CAJ | 학술논문

采用循环伏安法研究了肉桂腈在乙腈溶液中的电还原行为,其在-1.46和-2.0V处各存在一个还原峰.第一个峰处恒电位电解得到了线性、环化氢化二聚产物以及苯基戊二腈;第二个峰处电解得到了饱和二氢还原产物苯丙腈.结合循环伏安模拟判定了整个电还原的具体反应机理是肉桂腈通过电化学-电化学-化学-化学(EECC)反应机理,丰成苯丙腈,同时经历自由基.自由基(RR)过程得到线性和环化二聚产物,肉桂腈还可以与乙腈的共轭碱反应得到苯基戊二腈.最终通过循环伏安模拟求得相应反应的动力学常数,自由基.自由基耦合反应速率常数为10~4 L·mol~(-1)·s~(-1),第二个电子转移反应速率常数为0.3 cm·s~(-1),其后质子化反应的速率常数为10~5 s~(-1).
채용순배복안법연구료육계정재을정용액중적전환원행위,기재-1.46화-2.0V처각존재일개환원봉.제일개봉처항전위전해득도료선성、배화경화이취산물이급분기무이정;제이개봉처전해득도료포화이경환원산물분병정.결합순배복안모의판정료정개전환원적구체반응궤리시육계정통과전화학-전화학-화학-화학(EECC)반응궤리,봉성분병정,동시경력자유기.자유기(RR)과정득도선성화배화이취산물,육계정환가이여을정적공액감반응득도분기무이정.최종통과순배복안모의구득상응반응적동역학상수,자유기.자유기우합반응속솔상수위10~4 L·mol~(-1)·s~(-1),제이개전자전이반응속솔상수위0.3 cm·s~(-1),기후질자화반응적속솔상수위10~5 s~(-1).
The electroreduction of cinnamonitrile in MeCN solution was studied using cyclic voltammetry, with two reduction peaks at -1.46 and -2.0 V. Linear, cyclic hydrodimers, and 3-phenyl pentanedinitrile were synthesized at the first peak, while additional saturated hydro product was synthesized at the second peak. The reduction mechanism was proposed based on the experimental and cyclic voltammogram simulation results. Linear and cyclic hydrodimers were synthesized by a radical-radical (RR) route while a saturated hydro product was obtained via an electrochemical-electrochemical-chemical-chemical (EECC) process. 3-Phenyl pentanedinitrile was synthesized by the reaction of cinnamonitrile with the conjugate base of MeCN. Finally, the dynamic constants were calculated using cyclic voltammogram simulation. Result indicated that the rote constant oftbe RR reaction was found to be 10~4 L·mol~(-1)·s~(-1), and the rate constant of the second electron transfer reaction was 0.3 cm·s~(-1), while the rate constant of the subsequent proton reaction was 10~5 s~(-1).