Aryl chlorothionoformates (ROCSCl) are derivatizing agents that have also found wide use in the preparation of thionocarbamates that are effective fungicides. Over the past few years, our research group has analyzed in detail the solvolyses of p-tolyl-, phenyl-, p-chlorophenyl-, p-fluorophenyl-, and pentafluorophenyl chlorothionoformate esters in a variety of organic mixtures of widely varying nucleophilicity and ionizing power values. Here we present all of the solvolytic data of pentafluorophenyl chlorothionoformate accumulated at 25.0�C using the titration method. The rate data show that there is a significant dependence on substitution effects and an analysis using the extended (two-term) Grunwald-Winstein equation shows the occurrence of simultaneous side-by-side addition-elimination and unimolecular SN1 mechanisms. This work is supported, in part, by the Delaware INBRE and EPSCoR programs - supported by grants from the National Center for Research Resources-NCRR (5P20RR016472-12) and the National Institute of General Medical Sciences - NIGMS (8 P20 GM103446-12) from the National Institutes of Health (NIH); a National Science Foundation (NSF) Delaware EPSCoR grant EPS-0814251; and a NSF ARI-R2 grant 0960503.

Differentiating electronic effects in substituted aryl chlorothionoformate esters

245th National Meeting (2013)

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