Methanesulfonyl chloride
From Wikipedia, the free encyclopedia
| Methanesulfonyl chloride | |
|---|---|
 |
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| IUPAC name | Methanesulfonyl chloride |
| Other names | Mesyl chloride |
| Identifiers | |
| CAS number | [124-63-0] |
| SMILES | CS(Cl)(=O)=O |
| Properties | |
| Molecular formula | CH3ClO2S |
| Molar mass | 114.56 g/mol |
| Appearance | liquid |
| Density | 1.480 g/mL |
| Boiling point |
161 °C (21 mm Hg) |
| Hazards | |
| Main hazards | Lachrymator, Highly toxic, corrosive |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references |
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Methanesulfonyl chloride is a compound containing a sulfonyl chloride used to make methanesulfonates and to generate sulfene.
Contents |
[edit] Preparation, manufacture and handling
Methanesulfonyl chloride is highly toxic, moisture sensitive, corrosive, and a lachrymator. It should be stored in dry location, preferably in a dessicator. It is manufactued either via direct synthesis from methane and sulfuryl chloride in a radical reaction (1):
- CH4 (g) + SO2Cl2 (g) → CH3SO2Cl + HCl (g) (1)
other method of manufacture starts with methanesulfonic acid, which is accessible out of methane and sulfur trioxide (2) or by vigorous oxidation of methanethiol (3):
- CH4 (g) + SO3 (g) → CH3SO3H (l) (2)
- CH3SH + HNO3 → CH3SO3H + H2O + NOx (3)
methanesulfonic acid prepared is reacted with thionyl chloride (4) or phosgene (5) to form mesyl chloride:
- CH3SO3H + SOCl2 → CH3SO2Cl + SO2 + HCl (4)
- CH3SO3H + COCl2 → CH3SO2Cl + CO2 + HCl (5)
[edit] Applications
[edit] Methanesulfonates
The main use of methanesulfonyl chloride is the formation of methanesulfonates from alcohols and a non-nucleophilic base.[1] Methanesulfonates are used as intermediates in substitution reactions, elimination reactions, reductions, and rearrangement reactions. When treated with a Lewis acid, oxime methanesulfonates will undergo a facile Beckmann rearrangement.[2]
Methanesulfonates have been occasionally used as a protecting group for alcohols. It is stable to acidic conditions and is cleaved back to the alcohol using sodium amalgam.[3]
[edit] Methanesulfonamides
Methanesulfonyl chloride will react with amines to form a methanesulfonamide. Unlike, a methanesulfonate, a methanesulfonamide is a very stable functional group under both acidic and basic conditions. When used as a protecting group, they can be converted back to amines using lithium aluminium hydride or a dissolving metal reduction.[4]
[edit] Addition to alkynes
In the presence of copper(II) chloride, methanesulfonyl chloride will add across alkynes to form β-chloro sulfones.[5]
[edit] Formation of heterocycles
Upon treatment with a base, such as triethylamine, methanesulfonyl chloride will undergo an alpha-elimination to form sulfene. Sulfene can undergo cycloadditions to form various heterocycles. α-Hydroxyketones react with sulfene to form five-membered sultones.[6]
[edit] Miscellaneous
Forming acyliminium ions from α-hydroxyamides can be done using methanesulfonyl chloride and a base, typically triethylamine.[7]
[edit] References
- ^ Furst, A.; Koller, F. Helv. Chim. Acta 1947, 30, 1454.
- ^ Maruoke, K.; Miyazaki, T.; Ando, M.; Matsumura, Y.; Sakane, S.; Hattori, K.; Yamamoto, H. J. Am. Chem. Soc. 1983, 105, 2831.
- ^ Webster, K. T.; Eby, R.; Schuerch, C. Carbohydr. Res. 1983, 123, 335.
- ^ Merlin, P.; Braekman, J. C.; Daloze, D. Tetrahedron Lett. 1988, 29, 1691.
- ^ Amiel, Y. Tetrahedron Lett. 1971, 661.
- ^ Potonay, T.; Batta, G.; Dinya, Z. J. Heterocycl. Chem. 1988, 25, 343.
- ^ Chamgerlin, A. R.; Nguyen, H. D.; Chung, J. Y. L. J. Org. Chem. 1984, 49, 1682.
