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Currell, Brian Robert (1959) Certain reactions of organic chlorosilanes. Doctoral thesis, Northern Polytechnic.
The interaction of chlorosilanes and alcohols has been studied to obtain information on the mode of intervention of hydrogen chloride in these systems. It is shown that the hydrogen chloride formed initially associates with the unreacted alcohol so reducing the nucleophilic power of the alcoholic oxygen atom and rendering it much less reactive towards chlorosilanes. Thus in the n-butanol —— silicon tetrachloride system the reaction scheme at room temperature is as follows:
4BunOH + SiCl4 → (BunO)3SiCl + BunOH.HCl + 2HCl
Alkoxytrimethylsilanes have been prepared by a method not involving the use of a tertiary base, and therefore properties may be studied without catalytic intervention of base hydrochloride.
The stepwise alkoxylation of thionyl chloride using alkoxytrimethylsilanes has been demonstrated.
SOCl2 + Me3SiOR → ROSOCl + Me3SiCl + Me3SiCl
SOCl2 + 2Me3SiOR → (RO)2SO + 2Me3SiCl
The yields of unstable chlorosulphinates (such as e-octyl) were not as good as might be expected when it is considered that this reaction does not involve hydrogen chloride. Good yields of di-alkyl sulphite were obtained by this method.
The catalytic effect of pyridine hydrochloride was demonstrated in a number of reactions.
PCl3 + 3Me3SiOBun = P(OBun)3 + 3Me3SiCl
(RO)2SO + Me3SiCl = ROSOCl + Me3SiOR
SiCl4 + 4Me3SiOBun = Si(OBun)4 + 4Me3SiCl
The first of the above three reactions represents the first preparation of a trialkyl phosphite by a method not involving the use of a tertiary base or equivalent.
Two isomorphs of 2-phenylethoxytriphenylsilane have been separated and characterised.
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