Ketone

From Wikipedia, the free encyclopedia

Not to be confused with ketone bodies.

Ketone group

Acetone

In chemistry, a ketone (alkanone) /ˈkiːtoʊn/ is an organic compound with the structure

RC(=O)R', where R and R' can be a variety of carbon-containing substituents. Ketones and
aldehydes are simple compounds that contain a carbonyl group (a carbon-oxygen double bond).
They are considered "simple" because they do not have reactive groups like −OH or −Cl attached
directly to the carbon atom in the carbonyl group, as in carboxylic acids containing −COOH.[1]
Many ketones are known and many are of great importance in industry and in biology. Examples
include many sugars (ketoses) and the industrial solvent acetone, which is the smallest ketone.

Contents
 1 Nomenclature and etymology
 2 Structure and properties
o 2.1 Classes of ketones
 2.1.1 Diketones
 2.1.2 Unsaturated ketones
 2.1.3 Cyclic ketones
o 2.2 Keto-enol tautomerization
o 2.3 Acidity of ketones
  3 Characterization
o 3.1 Spectroscopy
o 3.2 Qualitative organic tests
 4 Synthesis
 5 Reactions
 6 Biochemistry
 7 Applications
 8 Toxicity
 9 See also
 10 References

Nomenclature and etymology

The word ketone is derived from Aketon, an old German word for acetone.[2][3]

According to the rules of IUPAC nomenclature, ketones are named by changing the suffix -ane
of the parent alkane to -anone. The position of the carbonyl group is usually denoted by a
number. For the most important ketones, however, traditional nonsystematic names are still
generally used, for example acetone and benzophenone. These nonsystematic names are
considered retained IUPAC names,[4] although some introductory chemistry textbooks use
systematic names such as "2-propanone" or "propan-2-one" for the simplest ketone
(CH3−CO−CH3) instead of "acetone".

The common names of ketones are obtained by writing separately the names of the two alkyl
groups attached to the carbonyl group, followed by "ketone" as a separate word. The names of
the alkyl groups are written alphabetically. When the two alkyl groups are the same, the prefix
di- is added before the name of alkyl group. The positions of other groups are indicated by Greek
letters, the α-carbon being the atom adjacent to carbonyl group. If both alkyl groups in a ketone
are the same then the ketone is said to be symmetrical, otherwise unsymmetrical.

Although used infrequently, oxo is the IUPAC nomenclature for a ketone functional group. Other
prefixes, however, are also used. For some common chemicals (mainly in biochemistry), keto or
oxo refer to the ketone functional group. The term oxo is used widely through chemistry. For
example, it also refers to an oxygen atom bonded to a transition metal (a metal oxo).

Structure and properties

Representative ketones, from the left: acetone, a common solvent; oxaloacetate, an intermediate
in the metabolism of sugars; acetylacetone in its (mono) enol form (the enol highlighted in blue);
cyclohexanone, precursor to nylon; muscone, an animal scent; and tetracycline, an antibiotic.
The ketone carbon is often described as "sp2 hybridized", a description that includes both their
electronic and molecular structure. Ketones are trigonal planar around the ketonic carbon, with
C−C−O and C−C−C bond angles of approximately 120°. Ketones differ from aldehydes in that
the carbonyl group (CO) is bonded to two carbons within a carbon skeleton. In aldehydes, the
carbonyl is bonded to one carbon and one hydrogen and are located at the ends of carbon chains.
Ketones are also distinct from other carbonyl-containing functional groups, such as carboxylic
acids, esters and amides.[5]

The carbonyl group is polar because the electronegativity of the oxygen is greater than that for
carbon. Thus, ketones are nucleophilic at oxygen and electrophilic at carbon. Because the
carbonyl group interacts with water by hydrogen bonding, ketones are typically more soluble in
water than the related methylene compounds. Ketones are hydrogen-bond acceptors. Ketones are
not usually hydrogen-bond donors and cannot hydrogen-bond to themselves. Because of their
inability to serve both as hydrogen-bond donors and acceptors, ketones tend not to "self-
associate" and are more volatile than alcohols and carboxylic acids of comparable molecular
weights. These factors relate to the pervasiveness of ketones in perfumery and as solvents.

