CN103288863A - Method for hydrosilylation - Google Patents
Method for hydrosilylation Download PDFInfo
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- CN103288863A CN103288863A CN201310116791XA CN201310116791A CN103288863A CN 103288863 A CN103288863 A CN 103288863A CN 201310116791X A CN201310116791X A CN 201310116791XA CN 201310116791 A CN201310116791 A CN 201310116791A CN 103288863 A CN103288863 A CN 103288863A
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- hydrogen
- reaction
- diphenylphosphine
- trichlororhodium
- silicon
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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 is a kind of method of utilizing the synthetic silicon-containing compound of addition reaction of silicon with hydrogen.
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, (Leslie D. Field occupies an important position in synthetic organic chemistry, Antony J. Ward, J. Organomet. Chem, 2003,681,91-97).Hydrosilylation of olefins carries out in the presence of Platinic chloride and title complex (as Speier ' catalyzer and Karstedt ' catalyzer etc.) thereof usually, though 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 complexes afterwards, find that transition metal (Pt, Rh, Ru etc.) has certain catalytic activity to addition reaction of silicon with hydrogen, but the addition reaction of silicon with hydrogen for some type, silicon hydrogen addition as alkene and organoalkoxysilane, catalytic activity not high (Bogdan Marciniec, and Jacek Guli
Ski, J. Organomet. Chem., 1983,253,349-362).We also once discovered (the PPh with transition metal Rh
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 the reaction medium, reaction conditions gentleness, safety, effective, can effectively suppress the generation of side reaction, product and catalyst separating are convenient, catalyzer recyclable recycling, the method for preparing catalyst of a kind of addition reaction of silicon with hydrogen that discloses as Chinese patent CN101032698; The disclosed a kind of silicon-hydrogen additive reaction method of CN101033235, but catalytic activity also needs further to improve in above-mentioned two inventions.So far, how improving activity of such catalysts, suppress the generation of side reaction simultaneously, still is 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, silicon hydrogen addition as 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, with Trichlororhodium as Primary Catalysts, contain the triphenylphosphine derivative of different substituents as part, high-activity high-selectivity carries out the method for addition reaction of silicon with hydrogen, this method reaction conditions gentleness, safety, the catalytic activity height, 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 is raw material with alkene and silane containing hydrogen, is Primary Catalysts with the Trichlororhodium, with the triphenylphosphine derivative as part, 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 taking back the stream condensation; add Trichlororhodium, with alkene, the triphenylphosphine derivative of Trichlororhodium reaction; under the nitrogen protection; be warming up to 50～90 ℃; drip the mixture of remaining alkene and silane containing hydrogen after stirring fully by dropping funnel; keep temperature of reaction; continuing to be stirred to reaction finishes; be cooled to room temperature; change underpressure distillation into and collect corresponding cut; obtaining silicon hydrogen adduct α affixture and β affixture, is 1:1～50 with the alkene of Trichlororhodium reaction, the mol ratio of Trichlororhodium wherein.Carry out purity check at the GC-MS combined instrument then, calculate the transformation efficiency of reaction and the selectivity of silicon H-H reaction β affixture.Room temperature is 18 ~ 25 ℃, reaction finish to be generally detect resultant and no longer increase by gas chromatograph till, be preferably reaction usually and be the reaction concluding time in 5 hours.
The 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 among the OPh,
Described triphenylphosphine derivative 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 the triphenylphosphine derivative is the triphenylphosphine derivative of functionalization.
Described alkene is selected from a kind of in hexene, heptene, octene, hendecene, vinylbenzene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, the 4-methoxy styrene.
Described silane containing hydrogen is selected from a kind of in triethoxy hydrogen silane, trimethoxy hydrogen silane, triethyl hydrogen silane, trichlorosilane alkane, monomethyl dichloro hydrogen silane, the Chlorodimethyl hydrogen silane.
The mol ratio of alkene, silane containing hydrogen, Trichlororhodium, triphenylphosphine derivative is 1000:1100～1200:1～50:3～250, as preferably, the mol ratio of alkene, silane containing hydrogen, Trichlororhodium, triphenylphosphine derivative is 1001:1200:1:3, and wherein alkene is alkene and the remaining alkene sum of reacting with Trichlororhodium.
The triphenylphosphine derivative is a class part of widespread use in transition-metal coordination catalysis, at many catalytic reaction processes, comprise the catalyzing addition reaction of silicon with hydrogen process, can pass through to change the substituting group on the phosphine part, thereby influence the performance of central metal coordination catalysis.
Key of the present invention be with Trichlororhodium as Primary Catalysts, contain the triphenylphosphine derivative of different substituents as part, make the silicon H-H reaction of alkene and hydrogen silane be easy to carry out, improve the selectivity of β affixture in the product simultaneously.
Compare with existent technique, the invention has the beneficial effects as follows:
(1) with Trichlororhodium as Primary Catalysts, contain the triphenylphosphine derivative of different substituents as part;
(2) reaction conditions gentleness, transformation efficiency height, the selectivity height of β affixture.
