芳香族硝基化合物与苯硫酚钠盐的亲核取代反应: 自由基IPSO取代机理

作者通过苯硫酚钠盐与对硝基苯甲酸甲酯(1), 对硝基苯甲酸苯酯(2), 间硝基苯甲酸甲酯(3), 3,5-二硝基苯甲酸甲酯(4)和对二硝基苯(5)反应研究, 用自旋捕获技术检测到苯硫基自由基; 同时, 从产物混合物中分离到二苯基二硫化物PhSSPh。提出苯硫基自由基与芳香族硝基化合物1,2,3,4和5反应的自由基IPSO亲核取代机理。

Studies on the reaction of aromatic nitro compounds with sodium phenylthiolate radical IPSO substitution mechanism

Aromatic nitro compounds I (R = 4-CO2Me, 4-CO2Ph, 3-NO2-4-CO2Me) reacted with sodium phenylthiolate giving radical IPSO substitution products and di-Ph disulfide. The reaction mixtures were ESR active and the ESR spectra were consistent with those for the radical anions of I, resp. Using tertiary nitrosobutane as the spin trapping agent, the ESR spectrum for nitroxide tert-BuN(O) SPh was obtained. A radical IPSO substitution mechanism is proposed.