Physical Sciences and Mathematics Commons^™

The Thermal Rearrangement Of Triarylacetonitrile Oxides., Leslie Wayne Gibbs

University of the Pacific Theses and Dissertations

This research is a detailed study of the rearrangement of triarylacetonitrile oxides to the corresponding triarylmethylisocyanates. The kinetics of the rearrangement of triphenylacetonitrlle oxide was followed by infrared absorption spectroscopy using the peak due to the N-0 stretching (1307cm^-1). A study, both, using the differential method (i.e., a plot of the logs of the initial slopes vs. the log of the concentration) and a check of the integrated forms of the rate expressions to determine which gave a constant value for the rate constant showed that the reaction is first order.

From measurements of the rate constant, k, …

Birch Reduction Of Benzamide, N-Substituted Benzamides And Biphenylene, Luther Dickson

University of the Pacific Theses and Dissertations

The Birch reduction of benzamide with sodium and absolute ethanol. 95% ethanol, or tert-butanol in liquid ammonia gave 1,4-dihydrobenzamide in varying amounts. The amide group was not reduced. The two most important variables encountered were the alcohol used and whether or not ammonium chloride was added after the reduction was completed. Without this addition of ammonium chloride, little or no 1,4-dihydrobenzamide was present after workup, while with its addition some 1,4-dihydrobenzamide formed whether the proton source was absolute ethanol, 95% ethanol, or tert-butanol. The highest yield was obtained with tert-butanol with ammonium chloride being added. Addition of ammonium chloride apparently …