| Revision as of 09:25, 23 May 2011 editCheMoBot (talk | contribs)Bots141,565 edits Updating {{chembox}} (no changed fields - added verified revid - updated 'UNII_Ref', 'ChemSpiderID_Ref', 'StdInChI_Ref', 'StdInChIKey_Ref', 'ChEMBL_Ref', 'KEGG_Ref') per Chem/Drugbox validation (← Previous edit |
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{{chembox |
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{{chembox |
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| verifiedrevid = 414760454 |
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| ImageFile = Triflic-anhydride-2D.png |
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|verifiedrevid = 430483180 |
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| ImageSize = 200px |
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| ImageName = Skeletal formula of triflic anhydride |
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|ImageFile = Triflic-anhydride-2D.png |
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|ImageName = Skeletal formula of triflic anhydride |
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| IUPACName = |
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|ImageFileR1 = Trifluoromethanesulfonic anhydride Space Fill.png |
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| Section1 = {{Chembox Identifiers |
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|ImageSizeR1 = 170px |
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| CASNo_Ref = {{cascite}} |
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|ImageFileL1 = Trifluoromethanesulfonic anhydride Ball and Stick.png |
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| CASNo = 358-23-6 |
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|ImageSizeL1 = 170px |
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| SMILES = |
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|PIN = Trifluoromethanesulfonic anhydride |
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| Section2 = {{Chembox Properties |
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|Section1 = {{Chembox Identifiers |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| C = 2 | F = 6 | O = 5 | S = 2 |
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|CASNo = 358-23-6 |
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| MeltingPt = |
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|ChEBI = 48509 |
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| BoilingPtC =82 |
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|EC_number = 206-616-8 |
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| Density = 1.6770 g/mL |
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|UNII_Ref = {{fdacite|correct|FDA}} |
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}} |
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|UNII = 8W034LHG1U |
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| Section7 = {{Chembox Hazards |
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|PubChem = 67749 |
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| ExternalMSDS = |
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|ChemSpiderID = 61068 |
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| FlashPt = |
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|SMILES = C(F)(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F |
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| RPhrases = {{R14}} {{R34}} |
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|StdInChI = 1S/C2F6O5S2/c3-1(4,5)14(9,10)13-15(11,12)2(6,7)8 |
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| SPhrases = {{S25}} {{S26}} {{S36/37/39}} {{S45}} |
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|StdInChIKey = WJKHJLXJJJATHN-UHFFFAOYSA-N |
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|Section2 = {{Chembox Properties |
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|C=2 | F=6 | O=5 | S=2 |
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|Appearance = colourless liquid |
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|BoilingPtC = 82 <ref>{{cite journal|last1=Bloodworth|first1=A.J.|last2=Curtis|first2=Richard J.|last3=Spencer|first3=Michael D.|last4=Tallant|first4=Neil A.|title=Oxymetallation. Part 24. Preparation of cyclic peroxides by cycloperoxymercuriation of unsaturated hydroperoxides.|journal=Tetrahedron|date=March 1993|volume=49|issue=13|pages=2729–2750|doi=10.1016/S0040-4020(01)86350-X}}</ref> |
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|Solubility = Reacts to form ] |
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|Density = 1.6770 g/mL |
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|Section3 = {{Chembox Hazards |
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|ExternalSDS = |
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|GHSPictograms = {{GHS03}}{{GHS05}}{{GHS07}} |
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|NFPA-H = 4 |
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|NFPA-F = 0 |
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|NFPA-R = 3 |
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|NFPA-S = W+OX |
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|GHSSignalWord = Danger |
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|HPhrases = {{H-phrases|272|302|314|335}} |
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|PPhrases = {{P-phrases|}} |
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'''Triflic anhydride''' is the ] with the formula (CF<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>O. This compound is a particularly strong ], useful for introducing the ], CF<sub>3</sub>SO<sub>2</sub>. Triflic anhydride is the ] of the strong acid ], CF<sub>3</sub>SO<sub>2</sub>OH.<ref>Chemical Transformations Induced by Triflic Anhydride, Tetrahedron 56 (2000) 3077-3119,Baraznenok</ref> |
