| Methanesulfonyl chloride | |
|---|---|
 |
 |
| 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 (730 mm Hg) |
| Hazards | |
| Main hazards | Lachrymator, Highly toxic, corrosive |
| (what is this?) (verify) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) |
|
| Infobox references | |
Methanesulfonyl chloride is a compound containing a sulfonyl chloride used to make methanesulfonates and to generate sulfene.
Contents |
Preparation, manufacture and handling
Methanesulfonyl chloride is highly toxic, moisture sensitive, corrosive, and a lachrymator. It should be stored in a dry location, preferably in a desiccator. 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)
The 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)
Applications
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]
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]
Addition to alkynes
In the presence of copper(II) chloride, methanesulfonyl chloride will add across alkynes to form β-chloro sulfones.[5]
Formation of heterocycles
Upon treatment with a base, such as triethylamine, methanesulfonyl chloride will undergo an elimination to form sulfene. Sulfene can undergo cycloadditions to form various heterocycles. α-Hydroxyketones react with sulfene to form five-membered sultones.[6]
Miscellaneous
Forming acyliminium ions from α-hydroxyamides can be done using methanesulfonyl chloride and a base, typically triethylamine.[7]
References
- ^ Furst, A.; Koller, F. (1947). "Über Steroide und Sexualhormone. Ein neuer Weg zur Herstellung der α-Oxyde von Cholesterin und trans-Dehydro-androsteron". Helv. Chim. Acta 30: 1454. doi:.
- ^ Maruoka, K.; Miyazaki, T.; Ando, M.; Matsumura, Y.; Sakane, S.; Hattori, K.; Yamamoto, H. (1983). "Organoaluminum-promoted Beckmann rearrangement of oxime sulfonates". J. Am. Chem. Soc. 105: 2831. doi:.
- ^ Webster, K. T.; Eby, R.; Schuerch, C. (1983). "Selective demesylation of 2-O-(methylsulfonyl)-?-mannopyranoside derivatives with sodium amalgam and 2-propanol". Carbohydr. Res. 123: 335. doi:.
- ^ Merlin, P.; Braekman, J. C.; Daloze, D. (1988). "Stereoselective synthesis of (±)-tetraponerine-8, a defence alkaloid of the ant Tetraponera sp". Tetrahedron Lett. 29: 1691. doi:.
- ^ Amiel, Y. (1971). "Addition of sulfonyl chlorides to acetylenes". Tetrahedron Lett. 12: 661. doi:.
- ^ Potonay, T.; Batta, G.; Dinya, Z. (1988). "Flavonoids. 41. Stereospecific synthesis of 2,3-dihydro-c-3-substituted-t-3-methyl-r-2-phenyl-4H-1-benzopyran-4-ones". Journal of Heterocyclic Chemistry 25: 343. doi:.
- ^ Chamberlin, A. R.; Nguyen, H. D.; Chung, J. Y. L. (1984). "Cationic cyclization of ketene dithioacetals. A general synthesis of pyrrolizidine, indolizidine, and quinolizidine alkaloid ring systems". J. Org. Chem. 49: 1682. doi:.
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