Methanesulfonyl azide
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| Other names
Mesyl azide
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3D model (JSmol)
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PubChem CID
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CompTox Dashboard (EPA)
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| Properties | |
| CH3N3O2S | |
| Molar mass | 121.12 g·mol−1 |
| Melting point | 18 °C (64 °F; 291 K) |
| Boiling point | 120 °C (248 °F; 393 K) decomposes |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Methanesulfonyl azide is the azide of methanesulfonic acid. It is used as a reagent for the production of diazo compounds.
Preparation
[edit]Methanesulfonyl azide can be prepared from methanesulfonyl chloride by reaction with sodium azide in ethanol[1] or methanol,[2] Preparation in situ is also possible, for example in acetonitrile, and is advantageous to avoid explosion hazards.[3]
Properties
[edit]Methanesulfonyl azide melts at 18 °C and decomposes from 120 °C.[1] Like many other azides, it is explosive.[3] At low temperature, methanesulfonyl azide crystallizes in the triclinic crystal system in the space group P1 with the lattice parameters a = 5.6240 Å; b = 5.9498 Å, c = 7.6329 Å, α = 72.216°, β = 70.897°, and γ = 88.601°, and two molecules per unit cell.[1]
Reactions
[edit]Methanesulfonyl azide is a suitable reagent for introducing diazo compounds into other compounds. Historically, tosylazide was mainly used for this purpose. However, nowadays, compounds that are less explosive and/or form an amide after diazo transfer, which can be easily separated from the reaction products, are often used. In addition to imidazole-1-sulfonyl azide and 4-acetamidobenzenesulfonyl azide, methanesulfonyl azide is also utilized.[4] The advantages of methanesulfonyl azide are particularly its simple and inexpensive production and the straightforward purification of the reaction mixture.[2] Starting from Ω-bromoacetophenone, by reaction with trimethylphosphite, and then with sodium hydride and methanesulfonyl azide, a diazo reagent can be produced, which can convert aldehydes into alkynes. This method works similarly to the reaction with the Ohira-Bestmann reagent but is significantly more expensive to produce.[5]
The photolysis of methanesulfonyl azide in a matrix of argon or neon yields a short-lived nitrene.[1] If methanesulfonyl azide is irradiated in the presence of a hydrocarbon, methanesulfonyl amide is formed, as well as N-substituted derivatives by reaction with the hydrocarbon.[6]
References
[edit]- ^ a b c d Deng, Guohai; Li, Dingqing; Wu, Zhuang; Li, Hongmin; Bernhardt, Eduard; Zeng, Xiaoqing (2016-07-21), "Methanesulfonyl Azide: Molecular Structure and Photolysis in Solid Noble Gas Matrices", The Journal of Physical Chemistry A, vol. 120, no. 28, pp. 5590–5597, doi:10.1021/acs.jpca.6b05533
- ^ a b Taber, Douglass F.; Ruckle, Robert E.; Hennessy, Michael J. (October 1986), "Mesyl azide: a superior reagent for diazo transfer", The Journal of Organic Chemistry, vol. 51, no. 21, pp. 4077–4078, doi:10.1021/jo00371a034
- ^ a b Lynch, Denis; O’Mahony, Rosella M.; McCarthy, Daniel G.; Bateman, Lorraine M.; Collins, Stuart G.; Maguire, Anita R. (2019-06-16), "Mechanistic Study of In Situ Generation and Use of Methanesulfonyl Azide as a Diazo Transfer Reagent with Real‐Time Monitoring by FlowNMR", European Journal of Organic Chemistry, vol. 2019, no. 22, pp. 3575–3580, doi:10.1002/ejoc.201900184, hdl:10468/8205
- ^ Maas, Gerhard (2009-10-19), "New Syntheses of Diazo Compounds", Angewandte Chemie International Edition, vol. 48, no. 44, pp. 8186–8195, doi:10.1002/anie.200902785
- ^ Taber, Douglass F.; Bai, Sha; Guo, Peng-fei (November 2008), "A convenient reagent for aldehyde to alkyne homologation", Tetrahedron Letters, vol. 49, no. 48, pp. 6904–6906, doi:10.1016/j.tetlet.2008.09.114, PMC 2634292, PMID 19946355
- ^ Torimoto, Noboru; Shingaki, Tadao; Nagai, Toshikazu (February 1978), "Sensitized photolyses of methanesulfonyl azide in hydrocarbons", The Journal of Organic Chemistry, vol. 43, no. 4, pp. 631–633, doi:10.1021/jo00398a023