BASE-CATALYSED SOLVOLYSIS OF ACYLSILANES

Article abstract of DOI:10.1016/S0022-328X(00)84449-6

Kinetic studies have been made of the hydrolysis of XC6H4COSiR3 compounds (R=Me, Et, Ph) in a mixture of THF (3 vol.) and aqueous sodium hydroxide (1 vol.).The rates of cleavage of p-NO2C6H4CH2SiMe3, C6H5COSiMe2C6H5 and C6H5COSiMe2C6H4Cl-p compounds under the same conditions have also been measured.Electron-attracting substituents on either side of the bond being broken lead to an increase in the rate.For the XC6H4COSiR3 compounds, the effects of the substituents X correlate excellently with their Hammett ? constants (ρ=3.5 and 2.5 for R=Me and Ph, respectively).The data are consistent with a mechanism in which the attack of the hydroxide ion occurs at the carbonyl C atom.