Ketones

In chemistry, a ketone (alkanone) is an organic compound with the structure RC(=O)R', where R and R' can be a variety of carbon-containing substituents. Ketones feature a carbonyl group (C=O) bonded to two other carbon atoms. 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.

Nomenclature and etymology

The word ketone derives its name from Aketon, an old German word for acetone. According to the rules of IUPAC nomenclature, ketones are named by changing the suffix -ane of the parent alkane to -anone. 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, although some introductory chemistry textbooks use names such as 2-propanone or propan-2-one instead of acetone, the simplest ketone (C H3-CO-CH3). The position of the carbonyl group is usually denoted by a number. 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. The carbonyl group is polar as a consequence of the fact that 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 "selfassociate" 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
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 3 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, 3methylpentadecanone, is an animal pheromone. Another cyclic ketone is cyclobutanone, having the formula C4H6O.

Keto-enol tautomerization
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 -hydrogen is important in the enolization reactions of ketones and other carbonyl compounds. The acidity of the -hydrogen also allows ketones and other carbonyl compounds to undergo nucleophilic reactions at that position, with either stoichiometric and catalytic base.