CN109021003A - A kind of vinyl silicon germanium stannane derivative preparation method - Google Patents
A kind of vinyl silicon germanium stannane derivative preparation method Download PDFInfo
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- CN109021003A CN109021003A CN201810736263.7A CN201810736263A CN109021003A CN 109021003 A CN109021003 A CN 109021003A CN 201810736263 A CN201810736263 A CN 201810736263A CN 109021003 A CN109021003 A CN 109021003A
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- Prior art keywords
- palladium
- preparation
- mentioned
- vinyl
- alkene
- Prior art date
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- -1 vinyl silicon germanium stannane derivative Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 239000012074 organic phase Substances 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical class CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000004440 column chromatography Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- 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 42
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 27
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 22
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 20
- 239000002585 base Substances 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical group 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical group 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 3
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical class COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- JHDCDEHVUADNKQ-UHFFFAOYSA-N 3-(trifluoromethyl)-1h-pyridin-2-one Chemical compound OC1=NC=CC=C1C(F)(F)F JHDCDEHVUADNKQ-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- TWKVUTXHANJYGH-UHFFFAOYSA-L allyl palladium chloride Chemical class Cl[Pd]CC=C.Cl[Pd]CC=C TWKVUTXHANJYGH-UHFFFAOYSA-L 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 229950011260 betanaphthol Drugs 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- MSBPSFSYBUUPMC-UHFFFAOYSA-N furan-2-ylphosphane Chemical class PC1=CC=CO1 MSBPSFSYBUUPMC-UHFFFAOYSA-N 0.000 claims description 3
- CTHCTLCNUREAJV-UHFFFAOYSA-N heptane-2,4,6-trione Chemical compound CC(=O)CC(=O)CC(C)=O CTHCTLCNUREAJV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- KASKWOMRRXLJGW-UHFFFAOYSA-N naphthalene phosphane Chemical class P.C1=CC=CC2=CC=CC=C12 KASKWOMRRXLJGW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 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 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003637 steroidlike Effects 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 claims 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 6
- 150000004756 silanes Chemical class 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 68
- 239000000758 substrate Substances 0.000 description 19
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 17
- 230000005311 nuclear magnetism Effects 0.000 description 17
- 239000003921 oil Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 238000001819 mass spectrum Methods 0.000 description 16
- 239000007832 Na2SO4 Substances 0.000 description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 12
- 229940094989 trimethylsilane Drugs 0.000 description 12
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 6
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229940017219 methyl propionate Drugs 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910000080 stannane Inorganic materials 0.000 description 2
- WLKSSWJSFRCZKL-UHFFFAOYSA-N trimethylgermanium Chemical compound C[Ge](C)C WLKSSWJSFRCZKL-UHFFFAOYSA-N 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- NJFRZBAZMPWJKQ-UHFFFAOYSA-N 2-iodo-3-methoxypyridine Chemical compound COC1=CC=CN=C1I NJFRZBAZMPWJKQ-UHFFFAOYSA-N 0.000 description 1
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 1
- ITSXFTQOJHEFBP-KHPPLWFESA-N CC(c1ccc(/C=C\[Si](C)(C)C)c([Si](C)(C)C)c1)=O Chemical compound CC(c1ccc(/C=C\[Si](C)(C)C)c([Si](C)(C)C)c1)=O ITSXFTQOJHEFBP-KHPPLWFESA-N 0.000 description 1
- 0 C[Si](C)(C)C1=CC=C(*)C(*)[C@]1C=C* Chemical compound C[Si](C)(C)C1=CC=C(*)C(*)[C@]1C=C* 0.000 description 1
- 238000003692 Hiyama coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- YQPYGWKBHDVUJE-UHFFFAOYSA-N iodobenzene methanol Chemical compound CO.IC1=CC=CC=C1 YQPYGWKBHDVUJE-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BCJOKHQYEDXBSF-UHFFFAOYSA-N n-(2-iodophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC=C1I BCJOKHQYEDXBSF-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical class [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- UKHQRARQNZOXRL-UHFFFAOYSA-N trimethyltin Chemical compound C[SnH](C)C UKHQRARQNZOXRL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
- 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
- C07F7/30—Germanium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
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Abstract
The invention discloses a kind of vinyl silicon germanium stannane derivative preparation method, include the following steps: that (1) sequentially adds alkali, palladium catalyst, ligand, alkene, halogenated aryl hydrocarbon, two silicon of hexamethyl (two germanium of hexamethyl or six dibutyltin dilaurates) and organic solvent into the reaction vessel purged through nitrogen, in 40~120 DEG C react 6~for 24 hours；(2) it by step (1) resulting material after ethyl acetate dilutes, then is washed, separates to obtain organic phase；(3) by step (2) resulting organic phase through drying, filtering, concentration and column chromatography chromatogram, obtain the vinyl silicon germanium stannane derivative.The present invention can obtain aryl Csp simultaneously2- Si key and vinyl Csp2The organic silane derivative of-Si key, and have good regioselectivity, can synthesize that other methods are difficult to obtain have vinyl silicon germanium stannane derivative.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of vinyl silicon germanium stannane derivative preparation side
Method.
