トリフルオロメタンスルホン酸

関: trifluoromethanesulfonate

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street name for lysergic acid diethylamide (同)back breaker, battery-acid, dose, dot, Elvis, loony toons, Lucy in the sky with diamonds, pane, superman, window pane, Zen
any of various water-soluble compounds having a sour taste and capable of turning litmus red and reacting with a base to form a salt
having the characteristics of an acid; "an acid reaction"

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酸性の / 酸味のある,すっぱい(sour) / (言葉・態度などが)厳しい,しんらつな / 酸 / すっぱいもの / 《俗》=LSD

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Trifluoromethanesulfonic acid, also known as triflic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF₃SO₃H. It is one of the strongest acids. Triflic acid is mainly used in research as a catalyst for esterification.^[1]^[2] It is a hygroscopic, colorless, slightly viscous liquid which is soluble in polar solvents.

Syntheses

Trifluoromethanesulfonic acid is produced industrially by electrochemical fluorination (ECF) of methanesulfonic acid:

CH₃SO₃H + 4 HF → CF₃SO₂F + H₂O + 1.5 H₂

The resulting CF₃SO₂F is hydrolyzed, and the resulting triflate salt is preprotonated. Alternatively, trifluoromethanesulfonic acid arises by oxidation of trifluoromethylsulfenyl chloride:^[3]

CF₃SCl + 2 Cl₂ + 2 H₂O → CF₃SO₂OH + 4 HCl

Triflic acid is purified by distillation from triflic anhydride.^[2]

Historical

Trifluoromethanesulfonic acid was first synthesized in 1954 by Haszeldine and Kidd by the following reaction:^[4]

Reactions

As an acid

In the laboratory, triflic acid is useful in protonations because the conjugate base of triflic acid is nonnucleophilic. It is also used as an acidic titrant in nonaqueous acid-base titration because it behaves as a strong acid in many solvents (acetonitrile, acetic acid, etc.) where common mineral acids (such as HCl or H₂SO₄) are only moderately strong.

With a K_a = 1 ×10¹² (pKa ~ −12)^[5] Triflic acid qualifies as a superacid. It owes many of its useful properties to its great thermal and chemical stability. Both the acid and its conjugate base CF₃SO−
3, known as triflate, resist oxidation/reduction reactions, whereas many strong acids are oxidizing, e.g. HClO₄ and HNO₃. Further recommending its use, triflic acid does not sulfonate substrates, which can be a problem with sulfuric acid, fluorosulfuric acid, and chlorosulfonic acid. Below is a prototypical sulfonation, which HOTf does not undergo:

C₆H₆ + H₂SO₄ → C₆H₅(SO₃H) + H₂O

Triflic acid fumes in moist air and forms a stable solid monohydrate, CF₃SO₃H·H₂O, melting point 34 °C.

Salt and complex formation

The triflate ligand is labile, reflecting its low basicity. Trifluoromethanesulfonic acid exothermically reacts with metal carbonates, hydroxides, and oxides. Illustrative is the synthesis of Cu(OTf)₂.^[6]

CuCO₃ + 2 CF₃SO₃H → Cu(O₃SCF₃)₂ + H₂O + CO₂

Chloride ligands can be converted to the corresponding triflates:

3 CF₃SO₃H + [Co(NH₃)₅Cl]Cl₂ → [Co(NH₃)₅O₃SCF₃](O₃SCF₃)₂ + 3 HCl

This conversion is conducted in neat HOTf at 100 °C, followed by precipitation of the salt upon the addition of ether.

Organic chemistry

Triflic acid reacts with acyl halides to give mixed triflate anhydrides, which are strong acylating agents, e.g. in Friedel-Crafts reactions.

CH₃C(O)Cl + CF₃SO₃H → CH₃C(O)OSO₂CF₃ + HCl

CH₃C(O)OSO₂CF₃ + C₆H₆ → CH₃C(O)C₆H₅ + CF₃SO₃H

Triflic acid catalyzes the reaction of aromatic compounds with sulfonyl chlorides, probably also via the intermediacy of a mixed anhydride of the sulfonic acid.

Triflic acid promotes other Friedel-Crafts-like reactions including the cracking of alkanes and alkylation of alkenes, which are very important to the petroleum industry. These triflic acid derivative catalysts are very effective in isomerizing straight chain or slightly branched hydrocarbons that can increase the octane rating of a particular petroleum-based fuel.

