In chemistry, a racemic mixture or racemate (), is one that has equal amounts of left- and right-handed enantiomers of a chiral molecule or salt. Racemic mixtures are rare in nature, but many compounds are produced industrially as racemates.
History
The first known racemic mixture was racemic acid, which Louis Pasteur found to be a mixture of the two enantiomeric isomers of tartaric acid. He manually separated the crystals of a mixture by hand, starting from an aqueous solution of the sodium ammonium salt of racemate tartaric acid. Pasteur benefited from the fact that ammonium tartrate salt gives enantiomeric crystals with distinct crystal forms (at 77 °F). Reasoning from the macroscopic scale down to the molecular, he reckoned that the molecules had to have non-superimposable mirror images. A sample with only a single enantiomer is an enantiomerically pure or enantiopure compound.
Etymology
From racemic acid found in grapes; from Latin racemus, meaning a bunch of grapes. This acid, when naturally produced in grapes, is only the right-handed version of the molecule, better known as tartaric acid. In many Germanic languages racemic acid is called “grape acid” e.g. German traubensäure and Swedish druvsyra. Carl von Linné gave red elderberry the scientific name Sambucus racemosa as the Swedish name, druvfläder, means 'grape elder', so called because its berries grow in a grape-like cluster.
Nomenclature
A racemic mixture is denoted by the prefix (±)- or dl- (for sugars the prefix - may be used), indicating an equal (1:1) mixture of dextro and levo isomers. Also the prefix rac- (or racem-) or the symbols RS and SR (all in italic letters) are used.
If the ratio is not 1:1 (or is not known), the prefix (+)/(−), - or d/l- (with a slash) is used instead.
The usage of d and l is discouraged by IUPAC.
Properties
A racemate is optically inactive (achiral), meaning that such materials do not rotate the polarization of plane-polarized light. Although the two enantiomers rotate plane-polarized light in opposite directions, the rotations cancel each other out because they are present in equal amounts of negative (-) counterclockwise (levorotatory) and positive (+) clockwise (dextrorotatory) enantiomers.
In contrast to the two pure enantiomers, which have identical physical properties except for the direction of rotation of plane-polarized light, a racemate sometimes has different properties from either of the pure enantiomers. Different melting points are most common, but different solubilities and boiling points are also possible.
Pharmaceuticals may be available as a racemate or as the pure enantiomer, which might have different potencies. Because biological systems have many chiral asymmetries, pure enantiomers frequently have very different biological effects; examples include glucose and methamphetamine.
Crystallization
There are four ways to crystallize a racemate; three of which H. W. B. Roozeboom had distinguished by 1899:
Conglomerate (sometimes racemic conglomerate)If the molecules of the substance have a much greater affinity for the same enantiomer than for the opposite one, a mechanical mixture of enantiomerically pure crystals will result. The mixture of enantiomerically pure R and S crystals forms a eutectic mixture. Consequently, the melting point of the conglomerate is always lower than that of the pure enantiomer. Addition of a small amount of one enantiomer to the conglomerate increases the melting point. Roughly 10% of racemic chiral compounds crystallize as conglomerates.
Racemic compound (sometimes true racemate)If molecules have a greater affinity for the opposite enantiomer than for the same enantiomer, the substance forms a single crystalline phase in which the two enantiomers are present in an ordered 1:1 ratio in the elementary cell. Adding a small amount of one enantiomer to the racemic compound decreases the melting point. But the pure enantiomer can have a higher or lower melting point than the compound. A special case of racemic compounds are kryptoracemic compounds (or kryptoracemates), in which the crystal itself has handedness (is enantiomorphic), despite containing both enantiomorphs in a 1:1 ratio.
Pseudoracemate (sometimes racemic solid solution) When there is no big difference in affinity between the same and opposite enantiomers, then in contrast to the racemic compound and the conglomerate, the two enantiomers will coexist in an unordered manner in the crystal lattice. Addition of a small amount of one enantiomer changes the melting point slightly or not at all.