Trifluoromethanesulfonic anhydride

Structural formula
General
Surname	Trifluoromethanesulfonic anhydride
Molecular formula	C 2 F 6 O 5 S 2
Brief description	colorless liquid
External identifiers / databases
EC number	206-616-8
ECHA InfoCard	100.006.016
PubChem	67749
Wikidata	Q6128335
properties
Molar mass	282.139 g mol −1
Physical state	liquid
density	1.677 g cm −3
boiling point	82 ° C
solubility	good in organic solvents
Refractive index	1.321
safety instructions
H and P phrases	H: 302-314
	P: 280-305-351-338-338-310
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Trifluoromethanesulfonic anhydride , abbreviated as Tf ₂ O, is a colorless, corrosive and toxic liquid that is readily soluble in organic solvents, but reacts violently with protic solvents with hydrolysis . It is the anhydride of trifluoromethanesulfonic acid . The compound is a particularly strong electrophile , it is used to introduce the triflyl group . An overview of various reactions is given in the literature.

Presentation and extraction

Trifluoromethanesulfonic anhydride can be obtained by condensation from trifluoromethanesulfonic acid using phosphorus pentoxide or phosphorus pentachloride .

use

In preparative organic chemistry, the triflyl group introduced by trifluoromethanesulfonic anhydride is used as a good leaving group . With alcohols , alkyl triflates result, which are used, among other things, for alkylations. Vinyl and aryl triflates are formed from carbonyl compounds and phenols , which are a superior alternative to halides in the Heck reaction or other cross-couplings . It also serves as a good leaving group in aminations, carbonylations, or heterocyclizations.

Individual evidence

↑ ^a ^b ^c Entry on trifluoromethanesulfonic anhydride. In: Römpp Online . Georg Thieme Verlag, accessed on June 23, 2020.
↑ ^a ^b ^c ^d data sheet Trifluoromethanesulfonic anhydride from Sigma-Aldrich , accessed on January 9, 2015 ( PDF ).
^ AJ Bloodworth, Richard J. Curtis, Michael D. Spencer, Neil A. Tallant: Oxymetallation. Part 24. Preparation of cyclic peroxides by cycloperoxymercuriation of unsaturated hydroperoxides. . In: Tetrahedron . 49, No. 13, March 1993, pp. 2729-2750. doi : 10.1016 / S0040-4020 (01) 86350-X .
↑ Ivan L. Baraznenok, Valentine G. Nenajdenko, Elizabeth S. Balenkova: Chemical Transformations Induced by Triflic Anhydride . In: Tetrahedron . 56, No. 20, May 2000, pp. 3077-3119. doi : 10.1016 / S0040-4020 (00) 00093-4 .
^ André B. Charette, Peter Chua: A new method for the conversion of secondary and tertiary amides to bridged orthoesters . In: Tetrahedron Letters . 38, No. 49, December 1997, pp. 8499-8502. doi : 10.1016 / S0040-4039 (97) 10310-0 .
↑ e-EROS Encyclopedia of Reagents for Organic Synthesis , 1999-2013, John Wiley and Sons, Inc., entry for Trifluoromethanesulfonic Anhydride, accessed January 6, 2015 .
↑ Kurt Ritter: Synthetic Transformations of Vinyl and Aryl Triflates . In: Synthesis . 1993, No. 08, 1993, pp. 735-762. doi : 10.1055 / s-1993-25931 .
↑ Farina Vittorio, Krishnamurthy Venkat, Scott J. William: The Stille Reaction . In: Organic Reactions . September. doi : 10.1002 / 0471264180.or050.01 .
↑ Rik R. Tykwinski, Yuming Zhao: Cross-Conjugated oligo (enynes) . In: Synlett . No. 12, 2002, pp. 1939-1953. doi : 10.1055 / s-2002-35578 .
↑ John F. Hartwig: Transition Metal Catalyzed Synthesis of Arylamines and Aryl Ethers from Aryl Halides and Triflates: Scope and Mechanism . In: Angewandte Chemie International Edition . 37, No. 15, August 17, 1998, pp. 2046-2067. doi : 10.1002 / (SICI) 1521-3773 (19980817) 37:15 <2046 :: AID-ANIE2046> 3.0.CO; 2-L .
↑ Sandro Cacchi, Giancarlo Fabrizi, Luca M. Parisi: Nitrogen-containing Heterocycles via Palladium-catalyzed Reaction of Alkynes with Organic Halides or Triflates . In: HETEROCYCLES . 58, No. 1, 2002, p. 667. doi : 10.3987 / REV-02-SR (M) 1 .
↑ Ernesto Occhiato: Lactam-derived Vinyl Triflates and Phosphates in the Synthesis of N-heterocycles . In: Mini-Reviews in Organic Chemistry . 1, No. 2, April 1, 2004, pp. 149-162. doi : 10.2174 / 1570193043488890 .

