廉价金属氢化物还原氯硅烷制备硅氢化合物
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摘要
探讨了以金属硼氢化合物、氢化铝锂等为催化剂,以常见的醚类作为溶剂,以氢化锂、氢化钠、氢化钙等金属氢化物为还原剂,由氯硅烷还原制备硅氢化合物的路线可行性。研究了还原剂强弱、溶剂种类、反应温度等对使用以上催化剂时还原效果的影响,并探讨了可能的催化还原机理。结果表明,相同催化条件下,还原剂及溶剂种类、反应温度等对还原反应效果具有重要影响。适宜反应条件下,可实现氯硅烷的高效还原。新路线具有简单、高效、成本低、安全性好的特点,可替代广泛使用的Li Al H4还原路线,对于硅氢化合物制备的低成本化具有重要的意义。
The reduction method for preparing hydrosilanes was discussed with metallic borohydride and lithium aluminum as the catalysts,the common ether as solvent,and lithium hydride,sodium hydride or calcium hydride as the reductants. The effects of reductants,types of solvent and reaction temperature on the reduction in present of the aboved catalysts were discussed,and the possible mechanism was proposed. Results showed that under the same catalytic conditions,the types of reductant and solvent and reaction temperature have important effects on the catalytic reduction. Under the suitable reaction conditions,chlorosilanes can be reduced efficiently. The new route is simple,efficient,economic and safer,which may replace the widelyused Li Al H4 reduction route and has great significance for the preparation of hydrosilanes with low cost.
The reduction method for preparing hydrosilanes was discussed with metallic borohydride and lithium aluminum as the catalysts,the common ether as solvent,and lithium hydride,sodium hydride or calcium hydride as the reductants. The effects of reductants,types of solvent and reaction temperature on the reduction in present of the aboved catalysts were discussed,and the possible mechanism was proposed. Results showed that under the same catalytic conditions,the types of reductant and solvent and reaction temperature have important effects on the catalytic reduction. Under the suitable reaction conditions,chlorosilanes can be reduced efficiently. The new route is simple,efficient,economic and safer,which may replace the widelyused Li Al H4 reduction route and has great significance for the preparation of hydrosilanes with low cost.
引文
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[2]耿金垚,李永明,徐彩虹,等.有机氢硅烷的低成本还原制备研究进展[J].有机硅材料,2016,30(1):70-74.
[3]AONO K,SAITO T,OKADA C.Process of preparing disilane by reduction of hexachlorodisilane:US,4639361A[P].1987-01-27.
[4]HERBERT J.Preparation of ethynyl silanes:US,3137718A[P].1964-06-16.
[5]LEPAGE J-L,SOULA G.Preparation of hydrogenosilanes by redistribution:US,4746752A[P].1988-05-24.
[6]BERGER A,LEWIS F M.Preparation of silicon hydrides:US,3704261A[P].1972-11-28.
[7]CHADWICK K M,HALM R L,KEYES B R.Process for hydrogenation of chlorosilane:US,5329038A[P].1994-07-12.
[8]CHALK A J.Reduction of halogen-containing silicon compounds:US,3535092A[P].1970-10-20.
[9]MARLETT E M.Process for reduction of organosilicon halides:US,4925963A[P].1990-05-15.
[10]FERGUSON S P,BAJZER W X,ODUNLAMI E B.Method for preparation of alkoxysilanes having reduced halide:US,20090270646A1[P].2009-10-29.
[11]SOULA G,LEPAGE J-L.Preparation of hydrogenosilanes:US,4629801A[P].1986-12-16.
[12]GORDON R G.Low temperature catalytic reduction:US,4295986A[P].1981-10-20.
[13]LANG J E,RAULEDER H,MUEH E.Method for producing higher silanes:US,20100080746A1[P].2010-04-01.
[14]JADHAV P K.Process for reducing silicon,germanium and tin halides:US,4824657A[P].1989-04-25.
[15]BERGER A.Method for making silicon hydrides:US,3496206A[P].1970-02-17.
[16]COOPER G D,Gilbert A R.Reduction of halogencontaining silicon compounds:US,3099672A[P].1963-07-30.
[17]HAGEMANN H,CERNY R.Synthetic approaches to inorganic borohydrides[J].Dalton Trans,2010,39(26):6006-6012.
[18]YAMATAKA H,HANAFUSA T.Kinetic isotope effect study of reductions of benzophenone with complex metal hydrides[J].J Am Chem Soc,1986,108(21):6643-6646.
[19]ASHNY E C,BOONE J R.Mechanism of lithium aluminum hydride reduction of ketones.Kinetics of reduction of mesityl phenyl ketone[J].J Am Chem Soc,1976,98(18):5524-5531.
[20]HEINZMAN S W,GANEM B.Mechanism of sodium borohydride-cobaltous chloride reductions[J].J Am Chem Soc,1982,104(24):6801-6802.
[21]HORI Y,IDA T,MIZUNO M.A comparative theoretical study of the hydride transfer mechanisms during Li Al H4and Li BH4reductions[J].Comput Theor Chem,2016,1076:86-93.
[22]SUZUKI Y,KANENO D,TOMODA S.Theoretical study on the mechanism and diastereoselectivity of Na BH4reduction[J].J Phys Chem A,2009,113(11):2578-2583.
[23]WIGFIELD D C.Stereochemistry and mechanism of ketone reductions by hydride reagents[J].Tetrahedron,1979,35(4):449-462.
[24]WIGFIELD D C,GOWLAND F W.Limited alkoxy group exchange in tetraalkoxyborohydrides:Evidence against the four-centre transition state in the borohydride reduction of ketones[J].Tetrahedron Lett,1976,17(38):3373-3376.
[25]ITO M,ITAZAKI M,ABE T,et al.Hydrogenation of Chlorosilanes by Na BH4[J].Chem Lett,2016,45(12):1434-1436.