CN112174995B - 一种双硅化合物、其制备方法及应用 - Google Patents
一种双硅化合物、其制备方法及应用 Download PDFInfo
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- CN112174995B CN112174995B CN202011162343.XA CN202011162343A CN112174995B CN 112174995 B CN112174995 B CN 112174995B CN 202011162343 A CN202011162343 A CN 202011162343A CN 112174995 B CN112174995 B CN 112174995B
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- -1 disilicon compound Chemical class 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical class CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 192
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 140
- 239000011261 inert gas Substances 0.000 claims description 67
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 13
- 150000004759 cyclic silanes Chemical class 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical class CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical class CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- OTOSIXGMLYKKOW-UHFFFAOYSA-M 1,3-bis(2,4,6-trimethylphenyl)imidazol-1-ium;chloride Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N1C=[N+](C=2C(=CC(C)=CC=2C)C)C=C1 OTOSIXGMLYKKOW-UHFFFAOYSA-M 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical class CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- CONTYZSPSXHNNJ-LQFQNGICSA-N (4s)-2-[1,3-bis(4-tert-butylphenyl)-2-[(4s)-4-phenyl-4,5-dihydro-1,3-oxazol-2-yl]propan-2-yl]-4-phenyl-4,5-dihydro-1,3-oxazole Chemical compound C1=CC(C(C)(C)C)=CC=C1CC(C=1OC[C@@H](N=1)C=1C=CC=CC=1)(C=1OC[C@@H](N=1)C=1C=CC=CC=1)CC1=CC=C(C(C)(C)C)C=C1 CONTYZSPSXHNNJ-LQFQNGICSA-N 0.000 claims description 2
- CSGQGLBCAHGJDR-HUUCEWRRSA-N (4s)-4-propan-2-yl-2-[6-[(4s)-4-propan-2-yl-4,5-dihydro-1,3-oxazol-2-yl]pyridin-2-yl]-4,5-dihydro-1,3-oxazole Chemical compound CC(C)[C@H]1COC(C=2N=C(C=CC=2)C=2OC[C@@H](N=2)C(C)C)=N1 CSGQGLBCAHGJDR-HUUCEWRRSA-N 0.000 claims description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- AVJBQMXODCVJCJ-UHFFFAOYSA-M 1,3-bis[2,6-di(propan-2-yl)phenyl]imidazol-1-ium;chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N1C=[N+](C=2C(=CC=CC=2C(C)C)C(C)C)C=C1 AVJBQMXODCVJCJ-UHFFFAOYSA-M 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical class CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical class CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- KVRSDIJOUNNFMZ-UHFFFAOYSA-L nickel(2+);trifluoromethanesulfonate Chemical compound [Ni+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F KVRSDIJOUNNFMZ-UHFFFAOYSA-L 0.000 claims description 2
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].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 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Chemical class 0.000 claims description 2
- VXFKMKXTPXVEMU-AWSIMMLFSA-N 2-diphenylphosphanyl-n-[(1r,2r)-2-[(2-diphenylphosphanylnaphthalene-1-carbonyl)amino]cyclohexyl]naphthalene-1-carboxamide Chemical group N([C@@H]1CCCC[C@H]1NC(=O)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C(=O)C(C1=CC=CC=C1C=C1)=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VXFKMKXTPXVEMU-AWSIMMLFSA-N 0.000 claims 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical group C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims 1
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- 239000010703 silicon Substances 0.000 abstract description 13
- 230000002194 synthesizing effect Effects 0.000 abstract description 7
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- 238000003786 synthesis reaction Methods 0.000 abstract description 5
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- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 192
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- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 29
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
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- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
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- ASAFCFKPKAOABA-UHFFFAOYSA-N COC1=CC=CC([SiH2]C2=CC=CC=C2)=C1 Chemical compound COC1=CC=CC([SiH2]C2=CC=CC=C2)=C1 ASAFCFKPKAOABA-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- CQCWJADEODBVCY-UHFFFAOYSA-N FC1=CC=CC([SiH2]C2=CC=CC=C2)=C1 Chemical compound FC1=CC=CC([SiH2]C2=CC=CC=C2)=C1 CQCWJADEODBVCY-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
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- 101150003085 Pdcl gene Proteins 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
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- SKDKWDVYZOKBPL-UHFFFAOYSA-N benzyl(dimethyl)silicon Chemical compound C[Si](C)CC1=CC=CC=C1 SKDKWDVYZOKBPL-UHFFFAOYSA-N 0.000 description 1
- NGKXZNRQECNGAY-UHFFFAOYSA-N benzyl(hexyl)silane Chemical compound C(C1=CC=CC=C1)[SiH2]CCCCCC NGKXZNRQECNGAY-UHFFFAOYSA-N 0.000 description 1
- UWAXDPWQPGZNIO-UHFFFAOYSA-N benzylsilane Chemical compound [SiH3]CC1=CC=CC=C1 UWAXDPWQPGZNIO-UHFFFAOYSA-N 0.000 description 1
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- VTMOWGGHUAZESJ-UHFFFAOYSA-N chloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](Cl)C1=CC=CC=C1 VTMOWGGHUAZESJ-UHFFFAOYSA-N 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- GQJFBGVILWZQAP-UHFFFAOYSA-N cyclohexyl(hexyl)silane Chemical compound CCCCCC[SiH2]C1CCCCC1 GQJFBGVILWZQAP-UHFFFAOYSA-N 0.000 description 1
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- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 1