Background technique
Aryl and vinyl silanes, germane, stannane derivative are the valuable synthetic intermediates in various organic reactions.
For example, aryl-silane and vinyl silanes are the important intermediates of Hiyama coupling reaction, and aryl stannane and vinyl stannane
It is the important intermediate of Stille coupling reaction.They similarly send out in fields such as material science, agriculture chemistry and pharmaceutical chemistry
Wave important function.For example, the synthesis in pharmaceuticals industry, to the silicon analog of known drug, it has also become one active to grind
Study carefully field.Therefore, exploitation is efficiently and novel C-Si key, C-Ge key and C-Sn key forming method are always synthesis chemical field
Research hotspot.
Summary of the invention
The purpose of the present invention is to provide a kind of vinyl silicon germanium stannane derivative preparation method.
Reaction equation of the invention is as follows:
Technical scheme is as follows:
A kind of vinyl silicon germanium stannane derivative preparation method, include the following steps:
(1) alkali, palladium catalyst, ligand, alkene, halogenated aryl hydrocarbon, preceding is sequentially added into the reaction vessel purged through nitrogen
Body compound and organic solvent, in 60~110 DEG C of 10~15h of reaction；Halogenated aryl hydrocarbon, precursor compound, alkene, palladium catalyst,
The molar ratio of ligand and alkali be 0.8~1.2: 1.2~1.6: 1.8~2.2: 0.08~0.12: 0.18~0.22: 1.8~
2.2, and the corresponding organic solvent of every moles of halogenated aromatic hydrocarbons is 1~3L；
Above-mentioned precursor compound is two silicon of hexamethyl, two germanium of hexamethyl or six dibutyltin dilaurates；
The structural formula of above-mentioned halogenated aryl hydrocarbon isWherein X is halogen, and R is hydrogen, alkyl, alkoxy, acyl group, ammonia
Base, three fluoroalkyls, aryl, substituted aryl, hydroxyl, methylol, halogen, heterocycle or steroidal；
The structural formula of above-mentioned alkene isWherein Z is C, O or N, R1For hydrogen, alkyl or aryl, R2For alkyl, virtue
Base, acyl group, carboxylic acid group, ester group, amide groups, sulfonyl or trifluoromethyl；
Above-mentioned palladium catalyst is palladium acetate, trifluoracetic acid palladium, palladium chloride, bi triphenyl phosphino- palladium chloride, double acetonitriles
Palladium chloride, palladium acetylacetonate, diacetyl acetone palladium, allyl palladium chloride dimer, tetra-triphenylphosphine palladium, [1,1 '-bis- (two
Phenylphosphine) ferrocene] palladium chloride or tris(dibenzylideneacetone) dipalladium；
Above-mentioned ligand be triphenylphosphine, three (2- furyl) phosphines, 2- dicyclohexyl phosphorus -2 ', 6 '-diisopropoxy -1,1 ' -
Biphenyl, three naphthalene phosphines, 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl, 2- dicyclohexyl phosphine -2 ', 6 '-dimethoxys connection
Bis- diphenylphosphine -9, the 9- xanthphos of benzene, tricyclohexyl phosphine, 4,5-, three (2- methoxyphenyl) phosphines, three (4- methoxyl groups
Phenyl) phosphine, pyridine, bipyridyl, 2- hydroxyl -3- trifluoromethyl pyridine, 1,1 '-dinaphthalene -2,2 '-bis- diphenyl phosphines, 1,1 '-bis- (two
Phenylphosphine) ferrocene or 1,1 '-union -2-naphthol；
Above-mentioned alkali is sodium hydroxide, potassium hydroxide, tert-butyl alcohol lithium, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, carbon
Sour sodium, potassium carbonate, potassium phosphate, potassium dihydrogen phosphate, cesium carbonate or 1,11 carbon -7- alkene of 8- diazabicylo；
Above-mentioned organic solvent is dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2- pyrrole
Pyrrolidone, 1,2- dichloroethanes, toluene, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran or glycol dimethyl ether；
(2) it by step (1) resulting material after ethyl acetate dilutes, then is washed, separates to obtain organic phase；
(3) by step (2) resulting organic phase through drying, filtering, concentration and column chromatography chromatogram, obtain described having vinyl
Silicon germanium stannane derivative.
In a preferred embodiment of the invention, the R is halogen, trifluoromethyl or methoxyl group.
It is further preferred that the halogen is fluorine, iodine, chlorine or bromine.
In a preferred embodiment of the invention, the palladium catalyst is palladium acetate, and the ligand is triphenylphosphine,
The alkali is cesium carbonate, and the organic solvent is n,N-Dimethylformamide.
In a preferred embodiment of the invention, the reaction temperature in the step (1) is 60~100 DEG C.
In a preferred embodiment of the invention, the reaction time in the step (1) is 12h.
In a preferred embodiment of the invention, the halogenated aryl hydrocarbon, precursor compound, alkene, palladium catalyst, match
The molar ratio of body and alkali is 1: 1.5: 2: 0.1: 0.2: 2, and the corresponding organic solvent of every moles of halogenated aromatic hydrocarbons is 1~2L.