Triflic acid reacts exothermically with alcohols to produce ethers and olefins.

Dehydration give the acid anhydride, trifluoromethanesulfonic anhydride, (CF₃SO₂)₂O.

Safety

Trifluoromethanesulfonic acid is one of the strongest acids. With contact with skin it causes severe burns with delayed tissue destruction. On inhalation it causes fatal spasms, inflammation and edema.^[7]

Addition of triflic acid to polar solvents can be dangerously exothermic.

References

^ Howells, R. D., McCown, J. D. (1977). "Trifluoromethanesulfonic Acid and Derivatives". Chemical Reviews 77 (1): 69–92. doi:10.1021/cr60305a005.
^ ^a ^b Subramanian, L. R.; Martinez, A. G.; Hanack, M.; Prakash, G. K. S.; Hu, J. (2006). "Trifluoromethanesulfonic Acid". Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289X.rt246.pub2. ISBN 0-471-93623-5.
^ Siegemund, G.; Schwertfeger, W.; Feiring, A.; Smart, B.; Behr, F.; Vogel, H.; McKusick, B. (2000). "Fluorine Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. John Wiley & Sons. doi:10.1002/14356007.a11_349.
^ Haszeldine, R. N.; Kidd, J. M. (1954). "Perfluoroalkyl derivatives of sulphur. Part I. Trifluoromethanesulphonic acid". Journal of the Chemical Society 1954: 4228–4232. doi:10.1039/JR9540004228.
^ Raamat, E.; Kaupmees, K.; Ovsjannikov, G.; Trummal, A.; Kütt, A.; Saame, J.; Koppel, I.; Kaljurand, I.; Lipping, L.; Rodima, T.; Pihl, V.; Koppel, I. A.; Leito, I. "Acidities of strong neutral Brønsted acids in different media." J. Phys. Org. Chem. 2013, 26, 162-170. doi:10.1002/poc.2946
^ Dixon, N. E.; Lawrance, G. A.; Lay, P. A.; Sargeson, A. M.; Taube, H. (1990). "Trifluoromethanesulfonates and trifluoromethanesulfonato-O complexes". Inorganic Syntheses 28: 70–76. doi:10.1002/9780470132593.ch16. ISBN 978-0-470-13259-3.
^ "Trifluoromethanesulfonic acid MSDS". ChemCAS.

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English Journal

Domino Friedel-Crafts-Type Cyclizations of Difluoroalkenes Promoted by the α-Cation-Stabilizing Effect of Fluorine: An Efficient Method for Synthesizing Angular PAHs.

Fuchibe K, Jyono H, Fujiwara M, Kudo T, Yokota M, Ichikawa J.SourceDepartment of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571 (Japan), Fax: (+81)?29-853-4237.
Chemistry (Weinheim an der Bergstrasse, Germany).Chemistry.2011 Oct 17;17(43):12175-85. doi: 10.1002/chem.201100618. Epub 2011 Sep 16.
In order to synthesize polycyclic aromatic hydrocarbons with nonlinear arrangements (angular PAHs), acid-promoted domino cyclizations of 1,1-difluoroalk-1-enes and 1,1-difluoroalka-1,3-dienes were studied. 1,1-Difluoroalkenes, each bearing two aryl substituents, were regioselectively protonated with
PMID 21922570

Bronsted acid assisted activation of imide carbonyl group: regioselective synthesis of isoindoloisoquinolinone alkaloid (±)-nuevamine.

Selvakumar J, Ramanathan CR.SourceDepartment of Chemistry, Pondicherry University, Puducherry, 605 014, India. crrnath.che@pondiuni.edu.in.
Organic & biomolecular chemistry.Org Biomol Chem.2011 Sep 22. [Epub ahead of print]
Activation of imide carbonyl group with trifluoromethanesulfonic acid facilitates the intramolecular cyclization of phenethylphthalimides to give a fused isoindoloisoquinolinone skeleton. The first one pot regioselective synthesis of isoindoloisoquinolinone alkaloid (±)-nuevamine has been successfu
PMID 21938306