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- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- QWQHNJRBBBSHKA-UHFFFAOYSA-N diphenyl(2-phenylethyl)silane Chemical compound C1(=CC=CC=C1)CC[SiH](C1=CC=CC=C1)C1=CC=CC=C1 QWQHNJRBBBSHKA-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ORZPLLPBZHORSD-LWTKGLMZSA-K manganese(3+) (Z)-2,2,6,6-tetramethyl-5-oxohept-3-en-3-olate Chemical compound [Mn+3].CC(C)(C)C(\[O-])=C\C(=O)C(C)(C)C.CC(C)(C)C(\[O-])=C\C(=O)C(C)(C)C.CC(C)(C)C(\[O-])=C\C(=O)C(C)(C)C ORZPLLPBZHORSD-LWTKGLMZSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000011259 mixed solution Substances 0.000 description 1
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- QIJVDMJQEWBRJO-UHFFFAOYSA-N octyl(phenyl)silane Chemical compound C(CCCCCCC)[SiH2]C1=CC=CC=C1 QIJVDMJQEWBRJO-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- QLPHTVSPKZNVOH-UHFFFAOYSA-N phenyl(1-phenylpropyl)silane Chemical compound CCC([SiH2]C1=CC=CC=C1)C1=CC=CC=C1 QLPHTVSPKZNVOH-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 1
- HSYLTRBDKXZSGS-UHFFFAOYSA-N silver;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ag+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSYLTRBDKXZSGS-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-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
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Abstract
本发明涉及有机合成的技术领域，具体涉及一种双硅化合物、其制备方法及应用，双硅化合物的分子结构式如下：
其中，R1、R2为芳基或烷基，可以相同也可以不同；R3、R4、R5为芳基、烷基、氢原子中的任意一种，可以相同也可以不同，R3、R4、R5最多同时两个为氢原子,R6为芳基、烷基、杂原子、氢原子中的任意一种。本发明的制备方法实现了四元环硅和硅烷的开环复分解反应，是一种新的反应模式，为合成双硅化合提供一种简便高效的方法，特别是两个硅都含有硅氢的情况下可以用于合成聚合物，具有非常大的应用前景。
Description
技术领域
本发明涉及有机合成的技术领域，具体涉及一种双硅化合物、其制备方法及应用。
背景技术
有机硅化合物不仅作为航空、技术、军事技术部门的特种材料使用，而且也用于国民经济各部门，其应用范围已扩到：建筑、电子电气、纺织、汽车、机械、皮革造纸、化工轻工、金属和油漆、医药医疗等[a)Ojima,I.；Li,Z.；Zhu,J.The chemistry of organosiliconcompounds；Rappoport,S.,Apeloig,Y.,Eds.；Wiley:New York,1998.b)Langkopf,E.；Schinzer,D.Uses of silicon-containing compounds in the synthesis of naturalproducts.Chem.Rev.1995,95,1375-1408.]作为有机硅材料的单体，含有硅氢的有机硅小分子的合成和应用是非常重要的一个研究方向[a)M.Birot,J.-P.Pillot,J.Dunogus,Chem.Rev.1995,95,1443-1477.b)J.M.Buriak,Chem.Mater.2014,26,763-772.c)L.V.Interrante,Q.Shen in Silicon-Containing Polymers(Eds.:R.G.Jones,W.Ando,J.Chojnowski),Kluwer,Dordrecht,2000,pp.247-321.目前，合成具有双硅化合物的方法不多，且大多都是局限于合成对称双硅化合物，对于合成非对称的双硅化合物却鲜有报道。对称双硅单体结构简单，官能团几乎没有。为了拓展双硅化合物的种类及其应用，我们发展了一种一步合成非对称双硅化合物的方法。
发明内容
本发明的目的之一在于提供一种双硅化合物，为非对称双硅化合物。
本发明的目的之二在于提供一种双硅化合物的制备方法，制备工艺简便，易于调节。
本发明的目的之三在于提供一种双硅化合物的应用。
本发明实现目的之一所采用的方案是：一种双硅化合物，其分子结构式如下：
其中，R1、R2为芳基或烷基，可以相同也可以不同；R3、R4、R5为芳基、烷基、氢原子中的任意一种，可以相同也可以不同，R3、R4、R5最多同时两个为氢原子,R6为芳基、烷基、杂原子、氢原子中的任意一种。
优选地，所述芳基带有一个或者多个取代基；当具有多个取代基时，取代基可以相同或不同。所述取代基不以任何方式限定，常见的取代基例如芳基、杂环芳基、烷基、烷氧基等。所述芳香基上可带有这些取代基中的一种或多种，当具有多个取代基时，这多个取代基可以相同或不同。
优选地，所述烷基具有1-20个碳原子，为直链结构、环状结构或者支链结构。
优选地，所述烷基带有一个或多个取代基，当具有多个取代基时，取代基可以相同也可以不同，位置可以相同也可以不相同。
本发明实现目的之一所采用的方案是：一种所述的双硅化合物的制备方法，在惰性气体保护下，先将环状硅烷A、硅烷B、催化剂、配体一起溶于有机溶剂中，然后在-78℃到180℃下搅拌反应，反应后分离提纯，即得到双硅化合物；
所述环状硅烷A的分子结构式为
所述硅烷B的分子结构式为R3R4R5SiH。
优选地，所述催化剂为CuOTf，Pd(TFA)2，AgNTf2，Ni(COD)2，Ni(PPh3)4，NiCl2,NiBr2,Ni(PPh3)2Cl2，Ni(TMHD)2，Ni(NTf2)2，Ni(OTf)2，Ni(PCy3)2Cl2，[Rh(Cp*)Cl2]2，[Rh(COD)Cl]2，[Ir(Cp*)Cl2]2，Pd(t-Bu3P)2，(Ph3P)AuCl，Cu(CH3CN)4PF6，AgOTf，Pd(acac)2，Pd(dba)2，Sc(OTf)3，PdCl2(dippp)，Pd(PPh3)2Cl2，PdCl2,[PdCl(C3H5)]2,Cu(OTf)2,CuCl2CpCo(CO)I2,CoCl(Ph3P)3,Mn(TMHD)3,Mn(NTf)2,[Rh(Cp*)Cl2]2,Rh(COD)2BF4,Rh(COD)2OTf,Ru(PPh3)3Cl2中的任意一种。可用商品化试剂，无需特殊处理。
优选地，所述配体为三芳基膦、三烷基膦、二环己基(2',4',6'-三异丙基-[1,1'-二苯基]-2-基)膦、二环己基(2',4',6'-三异丙基-3,6-二甲氧基-[1,1'-二苯基]-2-基)膦)、二环己基(2',6'-二甲氧基-[1,1'-二苯基]-2-基)膦、2'-(二环己基膦基)-N,N-二甲基-[1,1'-二苯基]-2-胺、二环己基(2',6'-二异丙氧基-[1,1'-二苯基]-2-基)膦、三(呋喃-2-基)膦、(3S,5S,7S)-金刚烷-1-基((1R,5S)-金刚烷-2-基)(丁基)膦、(-)-2,2'-双[(4S)-4-苯基-2-噁唑啉-2-亚基]丙烷、(4S,4'S)-2,2'-[1,3-双(4-叔丁基苯基)丙烷-2,2-二基]双(4-苯基-4,5-二氢噁唑)、2,6-双[(4S)-(-)-异丙基-2-噁唑啉-2-基]吡啶、(1R,2R)-(+)-1,2-二氨基环己烷-N,N'-双(2-二苯基膦-1-萘酰基)、1,3-双(2,6-二异丙基苯基)氯化咪唑鎓、(1R,2R)-(+)-1,2-二胺基环己基-N,N'-双(2'-二苯基膦基苯甲酰)、1,3-双(2,4,6-三甲基苯基)氯化咪唑、1,3-双(2,4,6-三甲苯基)氯化咪唑鎓中的任意一种。可用商品化试剂，无需特殊处理。
本发明的制备方法所涉及的反应使用的催化剂和膦配体，相比于之前的反应使用的催化剂或者络合物等是一个重要的改进。
优选地，所述有机溶剂为甲醇、乙醇、异丙醇、叔丁醇、四氢呋喃、2-甲基四氢呋喃、***、二甲基乙二醚、甲基叔丁基醚、1,4-环氧六烷、1,3-环氧六烷、二氯甲烷、1,2-二氯乙烷、氯仿、四氯化碳、C4-12的饱和烷烃、C3-12的氟代或者氯代烷烃、苯、甲苯、二甲苯、三甲苯、二甲亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、丙酮、N-甲基吡咯烷酮、乙腈、C3-12的饱和烷基腈中的至少一种。
优选地，所述反应的温度为-78℃到180℃。上述反应时间在3-12小时以内，反应温度为-78-180℃。加热过程可采用油浴(例如硅油、石蜡油等)或者其它加热方式。本发明在反应完成后对反应产物进行后处理，包括抽滤、浓缩、重结晶和柱层析等纯化方法。
所述抽滤过程可使用砂芯漏斗在减压的条件下过滤。
所述浓缩过程可采用常压蒸馏、减压蒸馏等方法，例如用旋转蒸发仪真空浓缩。
所述纯化过程是通过柱层析得到纯净的产物。
优选地，环状硅烷A和硅烷B之间的摩尔比例为1:1-5；催化剂的用量为环状硅烷A的摩尔量的1％-20％，配体的用量为环状硅烷A的摩尔量的2％-40％之间，溶剂中环状硅烷A的浓度在0.1M到1M之间。
本发明实现目的之一所采用的方案是：所述的双硅化合物在合成环状联双硅化合物及制备有机硅材料中的应用。
本发明方法的反应式可表示如下：
其中，式A化合物代表四元环硅，式B化合物代表各类硅烷化合物，式G代表双硅化合物。
本发明具有以下优点和有益效果：
(1)本发明的制备方法实现了四元环硅和硅烷的开环复分解反应，是一种新的反应模式，为合成双硅化合提供一种简便高效的方法，特别是两个硅都含有硅氢的情况下可以用于合成聚合物，具有非常大的应用前景。
(2)本发明的制备方法不需要用碱来促进，也不需要其他添加剂，反应条件简单。
(3)本发明的制备方法所涉及的反应条件具有良好的官能团容忍性和底物普适性，取代基可以为烷基、烷氧基、酯基等、杂芳环、氟原子，各种直链或者支链的烷基也可以完成反应。
(4)本发明的双硅化合物可用于合成环状联双硅化合物，或者作为制备有机硅材料中的单体。
具体实施方式
为更好的理解本发明，下面的实施例是对本发明的进一步说明，但本发明的内容不仅仅局限于下面的实施例。
实施例1：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％)，干燥的甲苯(0.25mL),A(29.6mg,0.2mmol)，二苯基硅烷B(73.6mg,0.4mmol,2equiv.)。封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体60mg，产率90％)。1H NMR(400MHz,CDCl3,25℃)δ7.57–7.56(m,2H),7.56–7.54(m,2H),7.46–7.41(m,2H),7.40–7.35(m,4H),7.35–7.29(m,2H),7.15–7.10(m,1H),7.07(td,J＝7.4,1.1Hz,1H),5.64(s,1H),3.92–3.86(m,1H),2.33(d,J＝3.4Hz,2H),0.02(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ147.4,137.3,136.1,133.7,130.8,130.2,129.8,128.7,128.2,124.0,25.1,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-10.7,-21.7.IR(ATR):ν3049,3000,2959,2117,1427,1248,1110,879,798,727,693.
