CN114835741A - Quaternary carbon gem-disilyl compound containing three silicon-hydrogen bonds and synthetic method and application thereof - Google Patents
Quaternary carbon gem-disilyl compound containing three silicon-hydrogen bonds and synthetic method and application thereof Download PDFInfo
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- CN114835741A CN114835741A CN202210418247.XA CN202210418247A CN114835741A CN 114835741 A CN114835741 A CN 114835741A CN 202210418247 A CN202210418247 A CN 202210418247A CN 114835741 A CN114835741 A CN 114835741A
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- phenyl
- silicon
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 20
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims abstract description 6
- -1 nitro, hydroxyl Chemical group 0.000 claims description 58
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 51
- 125000001424 substituent group Chemical group 0.000 claims description 31
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 13
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 10
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 10
- 125000004455 (C1-C3) alkylthio group Chemical group 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 6
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 125000000335 thiazolyl group Chemical group 0.000 claims description 5
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000001041 indolyl group Chemical group 0.000 claims description 4
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000005936 piperidyl group Chemical group 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 125000005493 quinolyl group Chemical group 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- CGRKYEALWSRNJS-UHFFFAOYSA-N sodium;2-methylbutan-2-olate Chemical compound [Na+].CCC(C)(C)[O-] CGRKYEALWSRNJS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 2
- PWKDHWCKSUMJID-UHFFFAOYSA-N 2-methylidene-1,3-dioxane Chemical compound C=C1OCCCO1 PWKDHWCKSUMJID-UHFFFAOYSA-N 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- XYEOALKITRFCJJ-UHFFFAOYSA-N o-benzylhydroxylamine Chemical compound NOCC1=CC=CC=C1 XYEOALKITRFCJJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- WZKSXHQDXQKIQJ-UHFFFAOYSA-N F[C](F)F Chemical group F[C](F)F WZKSXHQDXQKIQJ-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- 239000010948 rhodium Substances 0.000 abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000011734 sodium Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229910019443 NaSi Inorganic materials 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- NTQGILPNLZZOJH-UHFFFAOYSA-N disilicon Chemical compound [Si]#[Si] NTQGILPNLZZOJH-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- RWGLROKEYRSHME-UHFFFAOYSA-N 4-benzyl-4,5-dihydro-1,3-oxazole Chemical compound C=1C=CC=CC=1CC1COC=N1 RWGLROKEYRSHME-UHFFFAOYSA-N 0.000 description 1
- 241000029094 Acanthurus bahianus Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000006037 Brook Silaketone rearrangement reaction Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000346004 Daemonorops Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 240000000233 Melia azedarach Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000008096 xylene Substances 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
- C07F7/0896—Compounds with a Si-H linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a quaternary carbon and gem-disilicon compound containing three silicon-hydrogen bonds, which is shown as a formula V, and discloses a preparation method thereof: alkyne and silane are used as raw materials to synthesize the quaternary carbon gem-disilicon compound with high efficiency and high regioselectivity. The method has the advantages of mild reaction conditions, simple and convenient operation, high atom economy, no addition of toxic transition metal (such as ruthenium, rhodium, palladium and the like) salts, very high reaction zone selectivity and basically single zone selectivity. The quaternary carbon gem-disilicide containing three silicon-hydrogen bonds is synthesized for the first time, the compound can be used for synthesizing a silicon-containing polymer A, and the synthesized polymer has very high refractive index and is expected to be applied to the field of novel optical materials. The silicon polymer A is a hyperbranched polymer formed by connecting a formula B1 with a formula B2.
Description
Technical Field
The method relates to a quaternary carbon gem-disilyl compound containing three silicon-hydrogen bonds, and a synthesis method and application thereof.
Background
Organic alkyl silicon compound is synthesized in organic mode (a) Fleming, I; barbero, a.; walter, d.chem.rev.1997,97,2063.(b) Denmark, s.e.; regens, c.s.acc.chem.res.2008,41,1486.(c) Nakao, y.; hiyama, t.Soc.Rev.2011,40,4893.(d)Jensen,K.L.；Dickmeiss,G.；Jiang,H.；Albrecht,
K.A.Acc.Chem.Res.2012,45,248.(e)Zhang,H.-J.；Priebbenow,D.L.；Bolm,C.Chem.Soc.Rev.2013,42,8540.]Material Chemistry [ Silicon in Organic, Organometallic, and Polymer Chemistry; brook, m.a., ed.; wiley, New York,1999.]And medicinal chemistry [ (a) Pooni, P.K.; showell, g.a.mini-rev.med.chem.2006,6,1169, (b) gateway, s.; west, r.drug dev.res.2007,68,156.(c) Franz, a.k.; wilson, s.o.j.med.chem.2013,56,388.(d) Min, g.k.; hernandez, d.; skrydstrup, t.acc.chem.res.2013,46,457.]And the like, have numerous applications. Gem-disilylalkanes, i.e., compounds in which two silyl groups are attached to the same carbon of the alkyl group, are more versatile in conversion than monosilicon compounds due to the presence of two modifiable silyl groups in the class of compounds; on the other hand, the steric effect and the electronic effect of the gem-disilyl group can provide selectivity for organic chemical reactions different from the traditional reactions, so that the gem-disilyl group has wide application in organic synthesis. [ (a) Gao, l.; zhang, y. -b.; song, z. -l.synlett 2013,24,139.(b) Wu, y.; li, L.; li, H.; gao, l.; xie, h.; zhang, z.; su, s.; hu, c.; song, z.org.lett.2014,16, 1880-; lu, j.; song, z.l.; lin, x.l.; xu, y.j.; yin, z.p.chem.commu.2013, 49(79), 8961-; lin, x.l.; yang, n.; su, z.s.; hu, c.w.; xiao, p.h.; he, y.y.; song, z.l.j.am.chem.soc.2016,138(6), 1877-; wang, k.; gao, l.; song, z.l.chem.commu.2017, 53(21), 3078-; pu, q.; tang, z.x.; gao, l.; song, z.l. tetrahedron 2017,73(26), 3707-.]。
At present, the literature reports methods for preparing gem-disilylalkanes mainly include the following methods: the Song topic group in 2010 reported a method for the synthesis of allylic gem-disilanes by [1,4] -reverse Brook reaction on 3-silallylsilanols [ Song, z.l.; lei, z.; gao, l.; wu, x.; li, L.J.org.Lett.2010,12(22), 5298-. Wang group reported in 2015 that the synthesis of gem-disilylalkanes was achieved by a strategy of insertion of palladium carbene into silicon-silicon bond. [ Liu, z.x.; tan, h.c.; fu, t.r.; xia, y.; qiu, d.; zhang, y.; wang, J.B.J.Am.chem.Soc.2015,137(40),12800-12803.] Oestrreich project group reported in 2018 a copper-catalyzed dihalogenated hydrocarbon-bis-carbon-silicon bond coupling reaction to prepare disilylalkanes. [ Hazarti, H.; oestreich, M.org.Lett.2018,20(17), 5367-. However, the above reaction has problems of not easily available raw materials, poor reaction atom economy, and the like. Furthermore, none of the above reactions produces a gem-disilyl compound containing silicon-hydrogen bonds. The silicon-hydrogen bond can be converted into a silicon-carbon bond, a silicon-halogen bond, a silicon-oxygen bond and the like, so that the preparation of the organic silicon compound containing more silicon-hydrogen bonds is more beneficial to subsequent modification and conversion [ (a) Cheng, Z.Chin.J.chem.2019,37,632.(b) Cheng, Z.; xing, S.; guo, j.; cheng, b.; hu, l. -f.; zhang, x. -h.; lu, z.chi.j.chem.2019, 37,457.(c) Guo, j.; wang, h.; xing, S.; hong, x.; lu, z.chem 2019,5,881.(d) Hu, m. -y.; lian, j.; sun, w.; qiao, T. -Z.; zhu, s. -f.j.am.chem.soc.2019,141,4579 ] has greater value in preparing gem-disilyl compounds containing polysilicon hydrogen bonds.
