122887-63-2Relevant academic research and scientific papers
Esters of (Hydroxymethyl)diorganylsilanes: Synthesis and Thermally Induced Rearrangement
Tacke, Reinhold,Wiesenberger, Frank,Becker, Beate,Rohr-Aehle, Regine,Schneider, Petra B.,et al.
, p. 591 - 606 (2007/10/02)
Twenty silanes of the type R1R2Si(H)CH3OR3 (A) were synthesized 1,R2 = Me, Ph, 1-naphthyl, PhCH2, Me3SiCH2; OR3 = OC(O)Me, OC(O)CF3, OS(O)CF3, OP(O)Ph2, OC(O)Cl> and studied for their thermal behaviour.The silanes A undergo a thermally induced rearrangement to give the corresponding silanes R1R2Si(OR3)Me (B).For compounds with OR3 = OC(O)Cl, an additional decarboxylation takes place to yield the chlorosilanes R1R2Si(Cl)Me.Except for the derivatives with OR3 = OC(O)Cl, the energetic (reaction enthalpy) and kinetic data (reaction order, frequency factor, enthalpy and entropy of activation) of these reactions were studied by means of differential scanning calorimetry (DSC).In addition the kinetics of all reactions were investigated by 1H-NMR spectroscopy.The transition state of the rearrangement was investigated by an ab initio study based on the model compound H3SiCH2OC(O)H MeH2SiOC(O)H>.The theoretical data and the experimentally obtained energetic and kinetic data are discussed in terms of mechanistic aspects of the rearrangement reaction A -> B.
