Hexafluoroacetone

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)9 Key: VBZWSGALLODQNC-UHFFFAOYSA-N ; InChI=1/C3F6O/c4-2(5,6)1(10)3(7,8)9 Key: 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/m3) [skin]
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 [77 °F], 100 kPa). verify (what is ?) Infobox references

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.^[2] 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.^[3]

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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.

The industrial route to HFA involves treatment of hexachloroacetone with HF (a Finkelstein reaction):^[4]

(CCl₃)₂CO + 6 HF → (CF₃)₂CO + 6 HCl

Laboratory methods

Hydrated HFA can be converted to HFA by treatment with hot sulfuric acid.^[5]

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.^[6] 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.^[7] 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.^[8]

Hexafluoroacetone is used in the production of hexafluoroisopropanol:

(CF₃)₂CO + H₂ → (CF₃)₂CHOH

It is also used as a precursor to hexafluoroisobutylene,^[4] 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.

Thumb — Hexafluoroacetone imine is an unusual primary ketimine that is isolable.

With water, hexafluoroacetone converts to the hydrate. The equilibrium constant (K_eq) for the formation of this geminal diol is 10⁶ M⁻¹. The analogous equilibrium for acetone is an unfavorable 10⁻³ M⁻¹.^[9] 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.^[10]

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:^[5]

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

[1]
NIOSH Pocket Guide to Chemical Hazards. "#0319". National Institute for Occupational Safety and Health (NIOSH).
[2]
CDC - NIOSH Pocket Guide to Chemical Hazards
[3]
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.
[4]
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.
[5]
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.
[6]
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.
[7]
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.
[8]
Van Der Puy, M.; Anello, L. G. (1985). "Hexafluoroacetone". Organic Syntheses. 53: 154. doi:10.15227/orgsyn.063.015.
[9]
Lemal, David M. (2004). "Perspective on Fluorocarbon Chemistry". The Journal of Organic Chemistry. 69 (1): 1–11. doi:10.1021/jo0302556. PMID 14703372.
[10]
W. J. Middleton; H. D. Carlson (1970). "Hexafluoroacetone imine". Org. Syntheses. 50: 81–3. doi:10.15227/orgsyn.050.0081..

[PGCH-1] [1]
NIOSH Pocket Guide to Chemical Hazards. "#0319". National Institute for Occupational Safety and Health (NIOSH).

[2] [2]
CDC - NIOSH Pocket Guide to Chemical Hazards

[3] [3]
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.

[Ullmanns-4] [4]
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.

[ChemRev-5] [5]
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.

[6] [6]
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.

[7] [7]
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.

[8] [8]
Van Der Puy, M.; Anello, L. G. (1985). "Hexafluoroacetone". Organic Syntheses. 53: 154. doi:10.15227/orgsyn.063.015.

[Lemal2004-9] [9]
Lemal, David M. (2004). "Perspective on Fluorocarbon Chemistry". The Journal of Organic Chemistry. 69 (1): 1–11. doi:10.1021/jo0302556. PMID 14703372.

[10] [10]
W. J. Middleton; H. D. Carlson (1970). "Hexafluoroacetone imine". Org. Syntheses. 50: 81–3. doi:10.15227/orgsyn.050.0081..

[2]

[3]

[1]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

Hexafluoroacetone

Laboratory methods

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Synthesis

Uses

Reactivity

See also

References

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^Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:39429^Y
ChemSpider	13846015^Y
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)9^Y Key: VBZWSGALLODQNC-UHFFFAOYSA-N^Y InChI=1/C3F6O/c4-2(5,6)1(10)3(7,8)9 Key: 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^[1]
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)^[1]
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^[1]
NIOSH (US health exposure limits):
PEL (Permissible)	none^[1]
REL (Recommended)	TWA 0.1 ppm (0.7 mg/m³) [skin]^[1]
IDLH (Immediate danger)	N.D.^[1]
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 [77 °F], 100 kPa). Y verify (what is ^YN ?) Infobox references