- A novel one-pot synthesis of isothiocyanates and cyanamides from dithiocarbamate salts using environmentally benign reagent tetrapropylammonium tribromide
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A highly efficient and simple protocol for the synthesis of isothiocyanates and cyanamides from their respective amines in the presence of a mild, efficient, and non-toxic reagent tetrapropylammonium tribromide is described. High environmental acceptability of the reagents, cost effectiveness and high yields are the important attributes of this methodology.
- Kuotsu, Neivotsonuo Bernadette,Jamir, Latonglila,Phucho, Tovishe,Sinha, Upasana Bora
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p. 832 - 841
(2018/01/17)
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- The thiocarbonyl 'S' is softer than thiolate 'S': A catalyst-free one-pot synthesis of isothiocyanates in water
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Treatment of the preformed or the in situ generated aryl/alkyl dithiocarbamates triethylammonium salt (ArNHCSS-.Et 3NH+) 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.
- Jamir, Latonglila,Ali, Abdur Rezzak,Ghosh, Harisadhan,Chipem, Francis A. S.,Patel, Bhisma K.
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supporting information; experimental part
p. 1674 - 1678
(2010/07/04)
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- Reactions of Relevance to the Chemistry of Aminoglycoside Antibiotics. Part 14. A Useful Radical-deamination Reaction
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Primary, secondary, and tertiary aliphatic or alicyclic isocyanides are smoothly reduced under radical conditions using tri-n-butylstannane to the corresponding hydrocarbons.The relative ease of reduction is tertiary > secondary > primary.Aromatic isocyanides are not reduced under these conditions.The reduction of isothiocyanates (or isoselenocyanates) by tri-n-butylstannanae also affords hydrocarbons, but here the isocyanides have been shown to be intermediates.The reduction of a compound with isocyanide and xanthate functions in a 1,2-relationship gives a smooth radical fragmentation to furnish an olefin.An efficient synthesis of 2-deoxy-D-glucose starting with glucosamine is described.
- Barton, Derek H. R.,Bringmann, Gerhard,Lamotte, Genevieve,Motherwell, William B.,Motherwell, Robyn S. Hay,Porter, Alexander E. A.
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p. 2657 - 2664
(2007/10/02)
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