The alkyne tandem disilicon hydrogenation reaction has the advantages of easily obtained reaction raw materials, high reaction atom economy and the like, and is an ideal method for efficiently preparing the gem-disilicon-based compound [ relevant reviews (a), Zeng, X.chem.Rev.2013,113,6864 (b), Cheng, Z.; guo, j.; lu, z.chem.commun.2020,56,2229. In recent years, there have been some advances in the preparation of gem-disilane compounds containing silicon-hydrogen bonds by tandem bishydrosilation of alkynes. One example of a cobalt catalyzed 1, 1-disilicon hydrogenation of terminal alkynes to produce geminal disilicon was reported by the Khalimon project group at 12 months 2018, but the reaction efficiency was low, requiring 8 days of reaction time, and was not systematically studied (nurseait, a.; Janabel, j.; Gudun, k.a.; Kassymbek, a.; Segizbayev, m.; Seilkhanov, t.m.; Khalimon, a.y. chemcatchem 2019,11,790). In 2019, a cobalt-catalyzed alkyl-terminated alkyne 1, 1-disilylation reaction was studied systematically by a technical group at the Luzhou province, and asymmetric transformation was developed by a strategy of cobalt-catalyzed relay [ (a) Cheng, Z.; xing, S.; guo, j.; cheng, b.; hu, l. -f.; zhang, x. -h.; lu, z.chi.j.chem.2019, 37,457; (b) guo, j.; wang, h.; xing, S.; hong, x.; lu, z. chem 2019,5,881. Almost simultaneously, the Zhudian task group reported iron-catalyzed alkyl-terminated alkyne 1, 1-disililation (Hu, M. -Y.; Lian, J.; Sun, W.; Qiao, T. -Z.; Zhu, S. -F.J.am.Chem.Soc.2019,141, 4579.). In 2020, the tremoline and lie peak topic groups reported rare earth metal catalyzed internal alkyne 1, 1-disililation reactions, but they did not report disililation reactions of terminal alkynes (Chen, W.; Song, H.; Li, J.; Cui, C.Angew.Chem.int.Ed.2020,59,2365.). In 2021, the daemonorops topic group achieved a boron catalyzed 1, 1-bis hydrosilation reaction of terminal alkynes (Wang, g.; Su, x.; Gao, l.; Liu, x.; Li, g.; Li, s.chem.sci.2021,12,10883.). The above examples provide an efficient method for the synthesis of gem-disilicon compounds, but the alpha, alpha-bis hydrosilation of phenylacetylene compounds to prepare gem-disilicon compounds containing quaternary carbon centers has not been achieved to date.
Due to the characteristics of abundant reserves, low price, environmental protection, strong sustainability, good biocompatibility and the like, the research of earth high-yield metal cobalt catalysts has become the popular research field of organic chemistry in recent years [ relevant reviews (a) Guo, J.; cheng, z.; chen, j.; chen, x.; lu, z.acc.chem.res.2021,54,2701 (b) Cheng, z.; guo, j.; lu, z.chem.commun.2020,56,2229.(c) Ai, w.; zhong, r.; liu, x.; liu, q.chem.rev.2019,119,2876-2953.(d) Pellissier, h.coord.chem.rev.2018,360,122.(e) Wen, h.; liu, g.; huang, Z.Coord.chem.Rev.2019,386,138-153.(f) Obrigcation, J.V.; chirik, p.j.nat.rev.chem.2018,2,15-34. Therefore, the development of cobalt-catalyzed alpha, alpha-tandem disilicon hydrogenation reaction of phenylacetylene compounds with high efficiency and high selectivity to synthesize the poly-silicon hydrogen bond gem-disilicon compounds has great significance.
Disclosure of Invention
The invention aims to provide a novel quaternary carbon gem-disilicon compound containing silicon-hydrogen bonds and a synthesis method thereof.
The technical scheme adopted by the invention is as follows: a quaternary carbon-gem-disilicon compound containing three Si-H bonds is prepared from Co-OIP catalyst and sodium triethylborohydride (NaBHEt) 3 ) The method can synthesize the quaternary carbon gem-disilicon compound with high efficiency and high selectivity.
The invention provides a quaternary carbon gem-disilicon compound containing three silicon-hydrogen bonds, which is shown as a formula V:
in the formula V, R 1 Optionally selected from H, the following groups which are unsubstituted or contain substituent A: a heterocyclic aryl A of aryl A, C4 to C20 of C6 to C20; the substituent A is one or more than two of the following: C1-C16 alkyl, C1-C16 alkoxy, C1-C16 siloxy, C1-C3 alkylthio, halogen, trifluoromethyl, hydroxyl, C1-C3 aldehyde, C1-C3 carboxyl, amino, C1-C3 ester, phenyl, amide, methoxycarbonyl, nitro, hydroxyl, benzyloxy, acetoxymethyl;
in the formula V, R 2 、R 3 The substituent B is phenyl or substituted phenyl, and the substituent on the substituted phenyl is one or more of the following groups: halogen, C1-C16 alkyl, C1-C16 alkoxy, C1-C16 alkylthio, phenyl, trifluoromethyl, methoxycarbonyl, nitro, hydroxyl, C1-C3 aldehyde, C1-C3 carboxyl, amino, C1-C16 ester group, C1-C16 silane group, C1-C16 siloxy, benzyloxy, amide, acetoxymethyl, 2-methylene-1, 3-dioxycyclopentyl; the substituent C or the substituent D is one or more than two of the following components: C1-C16 alkyl, C1-C16 alkoxy, C1-C16 siloxy, C1-C3 alkylthio, halogen, trifluoromethyl, hydroxyl, C1-C3 aldehyde, C1-C3 carboxyl, amino, C1-C3 ester, phenyl, amide, methoxycarbonyl, nitro, hydroxyl, benzyloxy and acetoxymethyl.
Further, it is preferable that R is 1 Optionally selected from the following unsubstituted or substituted A-containing groups: a heterocyclic aryl A of aryl A, C4 to C20 of C6 to C20;
the aryl A of C6-C20 is preferably phenyl, 3 ', 4' - (2-methylene-1, 3-dioxane) -phenyl or naphthyl;
the heterocyclic aryl A of C4-C20 is preferably indolyl, thienyl, benzothienyl, pyridyl, piperidyl, quinolyl, carbazolyl or 1, 8-naphthyridinyl;
the substituent A is preferably one or more than two of the following: C1-C6 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, halogen, trifluoromethyl, hydroxyl, C1-C3 aldehyde group, C1-C3 carboxyl, amino, C1-C3 ester group, phenyl or amide.
Further, it is preferable that R is 2 、R 3 Optionally C1-C16 alkyl which is unsubstituted or contains a substituent B, C6-C20 aryl B which is unsubstituted or contains a substituent C, or C4-C20 heterocyclic aryl B;
the aryl B of C6-C20 is preferably phenyl or naphthyl; the heterocyclic aryl B of C4-C20 is preferably indolyl, thienyl, pyridyl, piperidyl, carbazolyl or quinolyl
Further, preferably, R is 2 Phenyl or substituted phenyl, preferably R 3 is-K 1 -a substituent B, phenyl or substituted phenyl; said K 1 Is C1-C6 alkylene, the substituent B is phenyl or substituted phenyl, and the substituent on the substituted phenyl is one or more than two of the following groups: C1-C6 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, halogen, trifluoromethyl, hydroxyl, C1-C3 aldehyde group, C1-C3 carboxyl, amino, C1-C3 ester group, phenyl or amide.
The invention also provides a synthesis method of the quaternary carbon gem-disilicide containing three silicon-hydrogen bonds, which comprises the following steps: under inert gas, alkyne shown in formula I and dihydro-silane shown in formula II are reacted in CoX 2 -carrying out a first hydrosilation reaction in the presence of a catalytic amount of an activating reagent in the presence of an OIP complex catalyst; then adding trihydrosilane shown in the formula III and a catalytic amount of hydrogen negative reagent to carry out a second step of hydrosilation reaction to obtain a gem-disilicon compound containing three silicon-hydrogen bonds shown in the formula V;
R 2 2 SiH 2 II
R 3 SiH 3 III
the reaction formula is shown as the following formula (1):
in the formula I, the formula II and the formula III, R 1 、R 2 、R 3 As defined above.
