CN103288863B - Method for hydrosilylation - Google Patents
Method for hydrosilylation Download PDFInfo
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- CN103288863B CN103288863B CN201310116791.XA CN201310116791A CN103288863B CN 103288863 B CN103288863 B CN 103288863B CN 201310116791 A CN201310116791 A CN 201310116791A CN 103288863 B CN103288863 B CN 103288863B
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- Prior art keywords
- hydrogen
- diphenylphosphine
- trichlororhodium
- reaction
- alkene
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006459 hydrosilylation reaction Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 239000001257 hydrogen Substances 0.000 claims abstract description 68
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 68
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910000077 silane Inorganic materials 0.000 claims abstract description 46
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 45
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 54
- 150000002431 hydrogen Chemical class 0.000 claims description 46
- 239000000377 silicon dioxide Substances 0.000 claims description 37
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 32
- 238000004821 distillation Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000010792 warming Methods 0.000 claims description 28
- 238000007259 addition reaction Methods 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- OBWURDWSVVRXLE-UHFFFAOYSA-N (3-bromophenyl)-diphenylphosphane Chemical compound BrC1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 OBWURDWSVVRXLE-UHFFFAOYSA-N 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 10
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 5
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 5
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 5
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 5
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 5
- XIONUQPOXCUMMB-UHFFFAOYSA-N (2-bromophenyl)-diphenylphosphane Chemical compound BrC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XIONUQPOXCUMMB-UHFFFAOYSA-N 0.000 claims description 3
- HQZUBUSJSTUEBF-UHFFFAOYSA-N (2-butylphenyl)-diphenylphosphane Chemical compound CCCCC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HQZUBUSJSTUEBF-UHFFFAOYSA-N 0.000 claims description 3
- YNLBCLNFEOKEHA-UHFFFAOYSA-N (4-bromophenyl)-diphenylphosphane Chemical compound C1=CC(Br)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNLBCLNFEOKEHA-UHFFFAOYSA-N 0.000 claims description 3
- IHGZKYLRNBICEF-UHFFFAOYSA-N 2-diphenylphosphanylbenzamide Chemical compound NC(=O)C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 IHGZKYLRNBICEF-UHFFFAOYSA-N 0.000 claims description 3
- KZUACPSBACWLPO-UHFFFAOYSA-N 4-diphenylphosphanylbenzamide Chemical compound C1=CC(C(=O)N)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZUACPSBACWLPO-UHFFFAOYSA-N 0.000 claims description 3
- GXMHDTPYKRTARV-UHFFFAOYSA-N 4-diphenylphosphanylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 GXMHDTPYKRTARV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000005052 trichlorosilane Substances 0.000 claims description 3
- -1 trichlorosilane alkane Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 230000009466 transformation Effects 0.000 description 28
- 230000008859 change Effects 0.000 description 27
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- JPYXQNWIQIBLJT-UHFFFAOYSA-N (2-ethylphenyl)methanamine Chemical compound CCC1=CC=CC=C1CN JPYXQNWIQIBLJT-UHFFFAOYSA-N 0.000 description 1
- BEBFJOSPYYGOKL-UHFFFAOYSA-N (3-ethylphenyl)methanamine Chemical compound CCC1=CC=CC(CN)=C1 BEBFJOSPYYGOKL-UHFFFAOYSA-N 0.000 description 1
- DGAGEFUEKIORSQ-UHFFFAOYSA-N (4-ethylphenyl)methanamine Chemical compound CCC1=CC=C(CN)C=C1 DGAGEFUEKIORSQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
The invention relates to the field of organic chemistry and provides a method for hydrosilylation to overcome the problem of poor catalytic activity of transition metals in certain types of hydrosilylation. According to the method, alkene and hydrogen-containing silane are used as raw materials, rhodium trichloride is used as a main catalyst and a triphenylphosphine derivative is used as a ligand so as to realize catalysis of hydrosilylation. The method for hydrosilylation provided by the invention has high activity and high selectivity and has the advantages of mild and safe reaction conditions, high catalytic activity and good selectivity of a beta addition product.
Description
Technical field
The present invention relates to organic chemistry filed, specifically a kind of method utilizing addition reaction of silicon with hydrogen to synthesize silicon-containing compound.
