示す。(Example 29)
The reaction was performed in the same manner as in Example 13 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 3.
（実施例３０）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例１４と同様の方法により反応を行った。結果を表３に示す。(Example 30)
The reaction was performed in the same manner as in Example 14 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 3.
（実施例３１）
鉄錯体化合物１の使用量を０．０１９ｍｍｏｌに、フェニルシランをジフェニル（メチル）シランに変更した以外、実施例６と同様の方法により反応を行った。結果を表４に示す。(Example 31)
The reaction was performed in the same manner as in Example 6 except that the amount of the iron complex compound 1 was changed to 0.019 mmol and phenylsilane was changed to diphenyl (methyl) silane. The results are shown in Table 4.
（実施例３２）
鉄錯体化合物１の使用量を０．０１９ｍｍｏｌに、フェニルシランをジフェニル（メチル）シランに変更した以外、実施例７と同様の方法により反応を行った。結果を表４に示す。(Example 32)
The reaction was performed in the same manner as in Example 7 except that the amount of iron complex compound 1 used was changed to 0.019 mmol and phenylsilane was changed to diphenyl (methyl) silane. The results are shown in Table 4.
（実施例３３）
鉄錯体化合物２の使用量を０．０１８ｍｍｏｌに、フェニルシランをジフェニル（メチル）シランに変更した以外、実施例８と同様の方法により反応を行った。結果を表４に示す。(Example 33)
The reaction was performed in the same manner as in Example 8 except that the amount of iron complex compound 2 used was changed to 0.018 mmol and phenylsilane was changed to diphenyl (methyl) silane. The results are shown in Table 4.
（実施例３４）
鉄錯体化合物２の使用量を０．０１８ｍｍｏｌに、フェニルシランをジフェニル（メチル）シランに変更した以外、実施例９と同様の方法により反応を行った。結果を表４に示す。(Example 34)
The reaction was performed in the same manner as in Example 9, except that the amount of iron complex compound 2 used was changed to 0.018 mmol and phenylsilane was changed to diphenyl (methyl) silane. The results are shown in Table 4.
（実施例３５）
鉄錯体化合物４の使用量を０．０１９ｍｍｏｌに、フェニルシランをジフェニル（メチル）シランに変更した以外、実施例１１と同様の方法により反応を行った。結果を表４に示す。(Example 35)
The reaction was performed in the same manner as in Example 11 except that the amount of iron complex compound 4 was changed to 0.019 mmol and phenylsilane was changed to diphenyl (methyl) silane. The results are shown in Table 4.
（実施例３６）
鉄錯体化合物４の使用量を０．０１９ｍｍｏｌに、フェニルシランをジフェニル（メチル）シランに変更した以外、実施例１２と同様の方法により反応を行った。結果を表４に示す。(Example 36)
The reaction was performed in the same manner as in Example 12 except that the amount of iron complex compound 4 was changed to 0.019 mmol and phenylsilane was changed to diphenyl (methyl) silane. The results are shown in Table 4.
（実施例３７）
鉄錯体化合物５の使用量を０．０１７ｍｍｏｌに、フェニルシランをジフェニル（メチル）シランに変更した以外、実施例１３と同様の方法により反応を行った。結果を表４に示す。(Example 37)
The reaction was performed in the same manner as in Example 13 except that the amount of iron complex compound 5 was changed to 0.017 mmol and phenylsilane was changed to diphenyl (methyl) silane. The results are shown in Table 4.
（実施例３８）
鉄錯体化合物５の使用量を０．０１７ｍｍｏｌに、フェニルシランをジフェニル（メチル）シランに変更した以外、実施例１４と同様の方法により反応を行った。結果を表４に示す。(Example 38)
The reaction was performed in the same manner as in Example 14 except that the amount of the iron complex compound 5 was changed to 0.017 mmol and phenylsilane was changed to diphenyl (methyl) silane. The results are shown in Table 4.
（実施例３９）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物５（３．０ｍｇ，０．００５２ｍｍｏｌ）を精密に量り取り、ヘキサン（７．５ｍＬ）を加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（０．８３ｍＬ，５．２ｍｍｏｌ）とフェニルシラン（０．６５ｍＬ，５．２ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニルシラン（変換率：９４％）及びジオクチルフェニルシラン（変換率：６％）の生成を確認した。結果を表５に示す。(Example 39)
Flame drying was carried out, and iron complex compound 5 (3.0 mg, 0.0052 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, hexane (7.5 mL) was added, and stirring was started at room temperature. 1-octene (0.83 mL, 5.2 mmol) and phenylsilane (0.65 mL, 5.2 mmol) were sequentially added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added. It was dripped. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, the production of octylphenylsilane (conversion rate: 94%) and dioctylphenylsilane (conversion rate: 6%) was confirmed. The results are shown in Table 5.
（実施例４０）
ヘキサンをトルエンに変更した以外、実施例３９と同様の方法により反応を行った。結果を表５に示す。(Example 40)
The reaction was performed in the same manner as in Example 39 except that hexane was changed to toluene. The results are shown in Table 5.
（実施例４１）
ヘキサンをジエチルエーテルに変更した以外、実施例３９と同様の方法により反応を行った。結果を表５に示す。(Example 41)
The reaction was conducted in the same manner as in Example 39 except that hexane was changed to diethyl ether. The results are shown in Table 5.
（実施例４２）
ヘキサンをテトラヒドロフラン（ＴＨＦ）に変更した以外、実施例３９と同様の方法により反応を行った。結果を表５に示す。(Example 42)
The reaction was performed in the same manner as in Example 39 except that hexane was changed to tetrahydrofuran (THF). The results are shown in Table 5.
（実施例４３）
フレームドライを行い、窒素を流入したシュレンク管に鉄錯体化合物１（１０ｍｇ，０．０１９ｍｍｏｌ）を精密に量り取り、シクロヘキセン（２．０ｍＬ，１９ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０．２４ｍＬ，１．９ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（７８μＬ，０．０７８ｍｍｏｌ）を滴下した。２分以内に反応溶液は無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて触媒前駆体の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、シクロヘキシルフェニルシラン（変換率：５０％）の生成を確認した。結果を表６に示す。(Example 43)
Flame drying was performed, and iron complex compound 1 (10 mg, 0.019 mmol) was accurately weighed into a Schlenk tube into which nitrogen was introduced, and cyclohexene (2.0 mL, 19 mmol) was added, and stirring was started at room temperature. To this slurry solution was added phenylsilane (0.24 mL, 1.9 mmol), and then a 1 M sodium triethylborohydride toluene solution (78 μL, 0.078 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (if the catalyst precursor was not dissolved, the sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, the formation of cyclohexylphenylsilane (conversion rate: 50%) was confirmed. The results are shown in Table 6.
（実施例４４）
フレームドライを行い、窒素を流入したシュレンク管に鉄錯体化合物１（１０ｍｇ，０．０１９ｍｍｏｌ）を精密に量り取り、シクロヘキセン（２．０ｍＬ，１９ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０．２４ｍＬ，１．９ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（７８μＬ，０．０７８ｍｍｏｌ）を滴下した。２分以内に反応溶液は無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて触媒前駆体の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。外温１００℃に設定して反応開始とし、２４時間後、室温まで冷却後、反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、シクロヘキシルフェニルシラン（変換率：９３％）の生成を確認した。結果を表６に示す。(Example 44)
Flame drying was performed, and iron complex compound 1 (10 mg, 0.019 mmol) was accurately weighed into a Schlenk tube into which nitrogen was introduced, and cyclohexene (2.0 mL, 19 mmol) was added, and stirring was started at room temperature. To this slurry solution was added phenylsilane (0.24 mL, 1.9 mmol), and then a 1 M sodium triethylborohydride toluene solution (78 μL, 0.078 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (if the catalyst precursor was not dissolved, the sodium triethylborohydride was added. And dissolve completely.) The reaction was started by setting the external temperature to 100 ° C. After 24 hours and cooling to room temperature, the reaction solution was analyzed by high performance liquid chromatography (199 nm). When the reaction product was quantified by the absolute calibration curve method, the formation of cyclohexylphenylsilane (conversion rate: 93%) was confirmed. The results are shown in Table 6.
（実施例４５）
鉄錯体化合物１を鉄錯体化合物２に変更した以外、実施例４３と同様の方法により反応を行った。結果を表６に示す。(Example 45)
The reaction was performed in the same manner as in Example 43 except that the iron complex compound 1 was changed to the iron complex compound 2. The results are shown in Table 6.
（実施例４６）
鉄錯体化合物１を鉄錯体化合物２に変更した以外、実施例４４と同様の方法により反応を行った。結果を表６に示す。(Example 46)
The reaction was performed in the same manner as in Example 44 except that the iron complex compound 1 was changed to the iron complex compound 2. The results are shown in Table 6.
（実施例４７）
鉄錯体化合物２の使用量を０．００５４ｍｍｏｌに変更した以外、実施例４３と同様の方法により反応を行った。結果を表６に示す。(Example 47)
The reaction was performed in the same manner as in Example 43 except that the amount of the iron complex compound 2 was changed to 0.0054 mmol. The results are shown in Table 6.
（実施例４８）
鉄錯体化合物２の使用量を０．００５４ｍｍｏｌに変更した以外、実施例４４と同様の方法により反応を行った。結果を表６に示す。(Example 48)
The reaction was performed in the same manner as in Example 44 except that the amount of the iron complex compound 2 was changed to 0.0054 mmol. The results are shown in Table 6.
（実施例４９）
鉄錯体化合物１を鉄錯体化合物４に変更した以外、実施例４３と同様の方法により反応を行った。結果を表６に示す。(Example 49)
The reaction was performed in the same manner as in Example 43 except that the iron complex compound 1 was changed to the iron complex compound 4. The results are shown in Table 6.
（実施例５０）
鉄錯体化合物１を鉄錯体化合物４に変更した以外、実施例４４と同様の方法により反応を行った。結果を表６に示す。(Example 50)
The reaction was performed in the same manner as in Example 44 except that the iron complex compound 1 was changed to the iron complex compound 4. The results are shown in Table 6.
（実施例５１）
鉄錯体化合物１を鉄錯体化合物５に変更した以外、実施例４３と同様の方法により反応を行った。結果を表６に示す。(Example 51)
The reaction was performed in the same manner as in Example 43 except that the iron complex compound 1 was changed to the iron complex compound 5. The results are shown in Table 6.
（実施例５２）
鉄錯体化合物１を鉄錯体化合物５に変更した以外、実施例４４と同様の方法により反応を行った。結果を表６に示す。(Example 52)
The reaction was performed in the same manner as in Example 44 except that the iron complex compound 1 was changed to the iron complex compound 5. The results are shown in Table 6.
（実施例５３）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０．７２ｍＬ，５．８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（４０μＬ，０．０４０ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、ジオクチルフェニルシラン（変換率：８９％）の生成を確認した。結果を表７に示す。(Example 53)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (9.2 mL, 58 mmol), and start stirring at room temperature. did. Phenylsilane (0.72 mL, 5.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (40 μL, 0.040 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, formation of dioctylphenylsilane (conversion rate: 89%) was confirmed. The results are shown in Table 7.
（実施例５４）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（７．２ｍＬ，５８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニルシラン（変換率：６４％）及びジオクチルフェニルシラン（変換率：９％）の生成を確認した。結果を表７に示す。(Example 54)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (9.2 mL, 58 mmol), and start stirring at room temperature. did. To this slurry solution was added phenylsilane (7.2 mL, 58 mmol), and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, the production of octylphenylsilane (conversion rate: 64%) and dioctylphenylsilane (conversion rate: 9%) was confirmed. The results are shown in Table 7.
