CN115215895A - Preparation method of five-membered silicon-containing fused heterocyclic compound - Google Patents
Preparation method of five-membered silicon-containing fused heterocyclic compound Download PDFInfo
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- CN115215895A CN115215895A CN202210801070.1A CN202210801070A CN115215895A CN 115215895 A CN115215895 A CN 115215895A CN 202210801070 A CN202210801070 A CN 202210801070A CN 115215895 A CN115215895 A CN 115215895A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 24
- 239000010703 silicon Substances 0.000 title claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].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 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 claims description 3
- UTFRXHNWUFPRPQ-UHFFFAOYSA-N 2,3-dichloro-1-methyl-4-propan-2-ylbenzene;ruthenium(2+) Chemical class [Ru+2].CC(C)C1=CC=C(C)C(Cl)=C1Cl UTFRXHNWUFPRPQ-UHFFFAOYSA-N 0.000 claims description 2
- NBKDKKAKVXRRGT-UHFFFAOYSA-N Cl.[Ru].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 Chemical compound Cl.[Ru].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 NBKDKKAKVXRRGT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- VSEDOGDGZDHDLF-UHFFFAOYSA-N carbon monoxide ruthenium monohydride triphenylphosphane Chemical compound [Ru][H].[C-]#[O+].c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 VSEDOGDGZDHDLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- KSLRDBLYEBCWDV-UHFFFAOYSA-N O.O.O.O.O.O.Cl.Cl.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 Chemical compound O.O.O.O.O.O.Cl.Cl.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 KSLRDBLYEBCWDV-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012327 Ruthenium complex Substances 0.000 abstract description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 description 40
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000004896 high resolution mass spectrometry Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- -1 Silicon heterocyclic compounds Chemical class 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- PXCVPYJXMUOIMP-UHFFFAOYSA-N formaldehyde;ruthenium;triphenylphosphane Chemical compound [Ru].O=C.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 PXCVPYJXMUOIMP-UHFFFAOYSA-N 0.000 description 7
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BIJNHUAPTJVVNQ-UHFFFAOYSA-N 1-Hydroxypyrene Chemical compound C1=C2C(O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 BIJNHUAPTJVVNQ-UHFFFAOYSA-N 0.000 description 2
- BOTGCZBEERTTDQ-UHFFFAOYSA-N 4-Methoxy-1-naphthol Chemical compound C1=CC=C2C(OC)=CC=C(O)C2=C1 BOTGCZBEERTTDQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RHTPMZBFKJRYMX-OAHLLOKOSA-N (2R)-1-[(2-methylpropan-2-yl)oxycarbonyl]azasilolidine-2-carboxylic acid Chemical compound C(=O)(OC(C)(C)C)N1[Si@@H](C(=O)O)CCC1 RHTPMZBFKJRYMX-OAHLLOKOSA-N 0.000 description 1
- OUNQUWORSXHSJN-UHFFFAOYSA-N 4-bromonaphthalen-1-ol Chemical compound C1=CC=C2C(O)=CC=C(Br)C2=C1 OUNQUWORSXHSJN-UHFFFAOYSA-N 0.000 description 1
- LVSPDZAGCBEQAV-UHFFFAOYSA-N 4-chloronaphthalen-1-ol Chemical compound C1=CC=C2C(O)=CC=C(Cl)C2=C1 LVSPDZAGCBEQAV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JAZCEXBNIYKZDI-UHFFFAOYSA-N [Ir+] Chemical compound [Ir+] JAZCEXBNIYKZDI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- UUSPGQXHSZVVNL-UHFFFAOYSA-L dichlororuthenium;1,10-phenanthroline;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 UUSPGQXHSZVVNL-UHFFFAOYSA-L 0.000 description 1
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000006437 ethyl cyclopropyl group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- RADGOBKLTHEUQO-UHFFFAOYSA-N ruthenium(4+) Chemical compound [Ru+4] RADGOBKLTHEUQO-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a preparation method of a five-membered silicon-containing fused heterocyclic compound, which comprises the following steps: in the presence of a solvent, reacting H 2 SiEt 2 Heating the compound shown in the formula II, unsaturated olefin and a ruthenium catalyst to react to obtain a compound shown in the formula I; the structural formulas of the compound shown in the formula I and the compound shown in the formula II are as follows:
wherein n.gtoreq.1, R is independently selected from C 1～6 Alkoxy, halogen, C 1～6 Alkyl, amino, C 2～6 Ester group of (2). The invention has the advantages of simple and easy preparation of the initial raw material, high reaction yield, convenient operation of the synthesis process and the like; the invention creatively synthesizes the five-membered silicon-oxygen-containing fused heterocyclic compound by using the relatively low-cost ruthenium complex catalyst under the condition of adding unsaturated olefin, uses a small amount of ruthenium catalyst and has low price, thereby reducing the investment of capital and labor force for industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a five-membered silicon-containing fused heterocyclic compound.
