Trifluoromethanesulfonic anhydride

Trifluoromethanesulfonic anhydride, also known as triflic anhydride, is the chemical compound with the formula (CF3SO2)2O. It is the acid anhydride derived from triflic acid. This compound is a strong electrophile, useful for introducing the triflyl group, CF3SO2. Abbreviated Tf2O, triflic anhydride is the acid anhydride of the superacid triflic acid, CF3SO2OH.[2][3]

Trifluoromethanesulfonic anhydride
Skeletal formula of triflic anhydride
Names
Preferred IUPAC name
Trifluoromethanesulfonic anhydride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.006.016
EC Number
  • 206-616-8
UNII
  • InChI=1S/C2F6O5S2/c3-1(4,5)14(9,10)13-15(11,12)2(6,7)8
    Key: WJKHJLXJJJATHN-UHFFFAOYSA-N
  • C(F)(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F
Properties
C2F6O5S2
Molar mass 282.13 g·mol−1
Appearance colourless liquid
Density 1.6770 g/mL
Boiling point 82[1] °C (180 °F; 355 K)
Reacts to form Triflic acid
Hazards
GHS labelling:
GHS03: OxidizingGHS05: CorrosiveGHS07: Exclamation mark
Danger
H272, H302, H314, H335
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
4
0
3
W
OX
Safety data sheet (SDS) Fisher MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Preparation and uses

Triflic anhydride is prepared by dehydration of triflic acid using P4O10.[2]

Triflic anhydride is useful for converting ketones into enol triflates.[4]

In a representative application, is used to convert an imine into a NTf group.[5] It will convert phenols into a triflic ester, which enables cleavage of the C-O bond.[6][7]

Assay

The typical impurity in triflic anhydride is triflic acid, which is also a colorless liquid. Samples of triflic anhydride can be assayed by 19F NMR spectroscopy: −72.6 ppm[8] vs. −77.3 for TfOH (std CFCl3).

Safety

It is an aggressive electrophile and readily hydrolyzes to the strong acid triflic acid. It is very harmful to skin and eyes.[9]

See also

References
  1. Bloodworth, A.J.; Curtis, Richard J.; Spencer, Michael D.; Tallant, Neil A. (March 1993). "Oxymetallation. Part 24. Preparation of cyclic peroxides by cycloperoxymercuriation of unsaturated hydroperoxides". Tetrahedron. 49 (13): 2729–2750. doi:10.1016/S0040-4020(01)86350-X.
  2. Martínez, A. G.; Subramanian, L. R.; Hanack, M. (2016). "Trifluoromethanesulfonic Anhydride". Encyclopedia of Reagents for Organic Synthesis: 1–17. doi:10.1002/047084289X.rt247.pub3. ISBN 9780470842898.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  3. Baraznenok, Ivan L.; Nenajdenko, Valentine G.; Balenkova, Elizabeth S. (May 2000). "Chemical Transformations Induced by Triflic Anhydride". Tetrahedron. 56 (20): 3077–3119. doi:10.1016/S0040-4020(00)00093-4.
  4. Cacchi, Sandro; Morera, Enrico; Ortar, Giorgio (2011). "Discussion Addendum for: Palladium-Catalyzed Reduction of Vinyl Trifluoromethanesulfonates to Alkenes: Cholesta-3,5-diene". Organic Syntheses. 88: 260. doi:10.15227/orgsyn.088.0260.
  5. Baker, T. J.; Tomioka, M.; Goodman, M. (2002). "Preparation and Use of N,N'-Di-BOC-N''-Triflylguanidine". Organic Syntheses. 78: 91. doi:10.15227/orgsyn.078.0091.
  6. McWilliams, J. C.; Fleitz, F. J.; Zheng, N.; Armstrong, III, J. D. "Preparation of n-Butyl 4-Chlorophenyl Sulfide". Organic Syntheses. 79: 43. doi:10.15227/orgsyn.079.0043.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  7. Cai, D.; Payack, J. F.; Bender, D. R.; Hughes, D. L.; Verhoeven, T. R.; Reider, P. J. (1999). "(R)-(+)- and (S)-(−)-2,2'-Bis(Diphenylphosphino)-1,1'-Binaphthyl (BINAP)". Organic Syntheses. 76: 6. doi:10.15227/orgsyn.076.0006.
  8. Dell'Amico, Daniela Belli; Boschi, Daniele; Calderazzo, Fausto; Labella, Luca; Marchetti, Fabio (28 February 2002). "Synthesis, and crystal and molecular structures of the triflato and trifluoroacetato complexes of zinc, Zn(O3SCF3)2(DME)2 and [Zn(O2CCF3)2(DME)]n" (PDF). Inorganica Chimica Acta. 330 (1): 149–154. doi:10.1016/S0020-1693(01)00739-3.
  9. "MSDS - 176176". www.sigmaaldrich.com. Retrieved 2020-08-09.
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