Mechanistic Studies for Electrochemical Oxidation of ${\iota}$-Sparteine

${\iota}$-Sparteine의 전기화학적 산화반응에 대한 메카니즘의 연구

  • Jin-Hyo Park (Department of Chemistry, Pusan National University) ;
  • Chang-Soo Jin (Department of Chemistry, Pusan National University) ;
  • Sung-Nak Choi (Department of Chemistry, Pusan National University) ;
  • Yoon-Bo Shim (Department of Chemistry, Pusan National University)
  • 박진효 (부산대학교 자연과학대학 화학과) ;
  • 진창수 (부산대학교 자연과학대학 화학과) ;
  • 최성락 (부산대학교 자연과학대학 화학과) ;
  • 심윤보 (부산대학교 자연과학대학 화학과)
  • Published : 1993.08.20

Abstract

The mechanism for electrochemical oxidation of natural alkaloid, ${\iota}$-sparteine (SP) was studied in acetonitrile solvent. The cyclic voltammogram of SP shows two irreversible anodic peaks at +0.75 V and +1.45 V vs. Ag/AgCl (0.1M AgNO$_2$ in acetonitrile) electrode. Coulometry reveals that the number of electrons involved in each oxidation peaks is in the range of 1.2∼1.3 respectively. Neutral imine radical was produced by fast deprotonation of SP radical cation formed by oxidation of one nitrogen atom in SP. Two pathways are possible for the reaction of the neutral radical: Due to the disproportionation of the radical, SP and enamine were mainly produced. Also, the 1,2-dehydrosparteinium cation was formed as minor product through the second one electron transfer oxidation of this radical. The (+)-lupanine was produced by treatment of sparteinium cation with potassium hydroxide. We have isolated and confirmed the electrolysis products using IR, GC-MS, UV-Vis, and thin-layer spectroelectrochemical method.

Keywords

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