Classes of ketones

Ketones are classified on the basis of their substituents. One broad classification subdivides
ketones into symmetrical and asymmetrical derivatives, depending on the equivalency of the two
organic substituents attached to the carbonyl center. Acetone and benzophenone
(C6H5C(O)C6H5) are symmetrical ketones. Acetophenone (C6H5C(O)CH3) is an asymmetrical
ketone. In the area of stereochemistry, asymmetrical ketones are known for being prochiral.

Diketones

Main article: diketone

Many kinds of diketones are known, some with unusual properties. The simplest is diacetyl
(CH3C(O)C(O)CH3), once used as butter-flavoring in popcorn. Acetylacetone (pentane-2,4-
dione) is virtually a misnomer (inappropriate name) because this species exists mainly as the
monoenol CH3C(O)CH=C(OH)CH3. Its enolate is a common ligand in coordination chemistry.

Unsaturated ketones

Ketones containing alkene and alkyne units are often called unsaturated ketones. The most
widely used member of this class of compounds is methyl vinyl ketone, CH3C(O)CH=CH2,
which is useful in the Robinson annulation reaction. Lest there be confusion, a ketone itself is a
site of unsaturation; that is, it can be hydrogenated.

Cyclic ketones

Many ketones are cyclic. The simplest class have the formula (CH2)nCO, where n varies from 2
for cyclopropanone to the teens. Larger derivatives exist. Cyclohexanone, a symmetrical cyclic
ketone, is an important intermediate in the production of nylon. Isophorone, derived from
acetone, is an unsaturated, asymmetrical ketone that is the precursor to other polymers. Muscone,
3-methylpentadecanone, is an animal pheromone. Another cyclic ketone is cyclobutanone,
having the formula C4H6O.

Keto-enol tautomerization

Main article: Enol

Keto-enol tautomerism. 1 is the keto form; 2 is the enol.

Ketones that have at least one alpha-hydrogen, undergo keto-enol tautomerization; the tautomer
is an enol. Tautomerization is catalyzed by both acids and bases. Usually, the keto form is more
stable than the enol. This equilibrium allows ketones to be prepared via the hydration of alkynes.

Acidity of ketones

Ketones are far more acidic (pKa ≈ 20) than a regular alkane (pKa ≈ 50). This difference reflects
resonance stabilization of the enolate ion that is formed upon deprotonation. The relative acidity
of the α-hydrogen is important in the enolization reactions of ketones and other carbonyl
compounds. The acidity of the α-hydrogen also allows ketones and other carbonyl compounds to
undergo nucleophilic reactions at that position, with either stoichiometric and catalytic base.

Characterization
An aldehyde differs from a ketone because of its hydrogen atom attached to its carbonyl group,
making aldehydes easier to oxidize. Ketones don't have a hydrogen atom bonded to the carbonyl
group, and are more resistant to oxidation. They are only oxidized by powerful oxidizing agents
which have the ability to cleave carbon-carbon bonds.

Spectroscopy

Ketones and aldehydes absorb strongly in the infra-red spectrum near 1700 cm−1. The exact
position of the peak depends on the substituents.

Whereas 1H NMR spectroscopy is generally not useful for establishing the presence of a ketone,
13
C NMR spectra exhibit signals somewhat downfield of 200 ppm depending on structure. Such
signals are typically weak due to the absence of nuclear Overhauser effects. Since aldehydes
resonate at similar chemical shifts, multiple resonance experiments are employed to definitively
distinguish aldehydes and ketones.