（実施例５５）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、ヘキサン（１８ｍＬ）を加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（１８．４ｍＬ，１２０ｍｍｏｌ）とフェニルシラン（７．２ｍＬ，５８ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニルシラン（変換率：３７％）及びジオクチルフェニルシラン（変換率：３％）の生成を確認した。結果を表７に示す。(Example 55)
Flame drying was performed, iron complex compound 1 (3.0 mg, 0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, hexane (18 mL) was added, and stirring was started at room temperature. 1-octene (18.4 mL, 120 mmol) and phenylsilane (7.2 mL, 58 mmol) were sequentially added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, the formation of octylphenylsilane (conversion rate: 37%) and dioctylphenylsilane (conversion rate: 3%) was confirmed. The results are shown in Table 7.
（実施例５６）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（８．５ｍＬ，５４ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０６６ｍＬ，５．４ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２２μＬ，０．０２２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、ジオクチルフェニルシラン（変換率：８６％）の生成を確認した。結果を表７に示す。(Example 56)
Perform flame drying, accurately weigh iron complex compound 2 (3.0 mg, 0.0054 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (8.5 mL, 54 mmol), and start stirring at room temperature. did. To this slurry solution was added phenylsilane (066 mL, 5.4 mmol), and then a 1 M sodium triethylborohydride toluene solution (22 μL, 0.022 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, production of dioctylphenylsilane (conversion rate: 86%) was confirmed. The results are shown in Table 7.
（実施例５７）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（１．１ｍＬ，５．８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０，０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：６５％）及びジオクチルジフェニルシラン（変換率：２２％）の生成を確認した。結果を表８に示す。(Example 57)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (9.2 mL, 58 mmol), and start stirring at room temperature. did. Diphenylsilane (1.1 mL, 5.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0,024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octyldiphenylsilane (conversion rate: 65%) and dioctyldiphenylsilane (conversion rate: 22%) were produced. The results are shown in Table 8.
（実施例５８）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、ヘキサン（３６ｍＬ）を加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（１８ｍＬ，１２０ｍｍｏｌ）とフェニルシラン（１１ｍＬ，５８ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：８１％）の生成を確認した。結果を表８に示す。(Example 58)
Flame drying was performed, iron complex compound 1 (3.0 mg, 0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, hexane (36 mL) was added, and stirring was started at room temperature. 1-octene (18 mL, 120 mmol) and phenylsilane (11 mL, 58 mmol) were sequentially added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octyldiphenylsilane (conversion rate: 81%) was produced. The results are shown in Table 8.
（実施例５９）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（８．５ｍＬ，５４ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（１．０ｍＬ，５．４ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２２μＬ，０．０２２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：５９％）及びジオクチルジフェニルシラン（変換率：２０％）の生成を確認した。結果を表８に示す。(Example 59)
Perform flame drying, accurately weigh iron complex compound 2 (3.0 mg, 0.0054 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (8.5 mL, 54 mmol), and start stirring at room temperature. did. Diphenylsilane (1.0 mL, 5.4 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (22 μL, 0.022 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, formation of octyldiphenylsilane (conversion rate: 59%) and dioctyldiphenylsilane (conversion rate: 20%) was confirmed. The results are shown in Table 8.
（実施例６０）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（１．７ｍＬ，１１ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（１．０ｍＬ，５．４ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２２μＬ，０．０２２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：７９％）及びジオクチルジフェニルシラン（変換率：６％）の生成を確認した。結果を表８に示す。(Example 60)
Perform flame drying, accurately weigh iron complex compound 2 (3.0 mg, 0.0054 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (1.7 mL, 11 mmol), and start stirring at room temperature. did. Diphenylsilane (1.0 mL, 5.4 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (22 μL, 0.022 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octyldiphenylsilane (conversion rate: 79%) and dioctyldiphenylsilane (conversion rate: 6%) were produced. The results are shown in Table 8.
（実施例６１）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（１７ｍＬ，１１０ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（１０ｍＬ，５４ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：９４％）及びジオクチルジフェニルシラン（変換率：０．７％）の生成を確認した。結果を表８に示す。(Example 61)
Flame drying was performed, and iron complex compound 2 (3.0 mg, 0.0054 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, 1-octene (17 mL, 110 mmol) was added, and stirring was started at room temperature. Diphenylsilane (10 mL, 54 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octyldiphenylsilane (conversion rate: 94%) and dioctyldiphenylsilane (conversion rate: 0.7%) were produced. The results are shown in Table 8.
（実施例６２）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、ヘキサン（３４ｍＬ）を加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（１７ｍＬ，１１０ｍｍｏｌ）とジフェニルシラン（１０ｍＬ，５４ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：９７％）の生成を確認した。結果を表８に示す。(Example 62)
Flame drying was performed, and iron complex compound 2 (3.0 mg, 0.0054 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, hexane (34 mL) was added, and stirring was started at room temperature. 1-octene (17 mL, 110 mmol) and diphenylsilane (10 mL, 54 mmol) were sequentially added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octyldiphenylsilane (conversion rate: 97%) was produced. The results are shown in Table 8.
（実施例６３）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニル（メチル）シラン（０．８１ｍＬ，５．８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、ジオクチルフェニル（メチル）シラン（変換率：８４％）の生成を確認した。結果を表９に示す。(Example 63)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (9.2 mL, 58 mmol), and start stirring at room temperature. did. Phenyl (methyl) silane (0.81 mL, 5.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, production of dioctylphenyl (methyl) silane (conversion rate: 84%) was confirmed. The results are shown in Table 9.
（実施例６４）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニル（メチル）シラン（８．１ｍＬ，５８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニル（メチル）シラン（変換率：８７％）の生成を確認した。結果を表９に示す。(Example 64)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (9.2 mL, 58 mmol), and start stirring at room temperature. did. Phenyl (methyl) silane (8.1 mL, 58 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octylphenyl (methyl) silane (conversion rate: 87%) was produced. The results are shown in Table 9.
（実施例６５）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、ヘキサン（１８ｍＬ）を加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）とフェニル（メチル）シラン（８．１ｍＬ，５８ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニル（メチル）シラン（変換率：７３％）の生成を確認した。結果を表９に示す。(Example 65)
Flame drying was performed, iron complex compound 1 (3.0 mg, 0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, hexane (18 mL) was added, and stirring was started at room temperature. 1-octene (9.2 mL, 58 mmol) and phenyl (methyl) silane (8.1 mL, 58 mmol) were sequentially added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. did. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octylphenyl (methyl) silane (conversion rate: 73%) was produced. The results are shown in Table 9.
（実施例６６）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、ヘキサン（３６ｍＬ）を加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（１８ｍＬ，１２０ｍｍｏｌ）とフェニル（メチル）シラン（８．１ｍＬ，５８ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニル（メチル）シラン（変換率：８７％）の生成を確認した。結果を表９に示す。Example 66
Flame drying was performed, iron complex compound 1 (3.0 mg, 0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, hexane (36 mL) was added, and stirring was started at room temperature. 1-octene (18 mL, 120 mmol) and phenyl (methyl) silane (8.1 mL, 58 mmol) were sequentially added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octylphenyl (methyl) silane (conversion rate: 87%) was produced. The results are shown in Table 9.
（実施例６７）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、ヘキサンを加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（４６ｍＬ，２９０ｍｍｏｌ）とフェニル（メチル）シラン（８．１ｍＬ，５８ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニル（メチル）シラン（変換率：１７％）の生成を確認した。結果を表９に示す。(Example 67)
Flame drying was performed, and iron complex compound 1 (3.0 mg, 0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, hexane was added, and stirring was started at room temperature. 1-octene (46 mL, 290 mmol) and phenyl (methyl) silane (8.1 mL, 58 mmol) were sequentially added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octylphenyl (methyl) silane (conversion rate: 17%) was produced. The results are shown in Table 9.
（実施例６８）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、トルエン（１８ｍＬ）を加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（９．２ｍＬ，５８ｍｍｏｌ）とフェニル（メチル）シラン（８．１ｍＬ，５８ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニル（メチル）シラン（変換率：７３％）の生成を確認した。結果を表９に示す。Example 68
Flame drying was performed, iron complex compound 1 (3.0 mg, 0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, toluene (18 mL) was added, and stirring was started at room temperature. 1-octene (9.2 mL, 58 mmol) and phenyl (methyl) silane (8.1 mL, 58 mmol) were sequentially added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added dropwise. did. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octylphenyl (methyl) silane (conversion rate: 73%) was produced. The results are shown in Table 9.
（実施例６９）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（８．５ｍＬ，５４ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニル（メチル）シラン（０．７５ｍＬ，５．４ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２２μＬ，０．０２２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、ジオクチルフェニル（メチル）シラン（変換率：７４％）の生成を確認した。結果を表９に示す。(Example 69)
Perform flame drying, accurately weigh iron complex compound 2 (3.0 mg, 0.0054 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (8.5 mL, 54 mmol), and start stirring at room temperature. did. Phenyl (methyl) silane (0.75 mL, 5.4 mmol) was added to the slurry solution, and then 1M sodium triethylborohydride in toluene (22 μL, 0.022 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, formation of dioctylphenyl (methyl) silane (conversion rate: 74%) was confirmed. The results are shown in Table 9.
（実施例７０）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（１７ｍＬ，１１０ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニル（メチル）シラン（７．５ｍＬ，５４ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１１０μＬ，０．１１ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニル（メチル）シラン（変換率：４１％）及びジオクチルフェニル（メチル）シラン（変換率：３４％）の生成を確認した。結果を表９に示す。(Example 70)
Flame drying was performed, and iron complex compound 2 (3.0 mg, 0.0054 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, 1-octene (17 mL, 110 mmol) was added, and stirring was started at room temperature. Phenyl (methyl) silane (7.5 mL, 54 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (110 μL, 0.11 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octylphenyl (methyl) silane (conversion rate: 41%) and dioctylphenyl (methyl) silane (conversion rate: 34%) were produced. The results are shown in Table 9.
（実施例７１）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（１０ｍｇ，０．０１９ｍｍｏｌ）を精密に量り取り、１−オクテン（３．１ｍＬ，１９ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニル（メチル）シラン（０．４１ｍＬ，１．９ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（７．８μＬ，０．０７８ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：７２％）の生成を確認した。結果を表１０に示す。(Example 71)
Flame drying was performed, and iron complex compound 1 (10 mg, 0.019 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, and 1-octene (3.1 mL, 19 mmol) was added, and stirring was started at room temperature. Diphenyl (methyl) silane (0.41 mL, 1.9 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (7.8 μL, 0.078 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 72%) was produced. The results are shown in Table 10.
（実施例７２）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（０．９２ｍＬ，５．８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニル（メチル）シラン（１．２ｍＬ，５．８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：６％）の生成を確認した。結果を表１０に示す。(Example 72)
Perform flame drying, accurately measure iron complex compound 1 (3.0 mg, 0.0058 mmol) in a Schlenk tube into which nitrogen gas has flowed, add 1-octene (0.92 mL, 5.8 mmol), and stir at room temperature. Started. Diphenyl (methyl) silane (1.2 mL, 5.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 6%) was produced. The results are shown in Table 10.
（実施例７３）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（１．８ｍＬ，１２ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニル（メチル）シラン（１．２ｍＬ，５．８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：２％）の生成を確認した。結果を表１０に示す。(Example 73)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (1.8 mL, 12 mmol), and start stirring at room temperature. did. Diphenyl (methyl) silane (1.2 mL, 5.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 2%) was produced. The results are shown in Table 10.
（実施例７４）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、ヘキサン（３．６ｍＬ）を加え、室温にて撹拌を開始した。このスラリー溶液に１−オクテン（１．８ｍＬ，１２ｍｍｏｌ）とジフェニル（メチル）シラン（１．２ｍＬ，５．８ｍｍｏｌ）を順次加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：３％）の生成を確認した。結果を表１０に示す。(Example 74)
Flame drying was performed, and iron complex compound 1 (3.0 mg, 0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, hexane (3.6 mL) was added, and stirring was started at room temperature. 1-octene (1.8 mL, 12 mmol) and diphenyl (methyl) silane (1.2 mL, 5.8 mmol) were sequentially added to the slurry solution, and then 1M sodium triethylborohydride in toluene (24 μL, 0.024 mmol) was added. Was dripped. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 3%) was produced. The results are shown in Table 10.
