STUDIES IN SILICO-ORGANIC COMPOUNDS. VIII. THE PREPARATION AND PROPERTIES OF POLYETHERS FROM TRICHLOROSILANE, CONTINUED^{1, 2}

Abstract

Hydrogen chloride has a definite part in this reaction as has been demonstrated in the course of this work and its predecessor (1). There was no action when triethoxysilane and ethyl alcohol were refluxed for twenty-four hours but when dry hydrogen chloride was passed through triethoxysilane at 80°a small amount of hydrogen was evolved and some triethoxychlorosilane formed. A mechanism has already been postulated (1).Hydrogen was also evolved with formation of tetraethoxysilane when dry hydrogen chloride was bubbled through a mixture of refluxing triethoxysilane and ethyl alcohol. Triethoxysilane and moist ethyl alcohol reacted on twentyfour hour reflux to form various hydrolysis products.To examine the effects of variation in radical size, possible differing effect of dissolved hydrogen chloride, and other factors, on these reactions, trichlorosilane was allowed to react separately with several different alcohols including phenol both with and without benzene as a solvent. Yields of trialkoxy-and tetraalkoxy-silanes are reported in Table I.In addition, the data already presented (1) with respect to ethyl, n-propyl, and n-butyl analogs were checked. ¿-Butyl alcohol led only to what was probably a polymerized 1,3-dioxodisiloxane, a hydrolysis product:Hydrolysis products also resulted from the interaction of allyl alcohol and trichlorosilane. Trialloxysilane polymerized at the boiling point, 188°( 760 mm). There was almost no evolution of hydrogen from the reaction using benzyl alcohol. After excess benzyl alcohol had been distilled from the reaction mixture, contact with sodium hydroxide showed the residue to be largely tribenzoxysilane. However, only tetrabenzoxysilane could be isolated on distillation. It has 1 The work on which this report is based comprises a part of a program of research carried out under contract with the Office of Naval Research.8 Submitted by the first author to the Graduate School of Arts and Sciences of the University of Buffalo in partial fulfillment of the requirements for the degree of Doctor of Philosophy.

Studies in Silico-Organic Compounds. XXIV. Hydrolysis and Disproportionation of α- and β-Chloroethyltrialkoxysilanes

“…Radical interchange was found to take place between two different silicoorthoesters in 1865 by Friedel and Crafts (8). Analogous reactions may be found, of later date (3)(4)(5).…”

The Chemistry of Silicon-Nitrogen Compounds.

“…The use of dilute mineral acid greatly facilitates the hydrolysis of silylamines in either heterogeneous (99,178,179,180,181) or homogeneous media (46,218).…”

“…Compounds containing a silicon-hydrogen bond must be hydrolyzed under mild acidic conditions to prevent the cleavage of the siliconhydrogen bond (178). Base has been reported both to retard (79,99,154,169) and to accelerate (78, 99, 157) the hydrolysis of silicon-nitrogen compounds.…”

STUDIES IN SILICO-ORGANIC COMPOUNDS. XII. THE ACTION OF CERTAIN ALIPHATIC ALCOHOLS ON TRIALKOXYSILANES1, 2

“…Interaction of aliphatic alcohols with polyalkoxysilanes is a common reaction (1-4). Analogous and related reactions of the trialkoxysilanes however have received only relatively slight attention (5,6).…”