CoX for use in the invention 2 The structural formula of the-OIP complex (OIP: oxazoline imine pyridine ligand) is a compound shown as a formula IV or an enantiomer thereof, wherein the enantiomer is a mirror image of the formula IV, and in the formula IV, R 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 ，R 15 ，R 16 ，R 17 ，R 18 ,R 19 ,R 20 Any one selected from the group consisting of H, C1-C16 alkyl, C1-C16 alkoxy, phenyl, naphthyl, or benzyl: h on the alkyl and the alkoxy is not substituted or is substituted by more than 1 substituent E, and the substituent E is nitro, halogen, phenyl, methoxycarbonyl, trifluoromethyl, hydroxyl, aldehyde group of C1-C3, carboxyl of C1-C3, amino, ester group or amide group of C1-C3;
h on the phenyl, the benzyl and the naphthyl is not substituted or is substituted by more than 1 substituent F, and the substituent F is alkyl of C1-C3, alkoxy of C1-C3, nitro, halogen, phenyl, methoxycarbonyl, trifluoromethyl, hydroxyl, aldehyde of C1-C3, carboxyl of C1-C3, amino, ester group or amide group of C1-C3;
x is F, Cl, Br, I, OAc, CF 3 SO 3 Any one of them.
Go toStep (b), the CoX 2 The structural formula of the-OIP complex is preferably a compound represented by formula IV, wherein R is preferably selected 9 、R 10 、R 11 、R 14 、R 16 、R 17 、R 19 、R 20 Are all H; r 12 Is methyl; r 13 Is C 1 -C 4 Alkyl of R 15 Is H, C 1 -C 4 Alkyl of (C) 1 -C 4 Alkoxy or halogen of (a); r 18 Is C 1 -C 4 Alkyl, benzyl or phenyl of (a); and X is Br.
More preferably, the CoX used 2 the-IIP complex is as shown in formula IV-1
In the process of the invention, CoX 2 The synthesis of-OIP complexes is described in Angew. chem. int. Ed.2016,55, 10835-10838.
As a further improvement, the synthesis method of the invention can be carried out in no solvent or in an organic solvent, and when the synthesis method is carried out in the organic solvent, the organic solvent can be any one of benzene, toluene, tetrahydrofuran, diethyl ether, dioxane, petroleum ether, cyclohexane, n-hexane and ethyl acetate, and tetrahydrofuran is preferably used as the reaction solvent.
The volume usage of the organic solvent is generally 0.1-10 mL/mmol based on the mass of the alkyne shown in the formula I.
The reactions of the present invention are all carried out under an inert gas, which may be nitrogen or argon.
In the first step of hydrosilation reaction, the activating reagent is used for reducing and activating the catalyst precursor into an active intermediate under the combined action of silane, and the activating reagent is preferably any one of sodium triethylborohydride, sodium tri-sec-butylborohydride and lithium triethylborohydride or strong alkali sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium tert-amylate, sodium ethoxide, sodium methoxide and potassium methoxide, preferably sodium triethylborohydride, sodium tert-butoxide, sodium ethoxide or sodium methoxide, and more preferably sodium triethylborohydride.
In the method of the present invention, in the second hydrosilylation reaction, the hydrogen negative reagent is a catalyst for the second hydrosilylation reaction, and the hydrogen negative reagent is preferably any one of sodium triethylborohydride, sodium tri-sec-butylborohydride, lithium triethylborohydride, or a strong base sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium tert-amylate, sodium ethoxide, sodium methoxide, and potassium methoxide, preferably sodium triethylborohydride, sodium tert-butoxide, sodium ethoxide, or sodium methoxide, and more preferably sodium triethylborohydride.
As a further improvement, in the synthesis method of the invention, in the first step of hydrosilation reaction, the alkyne shown in formula I, the dihydrosilane shown in formula II and CoX 2 The mass ratio of the-OIP complex to the activating agent is 1: 0.1-10: 0.0000005-0.01: 0.0000015-0.05, preferably 1:0.5-5:0.00005-0.01: 0.00015-0.03; more preferably 1:0.5-2:0.005-0.01: 0.015-0.03; more preferably 1: 1.0-1.5: 0.005-0.01: 0.015-0.03; most preferably 1: 1.0:0.01:0.03.
In the second step of hydrosilation reaction, the quantity ratio of the alkyne shown in the formula I, the trihydrosilane shown in the formula III and the hydrogen negative reagent is 1: 0.1-10: 0.01-0.30; preferably 1:0.5-5: 0.05-0.20; more preferably 1:0.5-3: 0.05-0.15; more preferably 1: 1.0-1.5: 0.05-0.15; most preferably 1:1.5: 0.10.
As a further improvement, in the synthesis method, the temperature of the first step of hydrosilation reaction is-30-100 ℃, preferably-10-50 ℃, and more preferably the reaction is carried out at normal temperature;
the reaction temperature of the second step hydrosilation reaction is-30 ℃ to 100 ℃, preferably-30 ℃ to 80 ℃. Particularly preferably 50 to 80 ℃.
In the synthesis method, the time of the first step of hydrosilation reaction is 5 seconds to 10 minutes, preferably 1 to 5 minutes;
the reaction time of the second hydrosilation reaction is preferably 1 hour to 100 hours, more preferably 1 hour to 60 hours, particularly preferably 24 hours.
As a further improvement, after the second step hydrosilation reaction is finished, the obtained crude product is subjected to post-treatment to obtain the quaternary carbon gem-disilicon compound shown as the formula V, and further, the post-treatment method is one or more than two of the following methods: recrystallization, thin layer chromatography, column chromatography or distillation under reduced pressure, preferably column chromatography.
The method of the invention provides an effective CoX 2 the-OIP complex and the hydrogen negative reagent are used as catalysts, alkyne and silane are used as raw materials, and the method for synthesizing the quaternary carbon gem-disilicon compound is high in efficiency and high in regioselectivity. The method has the advantages of mild reaction conditions, simple and convenient operation and high atom economy. In addition, the reaction does not need to add any other toxic transition metal (such as ruthenium, rhodium, palladium and the like) salts, and has great practical application value in the synthesis of medicines and materials. And the reaction has moderate to excellent yield (46% -89%), high regioselectivity (basically single regioselectivity), and good functional group tolerance.
The quaternary carbon gem-disilicon compound shown in the formula V can be used for synthesizing silicon-containing polymers. The synthesized polymer has very high refractive index and is expected to be applied to the field of novel optical materials.
Further, the quaternary carbon gem-disilicon compound shown as the formula V can be subjected to polymerization hydrosilation reaction with the diyne compound shown as the formula VI to synthesize the silicon-containing polymer A. The method comprises the step of carrying out polymerization hydrosilation reaction on a quaternary carbon gem-disilicon compound shown as a formula V and a diyne compound shown as a formula VI under the catalysis of a platinum catalyst to obtain a silicon-containing polymer A, wherein the reaction formula is shown as the following formula:
formula VI, R A Is phenyl, biphenyl or thiazolyl;
the silicon-containing polymer A is a hyperbranched polymer formed by connecting a formula B1 with a formula B2, and the formulae B1 and B2 are as follows:
in the formulae B1 and B2, R A Is phenyl, biphenyl or thiazolyl;
R 1 、R 2 、R 3 as defined above.
Further, the polymeric hydrosilation reaction is generally carried out in an organic solvent, preferably tetrahydrofuran.
The platinum catalyst is Karstedt's catalyst (kastet catalyst).
