Oxidation of substituted phenethyl alcohols by sodium N-chlorobenzenesulphonamide: A kinetic study

✍ Scribed by H. Ramachandra; K. S. Rangappa; D. S. Mahadevappa

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 498 KB
• Volume: 9
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199605)9:5<279::aid-poc772>3.0.co;2-n

✦ Synopsis

The kinetics of the oxidation of six substituted phenethyl alcohols by sodium N-chlorobenzenesulphonamide or chloramine-B (CAB) in the presence of HCI was studied at 35 "C. The rate shows a first order dependence on [CABIo and [H'] and is of fractional order in [PEA], and [Cl-1. Ionic strength variations, addition of the reaction product of benzenesulphonamide and variation of the dielectric constant of the medium have no effect on the rate. The solvent isotope effect k&,/k&,=O.78. Proton inventory studies were made in H,O-D,O mixtures. The rates correlate satisfactorily with Hammett's LFER. The reaction constant p was -3-5 for electron-releasing substituents and -0-30 for electron withdrawing groups at 35 OC. Activation parameters AH*, AS*, AG* and log A were computed for the reaction. An isokinetic relationship is observed with 8 = 3 3 8 K, indicating enthalpy as a controlling factor.