The beneficial effects of the present invention are:
1, the present invention can obtain aryl Csp simultaneously2- Si key and vinyl Csp2The organic silane derivative of-Si key, and
And have good regioselectivity, can synthesize that other methods are difficult to obtain have vinyl silicon germanium stannane derivative；
2, method of the invention is raw materials used is easy to get, and high income, reaction condition is mild, and the reaction time is short, and substrate spectrum is wide,
It is strong to react specificity, post-processing is easy and green.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment.
Embodiment 1
The preparation of (cis-)-(2- (2- (trimethyl silicon substrate) Nai Ji) vinyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 1- iodine naphthalene 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL are added to
In the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, reaction solution is used
Ethyl acetate dilution is washed three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains 24.5mg mesh
Mark product, yield 82%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz, CDCl3)δ
8.15-8.11 (m, 1H), 7.79 (dd, J=7.3,2.0Hz, 1H), 7.74-7.68 (m, 2H), 7.58 (d, J=8.3Hz, 1H),
7.47-7.40 (m, 2H), 6.25 (d, J=15.4Hz, 1H), 0.35 (s, 9H), -0.41 (s, 9H)；13C NMR (126MHz,
CDCl3) δ 145.5,144.8,136.9,134.2,133.7,131.8,130.0,127.8,126.7,126.0,125.8,
125.4,0.4, -1.3；HRMS(EI)for C18H26Si2[M]+: calculated 298.1573, found 298.1570.
Embodiment 2
The preparation of (cis-)-(the fluoro- 2- of 3- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 2- fluorine iodobenzene 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL addition
Into the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, reaction solution
It is diluted, is washed three times, organic phase anhydrous Na with ethyl acetate2SO4It dries, filters, is concentrated, column chromatographic purifying obtains 13.8mg
Target product, yield 52%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz, CDCl3)δ
7.25-7.17 (m, 3H), 7.04-6.99 (m, 1H), 6.11 (d, J=15.4Hz, 1H), 0.28 (s, 9H), -0.13 (s, 9H)；13C NMR (126MHz, CDCl3) δ 159.0 (d, J=245.3Hz), 141.5,138.6,137.5 (d, J=2.3Hz), 133.3
(d, J=13.6Hz), 129.3 (d, J=3.6Hz), 127.9 (d, J=7.4Hz), 116.1 (d, J=23.8Hz), -0.1, -
1.0 (d, J=0.9Hz)；HRMS(EI)for C14H23FSi2[M]+: calculated 266.1322, found 266.1321.
Embodiment 3
The preparation of (cis-)-(the chloro- 2- of 3- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 2- chloroiodobenzone 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL addition
Into the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, reaction solution
It is diluted, is washed three times, organic phase anhydrous Na with ethyl acetate2SO4It dries, filters, is concentrated, column chromatographic purifying obtains 20.4mg
Target product, yield 73%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz, CDCl3)δ
7.38-7.34 (m, 2H), 7.27 (d, J=15.4Hz, 1H), 7.16 (t, J=7.6Hz, 1H), 6.08 (d, J=15.4Hz,
1H), 0.27 (s, 9H), -0.17 (s, 9H)；13C NMR (126MHz, CDCl3) δ 144.7,142.8,140.9,136.8,
132.9,132.1,129.9,127.5,0.2, -1.3；HRMS(EI)for C14H23ClSi2[M]+: calculated
282.1027 found 282.1032.
Embodiment 4
The preparation of (cis-)-(3- methoxyl group -2- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 2- methoxyl group iodobenzene 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL
It is added in the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, instead
It answers liquid to be diluted with ethyl acetate, washes three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains
21.4mg target product, yield 77%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz,
CDCl3) δ 7.27 (d, J=15.8Hz, 1H), 7.21 (t, J=7.8Hz, 1H), 7.08 (dd, J=7.3,0.8Hz, 1H), 6.87
(d, J=8.1Hz, 1H), 6.06 (d, J=15.3Hz, 1H), 0.27 (s, 9H), -0.18 (s, 9H)；13C NMR (126MHz,
CDCl3) δ 155.7,141.5,139.8,135.9,135.1,127.3,125.9,111.1,55.0,0.1, -1.2；HRMS(EI)
for C15H26OSi2[M]+: calculated 278.1522, found 278.1522.
Embodiment 5
The system of (cis-)-(3- methyl -4- carboxylic acid formicester -2- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
It is standby
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
The fluoro- 3- carboxylate methyl ester iodobenzene 0.1mmol of norbornadiene 0.2mmol, 2-, two silicon 0.15mmol, N, N- dimethyl methyl of hexamethyl
Amide 1mL is added in the reaction tube of 15mL, and nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to
Room temperature, reaction solution are diluted with ethyl acetate, are washed three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying
Obtain 19.2mg target product, yield 60%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR
(500MHz, CDCl3) δ 7.66 (d, J=7.7Hz, 1H), 7.41 (d, J=15.4Hz, 1H), 7.36 (d, J=7.8Hz, 1H),
6.03 (d, J=15.4Hz, 1H), 3.88 (s, 3H), 2.46 (s, 3H), 0.27 (s, 9H), -0.23 (s, 9H)；13C NMR
(126MHz, CDCl3) δ 168.9,147.9,145.8,142.8,135.6,135.4,131.2,130.9,127.5,51.9,
18.4,0.3, -1.1；HRMS (ESI-TOF) m/z:calcd for C17H28NaO2Si2 +: 343.1520 (M+Na)+, found:
243.1514.