（実施例７５）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（０．９２ｍＬ，５．８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニル（メチル）シラン（２．４ｍＬ，１２ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：６７％）の生成を確認した。結果を表１０に示す。(Example 75)
Perform flame drying, accurately measure iron complex compound 1 (3.0 mg, 0.0058 mmol) in a Schlenk tube into which nitrogen gas has flowed, add 1-octene (0.92 mL, 5.8 mmol), and stir at room temperature. Started. Diphenyl (methyl) silane (2.4 mL, 12 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 67%) was produced. The results are shown in Table 10.
（実施例７６）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（０．３１ｍＬ，１．９ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニル（メチル）シラン（０．８１ｍＬ，３．９ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（２４μＬ，０．０２４ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：８７％）の生成を確認した。結果を表１０に示す。(Example 76)
Flame drying is performed, and iron complex compound 1 (3.0 mg, 0.0058 mmol) is accurately weighed into a Schlenk tube into which nitrogen gas has flowed, and 1-octene (0.31 mL, 1.9 mmol) is added and stirred at room temperature. Started. Diphenyl (methyl) silane (0.81 mL, 3.9 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (24 μL, 0.024 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 87%) was produced. The results are shown in Table 10.
（実施例７７）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（１０ｍｇ，０．０１８ｍｍｏｌ）を精密に量り取り、１−オクテン（２．８ｍＬ，１８ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニル（メチル）シラン（０．３８ｍＬ，１．８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（７２μＬ，０．０７２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：４３％）の生成を確認した。結果を表１０に示す。(Example 77)
Flame drying was performed, iron complex compound 2 (10 mg, 0.018 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, 1-octene (2.8 mL, 18 mmol) was added, and stirring was started at room temperature. Diphenyl (methyl) silane (0.38 mL, 1.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (72 μL, 0.072 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 43%) was produced. The results are shown in Table 10.
（実施例７８）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（１０ｍｇ，０．０１８ｍｍｏｌ）を精密に量り取り、１−オクテン（５．７ｍＬ，３６ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（３．４ｍＬ，１８ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（７２μＬ，０．０７２ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、１８分（０．３時間）後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：７９％）及び時刻チルジフェニルシラン（変換率：６％）の生成を確認した。結果を表１１に示す。(Example 78)
Flame drying was performed, and iron complex compound 2 (10 mg, 0.018 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, 1-octene (5.7 mL, 36 mmol) was added, and stirring was started at room temperature. Diphenylsilane (3.4 mL, 18 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (72 μL, 0.072 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 18 minutes (0.3 hours). When the reaction product was quantified by an absolute calibration curve method, the production of octyldiphenylsilane (conversion rate: 79%) and time tildiphenylsilane (conversion rate: 6%) was confirmed. The results are shown in Table 11.
（実施例７９）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（１７ｍＬ，１１０ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（１０ｍＬ，５４ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１１０μＬ，０．１１ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、６６分（１．１時間）後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：９４％）及び時刻チルジフェニルシラン（変換率：０．７％）の生成を確認した。結果を表１１に示す。(Example 79)
Flame drying was performed, and iron complex compound 2 (3.0 mg, 0.0054 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, 1-octene (17 mL, 110 mmol) was added, and stirring was started at room temperature. Diphenylsilane (10 mL, 54 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (110 μL, 0.11 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was regarded as the start of the reaction, and after 66 minutes (1.1 hours), the reaction solution was analyzed by high performance liquid chromatography (199 nm). When the reaction product was quantified by the absolute calibration curve method, the production | generation of octyl diphenylsilane (conversion rate: 94%) and time til diphenylsilane (conversion rate: 0.7%) was confirmed. The results are shown in Table 11.
（実施例８０）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（２１ｍＬ，１３０ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（１３ｍＬ，６７ｍｍｏｌ）を加えた後に１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１１０μＬ，０．１１ｍｍｏｌ）を滴下した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、１４１分（２．３時間）後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニルシラン（変換率：９６％）及びジオクチルジフェニルシラン（変換率：１．２％）の生成を確認した。結果を表１１に示す。(Example 80)
Flame drying was performed, and iron complex compound 2 (3.0 mg, 0.0054 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, and 1-octene (21 mL, 130 mmol) was added, and stirring was started at room temperature. Diphenylsilane (13 mL, 67 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (110 μL, 0.11 mmol) was added dropwise. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was regarded as the start of reaction, and after 141 minutes (2.3 hours), the reaction solution was analyzed by high performance liquid chromatography (199 nm). When the reaction product was quantified by an absolute calibration curve method, formation of octyldiphenylsilane (conversion rate: 96%) and dioctyldiphenylsilane (conversion rate: 1.2%) was confirmed. The results are shown in Table 11.
＜配位子合成＞
（合成例１１：６−ブロモ−２，２’−ビピリジンの合成）
２，６−ジブロモピリジン（７４．０ｇ，３１２ｍｍｏｌ）、２−（トリブチルスタニル）ピリジン（１１５ｇ，３１２ｍｍｏｌ）、及びテトラキス（トリフェニルホスフィン）パラジウム（１８．５ｇ，１６．０ｍｍｏｌ）のトルエン溶液（１２０ｍＬ）を窒素下で一晩還流した。室温に戻し、溶媒を留去して、クロロホルム（６３０ｍＬ）を加えた。６Ｎ塩酸水溶液（６３０ｍＬ）を加え、水層をクロロホルム（６３０ｍＬ×２）で洗浄した。水層に１０Ｎ水酸化ナトリウム水溶液（４２０ｍＬ）を加え、クロロホルム（６３０ｍＬ）で抽出した。有機相を集めて溶媒を留去した。粗生成物をカラムクロマトグラフィー（シリカ，ＡｃＯＥｔ：Ｈｅｘａｎｅ＝１：９）で精製し、白色粉末である６−ブロモ−２，２’−ビピリジンを得た（収率：６２％）。
1H NMR (400 MHz, CDCl3): 7.32 (dd, 1H, J = 4.8, 7.6 Hz), 7.48 (d, 1H, J = 7.8 Hz), 7.66 (t, 1H, J = 7.8 Hz), 7.81 (td, 1H, J = 1.5, 7.9 Hz), 8.37 (d, 1H, J = 7.7 Hz), 8.49 (d, 1H, J = 8.2 Hz), 8.66 (bd, 1H, J = 4.4 Hz). 13C{1H} NMR (100 MHz, CDCl3): 119.84, 121.62, 124.40, 128.12, 137.15, 139.36, 141.72, 149.34, 154.61, 157.46.<Ligand synthesis>
(Synthesis Example 11: Synthesis of 6-bromo-2,2′-bipyridine)
2,6-dibromopyridine (74.0 g, 312 mmol), 2- (tributylstannyl) pyridine (115 g, 312 mmol), and tetrakis (triphenylphosphine) palladium (18.5 g, 16.0 mmol) in toluene (120 mL) ) Was refluxed overnight under nitrogen. It returned to room temperature, the solvent was distilled off, and chloroform (630 mL) was added. A 6N aqueous hydrochloric acid solution (630 mL) was added, and the aqueous layer was washed with chloroform (630 mL × 2). To the aqueous layer was added 10N aqueous sodium hydroxide solution (420 mL), and the mixture was extracted with chloroform (630 mL). The organic phase was collected and the solvent was distilled off. The crude product was purified by column chromatography (silica, AcOEt: Hexane = 1: 9) to obtain 6-bromo-2,2′-bipyridine as a white powder (yield: 62%).
1 H NMR (400 MHz, CDCl 3 ): 7.32 (dd, 1H, J = 4.8, 7.6 Hz), 7.48 (d, 1H, J = 7.8 Hz), 7.66 (t, 1H, J = 7.8 Hz), 7.81 (td, 1H, J = 1.5 , 7.9 Hz), 8.37 (d, 1H, J = 7.7 Hz), 8.49 (d, 1H, J = 8.2 Hz), 8.66 (bd, 1H, J = 4.4 Hz). 13 C { 1 H} NMR (100 MHz, CDCl 3 ): 119.84, 121.62, 124.40, 128.12, 137.15, 139.36, 141.72, 149.34, 154.61, 157.46.
（合成例１２：１−［２，２’−ビピリジン］−６−イル−エタノンの合成）
６−ブロモ−２，２’−ビピリジン（１５．０ｇ，６３．８ｍｍｏｌ）をジエチルエーテル（４５ｍＬ）、ヘキサン（２３ｍＬ）、ＴＨＦ（２３ｍＬ）に溶解し、−８０℃に冷却した。温度を−８０℃以下に維持し、ｎ−ＢｕＬｉヘキサン溶液（２．６５Ｍ，２６．５ｍＬ，７０．２ｍｍｏｌ）を３０分かけて滴下した。−８０℃で３０分間撹拌を続けた後、過剰量のジメチルアセトアミド（１２．０ｍＬ，１２８ｍｍｏｌ）を１分間かけて滴下したところ発熱した。この反応溶液を一旦−８０℃以下に冷却した後、室温に戻し一晩撹拌した。反応を水（４５ｍＬ）でクエンチした。この溶液をＡｃＯＥｔ（９０ｍＬ×５）で抽出し、有機相を集めて溶媒を留去した。粗生成物をクーゲルロール蒸留（１４０℃，１７０Ｐａ）にて精製し、茶色粉末である１−［２，２’−ビピリジン］−６−イル−エタノンを得た（収率：８９％）。
1H NMR (400 MHz, CDCl3): 2.84 (s, 3H), 7.36 (bt, 1H, J = 5.9 Hz), 7.87 (bt, 1H, J = 8.1 Hz), 7.96 (t, 1H, J = 7.8 Hz), 8.05 (d, 1H, J = 7.6 Hz), 8.53 (d, 1H, J = 8.0 Hz), 8.62 (d, 1H, J = 7.9 Hz), 8.70 (bd, 1H, J = 4.0 Hz).
13C{1H} NMR (100 MHz, CDCl3): 25.86, 121.26, 121.59, 124.26, 124.42, 137.13, 137.95, 149.38, 153.10, 155.53, 155.56, 200.41.Synthesis Example 12 Synthesis of 1- [2,2′-bipyridine] -6-yl-ethanone
6-Bromo-2,2′-bipyridine (15.0 g, 63.8 mmol) was dissolved in diethyl ether (45 mL), hexane (23 mL), THF (23 mL), and cooled to −80 ° C. The temperature was maintained at −80 ° C. or lower, and an n-BuLi hexane solution (2.65 M, 26.5 mL, 70.2 mmol) was added dropwise over 30 minutes. After stirring at −80 ° C. for 30 minutes, an excessive amount of dimethylacetamide (12.0 mL, 128 mmol) was added dropwise over 1 minute to generate heat. The reaction solution was once cooled to −80 ° C. or lower, then returned to room temperature and stirred overnight. The reaction was quenched with water (45 mL). This solution was extracted with AcOEt (90 mL × 5), the organic phase was collected and the solvent was distilled off. The crude product was purified by Kugelrohr distillation (140 ° C., 170 Pa) to obtain 1- [2,2′-bipyridin] -6-yl-ethanone as a brown powder (yield: 89%).
1 H NMR (400 MHz, CDCl 3 ): 2.84 (s, 3H), 7.36 (bt, 1H, J = 5.9 Hz), 7.87 (bt, 1H, J = 8.1 Hz), 7.96 (t, 1H, J = 7.8 Hz), 8.05 (d, 1H, J = 7.6 Hz), 8.53 (d, 1H, J = 8.0 Hz), 8.62 (d, 1H, J = 7.9 Hz), 8.70 (bd, 1H, J = 4.0 Hz ).
13 C { 1 H} NMR (100 MHz, CDCl 3 ): 25.86, 121.26, 121.59, 124.26, 124.42, 137.13, 137.95, 149.38, 153.10, 155.53, 155.56, 200.41.
