Synthesis of a new polyfluorinated vinylogue of tetrathiafulvalene through 1,3-dipolar cycloaddition of ethyl beta-bromoperfluorodithiocrotonate with dimethyl acetylenedicarboxylate

Vadim M Timoshenko; Jean-Philippe Bouillon; Alexander N Chernega; Yuriy G Shermolovich; Charles Portella

doi:10.1002/chem.200304839

Synthesis of a new polyfluorinated vinylogue of tetrathiafulvalene through 1,3-dipolar cycloaddition of ethyl beta-bromoperfluorodithiocrotonate with dimethyl acetylenedicarboxylate

Chemistry. 2003 Sep 22;9(18):4324-9. doi: 10.1002/chem.200304839.

Authors

Vadim M Timoshenko¹, Jean-Philippe Bouillon, Alexander N Chernega, Yuriy G Shermolovich, Charles Portella

Affiliation

¹ Laboratoire Réactions Sélectives et Application, Associé au CNRS (UMR 6519), Faculté des Sciences, Université de Reims, B. P. 1039, 51687 Reims Cedex 2, France.

PMID: 14502617
DOI: 10.1002/chem.200304839

Abstract

The ethyl ester of beta-bromoperfluorodithiocrotonic acid reacts with dimethyl acetylenedicarboxylate to give 1,4-difluoro-2,3-bis(trifluoromethyl)-but-2-ene-1,4-diylidene-2,2'-bis(4',5'-dicarbomethoxy-1',3'-dithiole) (4), a new type of vinylogue of tetrathiafulvalene. The thermal transformations of this compound lead, depending on the temperature, to the formation of the cyclization products: 11,14-difluoro-2,3,8,9-tetra(carbomethoxy)-12,13-bis(trifluoromethyl)-1,4,7,10-tetrathiadispiro[4.0.4.4]tetradeca-2,8,11,13-tetraene (8) or 5,8-difluoro-6,7-bis(trifluoromethyl)-2,3-bis(carboxymethyl)-1,4-benzodithiine (11).