Embodiment 6
The system of (cis-)-(3- methyl -5- carboxylic acid formicester -2- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
It is standby
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
The fluoro- 4- carboxylate methyl ester iodobenzene 0.1mmol of norbornadiene 0.2mmol, 2-, two silicon 0.15mmol, N, N- dimethyl methyl of hexamethyl
Amide 1mL is added in the reaction tube of 15mL, and nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to
Room temperature, reaction solution are diluted with ethyl acetate, are washed three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying
Obtain 22.4mg target product, yield 70%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR
(500MHz, CDCl3) δ 7.99 (d, J=1.6Hz, 1H), 7.83 (d, J=1.2Hz, 1H), 7.39 (d, J=15.7Hz, 1H),
6.01 (d, J=15.6Hz, 1H), 3.91 (s, 3H), 2.29 (s, 3H), 0.29 (s, 9H), -0.22 (s, 9H)；13C NMR
(126MHz, CDCl3) δ 167.5,151.4,145.3,138.5,135.1,135.0,132.5,131.5,127.6,51.9,
20.7,0.3, -1.1；HRMS (ESI-TOF) m/z:calcd for C17H28NaO2Si2 +: 343.1520 (M+Na)+, found:
343.1516.
Embodiment 7
The preparation of (cis-)-(4- methoxyl group -2- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 3- methoxyl group iodobenzene 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL
It is added in the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, instead
It answers liquid to be diluted with ethyl acetate, washes three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains
15.6mg target product, yield 56%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz,
CDCl3) δ 7.59 (d, J=14.9Hz, 1H), 7.39 (d, J=8.0Hz, 1H), 6.80-6.75 (m, 2H), 5.86 (d, J=
14.9Hz, 1H), 3.82 (s, 3H), 0.26 (s, 9H), -0.05 (s, 9H)；13C NMR (126MHz, CDCl3) δ 159.9,
148.5,148.4,135.3,133.2,128.9,114.7,111.7,55.1,0.02, -0.03；HRMS(EI)for
C15H26OSi2[M]+: calculated 278.1522, found 278.1527.
Embodiment 8
The preparation of (cis-)-(5- acetyl group -2- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 4- acetyl group iodobenzene 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL
It is added in the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, instead
It answers liquid to be diluted with ethyl acetate, washes three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains
11.0mg target product, yield 38%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz,
CDCl3) δ 8.08 (d, J=1.8Hz, 1H), 7.88 (dd, J=7.9,1.9Hz, 1H), 7.59 (d, J=15.1Hz, 1H), 7.28
(d, J=7.9Hz, 1H), 5.97 (d, J=15.1Hz, 1H), 2.61 (s, 3H), 0.33 (s, 9H), -0.07 (s, 9H)；13C NMR
(126MHz, CDCl3) δ 198.23 (s), 151.7,147.4,138.6,135.1,134.9,133.7,128.9,128.6,
26.6,0.01, -0.3；HRMS (ESI-TOF) m/z:calcd for C16H26NaOSi2 +: 313.1414 (M+Na)+, found:
313.1416.
Embodiment 9
The preparation of (cis-)-(3- acetylaminohydroxyphenylarsonic acid 2- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 2- acetylamino iodobenzene 0.1mmol, two silicon 0.15mmol of hexamethyl, n,N-Dimethylformamide
1mL is added in the reaction tube of 15mL, and nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature,
Reaction solution is diluted with ethyl acetate, is washed three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains
18.9mg target product, yield 62%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz,
CDCl3) δ 7.67 (dd, J=8.2,2.2Hz, 1H), 7.54 (d, J=14.8Hz, 1H), 7.40 (d, J=2.2Hz, 1H), 7.38
(s, 1H), 7.17 (d, J=8.2Hz, 1H), 5.83 (d, J=14.8Hz, 1H), 2.17 (s, 3H), 0.28 (s, 9H), -0.07
(s, 9H)；13C NMR (126MHz, CDCl3) δ 168.3,147.8,142.8,138.8,136.4,133.1,129.4,124.7,
119.7,24.6,0.1, -0.3；HRMS (ESI-TOF) m/z:calcd for C16H27NNaOSi2 +: 328.1523 (M+Na)+,
Found:328.1523.
Embodiment 10
The preparation of (cis-)-(5- methylol -2- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 4- iodobenzene methanol 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL add
Enter into the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, reacts
Liquid is diluted with ethyl acetate, is washed three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains
15.6mg target product, yield 56%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz,
CDCl3) δ 7.60 (d, J=14.9Hz, 1H), 7.45 (d, J=1.3Hz, 1H), 7.31 (dd, J=7.7,1.3Hz, 1H), 7.20
(d, J=7.7Hz, 1H), 5.87 (d, J=14.9Hz, 1H), 4.69 (s, 2H), 0.29 (s, 9H), -0.08 (s, 9H)；13C NMR
(126MHz, CDCl3) δ 148.2,146.4,138.7,138.2,133.4,132.6,128.9,127.3,65.5,0.1, -0.2；
HRMS (ESI-TOF) m/z:calcd for C15H26NaOSi2 +: 301.1414 (M+Na)+, found:301.1413.
