Trifluoromethanesulfonyl azide

Trifluoromethanesulfonyl azide

Names
IUPAC name N-diazo-1,1,1-trifluoro-methanesulfonamide
Identifiers
CAS Registry Number	3855-45-6 N
ChemSpider	9161983 Y
InChI InChI=1S/CF3N3O2S/c2-1(3,4)10(8,9)7-6-5 Y Key: NQPHMXWPDCSHTE-UHFFFAOYSA-N Y InChI=1/CF3N3O2S/c2-1(3,4)10(8,9)7-6-5 Key: NQPHMXWPDCSHTE-UHFFFAOYAT
Jmol-3D images	Image
PubChem	10986786
SMILES FC(F)(F)S(=O)(=O)N=[N+]=[N-]
Properties
Molecular formula	CF3N3O2S
Molar mass	175.09 g·mol−1
Solubility in water	insoluble[1]
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
N verify (what is: Y/N?)
Infobox references

Trifluoromethanesulfonyl azide or triflyl azide is an organic azide used as a reagent in organic synthesis.

Preparation

Trifluoromethanesulfonyl azide is not commercially available. It is prepared before use by reacting trifluoromethanesulfonic anhydride with sodium azide, traditionally in dichloromethane.^[1] However, use of dichloromethane should be avoided because sodium azide is known to generate highly explosive azido-chloromethane and diazidomethane in situ by nucleophilic substitution on dichloromethane.^[2] Moreover, the volatility of dichloromethane is a liability, as unsolvated triflyl azide is a detonation hazard.^[2] The reaction may also be carried out in toluene,^[3] acetonitrile, or pyridine.^[4]

Tf₂O + NaN₃ → TfN₃ + NaOTf (Tf = CF₃SO₂)

The trifluoromethanesulfonic anhydride starting material is rather expensive, and the product is explosive, and does not store well. As a result, imidazole-1-sulfonyl azide has been developed as an alternative.^[5]

Reactions

Trifluoromethanesulfonyl azide generally converts amines to azides. Trifluoromethanesulfonyl azide may be formed in situ from trifluoromethanesulfonic anhydride and sodium azide; it reacts with the amine present in a one-pot reaction.^[1]

See also

• Tosyl azide
• Diphenylphosphoryl azide

References

1. ↑ 1.0 1.1 1.2 C. J. Cavender and V. J. Shiner (1972). "Trifluoromethanesulfonyl azide. Its reaction with alkyl amines to form alkyl azides". The Journal of Organic Chemistry 37 (22): 3567–3569. doi:10.1021/jo00795a052. 
2. ↑ 2.0 2.1 Cavender, C. J.; Shiner, V. J., Jr. J. Org. Chem. (1972), 37, 3567.
3. ↑ Titz, A.; Radic, Z.; Schwardt, O.; Ernst, B. Tetrahedron Lett. (2006), 47, 2383.
4. ↑ R.-B. Yan, F. Yang, Y. Wu, L.-H. Zhang and X.-S. Ye (2005). "An efficient and improved procedure for preparation of triflyl azide and application in catalytic diazotransfer reaction". Tetrahedron Letters 46 (52): 8993–8995. doi:10.1016/j.tetlet.2005.10.103. 
5. ↑ E. D. Goddard-Borger and R. V. Stick (2007). "An Efficient, Inexpensive, and Shelf-Stable Diazotransfer Reagent:  Imidazole-1-sulfonyl Azide Hydrochloride". Organic Letters 9 (19): 3797–3800. doi:10.1021/ol701581g. PMID 17713918.