Further, the reaction step of synthesizing the silicon-containing polymer A by the hydrogenation of the polymeric silicon is preferably as follows: under the protection of inert gas, uniformly stirring the gem-disilicon compound shown in the formula V and the diyne compound shown in the formula VI in a tetrahydrofuran solvent, adding Karstedt catalyst, and reacting for 24-72 hours at the temperature of 60-80 ℃ in a sealing and stirring manner; after the reaction is finished, cooling the reaction mixture to room temperature, and purifying to obtain a silicon-containing polymer A; the mass ratio of the gem-disilicon compound shown as the formula V, the diyne compound shown as the formula VI and the Karstedt catalyst is 1: 0.5-1.5: 0.005-0.02.
The purification method is generally as follows: adding methanol into the reaction mixture to generate yellow solid precipitate to obtain a two-phase mixture, and stirring and pulping vigorously; then standing for layering, and carefully taking out the top liquid layer; methanol was added to the remaining solid, this procedure was repeated twice, and a polymer solid was obtained by filtration and dried under vacuum to obtain a silicon-containing polymer a.
The invention also provides a silicon-containing polymer A prepared by carrying out polymerization hydrosilation on quaternary carbon gem-disilicon compounds containing three silicon-hydrogen bonds, wherein the silicon-containing polymer A is a hyperbranched polymer formed by connecting a formula B1 with a formula B2, and the formulae B1 and B2 are as follows:
in the formulae B1 and B2, R A Is phenyl or biphenyl;
R 1 、R 2 、R 3 is as defined in claim 1The above-mentioned processes are described.
The invention provides a quaternary carbon gem-disilicon compound and a method for synthesizing the quaternary carbon gem-disilicon compound with high efficiency and high regioselectivity by taking alkyne and silane as raw materials. The method has the advantages of mild reaction conditions, simple and convenient operation, high atom economy, no addition of toxic transition metal (such as ruthenium, rhodium, palladium and the like) salts, very high reaction zone selectivity and basically single zone selectivity.
The quaternary carbon gem-disilicide containing three silicon-hydrogen bonds is synthesized for the first time, the compound can be used for synthesizing silicon-containing polymers, and the synthesized polymers have very high refractive index and are expected to be applied to the field of novel optical materials.
Detailed Description
The technical solution of the present invention is further specifically described by the following specific examples, but the scope of the present invention is not limited thereto:
example 1: CoX 2 -OIP complex catalyzed cascade alpha, alpha-hydrosilation of alkynes with silanes
Standard conditions: OIP. CoBr was added to a dry 25mL Schlenk reaction tube under argon at room temperature in order 2 The complex (0.005mmol,1.0 mol%), THF (0.50mL,1.0M) and stirring was turned on. And then, diarylsilane (0.50mmol,1.0equiv.) represented by formula II and sodium triethylborohydride (NaBHEt) were sequentially added thereto 3 ) (0.015mmol,3.0 mol%) and the alkyne of formula I (0.50mmol,1.0equiv.) were stirred for 5 minutes under argon. After that, THF was carefully pumped off to make a solvent-free state. Subsequently, toluene (0.50mL,1.0M), trihydrosilane of formula III (0.75mmol,1.5equiv.) and NaBHEt were added in that order under argon 3 (0.050mmol,10 mol%) and the rubber stopper was replaced with a vacuum glass stopper (vacuum silicone grease applied). The reaction was stirred at 60 ℃ for 24 hours. Then, the product is obtained by column chromatography separation (the elution solvent is petroleum ether or a mixture of petroleum ether and ethyl acetate). (in individual reactions, CoX 2 -OIP complex, NaBHEt 3 The amounts and other conditions are varied, as specified under each product)
In example 1, CoX 2 -the OIP complex has the formula IV-1 below:
the specific method comprises the following steps:
palladium acetate (0.0284g,0.125mmol),1, 2-bis (diphenylphosphino) ethane (dppe) (0.0555g,0.140mmol), and anhydrous 1, 4-dioxane (40mL) were added to a dry 100mL Schlenk tube in succession under nitrogen blanket, and stirred for 5 minutes. Thereafter, 6- (1- (N-2, 4-dimethylphenyl) ethylimino) -2-bromo-pyridine (1.5451g,5.0mmol), 4-benzyl-oxazoline (0.7670g,6.0mmol) and Schlenk's tube were added in this order, degassed three times with liquid nitrogen, the reaction mixture was stirred in an oil bath at 110 ℃ for 14.5 hours, then cooled to room temperature, diluted with ethyl acetate containing 1% triethylamine and filtered with suction with a sand core poured over the silica gel, and the silica gel was washed with ethyl acetate containing 1% triethylamine. After removal of the solvent by rotary evaporation, the mixture was taken up in petroleum ether: ethyl acetate (10:1) mixed solvent as a mobile phase and silica gel as a stationary phase (basified with 1% triethylamine petroleum ether) were subjected to column chromatography to give VII-1(1.5349g,4.0mmol, 79% yield) as a yellow solid. 1 The data of H NMR and the like are consistent with those reported in the literature (Angew. chem. int. Ed.2016,55, 10835-10838).
CoBr was added sequentially to a dry 50mL Schlenk reaction tube under argon protection 2 (0.4381g,2.0mmol),VII-1(0.8440g,2.2mmol) and tetrahydrofuran (20mL), and then stirred at room temperature for 3 hours. Then, ether (10mL) was added under an air atmosphere and filtered through a sand funnel. The filter cake was washed with ether and dried under vacuum to give IV-1(1.0213g,1.7mmol, 85% yield). Dark green powdery solid. Single crystal diffraction of the corresponding chiral compound has been reported, CCDC 1435433.
V-1:
1-phenylsilyl-1-diphenylsilyl-ethylbenzene
Diphenyl(1-phenyl-1-(phenylsilyl)ethyl)silane
Standard conditions. White solid, 76% yield, M.p.40.6-42.6 ℃ IR (cm) -1 ):3049,3018,2924,2861,2136,1592,1428. 1 H NMR(400MHz,CDCl 3 ):δ7.52-7.46(m,2H),7.43-7.37(m,1H),7.37-7.28(m,5H),7.28-7.17(m,5H),7.17-7.05(m,7H),5.17(s,1H),4.63(d,J＝6.8Hz,1H),4.42(d,J＝6.8Hz,1H),1.53(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ143.1,136.3,136.1,136.0,132.9,132.7,130.2,129.8,129.6,129.5,128.3,127.8,127.6,127.5,127.3,124.2,19.0,16.7.HRMS(ESI)calculated for[C 26 H 26 NaSi 2 ] + (M+Na + )requires m/z 417.1465,found m/z 417.1465.
V-2:
1-benzyl-silyl-1-diphenylsilyl-ethylbenzene
(1-(Benzylsilyl)-1-phenylethyl)diphenylsilane
The standard conditions were slightly adjusted [ second step reaction for 25h]. White solid, 76% yield, M.p. 56.2-57.1 ℃ C. IR (cm) -1 ):3051,3022,2928,2862,2134,1595,1491. 1 H NMR(400MHz,CDCl 3 ):δ7.52(d,J＝7.2Hz,2H),7.44-7.37(m,1H),7.37-7.08(m,14H),7.05-6.99(m,1H),6.85(d,J＝7.6Hz,2H),5.10(s,1H),4.08-4.00(m,1H),3.91-3.82(m,1H),1.98-1.82(m,2H),1.58(s,3H). 13 C NMR(100MHz,CDCl 3 ):δ143.5,139.2,136.2,135.9,132.58,132.56,129.9,129.6,128.5,128.3,127.9,127.6,126.9,124.5,124.3,19.1,16.8,16.6.HRMS(ESI)calculated for[C 27 H 28 NaSi 2 ] + (M+Na + )requires m/z 431.1622,found m/z 431.1620.
