Carbonium ion rearrangements in reactions of cyclopropylcarbinyl and cyclobutyl derivatives

Citation

Cox, Eugene Floyd (1955) Carbonium ion rearrangements in reactions of cyclopropylcarbinyl and cyclobutyl derivatives. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-12042003-093721

Abstract

1-Methylcyclopropylcarbinylamine and 1-methylcyclobutylamine on treatment with aqueous nitrous acid gave only 1-methylcyclobutanol, while [beta]-methylallylcarbinylamine gave predominantly [beta]-methylallylcarbinol and 1-methylcyclobutanol, with smaller amounts of of [alpha]-methyl-[beta]-methylallyl alcohol and [beta]-methyl-[gamma]-methylallyl alcohol and possibly 2-3% of 1-methylcyclopropylcarbinol. The 1-methylcyclobutanol from 1-methylcyclopropylcarbinyl-C[superscript 14]-amine contained only 2.6 of the total C[superscript 14]-activity in C-3. The corresponding reaction in acetic acid gave 1-methylcyclobutyl acetate with 3.1% of the C[superscript 14] in C-3.

1-Methylcyclopropylcarbinyl chloride solvolyzes in 50% aqueous ethanol ca. 10 times faster than 1-methylcyclobutyl chloride and about as fast as t-butyl chloride.

It was concluded that the above carbonium-ion type reactions of 1-methylcyclobutyl and 1-methylcyclopropylcarbinyl derivatives are best accounted for by formation, as the important reaction intermediate, of an unsymmetrical, nonclassical carbonium ion, structurally similar to the classical 1-methylcyclobutyl cation.

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