Embodiment 11
The preparation of (cis-)-(2- (3- (trimethyl silicon substrate) thienyl) vinyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 2- iodothiophen 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL addition
Into the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, reaction solution
It is diluted, is washed three times, organic phase anhydrous Na with ethyl acetate2SO4It dries, filters, is concentrated, column chromatographic purifying obtains 9.2mg mesh
Mark product, yield 36%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz, CDCl3)δ7.46
(d, J=15.0Hz, 1H), 7.20 (d, J=5.0Hz, 1H), 7.05 (d, J=5.0Hz, 1H), 5.86 (d, J=15.0Hz,
1H), 0.27 (s, 9H), 0.10 (s, 9H)；13C NMR (126MHz, CDCl3) δ 148.8,139.2,139.0,134.2,133.1,
123.8, -0.02, -0.1；HRMS(EI)for C12H22SSi2[M]+: calculated 254.0981, found
254.0977.
Embodiment 12
The preparation of (cis-) -2- methoxyl group -4- (trimethyl silicon substrate) -3- (2- (trimethyl silicon substrate) vinyl) pyridine
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
The iodo- 3 methoxypyridine 0.1mmol of norbornadiene 0.2mmol, 2-, two silicon 0.15mmol of hexamethyl, n,N-Dimethylformamide
1mL is added in the reaction tube of 15mL, and nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature,
Reaction solution is diluted with ethyl acetate, is washed three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains
17.9mg target product, yield 64%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz,
CDCl3) δ 8.04 (d, J=5.0Hz, 1H), 7.20 (d, J=15.4Hz, 1H), 6.95 (d, J=4.9Hz, 1H), 6.09 (d, J
=15.4Hz, 1H), 3.91 (s, 3H), 0.28 (s, 9H), -0.17 (s, 9H)；13C NMR (126MHz, CDCl3) δ 160.2,
150.0,144.2,139.9,136.9,129.0,121.1,53.2, -0.5, -1.1；HRMS (ESI-TOF) m/z:calcd for
C14H26NOSi2+: 280.1547 (M+H)+, found:280.1548.
Embodiment 13
(S, cis-) -2- ((tertbutyloxycarbonyl) amino) -3- (3- (trimethyl silicon substrate) -4- (2- (trimethyl silicon substrate) ethylene
Base) phenyl) methyl propionate preparation
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 2- ((tertbutyloxycarbonyl) amino) -3- (4- iodophenyl) methyl propionate 0.1mmol, two silicon of hexamethyl
0.15mmol, n,N-Dimethylformamide 1mL are added in the reaction tube of 15mL, and nitrogen is filled 3 times repeatedly, are placed in 100 DEG C
In oil bath, 12h is reacted；It is cooled to room temperature, reaction solution is diluted with ethyl acetate, is washed three times, organic phase anhydrous Na2SO4It is dry
It is dry, it filters, concentration, column chromatographic purifying obtains 27mg target product, yield 60%.The nuclear-magnetism and high resolution mass spectrum of the compound
It is characterized as below:1H NMR (500MHz, CDCl3) δ 7.57 (d, J=14.8Hz, 1H), 7.18 (d, J=1.5Hz, 1H), 7.11 (d,
J=7.7Hz, 1H), 7.05 (q, 1H), 5.85 (d, J=14.8Hz, 1H), 4.95 (d, J=7.8Hz, 1H), 4.58 (dd, J=
13.4,5.9Hz, 1H), 3.69 (s, 3H), 3.02-3.14 (m, 2H), 1.43 (s, 9H), 0.27 (s, 9H), -0.10 (s, 9H)；13C NMR (126MHz, CDCl3) δ 172.3,155.0,148.2,145.7,138.0,134.7,133.9,133.4,129.4,
128.9,79.8,54.3,52.1,38.1,28.3,0.02, -0.2；HRMS (ESI-TOF) m/z:calcd for
C23H39NNaO4Si2 +: 472.2310 (M+Na)+, found:472.2310.
Embodiment 14
(8R, 9S, 13S, 14S) -13- methyl -2- (trimethyl silicon substrate) -3- ((cis-) -2- (trimethyl silicon substrate) ethylene
Base) -6,7,8,9,11,12,13,14,15,16- decahydro -17H- pentamethylene [a] phenanthrene -17- ketone
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
The iodo- 13- methyl -6,7 of norbornadiene 0.2mmol, (8R, 9S, 13S, 14S) -3-, 8,9,11,12,13,14,15,16- ten
Hydrogen -17H- pentamethylene [a] phenanthrene -17- ketone 0.1mmol, hexamethyl two silicon 0.15mmol, n,N-Dimethylformamide 1mL are added to
In the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, reaction solution is used
Ethyl acetate dilution is washed three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains 28mg target
Product, yield 66%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz, CDCl3)δ7.57
(d, J=14.8Hz, 1H), 7.41 (s, 1H), 6.97 (s, 1H), 5.81 (d, J=14.8Hz, 1H), 2.93-2.85 (m, 2H),
2.54-2.46 (m, 2H), 2.36-2.28 (m, 1H), 2.19-2.10 (m, 1H), 2.09-2.04 (m, 1H), 2.01-1.95 (m,
1H), 1.67-1.41 (m, 7H), 0.92 (s, 3H), 0.28 (s, 9H), -0.05 (s, 9H)；13C NMR (126MHz, CDCl3)δ
220.9,148.4,144.1,137.6,136.7,134.5,132.5,130.8,129.4,50.5,48.0,44.4,38.3,
35.8,31.6,29.2,26.5,25.7,21.6,13.9,0.2, -0.1；HRMS (ESI-TOF) m/z:calcd for
C26H40NaOSi2 +: 447.2510 (M+Na)+, found:447.2511.
