Sulfuryl chloride isocyanate
3D model (JSmol)
|Molar mass||141.53 g/mol|
|Melting point||−44 °C (−47 °F; 229 K)|
|Boiling point||107 °C (225 °F; 380 K)|
|Solubility in other solvents||Chlorocarbons
Refractive index (nD)
|tetrahedral at S|
|Main hazards||toxic, corrosive, flammable,
reacts violently with water
|Safety data sheet||"External MSDS"|
|R-phrases (outdated)||R14 R20 R24/25 R29 R34 R42/43|
|S-phrases (outdated)||(S1/2) S8 S24 S26 S30 S36/37/39 S38 S45 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
|what is ?)(|
Chlorosulfonyl isocyanate is the chemical compound ClSO2NCO, known as CSI. This compound is a versatile reagent in organic synthesis.
Preparation, structure, handling
- SO3 + ClCN → ClSO2NCO
In this transformation, both the carbon and the nitrogen termini of CN are functionalized.
The structure of CSI is represented as ClS(O)2-N=C=O. It consists of two electron-withdrawing components, the chlorosulfonyl group (SO2Cl) and the isocyanate group (-N=C=O). Because of its resulting electrophilicity, the use of CSI in chemical synthesis requires relatively inert solvents such as chlorocarbons, acetonitrile, and ethers.
The molecule has two electrophilic sites, the carbon and the S(VI) center.
CSI has been employed for the preparation of β-lactams, some of which are medicinally important. Thus, alkenes undergo a [2+2]-cycloaddition to give the sulfonamide. The SO2Cl group can be removed simply by hydrolysis, leaving the secondary amide. Other reactions of CSI:
- Cycloaddition to alkynes to give 1,2,3-oxathiazine-2,2-dioxide-6-chlorides.
- Conversion of primary alcohols to carbamates.
- Conversion of carboxylic acids and the acid chlorides into nitriles.
- Preparation of N,N-disubstituted sulfamides, R2NSO2NH2
CSI is toxic, corrosive and reacts violently with water. It cannot be stored in glass-stoppered flasks, requiring instead polyethylene bottles.
- Graf, R. "Chlorosulfonyl Isocyanate" Organic Syntheses, Collected Volume 5, pages 226ff.
- Miller, M. J.; Ghosh, M.; Guzzo, P. R.; Vogt, P. F.; Hu, J.; Filzen, G. F.; Geyer, A. G. "Chlorosulfonyl Isocyanate" in "Encyclopedia of Reagents for Organic Synthesis" 2005 John Wiley & Sons: New York.
- D. N. Dhar, K. S. K. Murthy "Recent Advances in the Chemistry of Chlorosulfonyl Isocyanate" Synthesis 1986; pages 437-449.
- Cremlyn, R. J. “An Introduction to Organosulfur Chemistry” John Wiley and Sons: Chichester (1996). ISBN 0-471-95512-4
- Burgess, E. M.; Penton, Jr., H. R.; Taylor, E. A.; Williams, W. M. "Conversion of Primary Alcohols to Urethanes via the Inner Salt of Triethylammonium Hydroxide: Methyl (Carboxylsulfamoyl) Triethylammonium Hydroxide Methyl n-Hexylcarbamate" Organic Syntheses, Coll. Vol. 6, p.788