V-3:
1-Methylenebenzylsilyl-1-diphenylsilyl-ethylbenzene
(1-(Phenethylsilyl)-1-phenylethyl)diphenylsilane
Standard conditions. Standard conditions. Colorless liquid, 89% yield, IR (cm) -1 ):3064,3024,2928,2860,2129,1594,1491. 1 H NMR(400MHz,CDCl 3 ):δ7.53-7.47(m,2H),7.43-7.37(m,1H),7.35-7.28(m,5H),7.26-7.14(m,8H),7.14-7.07(m,2H),6.98(d,J＝7.6Hz,2H),5.11(s,1H),4.03-3.97(m,1H),3.87-3.81(m,1H),2.51-2.35(m,2H),1.60(s,3H),0.87-0.71(m,2H)； 13 C NMR(100MHz,CDCl 3 ):δ144.1,143.8,136.2,135.9,132.8,132.7,129.8,129.5,128.4,128.2,127.8,127.7,127.6,126.9,125.6,124.2,31.2,18.3,16.9,9.3；HRMS(ESI)calculated for[C 28 H 30 NaSi 2 ] + (M+Na + )requires m/z 445.1778,found m/z 445.1774.
V-4:
1-benzyl-silyl-1-diphenylsilyl-3' -methyl ethylbenzene
(1-(Benzylsilyl)-1-(m-tolyl)ethyl)diphenylsilane
Standard conditions. Standard conditions. Colorless liquid, 76% yield, IR (cm) -1 ):3049,3023,2922,2861,2135,1598,1489. 1 H NMR(400MHz,CDCl 3 ):δ7.50(d,J＝7.2Hz,2H),7.43-7.37(m,1H),7.36-7.27(m,5H),7.25-7.09(m,5H),7.04-6.90(m,4H),6.85(d,J＝7.2Hz,2H),5.07(s,1H),4.05-3.98(m,1H),3.90-3.83(m,1H),2.26(s,3H),1.98-1.84(m,2H),1.56(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ143.3,139.2,137.8,136.2,136.0,132.8,132.7,129.9,129.6,128.31,128.27,127.8,127.5,125.1,124.5,123.8,21.6,18.8,16.8,16.7；HRMS(ESI)calculated for[C 28 H 30 NaSi 2 ] + (M+Na + )requires m/z 445.1778,found m/z 445.1775.
V-5:
1-phenylsilyl-1-diphenylsilyl-3' -methyl ethylbenzene
Diphenyl(1-(phenylsilyl)-1-(m-tolyl)ethyl)silane
Standard conditions. Standard conditions. Colorless liquid, 72% yield, IR (cm) -1 ):3049,2923,2860,2135,1597,1428. 1 H NMR(400MHz,CDCl 3 ):δ7.49-7.44(m,2H),7.42-7.20(m,9H),7.18-7.07(m,5H),6.95-6.88(m,3H),5.13(s,1H),4.60(d,J＝6.8Hz,1H),4.42(d,J＝6.8Hz,1H),2.22(s,3H),1.51(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ142.8,137.5,136.3,136.2,136.1,133.1,132.8,130.4,129.8,129.6,129.5,128.3,128.1,127.8,127.54,127.49,125.0,124.2,21.5,18.8,16.7；HRMS(EI)calculated for[C 27 H 28 Si 2 ] + (M + )requires m/z 408.1730,found m/z 408.1728.
V-6:
1-phenylsilyl-1-diphenylsilyl-3' -phenylethane
(1-([1,1'-Biphenyl]-3-yl)-1-(phenylsilyl)ethyl)diphenylsilane
The standard conditions are slightly adjusted [ second step reaction for 16h]. Colorless liquid, 66% yield, IR (cm) -1 ):3066,2925,2859,2137,1654,1593,1480,1428. 1 H NMR(400MHz,CDCl 3 ):δ7.52-7.47(m,2H),7.44-7.38(m,3H),7.37-7.22(m,14H),7.18-7.08(m,5H),5.19(s,1H),4.68(d,J＝6.8Hz,1H),4.48(d,J＝6.8Hz,1H),1.57(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ143.5,141.4,140.7,136.3,136.2,136.1,133.0,132.6,130.2,129.9,129.7,129.6,128.7,128.6,127.9,127.7,127.6,127.1,126.5,126.0,123.2,19.3,16.9.HRMS(EI)calculated for[C 32 H 30 Si 2 ] + (M + )requires m/z 470.1886,found m/z 470.1887.
V-7:
1-phenylsilyl-1-diphenylsilyl-3' -methoxyethylbenzene
(1-(3-Methoxyphenyl)-1-(phenylsilyl)ethyl)diphenylsilane
The standard conditions are slightly adjusted [ second step reaction for 16h]. Colorless liquid, 73% yield, IR (cm) -1 ):3049,3002,2956,2861,2140,1596,1428. 1 H NMR(400MHz,CDCl 3 ):δ7.51-7.46(m,2H),7.43-7.37(m,3H),7.36-7.22(m,6H),7.19-7.10(m,5H),6.73(d,1H),6.68-6.63(m,2H),5.14(s,1H),4.63(d,J＝6.8Hz,1H),4.43(d,J＝6.8Hz,1H),3.59(s,3H),1.51(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ159.4,144.8,136.2,136.15,136.06,133.0,132.6,130.2,129.8,129.7,129.6,129.2,127.8,127.6,127.5,119.7,112.9,110.3,54.9,19.4,16.8；HRMS(EI)calculated for[C 27 H 28 OSi 2 ] + (M + )requires m/z 424.1679,found m/z 424.1678.
V-8:
1-phenylsilyl-1-diphenylsilyl-3' -fluoroethylbenzene
(1-(3-Fluorophenyl)-1-(phenylsilyl)ethyl)diphenylsilane
The standard conditions are slightly adjusted [ second step reaction for 16h]. Colorless liquid, 53% yield, IR (cm) -1 ):3069,2951,2861,2140,1580,1484,1429. 1 H NMR(400MHz,CDCl 3 ):δ7.53-7.48(m,2H),7.44-7.39(m,1H),7.38-7.22(m,8H),7.20-7.13(m,3H),7.12-7.07(m,2H),6.95(d,J＝8.0Hz,1H),6.82-6.76(m,2H),5.16(s,1H),4.62(d,J＝6.8Hz,1H),4.40(d,J＝6.8Hz,1H),1.51(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ163.1(d,J＝245Hz,1C),146.4(d,J＝7Hz,1C),136.2,136.1,135.9,132.4,132.3,130.0,129.8,129.75,129.68,129.4(d,J＝8Hz,1C),127.9,127.7,127.6,123.2(d,J＝2Hz,1C),114.0(d,J＝23Hz,1C),111.0(d,J＝21Hz,1C),19.6,16.7； 19 F NMR(376MHz,CDCl 3 ):δ-113.0；HRMS(EI)calculated for[C 26 H 25 FSi 2 ] + (M + )requires m/z 412.1479,found m/z 412.1481.
V-9:
1-benzyl-silyl-1-diphenylsilyl-4' -methyl ethylbenzene
(1-(Benzylsilyl)-1-(p-tolyl)ethyl)diphenylsilane
White solid, 75% yield, M.p.57.3-59.2 ℃ IR (cm) -1 ):3052,3023,2923,2862,2135,1509,1454. 1 H NMR(400MHz,CDCl 3 ):δ7.54-7.50(m,2H),7.42-7.37(m,1H),7.35-7.28(m,5H),7.24-7.18(m,2H),7.15-6.98(m,7H),6.85(d,J＝7.2Hz,2H),5.08(s,1H),4.04-3.97(m,1H),3.88-3.81(m,1H),2.32(s,3H),1.96-1.83(m,2H),1.56(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ140.2,139.3,136.2,136.0,133.6,132.8,132.7,129.9,129.5,129.2,128.33,128.28,127.8,127.6,126.7,124.4,20.9,18.4,16.8,16.7；HRMS(ESI)calculated for[C 28 H 30 NaSi 2 ] + (M+Na + )requires m/z 445.1778,found m/z 445.1776.
V-10:
1-phenylsilyl-1-diphenylsilyl-4' -phenylethane
(1-([1,1'-Biphenyl]-4-yl)-1-(phenylsilyl)ethyl)diphenylsilane
Standard conditions. Colorless liquid, 72% yield, IR (cm) -1 ):3049,3027,2928,2860,2137,1595,1517,1464. 1 H NMR(400MHz,CDCl 3 ):δ7.62(d,J＝7.6Hz,2H),7.55-7.46(m,4H),7.45-7.36(m,5H),7.35-7.10(m,13H),5.20(s,1H),4.67(d,J＝6.8Hz,1H),4.46(d,J＝6.8Hz,1H),1.57(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ142.4,140.7,136.7,136.3,136.2,136.0,132.8,132.6,130.1,129.9,129.7,129.6,128.7,127.9,127.7,127.5,126.9,126.72,126.69,19.0,16.8.HRMS(ESI)calculated for[C 32 H 30 NaSi 2 ] + (M+Na + )requires m/z 493.1778,found m/z 493.1775.
