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Reactions of Thioketones with a Fluorinated Thione S ‐Imide
Author(s) -
Mloston Grzegorz,
Celeda Malgorzata,
Roesky Herbert W.,
Parisini Emilio,
Ahlemann JensThomas
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199803)1998:3<459::aid-ejoc459>3.0.co;2-f
Subject(s) - imide , chemistry , trifluoromethyl , sulfur , diffraction , dipole , medicinal chemistry , polymer chemistry , crystallography , organic chemistry , alkyl , physics , optics
N ‐(1‐Adamantyl)hexafluorothioacetone S ‐imide ( 1 ) reacts readily with aromatic thioketones 4a − e to afford 1,4,2‐dithiazolidines 5a − e as products of [3 + 2] dipolar cycloadditions. Unexpectedly, cycloadducts 5d and 5e , obtained from thioxanthione ( 4d ) and 4,4′‐(dimethoxy)thiobenzophenone ( 4e ), respectively, are found to decompose at room temperature and could not be isolated as pure compounds. Unlike aromatic thiones, adamantanethione ( 4f ) did not react with 1 at ambient temperature. However, reaction did occur upon heating in a sealed tube, and the new 1,4,2‐dithiazolidine 9 , bearing two adamantyl moieties, was isolated as the major product. The structure of 9 has been determined by X‐ray diffraction analysis. The connectivity of the heterocyclic ring in this product indicates that the mechanism of its formation must proceed by a different route involving another in situ generated sulfur‐centered 1,3‐dipole. Retrocycloaddition of the primary adamantanethione cycloadduct 13 liberates hexafluorothioacetone, which is subsequently captured by S ‐imide 1 to give tetrakis(trifluoromethyl)‐1,4,2‐dithiazolidine 8 as a crystalline product. The structure of 8 has also been confirmed by X‐ray diffraction analysis.