pseudo-cyclic face-to-face rigid structure caused by the intramolecular ion pair effectpseudo-cyclic面对面的刚性结构引起的分子内的离子对的效果.pdfVIP

Molecules 2009, 14, 1546-1560; doi:10.3390/molecule OPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Pseudo-cyclic Face-to-face Rigid Structure Caused by the Intramolecular Ion Pair Effect Sheng-Ling Zhang 1,*, Zhi-Shu Huang 2 and Lian-Quan Gu 2 1 Department of Chemistry, Shaoguan University, Shaoguan 512005, P. R. China 2 School of Pharmaceutical Science, Sun Yat-Sen University, Guangzhou 510275, People’s Republic of China; E-mails: huangzhishu@ (Z-S.H.), cesglq@ (L-Q.G.) * Author to whom correspondence should be addressed; E-mail: zhisland@. Received: 14 March 2009; in revised form: 9 April 2009 / Accepted: 10 April 2009 / Published: 14 April 2009 Abstract: Six 3-methylpyridine zwitterions and six quinoline zwitterions were synthesized through the reaction of 4-hydroxycoumarins, p -benzoquinone and the corresponding N- aromatics. The novel pseudo-cyclic face-to-face rigid structure of the zwitterion was elucidated by 1H-NMR at different temperatures, and assumed to be caused by both the intramolecular ion pair attraction and the steric interaction. Keywords: 4-Hydroxycoumarins; Zwitterion; Molecular structure. 1. Introduction Recently, the compounds with cyclic structures derived from the [2.2] paracyclophane backbone 1 (Figure 1) have stimulated considerable interest due to their special properties and applications. 4,12- Bis(diphenylphosphino)-[2.2]-paracyclophane was shown to be an excellent transition metal ligand for the catalytic asymmetric hydrogen