Publication Date


Document Type


First Advisor

Kevill, Dennis N.

Degree Name

M.S. (Master of Science)

Legacy Department

Department of Chemistry


Sulphonates; Alcoholysis


With clarification of previous views on tosylate/ bromide ratios as a mechanistic criterion for evaluating reaction processes in mind, a series of 2-adamantyl arene-sulfonates was prepared. The above series consisted of para-methoxy, -methyl, -bromo, -chloro, -nitro, and meta-nitro along with the unsubstituted benzenesulfonate. The compounds were characterized from their p.m.r. and IR spectra and elemental analysis. A kinetic study of these sulfonates in ethanol at 55°, 65°, 75°, 85° allowed determination of the integrated first-order rate coefficients. From these rate coefficients, at different temperatures, enthalpies and entropies of activation for the solvolyses were determined. Previous interpretations of tosylate/bromide ratios were opposed as to whether these values indicated different relative leaving capabilities due to electronic dispersal being easier in the tosylate group over the bromide, or whether the varying ratios reflected steric interactions in the ground state. Application of the Hammett pa equation to the series of arenesulfonates for extrapolated rate coefficients at 25° yielded a rho-value of 1.86±.07. The anomalous behavior of the nitro members of the series is comparable with other arenesulfonates. Although the rho-value above is indicative of electronic effects, it is nearly equal to the value for the 1-adamantyl arenesulfonates; therefore electronic effects for these substrates are not indicated in tosylate/bromide ratios.


Includes bibliographical references (pages [59!-61)


61 pages




Northern Illinois University

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