Calcium-amine reductions of epoxides, benzoic acids and phenylacetic acids
Abstract
Chapter 1. Calcium-ethylenediamine reduction of epoxides. Six simple epoxides were reduced to the "Markovnikov" alcohols with calcium in ethylenediamine. The results were similar to those found in the reductions of the same starting materials with lithium in ethylenediamine. Chapter 2. Calcium-ethylenediamine reduction of alkylbenzoic acids. Benzoic acid, $\alpha$-naphthoic acid, and ten methylated benzoic acids were reduced by calcium in ethylenediamine to 1,4-dihydrobenzoic acids. It was shown by trapping with alkyl halides that the $\alpha$ position of the product remains deprotonated until the reaction is quenched. The effects of mixed solvent systems and reduced temperature were studied for three 4-methylbenzoic acids. Gas evolution and reaction progress were monitored for several of the starting materials, and the reduction of calcium m-toluate was investigated. Chapter 3. Calcium-ethylenediamine reduction of phenylacetic acids. The calcium reduction behavior of phenylacetic acid, $\alpha$-methylphenylacetic acid, and $\alpha$,$\alpha$-dimethylphenylacetic acid was studied. The evidence suggests that the reaction involves the intermediacy of a Birch-type diene during the initial stages of reduction, and that the reductions of phenylacetic acid and $\alpha$-methylphenylacetic acid are slowed by $\alpha$-deprotonation.
Degree
Ph.D.
Advisors
Benkeser, Purdue University.
Subject Area
Organic chemistry
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