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Published June 1951 | public
Journal Article

Small-Ring Compounds. IV. Interconversion Reactions of Cyclobutyl, Cyclopropylcarbinyl and Allylcarbinyl Derivatives

Abstract

A number of reactions have been investigated which lead to interconversion of cyclobutyl, cyclopropylcarbinyl and allylcarbinyl derivatives. Some degree of interconversion was observed in the following : vapor-phase light-catalyzed chlorination of methylcyclopropane; reaction of cyclopropylcarbinol with thionyl chloride, Lucas reagent, phosphorus tribromide and hydrobromic acid; cleavage of cyclopropylcarbinyl triethylsilyl ether with thionyl chloride; reaction of cyclobutanol with thionyl chloride and Lucas reagent; reaction of cyclopropylcarbinyl-, cyclobutyl- and allylcarbinylamines with nitrous acid; hydrolysis and acetolysis of cyclopropylcarbinyl and cyclobutyl chlorides; reaction of N-cyclopropylcarbinyl- and Ncyclobutylbenzamides with phosphorus pentabromide; and Grignard reactions of cyclopropylcarbinyl halides. No interconversion was observed in the following : reaction of allylcarbinol with thionyl chloride and phosphorus tribromide; vapor-phase light-catalyzed chlorination of cyclobutane; and Grignard reactions of allylcarbinyl and cyclobutyl halides. The products of those interconversion reactions which may reasonably be expected to involve carbonium ion intermediates have been correlated by consideration of carbonium ion stability and ease of interconversion, as well as the degree of reversibility of the reactions involved and the stabilities of the possible products. Cyclopropylcarbinyl halides have been shown to be unusually reactive in solvolysis reactions and, in fact, considerably more reactive than analogously constituted allylic halides.

Additional Information

© 1951 American Chemical Society. Received August 9, 1950.

Additional details

Created:
August 19, 2023
Modified:
October 24, 2023