E-苯甲酰二茂铁亚胺的合成、晶体结构和反应性

Syntheses,Crystal Structure and Reactivity of E-Benzoylferrocenyl Schiff Bases

由苯甲酰二茂铁和一系列伯胺出发,用4?分子筛作为催化剂合成了6种相应的E-构型亚胺化合物,产率为50%～85%.该方法具有很好的通用性,同时适用于芳胺和脂肪胺,并且对杂原子具有耐受性.与文献中使用Al2O3作为催化剂的方法相比,该方法可使反应时间和催化剂的活化时间均大大缩短.所合成的席夫碱用于探索生物碱(-)-Sparteine促进的对映选择性地合成平面手性二茂铁中的反应性.根据所测定的化合物3d晶体结构数据,分析了这类化合物反应活性低的原因是空间位阻所致.而空间位阻较小的二茂铁醛亚胺用于该反应能够顺利进行.

A series of ferroceryl Schiff bases were synthesized by a new method using 4Angstrom molecular sieves as catalyst, of which the crystal structure of compound 3d was obtained. The reaction periods were largely reduced using this catalyst in contrast with Al2O3, which was a traditional catalyst used in the literatures. The reactivity of those Schiff bases in the enantioselective preparation of planar chiral ferrocene was studied. The crystal data of compound 3d indicated that it is the steric hindrance of these Schiff bases that cause their low reactivity. And the less hindered imines of ferrocenyl aldehyde can do well in this reaction.