The thiocarbonyl ‘S’ is softer than thiolate ‘S’: A catalyst-free one-pot synthesis of isothiocyanates in water

Latonglila Jamir; Abdur Rezzak Ali; Harisadhan Ghosh; Francis A. S. Chipem; Bhisma K. Patel

doi:10.1039/B923336A

The thiocarbonyl ‘S’ is softer than thiolate ‘S’: A catalyst-free one-pot synthesis of isothiocyanates in water

Latonglila Jamir,^a Abdur Rezzak Ali,^a Harisadhan Ghosh,^a Francis A. S. Chipem^a and Bhisma K. Patel*^a

* Corresponding authors

^a Indian Institute of Technology Guwahati, Guwahati, India
E-mail: patel@iitg.ernet.in
Fax: +91-361-2690762
Tel: +91-361-2582307

Abstract

Treatment of the preformed or the in situ generated aryl/alkyl dithiocarbamates triethylammonium salt (ArNHCSS⁻.Et₃NH⁺) 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 (ArNHCSSCH₂CH₂COOMe). 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.

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Publication details

The article was received on 10 Nov 2009, accepted on 18 Jan 2010 and first published on 05 Feb 2010

Article type: Paper

DOI: 10.1039/B923336A

Citation: Org. Biomol. Chem., 2010,8, 1674-1678

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The thiocarbonyl ‘S’ is softer than thiolate ‘S’: A catalyst-free one-pot synthesis of isothiocyanates in water

L. Jamir, A. R. Ali, H. Ghosh, F. A. S. Chipem and B. K. Patel, Org. Biomol. Chem., 2010, 8, 1674
DOI: 10.1039/B923336A
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Organic & Biomolecular Chemistry

The thiocarbonyl ‘S’ is softer than thiolate ‘S’: A catalyst-free one-pot synthesis of isothiocyanates in water

Abstract

Supplementary files

Publication details

The thiocarbonyl ‘S’ is softer than thiolate ‘S’: A catalyst-free one-pot synthesis of isothiocyanates in water

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