Synthesis, structure, and complexation behavior of 14- and 28-membered partially unsaturated thiacrown ethers

✍ Scribed by Toshio Shimizu; Satoru Komatsuzaki; Kazunori Hirabayashi

• Book ID: 102233823
• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 177 KB
• Volume: 22
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.20678

✦ Synopsis

Abstract

Partially unsaturated 14‐ and 28‐membered thiacrown ethers, 3 and 4, which possess alternating Z‐carbon‐‐carbon double bonds and propylene chains, were synthesized by stepwise reactions. The crystal structure of larger cyclic compound 4 was determined by X‐ray crystallographic analysis. 14‐Membered thiacrown ether 3 was found to be more easily oxidized electrochemically than larger cyclic compound 4 and the corresponding saturated system. Compounds 3 and 4 isomerized at temperatures exceeding 100°C in solution to give cyclic compounds with E‐olefin moieties but were stable at 80°C in solution. Compound 3 formed 1:1 complexes with silver and copper ions, and 4 formed 1:2 complexes mainly in solution. A complex of 3 with mercury(II) chloride was isolated, and its crystal structure was determined by X‐ ray analysis. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:287–293, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20678