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Updated: Jan 29, 2026

Calcium Carbonate Formation in the Presence of Biopolymeric Additives
Published on: May 14, 2019
Classical tosylate/chloride leaving group approach supports a tetrahedral transition state for additions to trigonal
Malcolm J D'Souza1, Jeremy Wirick1, Jasbir Deol1
1Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875.
Abstract:
The experimentally measured rates of solvolysis of 2-chloroethoxycarbonyl chloride (2-chloroethyl chloroformate, 3), 2-chloroethoxycarbonyl p-toluenesufonate (5), and phenoxycarbonyl p-toluenesulfonate (6) were followed at 25.0 °C in various pure and binary aqueous-organic solvents with varying degrees of polarity. An analysis of the rate constants for 3, 5, and 6, was carried out using the two-term extended Grunwald-Winstein equation and comparisons are made to the previously published results for ethyl and phenyl chloroformate esters. The k OTS/k Cl rate ratios and the Grunwald-Winstein l/m ratios indicate the probability of a dominant bimolecular carbonyl-addition pathway in the more nucleophilic solvents. Nevertheless in 3 and 5, in the strongly hydrogen-bonding 70% and 50% HFIP mixtures, a side-by-side ionization mechanism is favored.
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