Embodiment
Be described in further details below by the present invention of embodiment.Desired raw material is all commercially available in the embodiment reaction.
Embodiment 1
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); (2-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; continued 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 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 73.4 %, α affixture 1-triethoxy is silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 3.5 %.
Embodiment 2
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); (4-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 70 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; continued 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 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 61.4 %, α affixture 1-triethoxy is silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 8.2 %.
Embodiment 3
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol), Trichlororhodium (62.5mmol), (3-bromophenyl) diphenylphosphine (187.5mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is 99.9 %, the silica-based hexane (CH of β affixture 1-triethyl
3(CH
2)
5Si (CH
2CH
3)
3) yield be 100 %.
Embodiment 4
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol), Trichlororhodium (2.5mmol), (3-bromophenyl) diphenylphosphine (7.5mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is 97.0 %, the silica-based hexane (CH of β affixture 1-triethyl
3(CH
2)
5Si (CH
2CH
3)
3) yield be 100%.
Embodiment 5
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 50 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; continued 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 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 79.1 %, α affixture 1-triethoxy is silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 2.6 %.
Embodiment 6
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); (2-aminocarbonyl phenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 80 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; continued 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 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 55.2 %, α affixture 1-triethoxy is silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 6.4 %.
Embodiment 7
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); (4-aminocarbonyl phenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 60 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; open condensing reflux; continued stirring reaction 5 hours, and be cooled to room temperature, change underpressure distillation into and collect corresponding cut; measuring cinnamic transformation efficiency by GC-MS is 61.8 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 53.3 %, α affixture 1-triethoxy is silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 5.5 %.
Embodiment 8
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol), Trichlororhodium (5mmol), (3-bromophenyl) diphenylphosphine (15mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is 99.9 %, the silica-based hexane (CH of β affixture 1-triethyl
3(CH
2)
5Si (CH
2CH
3)
3) yield be 100 %.
Embodiment 9
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); (4-carboxyl phenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 85 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; continued 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 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 49.4 %, α affixture 1-triethoxy is silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 9.0 %.
Embodiment 10
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); (2-butyl phenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 55 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; continued 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 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 83.0 %, α affixture 1-triethoxy is silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 6.7 %.
Embodiment 11
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); [4-(triethyl is silica-based) phenyl] diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 75 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; continued 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 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 83.2 %, α affixture 1-triethoxy is silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 2.8 %.
Embodiment 12
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (7.5mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is the silica-based hexane (CH of 87.3%, β affixture 1-triethyl
3(CH
2)
5Si (CH
2CH
3)
3) yield be 95.2 %.
Embodiment 13
There-necked flask at 500 milliliters; add small amounts of styrene (1.25mmol); Trichlororhodium (1.25mmol); [2-(trimethyl silicon based) phenyl] diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 65 ℃; stirring reaction 0.5 hour; mixture by dropping funnel drip styrene (1.25mol) and triethoxy hydrogen silane (1.5mol); keep temperature of reaction; continued 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 %, β affixture 1-triethoxy is silica-based-and 2-diphenylphosphino ethane (PhCH
2CH
2Si (OCH
2CH
3)
3) yield be 84.8%, α affixture 1-triethoxy silica-based-1-diphenylphosphino ethane (PhCH(CH
3) Si (OCH
2CH
3)
3) yield be 6.2 %.
Embodiment 14
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and triethoxy hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is 91.0 %, and the yield of the silica-based hexane of β affixture 1-triethoxy is 100 %.
Embodiment 15
There-necked flask at 500 milliliters; add a small amount of heptene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 50 ℃; stirring reaction 0.5 hour; drip the mixture of heptene (1.25mol) and triethoxy hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring heptene by GC-MS is 90.5 %, and the yield of β affixture 1-triethoxysilicane base heptane is 100 %.
Embodiment 16
There-necked flask at 500 milliliters; add a small amount of octene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 70 ℃; stirring reaction 0.5 hour; drip the mixture of octene (1.25mol) and triethoxy hydrogen silane (1.5mol) successively by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring octene by GC-MS is 89.7 %, and the yield of the silica-based octane of β affixture 1-triethoxy is 100 %.
Embodiment 17
There-necked flask at 500 milliliters; add a small amount of hendecene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 80 ℃; stirring reaction 0.5 hour; drip the mixture of hendecene (1.25mol) and triethoxy hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hendecene by GC-MS is 89.7 %, and the silica-based undecanoic yield of β affixture 1-triethoxy is 100 %.
Embodiment 18
There-necked flask at 500 milliliters; add a small amount of 2-methyl styrene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 60 ℃; stirring reaction 0.5 hour; drip the mixture of 2-methyl styrene (1.25mol) and triethoxy hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring 2-methyl styrene by GC-MS is 95.8 %, and β affixture 1-triethoxy is silica-based-and the yield of 2-(2-aminomethyl phenyl) ethane is 87.4 %.