（合成例１３：Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンの合成）
２，４，６−トリメチルアニリン（１．４５ｍＬ，１０．１ｍｍｏｌ）及び１−［２，２’−ビピリジン］−６−イル−エタノン（２．００ｇ，１０．１ｍｍｏｌ）のメタノール（２０．０ｍＬ）溶液に蟻酸（５滴）を滴下し、２日間還流した。ガスクロマトグラフ質量分析を用いて反応の追跡を行い、１−［２，２’−ビピリジン］−６−イル−エタノンが全て消失するのを確認した。室温まで戻した後、減圧下で溶媒を留去した。粗生成物をクーゲルロール蒸留（２４０℃，１４０Ｐａ）により精製し、黄色の油性成分であるＮ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンを得た（収率：７１％）。なお、生成物は新規化合物であるが、少量の同定不可能な不純物が含まれている。しかし、実施例８１に影響がないため、上記の精製方法以上は行っていない。
1H NMR (400 MHz, CDCl3): 2.04 (s, 6H), 2.31 (s, 6H), 6.92 (s, 2H), 7.33 (m, 1H),7.84 (m, 1H), 7.94 (t, 1H, J = 7.8 Hz), 8.42 (d, 1H, J = 7.8 Hz), 8.55 (t, 2H, J = 8.2 Hz), 8.71 (m, 1H).
13C{1H} NMR (100 MHz, CDCl3): 16.58, 17.98, 20.84, 121.16, 121.26, 122.02, 123.88, 125.38, 128.66, 132.25, 136.96, 137.45, 146.42, 149.27, 154.94, 155.87, 156.15, 167.61.(Synthesis Example 13: Synthesis of N- (1- [2,2′-bipyridine] -6-ylethylidene) -2,4,6-trimethylbenzenamine)
2,4,6-Trimethylaniline (1.45 mL, 10.1 mmol) and 1- [2,2′-bipyridin] -6-yl-ethanone (2.00 g, 10.1 mmol) in methanol (20.0 mL) Formic acid (5 drops) was added dropwise to the solution and refluxed for 2 days. The reaction was traced using gas chromatography mass spectrometry, and it was confirmed that all of 1- [2,2′-bipyridin] -6-yl-ethanone disappeared. After returning to room temperature, the solvent was distilled off under reduced pressure. The crude product was purified by Kugelrohr distillation (240 ° C., 140 Pa) and N- (1- [2,2′-bipyridin] -6-ylethylidene) -2,4,6-trimethyl, a yellow oily component. Benzeneamine was obtained (yield: 71%). Although the product is a new compound, it contains a small amount of unidentifiable impurities. However, since Example 81 is not affected, the above purification method is not performed.
1 H NMR (400 MHz, CDCl 3 ): 2.04 (s, 6H), 2.31 (s, 6H), 6.92 (s, 2H), 7.33 (m, 1H), 7.84 (m, 1H), 7.94 (t, 1H, J = 7.8 Hz), 8.42 (d, 1H, J = 7.8 Hz), 8.55 (t, 2H, J = 8.2 Hz), 8.71 (m, 1H).
13 C { 1 H} NMR (100 MHz, CDCl 3 ): 16.58, 17.98, 20.84, 121.16, 121.26, 122.02, 123.88, 125.38, 128.66, 132.25, 136.96, 137.45, 146.42, 149.27, 154.94, 155.87, 156.15, 167.61 .
（合成例１４：Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミンの合成）
２，６−ジイソプロピルアニリン（２．１１ｍＬ，１０．１ｍｍｏｌ）及び１−［２，２’−ビピリジン］−６−イル−エタノン（２．００ｇ，１０．１ｍｍｏｌ）のメタノール（２０．０ｍＬ）溶液に蟻酸（５滴）を滴下し、還流した。ガスクロマトグラフ質量分析を用いて反応の追跡を行い、１−［２，２’−ビピリジン］−６−イル−エタノンが全て消失するのを確認した。室温まで戻した後、沈殿物を濾過で単離し、メタノール（１０ｍＬ）で２回洗浄、真空乾燥させて、黄色粉末であるＮ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミンを得た（収率：８８％）。
1H NMR (400 MHz, CDCl3): 1.16 (d, 12H, J = 6.8 Hz), 2.33 (s, 3H), 2.79 (sept, 2H, J = 6.6 Hz), 7.11 (m, 1H), 7.18 (m, 2H), 7.34 (m, 1H), 7.85 (m, 1H), 7.95 (t, 1H, J = 7.9 Hz), 8.40 (bd, 1H, J = 7.3 Hz), 8.55 (bt, 2H, J = 7.9 Hz), 8.71 (bd,1H, J = 4.4 Hz).
13C{1H} NMR (100 MHz, CDCl3): 17.67, 23.07, 23.36, 28.42, 121.22, 121.32, 122.07, 123.67, 123.94, 135.97, 137.02, 137.54, 146.69, 149.33, 155.04, 155.80, 156.21, 167.19. Anal. Calcd. for C24H27N3: C, 80.63; H, 7.61; N, 11.75. Found: C, 81.02; H, 7.70; N, 11.71.Synthesis Example 14 Synthesis of N- (1- [2,2′-bipyridine] -6-ylethylidene) -2,6-diisopropylbenzenamine
To a solution of 2,6-diisopropylaniline (2.11 mL, 10.1 mmol) and 1- [2,2′-bipyridin] -6-yl-ethanone (2.00 g, 10.1 mmol) in methanol (20.0 mL). Formic acid (5 drops) was added dropwise and refluxed. The reaction was traced using gas chromatography mass spectrometry, and it was confirmed that all of 1- [2,2′-bipyridin] -6-yl-ethanone disappeared. After returning to room temperature, the precipitate was isolated by filtration, washed twice with methanol (10 mL) and dried in vacuo to give N- (1- [2,2′-bipyridin] -6-ylethylidene as a yellow powder. ) -2,6-diisopropylbenzenamine was obtained (yield: 88%).
1 H NMR (400 MHz, CDCl 3 ): 1.16 (d, 12H, J = 6.8 Hz), 2.33 (s, 3H), 2.79 (sept, 2H, J = 6.6 Hz), 7.11 (m, 1H), 7.18 (m, 2H), 7.34 (m, 1H), 7.85 (m, 1H), 7.95 (t, 1H, J = 7.9 Hz), 8.40 (bd, 1H, J = 7.3 Hz), 8.55 (bt, 2H, J = 7.9 Hz), 8.71 (bd, 1H, J = 4.4 Hz).
13 C { 1 H} NMR (100 MHz, CDCl 3 ): 17.67, 23.07, 23.36, 28.42, 121.22, 121.32, 122.07, 123.67, 123.94, 135.97, 137.02, 137.54, 146.69, 149.33, 155.04, 155.80, 156.21, 167.19 Anal. Calcd. For C 24 H 27 N 3 : C, 80.63; H, 7.61; N, 11.75. Found: C, 81.02; H, 7.70; N, 11.71.
（合成例１５：２，２−ジメチル−１−［２，２’−ビピリジン］−６−イル−１−プロパノンの合成）
水素化ホウ素ナトリウム（７．８０ｇ，１９５ｍｍｏｌ）のＴＨＦ（５５０ｍＬ）溶液を０℃以下に冷却し、１−［２，２’−ビピリジン］−６−イル−エタノン（４．２９ｇ，２１．７ｍｍｏｌ）のＴＨＦ（４３．０ｍＬ）溶液を滴下した。この反応溶液を室温に戻し３時間撹拌を行い、再度０℃以下まで冷却した。温度を０℃以下に維持し、ヨードメタン（１３．５ｍＬ，２１７ｍｍｏｌ）を滴下した。この反応溶液を室温に戻し一晩撹拌した。反応溶液に水（７０．０ｍＬ）とＡｃＯＥｔ（７０．０ｍＬ）を加え、有機相を集めて溶媒を留去した。ＮＭＲ測定の結果、トリアルキル化体とジアルキル化体の混合物として観測されたため、再度上記と同じ操作を行い、全てトリアルキル化体に変換した。粗生成物をクーゲルロール蒸留（１５０℃，１８０Ｐａ）により精製し、黄色の油性成分である２，２−ジメチル−１−［２，２’−ビピリジン］−６−イル−１−プロパノンを得た（収率：７９％）。生成物には少量の同定不可能な不純物が含まれていたが、次のイミノ化反応に影響しないため、そのまま次の反応に使用した。不純物混合のため、13C NMRスペクトルの同定は行なっていない。
1H NMR (400 MHz, CDCl3): 1.55 (s, 9H), 7.34 (dd, 1H, J = 4.9, 7.3 Hz), 7.86 (m, 1H), 7.93 (m, 2H), 8.41 (d, 1H, J = 8.2 Hz), 8.56 (dd, 1H, J = 2.8, 6.4 Hz), 8.69 (d, 1H, J = 5.1 Hz).(Synthesis Example 15: Synthesis of 2,2-dimethyl-1- [2,2′-bipyridine] -6-yl-1-propanone)
A solution of sodium borohydride (7.80 g, 195 mmol) in THF (550 mL) was cooled to below 0 ° C. and 1- [2,2′-bipyridin] -6-yl-ethanone (4.29 g, 21.7 mmol). Of THF (43.0 mL) was added dropwise. The reaction solution was returned to room temperature, stirred for 3 hours, and cooled again to 0 ° C. or lower. The temperature was maintained below 0 ° C. and iodomethane (13.5 mL, 217 mmol) was added dropwise. The reaction solution was returned to room temperature and stirred overnight. Water (70.0 mL) and AcOEt (70.0 mL) were added to the reaction solution, the organic phase was collected, and the solvent was distilled off. As a result of NMR measurement, since it was observed as a mixture of a trialkylated product and a dialkylated product, the same operation as described above was performed again to convert all into a trialkylated product. The crude product was purified by Kugelrohr distillation (150 ° C., 180 Pa) to obtain 2,2-dimethyl-1- [2,2′-bipyridin] -6-yl-1-propanone as a yellow oily component. (Yield: 79%). Although the product contained a small amount of unidentifiable impurities, it did not affect the next imination reaction and was used as it was in the next reaction. The 13 C NMR spectrum has not been identified due to impurity mixing.
1 H NMR (400 MHz, CDCl 3 ): 1.55 (s, 9H), 7.34 (dd, 1H, J = 4.9, 7.3 Hz), 7.86 (m, 1H), 7.93 (m, 2H), 8.41 (d, 1H, J = 8.2 Hz), 8.56 (dd, 1H, J = 2.8, 6.4 Hz), 8.69 (d, 1H, J = 5.1 Hz).
（合成例１６：Ｎ−（２，２−ジメチル−［２，２’−ビピリジン］−６−イルプロピリデン）−２，４，６−トリメチルベンゼンアミンの合成）
２，４，６−トリメチルアニリン（０．８９ｍＬ，６．２４ｍｍｏｌ）及び２，２−ジメチル−１−［２，２’−ビピリジン］−６−イル−１−プロパノン（１．００ｇ，４．１６ｍｍｏｌ）のトルエン（２０．０ｍＬ）溶液にｐ−トルエンスルホン酸一水和物（４１．０ｍｇ，０．２１ｍｍｏｌ）を加え、Ｄｅａｎ−Ｓｔａｒｋ装置を用いて脱水した。室温まで戻した後、減圧下で溶媒を留去した。粗生成物をクーゲルロール蒸留（２４０℃，１７０Ｐａ）により精製し、黄色粉末であるＮ−（２，２−ジメチル−［２，２’−ビピリジン］−６−イルプロピリデン）−２，４，６−トリメチルベンゼンアミンを得た（収率：４３％）。生成物には少量の同定不可能な不純物が含まれていたが、実施例８３に影響がないため、次の反応にそのまま使用した。
1H NMR (400 MHz, CDCl3): 1.42 (s, 9H), 2.06 (s, 6H), 2.08 (s, 3H), 6.56 (s, 2H),6.76 (d, 1H, J = 7.4 Hz), 7.30 (m, 1H), 7.52 (t, 1H, J = 8.1 Hz), 7.82 (m, 1H),8.21 (d, 1H, J = 7.9 Hz), 8.40 (d, 1H, J = 7.9 Hz), 8.64 (bdt, 1H, J = 4.3 Hz).13C{1H} NMR (100 MHz, CDCl3): 18.39, 20.72, 29.13, 40.52, 119.69, 121.17, 121.55, 123.89, 125.48, 128.26, 131.60, 136.30, 137.10, 149.18, 155.93, 156.09.(Synthesis Example 16: Synthesis of N- (2,2-dimethyl- [2,2′-bipyridin] -6-ylpropylidene) -2,4,6-trimethylbenzenamine)
2,4,6-trimethylaniline (0.89 mL, 6.24 mmol) and 2,2-dimethyl-1- [2,2′-bipyridin] -6-yl-1-propanone (1.00 g, 4.16 mmol) P-toluenesulfonic acid monohydrate (41.0 mg, 0.21 mmol) was added to a toluene (20.0 mL) solution and dehydrated using a Dean-Stark apparatus. After returning to room temperature, the solvent was distilled off under reduced pressure. The crude product was purified by Kugelrohr distillation (240 ° C., 170 Pa) and N- (2,2-dimethyl- [2,2′-bipyridin] -6-ylpropylidene) -2,4,6- Trimethylbenzenamine was obtained (yield: 43%). The product contained a small amount of unidentifiable impurities, but had no effect on Example 83 and was used as such in the next reaction.