实施例3：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(间氟苯基)硅烷B(80.8mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G3(无色油状液体63mg，产率90％).1H NMR(400MHz,CDCl3,25℃)δ7.56–7.51(m,2H),7.47–7.42(m,1H),7.41–7.27(m,6H),7.24–7.20(m,1H),7.15–7.05(m,3H),5.63(s,1H),3.95–3.83(m,1H),2.31(d,J＝3.4Hz,2H),0.02(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ162.79(d,J＝248.6Hz),147.5,137.3,136.9(d,J＝4.4Hz),136.0,132.9,131.7(d,J＝3.2Hz),130.5,130.1,130.0,129.9(d,J＝7.0Hz),128.8,128.3,124.1,122.3(d,J＝19.0Hz),116.9(d,J＝21.1Hz),25.1,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-10.6,-21.8.IR(ATR):ν3052,3000,2959,2926,2124,1572,1408,1215,1107,879,783,730,689.
实施例4：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(联苯基)硅烷(104mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G6(无色油状液体60mg，产率74％).1H NMR(400MHz,CDCl3,25℃)δ7.66–7.56(m,8H),7.50–7.30(m,8H),7.18–7.02(m,2H),5.68(s,1H),4.10–3.59(m,1H),2.36(d,J＝3.4Hz,2H),0.03(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃).δ147.5,142.5,141.1,137.4,136.6,136.1,133.7,132.4,130.8,130.3,129.9,128.9,128.7,128.2,127.7,127.3,126.9,124.1,25.1,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-10.6,-21.7.IR(ATR):ν3053,3023,2959,2124,1252,1110,887,801,756,701.
实施例5：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(联苯基)硅烷(96mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G7(无色油状液体44mg，产率57％).1H NMR(400MHz,CDCl3,25℃)δ7.99-7.93(m,1H),7.79-7.74(m,1H),7.62-7.57(m，2H)，7.52(s，1H)，7.48 7.28(m，7H)，7.19 7.13(m，1H)，7.06(td，J＝7.4,1.1Hz,1H),5.87(s,1H),3.96 3.90(m,1H),2.37(dd,J＝3.4,1.4Hz,2H),0.04(dd,J＝3.7,1.4Hz,6H).13CNMR(101MHz,CDCl3,25℃)δ147.5,143.7,141.7,138.3,137.3,136.0,132.9,130.6,130.5,130.1,129.9,128.8,128.3,124.9,124.4,124.2,122.6,25.1,4.1,-4.2.29Si NMR(79 MHz,CDCl3,25℃)δ-10.5，-30.8.IR(ATR):ν3052,3000,2959,2124,1252,1110,965,887,812,752,726.
实施例6：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(3-甲基，4-氟苯基)硅烷(86.4mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G12(无色油状液体61mg，产率84％).1H NMR(400 MHz,CDCl3,25℃)δ7.52 7.49(m,2H),7.47–7.30(m,4H),7.24 7.17(m,2H),7.14(d,J＝7.7Hz,1H),7.06(td,J＝7.4,1.1Hz,1H),6.96(dd,J＝10.5,2.4Hz,1H),6.84(td,J＝8.5,2.6Hz,1H),5.70(s,1H),4.04–3.62(m,1H),2.37(s,3H),2.28(d,J＝3.4Hz,2H),0.03(t,J＝3.6Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ164.6(d,J＝248.8Hz),147.8(d,J＝7.6Hz),147.5,139.0(d,J＝8.1Hz),137.2,136.1,133.3,130.4,130.3,129.9,128.7,128.3,128.1(d,J＝3.3Hz),124.2,116.9(d,J＝19.8Hz),112.3(d,J＝19.4Hz),25.1,22.8(d,J＝2.1Hz),4.1,4.2.29Si NMR(79 MHz,CDCl3,25℃)δ10.7,25.3.IR(ATR):ν2959,2926,2124,1580,1479,1226,950,887,827,734,700.
实施例7：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(对叔丁基苯基)硅烷(96mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G14(无色油状液体72mg，产率92％).1H NMR(400MHz,CDCl3,25℃)δ7.59–7.55(m,2H),7.52–7.46(m,2H),7.43–7.29(m,7H),7.15–7.01(m,2H),5.62(s,1H),3.94–3.83(m,1H),2.34(d,J＝3.4Hz,2H),1.34(s,9H),0.00(dd,J＝3.7,1.3Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ152.9,147.4,137.4,136.1,136.0,134.0,131.2,130.1,129.9,129.7,128.6,128.1,125.2,123.9,34.9,31.4,25.0,-4.2.29SiNMR(79MHz,CDCl3,25℃)δ-10.7,-22.0.δIR(ATR):ν3049,2959,2903,2124,1267,1110,887,797,730。
实施例8：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基正辛基硅烷(88mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G15(无色油状液体63mg，产率86％).1H NMR(400MHz,CDCl3,25℃)δ7.55–7.51(m,2H),7.46(dd,J＝7.3,1.3Hz,1H),7.38–7.32(m,3H),7.29(td,J＝7.5,1.5Hz,1H),7.13–7.05(m,2H),4.99(t,J＝3.8Hz,1H),3.92–3.86(m,1H),2.30(t,J＝3.2Hz,2H),1.51–1.42(m,2H),1.41–1.34(m,2H),1.33–1.21(m,8H),1.19–1.12(m,2H),0.93–0.83(m,3H),0.02(dd,J＝5.5,3.6Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ147.0,136.2,135.5,135.3,132.1,129.8,129.4,128.6,128.0,123.9,33.4,32.0,29.3,29.3,24.8,24.8,22.8,14.3,12.5,-4.2,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-10.7,-17.6.IR(ATR):ν2955,2922,2855,2117,1248,1155,1110,883,805,726,697.
实施例9：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(1-五氟苯基乙基)硅烷(120mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G16(无色油状液体67.5mg，产率75％).1H NMR(400MHz,CDCl3,25℃)δ7.57–7.52(m,2H),7.46(dd,J＝7.4,1.4Hz,1H),7.43–7.29(m,4H),7.15–7.06(m,2H),5.07(t,J＝3.8Hz,1H),3.91–3.84(m,1H),2.88–2.80(m,2H),2.31(d,J＝3.5Hz,2H),1.53–1.46(m,2H),0.02(dd,J＝5.0,3.6Hz,6H).29Si NMR(79MHz,CDCl3,25℃)δ-10.6,-18.4..IR(ATR):ν3056,2959,2124,1502,1155,1118,987,954,887,834,730.
实施例10：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),联苯基正己基硅烷(107.2mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G18(无色油状液体70mg，产率84％).1H NMR(400MHz,CDCl3,25℃)δ7.70–7.58(m,6H),7.54(dd,J＝7.3,1.6Hz,1H),7.50–7.42(m,2H),7.41–7.30(m,2H),7.20–7.09(m,2H),5.08(t,J＝3.8Hz,1H),4.02–3.89(m,1H),2.46–2.27(m,2H),1.59–1.49(m,2H),1.49–1.38(m,2H),1.38–1.27(m,4H),1.27–1.18(m,2H),0.98–0.85(m,3H),0.08(dd,J＝5.0,3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ147.0,142.2,141.2,136.2,135.8,134.2,132.1,129.9,128.9,128.7,127.5,127.3,126.8,124.0,33.1,31.6,24.9,24.8,22.7,14.3,12.6,-4.1,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-10.6,-17.7.IR(ATR):ν2955,2922,2855,2121,2152,1110,887,827,756,697.
实施例11：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(1-苯基丙基)硅烷(90.4mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G21(无色油状液体64mg，产率85％).1H NMR(400MHz,CDCl3,25℃)δ7.54–7.49(m,2H),7.43(dd,J＝7.3,1.8Hz,1H),7.41–7.25(m,6H),7.22–7.13(m,3H),7.13–7.04(m,2H),5.02(t,J＝3.8Hz,1H),3.93–3.84(m,1H),2.70(t,J＝7.5Hz,2H),2.34–2.22(m,2H),1.87–1.74(m,2H),1.25–1.14(m,2H),0.02(dd,J＝5.6,3.6Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ147.0,142.4,136.1,135.3,135.1,131.7,129.9,129.5,128.7,128.6,128.4,128.1,125.8,123.9,39.4,26.7,24.8,12.2,-4.2,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-10.7,-17.7.IR(ATR):ν3049,2959,2903,2124,1267,1110,887,797,730.
