Hexafluoroacetone: Difference between revisions

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	{{~~chembox~~		{{Chembox
			\| Watchedfields = changed
	\| verifiedrevid = 443855695
			\| verifiedrevid = 445341920
	\| Name = Hexafluoroacetone
	\| ~~ImageFile~~ = Hexafluoroacetone ~~3D.png~~		\| Name = Hexafluoroacetone
			\| ImageFile = Hexafluoraceton.svg
	<!-- \| ImageSize = 200px -->
	\| ImageName = Hexafluoropropanone 3D structure		\| ImageName = Hexafluoropropanone skeletal structure
	\| ImageFile1 = ~~1,1,1,3,3,3-hexafluoropropanone-chemical~~.png		\| ImageFile1 = Hexafluoroacetone 3D.png
			\| ImageName1 = Hexafluoropropanone 3D structure
	<!-- \| ImageSize1 = 200px -->
	\| ~~ImageName1~~ = 1,1,1,3,3,3-~~hexafluoropropanone~~		\| PIN = 1,1,1,3,3,3-Hexafluoropropan-2-one
	\| ~~IUPACName~~ = ~~1,1,1,3,3,3-hexafluoro-~~<br />2-propanone		\| OtherNames = perfluoroacetone<br /> acetone hexafluoride<br /> perfluoro-2-propanone
			\|Section1={{Chembox Identifiers
	\| OtherNames = perfluoroacetone<br /> acetone hexafluoride<br /> perfluoro-2-propanone
			\| ChEBI_Ref = {{ebicite\|correct\|EBI}}
	\| Section1 = {{Chembox Identifiers
	\| ChEBI_Ref = {{ebicite\|correct\|EBI}}
	\| ChEBI = 39429		\| ChEBI = 39429
	\| SMILES = FC(F)(F)C(=O)C(F)(F)F		\| SMILES = FC(F)(F)C(=O)C(F)(F)F
	\| ChemSpiderID_Ref = {{chemspidercite\|correct\|chemspider}}		\| ChemSpiderID_Ref = {{chemspidercite\|correct\|chemspider}}
	\| ChemSpiderID = 13846015		\| ChemSpiderID = 13846015
	\| InChI = 1/C3F6O/c4-2(5,6)1(10)3(7,8)9		\| InChI = 1/C3F6O/c4-2(5,6)1(10)3(7,8)9
Line 24:		Line 23:
	\| CASNo_Ref = {{cascite\|correct\|CAS}}		\| CASNo_Ref = {{cascite\|correct\|CAS}}
	\| CASNo = 684-16-2		\| CASNo = 684-16-2
	\| ~~RTECS~~ = ~~UC2450000~~		\| PubChem = 12695
			\| EINECS = 211-676-3
	}}
			\| RTECS = UC2450000
	\| Section2 = {{Chembox Properties
			\| UNNumber = 2420
	\| Formula = C<sub>3</sub>F<sub>6</sub>O
			\| UNII = AKU9463N1Y
	\| MolarMass = 166.02 g/mol
			}}
	\| Appearance = Colorless gas
			\|Section2={{Chembox Properties
	\| Density = 1.32 g/ml, liquid
			\| Formula = C<sub>3</sub>F<sub>6</sub>O
	\| Solubility = Reacts with water
			\| MolarMass = 166.02 g/mol
	\| MeltingPt = −129 °C (144 K)
			\| Appearance = Colorless gas
	\| BoilingPt = −28 °C (245 K)
			\| Odor = musty<ref name=PGCH/>
	}}
			\| Density = 1.32 g/ml, liquid
	\| Section7 = {{Chembox Hazards
			\| Solubility = Reacts with water
	\| ExternalMSDS =
			\| MeltingPt = −129 °C (144 K)
	\| MainHazards = Toxic ('''T'''),<br />Corrosive ('''C''')
			\| BoilingPt = −28 °C (245 K)
	\| NFPA-H = 3
			\| VaporPressure = 5.8 atm (20 °C)<ref name=PGCH/>
	\| NFPA-F =
			}}
	\| NFPA-R = 2 \| Other=<s>W</s>
			\|Section7={{Chembox Hazards
	\| FlashPt = N/A
			\| ExternalSDS =
	\| RPhrases = {{R14}}, {{R23/24/25}},<br />{{R34}}, {{R60}}, {{R63}}
			\| MainHazards = Toxic ('''T'''),<br />Corrosive ('''C''')
	\| SPhrases = {{S7/9}}, {{S26}}, {{S28}},<br />{{S36}}, {{S45}}, {{S53}}
			\| NFPA-H = 3
	}}
			\| NFPA-F =0
	\| Section8 = {{Chembox Related
			\| NFPA-R = 2
	\| Function = ]s
			\| NFPA-S = W
	\| OtherFunctn = ]
			\| FlashPt_notes = Nonflammable<ref name=PGCH/>
	\| Function = organofluorides
			\| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}}{{GHS08}}
	\| OtherFunctn = ]
			\| GHSSignalWord = Danger
	}}
			\| HPhrases = {{H-phrases\|301\|310\|311\|314\|315\|330\|360\|370\|372}}
			\| 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}}
			\| PEL = none<ref name=PGCH>{{PGCH\|0319}}</ref>
			\| IDLH = N.D.<ref name=PGCH/>
			\| REL = TWA 0.1 ppm (0.7 mg/m<sup>3</sup>) <ref name=PGCH/>
			}}
			\|Section8={{Chembox Related
			\| OtherFunction_label = ]s;<br/>organofluorides
			\| OtherFunction = ];<br/>]
			}}
	}}		}}

