包结法拆分1,1'-联-2-萘酚:包结物的晶体结构及CD光谱

Abstract

以d/l-缬氨醇为原料,通过二步反应得到价廉易得的拆分剂碘化(r)/(S)-n,n,n-三甲基-1-羟基-3-甲基-2-丁铵,采用包结拆分法,成功实现了对1,1′-联-2-萘酚(bInOl)的拆分.对具有(r)-构型的季铵盐与(r)-bInOl在甲醇中所形成包结物的晶体结构分析结果表明:I-离子桥联主体(拆分剂)的醇羟基和客体(bInOl)的酚羟基形成O-H…I-氢键,以及相邻层的主客体分子之间的C-H…O氢键相互作用是在包结物中实现手性识别的关键.同时对两个包结物的溶液和固体圆二色(Cd)光谱进行了研究.

A highly efficient and environmentally friendly method for the resolution of racemic 1,1′-bi-2-naphthol (BINOL) was developed by inclusion complexation with the cheap and readily accessible (R)/(S)-N,N,N-trimethyl-1-hydroxyl-3-methyl-2-butanaminium iodide resolving agents, which were prepared by a simple two-step reaction starting with D/L-valinol.The X-ray structural analysis was carried out for the inclusion complex of the (R)-quaternary ammonium salt with (R)-BINOL in CH3OH.This showed that the O-H…I-hydrogen bonds among the bridged iodide anions with the alcoholic hydroxyl of the host (resolving agent) and the phenolic hydroxyls of the guests (BINOL) together with the C-H… O hydrogen-bond interactions between the host and guest molecules from the adjacent layers are responsible for the chiral recognition in the inclusion complex formation.In addition, the solution and solid-state circular dichiroism(CD) spectra of a pair of inclusion complexes were also carefully investigated.