17040-73-2Relevant articles and documents
Kinetics and mechanism of oxidation of some substituted 4-piperidones by pyridinium fluorochromate (PFC)
Dhar, R K,Varadarajan, R
, p. 936 - 940 (2007/10/02)
The kinetics of oxidation of several 3-alkyl and 3,5-dimethyl substituted 2,6-diphenylpiperidin-4-ones (1-6) by pyridinium fluorochromate (PFC) in the presence of perchloric acid in aqueous acetic acid medium have been investigated.Direct second order kinetics is observed, first order each in and .A primary isotope effect, kC-H/kC-D = 4.2, suggests that the aC-H bond is cleaved in the rate determining step.An interesting order of reactivity has been found to be: 3-ethyl above 3-methyl above 3-isopropyl above 3-H above 3,5-dimethyl.An explanation has been presented to justify the above rate differences.Further, the effect of electron-withdrawing NO2 group or electron-donating OCH3 group present at the para position of the phenyl ring of these piperidones (7,8) on the rate of oxidation suggests participation of the phenyl group. 3-Hydroxy-substituted piperidin-4-ones and substituted pyrrolidine-3-carboxylic acids are the major products of oxidation.Activation energies and related thermodynamic parameters have been determined and compared.A probable mechanism consistent with experimental observations has been proposed.