Methanesulfonamide

Last updated
Methanesulfonamide
Methanesulfonamide.svg
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.019.594 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 221-553-6
PubChem CID
  • InChI=1S/CH5NO2S/c1-5(2,3)4/h1H3,(H2,2,3,4)
    Key: HNQIVZYLYMDVSB-UHFFFAOYSA-N
  • CS(=O)(=O)N
Properties
CH5NO2S
Molar mass 95.12 g·mol−1
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P264, P264+P265, P271, P280, P302+P352, P304+P340, P305+P351+P338, P319, P321, P332+P317, P337+P317, P362+P364, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Methanesulfonamide is a chemical compound and the simplest representative of the substance group of sulfonic acid amides.

Contents

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]

Methanesulfonamide geometry.svg

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]

Synthesis N-(2-Methylthio-1-p-toluenesufonylethyl)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. 1 2 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
  2. ↑ US 3574740A,Martin Le Roy,"Method of Preparing Methane Sulfonamide and its Derivatives",published 1971-04-13, assigned to Pennwalt Corp.
  3. ↑ Horng-Chih Huang, Emily J. Reinhard, David B. Reitz (1994), "A novel one-pot conversion of methyl sulfones to sulfonamides", Tetrahedron Letters , vol. 35, no. 39, pp. 7201–7204, doi:10.1016/0040-4039(94)85360-6 {{citation}}: CS1 maint: multiple names: authors list (link)
  4. ↑ Bikash Pal, Parasuraman Jaisankar, Venkatachalam S. Giri (2004), "Versatile Reagent for Reduction of Azides to Amines", Synthetic Communications , vol. 34, no. 7, pp. 1317–1323, doi:10.1081/SCC-120030322 {{citation}}: CS1 maint: multiple names: authors list (link)
  5. ↑ L. G. Vorontsova (1967), "Crystal and molecular structure of methanesulfonamide", Journal of Structural Chemistry , vol. 7, no. 2, pp. 275–277, Bibcode:1967JStCh...7..275V, doi:10.1007/BF00744308
  6. ↑ 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 , vol. 18, no. 7, pp. 1107–1108, doi:10.1246/cl.1989.1107 {{citation}}: CS1 maint: multiple names: authors list (link)
  7. ↑ 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 , vol. 74, no. 8, pp. 3038–3047, doi:10.1021/jo8026998, PMID   19301884
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