物理化学学报 >> 2010, Vol. 26 >> Issue (07): 1832-1836.doi: 10.3866/PKU.WHXB20100633

结构化学 上一篇    下一篇

包结法拆分1,1'-联-2-萘酚: 包结物的晶体结构及CD光谱

赵珺, 郑明贤, 林以玑, 陈渊川, 阮源萍, 章慧   

  1. 固体表面物理化学国家重点实验室, 厦门大学化学化工学院化学系, 福建 厦门 361005
  • 收稿日期:2010-02-02 修回日期:2010-03-25 发布日期:2010-07-02
  • 通讯作者: 章慧 E-mail:huizhang@xmu.edu.cn

Inclusion Resolution of 1,1'-Bi-2-naphthol: Crystal Structure and CD Spectroscopy of the Inclusion Complexes

ZHAO Jun, ZHENG Ming-Xian, LIN Yi-Ji, CHEN Yuan-Chuan, RUAN Yuan-Ping, ZHANG Hui   

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
  • Received:2010-02-02 Revised:2010-03-25 Published:2010-07-02
  • Contact: ZHANG Hui E-mail:huizhang@xmu.edu.cn

摘要:

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.

关键词: 圆二色光谱, 1,1'-联-2-萘酚, 包结拆分, 碘化(R)/(S)-N,N,N-三甲基-1-羟基-3-甲基-2-丁铵, 晶体结构

Abstract:

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-butanaminiumiodide 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 ammoniumsalt 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.

Key words: Circular dichiroismspectroscopy, 1,1'-Bi-2-naphthol, Inclusion resolution, (R)/(S)-N,N,N-Trimethyl-1-hydroxyl-3-methyl-2-butanaminiumiodide, Crystal structure

MSC2000: 

  • O641.6