Syntheses of New Unsymmetrical and Symmetrical Diarylsulphides and Diarylsulphones Containing Thiazolinyl and Thiazolidinonyl Moieties Using 4,4'-DiacetyldiphenylsulphideAuthor(s): M. A. Abbady | Sh. H. Abdel-Hafez | M. M. Kandeel | M. I. Abdel-Monem
Journal: Molecules ISSN 1420-3049
Volume: 8; Issue: 8; Start page: 622; Date: 2003;
Keywords: Diarylsulphides | -sulphones | thiozolinyl and thiazolidinonyl moieties
Condensation of 4,4Ã¢Â€Â™-diacetyldiphenyl sulphide (2) with variable amounts of thiosemicarbazide (3) in refluxing ethanol and in the presence of catalytic amounts of dry piperidine afforded only 4-acetylthiosemicarbazone-4Ã¢Â€Â™-acetyldiphenyl sulphide (5). Condensation of 2 with excess semicarbazide hydrochloride (4) in the presence of fused sodium acetate and/or piperidine yielded 4,4Ã¢Â€Â™-diacetylsemicarbazone diphenyl sulphide (6), whereas use of equimolar amounts of 2 and 4 afforded 4-acetyl-semicarbazone-4Ã¢Â€Â™-acetyldiphenyl sulphide (7). 4-Acetylsemicarbazone-4Ã¢Â€Â™-acetylthiosemicarbazone diphenyl sulphide (8) was also obtained via two different routes. The effect of tautomeric structure 5d is discussed. 4-(4"-phenyl-ÃŽÂ”3-thiazoline-2"-acetylazino)-4Ã¢Â€Â™-acetyldiphenyl sulphide (9), 4-(5"-carboxyethyl-4"-thiazolidinone-2"-acetylazino)-4Ã¢Â€Â™-acetyldiphenyl sulphide (10), 4-(4"-thiazolidinone-2Ã¢Â€Â™-acetylazino)-4Ã¢Â€Â™-acetyldiphenyl sulphide (11) and 4-(4"-methyl-ÃŽÂ”3-thiazoline-2"-acetylazino)-4Ã¢Â€Â™-acetyldiphenyl sulphide (12) were prepared by interaction of 5 with phenacylbromide, bromodiethylmalonate, chloro ethylacetate and chloroacetone, respectively. Sulphides 9-12 were easily condensed with 3 to afford the corresponding 4-(heterocyclic moiety-2"-acetylazino)-4Ã¢Â€Â™-acetylthiosemicarbazone diphenyl sulphides 23-26. Oxidation of the prepared sulphides 5-7, 9-12, 23 and 25-26 using H2O2/glacial AcOH mixtures yielded only 4,4Ã¢Â€Â™-diacetyldiphenyl sulphone (13) as the main product in every case, besides 3 and 4 in certain cases. Unsymmetrical and symmetrical sulphones 14-22 were obtained starting from 13. The structures of the synthesized compounds are based on IR, 1H-NMR, 13C-NMR and mass spectral data. A theoretical study on some of the prepared compounds using molecular modeling was carried out.