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'''Trifluoromethanesulfonic anhydride''', also known as triflic anhydride, is the ] with the formula (CF<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>O. It is the acid anhydride derived from ]. This compound is a strong ], useful for introducing the ], CF<sub>3</sub>SO<sub>2</sub>. Abbreviated '''Tf<sub>2</sub>O''', triflic anhydride is the ] of the superacid ], CF<sub>3</sub>SO<sub>2</sub>OH.<ref name=eros>{{cite journal|author=Martínez, A. G.; Subramanian, L. R.; Hanack, M.|title=Trifluoromethanesulfonic Anhydride|journal=Encyclopedia of Reagents for Organic Synthesis|year=2016|pages=1–17|doi= 10.1002/047084289X.rt247.pub3|isbn=9780470842898}}</ref><ref>{{cite journal|last1=Baraznenok|first1=Ivan L.|last2=Nenajdenko|first2=Valentine G.|last3=Balenkova|first3=Elizabeth S.|title=Chemical Transformations Induced by Triflic Anhydride|journal=Tetrahedron|date=May 2000|volume=56|issue=20|pages=3077–3119|doi=10.1016/S0040-4020(00)00093-4}}</ref> |
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==Preparation and uses== |
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It can be assayed by <sup>19</sup>F NMR spectroscopy: −72.6 ppm vs. -77.3 for TfOH (std CFCl<sub>3</sub>). |
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Triflic anhydride is prepared by dehydration of triflic acid using P<sub>4</sub>O<sub>10</sub>.<ref name=eros/> |
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Triflic anhydride is useful for converting ketones into enol triflates.<ref>{{cite journal|doi=10.15227/orgsyn.088.0260|title=Discussion Addendum for: Palladium-Catalyzed Reduction of Vinyl Trifluoromethanesulfonates to Alkenes: Cholesta-3,5-diene|journal=Organic Syntheses|volume=88|pages=260|year=2011|first1=Sandro|last1=Cacchi|first2=Enrico |last2=Morera|first3=Giorgio |last3=Ortar}}</ref> |
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==Preparation== |
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The compound is prepared by dehydration of triflic acid using ]:<ref>{{OrgSynth | author = Stang, P. J.; Dueber, T. E. | title = Preparation of Vinyl Trifluoromethanesulfonates: 3-Methyl-2-Buten-2-yl Triflate | collvol = 6 | collvolpages = 757 | year = 1988 | prep = cv6p0757}}</ref> |
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:2CF<sub>3</sub>SO<sub>2</sub>OH + P<sub>4</sub>O<sub>10</sub> → <sub>2</sub>O + P<sub>4</sub>O<sub>9</sub>(OH)<sub>2</sub> |
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In a representative application, is used to convert an imine into a NTf group.<ref>{{OrgSynth |author1=Baker, T. J.|author2=Tomioka, M.|author3=Goodman, M. | title = Preparation and Use of N,N'-Di-BOC-N<nowiki>''</nowiki>-Triflylguanidine | page = 91| volume=78 | year = 2002 | doi= 10.15227/orgsyn.078.0091}}</ref> It will convert ]s into a triflic ester, which enables cleavage of the C-O bond.<ref>{{OrgSynth |author1=McWilliams, J. C.|author2= Fleitz, F. J.|author3=Zheng, N.|author4=Armstrong, III, J. D. | title = Preparation of n-Butyl 4-Chlorophenyl Sulfide | volume= 79 | page= 43 | doi= 10.15227/orgsyn.079.0043}}</ref><ref>{{OrgSynth |author1=Cai, D.|author2=Payack, J. F.|author3=Bender, D. R.|author4=Hughes, D. L.|author5=Verhoeven, T. R.|author6=Reider, P. J. | title = (R)-(+)- and (S)-(−)-2,2'-Bis(Diphenylphosphino)-1,1'-Binaphthyl (BINAP) | year=1999| volume= 76| page= 6| doi= 10.15227/orgsyn.076.0006}}</ref> |
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==Illustrative uses== |
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In a representative application, is used to convert an imine into a NTf group.<ref>{{OrgSynth | author = Baker, T. J. Tomioka, M.; Goodman, M. | title = Preparation and Use of N,N'-Di-BOC-N''-Triflylguanidine | collvol = 10 | collvolpages 266 | year = 2004 | prep = v78p0091}}</ref> |
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==Assay== |
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It will convert ]s into a triflic ester, which enables cleavage of the C-O bond.<ref>{{OrgSynth | author = McWilliams, J. C. Fleitz, F. J.; Zheng, N.; Armstrong, III, J. D. | title = Preparation of n-Butyl 4-Chlorophenyl Sulfide | collvol = 10 | collvolpages = 147 | prep = v79p0043}}</ref><ref>{{OrgSynth | author = Cai, D.; Payack, J. F.; Bender, D. R.; Hughes, D. L.; Verhoeven, T. R.; Reider, P. J. | title = (R)-(+)- and (S)-(−)-2,2'-Bis(Diphenylphosphino)-1,1'-Binaphthyl (BINAP) | collvol = 10 | collvolpages = 112 | prep = v76p0006}}</ref> |
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The typical impurity in triflic anhydride is triflic acid, which is also a colorless liquid. Samples of triflic anhydride can be assayed by <sup>19</sup>F NMR spectroscopy: −72.6 ppm<ref name=Amico2002>{{cite journal|last=Dell'Amico|first=Daniela Belli|author2=Boschi, Daniele |author3=Calderazzo, Fausto |author4=Labella, Luca |author5= Marchetti, Fabio |title=Synthesis, and crystal and molecular structures of the triflato and trifluoroacetato complexes of zinc, Zn(O3SCF3)2(DME)2 and n|journal=Inorganica Chimica Acta|date=28 February 2002|volume=330|issue=1|pages=149–154|doi=10.1016/S0020-1693(01)00739-3|url=http://144.206.159.178/ft/458/52133/914984.pdf}}</ref> vs. −77.3 for TfOH (std CFCl<sub>3</sub>). |
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==Safety== |
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It is an aggressive electrophile and readily hydrolyzes to the strong acid triflic acid. It is very harmful to skin and eyes.<ref>{{Cite web|title=MSDS - 176176|url=https://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=US&language=en&productNumber=176176&brand=ALDRICH&PageToGoToURL=https://www.sigmaaldrich.com/catalog/product/aldrich/176176?lang=en|access-date=2020-08-09|website=www.sigmaaldrich.com}}</ref> |
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==See also== |
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* ] |
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==References== |
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==References== |
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