Stereochemical Study of CycIopropylcarbinyl Derivatives in Carbonium-lon Reactions

Author: Vogel, Martin

Year: 1961

Degree: Dissertation (Ph.D.)

Advisor: Roberts, John D.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/7H4C-6W65

Abstract

Cyclopropylmethylcarbinylamine and cyclopropylmethylcarbinol were resolved and their configurations related. The former was deaminated with aqueous nitrous acid to give the latter with 0-4% net inversion of configuration. The solvolyses of several N-methyl-4-alkoxypyridinium salts were investigated. Solvolysis rates for N-methyl-4- (cyclopropylcarbinyloxy)-pyridinium iodide and perchlorate in water and in 80% ethanol and of N-methyl-4-(cyclopropylmethy1carbinyloxy)-pyridinium iodide in water were measured. The first-order rate constant for the hydrolysis of N-methyl-4-(cyclopropylmethylcarbinyloxy)-pyridinium iodide at 30° was calculated to be 6 x 10^3 times that of N-methyl-4-(cyclopropylcarbinyloxy)-pyridinium iodide. The hydrolysis of optically active N-methyl-4-(cyclopropylmethylcarbinyloxy)-pyridinium iodide produced cyclopropylmethylcarbinol with 4.4 ± 1.5% inversion of configuration.

The stereochemistry of the deamination of cyclopropylmethylcarbinylamine and of the hydrolysis of N-methyl-4-(cyclopropylroethylcarbinyloxy)-pyridinium iodide and the ratio of rate constants for the cyclopropylroethylcarbinyl and cyclopropylcarbinyl pyridinium salts are discussed with respect to the possible intervention of non-classical carbonium-ion intermediates in these reactions.

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