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{{chembox |
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{{Chembox |
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| Watchedfields = changed |
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| verifiedrevid = 443855695 |
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| verifiedrevid = 445341920 |
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| Name = Hexafluoroacetone |
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| ImageFile = Hexafluoroacetone 3D.png |
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| Name = Hexafluoroacetone |
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| ImageFile = Hexafluoraceton.svg |
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<!-- | ImageSize = 200px --> |
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| ImageName = Hexafluoropropanone 3D structure |
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| ImageName = Hexafluoropropanone skeletal structure |
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| ImageFile1 = 1,1,1,3,3,3-hexafluoropropanone-chemical.png |
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| ImageFile1 = Hexafluoroacetone 3D.png |
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| ImageName1 = Hexafluoropropanone 3D structure |
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<!-- | ImageSize1 = 200px --> |
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| ImageName1 = 1,1,1,3,3,3-hexafluoropropanone |
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| PIN = 1,1,1,3,3,3-Hexafluoropropan-2-one |
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| IUPACName = 1,1,1,3,3,3-hexafluoro-<br />2-propanone |
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| OtherNames = perfluoroacetone<br /> acetone hexafluoride<br /> perfluoro-2-propanone |
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|Section1={{Chembox Identifiers |
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| OtherNames = perfluoroacetone<br /> acetone hexafluoride<br /> perfluoro-2-propanone |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| Section1 = {{Chembox Identifiers |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 39429 |
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| ChEBI = 39429 |
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| SMILES = FC(F)(F)C(=O)C(F)(F)F |
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| SMILES = FC(F)(F)C(=O)C(F)(F)F |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 13846015 |
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| ChemSpiderID = 13846015 |
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| InChI = 1/C3F6O/c4-2(5,6)1(10)3(7,8)9 |
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| InChI = 1/C3F6O/c4-2(5,6)1(10)3(7,8)9 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 684-16-2 |
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| CASNo = 684-16-2 |
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| RTECS = UC2450000 |
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| PubChem = 12695 |
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| EINECS = 211-676-3 |
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}} |
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| RTECS = UC2450000 |
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| Section2 = {{Chembox Properties |
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| UNNumber = 2420 |
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| Formula = C<sub>3</sub>F<sub>6</sub>O |
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| UNII = AKU9463N1Y |
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| MolarMass = 166.02 g/mol |
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}} |
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| Appearance = Colorless gas |
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|Section2={{Chembox Properties |
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| Density = 1.32 g/ml, liquid |
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| Formula = C<sub>3</sub>F<sub>6</sub>O |
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| Solubility = Reacts with water |
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| MolarMass = 166.02 g/mol |
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| MeltingPt = −129 °C (144 K) |
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| Appearance = Colorless gas |
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| BoilingPt = −28 °C (245 K) |
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| Odor = musty<ref name=PGCH/> |
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}} |
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| Density = 1.32 g/ml, liquid |
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| Section7 = {{Chembox Hazards |
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| Solubility = Reacts with water |
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| ExternalMSDS = |
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| MeltingPt = −129 °C (144 K) |
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| MainHazards = Toxic ('''T'''),<br />Corrosive ('''C''') |
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| BoilingPt = −28 °C (245 K) |
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| NFPA-H = 3 |
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| VaporPressure = 5.8 atm (20 °C)<ref name=PGCH/> |
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| NFPA-F = |
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}} |
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| NFPA-R = 2 | Other=<s>W</s> |
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|Section7={{Chembox Hazards |
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| FlashPt = N/A |
