大规模生产甲基氯硅烷Me n SiCl 4− n(n = 1–3)的Müller-Rochow直接法(DP)产生乙硅烷残基(Me n Si 2 Cl 6− n,n = 1–6, DPR),每年数千吨。该报告是关于使用氯化nium作为裂解催化剂和反应伙伴的甲基氯二硅烷裂解反应,以优选获得双官能甲硅烷Me x SiH y Cl z(x = 2,y = z = 1; x,y = 1,z =2; x = z = 1,y = 2)。产物的形成是由反应温度,所用氯化phosphorus的量,磷原子上取代基的选择以及反应混合物中溶于醚中的氯化氢的存在控制的。乙硅烷骨架上的氢取代基取代氯可大大提高乙硅烷裂解的整体效率,从而在相对中等的条件下几乎可以定量形成硅烷单体。因此,DPR的这种高效处理不仅增加了DP的经济价值,而且使环境污染最小化。
Preparation and NMR spectroscopical investigations of (diethylamino)(methoxy)-methylchlorodi– and –trisilanes
作者:U. Herzog、K. Trommer、G. Roewer
DOI:10.1016/s0022-328x(97)00566-4
日期:1998.2
methylchlorotrisilanes SiClMe2–SiClMe–SiClMe2 and SiCl2Me–SiClMe–SiCl2Me the stepwise reaction with first HC(OMe)3/[AlCl3] and second HNEt2 leads to the formation of (diethylamino)(methoxy)-methylchlorooligosilanes. The products were investigated by means of 29Si, 1H NMR spectroscopy and GC/MS measurements.
Reaction of the SiCl bond with trialkyl orthoformates preparation of alkoxy-substituted silanes
作者:U Herzog、N Schulze、K Trommer、G Roewer
DOI:10.1016/s0022-328x(97)00204-0
日期:1997.11
Trialkyl orthoformates in the presence of aluminiumchloride represent quite useful reagents to generate silicon alkoxides from chlorosilanes. 3-Cyanopropyltrichlorosilane and 2-[(2-trichlorosily)ethyl]-pyridine give the triethoxy compounds 3-cyanopropyltriethoxysilane and 2-[(2-triethoxysilyl)ethyl]-pyridine respectively. Via this route, in methylchlorooligosilanes a partial or complete exchange of
Interactions of chloromethyldisilanes with tetrakis(dimethylamino)ethylene (TDAE), formation of [TDAE]+ [Si3Me2Cl7]−
作者:C Knopf、U Herzog、G Roewer、E Brendler、G Rheinwald、H Lang
DOI:10.1016/s0022-328x(02)01856-9
日期:2002.11
alkene tetrakis-(dimethylamino)-ethylene (TDAE) in n-hexane as well as in polar solvents. While 1 gave no reaction at all, 3 underwent a disproportionation reaction into SiCl4 and Si(SiCl3)4. Also 2 and mixtures of 2 and 4 were disproportionated into MeSiCl3 (2a) and methylchlorooligosilanes. Additionally a crystalline mixture of Si3Me3Cl6·TDAE (5a) plus Si3Me2Cl7·TDAE (5b) was obtained by reaction of
Methylchlorooligosilanes as products of the basecatalysed disproportionation of various methylchlorodisilanes
作者:U. Herzog、R. Richter、E. Brendler、G. Roewer
DOI:10.1016/0022-328x(95)05762-e
日期:1996.1
The methylchlorodisilanes SiCl2MeSiCl2Me (1), SiCl2MeSiClMe2 (2) and SiClMe2SiClMe2(3) disproportionate in the presence of a basic catalyst into methylchloromonosilanes and various methylchlorooligosilanes. Oligosilanes involving up to seven silicon atoms were identified by means of 29Si-, 13C- 1H-NMR and GC-MS measurements. Formation of methylchlorooligosilanes is thoughtto take place via silylene
The treatment of methylchlorodisilanes with ethynyldigrignard (BrMgC=CMgBr) resulted in oligomeric as well as polymeric ethynyldisilanes. The kind of this products is related to the chloro functionality of the starting disilane. The reaction of SiClMe(SiCl2Me)(2) as well as SiMe(SiCl2Me)(3) yielded polymers beside small amounts of the monomeric products (HC=C)MeSi[SiMe(C=CH)(2)](2) and MeSi[SiMe(C=CH)(2)](3).