实施例12：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(1-间三氟甲基苯基乙基)硅烷(112mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G22(无色油状液体72mg，产率84％).1H NMR(400MHz,CDCl3,25℃)δ7.56(dd,J＝7.8,1.7Hz,2H),7.50(dd,J＝7.5,1.5Hz,1H),7.47–7.29(m,8H),7.13(q,J＝7.5Hz,2H),5.06(t,J＝3.8Hz,1H),3.94–3.85(m,1H),2.87–2.81(m,2H),2.31(t,J＝3.1Hz,2H),1.58–1.50(m,2H),0.03(dd,J＝6.4,3.7Hz,6H).29Si NMR(79MHz,CDCl3,25℃)δ-10.6,-18.1.IR(ATR):ν3052，2959，2899，2124，1326，1162，1125，1073，887，801，730.
实施例13：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基(1-三甲基硅基丙基)硅烷(89mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G23(无色油状液体67mg，产率90％).1H NMR(400MHz,CDCl3,25℃)δ7.58–7.54(m,2H),7.49(dd,J＝7.5,1.6Hz,1H),7.42–7.28(m,4H),7.16–7.08(m,2H),5.03(t,J＝3.8Hz,1H),3.99–3.83(m,1H),2.33(t,J＝3.6Hz,2H),1.64–1.47(m,2H),1.35–1.18(m,2H),0.74–0.55(m,2H),0.05(dd,J＝5.2,3.6Hz,6H),-0.02(s,10H).13C NMR(101MHz,CDCl3,25℃)δ147.0,136.2,135.5,135.3,132.1,129.8,129.4,128.6,128.1,123.9,24.8,21.0,19.5,-1.4,-4.2,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ1.22,-10.8,-18.4.IR(ATR):ν2952，2914，2120，1248，1110，887，835，730，701.
实施例14：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),环己基正己基硅烷(79.2mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G24(无色油状液体54mg，产率77％).1H NMR(400MHz,CDCl3,25℃)δ7.38(dd,J＝7.6,1.5Hz,1H),7.27–7.21(m,1H),7.11–7.04(m,2H),4.28(q,J＝3.4Hz,1H),4.03–3.91(m,1H),2.43–2.25(m,2H),1.81–1.62(m,5H),1.38–1.18(m,14H),1.05–0.95(m,1H),0.89–0.85(m,4H),0.11(dd,J＝3.6,1.0Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ146.7,135.7,132.8,129.2,128.5,123.6,33.2,31.6,29.0,28.7,28.1,27.0,25.1,24.9,24.1,22.8,14.3,10.6,-4.1,-4.1.29Si NMR(79MHz,CDCl3,25℃)δ-9.9,-10.7.IR(ATR):ν2922,2847,2117,1446,1252,1103,887,838,745.
实施例15：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),三苯基硅烷(104mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G25(无色油状液体51mg，产率62％).1H NMR(400MHz,CDCl3,25℃)δ7.64–7.59(m,6H),7.45–7.34(m,10H),7.31–7.28(m,1H),7.21(dd,J＝7.5,0.9Hz,1H),7.07(td,J＝7.4,1.2Hz,1H),3.57–3.48(m,1H),2.14(d,J＝3.5Hz,2H),-0.28(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ148.1,138.6,136.6,135.1,131.9,130.2,129.5,129.0,128.0,124.1,25.7-4.0.29Si NMR(79MHz,CDCl3,25℃)δ-12.1,-14.2.IR(ATR):ν3049,2955,2922,2087,1584,1427,1248,1103,887,835,745,697.
实施例16:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基(苯乙基)硅烷(115.2mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G26(无色油状液体52mg，产率60％).1H NMR(400MHz,CDCl3,25℃)δ7.62–7.59(m,4H),7.54(dd,J＝7.5,1.2Hz,1H),7.45–7.32(m,7H),7.31–7.25(m,2H),7.21–7.12(m,5H),3.65–3.59(m,1H),2.79–2.61(m,2H),2.17(d,J＝3.6Hz,2H),1.82–1.71(m,2H),-0.23(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ147.7,145.2,137.2,135.8,135.7,132.4,129.9,129.5,129.0,128.5,128.1,127.9,125.8,124.1,30.5,25.2,17.1,-4.23.29Si NMR(79MHz,CDCl3,25℃)δ-10.9,-11.8.IR(ATR):ν3067,3026,2955,2117,1252,1107,887,723,697.
实施例17：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基(对氟苯乙基)硅烷(122.4mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G27(无色油状液体52mg，产率57％).1H NMR(400MHz,CDCl3,25℃)δ7.62–7.57(m,4H),7.53(dd,J＝7.4,1.5Hz,1H),7.47–7.31(m,7H),7.18–7.08(m,4H),6.98–6.90(m,2H),3.64–3.57(m,1H),2.77–2.60(m,2H),2.16(d,J＝3.6Hz,2H),1.78–1.66(m,2H),-0.23(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ161.2(d,J＝243.0Hz),147.7,140.7(d,J＝3.3Hz),137.2,135.8,135.6,132.2,130.0,129.5,129.2(d,J＝7.8Hz),129.1,128.2,124.2,115.1(d,J＝21.1Hz),29.7,25.2,17.3,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-11.0,-11.8.IR(ATR):ν3049,3008,2959,2117,1509,1427,1155,1107,887,820,700.
实施例18：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基(对叔丁基基苯乙基)硅烷(137.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G28(无色油状液体67mg，产率68％).1H NMR(400MHz,CDCl3,25℃)δ7.62–7.57(m,4H),7.53(dd,J＝7.2,1.4Hz,1H),7.44–7.28(m,9H),7.18–7.10(m,4H),3.66–3.57(m,1H),2.76–2.62(m,2H),2.16(d,J＝3.6Hz,2H),1.83–1.71(m,2H),1.32(s,9H),-0.23(d,J＝3.7Hz,6H).13CNMR(101MHz,CDCl3,25℃)δ148.6,147.7,142.1,137.3,135.8,135.8,132.5,129.9,129.5,129.0,128.1,127.5,125.4,124.1,34.5,31.6,29.8,25.1,16.8,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-11.3,-12.3.IR(ATR):ν3049，3011，2959，2117，1431，1252，1110，891，842，808，701.
实施例19:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苄基正己基硅烷(82.4mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G29(无色油状液体58mg，产率82％).1H NMR(400MHz,CDCl3,25℃)δ7.34(dd,J＝7.4,1.6Hz,1H),7.28–7.23(m,1H),7.21–7.16(m,2H),7.10–6.98(m,5H),4.52(p,J＝3.5Hz,1H),3.98–3.90(m,1H),2.45–2.32(m,2H),2.26(d,J＝3.4Hz,2H),1.36–1.16(m,8H),0.88–0.77(m,5H),0.08(d,J＝3.5Hz,6H).1H NMR(400MHz,CDCl3,25℃)δ7.34(dd,J＝7.4,1.6Hz,1H),7.28–7.23(m,1H),7.21–7.16(m,2H),7.10–6.98(m,5H),4.52(p,J＝3.5Hz,1H),3.98–3.90(m,1H),2.45–2.32(m,2H),2.26(d,J＝3.4Hz,2H),1.36–1.16(m,8H),0.88–0.77(m,5H),0.08(d,J＝3.5Hz,6H).13CNMR(101MHz,CDCl3,25℃)δ146.5,136.6,135.5,133.7,132.7,129.5,129.1,128.6,128.4,123.81,33.0,31.6,24.7(d,J＝5.7Hz),22.7,22.0,21.1,14.2,11.7,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-10.6,-13.5.IR(ATR):3049,2956,2922,2855,2117,1513,1465,1249,1200,1156,1103,958,883,746,712.