Background
Silicon heterocyclic compounds are a very important class of organic compounds, and the synthesis of silicon-substituted drug molecules by incorporating silicon elements into biologically active organic molecules is receiving increasing attention in pharmaceutical chemistry. In strategies for silylation of built-up C-Si bonds with transition metal-catalyzed C-H, aromatic C (sp) 2 ) The progress of silylation of the-H bond is excellent, but the catalytic synthesis schemes for intramolecular silylation to generate the silacycle compounds (such as silaroban, N-tert-butoxycarbonyl- (R) -silaproline and tetrahydrosilaquinoline are few, and the organosilicon compounds with unique structures, namely the silacycle compounds, have more outstanding biological and chemical properties compared with the parent carbon compounds, and have wide and important application value in the development of the silicon drugs. Therefore, it is important to construct this class of silicon heterocyclic compounds that do not occur in nature. In past experimental studies, transition metal-catalyzed silicidation of C-H bonds has become the primary method of forming C-Si bonds, where intramolecular silicon cyclization provides a useful route to the synthesis of silicon-containing heterocyclic compounds. In recent years, the noble metal rhodium and iridium complexes are prepared by a carbon-hydrogen bond activation mode, and the method is favored by organic chemists. However, the price of metal complexes such as rhodium, iridium and the like in the existing synthesis method is relatively expensive, and the industrialization of the preparation method is influenced.
Therefore, it is necessary to develop a new method for preparing a five-membered fused silicon-containing heterocyclic compound.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of the five-membered silicon-containing fused heterocyclic compound, which can effectively improve the yield, can react by adopting a ruthenium catalyst and reduce the cost.
A method for preparing a five-membered silicon-containing fused heterocyclic compound according to an embodiment of the first aspect of the present invention comprises the steps of:
in the presence of a solvent, reacting H 2 SiEt 2 A compound of the formula II, an unsaturated olefin andheating a ruthenium catalyst to react to obtain a compound shown in a formula I;
the structural formulas of the compound shown in the formula I and the compound shown in the formula II are as follows:
wherein n.gtoreq.1, R is independently selected from C 1～6 Alkoxy, halogen, C 1～6 Alkyl, amino, C 2～6 Ester group of (a).
The preparation method of the five-membered silicon-containing fused heterocyclic compound provided by the embodiment of the invention has at least the following beneficial effects:
in the related technology, an iridium catalyst is adopted to catalyze C-H bonds to carry out a C-Si cyclization reaction with the same ring; the method selects the ruthenium catalyst with lower catalytic activity and lower price to carry out the C-Si cyclization reaction of the heteromorphism: not only can realize the C-Si cyclization reaction of the hetero ring to obtain a novel silicon-containing heterocyclic product, but also enriches the synthesis method and structure of the silicon-containing heterocyclic compound; in addition, the mechanisms of iridium catalysis and ruthenium catalysis are completely different, the iridium catalyst is mostly catalyzed by active catalytic species of iridium (I) or iridium (III), and the ruthenium catalyst is mostly catalyzed by active catalytic species of ruthenium (0), ruthenium (II) or ruthenium (IV) to realize a catalytic cycle reaction.
The scheme of the invention has the advantages of simple and easy preparation of the initial raw material, high synthesis yield, convenient operation of the synthesis process and the like; the invention creatively synthesizes five-membered silicon-oxygen-containing fused heterocyclic compounds by using a relatively cheap ruthenium complex catalyst under the condition of adding unsaturated olefin, except for final products, intermediates in a series of conversion processes do not need to be separated and purified, only one reaction step is needed, the amount of the used ruthenium catalyst is less, the price is lower, and the investment of capital and labor force is reduced for industrial production; the scheme of the invention provides a simple and efficient preparation method for five-membered ring siloxane compounds.