Qualitative organic tests

Ketones give positive results in Brady's test, the reaction with 2,4-dinitrophenylhydrazine to give
the corresponding hydrazone. Ketones may be distinguished from aldehydes by giving a negative
result with Tollens' reagent or with Fehling's solution. Methyl ketones give positive results for
the iodoform test.[6] Ketones also give positive results when treated with Metadinitrobenzene(m-
dinitrobenzene) in presence of dilute Sodium Hydroxide to give violet coloration.

Synthesis
Many methods exist for the preparation of ketones in industrial scale and academic laboratories.
Ketones are also produced in various ways by organisms, see the section on biochemistry below.

In industry, the most important method probably involves oxidation of hydrocarbons, often with
air. For example, a billion kilograms of cyclohexanone are produced annually by aerobic
oxidation of cyclohexane. Acetone is prepared by air-oxidation of cumene.

For specialized or small scale organic synthetic applications, ketones are often prepared by
oxidation of secondary alcohols:

R2CH(OH) + O → R2C=O + H2O

Typical strong oxidants (source of "O" in the above reaction) include potassium permanganate or
a Cr(VI) compound. Milder conditions make use of the Dess–Martin periodinane or the Moffatt–
Swern methods.

Many other methods have been developed, examples include:[7]

 By geminal halide hydrolysis.[8]

 By hydration of alkynes.[9] Such processes occur via enols and require the presence of an
acid and HgSO4. Subsequent enol–keto tautomerization gives a ketone. This reaction
always produces a ketone, even with a terminal alkyne.
 From Weinreb Amides using stoichiometric organometallic reagents.
 Aromatic ketones can be prepared in the Friedel–Crafts acylation,[10] the related Houben–
Hoesch reaction,[11] and the Fries rearrangement.[9]
 Ozonolysis, and related dihydroxylation/oxidative sequences, cleave alkenes to give
aldehydes or ketones, depending on alkene substitution pattern.[12]
 In the Kornblum–DeLaMare rearrangement ketones are prepared from peroxides and
base.
 In the Ruzicka cyclization, cyclic ketones are prepared from dicarboxylic acids.
 In the Nef reaction, ketones form by hydrolysis of salts of secondary nitro compounds.[13]
 In the Fukuyama coupling, ketones form from a thioester and an organozinc compound.
 By the reaction of an acid chloride with organocadmium compounds or organocopper
compounds.
 The Dakin–West reaction provides an efficient method for preparation of certain methyl
ketones from carboxylic acids.[14]
 Ketones can also be prepared by the reaction of Grignard reagents with nitriles, followed
by hydrolysis.[15]
  By decarboxylation of carboxylic anhydride.
 Ketones can be prepared from haloketones in reductive dehalogenation of halo ketones.
 In ketonic decarboxylation symmetrical ketones are prepared from carboxylic acids.[9][16]
 Oxidation of amines with iron(III) chloride.[17]
 Hydrolysis of unsaturated secondary amides,[18] β-Keto acid esters,[9] or β-diketones.
 Acid-catalysed rearrangement of 1,2-diols.[9]

Reactions

The Haller-Bauer reaction occurs between a non-enolizable ketone and a strong amide base. In
this prototypical example involving benzophenone, the tetrahedral intermediate expels phenyl
anion to give benzamide and benzene as the organic products

Ketones engage in many organic reactions. The most important reactions follow from the
susceptibility of the carbonyl carbon toward nucleophilic addition and the tendency for the
enolates to add to electrophiles. Nucleophilic additions include in approximate order of their
generality:[7]

