Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

✍ Scribed by Nicolas Godbert; Martin R. Bryce; Slimane Dahaoui; Andrei S. Batsanov; Judith A. K. Howard; Paul Hazendonk

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: English
• Weight: 563 KB
• Volume: 2001
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/1099-0690(200102)2001:4<749::aid-ejoc749>3.0.co;2-v

✦ Synopsis

The synthesis of new derivatives of 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene is reported. 1 H NMR studies on compound 4 are consistent with two conformers of the saddle-shaped molecule which interconvert by a boat-boat flipping of the central ring at high temperature. The hydroxymethyl substituent of 4 is readily esterified to yield the benzoyl and 2-naphthaloyl ester derivatives 5a and 5b, respectively, and the dimer and the trimer structures 6 and 7, respectively, by reaction with benzoyl chloride, 2-naphthaloyl chloride, 1,4-benzenedicarbonyl chloride and 1,3,5benzenetricarbonyl chloride. Deprotonation of 9-(4,5-dimethyl-1,3-dithiol-2-ylidene)-10-(1,3-dithiol-2-ylidene)-9,10dihydroanthracene (8) using lithium bis(trimethylsilyl) amide (LHMDS) followed by in situ quenching of the lithiated intermediate with methylchloroformate gave the diester derivative 10 (96% yield), whereas using LDA gave the monoester [ ‡] Molecular Saddles, 3.