作者:Toshiaki Yoshimura、Kaoru Asada、Shigeru Oae
DOI:10.1246/bcsj.55.3000
日期:1982.9
Reduction of various tertiary amine oxides with carbon disulfide was examined and kinetic experiments were carried out. Trialkylamine oxides and N,N-dialkylarylamine N-oxides were readily reduced by CS2 to give the corresponding tertiary amines in good yields, while heteroaromatic amine N-oxides such as picoline N-oxide were not affected. The oxygen atom in the N-oxide was found to be transferred to
检查了用二硫化碳还原各种叔胺氧化物并进行了动力学实验。三烷基胺氧化物和 N,N-二烷基芳胺 N-氧化物很容易被 CS2 还原,以良好的产率得到相应的叔胺,而杂芳族胺 N-氧化物如甲基吡啶 N-氧化物不受影响。通过对释放的气体进行质谱分析,发现 N-氧化物中的氧原子被转移到 CO2 中。动力学实验是根据 N,N-二甲基苯胺 N-氧化物在 CH3CN 中的 UV 光谱进行的,该 CH3CN 含有大量过量的 CS2,发现 N-氧化物和 CS2 中的速率为二阶。活化参数 (ΔH\eweq=55.7 kJ mol−1, ΔS\eweq=−78.2 JK−1 mol−1 at 20 °C 是正常双分子反应的特征。对位取代 N 的速率常数的对数,N-二甲基苯胺 N-氧化物与 Hammett σ 值密切相关,并且获得了一个小的负 ρ 值 (ρ=-0.2)。极地的反应速度更快...