According to some embodiments of the invention, the ruthenium catalyst is selected from one or more of tris (2, 2' -bipyridine) dichloride ruthenium hexahydrate, dichloro (p-methylisoprophenyl) ruthenium (II) dimer, tris (triphenylphosphine) dichloride ruthenium, tris (triphenylphosphine) carbonyl hydride ruthenium, or tris (triphenylphosphine) carbonyl chloride ruthenium.
According to some embodiments of the invention, the ruthenium catalyst is selected from at least one of tris (triphenylphosphine) carbonyl ruthenium hydride, tris (triphenylphosphine) carbonyl ruthenium hydrochloride, dichloro (p-methylisopropylbenzene) ruthenium (II) dimer. These catalysts more easily undergo an oxidative addition reaction with Si — H to promote the progress of the reaction, thereby enabling the yield of the reaction to be further improved.
According to some embodiments of the invention, the unsaturated olefin is selected from at least one of cyclohexene, styrene, methyl acrylate or norbornene.
According to some embodiments of the invention, the solvent is selected from at least one of xylene, 1, 4-dioxane, toluene, N-dimethylformamide.
According to some embodiments of the invention, the compound of formula II, H 2 SiEt 2 And the molar ratio of the unsaturated olefin to the ruthenium catalyst is 1: (1-3): (1-6): (0.02-0.20).
According to some embodiments of the invention, the compound of formula II, H 2 SiEt 2 The molar ratio of unsaturated olefin to ruthenium catalyst is 1:1.1:6:0.1.
according to some embodiments of the invention, the heating is at a temperature of 50 ℃ to 150 ℃.
According to some embodiments of the invention, the heating time is 12h to 36h.
According to some embodiments of the invention, the heating time is 16h to 20h.
According to some embodiments of the invention, the reaction is carried out under oxygen-free conditions.
According to some embodiments of the invention, the reaction is performed under nitrogen.
Definitions and terms
"halogen" means one or more of fluorine, chlorine, bromine, iodine.
“C 1-6 Alkoxy of (2)"represents alkoxy having a total of 1 to 6 carbon atoms, including C 1-6 Linear alkoxy radical of (1), C 1-6 And C is a branched alkoxy group 2-6 The cycloalkoxy group of (2) may be, for example, a linear alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms in total, a branched alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms in total, or a cycloalkoxy group having 2, 3, 4, 5 or 6 carbon atoms in total, and may be, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group or the like.
“C 1-6 The "alkyl group" of (2) represents an alkyl group having a total number of carbon atoms of 1 to 6, including C 1-6 Straight chain alkyl group of (1), C 1-6 Branched alkyl and C 3-6 The cycloalkyl group of (b) may be, for example, a straight-chain alkyl group having 1, 2, 3, 4, 5 or 6 total carbon atoms, a branched-chain alkyl group having 1, 2, 3, 4, 5 or 6 total carbon atoms or a cycloalkyl group having 3, 4, 5 or 6 total carbon atoms, and may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a cyclopropyl group, a methylcyclopropyl group, an ethylcyclopropyl group, a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group or the like.
“C 2～6 The ester group of (A) is represented by-COOR 1 The total number of carbon atoms is 2 to 6.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the products obtained in examples 1 to 5 of the present invention;
FIG. 2 is a carbon NMR spectrum of the products obtained in examples 1 to 5 of the present invention;
FIG. 3 is a NMR spectrum of a product obtained in example 6 of the present invention;
FIG. 4 is a carbon NMR spectrum of a product obtained in example 6 of the present invention;
FIG. 5 is a NMR spectrum of a product obtained in example 7 of the present invention;
FIG. 6 is a NMR carbon spectrum of a product obtained in example 7 of the present invention;
FIG. 7 is a NMR spectrum of a product obtained in example 8 of the present invention;
FIG. 8 is a carbon NMR spectrum of a product obtained in example 8 of the present invention;
FIG. 9 is a NMR spectrum of a product obtained in example 9 of the present invention;
FIG. 10 is a NMR carbon spectrum of a product obtained in example 9 of the present invention.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following raw materials were used in the examples and comparative examples:
1-naphthol, 4-bromonaphthol, 4-chloronaphthol, 4-methoxynaphthol, 1-hydroxypyrene: from Zel technologies, inc., of Anhui, shanghai, bid, medicine technologies, inc., aladdin reagents, inc., shanghai, mcClin, biochemical technologies, inc.
