Tools
Tools
Wyvill, Percival Leslie (1950) Interaction of butyl alcohols and certain derivatives with thionyl and with phosphorus halides. Doctoral thesis, Northern Polytechnic.
With a view to testing the influence of structural environment on the reactivity of the alcoholic carbon atom of tertiary butyl alcohol and 1ts derivatives, experiments on trichloro-tert.-butyl alcohol, (CH3)2CC13C.OH chloretone, have been conducted.
Phosphorus trichlorlde does not interact wlth chloretone under those mild conditions in which tert.- butyl alcohol readily affords the chloride RC1. Much more rigorous treatment affords the chlorophosphites ROPC12, (Ro)2PC1, but still no chloride RC1. Furthermore, the compound (RO)2PC1 exhibits a most unusual inactivity towards a molecule of chloretone in the presence of pyridine; although it reacts readily with ethyl alcohol wider identical conditions. The dichloride ROPC12 interacts with only one molecule of chloretone but with two molecules of ethyl alchohol in the presence of pyridine. Most unusually vigorous treatment with phosphorus pentachloride is required to convert chloretone into the chloride RC1. The latter shows remarkable resistance to removal of chlorine by aqueous alkali, although this treatment readily removes all the chlorine in chloretone itself. Therefore, chloretone shows an unusual resistance to replacement not only of hydroxyl,. group, but also of the hydrogen atom of that group.
From a study of the interaction of tert .-butyl alcohol and phosphorus trichloride in the absence and in the presence of ether, and from a study of the influence of pyridine on this system, conclusions are drawn concerning the nature and sequence of the reactions which take place.
A similar study of the tert .-butyl alcohol - thionyl chloride system has been made.
The effect of branching in the isomeric butyl alcohols, and the experiments with other halides of phosphorus are also considered.
 |
View Item |