Publication Date


Document Type


First Advisor

Kevill, Dennis N.

Degree Name

M.S. (Master of Science)

Legacy Department

Department of Chemistry


Solvolysis; Organochlorine compounds


A scheme has been developed for the synthesis of N-ladamantyl- N-p-tolylcarbamoyl chloride and the kinetics of its solvolysis in pure ethanol, methanol, isopropanol, acetone, 2,2,2-trifluoroethanol (TFE), TFE-ethanol mixtures, and in several aqueous binary solvent mixtures, were investigated by titrimetric methods. The kinetic experiments showed a high dependence of the rates on solvent ionizing power, with the fastest reactions in the fluorinated alcohols and their mixtures with water or ethanol and the slowest in the poorly ionizing ethanol. A reasonable correlation was obtained of the logarithms of the specific rates of solvolysis against solvent ionizing power values, with the solvent ionizing power scale used being the Xci scale, based on the relative specific rates of solvolysis of 1-adamantyl chloride. The relatively high dependence on ionizing power, coupled with a very low dependence on solvent nucleophilicity, suggests that the solvolyses follow an SN1 pathway involving loss of chloride ion to give an acylium ion, which either reacts with solvent or in poorly nucleophilic solvents such as TFE or 1,1,1,3,3,3-hexafluoro-2-propanol, undergoes ejection of ptolyl isocyanate to give the 1-adamantyl carbocation. This carbocation can then be captured by chloride ion or by ABSTRACT solvent to give products which were quantitatively determined by gas chromatography monitoring.


Includes bibliographical references (pages [95]-100)


x, 100 pages




Northern Illinois University

Rights Statement

In Copyright

Rights Statement 2

NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.

Media Type