Methanesulfonyl chloride
| Methanesulfonyl chloride | |
|---|---|
 |
 |
| IUPAC name Methanesulfonyl chloride | |
| Other names Mesyl chloride | |
| Identifiers | |
| CAS number | 124-63-0  |
| ChemSpider | 29037  |
| Jmol-3D images | Image 1 |
| |
| Properties | |
| Molecular formula | CH3ClO2S |
| Molar mass | 114.55 g mol−1 |
| Appearance | Liquid |
| Density | 1.480 g/mL |
| Boiling point | 161 °C; 322 °F; 434 K (730 mmHg) |
| Solubility in water | Reacts[1][2] |
| Hazards | |
| Main hazards | Lachrymator, highly toxic, corrosive |
| Related compounds | |
| Other anions | Methanesulfonyl fluoride |
| (verify) (what is: /?) Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa) | |
| Infobox references | |
Methanesulfonyl chloride (mesyl chloride) is a compound containing a sulfonyl chloride used to make methanesulfonates and to generate sulfene.
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 manufactured either via direct synthesis from methane and sulfuryl chloride in a radical reaction (1):
- CH4 (g) + SO2Cl2 (g) → CH3SO2Cl + HCl (g) (1)
Another method of manufacture starts with methanesulfonic acid, which is accessible from 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 methanesulfonyl 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 in the presence of a non-nucleophilic base.[3] 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.[4]
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.[5]
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.[6]
Addition to alkynes
In the presence of copper(II) chloride, methanesulfonyl chloride will add across alkynes to form β-chloro sulfones.[7]
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.[8]
Miscellaneous
Forming acyliminium ions from α-hydroxyamides can be done using methanesulfonyl chloride and a base, typically triethylamine.[9]
References
- ↑ cameochemicals.noaa.gov/chemical/11835
- ↑ http://www.conncoll.edu/offices/envhealth/MSDS/chemistry/M/methanesulfonylchloride.htm
- ↑ 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 (6): 1454. doi:10.1002/hlca.19470300609.
- ↑ 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 (9): 2831. doi:10.1021/ja00347a052.
- ↑ 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 (2): 335. doi:10.1016/0008-6215(83)88490-0.
- ↑ Merlin, P.; Braekman, J. C.; Daloze, D. (1988). "Stereoselective synthesis of (±)-tetraponerine-8, a defence alkaloid of the ant Tetraponera sp". Tetrahedron Lett. 29 (14): 1691. doi:10.1016/S0040-4039(00)82019-5.
- ↑ Amiel, Y. (1971). "Addition of sulfonyl chlorides to acetylenes". Tetrahedron Lett. 12 (8): 661. doi:10.1016/S0040-4039(01)96524-4.
- ↑ 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:10.1002/jhet.5570250158.
- ↑ 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 (10): 1682. doi:10.1021/jo00184a002.