Diethyl silane: purchased from zel technologies ltd, anhui;
norbornene: purchased from Anhui Zerise technologies, inc.;
tris (triphenylphosphine) ruthenium carbonyl dihydride, tris (triphenylphosphine) ruthenium dichloride, tris (2, 2' -bipyridine) ruthenium dichloride hexahydrate, dichloro (p-methylisopropylene) ruthenium (II) dimer, tris (triphenylphosphine) ruthenium carbonyl hydrochloride: purchased from zel technologies, inc, anhui, and bi-d, shanghai, pharmaceutical technologies, inc.
Example 1
1-naphthol (72.1mg, 0.5mmo 1), diethylsilane (71. Mu.L, 0.55mmo 1), norbornene (282.5 mg,3.0mmo 1) and tris (triphenylphosphine) ruthenium carbonyl dihydride (45.8 mg, 0.05mmol) were sequentially added to a 20mL schleck tube, and the reaction was electromagnetically stirred (500-800 rpm) at a reaction temperature of 120 ℃ in the presence of toluene (2 mL) and nitrogen for 12 hours, and the yield was 93% as measured by GC-MS.
Example 2
Example 2 also provides a method for preparing a five-membered silicon-containing fused heterocyclic compound, which is the same as example 1 except that the solvent is 1, 4-dioxane; the yield was 47%.
Examples 3 to 5
Examples 3 to 5 also provide a method for preparing a fused heterocyclic compound containing silicon in five members, which is the same as example 1 except that the ruthenium catalyst is different from the fused heterocyclic compound containing silicon in five members, as shown in Table 1.
TABLE 1
The products obtained in examples 1 to 5 were subjected to qualitative detection by Nuclear Magnetic Resonance (NMR) and High Resolution Mass Spectrometry (HRMS), respectively, and the results showed that the detection data of the products were consistent, specifically as follows:
1 H NMR(500MHz,CDCl 3 ): as shown in fig. 1, δ =7.91-7.89 (m, 1H), 7.73-7.72 (d, 1h, j =7.0 hz), 7.60-7.58 (m, 1H), 7.44-7.38 (m, 2H), 6.95-6.93 (m, 1H), 1.07-1.03 (m, 10H).
Other parameters during the test were as follows: temperature (temperature): 296.1; pulse sequence (pulse sequence): zg30; number of scans (number of scans): 16; receive gain (receiver gain): 101; relaxation delay (relaxation delay): 1.0000; pulse width (pulse width): 9.7200; scanning frequency (spctrometer frequency): 500.15 of the total weight of the mixture; spectral width (spectral width): 10000.0; lowest frequency (lowest frequency): -1911.6; nucleus (nucleus): 1H; size obtained (acquired size): 32768; spectral size (spectral size): 65536.
13 C{ 1 H}NMR(125MHz,CDCl 3 ): as shown in fig. 2, δ =159.1,134.3,132.4,132.1,129.3,128.1,128.0,127.6,118.0,106.9,6.4,6.2.
Other parameters in the test procedure were as follows: temperature (temperature): 296.2; pulse sequence (pulse sequence): zgpg30; number of scans (number of scans): 200 of a carrier; receive gain (receiver gain): 101, a first electrode and a second electrode; relaxation delay (relaxation delay): 2.0000; pulse width (pulse width): 10.0000; scanning frequency (spctrometer frequency): 125.78; spectral width (spectral width): 30120.5; lowest frequency (lowest frequency): -2465.8; nucleus (nucleous): 13C; size obtained (acquired size): 32768; spectral size (spectral size): 65536.