	'''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 ~~geminal~~ ~~diol~~.		'''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>

			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.
	==Synthesis and reactions==

	(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>
			==Synthesis==
			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>
			:(CCl<sub>3</sub>)<sub>2</sub>CO + 6 HF → (CF<sub>3</sub>)<sub>2</sub>CO + 6 HCl

			===Laboratory methods===
			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>

			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.

			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>

	==Uses==		==Uses==
	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.~~		Hexafluoroacetone is used in the production of ]:
			:(CF<sub>3</sub>)<sub>2</sub>CO + H<sub>2</sub> → (CF<sub>3</sub>)<sub>2</sub>CHOH

			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 ].

	==Reactivity==		==Reactivity==
			]
	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>
			]
			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>

			]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/>
			:{{chem2\|RCH(OH)CO2H + O\dC(CF3)2 -> RCH(O)CO2C(CF3)2 + (HO)2C(CF3)2}}

			==See also==
			*]
			*]
			*]
			*]
			*]
			*]

	==References==		==References==
			{{Reflist}}
	<references/>

	]		]
	]		]
			]

			]
	]
	]
	]
	]
	]

Latest revision as of 13:34, 21 December 2024

Hexafluoroacetone
Names


Preferred IUPAC name 1,1,1,3,3,3-Hexafluoropropan-2-one
Other names perfluoroacetone acetone hexafluoride perfluoro-2-propanone
Identifiers
CAS Number	684-16-2
3D model (JSmol)	Interactive image
ChEBI	CHEBI:39429
ChemSpider	13846015
ECHA InfoCard	100.010.616
EC Number	211-676-3
PubChem CID	12695
RTECS number	UC2450000
UNII	AKU9463N1Y
UN number	2420
CompTox Dashboard (EPA)	DTXSID9043778
InChI InChI=1S/C3F6O/c4-2(5,6)1(10)3(7,8)9Key: VBZWSGALLODQNC-UHFFFAOYSA-N InChI=1/C3F6O/c4-2(5,6)1(10)3(7,8)9Key: VBZWSGALLODQNC-UHFFFAOYAI
SMILES FC(F)(F)C(=O)C(F)(F)F
Properties
Chemical formula	C₃F₆O
Molar mass	166.02 g/mol
Appearance	Colorless gas
Odor	musty
Density	1.32 g/ml, liquid
Melting point	−129 °C (144 K)
Boiling point	−28 °C (245 K)
Solubility in water	Reacts with water
Vapor pressure	5.8 atm (20 °C)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	Toxic (T), Corrosive (C)
GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H301, H310, H311, H314, H315, H330, H360, H370, H372
Precautionary statements	P201, P202, P260, P262, P264, P270, P271, P280, P281, P284, P301+P310, P301+P330+P331, P302+P350, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P307+P311, P308+P313, P310, P312, P314, P320, P321, P322, P330, P332+P313, P361, P362, P363, P403+P233, P405, P410+P403, P501
NFPA 704 (fire diamond)	3 0 2 W
Flash point	Nonflammable
NIOSH (US health exposure limits):
PEL (Permissible)	none
REL (Recommended)	TWA 0.1 ppm (0.7 mg/m)
IDLH (Immediate danger)	N.D.
Related compounds
Related ketones; organofluorides	Acetone; Hexafluoro-2-propanol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). Y verify (what is ?) Infobox references

Chemical compound

Hexafluoroacetone (HFA) is a chemical compound with the formula (CF₃)₂CO. It is structurally similar to acetone; however, its reactivity is markedly different. It is a colourless, hygroscopic, nonflammable, highly reactive gas characterized by a musty odour. According to electron diffraction, HFA and acetone adopt very similar structures, the C-O distance being only longer in the fluorinated compound (124.6 vs 121.0 pm), possibly due to steric effects.