V-11:
1-benzyl-silyl-1-diphenylsilyl-4' -methoxy-ethylbenzene
(1-(Benzylsilyl)-1-(4-methoxyphenyl)ethyl)diphenylsilane
The standard conditions were slightly adjusted [ second step, NaBHEt 3 (15 mol%) and reacted for 28h]. Colorless liquid, 60% yield, IR (cm) -1 ):3050,3027,2901,2835,2134,1603,1506. 1 H NMR(400MHz,CDCl 3 ):δ7.51(d,J＝7.2Hz,2H),7.40(dd,J＝7.6,7.2Hz,1H),7.36-7.28(m,5H),7.26-7.19(m,2H),7.16-6.99(m,5H),6.88-6.80(m,4H),5.07(s,1H),4.04-3.96(m,1H),3.89-3.83(m,1H),3.81(s,3H),1.97-1.84(m,2H),1.55(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ156.6,139.3,136.2,135.9,135.2,132.7,129.9,129.6,128.30,128.29,127.9,127.7,127.6,124.5,113.9,55.2,17.7,17.0,16.6；HRMS(ESI)calculated for[C 28 H 30 ONaSi 2 ] + (M+Na + )requires m/z 461.1727,found m/z 461.1727.
V-12:
1-benzyl-silyl-1-diphenylsilyl-3 ', 4' -dimethylethylbenzene
(1-(Benzylsilyl)-1-(3,4-dimethylphenyl)ethyl)diphenylsilane
Standard conditions. Colorless liquid, 70% yield, IR (cm) -1 ):3051,3020,2962,2864,2134,1599,1497. 1 H NMR(400MHz,CDCl 3 ):δ7.53-7.48(m,2H),7.42-7.37(m,1H),7.35-7.29(m,5H),7.25-7.19(m,2H),7.15-7.09(m,2H),7.04-6.98(m,2H),6.91-6.83(m,4H),5.06(s,1H),4.02-3.95(m,1H),3.89-3.82(m,1H),2.24(s,3H),2.17(s,3H),1.97-1.84(m,2H),1.55(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ140.4,139.4,136.3,136.2,136.0,133.0,132.9,132.3,129.8,129.7,129.5,128.4,128.3,128.2,127.8,127.5,124.4,124.1,19.9,19.2,18.2,16.8,16.8.HRMS(ESI)calculated for[C 29 H 32 NaSi 2 ] + (M+Na + )requires m/z 459.1935,found m/z 459.1937.
V-13:
1-benzyl-silyl-1-diphenylsilyl-3 '-chloro-4' -methyl ethylbenzene
(1-(Benzylsilyl)-1-(3-chloro-4-methylphenyl)ethyl)diphenylsilane
And (4) standard conditions. Colorless liquid, 48% yield, IR (cm) -1 ):3052,3022,2927,2863,2136,1601,1492. 1 H NMR(400MHz,CDCl 3 ):δ7.52(d,J＝7.2Hz,2H),7.44-7.38(m,1H),7.37-7.30(m,5H),7.27-7.21(m,2H),7.15-7.06(m,4H),7.05-7.99(m,1H),6.95(d,J＝8.4Hz,1H),6.85(d,J＝7.6Hz,2H),5.06(s,1H),4.04-3.97(m,1H),3.89-3.82(m,1H),2.35(s,3H),1.97-1.85(m,2H),1.54(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ143.0,138.9,136.2,135.9,134.6,132.3,131.7,130.8,130.0,129.8,128.3,127.9,127.7,127.1,125.3,124.6,19.4,18.7,16.8,16.7；HRMS(ESI)calculated for[C 28 H 29 ClNaSi 2 ] + (M+Na + )requires m/z 479.1389,foundm/z 479.1388.
V-14:
1-phenylsilyl-1-diphenylsilyl-3 ', 4' - (2-methylene-1, 3-dioxane) -ethylbenzene
(1-(Benzo[d][1,3]dioxol-5-yl)-1-(phenylsilyl)ethyl)diphenylsilane
Standard conditions. Colorless liquid, 60% yield, IR (cm) -1 ):3068,3015,2897,2775,2138,1482,1428. 1 H NMR(400MHz,CDCl 3 ):δ7.52(d,J＝7.6Hz,2H),7.43-7.21(m,9H),7.20-7.10(m,4H),6.72-6.64(m,2H),6.59(d,J＝8.4Hz,1H),5.94-5.87(m,2H),5.13(s,1H),4.59(d,J＝6.8Hz,1H),4.39(d,J＝6.8Hz,1H),1.49(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ147.7,144.4,137.0,136.2,136.1,136.0,132.8,132.7,130.1,129.9,129.7,129.6,127.8,127.7,127.6,120.1,108.1,107.9,100.7,18.6,17.1；HRMS(EI)calculated for[C 27 H 26 O 2 Si 2 ] + (M + )requires m/z 438.1471,foundm/z 438.1473.
V-15:
(1-phenylsilyl-1-diphenylsilyl) ethyl-5-benzothiophene
(1-(Benzo[b]thiophen-5-yl)-1-(phenylsilyl)ethyl)diphenylsilane
Standard conditions. Colorless liquid, 68% yield, IR (cm) -1 ):3067,3018,2954,2860,2136,1592,1430. 1 H NMR(400MHz,CDCl 3 ):δ7.71(d,J＝8.4Hz,1H),7.51-7.45(m,3H),7.42-7.19(m,11H),7.16(d,J＝5.2Hz,1H),7.14-7.06(m,4H),5.19(s,1H),4.65(d,1H),4.47(d,1H),1.61(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ140.1,139.3,136.2,136.1,136.0,135.9,132.9,132.6,130.2,129.8,129.63,129.60,127.8,127.6,127.5,126.2,124.6,124.0,122.0,121.7,18.9,17.1；HRMS(ESI)calculated for[C 28 H 26 NaSSi 2 ] + (M+Na + )requires m/z 473.1186,found m/z 473.1181.
V-16:
(1-phenylsilyl-1-diphenylsilyl) ethyl-2-thiophene
Diphenyl(1-(phenylsilyl)-1-(thiophen-2-yl)ethyl)silane
The standard conditions were adjusted slightly (first step reaction 1h, first step reaction 26 h). Yellow liquid, 46% yield, IR (cm) -1 ):3068,2996,2924,2859,2139,1429. 1 H NMR(400MHz,CDCl 3 ):δ7.58-7.52(m,2H),7.46-7.39(m,3H),7.38-7.23(m,6H),7.22-7.14(m,4H),7.04(dd,J＝5.2,0.8Hz,1H),6.94(dd,J＝5.2,3.6Hz,1H),6.65(dd,J＝3.6,0.8Hz,1H),5.15(s,1H),4.57(d,J＝7.2Hz,1H),4.41(d,J＝7.2Hz,1H),1.58(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ149.2,136.2,136.1,136.0,132.3,132.2,130.0,129.8,129.7,127.9,127.7,127.6,127.1,122.7,121.6,18.9,17.5；HRMS(ESI)calculated for[C 24 H 25 SSi 2 ] + (M+H + )requires m/z 401.1210,foundm/z 401.1211.