Background technology
Hydrosilylation of olefins is synthesizing organo-silicon coupling agent and one of function silicoorganic compound and the most important approach of polymkeric substance, occupy an important position (Leslie D. Field in synthetic organic chemistry, Antony J. Ward, J. Organomet. Chem, 2003,681,91-97).Hydrosilylation of olefins carries out usually under Platinic chloride and title complex (as Speier ' catalyzer and Karstedt ' catalyzer etc.) thereof exist, although this catalyst system has greater activity, byproduct of reaction is more.（Chisso Corp. JP., 8204995, 1982)。People were by the research to various transition metal complex afterwards, find that transition metal (Pt, Rh, Ru etc.) has certain catalytic activity to addition reaction of silicon with hydrogen, but for the addition reaction of silicon with hydrogen of some type, as the Si―H addition reaction of alkene and organoalkoxysilane, not high (Bogdan Marciniec, the and Jacek Guli of catalytic activity
ski, J. Organomet. Chem., 1983,253,349-362).We also once studied and found with transition metal Rh (PPh
3)
3cl, Ru (PPh
3)
3cl
2as Primary Catalysts, ionic liquid at room temperature is as the method for carrying out addition reaction of silicon with hydrogen under reaction medium, reaction conditions is gentle, safe, effective, effectively can suppress the generation of side reaction, product and catalyst separating are conveniently, the recyclable recycling of catalyzer, as the method for preparing catalyst of a kind of addition reaction of silicon with hydrogen that Chinese patent CN101032698 discloses; A kind of silicon-hydrogen additive reaction method disclosed in CN101033235, but in above-mentioned two inventions, catalytic activity also needs further raising.So far, how improving the activity of catalyzer, suppress the generation of side reaction simultaneously, is still the research emphasis of addition reaction of silicon with hydrogen.
Summary of the invention
Transition metal (Pt, Rh, Ru etc.) has certain catalytic activity to addition reaction of silicon with hydrogen, for solving the addition reaction of silicon with hydrogen for some type, as the Si―H addition reaction of alkene and organoalkoxysilane, the problem that transition metal-catalyzed activity is not high, the present invention proposes a kind of method of addition reaction of silicon with hydrogen, using Trichlororhodium as Primary Catalysts, containing the triphenylphosphine derivates of different substituents as part, high-activity high-selectivity carries out the method for addition reaction of silicon with hydrogen, this method reaction conditions is gentle, safety, catalytic activity is high, and β adduct selectivity is good.
The present invention is achieved by the following technical solutions: a kind of method of addition reaction of silicon with hydrogen, with alkene and silane containing hydrogen for raw material, is Primary Catalysts with Trichlororhodium, using triphenylphosphine derivates as part, and the method for catalyzing addition reaction of silicon with hydrogen.
The detailed process of addition reaction of silicon with hydrogen is: at the there-necked flask of band reflux condensation mode; the alkene, the triphenylphosphine derivates that add Trichlororhodium, react with Trichlororhodium; under nitrogen protection; be warming up to 50 ~ 90 DEG C; stir the mixture being dripped remaining alkene and silane containing hydrogen fully by dropping funnel; keep temperature of reaction; continue to be stirred to reaction to terminate; be cooled to room temperature; change underpressure distillation into and collect corresponding cut; obtain Si―H addition reaction product α affixture and β affixture, the alkene wherein reacted with Trichlororhodium, the mol ratio of Trichlororhodium are 1:1 ~ 50.Then on GC-MS combined instrument, carry out purity check, calculate the transformation efficiency of reaction and the selectivity of silicon H-H reaction β affixture.Room temperature is 18 ~ 25 DEG C, and till reaction end is generally and is no longer increased by gas chromatograph detection resultant, being usually preferably reaction 5 hours is the reaction end time.