 With water (hydration) gives geminal diols, which are usually not formed in appreciable
(or observable) amounts
 With an acetylide to give the α-hydroxyalkyne
 With ammonia or a primary amine gives an imine
 With secondary amine gives an enamine
 With Grignard and organolithium reagents to give, after aqueous workup, a tertiary
alcohol
 With an alcohols or alkoxides to gives the hemiketal or its conjugate base. With a diol to
the ketal. This reaction is employed to protect ketones.
 With sodium amide resulting in C–C bond cleavage with formation of the amide
RCONH2 and the alkane R'H, a reaction called the Haller–Bauer reaction.[19]
 With strong oxidizing agents to give carboxylic acids.
 Electrophilic addition, reaction with an electrophile gives a resonance stabilized cation
 With phosphonium ylides in the Wittig reaction to give the alkenes
 With thiols to give the thioacetal
 With hydrazine or 1-disubstituted derivatives of hydrazine to give hydrazones.
 With a metal hydride gives a metal alkoxide salt, hydrolysis of which gives the alcohol,
an example of ketone reduction
 With halogens to form an α-haloketone, a reaction that proceeds via an enol (see
Haloform reaction)
 With heavy water to give an α-deuterated ketone
 Fragmentation in photochemical Norrish reaction
 Reaction of 1,4-aminodiketones to oxazoles by dehydration in the Robinson–Gabriel
synthesis
 In the case of aryl–alkyl ketones, with sulfur and an amine give amides in the Willgerodt
reaction
  With hydroxylamine to produce oximes
 With reducing agents to form secondary alcohols
 With peroxy acids to form esters in the Baeyer–Villiger oxidation

Biochemistry
Ketones are pervasive in nature. The formation of organic compounds in photosynthesis occurs
via the ketone ribulose-1,5-bisphosphate. Many sugars are ketones, known collectively as
ketoses. The best known ketose is fructose, which exists as a cyclic hemiketal, which masks the
ketone functional group. Fatty acid synthesis proceeds via ketones. Acetoacetate is an
intermediate in the Krebs cycle which releases energy from sugars and carbohydrates.[20]

In medicine, acetone, acetoacetate, and beta-hydroxybutyrate are collectively called ketone

bodies, generated from carbohydrates, fatty acids, and amino acids in most vertebrates, including
humans. Ketone bodies are elevated in the blood (ketosis) after fasting, including a night of
sleep; in both blood and urine in starvation; in hypoglycemia, due to causes other than
hyperinsulinism; in various inborn errors of metabolism, and intentionally induced via a
ketogenic diet, and in ketoacidosis (usually due to diabetes mellitus). Although ketoacidosis is
characteristic of decompensated or untreated type 1 diabetes, ketosis or even ketoacidosis can
occur in type 2 diabetes in some circumstances as well.

Applications
Ketones are produced on massive scales in industry as solvents, polymer precursors, and
pharmaceuticals. In terms of scale, the most important ketones are acetone, methylethyl ketone,
and cyclohexanone.[21] They are also common in biochemistry, but less so than in organic
chemistry in general. The combustion of hydrocarbons is an uncontrolled oxidation process that
gives ketones as well as many other types of compounds.

Toxicity
Although it is difficult to generalize on the toxicity of such a broad class of compounds, simple
ketones are, in general, not highly toxic. This characteristic is one reason for their popularity as
solvents. Exceptions to this rule are the unsaturated ketones such as methyl vinyl ketone with
LD50 of 7 mg/kg (oral).[21]

See also

Wikiquote has quotations related to: Ketone

 Diketone
 Ketone bodies
 Thioketone
  Triketone
 Ynone

References
1.

 an introduction to aldehydes and ketones. Chemguide.co.uk. Retrieved on 2016-10-28.