Embodiment 19
There-necked flask at 500 milliliters; add a small amount of 3-vinyl toluene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of 3-vinyl toluene (1.25mol) and triethoxy hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring the 3-vinyl toluene by GC-MS is 87.3 %, and β affixture 1-triethoxy is silica-based-and the yield of 2-(3-aminomethyl phenyl) ethane is 86.6 %.
Embodiment 20
There-necked flask at 500 milliliters; add a small amount of 4-vinyl toluene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of 4-vinyl toluene (1.25mol) and triethoxy hydrogen silane (1.5mol) successively by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring the 4-vinyl toluene by GC-MS is 83.2 %, and β affixture 1-triethoxy is silica-based-and the yield of 2-(4-aminomethyl phenyl) ethane is 82.5 %.
Embodiment 21
There-necked flask at 500 milliliters; add a small amount of 4-methoxy styrene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of 4-methoxy styrene (1.25mol) and triethoxy hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring the 4-methoxy styrene by GC-MS is 88.6 %, and β affixture 1-triethoxy is silica-based-and the yield of 2-(4-p-methoxy-phenyl) ethane is 86.5 %.
Embodiment 22
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol); Trichlororhodium (1.25mmol); (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and trimethoxy hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is 90.0 %, and the yield of the silica-based hexane of β affixture 1-trimethoxy is 100 %.
Embodiment 23
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and triethyl hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is 93.2 %, the silica-based hexane (CH of β affixture 1-triethyl
3(CH
2)
5Si (CH
2CH
3)
3) yield be 100%.
Embodiment 24
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and trichlorosilane alkane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is the silica-based hexane (CH of 100%, β affixture 1-trichlorine
3(CH
2)
5SiCl
3) yield be 100%.
Embodiment 25
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and monomethyl dichloro hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is the silica-based hexane (CH of 100%, β affixture 1-methyl dichloro
3(CH
2)
5SiCl
2(CH
3)) yield be 100%.
Embodiment 26
There-necked flask at 500 milliliters; add a small amount of hexene (1.25mmol), Trichlororhodium (1.25mmol), (3-bromophenyl) diphenylphosphine (3.75mmol); under the nitrogen protection; slowly be warming up to 90 ℃; stirring reaction 0.5 hour; drip the mixture of hexene (1.25mol) and a Chlorodimethyl hydrogen silane (1.5mol) by dropping funnel; keep temperature of reaction; continued stirring reaction 5 hours; be cooled to room temperature; change underpressure distillation into and collect corresponding cut, the transformation efficiency of measuring hexene by GC-MS is the silica-based hexane (CH of 100%, β affixture 1-, one Chlorodimethyl
3(CH
2)
5SiCl (CH
3)
2) yield be 100%.
Claims (7)
1. the method for an addition reaction of silicon with hydrogen is characterized in that, is raw material with alkene and silane containing hydrogen, is Primary Catalysts with the Trichlororhodium, with the triphenylphosphine derivative as part, the method for catalyzing addition reaction of silicon with hydrogen.
2. the method for a kind of addition reaction of silicon with hydrogen according to claim 1; it is characterized in that; at the there-necked flask of taking back the stream condensation; add Trichlororhodium; alkene with the Trichlororhodium reaction; the triphenylphosphine derivative; under the nitrogen protection; be warming up to 50～90 ℃; drip the mixture of remaining alkene and silane containing hydrogen after stirring fully by dropping funnel; keep temperature of reaction; continue to be stirred to reaction and finish, be cooled to room temperature, corresponding cut is collected in underpressure distillation; obtaining silicon hydrogen adduct α affixture and β affixture, is 1:1～50 with the alkene of Trichlororhodium reaction and the mol ratio of Trichlororhodium wherein.
3. the method for a kind of addition reaction of silicon with hydrogen according to claim 1 and 2, it is characterized in that described triphenylphosphine derivative 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.
4. the method for a kind of addition reaction of silicon with hydrogen according to claim 1 and 2, it is characterized in that described alkene is selected from a kind of in hexene, heptene, octene, hendecene, vinylbenzene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, the 4-methoxy styrene.
5. the method for a kind of addition reaction of silicon with hydrogen according to claim 1 and 2, it is characterized in that described silane containing hydrogen is selected from a kind of in triethoxy hydrogen silane, trimethoxy hydrogen silane, triethyl hydrogen silane, trichlorosilane alkane, monomethyl dichloro hydrogen silane, the Chlorodimethyl hydrogen silane.
6. the method for a kind of addition reaction of silicon with hydrogen according to claim 1 and 2, it is characterized in that, the mol ratio of alkene, silane containing hydrogen, Trichlororhodium, triphenylphosphine derivative is 1000:1100～1200:1～50:3～250, and wherein alkene is alkene and the remaining alkene sum of reacting with Trichlororhodium.
7. the method for a kind of addition reaction of silicon with hydrogen according to claim 6 is characterized in that, the mol ratio of alkene, silane containing hydrogen, Trichlororhodium, triphenylphosphine derivative is 1001:1200:1:3.
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