HRMS (with EI source mode): m/z C 14 H 17 OSi[M+H] + The theoretical value (calibrated value, calcd.) of (1) is: 259.1043, found (found): 259.1042.
example 6
Example 6 provides a method for preparing a five-membered silicon-containing fused heterocyclic compound, wherein the reaction equation is as follows:
4-Bromobenzol (111.5 mg,0.5mmo 1), diethylsilane (71. Mu.L, 0.55mmo 1), norbornene (282.5 mg,3.0mmo 1), and tris (triphenylphosphine) ruthenium carbonyl dihydride (45.8 mg, 0.05mmol) were sequentially added to a 20mL Schlenk tube, and the reaction was carried out under the conditions of toluene (2 mL) and nitrogen at a reaction temperature of 120 ℃ with electromagnetic stirring (500-800 revolutions) for 20 hours. After completion of the reaction, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography using ethyl acetate and petroleum ether as eluents to give a pale yellow liquid (127mg, 83%) after separation.
The product obtained in example 6 was subjected to NMR and HRMS qualitative detection, and the product detection data were as follows:
1 H NMR(500MHz,CDCl 3 ): as shown in fig. 3, δ =8.14-8.12 (m, 1H), 7.77-7.65 (m, 3H), 6.83 (d, 2h, j =8.0 hz), 1.09-1.01 (m, 10H).
Temperature (temperature): 292.6; pulse sequence (pulse sequence): zg30; number of scans (number of scans): 16; receive gain (receiver gain): 71; relaxation delay (relaxation delay): 1.0000; pulse width (pulse width): 10.0000; scanning frequency (spctrometer frequency): 500.15 of the total weight of the mixture; spectral width (spectral width): 10000.0; lowest frequency (lowest frequency): -1911.6; nucleus (nucleus): 1H; size obtained (acquired size): 32768; spectral size (spectral size): 65536.
13 C{ 1 H}NMR(125MHz,CDCl 3 ): as shown in fig. 4, δ =158.9,135.3,132.7,131.2,131.1,130.2,128.7,127.7,110.7,108.0,6.3,6.2.
Other parameters in the test procedure were as follows: temperature (temperature): 293.4; pulse sequence (pulse sequence): zgpg30; number of scans (number of scans): 256 of; receive gain (receiver gain): 101; relaxation delay (relaxation delay): 2.0000; pulse width (pulse width): 10.0000; scan frequency (spctrometer frequency): 125.76; spectral width (spectral width): 30120.5; lowest frequency (lowest frequency): -2467.6; nucleus (nucleous): 13C; size obtained (acquired size): 32768; spectral size (spectral size): 32768.
HRMS (with EI source mode): m/z C 14 H 15 BrOSi[M+H] + The theoretical value (calibrated value) of (d) is: 306.0070, found (found) is: 306.0065.
example 7
Example 7 provides a method for preparing a five-membered silicon-containing fused heterocyclic compound, wherein the reaction equation is as follows:
4-Chlorophthalol (89.3mg, 0.5mmo1), diethylsilane (71. Mu.L, 0.55mmo1), norbornene (282.5mg, 3.0mmo1), and tris (triphenylphosphine) ruthenium carbonyl dihydride (45.8mg, 0.05mmol) were sequentially added to a 20mL Schlenk tube, and the reaction was carried out under the conditions of toluene (2 mL) and nitrogen at a reaction temperature of 120 ℃ with electromagnetic stirring (500-800 rpm), for 12 hours. After completion of the reaction, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography using ethyl acetate and petroleum ether as eluents to give a pale yellow liquid (72mg, 55%) after separation.
The product obtained in example 7 was subjected to NMR and HRMS qualitative detection, and the product detection data were as follows:
1 H NMR(500MHz,CDCl 3 ): as shown in fig. 5, δ =8.18-8.17 (m, 1H), 7.78-7.68 (m, 2H), 7.45 (d, 1h, j =8.0 hz), 6.84 (d, 1h, j =8.0 hz), 1.08-1.00 (m, 10H).
Temperature (temperature): 292.8; pulse sequence (pulse sequence): zg30; number of scans (number of scans): 16; receive gain (receiver gain): 71; relaxation delay (relaxation delay): 1.0000; pulse width (pulse width): 10.0000; scan frequency (spctrometer frequency): 500.15 of the total weight of the mixture; spectral width (spectral width): 10000.0; lowest frequency (lowest frequency): -1911.6; nucleus (nucleus): 1H; size obtained (acquired size): 32768; spectral size (spectral size): 65536.
