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芳卤氰基化

1、Cu 催化下芳香卤代烃或(TfO- )和K 4 [Fe(CN) 6 ]反应氰基取代

       Thornds Schdreind, Alexander zapf 报道了一种在Cu催化下芳香卤代烃或(TfO-)和K 4 [Fe(CN) 6 ]反应高收率生成氰基化合物的方法。作者经过一系列实验,使用不同的铜催化剂,以及不同的配体与溶剂,从而得到了最好的实验条件。即:Cu(BF 4 ) 2 . 6 H 2 O为催化剂,DMEDA为配体,DMAc为溶剂。

     No condition details were available in this literature. The general reaction conditions that the author gave were: 2.0 mmol aryl halide, Cu(BF 4 ) 2 .6H2O(0.1 eq), 20 mol% dry K 4 [Fe(CN) 6 ], 2 mL DMAc, 20 mol% KI, 20 mol % Na 2 CO 3 , 100 mol % DMEDA.

2、微波反应芳卤氰基化

     直接取代大多用高温反应,有人开发了使用微波反应做这一取代。

       A dried heavy-walled pyrex tube was charged with organo-bromide (0.2 mmol), Zn(CN) 2 (23.5 mg, 0.2 mmol) and Pd(PPh 3 ) 4 (6.9 mg, 6.0 ímol) in DMF (1 ml). The reaction mixture  was flushed with nitrogen and the screw cap tightened thoroughly before mixing with a Whirlimixer. The reaction mixture was exposed to microwave irradiation (60 W) for 2 min (for 2g 2.5 min). The reaction tube was allowed to reach room temperature before the reaction mixture was diluted in EtOAc (60 mL) and washed with water. The organic phase was dried and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to give the pure nitrile.


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