1 H NMR (400 MHz, CDCl 3 ): 1.42 (s, 9H), 2.06 (s, 6H), 2.08 (s, 3H), 6.56 (s, 2H), 6.76 (d, 1H, J = 7.4 Hz) , 7.30 (m, 1H), 7.52 (t, 1H, J = 8.1 Hz), 7.82 (m, 1H), 8.21 (d, 1H, J = 7.9 Hz), 8.40 (d, 1H, J = 7.9 Hz) , 8.64 (bdt, 1H, J = 4.3 Hz) 13 C {1 H} NMR (100 MHz, CDCl 3):. 18.39, 20.72, 29.13, 40.52, 119.69, 121.17, 121.55, 123.89, 125.48, 128.26, 131.60, 136.30, 137.10, 149.18, 155.93, 156.09.
（合成例１７：２，２，２−トリフルオロ−１−［２，２’−ビピリジン］−６−イル−エタノンの合成）
６−ブロモ−２，２’−ビピリジン（７．５２ｇ，３２．０ｍｍｏｌ）をジエチルエーテル（２３ｍＬ）、ヘキサン（１２ｍＬ）、ＴＨＦ（１２ｍＬ）に溶解し、−８０℃に冷却した。温度を−８０℃以下に維持し、ｎ−ＢｕＬｉヘキサン溶液（２．６５Ｍ，１４．０ｍＬ，３５．２ｍｍｏｌ）を３０分かけて滴下した。−８０℃で３０分間撹拌を続けた後、過剰量の２，２，２−トリフルオロ−Ｎ，Ｎ−ジメチルアセトアミド（７．２ｍＬ，６４．０ｍｍｏｌ）を１分間かけて滴下したところ、発熱反応が生じた。この反応溶液を一旦−８０℃以下に冷却した後、室温に戻し一晩撹拌した。反応を水（７５ｍＬ）でクエンチした。この溶液をＡｃＯＥｔ（１５０ｍＬ×５）で抽出し、有機相を集めて溶媒を留去した。粗生成物をクーゲルロール蒸留（１２０℃，１４０Ｐａ）により精製し、茶白色粉末である２，２，２−トリフルオロ−１−［２，２’−ビピリジン］−６−イル−エタノンを得た（収率：５４％）。生成物には少量の同定不可能な不純物が含まれていたが、次のイミノ化反応に影響しないため、そのまま使用した。また、不純物の混合および生成物のクロロホルムへの難溶性のため、13C NMRスペクトルが複雑になり帰属は行っていない。
1H NMR (400 MHz, CDCl3): 7.38 (m, 1H), 7.87 (qd, 1H, J = 1.6, 7.8 Hz), 8.05 (t, 1H, J = 7.8 Hz), 8.17 (dd, 1H, J = 0.9, 7.8 Hz), 8.54 (bd, 1H, J = 7.8 Hz), 8.71(bt, 1H, J = 5.8 Hz), 8.77 (dd, 1H, J = 0.7, 8.2 Hz).(Synthesis Example 17: Synthesis of 2,2,2-trifluoro-1- [2,2′-bipyridin] -6-yl-ethanone)
6-Bromo-2,2′-bipyridine (7.52 g, 32.0 mmol) was dissolved in diethyl ether (23 mL), hexane (12 mL), THF (12 mL), and cooled to −80 ° C. The temperature was maintained at −80 ° C. or lower, and an n-BuLi hexane solution (2.65 M, 14.0 mL, 35.2 mmol) was added dropwise over 30 minutes. After stirring at −80 ° C. for 30 minutes, an excessive amount of 2,2,2-trifluoro-N, N-dimethylacetamide (7.2 mL, 64.0 mmol) was added dropwise over 1 minute, resulting in an exothermic reaction. Occurred. The reaction solution was once cooled to −80 ° C. or lower, then returned to room temperature and stirred overnight. The reaction was quenched with water (75 mL). This solution was extracted with AcOEt (150 mL × 5), the organic phase was collected, and the solvent was distilled off. The crude product was purified by Kugelrohr distillation (120 ° C., 140 Pa) to obtain 2,2,2-trifluoro-1- [2,2′-bipyridin] -6-yl-ethanone as a brownish white powder. (Yield: 54%). The product contained a small amount of unidentifiable impurities, but was used as it was because it did not affect the next imination reaction. In addition, due to the mixture of impurities and the poor solubility of the product in chloroform, the 13 C NMR spectrum is complicated and no assignment is made.
1 H NMR (400 MHz, CDCl 3 ): 7.38 (m, 1H), 7.87 (qd, 1H, J = 1.6, 7.8 Hz), 8.05 (t, 1H, J = 7.8 Hz), 8.17 (dd, 1H, J = 0.9, 7.8 Hz), 8.54 (bd, 1H, J = 7.8 Hz), 8.71 (bt, 1H, J = 5.8 Hz), 8.77 (dd, 1H, J = 0.7, 8.2 Hz).
（合成例１８：Ｎ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンの合成）
２，４，６−トリメチルアニリン（０．４３ｍＬ，３．０３ｍｍｏｌ）及び２，２，２−トリフルオロ−１−［２，２’−ビピリジン］−６−イル−エタノン（０．６４ｇ，２．５３ｍｍｏｌ）のトルエン（６．４０ｍＬ）溶液にｐ−トルエンスルホン酸一水和物（１４．６ｍｇ，０．０８ｍｍｏｌ）を加え、Ｄｅａｎ−Ｓｔａｒｋ装置を用いて脱水した。室温まで戻した後、減圧下で溶媒を留去した。粗生成物をクーゲルロール蒸留（２００℃，２００Ｐａ）により精製し、黄色粉末であるＮ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンを得た（収率：７９％）。
1H NMR (400 MHz, CDCl3): 1.98 (s, 6H), 2.21 (s, 3H), 6.76 (s, 2H), 7.12 (d, 1H, J = 7.6 Hz), 7.31 (m, 1H), 7.74 (m, 2H), 8.07 (d, 1H, J = 8.1 Hz), 8.40 (d, 1H, J = 8.0 Hz), 8.63 (br, 1H).
13C{1H} NMR (100 MHz, CDCl3): 17.91, 20.82, 121.77, 122.20, 123.10, 124.32, 128.84, 133.61, 137.07, 137.49, 143.48, 147.92, 149.14, 155.18, 156.17. Anal. Calcd.for C21H18F3N3: C, 68.28; H, 4.91; N, 11.38. Found: C, 68.16; H, 5.00; N, 11.42.(Synthesis Example 18: Synthesis of N- (2,2,2-trifluoro- [2,2′-bipyridine] -6-ylethylidene) -2,4,6-trimethylbenzenamine)
2,4,6-Trimethylaniline (0.43 mL, 3.03 mmol) and 2,2,2-trifluoro-1- [2,2′-bipyridin] -6-yl-ethanone (0.64 g, 2. 53 mmol) in toluene (6.40 mL) was added p-toluenesulfonic acid monohydrate (14.6 mg, 0.08 mmol) and dehydrated using a Dean-Stark apparatus. After returning to room temperature, the solvent was distilled off under reduced pressure. The crude product was purified by Kugelrohr distillation (200 ° C., 200 Pa) to give N- (2,2,2-trifluoro- [2,2′-bipyridine] -6-ylethylidene) -2, a yellow powder. 4,6-trimethylbenzenamine was obtained (yield: 79%).
1 H NMR (400 MHz, CDCl 3 ): 1.98 (s, 6H), 2.21 (s, 3H), 6.76 (s, 2H), 7.12 (d, 1H, J = 7.6 Hz), 7.31 (m, 1H) , 7.74 (m, 2H), 8.07 (d, 1H, J = 8.1 Hz), 8.40 (d, 1H, J = 8.0 Hz), 8.63 (br, 1H).
13 C { 1 H} NMR (100 MHz, CDCl 3 ): 17.91, 20.82, 121.77, 122.20, 123.10, 124.32, 128.84, 133.61, 137.07, 137.49, 143.48, 147.92, 149.14, 155.18, 156.17. Anal. Calcd.for C 21 H 18 F 3 N 3 : C, 68.28; H, 4.91; N, 11.38.Found: C, 68.16; H, 5.00; N, 11.42.
（合成例１９：Ｎ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミンの合成）
２，６−ジイソプロピルアニリン（０．８５ｍＬ，４．０３ｍｍｏｌ）及び２，２，２−トリフルオロ−１−［２，２’−ビピリジン］−６−イル−エタノン（１．０２ｇ，４．０３ｍｍｏｌ）のトルエン（１０．２ｍＬ）溶液にｐ−トルエンスルホン酸一水和物（２３．３ｍｇ，０．１２ｍｍｏｌ）を加え、Ｄｅａｎ−Ｓｔａｒｋ装置を用いて脱水した。室温まで戻した後、減圧下で溶媒を留去した。粗生成物をクーゲルロール蒸留（２１０℃，１４０Ｐａ）により精製し、黄色粉末であるＮ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミンを得た（収率：５５％）。なお、生成物は新規化合物であるが、少量の同定不可能な不純物が含まれている。しかし、実施例８５に影響しないため、上記の精製方法以上は行っていない。
1H NMR (400 MHz, CDCl3): 0.86 (m, 5H, J = 5.1 Hz), 1.18 (m, 7H, J = 6.8 Hz), 2.78 (sept, 2H, J = 6.4 Hz), 7.10 (m, 3H), 7.17 (d, 1H, J = 6.7 Hz), 7.29 (t, 1H, J= 6.2 Hz), 7.72 (t, 2H, J = 6.7 Hz), 7.87 (d, 1H, J = 7.1 Hz), 8.40 (d, 1H, J =7.6 Hz), 8.62 (br, 1H).
13C{1H} NMR (100 MHz, CDCl3): 22.36, 28.45, 28.46, 121.92, 122.31, 123.43, 123.78, 124.33, 124.77, 134.57, 137.00, 137.46, 143.73, 147.06, 149.09, 155.08, 156.06.Synthesis Example 19 Synthesis of N- (2,2,2-trifluoro- [2,2′-bipyridin] -6-ylethylidene) -2,6-diisopropylbenzenamine)
2,6-diisopropylaniline (0.85 mL, 4.03 mmol) and 2,2,2-trifluoro-1- [2,2′-bipyridin] -6-yl-ethanone (1.02 g, 4.03 mmol) P-Toluenesulfonic acid monohydrate (23.3 mg, 0.12 mmol) was added to a toluene (10.2 mL) solution, and dehydrated using a Dean-Stark apparatus. After returning to room temperature, the solvent was distilled off under reduced pressure. The crude product was purified by Kugelrohr distillation (210 ° C., 140 Pa) to give N- (2,2,2-trifluoro- [2,2′-bipyridin] -6-ylethylidene) -2, a yellow powder. 6-Diisopropylbenzenamine was obtained (yield: 55%). Although the product is a new compound, it contains a small amount of unidentifiable impurities. However, since it does not affect Example 85, the above purification method is not performed.