实施例20:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),对甲基苄基正己基硅烷(88mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G30(无色油状液体57mg，产率77％).1H NMR(400MHz,CDCl3,25℃)δ7.34(dd,J＝7.4,1.6Hz,1H),7.28–7.22(m,1H),7.10–6.97(m,4H),6.91(d,J＝8.1Hz,2H),4.55–4.42(m,1H),4.02–3.83(m,1H),2.41–2.31(m,2H),2.31–2.25(m,5H),1.35–1.13(m,8H),0.88-0.77(m,5H),0.08(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ146.5,136.6,135.5,133.7,132.7,129.5,129.1,128.6,128.4,123.8,33.0,31.6,24.7,24.6,22.7,22.0,21.1,14.2,11.7,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-10.6,-13.5.IR(ATR):ν3056,2956,2922,2855,2117,1599,1491,1249,1204,1156,1103,883,839,746,697.
实施例21:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基二甲基硅烷(60mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G31(无色油状液体40mg，产率70％).1H NMR(400MHz,CDCl3,25℃)δ7.52–7.44(m,3H),7.37–7.27(m,6H),7.09(dd,J＝17.4,7.3Hz,2H),3.91–3.59(m,1H),2.18(d,J＝3.6Hz,2H),0.58(s,6H),-0.07(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ146.8,139.5,136.0,135.1,134.3,129.6,129.1,128.7,128.0,123.9,24.7,-0.6,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-8.0,-11.2.IR(ATR):ν3049,2956,2117,1588,1469,1428,1249,1197,1156,1107,887,831,775,731,701.
实施例22:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苄基二甲基硅烷(63mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G32(无色油状液体45mg，产率76％).
1H NMR(600MHz,CDCl3,25℃)δ7.41(d,J＝7.4Hz,1H),7.30–7.26(m,1H),7.20(t,J＝7.7Hz,2H),7.14–7.06(m,3H),6.98(d,J＝6.8Hz,2H),4.05-3.99(m,1H),2.39(s,2H),2.33(d,J＝3.6Hz,2H),0.30(s,6H),0.14(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ146.3,140.1,135.6,135.4,129.3,128.8,128.5,128.3,124.2,123.9,26.9,24.8,-1.3,-4.0.29Si NMR(79MHz,CDCl3,25℃)δ-4.2,-11.4.IR(ATR):ν3056,2956,2117,1599,1491,1431,1249,1204,1156,1103,1059,883,831,746,701.
实施例23:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二乙基硅烷(34mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G33(无色油状液体39mg，产率82％).
1H NMR(600MHz,CDCl3,25℃)δ7.40(dd,J＝7.4,2.0Hz,1H),7.30–7.22(m,1H),7.12–7.03(m,2H),4.41–4.33(m,1H),4.01–3.88(m,1H),2.35(d,J＝3.5Hz,2H),1.06–0.97(m,6H),0.90–0.80(m,4H),0.11(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ146.6,135.4,133.1,129.3,128.5,123.8,24.7,8.6,3.9,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-9.4,-10.6.IR(ATR):ν3056,2956,2874,2117,1588,1465,1249,1156,1103,1010,973,883,835,746,712.
实施例24:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基甲基硅烷B(79.2mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G34(无色油状液体53mg，产率77％).
1H NMR(600MHz,CDCl3,25℃)δ7.56–7.52(m,4H),7.44–7.31(m,8H),7.16(d,J＝7.0,1.3Hz,1H),7.09(td,J＝7.4,1.2Hz,1H),3.78–3.71(m,1H),2.20(d,J＝3.6Hz,2H),0.91(s,3H),-0.11(d,J＝3.7Hz,6H).13C NMR(101MHz,CDCl3,25℃)δ147.4,137.5,137.1,135.4,133.3,129.9,129.4,128.8,128.0,124.0,25.2,-1.20,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-11.1,-12.0.IR(ATR):ν3049,2956,2922,2117,1588,1469,1428,1252,1197,1156,1107,887,842,790,719.
实施例25:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基甲基硅烷B(48.8mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G35(无色油状液体38mg，产率70％).
1H NMR(600MHz,CDCl3,25℃)δ7.55(d,J＝8.0Hz,2H),7.46(d,J＝7.4Hz,1H),7.42–7.35(m,3H),7.31(t,J＝7.6Hz,1H),7.16–7.07(m,2H),5.16–5.04(m,1H),4.00–3.85(m,1H),2.40–2.27(m,2H),0.69–0.60(m,3H),0.07–0.03(m,6H).13C NMR(151MHz,CDCl3,25℃)δ146.9,136.1,136.0,135.0,132.7,129.9,129.5,128.6,128.1,124.0,77.2,24.8,-4.2,-4.2.29Si NMR(79MHz,CDCl3,25℃)δ-11.2,-21.8.IR(ATR):ν3049,2960,2117,1588,1513,1469,1428,1249,1197,1156,1111,1021,887,835,701.
实施例26:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(54.4mg,0.2mmol),苯丙氨酸硅烷衍生物B(182mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G36(无色油状液体86mg，产率59％).
1H NMR(600MHz,CDCl3,25℃)δ7.45(d,J＝6.5Hz,2H),7.43–7.39(m,5H),7.39–7.34(m,3H),7.33–7.28(m,6H),7.27–7.23(m,2H),7.21–7.06(m,5H),6.92(d,J＝7.7Hz,1H),4.97(d,J＝8.3Hz,1H),4.93(t,J＝3.8Hz,1H),4.85(t,J＝3.7Hz,1H),4.59–4.52(m,1H),4.09–3.99(m,2H),3.14–2.99(m,2H),2.86–2.73(m,2H),1.55–1.48(m,2H),1.41(s,9H),1.35–1.16(m,6H),1.11–0.97(m,2H).13C NMR(151MHz,CDCl3,25℃)δ172.1,155.2,145.4,136.2,136.1,135.5,135.4,135.2,135.0,133.8,133.7,132.5,129.8,129.5,129.5,129.2,128.6,128.1,128.0,128.0,127.1,124.4,80.0,65.6,54.6,38.6,32.9,28.5,28.4,25.6,24.6,23.0,12.4.29Si NMR(119MHz,CDCl3,25℃)δ-13.7,-18.5.IR(ATR):ν3425,2922,2855,2125,1715,1495,1428,1249,1163,1111,1059,820,734,701.
实施例27:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(54.4mg,0.2mmol),苯基含氮烷基硅烷(182mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G37(无色油状液体95mg，产率83％).
1H NMR(600MHz,CDCl3,25℃)δ7.52–7.37(m,9H),7.37–7.32(m,5H),7.23–7.18(m,1H),7.15–7.08(m,3H),6.97(d,J＝7.7Hz,1H),6.86(d,J＝8.6Hz,2H),5.02(t,J＝3.8Hz,1H),4.91(t,J＝3.7Hz,1H),3.92–3.83(m,4H),3.18–3.06(m,4H),2.91–2.78(m,2H),2.72–2.57(m,2H),1.50–1.37(m,2H).13C NMR(151MHz,CDCl3,25℃)δ149.5,145.4,136.3,136.1,135.5,135.5,135.3,134.7,133.7,133.6,132.2,129.9,129.8,129.8,129.6,129.3,128.6,128.1,128.0,128.0,124.4,116.1,67.1,49.9,29.8,23.0,14.5.29Si NMR(119MHz,CDCl3,25℃)δ-13.7,-18.8.IR(ATR):ν3049,2922,2851,2125,1610,1513,1428,1379,1301,1234,1118,928,820,734,701.
实施例28:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基1,3,5-三甲基硅烷(90mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G38(无色油状液体54mg，产率72％).
1H NMR(600MHz,CDCl3,25℃)δ7.54–7.50(m,2H),7.42–7.38(m,1H),7.37–7.33(m,2H),7.32–7.28(m,2H),7.11(dd,J＝8.1,1.2Hz,1H),7.06–7.01(m,1H),6.87(s,1H),5.84(s,1H),3.95–3.81(m,1H),2.31(s,3H),2.26(t,J＝3.1Hz,2H),2.24(s,6H),0.05(d,J＝3.6Hz,3H),-0.00(d,J＝3.6Hz,3H).13C NMR(151MHz,CDCl3,25℃)δ147.5,145.7,139.9,137.1,136.0,134.3,131.7,129.9,129.5,129.0,128.4,128.1,127.3,124.1,24.8,24.6,21.4,-3.9,-4.1.29Si NMR(119MHz,CDCl3,25℃)δ-11.5,-32.5.IR(ATR):ν3049,2960,2922,2125,1603,1431,1249,1197,1156,1103,887,842,734,701.
实施例29:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),苯基间甲氧苯基硅烷(85.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G39(无色油状液体57mg，产率78％).