13 C{ 1 H}NMR(125MHz,CDCl 3 ): as shown in fig. 6, δ =158.2,135.1,132.6,130.1,129.8,128.4,127.6,125.3,121.2,107.2,6.3,6.2.
Other parameters during the test were as follows: temperature (temperature): 293.8; pulse sequence (pulse sequence): zgpg30; number of scans (number of scans): 512; receive gain (receiver gain): 101; relaxation delay (relaxation delay): 2.0000; pulse width (pulse width): 10.0000; scanning frequency (spctrometer frequency): 125.76; spectral width (spectral width): 30120.5; lowest frequency (lowest frequency): -2484.0; nucleus (nucleus): 13C; size obtained (acquired size): 32768; spectral size (spectral size): 32768.
HRMS (with EI source mode): m/z C 14 H 16 ClOSi[M+H] + The theoretical value (calibrated value, calcd.) of (1) is: 263.0653, found (found) as: 263.0648.
example 8
Example 8 provides a method for preparing a five-membered silicon-containing fused heterocyclic compound, wherein the reaction equation is as follows:
4-methoxynaphthol (87.1mg, 0.5mmo 1), diethylsilane (71. Mu.L, 0.55mmo 1), norbornene (282.5 mg,3.0mmo 1) and tris (triphenylphosphine) ruthenium carbonyl dihydride (45.8 mg, 0.05mmol) were added in this order to a 20mL Schlenk tube, and the reaction was electromagnetically stirred (500-800 rpm) under toluene (2 mL) and nitrogen at a reaction temperature of 120 ℃ for 12 hours. After completion of the reaction, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography using ethyl acetate and petroleum ether as eluents to give a pale yellow liquid (63mg, 49%) after separation.
The product prepared in example 8 was subjected to NMR and HRMS qualitative detection, and the product detection data were as follows:
1 H NMR(500MHz,CDCl 3 ): as shown in fig. 7, δ =8.23-8.21 (m, 1H), 7.77-7.76 (m, 1H), 7.63-7.60 (m, 1H), 6.84 (d, 1h, j =8.0 hz), 6.72 (d, 1h, j =8.5 hz), 3.99 (s, 3H), 1.09-1.03 (m, 10H).
Temperature (temperature): 291.3; pulse sequence (pulse sequence): zg30; number of scans (number of scans): 16; receive gain (receiver gain): 32, a first step of removing the first layer; relaxation delay (relaxation delay): 1.0000; pulse width (pulse width): 10.0000; scan frequency (spctrometer frequency): 500.15 of the total weight of the mixture; spectral width (spectral width): 10000.0; lowest frequency (lowest frequency): -1911.6; nucleus (nucleous): 1H; size obtained (acquired size): 32768; spectral size (spectral size): 65536.
13 C{ 1 H}NMR(125MHz,CDCl 3 ): as shown in fig. 8, δ =152.7,148.8,134.9,131.8,129.9,126.9,124.4,123.2,105.4,104.9,55.9,6.5,6.2.
Other parameters during the test were as follows: temperature (temperature): 292.6; pulse sequence (pulse sequence): zgpg30; number of scans (number of scans): 512; receive gain (receiver gain): 101, a first electrode and a second electrode; relaxation delay (relaxation delay): 2.0000; pulse width (pulse width): 10.0000; scan frequency (spctrometer frequency): 125.76; spectral width (spectral width): 30120.5; lowest frequency (lowest frequency): -2484.0; nucleus (nucleus): 13C; size obtained (acquired size): 32768; spectral size (spectral size): 32768.
HRMS (with EI source mode): m/z C 15 H 19 O 2 Si[M+H] + The theoretical value (calibrated value, calcd.) of (1) is: 259.1148, found (found) as: 259.1149.
example 9
Example 9 provides a method for preparing a five-membered silicon-containing fused heterocyclic compound, wherein the reaction equation is as follows:
1-hydroxypyrene (109.1mg, 0.5mmo1), diethylsilane (71. Mu.L, 0.55mmo1), norbornene (282.5mg, 3.0mmo1), and tris (triphenylphosphine) ruthenium carbonyl dihydride (45.8mg, 0.05mmol) were sequentially added to a 20mL Schlenk tube, and the reaction was carried out under the conditions of toluene (2 mL) and nitrogen gas at a reaction temperature of 120 ℃ with electromagnetic stirring (500-800 revolutions) for 12 hours. After completion of the reaction, the solvent was removed by rotary evaporation and the mixture was separated by column chromatography eluting with ethyl acetate and petroleum ether to give a pale yellow liquid (80mg, 53%).
