Sauer Marc, Yeung Charles, Chong Jonathan H, Patrick Brian O, MacLachlan Mark J
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1 Canada.
J Org Chem. 2006 Jan 20;71(2):775-88. doi: 10.1021/jo052277t.
[structure: see text] The synthesis, characterization, and solid-state structures of new salicylaldimines are reported. Bis(N-salicylideneaniline)s (BSANs) and tris(N-salicylideneaniline)s (TSANs) are sterically encumbered compounds featuring a central six-membered ring in the keto-enamine tautomer. When extended with additional functional groups, these molecules may form hydrogen-bonded capsules, clefts, and extended structures. A TSAN with N-(t)()BOC-o-phenylenediamine groups has been structurally investigated. The complementary hydrogen-bonding motif in this molecule leads it to form dimers in solution and in the solid state. A BSAN with N-(t)()BOC-o-phenylenediamine substituents forms a hydrogen-bonded cleft in solution but forms an extended hydrogen-bonded ladder assembly of cofacial dimers in the solid state. When N-(t)()BOC-1,8-naphthalenediamine was utilized to extend the cleft, an unusual perimidine structure was obtained with the central core in the enol tautomer. In addition, ab initio calculations have been used to support the assignment of the keto-enamine or enol-imine tautomers of the BSANs and TSANs and to predict tautomerization in related BSANs and TSANs.
[结构：见正文] 报道了新型水杨醛亚胺的合成、表征及固态结构。双（N - 水杨醛苯胺）（BSANs）和三（N - 水杨醛苯胺）（TSANs）是位阻化合物，在酮 - 烯胺互变异构体中具有一个中心六元环。当用额外的官能团扩展时，这些分子可能形成氢键包囊、裂缝和扩展结构。对一种带有N -（叔丁氧羰基） - 邻苯二胺基团的TSAN进行了结构研究。该分子中互补的氢键基序使其在溶液和固态中形成二聚体。一种带有N -（叔丁氧羰基） - 邻苯二胺取代基的BSAN在溶液中形成氢键裂缝，但在固态中形成共面二聚体的扩展氢键阶梯组装体。当使用N -（叔丁氧羰基） - 1,8 - 萘二胺来扩展裂缝时，得到了一种不寻常的嘧啶结构，其中心核处于烯醇互变异构体形式。此外，已使用从头算计算来支持对BSANs和TSANs的酮 - 烯胺或烯醇 - 亚胺互变异构体的归属，并预测相关BSANs和TSANs中的互变异构化。