Addition reaction of silicon with hydrogen general formula is:
Wherein, R is selected from C
5h
9, C
6h
11, C
7h
13, C
10h
19, Ph, 2-CH
3ph, 3-CH
3ph, 4-CH
3ph
, 2-CH
3it is a kind of in OPh,
Described triphenylphosphine derivates is selected from (2-bromophenyl) diphenylphosphine, (3-bromophenyl) diphenylphosphine, (4-bromophenyl) diphenylphosphine, (2-aminocarbonyl phenyl) diphenylphosphine, (4-aminocarbonyl phenyl) diphenylphosphine, (4-carboxyl phenyl) diphenylphosphine, (2-butyl phenyl) diphenylphosphine, [2-(trimethyl silicon based) phenyl] diphenylphosphine, [4-(triethyl is silica-based) phenyl] diphenylphosphine a kind of, and triphenylphosphine derivates is the triphenylphosphine derivates of functionalization.
Described alkene is selected from the one in hexene, heptene, octene, hendecene, vinylbenzene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 4-methoxy styrene.
Described silane containing hydrogen is selected from the one in triethoxy hydrogen silane, trimethoxy hydrogen silane, triethyl hydrogen silane, trichlorosilane alkane, monomethyl dichloro hydrogen silane, a Chlorodimethyl hydrogen silane.
The mol ratio of alkene, silane containing hydrogen, Trichlororhodium, triphenylphosphine derivates is 1000:1100 ~ 1200:1 ~ 50:3 ~ 250, as preferably, the mol ratio of alkene, silane containing hydrogen, Trichlororhodium, triphenylphosphine derivates is 1001:1200:1:3, and wherein alkene is the alkene and remaining alkene sum that react with Trichlororhodium.
Triphenylphosphine derivates is a class part of widespread use in transition-metal coordination catalysis, at many catalytic reaction processes, comprising catalyzing addition reaction of silicon with hydrogen process, by changing the substituting group on Phosphine ligands, thus the performance of central metal coordination catalysis can be affected.
key of the present invention is using Trichlororhodium as Primary Catalysts, containing the triphenylphosphine derivates of different substituents as part, makes the silicon H-H reaction of alkene and hydrogen silane be easy to carry out, and improves the selectivity of β affixture in product simultaneously.
Compared with existent technique, the invention has the beneficial effects as follows:
(1) using Trichlororhodium as Primary Catalysts, containing the triphenylphosphine derivates of different substituents as part;
(2) reaction conditions is gentle, and transformation efficiency is high, and the selectivity of β affixture is high.
Embodiment
Below by embodiment, the present invention is described in further details.In embodiment reaction, desired raw material is all commercially available.
Embodiment 1
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), (2-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into, collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 69 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 73.4 %, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 3.5 %.
Embodiment 2
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), (4-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 70 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 80.7 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 61.4 %, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 8.2 %.
Embodiment 3
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (62.5mmol), (3-bromophenyl) diphenylphosphine (187.5mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 99.9 %, silica-based hexane (the CH of β affixture 1-triethyl
3(CH
2)
5si (CH
2cH
3)
3) yield be 100 %.
Embodiment 4
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (2.5mmol), (3-bromophenyl) diphenylphosphine (7.5mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 97.0 %, silica-based hexane (the CH of β affixture 1-triethyl
3(CH
2)
5si (CH
2cH
3)
3) yield be 100%.
Embodiment 5
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 50 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 100 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 79.1 %, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 2.6 %.
Embodiment 6
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), (2-aminocarbonyl phenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 80 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 6.8 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 55.2 %, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 6.4 %.
Embodiment 7
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), (4-aminocarbonyl phenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 60 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, open condensing reflux, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 61.8 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 53.3 %, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 5.5 %.
Embodiment 8
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (5mmol), (3-bromophenyl) diphenylphosphine (15mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 99.9 %, silica-based hexane (the CH of β affixture 1-triethyl
3(CH
2)
5si (CH
2cH
3)
3) yield be 100 %.
Embodiment 9
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), (4-carboxyl phenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 85 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 68.3 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 49.4 %, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 9.0 %.
Embodiment 10
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), (2-butyl phenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 55 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 100 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 83.0 %, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 6.7 %.
Embodiment 11
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), [4-(triethyl is silica-based) phenyl] diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 75 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 95.8 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 83.2 %, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 2.8 %.
Embodiment 12
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (7.5mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 87.3%, silica-based hexane (the CH of β affixture 1-triethyl
3(CH
2)
5si (CH
2cH
3)
3) yield be 95.2 %.
