ChemInform Abstract: DIE ADDITION VON HYDROSILANEN AN BUTADIEN

Abstract

Bei der mit Hexachloroplatinsäure katalysierten Addition der Silane (I) an ‐Butadien (II) entstehen überwiegend die 1,4‐Addukte (III) und in geringen Mengen die 1,2‐Addukte (IV).

Synthesis of para-substituted 1,4,5,6,7,7-hexachlorobicyclo-[2.2.1]hepta-2,5-dien-2-ylmethyl benzoates

“…Hexachlorocyclopentadiene (IV) was synthesized according to the procedure described in [12]; bp 109-111°C (11 mm), n D 20 = 1.5654, d 4 20 = 1.7210; published data [12]: n D 20 = 1.5652, d 4 20 = 1.7213. para-Substituted prop-2-yn-1-yl benzoates IIIaIIIg were prepared as reported in [10]. Phosphoryl chloride, 0.7 mol, was added dropwise under vigorous stirring to 0.1 mol of para-substituted benzoic acid IIa-IIg in a flask protected from atmospheric moisture.…”

“…Under these conditions, the yields of adducts Va-Vg were 65-90%. The structure of compounds Va-Vg was proved by independent synthesis, by esterification of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hepta-2,5-dien-2-ylmethanol (VI) (prepared by cycloaddition of hexachlorocyclopentadiene to prop-2-yn-1-ol [9]) with para-substituted benzoic acids IIa-IIg according to the procedure described in [10] (Scheme 2). Samples of Va-Vg obtained by the two methods were identical.…”

Reaction of dimethylsilylene with allylic methyl sulfides

“…bp 134 °C). 14 Preparation of (7-Methylallyl)dimethyl(methylthio)silane. A 300-mL three-neck round-bottom flask was fitted with an overhead mechanical stirrer, a pressure-equalizing additional funnel, and a dry ice/actone cold finger condenser.…”