Japanese Journal

Comparisons of O-acylation and Friedel–Crafts acylation of phenols and acyl chlorides and Fries rearrangement of phenyl esters in trifluoromethanesulfonic acid: effective synthesis of optically active homotyrosines

Murashige Ryo,Hayashi Yuka,Ohmori Syo,Torii Ayuko,Aizu Yoko,Muto Yasuyuki,Murai Yuta,Oda Yuji,Hashimoto Makoto
Tetrahedron 67(3), 641-649, 2011-01-21
… The extent for these reactions in trifluoromethanesulfonic acid (TfOH), which is used as catalyst and solvent, is examined. …
NAID 120002741676

トリフルオロメタンスルホン酸を用いる芳香族ポリカルボシランの迅速分解反応

池永和敏,泰永茂伸
高分子論文集 67(5), 326-335, 2010-05-25
NAID 10026213804

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リンク元	「trifluoromethanesulfonate」「トリフルオロメタンスルホン酸」

「trifluoromethanesulfonate」

Trifluoromethanesulfonic acid
Names
	IUPAC name Trifluoromethanesulfonic acid
	Other names Triflic acid
Identifiers
CAS Registry Number	1493-13-6
ChEBI	CHEBI:48511
ChemSpider	56192
	InChI InChI=1S/CHF3O3S/c2-1(3,4)8(5,6)7/h(H,5,6,7) ; Key: ITMCEJHCFYSIIV-UHFFFAOYSA-N ; InChI=1/CHF3O3S/c2-1(3,4)8(5,6)7/h(H,5,6,7); Key: ITMCEJHCFYSIIV-UHFFFAOYAW ;
Jmol-3D images	Image
PubChem	62406
	SMILES C(F)(F)(F)S(=O)(=O)O ;
Properties
Chemical formula	CF3SO3H
Molar mass	150.08 g/mol
Appearance	Colorless liquid
Density	1.696 g/mL
Melting point	−40 °C (−40 °F; 233 K)
Boiling point	162 °C (324 °F; 435 K)
Solubility in water	Miscible
Hazards
Main hazards	Corrosive, eye irritant
	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

　　[★] トリフルオロメタンスルホン酸、トリフルオロメタンスルホン酸塩

関: trifluoromethanesulfonic acid

「トリフルオロメタンスルホン酸」

　　[★]

英: trifluoromethanesulfonic acid、trifluoromethanesulfonate
関: トリフルオロメタンスルホン酸塩

[1] Howells, R. D., McCown, J. D. (1977). "Trifluoromethanesulfonic Acid and Derivatives". Chemical Reviews 77 (1): 69–92. doi:10.1021/cr60305a005.

[eros-2] Subramanian, L. R.; Martinez, A. G.; Hanack, M.; Prakash, G. K. S.; Hu, J. (2006). "Trifluoromethanesulfonic Acid". Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289X.rt246.pub2. ISBN 0-471-93623-5.

[Gunt-3] Siegemund, G.; Schwertfeger, W.; Feiring, A.; Smart, B.; Behr, F.; Vogel, H.; McKusick, B. (2000). "Fluorine Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. John Wiley & Sons. doi:10.1002/14356007.a11_349.

[Haszeldine-4] Haszeldine, R. N.; Kidd, J. M. (1954). "Perfluoroalkyl derivatives of sulphur. Part I. Trifluoromethanesulphonic acid". Journal of the Chemical Society 1954: 4228–4232. doi:10.1039/JR9540004228.

[5] Raamat, E.; Kaupmees, K.; Ovsjannikov, G.; Trummal, A.; Kütt, A.; Saame, J.; Koppel, I.; Kaljurand, I.; Lipping, L.; Rodima, T.; Pihl, V.; Koppel, I. A.; Leito, I. "Acidities of strong neutral Brønsted acids in different media." J. Phys. Org. Chem. 2013, 26, 162-170. doi:10.1002/poc.2946

[6] Dixon, N. E.; Lawrance, G. A.; Lay, P. A.; Sargeson, A. M.; Taube, H. (1990). "Trifluoromethanesulfonates and trifluoromethanesulfonato-O complexes". Inorganic Syntheses 28: 70–76. doi:10.1002/9780470132593.ch16. ISBN 978-0-470-13259-3.

[7] "Trifluoromethanesulfonic acid MSDS". ChemCAS.

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trifluoromethanesulfonic acid