The product prepared in example 9 was subjected to NMR and HRMS qualitative detection, and the product detection data were as follows:
1 H NMR(500MHz,CDCl 3 ): as shown in fig. 9, δ =8.33 (s, 1H), 8.21-8.12 (m, 3H), 8.04-8.02 (m, 2H), 7.92 (d, 1h, j =9.0 hz), 7.63 (d, 1h, j =8.5 hz), 1.21-1.13 (m, 10H).
Temperature (temperature): 291.9; pulse sequence (pulse sequence): zg30; number of scans (number of scans): 16; receive gain (receiver gain): 32, a first step of removing the first layer; relaxation delay (relaxation delay): 1.0000; pulse width (pulse width): 10.0000; scanning frequency (spctrometer frequency): 500.15 of the total weight of the mixture; spectral width (spectral width): 10000.0; lowest frequency (lowest frequency): -1911.6; nucleus (nucleous): 1H; size obtained (acquired size): 32768; spectral size (spectral size): 65536.
13 C{ 1 H}NMR(125MHz,CDCl 3 ): as shown in fig. 10, δ =157.3,132.5,131.8,131.1,131.0,127.5,127.1,126.5,126.2,125.6,124.8,124.6,124.4,123.5,111.4,6.5,6.3.
Other parameters during the test were as follows: temperature (temperature): 293.4; pulse sequence (pulse sequence): zgpg30; number of scans (number of scans): 512; receive gain (receiver gain): 101; relaxation delay (relaxation delay): 2.0000; pulse width (pulse width): 10.0000; scanning frequency (spctrometer frequency): 125.76; spectral width (spectral width): 30120.5; lowest frequency (lowest frequency): -2484.0; nucleus (nucleous): 13C; size obtained (acquired size): 32768; spectral size (spectral size): 32768.
HRMS (with EI source mode): m/z C 20 H 21 OSi[M+H] + The theoretical value (calibrated value) of (d) is: 305.1356, found (found) as: 305.1364.
the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A preparation method of a five-membered silicon-containing fused heterocyclic compound is characterized by comprising the following steps:
in the presence of a solvent, reacting H 2 SiEt 2 Heating the compound shown in the formula II, unsaturated olefin and a ruthenium catalyst to react to obtain a compound shown in the formula I;
the structural formulas of the compound shown in the formula I and the compound shown in the formula II are as follows:
wherein n is not less than 1, R is independently selected from C 1～6 Alkoxy, halogen, C 1～6 Alkyl, amino, C 2～6 Ester group of (a).
2. The production method according to claim 1, wherein the ruthenium catalyst is selected from at least one of tris (2, 2' -bipyridine) dichloride hexahydrate, dichloro (p-methylisopropylbenzene) ruthenium (II) dimer, tris (triphenylphosphine) ruthenium dichloride, tris (triphenylphosphine) carbonyl ruthenium hydride, or tris (triphenylphosphine) carbonyl ruthenium hydrochloride.
3. The production method according to claim 1 or 2, characterized in that the unsaturated olefin is selected from at least one of cyclohexene, styrene, methyl acrylate, or norbornene.
4. The production method according to claim 1 or 2, characterized in that the solvent is at least one selected from the group consisting of xylene, 1, 4-dioxane, toluene, N-dimethylformamide.
5. The process according to claim 1 or 2, wherein the compound of formula II, H 2 SiEt 2 The molar ratio of unsaturated olefin to ruthenium catalyst is 1: (1-3): (1-6): (0.02-0.20).
6. According to claimThe process according to claim 5, wherein the compound of formula II, H 2 SiEt 2 The molar ratio of unsaturated olefin to ruthenium catalyst is 1:1.1:6:0.1.
7. the method according to claim 1, wherein the heating temperature is 50 ℃ to 150 ℃.
8. The method according to claim 1, wherein the heating time is 12 to 36 hours.
9. The method according to claim 8, wherein the heating time is 16 to 20 hours.
10. The method of claim 1, wherein the reaction is carried out in the absence of oxygen.
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