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Please login to access the full content or check if you have access via Method 8: Replacement of an Alcoholic Hydroxy Group via Oxyphosphonium Intermediates

DOI: 10.1055/sos-SD-035-00055

Margaretha, P.Science of Synthesis, (20073578.

Replacement of the hydroxy group of an alcohol by chlorine using one of the classic reagents hydrogen chloride, thionyl chloride, or a phosphorus chloride, is often accompanied by elimination (in the case of cycloalkanols) or rearrangement (in the case of secondary pentyl or neopentyl alcohols). This is mainly due to the fact that hydrogen chloride is either present from the beginning or is formed by the reaction of the (inorganic) acid chloride with the alcohol. The first report of a tertiary phosphine dichloride reagent, which limits these side reactions, appeared in 1964 (Scheme 22). Using this technique, yields of 9099% (determined by GC) are obtained for 1-chlorobutane, 1-chloro-2,2-dimethylpropane, chlorocyclohexane, and 2-chloro-2-methylpropane; the gas chromatographic analyses of the crude reaction mixtures show no byproducts, except in the last case where the chloride is accompanied by isobutene (10%).[‌54‌]

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