Dn. Kevill et al., Solvolysis of N,N-dimethylthiocarbamoyl chloride: effect of sulfur-for-oxygen substitution upon kinetics and product partitioning, J PHYS ORG, 13(4), 2000, pp. 192-196
A study of the solvolyses of N,N-dimethylcarbamoyl chloride (1) was extende
d to the solvolyses of N,N-dimethylthiocarbamoyl chloride (2). The specific
rates of solvolysis of 2 at 0.0 degrees C are two to three orders of magni
tude greater than those for 1. Analysis of the data using the extended Grun
wald-Winstein equation leads to sensitivities l and m and an l/m ratio whic
h are lower for 2 than those previously reported fur 1. product selectiviti
es in mixtures of water with ethanol or methanol indicate a greater prefere
nce for reaction with alcohol for 2. All observations can be rationalized i
n terms of the formation of a more stable carbocation from 2. leading to an
earlier transition state, reduced nucleophilic solvation and the possibili
ty of extensive progression to a free carbocation prior to product formatio
n. Copyright (C) 2000 John Wiley & Sons, Ltd.