The cleavage of siloxane bonds by BF3 was investigated kinetically by 1H NMR spectroscopy. The reactions could be evaluated by use of a pseudo-first order rate law, when a sufficiently large excess of BF3 was used. The order with respect to BF3 was found to be 4.7. The rate constants obtained could be correlated to σ*-values with a ϱ*-value of −1.0. The σ*-value found previously by 29Si NMR spectroscopy
通过1 H NMR光谱动力学研究了BF 3对硅氧烷键的裂解。当使用足够过量的BF 3时,可以通过使用伪一级速率定律评估反应。发现相对于BF 3的顺序为4.7。所得到的速率常数可以被关联到σ * -值与ρ * -1.0 -值。确认了先前通过29 Si NMR光谱法测得的Me 3 SiO基为0.35的σ *值。
23. Organosilicon compounds. Part XVIII. The interaction of (aryldimethylsilyl)methyl chlorides and sodium ethoxide in ethanol
作者:C. Eaborn、J. C. Jeffrey
DOI:10.1039/jr9570000137
日期:——
Ruehlmann, K., Phosphorus and Sulfur and the Related Elements, 1986, vol. 27, p. 139 - 152
作者:Ruehlmann, K.
DOI:——
日期:——
SCHEIM, U.;PORZEL, A.;RUHLMANN, K., J. ORGANOMET. CHEM., 354,(1988) N 1, C. 31-37
作者:SCHEIM, U.、PORZEL, A.、RUHLMANN, K.
DOI:——
日期:——
Anchimeric assistance by γ-aryl groups in solvolysis of organosilicon iodides. Some remarkably large remote substituent effects
作者:Colin Eaborn、Karen L. Jones、Paul D. Lickiss
DOI:10.1039/c39890000595
日期:——
The very large spread of rates in reactions of the iodides (Me3Si)2C(SiMe2C6H4X)(SiMe2l)(X =p-OMe, p-Me, H, p-Cl, or m-CF3) with (CF3)2CHOH and CF3CH2OH (the compound with X =p-OMe is 1.9 × 105 and 6.5 × 104 times, respectively, as reactive as that with X =m-CF3) is attributed to nucleophilic assistance by the aryl group to the leaving of the I– ion.