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| ExternalSDS = |
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| RPhrases = {{R14}}, {{R23/24/25}},<br />{{R34}}, {{R60}}, {{R63}} |
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| MainHazards = Toxic ('''T'''),<br />Corrosive ('''C''') |
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| SPhrases = {{S7/9}}, {{S26}}, {{S28}},<br />{{S36}}, {{S45}}, {{S53}} |
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| NFPA-H = 3 |
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}} |
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| NFPA-F =0 |
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| Section8 = {{Chembox Related |
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| NFPA-R = 2 |
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| Function = ]s |
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| NFPA-S = W |
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| OtherFunctn = ] |
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| FlashPt_notes = Nonflammable<ref name=PGCH/> |
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| Function = organofluorides |
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| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}}{{GHS08}} |
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| OtherFunctn = ] |
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| GHSSignalWord = Danger |
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}} |
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| HPhrases = {{H-phrases|301|310|311|314|315|330|360|370|372}} |
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| PPhrases = {{P-phrases|201|202|260|262|264|270|271|280|281|284|301+310|301+330+331|302+350|302+352|303+361+353|304+340|305+351+338|307+311|308+313|310|312|314|320|321|322|330|332+313|361|362|363|403+233|405|410+403|501}} |
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| PEL = none<ref name=PGCH>{{PGCH|0319}}</ref> |
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| IDLH = N.D.<ref name=PGCH/> |
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| REL = TWA 0.1 ppm (0.7 mg/m<sup>3</sup>) <ref name=PGCH/> |
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}} |
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|Section8={{Chembox Related |
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| OtherFunction_label = ]s;<br/>organofluorides |
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| OtherFunction = ];<br/>] |
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}} |
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}} |
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}} |
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'''Hexafluoroacetone''' is a ] with the ] CF<sub>3</sub>-CO-CF<sub>3</sub>. It is structurally similar to ], however its reactivity is markedly different. It comes in the form of a colourless, hygroscopic, nonflammable, highly reactive gas characterized by a musty odour. The most common form of this substance is hexafluoroacetone sesquihydrate (1.5 ], which is a gem-diol. |
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'''Hexafluoroacetone''' (HFA) is a ] with the ] (CF<sub>3</sub>)<sub>2</sub>CO. It is structurally similar to ]; however, its reactivity is markedly different. It is a colourless, hygroscopic, nonflammable, highly reactive gas characterized by a musty odour.<ref></ref> According to ], HFA and acetone adopt very similar structures, the C-O distance being only longer in the fluorinated compound (124.6 vs 121.0 ]), possibly due to steric effects.<ref>{{cite journal |doi=10.1021/j100702a030 |title=Electron diffraction investigation of hexafluoroacetone, hexafluoropropylimine, and hexafluoroisobutene |date=1970 |last1=Hilderbrandt |first1=R. L. |last2=Andreassen |first2=A. L. |last3=Bauer |first3=Simon Harvey |journal=The Journal of Physical Chemistry |volume=74 |issue=7 |pages=1586–1592 }}</ref> |
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The term "hexafluoroacetone" can refer to the ] (1.5 ], which is a ] of ] {{chem|(|F|3|C|)|2|C|(|OH|)|2}}, a ]. Hydrated HFA behaves differently from the anhydrous material. |
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==Synthesis and reactions== |
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(CF<sub>3</sub>)<sub>2</sub>CO is prepared in a two step process from perfluoropropene. In the first step KF catalyzes the reaction of the alkene with elemental sulfur to give the 1,3-dithete <sub>2</sub>. This species is then oxidized by iodate to give (CF<sub>3</sub>)<sub>2</sub>CO.<ref>{{OrgSynth | author = Van Der Puy, M. ; Anello, L. G. | title = Hexafluoroacetone | collvol = 7 | collvolpages = 251 | year = 1990 | prep = CV7P0251}}</ref> |
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==Synthesis== |
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The industrial route to HFA involves treatment of ] with ] (a ]):<ref name=Ullmanns>{{cite encyclopedia|author=Günter Siegemund|author2=Werner Schwertfeger|author3=Andrew Feiring|author4=Bruce Smart|author5=Fred Behr|author6=Herward Vogel|author7=Blaine McKusick|title=Fluorine Compounds, Organic|encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry|publisher=Wiley-VCH|place=Weinheim|year=2002|doi=10.1002/14356007.a11_349}}</ref> |
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:(CCl<sub>3</sub>)<sub>2</sub>CO + 6 HF → (CF<sub>3</sub>)<sub>2</sub>CO + 6 HCl |
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===Laboratory methods=== |
