Chemistry:Methanesulfonic anhydride

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Methanesulfonic anhydride
Skeletal formula
Ball-and-stick model
Names
Preferred IUPAC name
Methanesulfonic anhydride
Other names
methanesulfonic acid methylsulfonyl ester
Identifiers
3D model (JSmol)
ChemSpider
UNII
Properties
C2H6O5S2
Molar mass 174.19 g·mol−1
Appearance White solid
Density 0.92 g/ml[1]
Melting point 69.5–70 °C (157.1–158.0 °F; 342.6–343.1 K)[2]
Hydrolysis
Solubility Soluble in most aprotic organic solvents
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Methanesulfonic anhydride (Ms2O) is the acid anhydride of methanesulfonic acid. Like methanesulfonyl chloride (MsCl), it may be used to generate mesylates (methanesulfonyl esters).

Preparation & purification

Ms2O may be prepared by the dehydration of methanesulfonic acid with phosphorus pentoxide.[2]

P2O5 + 6 CH3SO3H → 3 (CH3SO2)2O + 2 H3PO4

Ms2O can be purified by distillation under vacuum (distillation of a solid) or by recrystallization from Methyl tert-butyl ether/toluene.

Reactions & Applications in synthesis

Passage of hydrogen chloride through molten Ms2O yields MsCl.[3]

Similar to MsCl, Ms2O can perform mesylation of alcohols to form sulfonates. Use of Ms2O avoids the alkyl chloride, which often appears as a side-product when MsCl is used.[4] Unlike MsCl, Ms2O may not be suitable for mesylation of the unsaturated alcohols.[5]

Examples of mesylation of alcohols with Ms2O:

  • Octadecyl methanesulfonate was prepared from octadecanol in pyridine.[5]
  • Secondary alcohol at the anomeric carbon of 2,3,4,5-O-Benzyl-protected glucose reacted to form a glycosyl mesylate, which was found to be more stable than its triflate counterpart, in 2,4,6-collidine.[6]

Ms2O also converts amines to sulfonamides.[7]

Aromatic sulfonation

Assisted by Lewis acid catalyst, Friedel-Crafts methylsulfonation of aryl ring can be achieved by Ms2O. In contrast to MsCl, either activated or deactivated benzene derivatives can form the corresponding sulfonatesin satisfactory yields with Ms2O.[8]

Examples of aromatic sulfonation with Ms2O:

Esterification

Ms2O catalyzes the esterification of alcohols by carboxylic acids. 2-Naphthyl acetate was prepared from 2-naphthol and glacial (anhydrous) acetic acid in the presence of Ms2O. Both alcohols on ethylene glycol successfully benzoylated with benzoic acid and Ms2O. However, for free alcohols on monosaccharides, the acetylation was not completed.[2]

Oxidation of alcohols

Like Pfitzner–Moffatt oxidation and Swern oxidation, with DMSO, Ms2O can oxidize primary and secondary alcohols to aldehydes and ketones, respectively, in HMPA.[10] This method applies to benzylic alcohol.[10] HMPA may be substituted by dichloromethane but may result in more side-products.[10]

See also

References

  1. ↑ Wachtmeister, C. A.; Pring, B.; Osterman, Siv; Ehrenberg, L.; Brunvoll, J.; Bunnenberg, E.; Djerassi, Carl; Records, Ruth (1966). "The Synthesis of Some Tritium-labelled Mutagenic Alkyl Alkanesulfonates.". Acta Chemica Scandinavica 20: 908–910. doi:10.3891/acta.chem.scand.20-0908. 
  2. ↑ 2.0 2.1 2.2 Field, Lamar; Settlage, Paul H. (March 1954). "Alkanesulfonic Acid Anhydrides". Journal of the American Chemical Society 76 (5): 1222–1225. doi:10.1021/ja01634a005. 
  3. ↑ Field, Lamar; Settlage, Paul H. (January 1955). "Reaction of Methanesulfonic Anhydride with Hydrogen Halides 1" (in en). Journal of the American Chemical Society 77 (1): 170–171. doi:10.1021/ja01606a053. ISSN 0002-7863. https://pubs.acs.org/doi/10.1021/ja01606a053. 
  4. ↑ Baumann, W. J.; Jones, L. L.; Barnum, B. E.; Mangold, H. K. (1 November 1966). "The formation of alkyl and alkenyl methanesulfonates and their reduction to hydrocarbons" (in en). Chemistry and Physics of Lipids 1 (1): 63–67. doi:10.1016/0009-3084(66)90008-9. ISSN 0009-3084. https://www.sciencedirect.com/science/article/abs/pii/0009308466900089. 
  5. ↑ 5.0 5.1 Cegla, Gad; Mangold, Helmut K. (1 May 1973). "A new procedure for the preparation of alkyl methanesulfonates" (in en). Chemistry and Physics of Lipids 10 (4): 354–355. doi:10.1016/0009-3084(73)90059-5. ISSN 0009-3084. https://www.sciencedirect.com/science/article/abs/pii/0009308473900595. 
  6. ↑ Leroux, Jacques; Perlin, Arthur S. (1 November 1978). "Synthesis of glycosyl halides and glycosides via 1-O-sulfonyl derivatives" (in en). Carbohydrate Research 67 (1): 163–178. doi:10.1016/S0008-6215(00)83739-8. ISSN 0008-6215. https://www.sciencedirect.com/science/article/abs/pii/S0008621500837398. 
  7. ↑ Lis, Randall; Morgan, Thomas K.; Marisca, Anthony J.; Gomez, Robert P.; Lind, Joan M.; Davey, David D.; Phillips, Gary B.; Sullivan, Mark E. (October 1990). "Synthesis of novel (aryloxy)propanolamines and related compounds possessing both class II and class III antiarrhythmic activity" (in en). Journal of Medicinal Chemistry 33 (10): 2883–2891. doi:10.1021/jm00172a033. ISSN 0022-2623. https://doi.org/10.1021/jm00172a033. 
  8. ↑ 8.0 8.1 Vaillancourt, Valerie; Cudahy, Michele M. (15 April 2001). "Methanesulfonic Anhydride" (in en). Encyclopedia of Reagents for Organic Synthesis (John Wiley & Sons, Ltd): rm068. doi:10.1002/047084289x.rm068. https://onlinelibrary.wiley.com/doi/10.1002/047084289X.rm068. 
  9. ↑ Tyobeka, Themba E.; Hancock, Richard A.; Weigel, Helmut (1 January 1980). "Novel sulphonylating reagent: sulphuric acid–hexafluoroacetic anhydride" (in en). Journal of the Chemical Society, Chemical Communications (3): 114–115. doi:10.1039/C39800000114. ISSN 0022-4936. https://pubs.rsc.org/en/content/articlelanding/1980/c3/c39800000114. 
  10. ↑ 10.0 10.1 10.2 Albright, J. Donald (June 1974). "Sullfoxonium salts as reagents for oxidation of primary and secondary alcohols to carbonyl compounds" (in en). The Journal of Organic Chemistry 39 (13): 1977–1979. doi:10.1021/jo00927a054. ISSN 0022-3263. https://pubs.acs.org/doi/pdf/10.1021/jo00927a054. 



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