Embodiment 13
At the there-necked flask of 500 milliliters, add a small amount of vinylbenzene (1.25mmol), Trichlororhodium (1.25mmol), [2-(trimethyl silicon based) phenyl] diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 65 DEG C, stirring reaction 0.5 hour, the mixture of vinylbenzene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, measuring cinnamic transformation efficiency by GC-MS is 95.4 %, silica-based-2-the diphenylphosphino ethane of β affixture 1-triethoxy (PhCH
2cH
2si (OCH
2cH
3)
3) yield be the silica-based-1-diphenylphosphino ethane of 84.8%, α affixture 1-triethoxy (PhCH(CH
3) Si (OCH
2cH
3)
3) yield be 6.2 %.
Embodiment 14
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 91.0 %, the yield of the silica-based hexane of β affixture 1-triethoxy is 100 %.
Embodiment 15
At the there-necked flask of 500 milliliters, add a small amount of heptene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 50 DEG C, stirring reaction 0.5 hour, the mixture of heptene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured heptene by GC-MS is 90.5 %, the yield of β affixture 1-triethoxysilicane base heptane is 100 %.
Embodiment 16
At the there-necked flask of 500 milliliters, add a small amount of octene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 70 DEG C, stirring reaction 0.5 hour, the mixture of octene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped successively by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured octene by GC-MS is 89.7 %, the yield of the silica-based octane of β affixture 1-triethoxy is 100 %.
Embodiment 17
At the there-necked flask of 500 milliliters, add a small amount of hendecene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 80 DEG C, stirring reaction 0.5 hour, the mixture of hendecene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hendecene by GC-MS is 89.7 %, the silica-based undecanoic yield of β affixture 1-triethoxy is 100 %.
Embodiment 18
At the there-necked flask of 500 milliliters, add a small amount of 2-methyl styrene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 60 DEG C, stirring reaction 0.5 hour, the mixture of 2-methyl styrene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured 2-methyl styrene by GC-MS is 95.8 %, the yield of the silica-based-2-of β affixture 1-triethoxy (2-aminomethyl phenyl) ethane is 87.4 %.
Embodiment 19
At the there-necked flask of 500 milliliters, add a small amount of 3-vinyl toluene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of 3-vinyl toluene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured 3-vinyl toluene by GC-MS is 87.3 %, the yield of the silica-based-2-of β affixture 1-triethoxy (3-aminomethyl phenyl) ethane is 86.6 %.
Embodiment 20
At the there-necked flask of 500 milliliters, add a small amount of 4-vinyl toluene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of 4-vinyl toluene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped successively by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured 4-vinyl toluene by GC-MS is 83.2 %, the yield of the silica-based-2-of β affixture 1-triethoxy (4-aminomethyl phenyl) ethane is 82.5 %.
Embodiment 21
At the there-necked flask of 500 milliliters, add a small amount of 4-methoxy styrene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of 4-methoxy styrene (1.25mol) and triethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured 4-methoxy styrene by GC-MS is 88.6 %, the yield of the silica-based-2-of β affixture 1-triethoxy (4-p-methoxy-phenyl) ethane is 86.5 %.
Embodiment 22
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and trimethoxy hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 90.0 %, the yield of the silica-based hexane of β affixture 1-trimethoxy is 100 %.
Embodiment 23
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 93.2 %, silica-based hexane (the CH of β affixture 1-triethyl
3(CH
2)
5si (CH
2cH
3)
3) yield be 100%.
Embodiment 24
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and trichlorosilane alkane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 100%, silica-based hexane (the CH of β affixture 1-trichlorine
3(CH
2)
5siCl
3) yield be 100%.
Embodiment 25
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and monomethyl dichloro hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 100%, silica-based hexane (the CH of β affixture 1-methyl dichloro
3(CH
2)
5siCl
2(CH
3)) yield be 100%.
Embodiment 26
At the there-necked flask of 500 milliliters, add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol), under nitrogen protection, slowly be warming up to 90 DEG C, stirring reaction 0.5 hour, the mixture of hexene (1.25mol) and a Chlorodimethyl hydrogen silane (1.5mol) is dripped by dropping funnel, keep temperature of reaction, continue stirring reaction 5 hours, be cooled to room temperature, change underpressure distillation into and collect corresponding cut, the transformation efficiency being measured hexene by GC-MS is 100%, silica-based hexane (the CH of β affixture 1-mono-Chlorodimethyl
3(CH
2)
5siCl (CH
3)
2) yield be 100%.
