Kinetics of oxidation of heterocyclic secondary alcohols by N-chloro-r-2,c-6-diphenyl-t-3 methyl piperidin-4-one (NCP) in perchloric acid medium

✍ Scribed by Kuppusamy Selvaraj; Vinayagam Venkateswaran; Krishnasamy Ramarajan

• Publisher: John Wiley and Sons
• Year: 1994
• Tongue: English
• Weight: 406 KB
• Volume: 26
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550260806

✦ Synopsis

An investigation of the kinetics of oxidation of epimeric piperidin-4-ols, oxan-4-ols, and cyclohexanol by N-chloro-r-2, c-6-diphenyl-t-3-methylpiperidin-4-one (NCP) in aqueous acetic acid in the presence of perchloric acid shows that the reaction is first-order each in substrate and oxidant. Both H 3 0 ' and C1which catalyze the reaction, exhibit a fractional order kinetics. While increase in ionic strength increases the rate slightly, an inverse dependence is observed between rate and solvent polarity. Addition of 11-2c-6-diphenyl-t-3-methylpiperidin-4-one, one of the reaction products, did not influence the rate. Also, no kinetic isotope effect has been observed. A plausible mechanism consistent with these observations is proposed and the relative reactivities of the substrates are explained on conformational grounds.