1 H NMR (400 MHz, CDCl 3 ): 0.86 (m, 5H, J = 5.1 Hz), 1.18 (m, 7H, J = 6.8 Hz), 2.78 (sept, 2H, J = 6.4 Hz), 7.10 (m , 3H), 7.17 (d, 1H, J = 6.7 Hz), 7.29 (t, 1H, J = 6.2 Hz), 7.72 (t, 2H, J = 6.7 Hz), 7.87 (d, 1H, J = 7.1 Hz ), 8.40 (d, 1H, J = 7.6 Hz), 8.62 (br, 1H).
13 C { 1 H} NMR (100 MHz, CDCl 3 ): 22.36, 28.45, 28.46, 121.92, 122.31, 123.43, 123.78, 124.33, 124.77, 134.57, 137.00, 137.46, 143.73, 147.06, 149.09, 155.08, 156.06.
＜鉄錯体化合物の調製＞
（実施例８１：Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミドの合成）
窒素雰囲気、室温下で激しく撹拌しながら、臭化鉄（ＩＩ）（１．９８ｇ，６．２６ｍｍｏｌ）を、Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミン（１．３８ｇ，６．２６ｍｍｏｌ）のＴＨＦ（１００ｍＬ）溶液に加えた。沈殿物を濾過で単離し、ＴＨＦ（１０ｍＬ）で３回洗浄後、真空乾燥した。茶紫色粉末であるＮ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物６」と略す場合がある。）を得た（収率：９９％）。なお、生成物には０．５当量の水が含まれている。
Anal. Calcd. for C42H44Br4Fe2N6O (2M + H2O): C, 46.70; H, 4.11; N, 7.78. Found: C, 47.12; H, 4.22; N, 7.37.<Preparation of iron complex compound>
Example 81 Synthesis of N- (1- [2,2′-bipyridin] -6-ylethylidene) -2,4,6-trimethylbenzenamine iron (II) bromide
With vigorous stirring under a nitrogen atmosphere at room temperature, iron (II) bromide (1.98 g, 6.26 mmol) was added to N- (1- [2,2′-bipyridin] -6-ylethylidene) -2, 4,6-Trimethylbenzenamine (1.38 g, 6.26 mmol) was added to a THF (100 mL) solution. The precipitate was isolated by filtration, washed 3 times with THF (10 mL) and then dried in vacuo. N- (1- [2,2′-bipyridin] -6-ylethylidene) -2,4,6-trimethylbenzenamine iron (II) bromide (hereinafter abbreviated as “iron complex compound 6”) which is a brownish purple powder (Yield: 99%). The product contains 0.5 equivalent of water.
Anal.Calcd.for C 42 H 44 Br 4 Fe 2 N 6 O (2M + H 2 O): C, 46.70; H, 4.11; N, 7.78.Found: C, 47.12; H, 4.22; N, 7.37.
（実施例８２：Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミン鉄（ＩＩ）ブロミドの合成）
Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンをＮ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミンに変更した以外、実施例８１と同様の方法を行って、赤紫色粉末であるＮ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物７」と略す場合がある。）を得た（収率：８３％）。
Anal. Calcd. for C24H27Br2FeN3: C, 50.29; H, 4.75; N, 7.33. Found: C, 49.99; H, 4.82; N, 7.20.Example 82 Synthesis of N- (1- [2,2′-bipyridin] -6-ylethylidene) -2,6-diisopropylbenzenamineiron (II) bromide
N- (1- [2,2′-bipyridin] -6-ylethylidene) -2,4,6-trimethylbenzenamine is converted to N- (1- [2,2′-bipyridin] -6-ylethylidene)- N- (1- [2,2′-bipyridin] -6-ylethylidene) -2, which is a magenta powder, was performed in the same manner as in Example 81 except that it was changed to 2,6-diisopropylbenzeneamine. 6-Diisopropylbenzeneamine iron (II) bromide (hereinafter sometimes abbreviated as “iron complex compound 7”) was obtained (yield: 83%).
Anal.Calcd.for C 24 H 27 Br 2 FeN 3 : C, 50.29; H, 4.75; N, 7.33. Found: C, 49.99; H, 4.82; N, 7.20.
（実施例８３：Ｎ−（２，２−ジメチル−［２，２’−ビピリジン］−６−イルプロピリデン）−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミドの合成）
Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンをＮ−（２，２−ジメチル−［２，２’−ビピリジン］−６−イルプロピリデン）−２，４，６−トリメチルベンゼンアミンに変更した以外、実施例８１と同様の方法を行って、青紫色粉末であるＮ−（２，２−ジメチル−［２，２’−ビピリジン］−６−イルプロピリデン）−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物８」と略す場合がある。）を得た（収率：５６％）。
Anal. Calcd. for C240H270Br22Fe11N30(10M + FeBr2): C, 48.47; H, 4.58; N, 7.07. Found: C, 48.46; H, 4.73; N, 7.10.Example 83 Synthesis of N- (2,2-dimethyl- [2,2′-bipyridin] -6-ylpropylidene) -2,4,6-trimethylbenzenamine iron (II) bromide
N- (1- [2,2′-bipyridine] -6-ylethylidene) -2,4,6-trimethylbenzenamine is converted to N- (2,2-dimethyl- [2,2′-bipyridine] -6- N- (2,2-dimethyl- [2,2′-bipyridine], a blue-violet powder, was prepared in the same manner as in Example 81, except that it was changed to ylpropylidene) -2,4,6-trimethylbenzenamine. -6-ylpropylidene) -2,4,6-trimethylbenzenamine iron (II) bromide (hereinafter sometimes abbreviated as “iron complex compound 8”) was obtained (yield: 56%).
Anal.Calcd.for C 240 H 270 Br 22 Fe 11 N 30 (10M + FeBr 2 ): C, 48.47; H, 4.58; N, 7.07. Found: C, 48.46; H, 4.73; N, 7.10.
（実施例８４：Ｎ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミドの合成）
Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンをＮ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンに変更した以外、実施例８１と同様の方法を行って、茶色粉末であるＮ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物９」と略す場合がある。）を得た（収率：８８％）。なお、生成物には０．５当量のヘキサンが含まれている。
Anal. Calcd. for C48H50Br4F6Fe2N6(2M + hexane): C, 45.89; H, 4.01; N, 6.69. Found: C, 45.81; H, 4.00; N, 6.51.Example 84 Synthesis of N- (2,2,2-trifluoro- [2,2′-bipyridin] -6-ylethylidene) -2,4,6-trimethylbenzenamine iron (II) bromide
N- (1- [2,2′-bipyridine] -6-ylethylidene) -2,4,6-trimethylbenzenamine is converted to N- (2,2,2-trifluoro- [2,2′-bipyridine]. N- (2,2,2-trifluoro- [2], which is a brown powder, was carried out in the same manner as in Example 81 except that it was changed to -6-ylethylidene) -2,4,6-trimethylbenzenamine. , 2′-bipyridine] -6-ylethylidene) -2,4,6-trimethylbenzenamine iron (II) bromide (hereinafter sometimes abbreviated as “iron complex compound 9”) (yield: 88%). The product contains 0.5 equivalent of hexane.
Anal.Calcd.for C 48 H 50 Br 4 F 6 Fe 2 N 6 (2M + hexane): C, 45.89; H, 4.01; N, 6.69.Found: C, 45.81; H, 4.00; N, 6.51.
（実施例８５：Ｎ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミン鉄（ＩＩ）ブロミドの合成）
Ｎ−（１−［２，２’−ビピリジン］−６−イルエチリデン）−２，４，６−トリメチルベンゼンアミンをＮ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミンに変更した以外、実施例８１と同様の方法を行って、緑色粉末であるＮ−（２，２，２−トリフルオロ−［２，２’−ビピリジン］−６−イルエチリデン）−２，６−ジイソプロピルベンゼンアミン鉄（ＩＩ）ブロミド（以下、「鉄錯体化合物１０」と略す場合がある。）を得た（収率：５６％）。
Anal. Calcd. for C24H24Br2F3FeN3: C, 45.97; H, 3.96; N, 6.70. Found: C, 45.91; H, 3.97; N, 6.72.Example 85 Synthesis of N- (2,2,2-trifluoro- [2,2′-bipyridin] -6-ylethylidene) -2,6-diisopropylbenzenamine iron (II) bromide
N- (1- [2,2′-bipyridine] -6-ylethylidene) -2,4,6-trimethylbenzenamine is converted to N- (2,2,2-trifluoro- [2,2′-bipyridine]. N- (2,2,2-trifluoro- [2,2], which is a green powder, was carried out in the same manner as in Example 81 except that it was changed to -6-ylethylidene) -2,6-diisopropylbenzenamine. '-Bipyridin] -6-ylethylidene) -2,6-diisopropylbenzenamine iron (II) bromide (hereinafter sometimes abbreviated as “iron complex compound 10”) was obtained (yield: 56%).
Anal.Calcd.for C 24 H 24 Br 2 F 3 FeN 3 : C, 45.97; H, 3.96; N, 6.70. Found: C, 45.91; H, 3.97; N, 6.72.
＜有機ケイ素化合物の製造（ヒドロシリル化反応）＞
（実施例８６）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（１８ｍＬ，１２０ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（７．２ｍＬ，５８ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１２０μＬ，０．１２ｍｍｏｌ）を添加した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルフェニルシラン（変換率：２１％）及びジオクチルフェニルシラン（０．８％）の生成を確認した。結果を表１２に示す。<Production of organosilicon compounds (hydrosilylation reaction)>
(Example 86)
Flame-drying was performed, and iron complex compound 1 (3.0 mg, 0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, and 1-octene (18 mL, 120 mmol) was added, and stirring was started at room temperature. To this slurry solution was added phenylsilane (7.2 mL, 58 mmol), and then a 1 M sodium triethylborohydride toluene solution (120 μL, 0.12 mmol) was added. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, the production of octylphenylsilane (conversion rate: 21%) and dioctylphenylsilane (0.8%) was confirmed. The results are shown in Table 12.
（実施例８７）
鉄錯体化合物１を鉄錯体化合物２に変更した以外、実施例８６と同様の方法により反応を行った。結果を表１２に示す。(Example 87)
The reaction was performed in the same manner as in Example 86 except that the iron complex compound 1 was changed to the iron complex compound 2. The results are shown in Table 12.
（実施例８８）
鉄錯体化合物１を鉄錯体化合物６に変更した以外、実施例８６と同様の方法により反応を行った。結果を表１２に示す。(Example 88)
The reaction was performed in the same manner as in Example 86 except that the iron complex compound 1 was changed to the iron complex compound 6. The results are shown in Table 12.
（実施例８９）
鉄錯体化合物１を鉄錯体化合物７に変更した以外、実施例８６と同様の方法により反応を行った。結果を表１２に示す。Example 89
The reaction was performed in the same manner as in Example 86 except that the iron complex compound 1 was changed to the iron complex compound 7. The results are shown in Table 12.
（実施例９０）
鉄錯体化合物１を鉄錯体化合物８に変更した以外、実施例８６と同様の方法により反応を行った。結果を表１２に示す。(Example 90)
The reaction was performed in the same manner as in Example 86 except that the iron complex compound 1 was changed to the iron complex compound 8. The results are shown in Table 12.
（実施例９１）
鉄錯体化合物１を鉄錯体化合物９に変更した以外、実施例８６と同様の方法により反応を行った。結果を表１２に示す。(Example 91)
The reaction was performed in the same manner as in Example 86 except that the iron complex compound 1 was changed to the iron complex compound 9. The results are shown in Table 12.