Claims (4)
1. a method for addition reaction of silicon with hydrogen, is characterized in that, with alkene and silane containing hydrogen for raw material, is Primary Catalysts with Trichlororhodium, using triphenylphosphine derivates as part, and the method for catalyzing addition reaction of silicon with hydrogen,
Preparation method is: at the there-necked flask of band reflux condensation mode; the alkene, the triphenylphosphine derivates that add Trichlororhodium, react with Trichlororhodium; under nitrogen protection; be warming up to 50 ~ 90 DEG C; stir the mixture being dripped remaining alkene and silane containing hydrogen fully by dropping funnel; keep temperature of reaction; continue to be stirred to reaction to terminate; be cooled to room temperature; corresponding cut is collected in underpressure distillation; obtain Si―H addition reaction product α affixture and β affixture, the alkene wherein reacted with Trichlororhodium and the mol ratio of Trichlororhodium are 1:1 ~ 50
Described triphenylphosphine derivates is selected from (2-bromophenyl) diphenylphosphine, (3-bromophenyl) diphenylphosphine, (4-bromophenyl) diphenylphosphine, (2-aminocarbonyl phenyl) diphenylphosphine, (4-aminocarbonyl phenyl) diphenylphosphine, (4-carboxyl phenyl) diphenylphosphine, (2-butyl phenyl) diphenylphosphine, [2-(trimethyl silicon based) phenyl] diphenylphosphine, [4-(triethyl is silica-based) phenyl] diphenylphosphine a kind of.
2. the method for a kind of addition reaction of silicon with hydrogen according to claim 1, it is characterized in that, described alkene is selected from the one in hexene, heptene, octene, hendecene, vinylbenzene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 4-methoxy styrene.
3. the method for a kind of addition reaction of silicon with hydrogen according to claim 1, it is characterized in that, described silane containing hydrogen is selected from the one in triethoxy hydrogen silane, trimethoxy hydrogen silane, triethyl hydrogen silane, trichlorosilane alkane, monomethyl dichloro hydrogen silane, a Chlorodimethyl hydrogen silane.
4. the method for a kind of addition reaction of silicon with hydrogen according to claim 1, it is characterized in that, the mol ratio of alkene, silane containing hydrogen, Trichlororhodium, triphenylphosphine derivates is 1000:1100 ~ 1200:1 ~ 50:3 ~ 250, and wherein alkene is the alkene and remaining alkene sum that react with Trichlororhodium.
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| EP3645606B1 (en) * | 2017-06-26 | 2024-06-26 | Dow Silicones Corporation | Method for hydrosilylation of aliphatically unsaturated alkoxysilanes and hydrogen terminated organosiloxane oligomers to prepare alkoxysilyl terminated polymers useful for functionalizing polyorganosiloxanes using a rhodium catalyst |
| CN107857776B (en) * | 2017-10-27 | 2021-03-09 | 杭州师范大学 | Hydrosilylation reaction method |
| CN107857777B (en) * | 2017-10-27 | 2021-03-09 | 杭州师范大学 | Hydrosilylation reaction using recyclable platinum compound as catalyst |
| CN109608564B (en) * | 2018-12-03 | 2021-03-26 | 大连理工大学 | Azo-phenyl-containing side chain type liquid crystal polymer with microphase separation structure and preparation method thereof |
| CN109503650A (en) * | 2018-12-27 | 2019-03-22 | 湖北新蓝天新材料股份有限公司 | The preparation method of γ-(2,3- glycidoxy) propyl trimethoxy silicane |
| CN113399001A (en) * | 2021-07-21 | 2021-09-17 | 山东省科学院新材料研究所 | Catalyst for olefin hydrosilylation reaction, preparation method and application thereof |
| CN113563589B (en) * | 2021-08-17 | 2023-05-23 | 烟台顺明新材料有限公司 | Application of rhodium catalyst in organic silicon addition reaction |
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