Solvolysis of N,N-dimethylthiocarbamoyl chloride: effect of sulfur-for-oxygen substitution upon kinetics and product partitioning
✍ Scribed by Dennis N. Kevill; Todd M. Rudolph; Malcolm J. D'Souza
- Publisher
- John Wiley and Sons
- Year
- 2000
- Tongue
- English
- Weight
- 58 KB
- Volume
- 13
- Category
- Article
- ISSN
- 0894-3230
No coin nor oath required. For personal study only.
✦ Synopsis
A study of the solvolyses of N,N-dimethylcarbamoyl chloride (1) was extended to the solvolyses of N,N-dimethylthiocarbamoyl chloride (2). The specific rates of solvolysis of 2 at 0.0 °C are two to three orders of magnitude greater than those for 1. Analysis of the data using the extended Grunwald-Winstein equation leads to sensitivities l and m and an l/m ratio which are lower for 2 than those previously reported for 1. Product selectivities in mixtures of water with ethanol or methanol indicate a greater preference for reaction with alcohol for 2. All observations can be rationalized in terms of the formation of a more stable carbocation from 2, leading to an earlier transition state, reduced nucleophilic solvation and the possibility of extensive progression to a free carbocation prior to product formation.