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Hydrated HFA can be converted to HFA by treatment with hot ].<ref name=ChemRev>{{cite journal |doi=10.1021/cr0509962 |title=Hexafluoroacetone as Protecting and Activating Reagent: New Routes to Amino, Hydroxy, and Mercapto Acids and Their Application for Peptide and Glyco- and Depsipeptide Modification |date=2006 |last1=Spengler |first1=Jan |last2=Böttcher |first2=Christoph |last3=Albericio |first3=Fernando |last4=Burger |first4=Klaus |journal=Chemical Reviews |volume=106 |issue=11 |pages=4728–4746 |pmid=17091933 }}</ref> |
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It has also be prepared from ], which will rearrange to give HFA when heated in the presence of a ] such as ].<ref>{{cite journal |last1=Millauer |first1=Hans |last2=Schwertfeger |first2=Werner |last3=Siegemund |first3=Günter |title=Hexafluoropropene Oxide — A Key Compound in Organofluorine Chemistry |journal=Angewandte Chemie International Edition in English |date=March 1985 |volume=24 |issue=3 |pages=161–179 |doi=10.1002/anie.198501611}}</ref> The Lewis acid catalysed oxidation of ] will also produce HFA, via a similar mechanism. |
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Although it is commercially available, HFA can be prepared on the laboratory-scale from hexafluoropropylene.<ref>{{cite journal |last1=Anello |first1=Louis G. |last2=Van der Puy |first2=Michael |title=A convenient synthesis of hexafluoroacetone |journal=The Journal of Organic Chemistry |date=January 1982 |volume=47 |issue=2 |pages=377–378 |doi=10.1021/jo00341a046}}</ref> In the first step ] catalyzes the reaction of the alkene with elemental sulfur to give the 1,3-] dimer of ]. This species is then oxidized by ] to give HFA.<ref>{{OrgSynth | author = Van Der Puy, M. | author2 = Anello, L. G. | title = Hexafluoroacetone | volume = 53 | page = 154 | year = 1985 | doi = 10.15227/orgsyn.063.015}}</ref> |
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==Uses== |
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==Uses== |
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Hexafluoroacetone is mostly employed in ], but it is also the main chemical intermediate used in the production of ], as well as ]s and ]s for textile coating. Hexafluoroacetone can be employed as a solvent for acetal resins, ]s, ], ], and ] or as a ] adhesive. |
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Hexafluoroacetone is used in the production of ]: |
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:(CF<sub>3</sub>)<sub>2</sub>CO + H<sub>2</sub> → (CF<sub>3</sub>)<sub>2</sub>CHOH |
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It is also used as a precursor to ],<ref name=Ullmanns/> a monomer used in polymer chemistry, and as a ] in the synthesis of ], ], ], and ]. |
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==Reactivity== |
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==Reactivity== |
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] |
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Hexafluoroacetone is a reactive substance, acting primarily as an ]. In water hexafluoroacetone is highly reactive as its ] sharply favors (~10<sup>6</sup>) forming a ]-] ], unlike the identical unfavorable equilibrium with acetone (10<sup>-3</sup>).<ref name="Lemal2004">{{cite journal |doi=10.1021/jo0302556 |title=Perspective on Fluorocarbon Chemistry |year=2004 |last1=Lemal |first1=David M. |journal=The Journal of Organic Chemistry |volume=69 |pages=1–11 |pmid=14703372 |issue=1}}</ref> This makes the equilibria of two chemicals differ by about a ''billion'' regarding this addition of water.<ref name="Lemal2004"/> Hexafluoroacetone-hydrates are acidic and react with most metals to generate ]. Hexafluoroacetone violently reacts in the presence of alkali. Related to its tendency to hydrate, (CF<sub>3</sub>)<sub>2</sub>CO adds ] to give (CF<sub>3</sub>)<sub>2</sub>C(OH)(NH<sub>2</sub>) which can be dehydrated with ] to give (CF<sub>3</sub>)<sub>2</sub>CNH.<ref>{{OrgSynth | author = Middleton, W. J.; Carlson, H. D. | title = Hexafluoroacetoneimine | collvol = 6 | collvolpages = 664 | year = 1988 | prep = CV6P0664}}</ref> |
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] |
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With water, hexafluoroacetone converts to the hydrate. The ] (K<sub>eq</sub>) for the formation of this ] is 10<sup>6</sup> M<sup>−1</sup>. The analogous equilibrium for acetone is an unfavorable 10<sup>−3</sup> M<sup>−1</sup>.<ref name="Lemal2004">{{cite journal |doi=10.1021/jo0302556 |title=Perspective on Fluorocarbon Chemistry |year=2004 |last1=Lemal |first1=David M. |journal=The Journal of Organic Chemistry |volume=69 |pages=1–11 |pmid=14703372 |issue=1}}</ref> Hexafluoroacetone-hydrates are acidic. In an analogous reaction, ] adds to hexafluoroacetone to give the ] (CF<sub>3</sub>)<sub>2</sub>C(OH)(NH<sub>2</sub>) which can be dehydrated with ] to give the ] (CF<sub>3</sub>)<sub>2</sub>CNH.<ref>{{cite journal| author = W. J. Middleton| author2 = H. D. Carlson | title = Hexafluoroacetone imine | journal= Org. Syntheses | volume = 50| year = 1970| pages=81–3|doi=10.15227/orgsyn.050.0081}}.</ref> |
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]s attack occurs at the ] carbon of Hexafluoroacetone, as illustrated above. Thus, HFA readily forms lactones when treated with hydroxy- and amine-substituted carboxylic acids. In such reactions, HFA serves both as electrophile and dehydrating agent:<ref name=ChemRev/> |
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:{{chem2|RCH(OH)CO2H + O\dC(CF3)2 -> RCH(O)CO2C(CF3)2 + (HO)2C(CF3)2}} |
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==See also== |
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==References== |
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==References== |
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{{Reflist}} |
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<references/> |
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