Date of Award
1972
Document Type
Dissertation
Degree Name
Doctor of Philosophy (Ph.D.)
Department
Graduate School
First Advisor
Donald K. Wedegaertner
First Committee Member
Charles A. Matuszak
Second Committee Member
Richard P. Dodge
Third Committee Member
Charles W. Roscoe
Abstract
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, at several different temperatures, values of △ H and △ S were determined from the Eyring equation to be 8.66 kcal/mol and -59.3 cal/mol-°A, respectively.
The rearrangement rates of several substituted triphenylacetonitrile oxides were measured and it was learned that the presence of various substituent groups on the phenyl ring either did not effect or slightly increased the rate of rearrangement.
In the light of the evidence obtained, a concerted mechanism for the reaction seems most feasible. The highly negative entropy of activation value indicates a highly ordered transition state as would be obtained by such a mechanism. The fact that substitutes uniformly accelerate the reaction, also, seems to indicate that the intermediate possesses a degree of radical character.
Attempts to synthesize a series of substituted tetraphenyldiazoethanes via a route involving the triphenylacetonitrile oxides proved unsuccessful.
Pages
122
Recommended Citation
Gibbs, Leslie Wayne. (1972). The Thermal Rearrangement Of Triarylacetonitrile Oxides.. University of the Pacific, Dissertation. https://scholarlycommons.pacific.edu/uop_etds/3518
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