Embodiment 15
The preparation of (cis-)-(5- methoxyl group -2- (2- (trimethyl silicon substrate) vinyl) phenyl) trimethyl silane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 4- methoxyl group iodobenzene 0.1mmol, hexamethyl two germanium 0.15mmol, n,N-Dimethylformamide 1mL
It is added in the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, instead
It answers liquid to be diluted with ethyl acetate, washes three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains
30.9mg target product, yield 84%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz,
CDCl3) δ 7.48 (d, J=13.6Hz, 1H), 7.15 (d, J=8.4Hz, 1H), 6.98 (d, J=2.7Hz, 1H), 6.79 (dd, J
=8.3,2.7Hz, 1H), 5.93 (d, J=13.6Hz, 1H), 3.82 (s, 3H), 0.39 (s, 9H), 0.08 (s, 9H)；13C NMR
(126MHz, CDCl3) δ 158.1,145.9,142.0,138.6,133.7,129.4,119.2,112.3,55.1, -0.2, -
0.8；HRMS(EI)for C15H26Ge2O[M]+: calculated 370.0407, found 370.0411.
Embodiment 16
(S, cis-) -2- ((tertbutyloxycarbonyl) amino) -3- (3- (trimethyl germanium base) -4- (2- (trimethyl germanium base) ethylene
Base) phenyl) methyl propionate preparation
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 2- ((tertbutyloxycarbonyl) amino) -3- (4- iodophenyl) methyl propionate 0.1mmol, two germanium of hexamethyl
0.15mmol, n,N-Dimethylformamide 1mL are added in the reaction tube of 15mL, and nitrogen is filled 3 times repeatedly, are placed in 100 DEG C
In oil bath, 12h is reacted；It is cooled to room temperature, reaction solution is diluted with ethyl acetate, is washed three times, organic phase anhydrous Na2SO4It is dry
It is dry, it filters, concentration, column chromatographic purifying obtains 32.3mg target product, yield 60%.The nuclear-magnetism and high-resolution matter of the compound
Spectrum is characterized as below:1H NMR (500MHz, CDCl3) δ 7.51 (d, J=13.7Hz, 1H), 7.12 (d, J=8.3Hz, 2H), 7.05-
7.01 (m, 1H), 6.00 (d, J=13.7Hz, 1H), 4.96 (d, J=7.8Hz, 1H), 4.58 (q, J=5.8Hz, 1H), 3.70
(s, 3H), 3.15-3.01 (m, 2H), 1.43 (s, 9H), 0.39 (s, 9H), 0.04 (s, 9H)；13C NMR (126MHz, CDCl3)δ
172.3,155.0,146.0,144.9,140.4,135.1,134.0,133.8,129.0,128.5,79.8,54.3,52.1,
38.0,28.3, -0.3, -0.7；HRMS(ESI-TOF)for C23H39Ge2NnaO4 +: 564.1195 (M+Na)+, found:
564.1195.
Embodiment 17
The preparation of (cis-)-(2- (2- (trimethyl-tin-radical) Nai Ji) vinyl) trimethyl stannane
By potassium carbonate 0.2mmol, palladium acetate 0.01mmol, triphenylphosphine 0.02mmol, 2,3- dicarboxylic acid methylester's -7- oxa-s
Norbornadiene 0.2mmol, 1- iodine naphthalene 0.1mmol, six dibutyltin dilaurate 0.15mmol, n,N-Dimethylformamide 1mL are added to
In the reaction tube of 15mL, nitrogen is filled 3 times repeatedly, is placed in 100 DEG C of oil bath, and 12h is reacted；It is cooled to room temperature, reaction solution is used
Ethyl acetate dilution is washed three times, organic phase anhydrous Na2SO4It dries, filters, is concentrated, column chromatographic purifying obtains 36.6mg mesh
Mark product, yield 50%.The nuclear-magnetism and high resolution mass spectrum of the compound are characterized as below:1H NMR (500MHz, CDCl3)δ
8.22-8.14 (m, 1H), 7.87 (d, J=14.0Hz, 1H), 7.84-7.79 (m, 1H), 7.74-7.67 (m, 1H), 7.60-
7.50 (m, 1H), 7.49-7.39 (m, 2H), 6.76 (d, J=14.0Hz, 1H), 1.62-1.52 (m, 6H), 1.42-1.32 (m,
6H), 1.21-1.02 (m, 18H), 0.92 (t, J=7.3,7.3Hz, 9H), 0.85-0.75 (m, 9H), 0.44-0.26 (m, 6H)
；13C NMR (126MHz, CDCl3) δ 147.4,147.3,139.0,138.6,133.9,132.3,131.7,128.0,126.4,
125.7,125.5,125.4,29.2,28.9,27.5,27.3,13.7,13.6,10.6,9.6；HRMS(EI)for C32H53Sn2
[M-C4H9]+: calculated 677.2186, found 677.2184.
