Tetramercaptotetrathiacalix[4]arene the most sulfur enriched ligand: Synthesis and structural analysis

Akdas H., Graf E., Hosseini M. W., Rao P., De Cian A.

Journal of Supramolecular Chemistry, vol.2, no.1-3, pp.21-28, 2002 (Scopus) identifier

  • Publication Type: Article / Article
  • Volume: 2 Issue: 1-3
  • Publication Date: 2002
  • Doi Number: 10.1016/s1472-7862(02)00069-2
  • Journal Name: Journal of Supramolecular Chemistry
  • Journal Indexes: Scopus
  • Page Numbers: pp.21-28
  • Keywords: Calixarene, Crystal structure, Mercaptocalixarene, Synthesis, Thiacalixarene, Thiol
  • Yıldız Technical University Affiliated: No


p-tert- Butyltetramercaptotetrathiacalix[4]arene 1 bearing 8 sulphur atoms was synthesised in high overall yield (80%). The synthetic strategy followed to prepare the compound 1 was based on the Newman and Kwart thermal rearrangement. The treatment of p-tert-butyltetrathiacalix[4]arene 2 by N,N-dimethylthiacarbamoyl chloride under mild conditions afforded the tetra O-thiacarbamoyl derivative which under thermal transposition gave the S-thiacarbamoyl derivatives in quantitative yield. The treatment of the rearranged product by hydrazine hydrate gave the compound 1. The conformation adopted in the solid state by 1 was demonstrated by X-ray diffraction studies on a single crystal to be the 1,3-alternate. © 2003 Elsevier Ltd. All rights reserved.