The term "hexafluoroacetone" can refer to the sesquihydrate (1.5 H₂O), which is a hemihydrate of hexafluoropropane-2,2-diol (F
₃C)
₂C(OH)
₂, a geminal diol. Hydrated HFA behaves differently from the anhydrous material.

Synthesis

The industrial route to HFA involves treatment of hexachloroacetone with HF (a Finkelstein reaction):

(CCl₃)₂CO + 6 HF → (CF₃)₂CO + 6 HCl

Laboratory methods

Hydrated HFA can be converted to HFA by treatment with hot sulfuric acid.

It has also be prepared from hexafluoropropylene oxide, which will rearrange to give HFA when heated in the presence of a Lewis acid such as AlCl3. The Lewis acid catalysed oxidation of hexafluoropropylene will also produce HFA, via a similar mechanism.

Although it is commercially available, HFA can be prepared on the laboratory-scale from hexafluoropropylene. In the first step KF catalyzes the reaction of the alkene with elemental sulfur to give the 1,3-dithietane dimer of hexafluorothioacetone. This species is then oxidized by potassium iodate to give HFA.

Uses

Hexafluoroacetone is used in the production of hexafluoroisopropanol:

(CF₃)₂CO + H₂ → (CF₃)₂CHOH

It is also used as a precursor to hexafluoroisobutylene, a monomer used in polymer chemistry, and as a building block in the synthesis of midaflur, bisphenol AF, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, and alitame.

Reactivity

With water, hexafluoroacetone converts to the hydrate. The equilibrium constant (K_eq) for the formation of this geminal diol is 10 M. The analogous equilibrium for acetone is an unfavorable 10 M. Hexafluoroacetone-hydrates are acidic. In an analogous reaction, ammonia adds to hexafluoroacetone to give the hemiaminal (CF₃)₂C(OH)(NH₂) which can be dehydrated with phosphoryl chloride to give the imine (CF₃)₂CNH.

Nucleophiles attack occurs at the carbonyl 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:

RCH(OH)CO₂H + O=C(CF₃)₂ → RCH(O)CO₂C(CF₃)₂ + (HO)₂C(CF₃)₂

References

^ NIOSH Pocket Guide to Chemical Hazards. "#0319". National Institute for Occupational Safety and Health (NIOSH).
CDC - NIOSH Pocket Guide to Chemical Hazards
Hilderbrandt, R. L.; Andreassen, A. L.; Bauer, Simon Harvey (1970). "Electron diffraction investigation of hexafluoroacetone, hexafluoropropylimine, and hexafluoroisobutene". The Journal of Physical Chemistry. 74 (7): 1586–1592. doi:10.1021/j100702a030.
^ Günter Siegemund; Werner Schwertfeger; Andrew Feiring; Bruce Smart; Fred Behr; Herward Vogel; Blaine McKusick (2002). "Fluorine Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_349.
^ Spengler, Jan; Böttcher, Christoph; Albericio, Fernando; Burger, Klaus (2006). "Hexafluoroacetone as Protecting and Activating Reagent: New Routes to Amino, Hydroxy, and Mercapto Acids and Their Application for Peptide and Glyco- and Depsipeptide Modification". Chemical Reviews. 106 (11): 4728–4746. doi:10.1021/cr0509962. PMID 17091933.
Millauer, Hans; Schwertfeger, Werner; Siegemund, Günter (March 1985). "Hexafluoropropene Oxide — A Key Compound in Organofluorine Chemistry". Angewandte Chemie International Edition in English. 24 (3): 161–179. doi:10.1002/anie.198501611.
Anello, Louis G.; Van der Puy, Michael (January 1982). "A convenient synthesis of hexafluoroacetone". The Journal of Organic Chemistry. 47 (2): 377–378. doi:10.1021/jo00341a046.
Van Der Puy, M.; Anello, L. G. (1985). "Hexafluoroacetone". Organic Syntheses. 53: 154. doi:10.15227/orgsyn.063.015.
Lemal, David M. (2004). "Perspective on Fluorocarbon Chemistry". The Journal of Organic Chemistry. 69 (1): 1–11. doi:10.1021/jo0302556. PMID 14703372.
W. J. Middleton; H. D. Carlson (1970). "Hexafluoroacetone imine". Org. Syntheses. 50: 81–3. doi:10.15227/orgsyn.050.0081..

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