1H NMR(400MHz,CDCl3,25℃)δ7.59–7.52(m,2H),7.46–7.22(m,7H),7.14–7.00(m,2H),6.97–6.86(m,2H),5.63(s,1H),3.94–3.85(m,1H),3.68(s,3H),2.31(d,J＝2.8Hz,2H),0.01(dd,J＝3.7,1.6Hz,6H).13C NMR(151MHz,CDCl3,25℃)δ164.7,147.1,137.9,137.1,136.0,134.2,132.0,131.3,129.8,129.4,128.4,127.9,123.8,122.2,120.9,110.1,55.4,24.8,-4.2,-4.3.29Si NMR(119MHz,CDCl3,25℃)δ-11.3,-25.3.IR(ATR):ν3049,3001,2956,2121,1588,1461,1428,1241,1178,1111,1025,887,813,734.
实施例30:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A 2(54.4mg,0.2mmol),苯基含氮烷基硅烷(108mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G40(无色油状液体82mg，产率75％).
1H NMR(600MHz,CDCl3,25℃)δ7.48–7.44(m,4H),7.43–7.40(m,2H),7.39–7.32(m,9H),7.21–7.16(m,1H),7.06(t,J＝8.0Hz,1H),6.98(d,J＝7.7Hz,1H),6.73(d,J＝8.6Hz,4H),5.54(s,1H),4.94(t,J＝3.7Hz,1H),2.99(s,12H),2.89(d,J＝3.7Hz,2H).13C NMR(151MHz,CDCl3,25℃)δ151.3,145.6,137.3,137.2,135.6,134.1,133.6,129.6,129.5,128.9,127.9,124.19,119.0,112.1,40.3,22.9.29Si NMR(119MHz,CDCl3,25℃)δ-13.6,-23.5.IR(ATR):ν3068,2922,2851,2117,1595,1513,1428,1357,1226,1111,947,801,764,734.
实施例31:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A2(54.4mg,0.2mmol),二乙氧基甲基硅烷(64uL,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G41(无色油状液体60mg，产率74％).
1H NMR(400MHz,CDCl3,25℃)δ7.61(dd,J＝7.2,1.8Hz,1H),7.53–7.47(m,4H),7.42–7.30(m,6H),7.18–7.07(m,2H),6.89(d,J＝7.5Hz,1H),4.93(t,J＝3.7Hz,1H),3.84–3.68(m,4H),3.02(d,J＝3.7Hz,2H),1.19(t,J＝7.0Hz,6H),0.26(s,3H).13C NMR(101MHz,CDCl3,25℃)δ145.2,135.9,135.5,134.3,132.9,129.9,129.7,129.4,128.0,124.1,58.5,22.3,18.4,-2.9.29Si NMR(79MHz,CDCl3,25℃)δ-12.9,-16.1.
实施例32:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A2(54mg,0.2mmol),氨基酸硅烷衍生物(152mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G43(无色油状液体58mg，产率45％).1H NMR(600MHz,CDCl3,25℃)δ7.47–7.44(m,2H),7.44–7.34(m,8H),7.34–7.28(m,6H),7.19–7.14(m,1H),7.11–7.07(m,1H),6.95–6.90(m,1H),5.12–5.00(m,1H),4.94(t,J＝3.8Hz,1H),4.86(t,J＝3.7Hz,1H),4.35–4.23(m,1H),4.16–4.02(m,2H),2.88–2.72(m,2H),1.59(m,2H),1.45(s,9H),1.42–1.28(m,9H),1.12–1.00(m,2H).13C NMR(151MHz,CDCl3,25℃)δ173.6,155.2,145.4,136.1,135.5(d,J＝4.0Hz),135.2,135.0,133.8,133.7,132.6,129.8(d,J＝2.6Hz),129.5,129.2,128.1,128.0(d,J＝2.3Hz),124.4,79.9,65.6,49.4,32.9,28.6,28.5,25.6,24.7,23.0,18.9,12.4.29Si NMR(119MHz,CDCl3,25℃)δ-13.7,-18.5.
实施例33:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A2(54mg,0.2mmol),氨基酸硅烷衍生物(162mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G44(无色油状液体80mg，产率59％).1H NMR(600MHz,CDCl3,25℃)δ7.47–7.43(m,2H),7.43–7.39(m,5H),7.40–7.34(m,3H),7.33–7.28(m,6H),7.19–7.14(m,1H),7.11–7.06(m,1H),6.92(d,J＝7.7Hz,1H),4.96–4.91(m,2H),4.85(t,J＝3.7Hz,1H),4.33–4.17(m,1H),4.16–4.01(m,2H),3.58–3.32(m,2H),2.85–2.74(m,2H),2.25–2.11(m,1H),1.98–1.79(m,3H),1.61–1.55(m,2H),1.45(s,3H),1.40(s,6H),1.39–1.25(m,6H),1.12–0.99(m,2H),0.92–0.85(m,1H).13C NMR(151MHz,DMSO-d6,80℃)δ173.1,153.5,145.4,136.2,135.3(d,J＝4.7Hz),135.2,134.9,133.8(d,J＝12.0Hz),132.7,130.2(d,J＝3.1Hz),130.0,129.9,129.3,128.5,128.4(d,J＝2.5Hz),124.7,79.2,64.7,59.2,46.7,32.2,30.7,29.4,28.5,25.3,24.5,23.5,22.7,12.1.29SiNMR(119MHz,CDCl3,25℃)δ-13.7,-18.5.IR(ATR):3414,3049,2922,2125,1744,1700,1428,1394,1260,1159,1115,1029,820,734,701.
实施例34:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A2(54mg,0.2mmol),氨基酸硅烷衍生物(176mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G45(无色油状液体86mg，产率60％).
实施例35:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A2(54mg,0.2mmol),二苯基一氯硅烷(78uL,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，用饱和碳酸氢钠水溶液淬灭反应，30ml二氯甲烷萃取三次。有机相收集后旋干柱层析，洗脱剂为石油醚与乙酸乙酯混合溶液(10:1)，得到G46(无色油状液体67mg，产率71％).1H NMR(600MHz,CDCl3,25℃)δ7.47(d,J＝6.5Hz,4H),7.42–7.37(m,4H),7.36–7.28(m,12H),7.26–7.21(m,2H),7.08–7.01(m,2H),4.87(t,J＝3.7Hz,1H),2.83(d,J＝3.7Hz,2H).13C NMR(101MHz,CDCl3,25℃)δ145.9,137.4,136.1,135.6,135.0,133.7,133.2,130.4,130.0,130.0,129.7,128.2,128.0,124.2,23.6.29SiNMR(79MHz,CDCl3,25℃)δ-10.5,-13.3.IR(ATR):3612,3049,2922,2128,1666,1588,1469,1428,1264,1156,1115,969,820,738,701.
实施例36:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A2(54mg,0.2mmol),三乙氧基硅烷(66mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚/乙酸乙酯(50:1)，得到G47(无色油状液体63mg，产率72％).1H NMR(600MHz,CDCl3,25℃)δ7.70(dd,J＝7.9,1.7Hz,1H),7.60–7.53(m,4H),7.43–7.38(m,2H),7.38–7.32(m,4H),7.18–7.14(m,1H),7.12–7.08(m,1H),6.89(d,J＝8.9Hz,1H),4.94(t,J＝3.7Hz,1H),3.87–3.79(m,6H),3.04(d,J＝3.7Hz,2H),1.22(t,J＝7.0Hz,9H).13C NMR(151MHz,CDCl3,25℃)δ145.9,136.8,135.5,134.4,130.3,129.7,129.4,129.3,128.0,124.0,58.7,22.6,18.3.29Si NMR(119MHz,CDCl3,25℃)δ-13.3,-56.4.IR(ATR):3049,2974,2922,2136,1588,1428,1390,1163,1077,958,846,731,701.
实施例37:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A2(54mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚/乙酸乙酯(100:1)，得到G48(无色油状液体81mg，产率89％).1H NMR(400MHz,CDCl3,25℃)δ7.48–7.36(m,12H),7.36–7.28(m,8H),7.25–7.16(m,2H),7.07–7.01(m,1H),6.97(d,J＝6.9Hz,1H),5.52(s,1H),4.87(t,J＝3.7Hz,1H),2.81(d,J＝3.7Hz,2H).13C NMR(101MHz,CDCl3,25℃)δ145.8,137.3,136.1,135.5,133.7,133.5,131.5,130.1,129.8,129.8,129.2,128.2,128.0,124.4,23.2.29SiNMR(79MHz,CDCl3,25℃)δ-13.2,-22.0.
