Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.
J Org Chem. 2012 Aug 3;77(15):6653-6. doi: 10.1021/jo301244p. Epub 2012 Jul 25.
Diamination of phenylene dihalides with aqueous ammonia to give the corresponding phenylenediamines can be achieved by using a dicopper complex [Cu(2)(bpnp)(OH)(CF(3)COO)(3)] (1) (bpnp = 2,7-bis(pyridine-2-yl)-l,8-naphthyridine) as the catalyst in the presence of Bu(4)NBr and Cs(2)CO(3) in high yields. In addition, 1,3,5-tribromobenzene was converted into benzenetriamine quantitatively under the same conditions. This method offers a new opportunity, particularly simplifying steps and increasing yields, for the preparation of aryl diamines.
二价铜配合物[Cu(2)(bpnp)(OH)(CF(3)COO)(3)](1)(bpnp=2,7-双(吡啶-2-基)-1,8-萘啶)在 Bu(4)NBr 和 Cs(2)CO(3)的存在下,可以作为催化剂,将苯二卤化物与氨水溶液反应转化为相应的苯二胺,产率很高。此外,在相同条件下,1,3,5-三溴苯定量转化为苯三胺。该方法为芳基二胺的制备提供了一个新的机会,特别是简化了步骤并提高了产率。