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 σ 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
Pietropaolo, D., Fiorenza, M., Ricci, A., Taddei, M. (1980). Base-catalysed solvolysis of acylsilanes. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 197(1), 7-11 [10.1016/S0022-328X(00)84449-6].
Base-catalysed solvolysis of acylsilanes
Taddei, M.
1980-01-01
Abstract
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 σ 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
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https://hdl.handle.net/11365/33884
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