THE REDUCTION OF ORGANIC COMPOUNDS BY CALCIUM IN LOW MOLECULAR WEIGHT AMINES
Abstract
The reduction of organic substrates by calcium in low molecular weight amines was studied. The amine mixtures typically consisted of ethylenediamine plus a primary amine co-solvent. The reduction of aromatic hydrocarbons to monoalkenes was investigated. Various reaction parameters, such as temperature, solvent effects, and metal concentration, were examined. The calcium/amine reducing system cleanly reduced aromatic hydrocarbons to monoalkene products, with the product mixture highly in favor of the thermodynamically most stable isomer. Durene and anthracene were exceptions, being reduced to non-conjugated diene products. Other organic substrates such as alkenes and epoxides were subjected to the calcium/amine reducing system. Only terminal double bonds underwent reduction to the saturated hydrocarbon. Epoxide rings were cleaved cleanly to the most highly substituted Markovnikov alcohol products. Diene intermediates were trapped out by the use of a more acidic proton source, such as an alcohol, in the calcium/amine reducing system. Calcium alkylamides, potent bases generated as a byproduct of the reduction, were also studied. They were found to act as catalysts, promoting direct reaction between calcium and the amine solvent. The calcium alkylamides were also capable of isomerizing isolated double bonds and of aromatizing six-membered ring dienes, such as (alpha)-terpinene, (gamma)-terpinene, and d-limonene, in refluxing ethylenediamine.
Degree
Ph.D.
Subject Area
Organic chemistry
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