Kinetics of oxidation of heterocyclic secondary alcohols byN-chloro-r-2,c-6-diphenyl-t-3 methyl piperidin-4-one (NCP) in perchloric acid medium
                                
                                    
                                        作者:Kuppusamy Selvaraj、Vinayagam Venkateswaran、Krishnasamy Ramarajan                                    
                                    
                                        DOI:10.1002/kin.550260806
                                    
                                    
                                        日期:1994.8
                                    
                                    AbstractAn 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 H3O+ and Cl− which 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 r‐2‐c‐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. © 1994 John Wiley & Sons, Inc.