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(b) Private communication from Prof. Howard T. Black (Eastern Illinois University). Although ethoxyacetylene is commercially available, (Aldrich, Lancaster) it is rather expensive ($10/g) and, in our experience, the purity is variable and thus distillation is required prior to use. We have prepared ethoxyacetylene by the above methods in 0-75% yields (from chloroacetaldehyde diethyl acetal) and, also in our hands (as communicated by Black), very careful quenching of the intermediate sodium acetylide was critical for reproducible and reasonable yields (50-75%). Several other reported methods for silylketene synthesis have been studied in our laboratory but the silylation of ethoxyacetylene followed by thermolytic retro-ene reaction (ref 33) provided the highest purity and yields of silylketenes.
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