[Römpp-1] Entry on trifluoromethanesulfonic anhydride. In: Römpp Online . Georg Thieme Verlag, accessed on June 23, 2020.

[Sigma-Aldrich-2] ta sheet Trifluoromethanesulfonic anhydride from Sigma-Aldrich , accessed on January 9, 2015 ( PDF ).

[3] AJ Bloodworth, Richard J. Curtis, Michael D. Spencer, Neil A. Tallant: Oxymetallation. Part 24. Preparation of cyclic peroxides by cycloperoxymercuriation of unsaturated hydroperoxides. . In: Tetrahedron . 49, No. 13, March 1993, pp. 2729-2750. doi : 10.1016 / S0040-4020 (01) 86350-X .

[4] Ivan L. Baraznenok, Valentine G. Nenajdenko, Elizabeth S. Balenkova: Chemical Transformations Induced by Triflic Anhydride . In: Tetrahedron . 56, No. 20, May 2000, pp. 3077-3119. doi : 10.1016 / S0040-4020 (00) 00093-4 .

[5] André B. Charette, Peter Chua: A new method for the conversion of secondary and tertiary amides to bridged orthoesters . In: Tetrahedron Letters . 38, No. 49, December 1997, pp. 8499-8502. doi : 10.1016 / S0040-4039 (97) 10310-0 .

[eEROS-6] -EROS Encyclopedia of Reagents for Organic Synthesis , 1999-2013, John Wiley and Sons, Inc., entry for Trifluoromethanesulfonic Anhydride, accessed January 6, 2015 .

[7] Kurt Ritter: Synthetic Transformations of Vinyl and Aryl Triflates . In: Synthesis . 1993, No. 08, 1993, pp. 735-762. doi : 10.1055 / s-1993-25931 .

[8] Farina Vittorio, Krishnamurthy Venkat, Scott J. William: The Stille Reaction . In: Organic Reactions . September. doi : 10.1002 / 0471264180.or050.01 .

[9] Rik R. Tykwinski, Yuming Zhao: Cross-Conjugated oligo (enynes) . In: Synlett . No. 12, 2002, pp. 1939-1953. doi : 10.1055 / s-2002-35578 .

[10] John F. Hartwig: Transition Metal Catalyzed Synthesis of Arylamines and Aryl Ethers from Aryl Halides and Triflates: Scope and Mechanism . In: Angewandte Chemie International Edition . 37, No. 15, August 17, 1998, pp. 2046-2067. doi : 10.1002 / (SICI) 1521-3773 (19980817) 37:15 <2046 :: AID-ANIE2046> 3.0.CO; 2-L .

[11] Sandro Cacchi, Giancarlo Fabrizi, Luca M. Parisi: Nitrogen-containing Heterocycles via Palladium-catalyzed Reaction of Alkynes with Organic Halides or Triflates . In: HETEROCYCLES . 58, No. 1, 2002, p. 667. doi : 10.3987 / REV-02-SR (M) 1 .

[12] Ernesto Occhiato: Lactam-derived Vinyl Triflates and Phosphates in the Synthesis of N-heterocycles . In: Mini-Reviews in Organic Chemistry . 1, No. 2, April 1, 2004, pp. 149-162. doi : 10.2174 / 1570193043488890 .