V-17:
(1-benzylsilyl-1-diphenylsilyl) ethyl-2-naphthalene
(1-(Benzylsilyl)-1-(naphthalen-2-yl)ethyl)diphenylsilane
White solid, 73% yield, M.p.86.0-87.7 ℃ IR (cm) -1 ):3054,3022,2929,2862,2134,1595,1495,1428. 1 H NMR(400MHz,CDCl 3 ):δ7.80(d,J＝7.6Hz,1H),7.71(dd,J＝8.4,8.0Hz,2H),7.55-7.49(m,3H),7.48-7.37(m,4H),7.35-7.27(m,5H),7.22-7.16(m,2H),7.11-7.05(m,2H),7.02-6.96(m,1H),6.81(d,J＝7.6Hz,2H),5.17(s,1H),4.15-4.08(m,1H),3.95-3.88(m,1H),1.97-1.89(m,1H),1.89-1.81(m,1H),1.70(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ141.4,139.0,136.2,135.9,133.9,132.6,132.5,131.0,130.0,129.7,128.30,128.27,127.9,127.8,127.6,127.49,127.47,126.4,125.9,124.9,124.5,124.4,19.8,17.1,16.6；HRMS(ESI)calculated for[C 31 H 30 NaSi 2 ] + (M+Na + )requires m/z 481.1778,found m/z 481.1778.
V-18:
1-benzylsilyl-1- (bis (4-tert-butylphenyl) silyl) ethylbenzene
Bis(4-(tert-butyl)phenyl)(1-phenyl-1-(phenylsilyl)ethyl)silane
Standard conditions. Colorless liquid, 77% yield, IR (cm) -1 ):3059,3022,2960,2866,2134,1597,1492,1387. 1 H NMR(400MHz,CDCl 3 ):δ7.47(d,J＝8.4Hz,2H),7.35(d,J＝8.4Hz,2H),7.31-7.19(m,8H),7.16-7.09(m,3H),7.04-6.99(m,1H),6.83(d,J＝7.2Hz,2H),5.08(s,1H),4.03-3.96(m,1H),3.88-3.81(m,1H),1.87(dd,J＝4.4,4.0Hz,2H),1.58(s,3H),1.31(s,9H),1.26(s,9H)； 13 C NMR(100MHz,CDCl 3 ):δ152.9,152.5,144.0,139.4,136.1,135.9,129.2,128.4,128.32,128.27,126.9,124.8,124.6,124.4,124.1,34.7,34.6,31.2,31.1,19.2,16.8,16.7；HRMS(ESI)calculated for[C 35 H 44 NaSi 2 ] + (M+Na + )requires m/z 543.2874,found m/z 543.2870.
V-19:
1-benzylsilyl-1- (bis (3, 5-dimethylphenyl) silyl) ethylbenzene
(1-(Benzylsilyl)-1-phenylethyl)bis(3,5-dimethylphenyl)silane
Standard conditions. Colorless liquid, 75% yield, IR (cm) -1 ):3083,3056,2913,2860,2136,1596,1492. 1 H NMR(400MHz,CDCl 3 ):δ7.30-7.24(m,2H),7.20-7.07(m,7H),7.05-6.99(m,2H),6.94(s,1H),6.89-6.83(m,4H),5.00(s,1H),4.03-3.96(m,1H),3.90-3.84(m,1H),2.28(s,6H),2.18(s,6H),1.97-1.85(m,2H),1.55(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ143.9,139.4,137.0,136.7,134.0,133.7,132.3,131.6,131.2,128.34,128.29,128.27,127.0,124.4,124.2,21.4,21.3,19.2,16.90,16.85.HRMS(ESI)calculated for[C 31 H 36 NaSi 2 ] + (M+Na + )requires m/z 487.2248,found m/z 487.2247.
Example 2: synthesis of Silicone Polymer with Gem-disilicon Compound (application example)
Formula VI, RA is phenyl, biphenyl;
the silicon polymer A is a hyperbranched polymer formed by connecting a formula B1 with a formula B2, and the formula B1 and the formula B2 are shown as follows:
in the formulas B1 and B2, RA is phenyl or biphenyl;
R 1 、R 2 、R 3 is as defined in claim 1.
In a nitrogen-protected glove box (H) 2 O<0.1ppm,O 2 <0.1ppm,25 ℃), 15mL of a dried sealed tube was charged with the gem-disilicide compound V (0.40mmol,1.0equiv.),1, 4-divinylbenzene or 4,4 '-divinyl-1, 1' -biphenyl (0.40mmol,1.0equiv.), and THF (0.80mL,0.50M) in that order, dissolved at 25 ℃ and stirred uniformly. Karstedt's catalyst (. about.2% Pt, xylene solution) (1.1 mol%) was then added and the reaction turned dark brown. Then, sealThe tube was sealed and removed from the glovebox to the laboratory bench for reaction. The reaction was carried out at 68 ℃ for 2 to 3 days. After the reaction was completed, the mixture was cooled to room temperature and purified by precipitation by adding methanol (10mL) to the reaction solution to produce a yellow solid precipitate, and a two-phase mixture was obtained and slurried with vigorous stirring for 10 minutes. The layers were then allowed to settle and the top liquid layer was carefully removed. Next, methanol was added again, this step was repeated twice, and a polymer was obtained by filtration and dried under vacuum. [ M ] A w Is the weight average molecular weight; m n Is the number average molecular weight; m w /M n Is a polydispersity; n is d Refractive index at a wavelength of 587.6 nm; abbe number v d ＝(n d -1)/(n f -n c ) (wherein, n is f And n c Refractive indices at wavelengths of 486.1nm and 656.3nm, respectively);]
the following products were synthesized into silicone polymers as shown in the following two formulas, with reference to the above-described method.
Polymer A-1. 78% yield according to the standard procedure described above. A pale yellow solid. 1 H NMR(400MHz,CDCl 3 ):δ8.00-5.30(m,28H,H a ),5.27-5.10(m,0.37H,H c ),5.02-4.80(m,0.32H,H d ),4.74-4.57(m,0.09H,H d ),1.96-1.40(m,3H,H b ).M w ＝21,830g/mol；M n ＝4,840g/mol；M w /M n ＝4.51；n d ＝1.692,n f ＝1.727,n c ＝1.677；v d ＝(n d -1)/(n f -n c )＝13.84≈14.
Polymer A-2. According to the standard procedure, 92% yield. A pale yellow solid. 1 H NMR(400MHz,CDCl 3 ):δ8.60-5.38(m,32H,H a ),5.30-5.04(m,0.48H,H c ),5.02-4.82(m,0.30H,H d ),4.74-4.64(m,0.07H,H d ),2.00-1.42(m,3H,H b ).M w ＝22,010g/mol；M n ＝3,141g/mol；M w /M n 7.01 (resulting from a partially poorly soluble cross-linked solid).
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
1. A quaternary carbon gem-disilicon compound containing three silicon-hydrogen bonds, characterized in that the compound is represented by formula V:
in the formula V, R 1 Optionally H, the following groups which are unsubstituted or contain substituent A: a heterocyclic aryl A of aryl A, C4 to C20 of C6 to C20; the substituent A is one or more than two of the following: C1-C16 alkyl, C1-C16 alkoxy, C1-C16 siloxy, C1-C3 alkylthio, halogen, trifluoromethyl, hydroxyl, C1-C3 aldehyde, C1-C3 carboxyl, amino, C1-C3 ester, phenyl, amide, methoxycarbonyl, nitro, hydroxyl, benzyloxy, acetoxymethyl;
in the formula V, R 2 、R 3 The substituent B is phenyl or substituted phenyl, and the substituent on the substituted phenyl is one or more of the following groups: halogen, C1-C16 alkyl, C1-C16 alkoxy, C1-C16 alkylthio, phenyl, trifluoromethyl, methoxycarbonyl, nitro, hydroxyl, C1-C3 aldehyde, C1-C3 carboxyl, amino, C1-C16 ester group, C1-C16 silane group, C1-C16 siloxy, benzyloxy, amide, acetoxymethyl, 2-methylene-1, 3-dioxycyclopentyl;
the substituent C or the substituent D is one or more than two of the following components: C1-C16 alkyl, C1-C16 alkoxy, C1-C16 siloxy, C1-C3 alkylthio, halogen, trifluoromethyl, hydroxyl, C1-C3 aldehyde, C1-C3 carboxyl, amino, C1-C3 ester, phenyl, amide, methoxycarbonyl, nitro, hydroxyl, benzyloxy and acetoxymethyl.