实施例38:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A4(42mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G49(无色油状液体61mg，产率77％).1H NMR(600MHz,CDCl3,25℃)δ7.52–7.45(m,4H),7.43–7.38(m,4H),7.38–7.29(m,7H),7.27(d,J＝8.0Hz,2H),7.09–7.03(m,2H),5.57(s,1H),4.40–4.33(m,1H),2.62–2.42(m,2H),0.23(dd,J＝3.8,1.1Hz,3H).13C NMR(151MHz,CDCl3,25℃)δ146.6,137.3,136.1(d,J＝1.8Hz),135.8,134.6,133.6,131.1,130.2,129.8(d,J＝2.6Hz),129.6,128.9,128.2(d,J＝2.5Hz),127.9,124.2,24.5,-5.9.29Si NMR(79MHz,CDCl3,25℃)δ-11.9,-21.8.IR(ATR):3049,3001,2922,2125,1588,1469,1428,1252,1197,1156,1115,850,813,731,701.
实施例39:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A6(46mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G51(无色油状液体53mg，产率64％).1H NMR(600MHz,CDCl3,25℃)δ7.59–7.54(m,4H),7.47–7.43(m,2H),7.42–7.37(m,4H),7.37–7.32(m,2H),7.16–7.08(m,2H),5.64(s,1H),3.91–3.81(m,1H),2.46–2.28(m,2H),1.99–1.80(m,2H),0.82–0.66(m,2H),0.04(d,J＝3.8Hz,3H).13C NMR(151MHz,CDCl3,25℃).δ146.3,137.6,136.1,133.4(d,J＝4.5Hz),131.0,130.5,130.0,128.6,128.3,127.6(q,J＝276.7Hz)124.5,29.3(q,J＝30.0Hz),23.2,4.8,-6.3.29Si NMR(119MHz,CDCl3,25℃)δ-7.8,-21.9.IR(ATR):3049,3001,2930,2125,1588,1431,1364,1264,1208,1111,1066,913,805,731,701.
实施例40:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A7(33mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G52(无色油状液体53mg，产率76％).1H NMR(600MHz,CDCl3,25℃)δ7.58–7.52(m,4H),7.48–7.43(m,2H),7.42–7.37(m,4H),7.30–7.25(m,1H),6.88–6.83(m,1H),6.82–6.76(m,1H),5.62(s,1H),3.98–3.85(m,1H),2.34(d,J＝3.4Hz,2H),0.04(d,J＝3.6Hz,6H).13C NMR(151MHz,CDCl3,25℃)δ164.6(d,J＝248.7Hz),150.6(d,J＝7.6Hz),139.2(d,J＝8.2Hz),136.0,133.4,129.9,128.3,126.4(d,J＝3.2Hz),115.4(d,J＝20.1Hz),111.3(d,J＝19.7Hz),25.3,-4.3.29Si NMR(119MHz,CDCl3,25℃)δ-10.9,-22.4.IR(ATR):3068,2960,2125,1573,1476,1428,1275,1223,1156,1111,1055,962,887,798,734
实施例41:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A9(57mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G54(无色油状液体79.5mg，产率85％).1H NMR(600MHz,CDCl3,25℃)δ7.49–7.41(m,5H),7.41–7.28(m,10H),7.28–7.22(m,3H),7.20–7.12(m,3H),7.03(t,J＝7.4Hz,1H),6.96(d,J＝7.7Hz,1H),5.50(s,1H),4.96(t,J＝3.8Hz,1H),2.84(d,J＝3.8Hz,2H),2.18(s,3H).13C NMR(151MHz,CDCl3,25℃)δ146.0,144.6,137.3,136.2,136.1(d,J＝3.8Hz),135.4,134.0,133.5(d,J＝3.7Hz),132.6,131.5,130.2,130.1,129.8,129.8,129.6,129.3,128.1(d,J＝3.8Hz),127.9,125.2,124.4,22.9,22.8.29Si NMR(119MHz,CDCl3,25℃)δ-17.0,-22.5.
实施例42:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A10(45mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G55(无色油状液体72mg，产率88％).1H NMR(400MHz,CDCl3,25℃)δ7.53–7.45(m,4H),7.43–7.21(m,10H),7.17–7.11(m,2H),7.07–7.01(m,2H),5.59(s,1H),4.56–4.43(m,1H),2.64–2.44(m,2H),2.31(s,3H),0.23(d,J＝3.7Hz,3H).13C NMR(151MHz,CDCl3,25℃)δ146.8,144.0,137.3,136.1,135.2,134.7,133.6,133.6,131.1,130.2,129.8,129.7,129.0,128.2,125.2,124.2,24.3,22.7,-5.5.29Si NMR(119MHz,CDCl3,25℃)δ-15.6,-22.5.
实施例43:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A12(45mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G56(无色油状液体73mg，产率90％).1H NMR(600MHz,CDCl3,25℃)δ7.52–7.44(m,4H),7.42–7.36(m,2H),7.36–7.31(m,4H),7.30–7.23(m,4H),7.15–7.11(m,2H),7.08–7.01(m,2H),5.57(s,1H),4.44–4.18(m,1H),2.69–2.40(m,2H),2.34(s,3H),0.21(d,J＝3.7Hz,3H).
实施例44:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A13(50mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G57(无色油状液体64mg，产率74％).1H NMR(600MHz,CDCl3,25℃)δ7.50–7.44(m,4H),7.42–7.36(m,4H),7.36–7.31(m,5H),7.31–7.26(m,2H),7.26–7.20(m,2H),7.05–6.97(m,2H),5.56(s,1H),4.48–4.29(m,1H),2.50(d,J＝3.7Hz,2H),1.68–1.57(m,1H),0.86–0.82(m,6H),0.81–0.68(m,2H).
实施例45:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A14(50mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G59(无色油状液体74mg，产率85％).1H NMR(400MHz,CDCl3,25℃)δ7.56–7.51(m,4H),7.47–7.28(m,13H),7.11–7.05(m,2H),5.62(s,1H),4.42–4.28(m,1H),2.58(d,J＝3.7Hz,2H),1.37–1.20(m,4H),0.90–0.75(m,5H).
实施例46:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A15(50mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G60(无色油状液体73mg，产率89％).1H NMR(400MHz,CDCl3,25℃)δ7.58–7.53(m,4H),7.47–7.31(m,13H),7.14–7.08(m,2H),5.64(s,1H),4.41–4.26(m,1H),2.60(d,J＝3.5Hz,2H),1.01–0.94(m,3H),0.87–0.78(m,2H).
实施例47:
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A17(46mg,0.2mmol),二苯基硅烷(73mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G60(无色油状液体76mg，产率92％).1H NMR(600MHz,CDCl3,25℃)δ7.54–7.47(m,4H),7.46–7.41(m,2H),7.40–7.33(m,6H),7.32–7.27(m,2H),7.11–6.99(m,4H),5.55(s,1H),4.45–4.34(m,1H),2.70–2.29(m,2H),0.26(d,J＝3.8Hz,3H).13C NMR(151MHz,CDCl3,25℃)δ164.1(d,J＝248.6Hz),146.3,137.4,136.5(d,J＝7.5Hz),136.1,133.5,131.2(d,J＝3.8Hz),131.1,130.2,129.9(d,J＝1.9Hz),128.9,128.2(d,J＝1.9Hz),124.3,115.1(d,J＝19.7Hz),24.6,-5.6.29Si NMR(119MHz,CDCl3,25℃)δ-12.7,-22.4.
