Acid-catalysed hydrolysis of S(IV)N bond in N-sulphonyl sulphilimines—I : Mechanism and substituent effect
✍ Scribed by I. Kapovits; F. Ruff; Á. Kucsman
- Publisher
- Elsevier Science
- Year
- 1972
- Tongue
- French
- Weight
- 494 KB
- Volume
- 28
- Category
- Article
- ISSN
- 0040-4020
No coin nor oath required. For personal study only.
✦ Synopsis
Ah&r&-The acid-catalysed hydrolysis of sulphilimines of XC,H,(Me)SNTs and MePhSNSO,C,H,Y type has been studied by a kinetic method in moderately concentrated (l-6 M) aqueous H,SO, and HCIO, solutions. The rate law: rate = k,[sulphilimine] is valid for hydrolysis leading to sulphoxides and sulphonamides The dependence of k, on acidity, temperature and substituents X and Y has been measured and interpreted. px, p,. and AS* data ( + 1.19, + 1W and -18.7--22.6 e.u., resp) show that the nucleophilic attack of water on the positively polarized S(IV) atom of protonated sulphilimines can be regarded as the rate-determining step of the hydrolysis. From 4 parameters (094-1.5) calculated for the hydrolysis of MePhSNTs it follows that water participatn in the reaction as a nucleophile and proton-transfer agent.