亚硝酸钠/盐酸催化氧气氧化碘化芳烃、醚、酚化合物

以廉价易得的盐酸/亚硝酸钠为催化剂,碘为碘化试剂,通过分子氧,氧化碘化芳烃、醚、酚的活泼芳香底物,发展了温和条件下高效碘化方法。以苯甲醚为模型底物,系统考察了影响反应的因素,确定的最佳反应条件为:20℃氧气条件下,1,2-二氯乙烷(DCE)为溶剂,n(苯甲醚)∶n(碘)∶n(亚硝酸钠)∶n(HC l)=1∶0.515∶0.05∶0.1。该方法碘原子经济性好,催化剂廉价易得,反应时间大为缩短,选择性好、转化率高,副产物仅为水,容易处理,绿色环保、易于工业化;通过反应机理验证实验,提出了可能的催化循环机理。

Aerobic Oxyiodination of Acticated Aromatics Using HCI/NaNO2/I2

Hydrochloric acid/NaNO2,are the inexpensive and available catalyst system,which can be developed to cooperate exquisitely with I2 in catalyzing the aerobic oxyiodination of arenes,aryl ethers and phenols to the corresponding aromatic iodides under mild conditions.Based on the systematic investigation of reaction conditions using anisole as model substrate,the optimal conditions showed that n(substrate)∶n(I2)∶n(NaNO2)∶n(HCl)=1∶0.515∶0.05∶0.1,while 1,2-dichlorethane(DCE)as solvent and O2 as oxidant at 20 ℃.The newly developed catalyst system exhibited many advantages:100% iodine atom economy,high efficiency,excellent selectivity and conversion and innocuous water as the only by-product,environment-friendly and easily industrialized production.Furthermore,the mechanism for the catalytic oxyiodination reaction was proposed in this paper.