2. The quaternary carbon gem-disilicon compound with three silicon-hydrogen bonds as claimed in claim 1, wherein R is selected from the group consisting of 1 Optionally selected from the following unsubstituted or substituted A-containing groups: a heterocyclic aryl A of aryl A, C4 to C20 of C6 to C20;
the aryl A of C6-C20 is phenyl, 3 ', 4' - (2-methylene-1, 3-dioxane) -phenyl or naphthyl;
the heterocyclic aryl A of C4-C20 is indolyl, thienyl, benzothienyl, pyridyl, piperidyl, quinolyl, carbazolyl or 1, 8-naphthyridinyl;
the substituent A is one or more than two of the following: C1-C6 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, halogen, trifluoromethyl, hydroxyl, C1-C3 aldehyde group, C1-C3 carboxyl, amino, C1-C3 ester group, phenyl or amide.
3. The quaternary carbon gem-disilicon compound with three silicon-hydrogen bonds as claimed in claim 1, wherein R is selected from the group consisting of 2 、R 3 Heterocyclic aryl B selected from C1-C16 alkyl which is unsubstituted or contains substituent B, and C6-C20 aryl B, C4-C20 which is unsubstituted or contains substituent C;
the aryl B of C6-C20 is phenyl or naphthyl; the heterocyclic aryl B of C4-C20 is indolyl, thienyl, pyridyl, piperidyl, carbazolyl or quinolyl.
4. The quaternary carbon gem-disilicon compound with three silicon-hydrogen bonds as claimed in claim 1, wherein R is selected from the group consisting of 2 Phenyl or substituted phenyl, R 3 is-K 1 -a substituent B, phenyl or substituted phenyl; said K 1 Is C1-C6 alkylene, said substitutionThe group B is phenyl or substituted phenyl, and the substituent on the substituted phenyl is one or more than two of the following groups: C1-C6 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, halogen, trifluoromethyl, hydroxyl, C1-C3 aldehyde group, C1-C3 carboxyl, amino, C1-C3 ester group, phenyl or amide.
5. The method for synthesizing the quaternary carbon gem-disilicon compound with three silicon-hydrogen bonds as claimed in claim 1, characterized in that the method comprises: under inert gas, alkyne shown in formula I and dihydro-silane shown in formula II are reacted in CoX 2 -carrying out a first hydrosilation reaction in the presence of a catalytic amount of an activating reagent in the presence of an OIP complex catalyst; then adding trihydrosilane shown in the formula III and a catalytic amount of hydrogen negative reagent to carry out a second step of hydrosilation reaction to obtain a gem-disilicon compound containing three silicon-hydrogen bonds shown in the formula V;
R 2 2 SiH 2 II
R 3 SiH 3 III
in the formula I, the formula II and the formula III, R 1 、R 2 、R 3 Is as defined in claim 1.
6. The method of claim 5, wherein the CoX is 2 -OIP complex having the formula of a compound of formula IV or an enantiomer thereof, said enantiomer being the mirror image of formula IV wherein R is 9 ，R 10 ，R 11 ，R 12 ，R 13 ，R 14 ，R 15 ，R 16 ，R 17 ，R 18 ,R 19 ,R 20 Any one selected from the group consisting of H, C1-C16 alkyl, C1-C16 alkoxy, phenyl, naphthyl, or benzyl: h on the alkyl and the alkoxy is not substituted or substituted by more than 1 substituent E, and the substituent E is nitro, halogen, phenyl, methoxycarbonyl and trifluoroMethyl, hydroxyl, aldehyde group of C1-C3, carboxyl group of C1-C3, amino group, ester group or amide group of C1-C3;
h on the phenyl, the benzyl and the naphthyl is not substituted or is substituted by more than 1 substituent F, and the substituent F is alkyl of C1-C3, alkoxy of C1-C3, nitro, halogen, phenyl, methoxycarbonyl, trifluoromethyl, hydroxyl, aldehyde of C1-C3, carboxyl of C1-C3, amino, ester group or amide group of C1-C3;
x is F, Cl, Br, I, OAc, CF 3 SO 3 Any one of
7. The method of claim 6, wherein the CoX is 2 the-OIP complex is shown as the formula IV-1
8. The method according to claim 5, wherein in the first hydrosilation reaction, the activating reagent is any one of sodium triethylborohydride, sodium tri-sec-butylborohydride, lithium triethylborohydride or strong alkali sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium tert-amylate, sodium ethoxide, sodium methoxide and potassium methoxide; in the second step of hydrosilation reaction, the hydrogen negative reagent is any one of sodium triethylborohydride, sodium tri-sec-butylborohydride and lithium triethylborohydride or strong alkali sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium tert-amylate, sodium ethoxide, sodium methoxide and potassium methoxide.
9. The use of the quaternary carbon gem-disilicon compound containing three silicon-hydrogen bonds as claimed in claim 1 in the synthesis of silicon-containing polymers by: carrying out polymerization hydrosilation reaction on the quaternary carbon gem-disilicon compound shown as the formula V and the diyne compound shown as the formula VI to synthesize the silicon-containing polymer A, wherein the reaction formula is shown as the following formula:
formula VI, R A Is phenyl, biphenyl or thiazolyl;
the silicon-containing polymer A is a hyperbranched polymer formed by connecting a formula B1 with a formula B2, and the formulae B1 and B2 are as follows:
in the formulae B1 and B2, R A Is phenyl, biphenyl or thiazolyl;
R 1 、R 2 、R 3 is defined as in claim 1.
10. The silicon-containing polymer A prepared by carrying out the polymeric hydrosilation reaction on the quaternary carbon gem-disilicon compound containing three silicon-hydrogen bonds according to claim 1, wherein the silicon-containing polymer A is a hyperbranched polymer formed by connecting a formula B1 with a formula B2, and the formulae B1 and B2 are as follows:
in the formulae B1 and B2, R A Is phenyl, biphenyl or thiazolyl;
R 1 、R 2 、R 3 as defined in claim 1;
the silicon-containing polymer A is prepared by the following method: under the protection of inert gas, uniformly stirring the gem-disilicon compound shown in the formula V and the diyne compound shown in the formula VI in a tetrahydrofuran solvent, adding Karstedt catalyst, and reacting for 24-72 hours at the temperature of 60-80 ℃ in a sealing and stirring manner; after the reaction is finished, cooling the reaction mixture to room temperature, and purifying to obtain a silicon-containing polymer A; the mass ratio of the gem-disilicon compound shown as the formula V, the diyne compound shown as the formula VI and the Karstedt catalyst is 1: 0.5-1.5: 0.005-0.02.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140065576A (en) * | 2012-11-16 | 2014-05-30 | 부산대학교 산학협력단 | Siloxane polyhydric alcohol and thermosetting resin omposite containing the same |
| CN109111333A (en) * | 2018-06-26 | 2019-01-01 | 浙江大学 | It is a kind of chiral together with two silicon substrate alkane compounds and its synthetic method and application |
| CN109705154A (en) * | 2018-11-14 | 2019-05-03 | 浙江大学 | It is a kind of containing there are four the outer of si-h bond to disappear together with two silicon substrate alkane compounds and its synthetic method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140065576A (en) * | 2012-11-16 | 2014-05-30 | 부산대학교 산학협력단 | Siloxane polyhydric alcohol and thermosetting resin omposite containing the same |
| CN109111333A (en) * | 2018-06-26 | 2019-01-01 | 浙江大学 | It is a kind of chiral together with two silicon substrate alkane compounds and its synthetic method and application |
| CN109705154A (en) * | 2018-11-14 | 2019-05-03 | 浙江大学 | It is a kind of containing there are four the outer of si-h bond to disappear together with two silicon substrate alkane compounds and its synthetic method and application |
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| ZHAOYANG CHENG ET AL.: "Cobalt-Catalyzed Regiodivergent DoubleHydrosilylation of Arylacetylenes", 《ANGEWANDTE CHEMIE》 * |
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