Chemistry:Methanesulfonamide
Methanesulfonamide is a chemical compound and the simplest representative of the substance group of sulfonic acid amides.
Preparation and synthesis
Methanesulfonamide is prepared by reacting methanesulfonyl chloride with ammonia.[1][2] Alternatively, the compound can be obtained by reacting the magnesium salt of methanesulfonic acid with hydroxylamine-O-sulfonic acid [3] or by reduction (here: the Staudinger reaction) of methanesulfonyl azide with triphenylphosphine in methanol.[4]
Properties
From a solution of methanesulfonamide in heptane, single crystals of the compound are obtained as semi-transparent, white tablets. X-ray structure analysis yields an O–S–O valence angle of 119°, which deviates significantly from the tetrahedral angle of 109.47°. At 161 picometers, the sulfur–nitrogen bond length is significantly shorter than that of a typical single bond (173 picometers) and corresponds to the shortened bond length observed in other sulfonamides. This is presumably caused by a coordinative bond between the lone pair of the amino group and the atomic orbital of the sulfur atom.[5]
Use
Various reagents for chemical syntheses can be produced from methanesulfonamide. For example, methanesulfonamide 1, p-toluenesulfonic acid 2 and 1,1-dimethoxy-2-(methylthio)ethane 3 yield N-(2-methylthio-1-p-toluenesufonylethyl)methanesulfonamide 4, a key compound in the synthesis of symmetrically substituted porphyrins.[1][6]
methanesulfonamide.svg)
In Sharpless dihydroxylation, the oxidation of olefins with potassium hexacyanidoferrate(III) and osmium(VIII) oxide to cis-vicinal-diols, methanesulfonamide acts as a catalyst in the final hydrolysis step during protonation of the osmium intermediate.[7]
References
- ↑ 1.0 1.1 Nachimuthu Soundararajan, Danielle Jacobs (2007), "Methanesulfonamide", Encyclopedia of Reagents for Organic Synthesis, Chichester, UK: John Wiley & Sons, Ltd, doi:10.1002/9780470842898.rm074.pub2, ISBN 978-0-471-93623-7
- ↑ "Method of Preparing Methane Sulfonamide and its Derivatives" US patent 3574740A, published 1971-04-13
- ↑ Horng-Chih Huang, Emily J. Reinhard, David B. Reitz (1994), "A novel one-pot conversion of methyl sulfones to sulfonamides", Tetrahedron Letters 35 (39): 7201–7204, doi:10.1016/0040-4039(94)85360-6
- ↑ Bikash Pal, Parasuraman Jaisankar, Venkatachalam S. Giri (2004), "Versatile Reagent for Reduction of Azides to Amines", Synthetic Communications 34 (7): 1317–1323, doi:10.1081/SCC-120030322
- ↑ L. G. Vorontsova (1967), "Crystal and molecular structure of methanesulfonamide", Journal of Structural Chemistry 7 (2): 275–277, doi:10.1007/BF00744308, Bibcode: 1967JStCh...7..275V
- ↑ Hideki Kinoshita, Shingo Tanaka, Katsuhiko Inomata (1989), "An Improved Method for the Preparation of Symmetrically Substituted Porphyrins via 2-Methoxymethyl-3,4-disubstituted Pyrrole Derivatives", Chemistry Letters 18 (7): 1107–1108, doi:10.1246/cl.1989.1107
- ↑ Mikko H. Junttila, Osmo O. E. Hormi (2009), "Methanesulfonamide: a Cosolvent and a General Acid Catalyst in Sharpless Asymmetric Dihydroxylations", The Journal of Organic Chemistry 74 (8): 3038–3047, doi:10.1021/jo8026998, PMID 19301884
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