Journal of the Brazilian Chemical Society | |
Kinetics and mechanism of oxidation of the drug intermediate 1-(2-Hydroxyethyl)piperidine by Bis(hydrogenperiodato)argentate(III) | |
Huo, Shuying1  Kang, Weijun1  Shi, Tiesheng1  Shen, Shigang1  Hebei Medical University, Shijiazhuang, China1  Hebei University, Baoding, China1  Hongmei, Shi1  Zhang, Jiong1  | |
关键词: 1-(2-hydroxyethyl)piperidine; Ag(III); oxidation; kinetics; mechanism; | |
DOI : 10.5935/0103-5053.20130165 | |
学科分类:化学(综合) | |
来源: SciELO | |
【 摘 要 】
1-(2-Hydroxyethyl)piperidine (HEP) is involved in many drugs and drug leads, but its oxidation mechanisms are poorly understood. The oxidation of HEP by bis(hydrogenperiodato)-argentate(III) ([Ag(HIO6)2]5-;) in aqueous alkaline medium was shown, by electrospray ionization mass spectrometry (ESI-MS), to generate piperidine and formaldehyde as the major products. The reaction was monitored spectrophotometrically in the 25.0 to 40.0 ºC range revealing that the oxidation followed a first-order kinetics in [Ag(III)] and a fractional-order in [HEP]. A rate law and a reaction mechanism were proposed based on the study of the dependency of the pseudo-first-order rate constants, kobsd, on [OHˉ] and on [IO4ˉ]tot (total concentration of periodate). The mechanism involves the formation of a periodato-Ag(III)-HEP ternary complex, whose decomposition generates Ag(I) by means of two pathways: one independent and another facilitated by OHˉ. The reaction rate constants and associated equilibrium constants as well as the activation parameters of the rate-determining steps were calculated.
【 授权许可】
Unknown
【 预 览 】
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