铜催化C-O偶联合成氨基甲酸苯酯

The Synthesis of Phenyl Carbamate by Copper-catalyzed C-O coupling reaction

以邻取代苯酚与甲酰胺为原料合成了氨基甲酸苯酯,考察了不同溶剂、催化剂、氧化剂、温度、时间对反应的影响,最终确定了20%CuCl_(2)为催化剂,DMF为溶剂,3倍当量TBHP为氧化剂,80℃反应3 h。产物经过了^(1)HNMR、^(13)C NMR、GC-MS鉴定,成功合成了四种产物:二甲氨基甲酸邻硝基苯酯、二甲氨基甲酸邻氰基苯酯、二甲氨基甲酸-6-氯-2-羟基偶氮苯酯、二乙胺基甲酸-6-氯-2羟基偶氮苯酯。

Phenyl carbamates were obtained by copper-catalyzed C-O coupling reaction of o-substituted phenolswithmethanamide.The optimal reaction condition was investigated including catalyst,oxidant,temperature and time.The ultimate reaction condition was 10 mol%CuCl as catalyst,3 equiv TBHP asoxidant,DMF as the solvent at 80℃for 24 h.The chemical structure of the product was identified by ^(1)H NMR,^(13)C NMR and GC-MS.Meanwhile,four desired products were synthesized including 2-cyanophenyl dimethylcarbamate,2-nitrophenyl dimethylcarbamate,2-(phenyldiazenyl)phenyl dimethylcarbamate and 2-(phenyldiazenyl)phenyl diethylcarbamate.