Trifluoroacetone

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1,1,1-Trifluoroacetone
1,1,1-Trifluoroacetone.svg
Names
Preferred IUPAC name
1,1,1-Trifluoropropan-2-one
Other names
Trifluoracetone, TFA
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.006.370 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 207-005-9
PubChem CID
UNII
  • InChI=1S/C3H3F3O/c1-2(7)3(4,5)6/h1H3
    Key: FHUDAMLDXFJHJE-UHFFFAOYSA-N
  • CC(=O)C(F)(F)F
Properties
C3H3F3O
Molar mass 112.051 g·mol−1
AppearanceColorless liquid
Density 1.252 g/mL
Melting point −78 °C (−108 °F; 195 K)
Boiling point 21–24 °C (70–75 °F; 294–297 K)
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-exclam.svg
Danger
H224, H315, H319, H335
P210, P261, P303, P338, P351
Flash point −30 °C (−22 °F; 243 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Trifluoroacetone (1,1,1-trifluoroacetone) is an organofluorine compound with the chemical formula CF3C(O)CH3. [1] The compound is a colorless liquid with chloroform-like odour. [2]

Contents

Preparation, reactions, uses

Trifluoroacetone is produced from trifluoroacetoacetic acid, which is synthesized by condensation of ethyl trifluoroacetate and ethyl acetate:

CF3CO2C2H5 + CH3CO2C2H5 → CF3C(O)CH2CO2C2H5 + C2H5OH

Hydrolysis of the keto-ester, followed by decarboxylation affords trifluoroacetone:

CF3C(O)CH2CO2C2H5 + H2O → CF3C(O)CH2CO2H + C2H5OH
CF3C(O)CH2CO2H → CF3C(O)CH3 + CO2

Alternatively, addition of methylmagnesium iodide to trifluoroacetic acid gives the ketone according to this idealized equation: [2]

CF3CO2H + 2 CH3MgI → CF3C(O)CH3 + MgI2 + CH4 + MgO

Reactions

Many studies report on the reactions of trifluoroacetone. [3] It is less prone to hydrate than hexafluoroacetone and more electrophilic than acetone itself. Unlike both of those ketones, trifluoroacetone is prochiral.

Hydrogenation of trifluoroacetone over platinum catalyst gives trifluoroisopropanol. The reduction can also be achieved asymmetrically. Similarly, alkylation with Grignard reagents provides a route to tertiary alcohols. Alkylation and arylation can be achieved using malonate anions and arenes/ AlCl3 , respectively.

Trifluoroacetone has been converted to the dioxirane using oxone.

It serves as an oxidizing agent in Oppenauer oxidation. [4]

Trifluoracetone is also used in a synthesis of 2-trifluoromethyl-7-azaindoles starting with 2,6-dihalopyridines. The derived chiral imine is used to prepare enantiopure α-trifluoromethyl alanines and diamines by a Strecker reaction followed by either nitrile hydrolysis or reduction. [5]

See also

Related Research Articles

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In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom bonded to two organyl groups. They have the general formula R−O−R′, where R and R′ represent the organyl groups. Ethers can again be classified into two varieties: if the organyl groups are the same on both sides of the oxygen atom, then it is a simple or symmetrical ether, whereas if they are different, the ethers are called mixed or unsymmetrical ethers. A typical example of the first group is the solvent and anaesthetic diethyl ether, commonly referred to simply as "ether". Ethers are common in organic chemistry and even more prevalent in biochemistry, as they are common linkages in carbohydrates and lignin.

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

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<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

<span class="mw-page-title-main">Acetoacetic acid</span> Chemical compound

Acetoacetic acid is the organic compound with the formula CH3COCH2COOH. It is the simplest beta-keto acid, and like other members of this class, it is unstable. The methyl and ethyl esters, which are quite stable, are produced on a large scale industrially as precursors to dyes. Acetoacetic acid is a weak acid.

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<span class="mw-page-title-main">Imine</span> Organic compound or functional group containing a C=N bond

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<span class="mw-page-title-main">2-Iodoxybenzoic acid</span> Chemical compound

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<span class="mw-page-title-main">Trifluoroacetic acid</span> One of the lightest perfluoro compounds

Trifluoroacetic acid (TFA) is a synthetic organofluorine compound with the chemical formula CF3CO2H. It is a haloacetic acid, with all three of the acetyl group's hydrogen atoms replaced by fluorine atoms. It is a colorless liquid with a vinegar-like odor. TFA is a stronger acid than acetic acid, having an acid ionisation constant, Ka, that is approximately 34,000 times higher, as the highly electronegative fluorine atoms and consequent electron-withdrawing nature of the trifluoromethyl group weakens the oxygen-hydrogen bond (allowing for greater acidity) and stabilises the anionic conjugate base. TFA is commonly used in organic chemistry for various purposes.

Organoselenium chemistry is the science exploring the properties and reactivity of organoselenium compounds, chemical compounds containing carbon-to-selenium chemical bonds. Selenium belongs with oxygen and sulfur to the group 16 elements or chalcogens, and similarities in chemistry are to be expected. Organoselenium compounds are found at trace levels in ambient waters, soils and sediments.

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<span class="mw-page-title-main">Trifluoromethyl group</span> Functional group

The trifluoromethyl group is a functional group that has the formula -CF3. The naming of is group is derived from the methyl group (which has the formula -CH3), by replacing each hydrogen atom by a fluorine atom. Some common examples are trifluoromethane H–CF
3
, 1,1,1-trifluoroethane H
3
C
CF
3
, and hexafluoroacetone F
3
C
–CO–CF
3
. Compounds with this group are a subclass of the organofluorines.

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<span class="mw-page-title-main">Trifluoroperacetic acid</span> Chemical compound

Trifluoroperacetic acid is an organofluorine compound, the peroxy acid analog of trifluoroacetic acid, with the condensed structural formula CF
3
COOOH
. It is a strong oxidizing agent for organic oxidation reactions, such as in Baeyer–Villiger oxidations of ketones. It is the most reactive of the organic peroxy acids, allowing it to successfully oxidise relatively unreactive alkenes to epoxides where other peroxy acids are ineffective. It can also oxidise the chalcogens in some functional groups, such as by transforming selenoethers to selones. It is a potentially explosive material and is not commercially available, but it can be quickly prepared as needed. Its use as a laboratory reagent was pioneered and developed by William D. Emmons.

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References

  1. "1,1,1-Trifluoracetone 95%". dk.vwr.com. Retrieved 6 June 2017.
  2. 1 2 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. ISBN   978-3-527-30673-2.
  3. Prakash, G. K.Surya; Wang, Fang (2011). "1,1,1-Trifluoroacetone". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn01348. ISBN   978-0-471-93623-7.
  4. Mello, Rossella; Martínez-Ferrer, Jaime; Asensio, Gregorio; González-Núñez, María Elena (2007). "Oppenauer Oxidation of Secondary Alcohols with 1,1,1-Trifluoroacetone as Hydride Acceptor". J. Org. Chem. 24 (72): 9376–9378. doi:10.1021/jo7016422. PMID   17975928.
  5. "Concise synthesis of enantiopure alpha-trifluoromethyl alanines, diamines, and amino alcohols by the Strecker-type reaction". sigmaaldrich.com. Retrieved 6 June 2017.