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
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.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||1 January 1955|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||09 Dec 2003|
|Last Modified:||26 Dec 2012 03:11|
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