Those of ordinary skill in the art still are able to it is found that when technical solution of the present invention changes in following ranges
To same as the previously described embodiments or similar technical effect:
A kind of vinyl silicon germanium stannane derivative preparation method, include the following steps:
(1) alkali, palladium catalyst, ligand, alkene, halogenated aryl hydrocarbon, preceding is sequentially added into the reaction vessel purged through nitrogen
Body compound and organic solvent, in 60~110 DEG C (preferably 60~100 DEG C) 10~15h of reaction；Halogenated aryl hydrocarbon, precursor compound,
Alkene, palladium catalyst, ligand and alkali molar ratio be 0.8~1.2: 1.2~1.6: 1.8~2.2: 0.08~0.12: 0.18
~0.22: 1.8~2.2, and the corresponding organic solvent of every moles of halogenated aromatic hydrocarbons is 1~3L；
Above-mentioned precursor compound is two silicon of hexamethyl, two germanium of hexamethyl or six dibutyltin dilaurates；
The structural formula of above-mentioned halogenated aryl hydrocarbon isWherein X is halogen, and R is hydrogen, alkyl, alkoxy, acyl group, ammonia
Base, three fluoroalkyls, aryl, substituted aryl, hydroxyl, methylol, halogen, heterocycle or steroidal；
The structural formula of above-mentioned alkene isWherein Z is C, O or N, R1For hydrogen, alkyl or aryl, R2For alkyl, virtue
Base, acyl group, carboxylic acid group, ester group, amide groups, sulfonyl or trifluoromethyl；
Above-mentioned palladium catalyst is palladium acetate, trifluoracetic acid palladium, palladium chloride, bi triphenyl phosphino- palladium chloride, double acetonitriles
Palladium chloride, palladium acetylacetonate, diacetyl acetone palladium, allyl palladium chloride dimer, tetra-triphenylphosphine palladium, [1,1 '-bis- (two
Phenylphosphine) ferrocene] palladium chloride or tris(dibenzylideneacetone) dipalladium；
Above-mentioned ligand be triphenylphosphine, three (2- furyl) phosphines, 2- dicyclohexyl phosphorus -2 ', 6 '-diisopropoxy -1,1 ' -
Biphenyl, three naphthalene phosphines, 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl, 2- dicyclohexyl phosphine -2 ', 6 '-dimethoxys connection
Bis- diphenylphosphine -9, the 9- xanthphos of benzene, tricyclohexyl phosphine, 4,5-, three (2- methoxyphenyl) phosphines, three (4- methoxyl groups
Phenyl) phosphine, pyridine, bipyridyl, 2- hydroxyl -3- trifluoromethyl pyridine, 1,1 '-dinaphthalene -2,2 '-bis- diphenyl phosphines, 1,1 '-bis- (two
Phenylphosphine) ferrocene or 1,1 '-union -2-naphthol；
Above-mentioned alkali is sodium hydroxide, potassium hydroxide, tert-butyl alcohol lithium, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, carbon
Sour sodium, potassium carbonate, potassium phosphate, potassium dihydrogen phosphate, cesium carbonate or 1,11 carbon -7- alkene of 8- diazabicylo；
Above-mentioned organic solvent is dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2- pyrrole
Pyrrolidone, 1,2- dichloroethanes, toluene, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran or glycol dimethyl ether；
(2) it by step (1) resulting material after ethyl acetate dilutes, then is washed, separates to obtain organic phase；
(3) by step (2) resulting organic phase through drying, filtering, concentration and column chromatography chromatogram, obtain described having vinyl
Silicon germanium stannane derivative.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (7)
1. a kind of vinyl silicon germanium stannane derivative preparation method, characterized by the following steps:
(1) alkali, palladium catalyst, ligand, alkene, halogenated aryl hydrocarbon, precursor is sequentially added into the reaction vessel purged through nitrogen
Object and organic solvent are closed, in 60~110 DEG C of 10~15h of reaction；Halogenated aryl hydrocarbon, precursor compound, alkene, palladium catalyst, ligand
And the molar ratio of alkali is 0.8~1.2: 1.2~1.6: 1.8~2.2: 0.08~0.12: 0.18~0.22: 1.8~2.2, and
The corresponding organic solvent of every moles of halogenated aromatic hydrocarbons is 1~3L；
Above-mentioned precursor compound is two silicon of hexamethyl, two germanium of hexamethyl or six dibutyltin dilaurates；
The structural formula of above-mentioned halogenated aryl hydrocarbon isWherein x is halogen, and R is hydrogen, alkyl, alkoxy, acyl group, amino, three
Fluoroalkyl, aryl, substituted aryl, hydroxyl, methylol, halogen, heterocycle or steroidal；
The structural formula of above-mentioned alkene isWherein Z is C, O or N, R1For hydrogen, alkyl or aryl, R2For alkyl, aryl,
Acyl group, carboxylic acid group, ester group, amide groups, sulfonyl or trifluoromethyl；
Above-mentioned palladium catalyst is palladium acetate, trifluoracetic acid palladium, palladium chloride, bi triphenyl phosphino- palladium chloride, double acetonitrile dichloros