（実施例９２）
鉄錯体化合物１を鉄錯体化合物１０に変更した以外、実施例８６と同様の方法により反応を行った。結果を表１２に示す。(Example 92)
The reaction was performed in the same manner as in Example 86 except that the iron complex compound 1 was changed to the iron complex compound 10. The results are shown in Table 12.
（実施例９３）
フェニルシランをジフェニルシランに変更した以外、実施例８６と同様の方法により反応を行った。結果を表１３に示す。(Example 93)
The reaction was performed in the same manner as in Example 86, except that phenylsilane was changed to diphenylsilane. The results are shown in Table 13.
（実施例９４）
フェニルシランをジフェニルシランに変更した以外、実施例８８と同様の方法により反応を行った。結果を表１３に示す。(Example 94)
The reaction was conducted in the same manner as in Example 88 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 13.
（実施例９５）
フェニルシランをジフェニルシランに変更した以外、実施例８９と同様の方法により反応を行った。結果を表１３に示す。(Example 95)
The reaction was performed in the same manner as in Example 89 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 13.
（実施例９６）
フェニルシランをジフェニルシランに変更した以外、実施例９０と同様の方法により反応を行った。結果を表１３に示す。Example 96
The reaction was performed in the same manner as in Example 90 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 13.
（実施例９７）
フェニルシランをジフェニルシランに変更した以外、実施例９１と同様の方法により反応を行った。結果を表１３に示す。(Example 97)
The reaction was conducted in the same manner as in Example 91 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 13.
（実施例９８）
フェニルシランをジフェニルシランに変更した以外、実施例９２と同様の方法により反応を行った。結果を表１３に示す。(Example 98)
The reaction was conducted in the same manner as in Example 92 except that phenylsilane was changed to diphenylsilane. The results are shown in Table 13.
（実施例９９）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例８６と同様の方法により反応を行った。結果を表１４に示す。Example 99
The reaction was performed in the same manner as in Example 86, except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 14.
（実施例１００）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例８７と同様の方法により反応を行った。結果を表１４に示す。(Example 100)
The reaction was conducted in the same manner as in Example 87 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 14.
（実施例１０１）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例８８と同様の方法により反応を行った。結果を表１４に示す。(Example 101)
The reaction was performed in the same manner as in Example 88 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 14.
（実施例１０２）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例８９と同様の方法により反応を行った。結果を表１４に示す。(Example 102)
The reaction was conducted in the same manner as in Example 89 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 14.
（実施例１０３）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例９０と同様の方法により反応を行った。結果を表１４に示す。(Example 103)
The reaction was performed in the same manner as in Example 90 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 14.
（実施例１０４）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例９１と同様の方法により反応を行った。結果を表１４に示す。(Example 104)
The reaction was conducted in the same manner as in Example 91 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 14.
（実施例１０５）
フェニルシランをフェニル（メチル）シランに変更した以外、実施例９２と同様の方法により反応を行った。結果を表１４に示す。(Example 105)
The reaction was performed in the same manner as in Example 92 except that phenylsilane was changed to phenyl (methyl) silane. The results are shown in Table 14.
（実施例１０６）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物１（３．０ｍｇ，０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（１.８ｍＬ，１１ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニル（メチル）シラン（１．２ｍＬ，５.８ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（４６μＬ，０．０４６ｍｍｏｌ）を添加した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：７４％）の生成を確認した。結果を表１５に示す。(Example 106)
Perform flame drying, accurately weigh iron complex compound 1 (3.0 mg, 0.0058 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (1.8 mL, 11 mmol), and start stirring at room temperature. did. To this slurry solution was added diphenyl (methyl) silane (1.2 mL, 5.8 mmol), followed by 1M sodium triethylborohydride in toluene (46 μL, 0.046 mmol). Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 74%) was produced. The results are shown in Table 15.
（実施例１０７）
鉄錯体化合物１を鉄錯体化合物２に変更した以外、実施例１０６と同様の方法により反応を行った。結果を表１５に示す。(Example 107)
The reaction was performed in the same manner as in Example 106 except that the iron complex compound 1 was changed to the iron complex compound 2. The results are shown in Table 15.
（実施例１０８）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物２（３．０ｍｇ，０．００５４ｍｍｏｌ）を精密に量り取り、１−オクテン（１.７ｍＬ，１１ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニル（メチル）シラン（１．１ｍＬ，５.４ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１１０μＬ，０．１１ｍｍｏｌ）を添加した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、オクチルジフェニル（メチル）シラン（変換率：６％）の生成を確認した。結果を表１５に示す。(Example 108)
Perform flame drying, accurately weigh iron complex compound 2 (3.0 mg, 0.0054 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (1.7 mL, 11 mmol), and start stirring at room temperature. did. Diphenyl (methyl) silane (1.1 mL, 5.4 mmol) was added to the slurry solution, and then 1M sodium triethylborohydride in toluene (110 μL, 0.11 mmol) was added. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by an absolute calibration curve method, it was confirmed that octyldiphenyl (methyl) silane (conversion rate: 6%) was produced. The results are shown in Table 15.
（実施例１０９）
鉄錯体化合物１を鉄錯体化合物６に、ジフェニル（メチル）シランをフェニルジ（メチル）シランに変更した以外、実施例１０６と同様の方法により反応を行った。結果を表１５に示す。(Example 109)
The reaction was performed in the same manner as in Example 106 except that the iron complex compound 1 was changed to the iron complex compound 6 and diphenyl (methyl) silane was changed to phenyldi (methyl) silane. The results are shown in Table 15.
（実施例１１０）
鉄錯体化合物１を鉄錯体化合物６に、ジフェニル（メチル）シランをフェニルジ（メチル）シランに変更した以外、実施例１０８と同様の方法により反応を行った。結果を表１５に示す。(Example 110)
The reaction was performed in the same manner as in Example 108, except that the iron complex compound 1 was changed to the iron complex compound 6 and diphenyl (methyl) silane was changed to phenyldi (methyl) silane. The results are shown in Table 15.
（実施例１１１）
鉄錯体化合物１を鉄錯体化合物６に変更した以外、実施例１０６と同様の方法により反応を行った。結果を表１５に示す。(Example 111)
The reaction was performed in the same manner as in Example 106 except that the iron complex compound 1 was changed to the iron complex compound 6. The results are shown in Table 15.
（実施例１１２）
鉄錯体化合物１を鉄錯体化合物６に変更した以外、実施例１０８と同様の方法により反応を行った。結果を表１５に示す。(Example 112)
The reaction was performed in the same manner as in Example 108 except that the iron complex compound 1 was changed to the iron complex compound 6. The results are shown in Table 15.
（実施例１１３）
鉄錯体化合物１を鉄錯体化合物６に、ジフェニル（メチル）シランをトリフェニルシランに変更した以外、実施例１０６と同様の方法により反応を行った。結果を表１５に示す。(Example 113)
The reaction was performed in the same manner as in Example 106 except that the iron complex compound 1 was changed to the iron complex compound 6 and diphenyl (methyl) silane was changed to triphenylsilane. The results are shown in Table 15.
（実施例１１４）
鉄錯体化合物１を鉄錯体化合物７に変更した以外、実施例１０６と同様の方法により反応を行った。結果を表１５に示す。(Example 114)
The reaction was performed in the same manner as in Example 106 except that the iron complex compound 1 was changed to the iron complex compound 7. The results are shown in Table 15.
（実施例１１５）
鉄錯体化合物１を鉄錯体化合物７に変更した以外、実施例１０８と同様の方法により反応を行った。結果を表１５に示す。(Example 115)
The reaction was performed in the same manner as in Example 108 except that the iron complex compound 1 was changed to the iron complex compound 7. The results are shown in Table 15.
（実施例１１６）
鉄錯体化合物１を鉄錯体化合物８に変更した以外、実施例１０６と同様の方法により反応を行った。結果を表１５に示す。(Example 116)
The reaction was performed in the same manner as in Example 106 except that the iron complex compound 1 was changed to the iron complex compound 8. The results are shown in Table 15.
（実施例１１７）
鉄錯体化合物１を鉄錯体化合物９に変更した以外、実施例１０６と同様の方法により反応を行った。結果を表１５に示す。(Example 117)
The reaction was performed in the same manner as in Example 106 except that the iron complex compound 1 was changed to the iron complex compound 9. The results are shown in Table 15.
（実施例１１８）
鉄錯体化合物１を鉄錯体化合物１０に変更した以外、実施例１０６と同様の方法により反応を行った。結果を表１５に示す。(Example 118)
The reaction was performed in the same manner as in Example 106 except that the iron complex compound 1 was changed to the iron complex compound 10. The results are shown in Table 15.
（実施例１１９）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物６（１０ｍｇ，０．０１９ｍｍｏｌ）を精密に量り取り、シクロヘキセン（２．０ｍＬ，１９ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にフェニルシラン（０．２３ｍＬ，１．９ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（７５μＬ，０．０７５ｍｍｏｌ）を添加した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、シクロヘキシルフェニルシラン（変換率：７４％）の生成を確認した。結果を表１６に示す。(Example 119)
Flame drying was performed, and iron complex compound 6 (10 mg, 0.019 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, and cyclohexene (2.0 mL, 19 mmol) was added, and stirring was started at room temperature. Phenylsilane (0.23 mL, 1.9 mmol) was added to the slurry solution, and then 1 M sodium triethylborohydride in toluene (75 μL, 0.075 mmol) was added. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and the reaction solution was analyzed by high performance liquid chromatography (199 nm) after 24 hours. When the reaction product was quantified by the absolute calibration curve method, the formation of cyclohexylphenylsilane (conversion rate: 74%) was confirmed. The results are shown in Table 16.
（実施例１２０）
鉄錯体化合物６を鉄錯体化合物７に変更した以外、実施例１１９と同様の方法により反応を行った。結果を表１６に示す。(Example 120)
The reaction was performed in the same manner as in Example 119 except that the iron complex compound 6 was changed to the iron complex compound 7. The results are shown in Table 16.
（実施例１２１）
鉄錯体化合物６を鉄錯体化合物８に変更した以外、実施例１１９と同様の方法により反応を行った。結果を表１６に示す。(Example 121)
The reaction was performed in the same manner as in Example 119 except that the iron complex compound 6 was changed to the iron complex compound 8. The results are shown in Table 16.
（実施例１２２）
鉄錯体化合物６を鉄錯体化合物９に変更した以外、実施例１１９と同様の方法により反応を行った。結果を表１６に示す。(Example 122)
The reaction was performed in the same manner as in Example 119 except that the iron complex compound 6 was changed to the iron complex compound 9. The results are shown in Table 16.
（実施例１２３）
鉄錯体化合物６を鉄錯体化合物１０に変更した以外、実施例１１９と同様の方法により反応を行った。結果を表１６に示す。(Example 123)
The reaction was performed in the same manner as in Example 119 except that the iron complex compound 6 was changed to the iron complex compound 10. The results are shown in Table 16.
（実施例１２４）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物６（３．０ｍｇ，０．００５６ｍｍｏｌ）を精密に量り取り、１−オクテン（１．８ｍＬ，１１ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジエチルシラン（０．７７ｍＬ，５．７ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（４５μＬ，０．０７５ｍｍｏｌ）を添加した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液をガスクロマトグラフ質量分析によって分析した。反応生成物をクーゲルロール蒸留により単離したところ、ジエチルオクチルシラン（変換率：６８％）及びジエチルジオクチルシラン（２６％）の生成を確認した。結果を表１７に示す。(Example 124)
Perform flame drying, accurately weigh iron complex compound 6 (3.0 mg, 0.0056 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (1.8 mL, 11 mmol), and start stirring at room temperature. did. Diethylsilane (0.77 mL, 5.7 mmol) was added to the slurry solution, and then 1 M sodium triethylborohydride in toluene (45 μL, 0.075 mmol) was added. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and after 24 hours, the reaction solution was analyzed by gas chromatography mass spectrometry. When the reaction product was isolated by Kugelrohr distillation, it was confirmed that diethyloctylsilane (conversion rate: 68%) and diethyldioctylsilane (26%) were formed. The results are shown in Table 17.
