The thiocarbonyl 'S' is softer than thiolate 'S': a catalyst-free one-pot synthesis of isothiocyanates in water

Treatment of the preformed or the in situ generated aryl/alkyl dithiocarbamates triethylammonium salt (ArNHCSS(-).Et(3)NH(+)) with methyl acrylate in an aqueous medium gave solely arylisothiocyanate (ArNCS), whereas the in situ generated aryl dithiocarbamic acid (ArNHCSS(-).H(+)) yielded exclusively...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2010-01, Vol.8 (7), p.1674-1678
Main Authors: Jamir, Latonglila, Ali, Abdur Rezzak, Ghosh, Harisadhan, Chipem, Francis A S, Patel, Bhisma K
Format: Article
Language:English
Subjects:
Isothiocyanates - chemical synthesis
Isothiocyanates - chemistry
Models, Molecular
Molecular Structure
Water - chemistry
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Summary:Treatment of the preformed or the in situ generated aryl/alkyl dithiocarbamates triethylammonium salt (ArNHCSS(-).Et(3)NH(+)) with methyl acrylate in an aqueous medium gave solely arylisothiocyanate (ArNCS), whereas the in situ generated aryl dithiocarbamic acid (ArNHCSS(-).H(+)) yielded exclusively the thia-Michael adduct (ArNHCSSCH(2)CH(2)COOMe). This differential reactivity can be explained by two alternative mechanisms which is dependent both on the nature of the counter cation and on the pH of the reaction medium. Irrespective of the counter cations, the thiocarbonyl sulfur (=S) atom, having large orbital-coefficient, is softer compared to the thiol/thiolate sulfur (-SH/S(-)) in a dithiocarbamate salt and the former adds to the Michael acceptor by a 1,4-addition.
ISSN:1477-0520
1477-0539
DOI:10.1039/b923336a