  Harper, Douglas. "ketone". Online Etymology Dictionary.
  The word "ketone" was coined in 1848 by the German chemist Leopold Gmelin. See:
Leopold Gmelin, ed., Handbuch der organischen Chemie: Organische Chemie im Allgemeinen
… (Handbook of organic chemistry: Organic chemistry in general … ), 4th ed., (Heidelberg,
(Germany): Karl Winter, 1848), volume 1, p. 40. From page 40: "Zu diesen Syndesmiden
scheinen auch diejenigen Verbindungen zu gehören, die als Acetone im Allegemeinen (Ketone?)
bezeichnet werden." (To these syndesmides*, those compounds also seem to belong, which are
designated as acetones in general (ketones?).") [*Note: In 1844, the French chemist Auguste
Laurent suggested a new nomenclature for organic compounds. One of his new classes of
compounds was "syndesmides", which were compounds formed by the combination of two or
more simpler organic molecules (from the Greek σύνδεσμος (syndesmos, union) + -ide
(indicating a group of related compounds)). For example, acetone could be formed by the dry
distillation of metal acetates, so acetone was the syndesmide of two acetate ions. See: Laurent,
Auguste (1844) "Classification chimique," Comptes rendus, 19 : 1089–1100 ; see especially p.
1097.
  List of retained IUPAC names retained IUPAC names Link
  McMurry, John E. (1992), Organic Chemistry (3rd ed.), Belmont: Wadsworth, ISBN 0-534-
16218-5
  Mendham, J.; Denney, R. C.; Barnes, J. D.; Thomas, M. J. K. (2000), Vogel's Quantitative
Chemical Analysis (6th ed.), New York: Prentice Hall, ISBN 0-582-22628-7
  Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions,
Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN 0-471-72091-7
  Marvel, C. S.; Sperry, W. M. (1928). "Benzophenone". Organic Syntheses. 8: 26.
doi:10.15227/orgsyn.008.0026.
  Furniss, Brian; Hannaford, Antony; Smith, Peter; Tatchell, Austin (1996). Vogel's Textbook
of Practical Organic Chemistry (5th ed.). London: Longman Science & Technical. pp. 612–623,
976–977, 982–983,. ISBN 9780582462366.
  Allen, C. F. H.; Barker, W. E. (1932). "Desoxybenzoin". Organic Syntheses. 12: 16.
doi:10.15227/orgsyn.012.0016.
  Gulati, K. C.; Seth, S.R.; Venkataraman, K. (1935). "Phloroacetophenone". Organic
Syntheses. 15: 70. doi:10.15227/orgsyn.015.0070.
  Tietze, Lutz F.; Bratz, Matthias (1993). "Dialkyl Mesoxalates by Ozonolysis of Dialkyl
Benzalmalonates: Dimethyl Mesoxalate". Organic Syntheses. 71: 214.
doi:10.15227/orgsyn.071.0214.
  Heinzelman, R. V. (1955). "o-Methoxyphenylacetone". Organic Syntheses. 35: 74.
doi:10.15227/orgsyn.035.0074.
  Wiley, Richard H.; Borum, O. H. (1953). "3-Acetamido-2-butanone". Organic Syntheses.
33: 1. doi:10.15227/orgsyn.033.0001.
  Moffett, R. B.; Shriner, R. L. (1941). "ω-Methoxyacetophenone". Organic Syntheses. 21: 79.
doi:10.15227/orgsyn.021.0079.
  Thorpe, J. F.; Kon, G. A. R. (1925). "Cyclopentanone". Organic Syntheses. 5: 37.
doi:10.15227/orgsyn.005.0037.
  Fieser, Louis F. (1937). "1,2-Naphthoquinone". Organic Syntheses. 17: 68.
doi:10.15227/orgsyn.017.0068.
  Herbst, R. M.; Shemin, D. (1939). "Phenylpyruvic acid". Organic Syntheses. 19: 77.
doi:10.15227/orgsyn.019.0077.
  Haller–Bauer Reaction. homeip.net
  Nelson, D. L.; Cox, M. M. (2000) Lehninger, Principles of Biochemistry. 3rd Ed. Worth
Publishing: New York. ISBN 1-57259-153-6.

21.  Siegel, Hardo and Eggersdorfer, Manfred (2005) "Ketones" in Ullmann's Encyclopedia
of Industrial Chemistry, Wiley-VCH, Weinheim. doi:10.1002/14356007.a15_077

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