（実施例１２５）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物６（３．０ｍｇ，０．００５６ｍｍｏｌ）を精密に量り取り、１−オクテン（１．８ｍＬ，１１ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にトリエチルシラン（０．９２ｍＬ，５．７ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（４５μＬ，０．０７５ｍｍｏｌ）を添加した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液をガスクロマトグラフ質量分析によって分析した。反応生成物をクーゲルロール蒸留（１２０℃，１６０Ｐａ）により単離したところ、トリエチルオクチルシラン（変換率：１０％）の生成を確認した。結果を表１７に示す。(Example 125)
Perform flame drying, accurately weigh iron complex compound 6 (3.0 mg, 0.0056 mmol) into a Schlenk tube into which nitrogen gas has flowed, add 1-octene (1.8 mL, 11 mmol), and start stirring at room temperature. did. Triethylsilane (0.92 mL, 5.7 mmol) was added to the slurry solution, and then 1 M sodium triethylborohydride in toluene (45 μL, 0.075 mmol) was added. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and after 24 hours, the reaction solution was analyzed by gas chromatography mass spectrometry. When the reaction product was isolated by Kugelrohr distillation (120 ° C., 160 Pa), production of triethyloctylsilane (conversion rate: 10%) was confirmed. The results are shown in Table 17.
（実施例１２６）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物６（２０ｍｇ，０．０３８ｍｍｏｌ）を精密に量り取り、６−クロロ−１−ヘキセン（１．０ｍＬ，７．５ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（０．７２ｍＬ，３．８ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（１５０μＬ，０．１５ｍｍｏｌ）を添加した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液をガスクロマトグラフ質量分析によって分析した。反応生成物をクーゲルロール蒸留（１９０℃，１５０Ｐａ）により単離したところ、１−クロロ−（６−ジフェニルシリル）ヘキサン（変換率：８１％）の生成を確認した。結果を表１７に示す。(Example 126)
Flame drying was performed, and iron complex compound 6 (20 mg, 0.038 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, and 6-chloro-1-hexene (1.0 mL, 7.5 mmol) was added to room temperature. And stirring was started. Diphenylsilane (0.72 mL, 3.8 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (150 μL, 0.15 mmol) was added. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and after 24 hours, the reaction solution was analyzed by gas chromatography mass spectrometry. When the reaction product was isolated by Kugelrohr distillation (190 ° C., 150 Pa), production of 1-chloro- (6-diphenylsilyl) hexane (conversion rate: 81%) was confirmed. The results are shown in Table 17.
（実施例１２７）
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物６（３．０ｍｇ，０．００５６ｍｍｏｌ）を精密に量り取り、６−クロロ−１−ヘキセン（１．６ｍＬ，１１ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（１．１ｍＬ，５．７ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（４５μＬ，０．０４５ｍｍｏｌ）を添加した。２分以内に反応溶液は、無色から深緑〜赤紫色への変化を伴って均一溶液となった（目視にて鉄錯体化合物の溶け残りが確認された場合には、水素化トリエチルホウ素ナトリウムを追加して完全に溶解させる。）。この状態を反応開始とし、２４時間後に反応溶液をガスクロマトグラフ質量分析によって分析した。反応生成物をクーゲルロール蒸留（１９０℃，１５０Ｐａ）により単離したところ、１−クロロ−（６−ジフェニルシリル）ヘキサン（変換率：６７％）の生成を確認した。結果を表１７に示す。(Example 127)
Flame drying was performed, and iron complex compound 6 (3.0 mg, 0.0056 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, and 6-chloro-1-hexene (1.6 mL, 11 mmol) was added to room temperature. And stirring was started. Diphenylsilane (1.1 mL, 5.7 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (45 μL, 0.045 mmol) was added. Within 2 minutes, the reaction solution became a homogeneous solution with a change from colorless to deep green to reddish purple (when the undissolved iron complex compound was visually confirmed, sodium triethylborohydride was added. And dissolve completely.) This state was set as the start of reaction, and after 24 hours, the reaction solution was analyzed by gas chromatography mass spectrometry. When the reaction product was isolated by Kugelrohr distillation (190 ° C., 150 Pa), production of 1-chloro- (6-diphenylsilyl) hexane (conversion rate: 67%) was confirmed. The results are shown in Table 17.
（実施例１２８）
６−クロロ−１−ヘキセンをＮ，Ｎ−ジメチルアリルアミンに変更した以外、実施例４６と同様の方法により反応を行った。結果を表１７に示す。(Example 128)
The reaction was performed in the same manner as in Example 46 except that 6-chloro-1-hexene was changed to N, N-dimethylallylamine. The results are shown in Table 17.
（実施例１２９）
６−クロロ−１−ヘキセンをＮ，Ｎ−ジメチルアリルアミンに変更した以外、実施例１２７と同様の方法により反応を行った。結果を表１７に示す。(Example 129)
The reaction was conducted in the same manner as in Example 127 except that 6-chloro-1-hexene was changed to N, N-dimethylallylamine. The results are shown in Table 17.
（実施例１３０）
６−クロロ−１−ヘキセンをアリルフェニルスルフィドに変更した以外、実施例１２６と同様の方法により反応を行った。結果を表１７に示す。(Example 130)
The reaction was conducted in the same manner as in Example 126 except that 6-chloro-1-hexene was changed to allyl phenyl sulfide. The results are shown in Table 17.
（実施例１３１）
上記実施例では、鉄錯体触媒量を０．０１モル％以上使用しているが、さらに触媒量を０．００１モル％まで減らした場合の検討を行った。実施例８６、８８、９４を参考に以下のヒドロシリル化反応を行った。
フレームドライを行い、窒素ガスを流入したシュレンク管に鉄錯体化合物６（０．００５８ｍｍｏｌ）を精密に量り取り、１−オクテン（１２０ｍｍｏｌ）を加え室温にて撹拌を開始した。このスラリー溶液にジフェニルシラン（５８ｍｍｏｌ）を加えた後、１Ｍ水素化トリエチルホウ素ナトリウムのトルエン溶液（０．１２ｍｍｏｌ）を添加した。この溶液を室温で５〜１０分間撹拌し、得られた均一溶液の約十分の一液量を、別途調製したジフェニルシランと１−オクテンが１：２モル比で含む溶液に滴下し、鉄錯体がジフェニルシランの０．００１モル％となるように調整した。この溶液を２４時間室温で撹拌し、反応溶液を高速液体クロマトグラフィー（１９９ｎｍ）によって分析した。絶対検量線法により反応生成物を定量したところ、ヒドロシリル化生成物としてオクチルジフェニルシランのみが生成しており、触媒活性（ＴＯＮ）は４２０００であることを確認した。(Example 131)
In the above examples, the amount of the iron complex catalyst is 0.01% by mole or more, but examination was performed when the amount of the catalyst was further reduced to 0.001% by mole. The following hydrosilylation reaction was carried out with reference to Examples 86, 88 and 94.
Flame drying was performed, and iron complex compound 6 (0.0058 mmol) was accurately weighed into a Schlenk tube into which nitrogen gas was introduced, and 1-octene (120 mmol) was added, and stirring was started at room temperature. Diphenylsilane (58 mmol) was added to the slurry solution, and then a 1 M sodium triethylborohydride toluene solution (0.12 mmol) was added. This solution was stirred at room temperature for 5 to 10 minutes, and about one-tenth amount of the obtained uniform solution was dropped into a separately prepared solution containing diphenylsilane and 1-octene in a molar ratio of 1: 2 to obtain an iron complex. Was adjusted to 0.001 mol% of diphenylsilane. The solution was stirred for 24 hours at room temperature, and the reaction solution was analyzed by high performance liquid chromatography (199 nm). When the reaction product was quantified by the absolute calibration curve method, it was confirmed that only octyldiphenylsilane was produced as the hydrosilylation product and the catalytic activity (TON) was 42,000.
本発明によって得られた有機ケイ素化合物は、様々な材料の原料として使用することができる。 The organosilicon compound obtained by the present invention can be used as a raw material for various materials.
Claims (4)
前記反応工程が、触媒として下記式（Ａ）で表される鉄錯体化合物とヒドリド還元剤を使用する工程であることを特徴とする、有機ケイ素化合物の製造方法。
（式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、Ｘはそれぞれ独立してハロゲン原子を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）A process for producing an organosilicon compound comprising a reaction step of reacting an alkene and / or alkyne with hydrosilane in the presence of a catalyst,
The method for producing an organosilicon compound, wherein the reaction step is a step of using an iron complex compound represented by the following formula (A) and a hydride reducing agent as a catalyst.
(In Formula (A), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, X is independently a halogen atom, m is an integer of 0 to 4, and n is an integer of 0 to 3. However, when m is an integer of 2 to 4, the hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon group of R 2 They may be linked together to form an annular structure.)
（式（Ｉ−１）〜（Ｉ−９）及び式（ＩＩ−１）〜（ＩＩ−３０）中、Ｒ５〜Ｒ８はそれぞれ独立して水素原子、ハロゲン原子、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を、Ｒ９はそれぞれ独立して水素原子、ハロゲン原子、シロキシ基、ケイ素数１〜５０のポリシロキシ基、又は窒素原子、酸素原子、ケイ素原子、硫黄原子、及びハロゲン原子からなる群より選択される少なくとも１種を含んでいてもよい炭素数１〜２０の炭化水素基を表す。但し、Ｒ５〜Ｒ８の２個以上が炭化水素基である場合、その２個以上の炭化水素基が連結して環状構造を形成していてもよい。）A method for producing at least one compound selected from the group consisting of compounds represented by the following formulas (I-1) to (I-9) and (II-1) to (II-30): Item 2. A method for producing an organosilicon compound according to Item 1.
(In formulas (I-1) to (I-9) and formulas (II-1) to (II-30), R 5 to R 8 are each independently a hydrogen atom, a halogen atom, a nitrogen atom, or an oxygen atom. A hydrocarbon group having 1 to 20 carbon atoms which may contain at least one selected from the group consisting of a silicon atom, a sulfur atom, and a halogen atom, R 9 is independently a hydrogen atom, a halogen atom, 1 to 50 carbon atoms which may contain at least one selected from the group consisting of a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a nitrogen atom, oxygen atom, silicon atom, sulfur atom and halogen atom Represents a hydrocarbon group, provided that when two or more of R 5 to R 8 are hydrocarbon groups, the two or more hydrocarbon groups may be linked to form a cyclic structure.)
（式（ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）An iminobipyridine compound represented by the following formula (a).
(In formula (a), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, m is an integer of 0 to 4, and n is an integer of 0 to 3, provided that m is an integer of 2 to 4. The hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon groups of R 2 are linked to form a cyclic structure. May be.)
（式（Ａ）中、Ｒ１及びＲ２はそれぞれ独立して炭素数１〜６の炭化水素基を、Ｒ３は水素原子又はハロゲン原子を含んでいてもよい炭素数１〜１０の炭化水素基を、Ｒ４は水素原子又は炭素数６〜２０の芳香族炭化水素基を、Ｘはそれぞれ独立してハロゲン原子を、ｍは０〜４の整数を、ｎは０〜３の整数を表す。但し、ｍが２〜４の整数である場合、Ｒ１の炭化水素基同士が連結して環状構造を形成していてもよく、ｎが２又は３である場合、Ｒ２の炭化水素基同士が連結して環状構造を形成していてもよい。）An iron complex compound represented by the following formula (A).
(In Formula (A), R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon having 1 to 10 carbon atoms which may contain a hydrogen atom or a halogen atom. R 4 is a hydrogen atom or an aromatic hydrocarbon group having 6 to 20 carbon atoms, X is independently a halogen atom, m is an integer of 0 to 4, and n is an integer of 0 to 3. However, when m is an integer of 2 to 4, the hydrocarbon groups of R 1 may be linked to form a cyclic structure, and when n is 2 or 3, the hydrocarbon group of R 2 They may be linked together to form an annular structure.)
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