Change palladium, palladium acetylacetonate, diacetyl acetone palladium, allyl palladium chloride dimer, tetra-triphenylphosphine palladium, [1,1 '-bis- (diphenyl
Phosphine) ferrocene] palladium chloride or tris(dibenzylideneacetone) dipalladium；
Above-mentioned ligand be triphenylphosphine, three (2- furyl) phosphines, 2- dicyclohexyl phosphorus -2 ', 6 '-diisopropoxy -1,1 '-connection
Benzene, three naphthalene phosphines, 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl, 2- dicyclohexyl phosphine -2 ', 6 '-dimethoxy-biphenyls,
Bis- diphenylphosphine -9, the 9- xanthphos of tricyclohexyl phosphine, 4,5-, three (2- methoxyphenyl) phosphines, three (4- methoxybenzenes
Base) phosphine, pyridine, bipyridyl, 2- hydroxyl -3- trifluoromethyl pyridine, 1,1 '-dinaphthalene -2,2 '-bis- diphenyl phosphines, 1,1 '-bis- (hexichol
Base phosphine) ferrocene or 1,1 '-union -2-naphthol；
Above-mentioned alkali is sodium hydroxide, potassium hydroxide, tert-butyl alcohol lithium, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, carbonic acid
Sodium, potassium carbonate, potassium phosphate, potassium dihydrogen phosphate, cesium carbonate or 1,11 carbon -7- alkene of 8- diazabicylo；
Above-mentioned organic solvent is dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2- pyrrolidines
Ketone, 1,2- dichloroethanes, toluene, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran or glycol dimethyl ether；
(2) it by step (1) resulting material after ethyl acetate dilutes, then is washed, separates to obtain organic phase；
(3) by step (2) resulting organic phase through drying, filtering, concentration and column chromatography chromatogram, obtain it is described have vinyl silicon
Germanium stannane derivative.
2. preparation method as described in claim 1, it is characterised in that: the R is halogen, trifluoromethyl or methoxyl group.
3. preparation method as claimed in claim 2, it is characterised in that: the halogen is fluorine, iodine, chlorine or bromine.
4. preparation method as described in claim 1, it is characterised in that: the palladium catalyst is palladium acetate, and the ligand is three
Phenylphosphine, the alkali are cesium carbonate, and the organic solvent is n,N-Dimethylformamide.
5. preparation method as described in claim 1, it is characterised in that: the reaction temperature in the step (1) is 60~100
℃。
6. preparation method as described in claim 1, it is characterised in that: the reaction time in the step (1) is 12h.
7. the preparation method as described in any claim in claim 1 to 6, it is characterised in that: the halogenated aryl hydrocarbon, precursor
Compound, alkene, palladium catalyst, ligand and alkali molar ratio be 1: 1.5: 2: 0.1: 0.2: 2, and every moles of halogenated aromatic hydrocarbons pair
The organic solvent answered is 1~2L.
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| CN109879713A (en) * | 2019-02-22 | 2019-06-14 | 华侨大学 | A kind of preparation method of trans- four substituted olefines derivative |
| CN109879899A (en) * | 2019-02-22 | 2019-06-14 | 华侨大学 | A kind of preparation method of trans- three substituted olefines derivative |
| CN110229180A (en) * | 2019-07-16 | 2019-09-13 | 南京大学 | A kind of method that selectivity prepares alkenyl silanes |
| CN115160356A (en) * | 2022-07-05 | 2022-10-11 | 南阳师范学院 | Method for effectively preparing vinyl silane derivative through cascade three-component reaction |
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| CN108586519A (en) * | 2018-05-03 | 2018-09-28 | 华侨大学 | A kind of preparation method of organosilan or organic germanium alkane derivatives |
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| CN109879713A (en) * | 2019-02-22 | 2019-06-14 | 华侨大学 | A kind of preparation method of trans- four substituted olefines derivative |
| CN109879899A (en) * | 2019-02-22 | 2019-06-14 | 华侨大学 | A kind of preparation method of trans- three substituted olefines derivative |
| CN109879899B (en) * | 2019-02-22 | 2021-08-31 | 华侨大学 | Preparation method of trans-tri-substituted olefin derivative |
| CN109879713B (en) * | 2019-02-22 | 2021-11-02 | 华侨大学 | Preparation method of trans-tetrasubstituted olefin derivative |
| CN110229180A (en) * | 2019-07-16 | 2019-09-13 | 南京大学 | A kind of method that selectivity prepares alkenyl silanes |
| CN110229180B (en) * | 2019-07-16 | 2021-11-16 | 南京大学 | Method for selectively preparing alkenyl silane |
| CN115160356A (en) * | 2022-07-05 | 2022-10-11 | 南阳师范学院 | Method for effectively preparing vinyl silane derivative through cascade three-component reaction |
| CN115160356B (en) * | 2022-07-05 | 2024-01-26 | 南阳师范学院 | Method for effectively preparing vinyl silane derivative through cascade three-component reaction |
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