实施例48：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(PPh3)4(22mg,0.02mmol,10mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体43mg，产率65％)。
实施例49：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(TMHD)2(8.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体30mg，产率45％)。
实施例50：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(acac)2(5.12mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体30mg，产率45％)。
实施例51：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Pd(PPh3)4(11.5mg,0.02mmol,10mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体15mg，产率20％)。
实施例52：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(Cy)3P(11.2mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体33mg，产率50％)。
实施例53：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),PPh3(11mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体45mg，产率67％)。
实施例54：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),DPPF(22mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体10mg，产率15％)。
实施例55：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),DPPP(16mg,0.04mmol,20mol％),干燥的甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体8mg，产率12％)。
实施例56：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的THF(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体44mg，产率60％)。
实施例57：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的1,4-dioxane(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体30mg，产率45％)。
实施例58：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的均三甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体50mg，产率75％)。
实施例59：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％),干燥的均三甲苯(0.25mL),A(29.6mg,0.2mmol),二苯基硅烷(73.6mg,0.4mmol,2equiv.).封紧封管，然后在40℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体32mg，产率48％)。
实施例60：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％)，干燥的甲苯(0.25mL),A(29.6mg,0.2mmol)，二苯基硅烷B(73.6mg,0.4mmol,2equiv.)。封紧封管，然后在-78℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体5mg，产率8％)
实施例61：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％)，干燥的甲苯(0.25mL),A(29.6mg,0.2mmol)，二苯基硅烷B(73.6mg,0.4mmol,2equiv.)。封紧封管，然后在180℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体40mg，产率60％)。
实施例62：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％)，干燥的甲苯(0.25mL),A(29.6mg,0.2mmol)，二苯基硅烷B(73.6mg,0.4mmol,2equiv.)。封紧封管，然后在10℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体40mg，产率60％)。
实施例63：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％)，干燥的甲苯(0.25mL),A(29.6mg,0.2mmol)，二苯基硅烷B(73.6mg,0.4mmol,2equiv.)。封紧封管，然后在100℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体30mg，产率45％)
实施例64：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％)，干燥的甲苯(0.25mL),A(29.6mg,0.2mmol)，二苯基硅烷B(73.6mg,0.4mmol,2equiv.)。封紧封管，然后在10℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体30mg，产率45％)。
实施例65：
在惰性气体保护下，向干燥并装有磁力搅拌子的10.0mL反应管中加入Ni(COD)2(5.5mg,0.02mmol,10mol％),(p-MeC6H4)3P(12.2mg,0.04mmol,20mol％)，干燥的甲苯(0.25mL),A(29.6mg,0.2mmol)，二苯基硅烷B(73.6mg,0.4mmol,2equiv.)。封紧封管，然后在10℃下加热三个小时。然后冷却到室温，将反应液用硅藻土抽滤，30ml乙酸乙酯作为洗脱剂。滤液减压旋干后用硅胶柱纯化，洗脱剂为石油醚，得到G1(无色油状液体10mg，产率15％)。
合成双硅化合物的应用：
应用1：合成环状联双硅化合物
在惰性气体保护下，向干燥的并装有磁力搅拌子的10.0mL反应管中加入RhCl(PPh3)3(1.85mg,0.002mmol,2mol％),干燥的甲苯(0.5mL),双硅原料(33.2mg,0.1mmol),封紧封管，110℃下反应24h.反应结束后用石油醚作为洗脱剂经过柱层析分离得到联双硅产物(24mg,产率71％).1H NMR(600MHz,CDCl3,25℃)δ7.49(d,J＝7.8Hz,5H),7.41–7.29(m,8H),7.21–7.14(m,1H),2.36(s,2H),0.31(s,6H).13C NMR(151MHz,CDCl3,25℃)δ150.8,138.8,135.9,135.6,134.9,130.0,129.9,129.2,128.1,125.3,25.8,-3.6.29Si NMR(119MHz,CDCl3,25℃)δ-5.6,-18.0.
应用2：
在惰性气体保护下，向干燥的并装有磁力搅拌子的10.0mL反应管中加入B(C6F5)3(2.56mg,0.005mmol,1.5mol％),干燥的甲苯(0.5mL),双硅原料(105mg,0.32mmol),2,3-丁二酮(166mg,1.93mmol)封紧封管，室温下反应24h.反应结束后用石油醚作为洗脱剂经过柱层析分离得到双硅醚产物(100mg,产率90％)1H NMR(400MHz,CDCl3,25℃)δ7.70–7.58(m,4H),7.52–7.30(m,8H),7.24–7.12(m,2H),2.20(s,2H),0.31(s,6H).13C NMR(151MHz,CDCl3,25℃)δ145.9,135.4,135.1,133.8,130.4,130.3,130.2,128.0,124.5,25.9,0.1.29Si NMR(119MHz,CDCl3,25℃)δ12.7,-16.1.
以上所述是本发明的优选实施方式而已，当然不能以此来限定本发明之权利范围，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和变动，这些改进和变动也视为本发明的保护范围。
Claims (6)
1.一种双硅化合物的制备方法，其特征在于：在惰性气体保护下，先将环状硅烷A、硅烷B、催化剂、配体一起溶于有机溶剂中，然后在-78℃到180℃下搅拌反应，反应后分离提纯，即得到双硅化合物；
所述双硅化合物的分子结构式如下：
其中，R1、R2为芳基或烷基，可以相同也可以不同；R3、R4、R5为芳基、烷基、氢原子中的任意一种，可以相同也可以不同，R3、R4、R5最多同时两个为氢原子，R6为芳基、烷基、杂原子、氢原子中的任意一种；
所述环状硅烷A的分子结构式为
；
所述硅烷B的分子结构式为R3R4R5SiH；
所述催化剂为Ni(COD)2，Ni(PPh3)4，NiCl2, NiBr2, Ni(PPh3)2Cl2，Ni(TMHD)2，Ni(NTf2)2，Ni(OTf)2，Ni(PCy3)2Cl2中的任意一种；
所述配体为二环己基(2',4',6'-三异丙基-[1,1'-二苯基]-2-基)膦、二环己基(2',4',6'-三异丙基-3,6-二甲氧基-[1,1'-二苯基]-2-基)膦）、二环己基(2',6'-二甲氧基-[1,1'-二苯基]-2-基)膦、2'-(二环己基膦基)-N,N-二甲基-[1,1'-二苯基]-2-胺、二环己基(2',6'-二异丙氧基-[1,1'-二苯基]-2-基)膦、三(呋喃-2-基)膦、(3S,5S,7S)-金刚烷-1-基((1R,5S)-金刚烷-2-基)(丁基)膦、(-)-2,2'-双[(4S)-4-苯基-2-噁唑啉-2-亚基]丙烷、(4S,4'S)-2,2'-[1,3-双(4-叔丁基苯基)丙烷-2,2-二基]双(4-苯基-4,5-二氢噁唑)、2,6-双[(4S)-(-)-异丙基-2-噁唑啉-2-基]吡啶、(1R,2R)-(+)-1,2-二氨基环己烷-N,N'-双(2-二苯基膦-1-萘酰基)、1,3-双（2,6-二异丙基苯基）氯化咪唑鎓、(1R,2R)-(+)-1,2-二胺基环己基-N,N'-双(2'-二苯基膦基苯甲酰)、1,3-双(2,4,6-三甲基苯基)氯化咪唑、1,3-双( 2,4,6 -三甲苯基)氯化咪唑鎓中的任意一种。
2.根据权利要求1所述的双硅化合物的制备方法，其特征在于：所述有机溶剂为甲醇、乙醇、异丙醇、叔丁醇、四氢呋喃、2-甲基四氢呋喃、***、二甲基乙二醚、甲基叔丁基醚、1,4-环氧六烷、1,3-环氧六烷、二氯甲烷、1,2-二氯乙烷、C4-12的饱和烷烃、C3-12的氟代或者氯代烷烃、苯、甲苯、二甲苯、三甲苯、二甲亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、丙酮、N-甲基吡咯烷酮、乙腈、C3-12的饱和烷基腈中的至少一种。
3.根据权利要求1所述的双硅化合物的制备方法，其特征在于：环状硅烷A和硅烷B之间的摩尔比例为1:1-5；催化剂的用量为环状硅烷A的摩尔量的1%-20%，配体的用量为环状硅烷A的摩尔量的2%-40%之间，溶剂中环状硅烷A的浓度在0.1M到1M之间。
4.根据权利要求1所述的双硅化合物的制备方法，其特征在于：所述芳基带有一个或者多个取代基；当具有多个取代基时，取代基可以相同或不同。
5.根据权利要求1所述的双硅化合物的制备方法，其特征在于：所述烷基具有1-20个碳原子，为直链结构、环状结构或者支链结构。
6.根据权利要求1所述的双硅化合物的制备方法，其特征在于：所述烷基带有一个或多个取代基，当具有多个取代基时，取代基可以相同也可以不同，位置可以相同也可以不相同。
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