Overview

Aniline, phenylamine or aminobenzene is an organic compound with the formula C6H7N. It is the simplest and one of the most important aromatic amines, being used as a precursor to more complex chemicals. Its main application is in the manufacture of polyurethane. Like most volatile amines, it possesses the somewhat unpleasant odour of rotten fish and also has a burning aromatic taste; it is a highly-acrid poison. It ignites readily, burning with a smoky flame.

Synthesis

Aniline is usually produced in two steps starting from benzene. First, benzene is nitrated using a concentrated mixture of nitric acid and sulphuric acid at 50 to 60 °C, which gives nitrobenzene. In the second step, the nitrobenzene is hydrogenated, typically at 600 °C in presence of a nickel catalyst to give aniline. As an alternative, aniline is also prepared from phenol and ammonia, the phenol being derived from cumene.

Uses

The great commercial value of aniline was due to the readiness with which it yields, directly or indirectly, dyestuffs. The discovery of mauve in 1856 by William Henry Perkin was the first of a series of dyestuffs that are now to be numbered by hundreds. Reference should be made to the articles dyeing, fuchsine, safranine, indulines, for more details on this subject. In addition to its use as a precursor to dyestuffs, it is a starting-product for the manufacture of many drugs, such as paracetamol (acetaminophen, Tylenol).

It is used to stain neural RNA blue in the Nissl stain.

At the present time, the largest market for aniline is preparation of methylene diphenyl diisocyanate (MDI), some 85% of aniline serving this market. Other uses include rubber processing chemicals (9%), herbicides (2%), and dyes and pigments (2%).

When polymerized, aniline can be used as a type of nanowire for use as a semiconducting electrode bridge, most recently used for nano-scale devices such as biosensors. These polyaniline nanowires can be doped with a dopant accordingly in order to achieve certain semiconducting properties.

Derivatives

Many derivatives of aniline can be prepared in similar fashion. In commerce, three brands of aniline are distinguished: aniline oil for blue, which is pure aniline; aniline oil for red, a mixture of equimolecular quantities of aniline and ortho- and para-toluidines; and aniline oil for safranine, which contains aniline and ortho-toluidine, and is obtained from the distillate of the fuchsine fusion.

History

Aniline was first isolated from the destructive distillation of indigo in 1826 by Otto Unverdorben, who named it crystalline. In 1834, Friedrich Runge (Pogg. Ann., 1834, 31, p. 65; 32, p. 331) isolated from coal tar a substance that produced a beautiful blue colour on treatment with chloride of lime, which he named kyanol or cyanol. In 1841, C. J. Fritzsche showed that, by treating indigo with caustic potash, it yielded an oil, which he named aniline, from the specific name of one of the indigo-yielding plants, Indigofera anil, anil being derived from the Sanskrit n?la, dark-blue, and n?l?, the indigo plant. About the same time N. N. Zinin found that, on reducing nitrobenzene, a base was formed, which he named benzidam. August Wilhelm von Hofmann investigated these variously-prepared substances, and proved them to be identical (1855), and thenceforth they took their place as one body, under the name aniline or phenylamine.

Its first industrial-scale use was in the manufacture of mauveine, a purple dye discovered in 1856 by Hofmann's student William Henry Perkin. At the time of mauveine's discovery, aniline was an expensive laboratory compound, but it was soon prepared "by the ton" using a process previously discovered by Antoine Béchamp. The synthetic dye industry grew rapidly as new aniline-based dyes were discovered in the late 1850s and 1860s.

p-Toluidine, an aniline derivative, can be used in qualitative analysis to prepare carboxylic acid derivatives.

Toxicology

Aniline is toxic by inhalation of the vapour, absorption through the skin or swallowing. It causes headache, drowsiness, cyanosis, and mental confusion, and, in severe cases, can cause convulsions. Prolonged exposure to the vapour or slight skin exposure over a period of time affects the nervous system and the blood, causing tiredness, loss of appetite, headache, and dizziness.

Oil mixtures containing rapeseed oil denatured with aniline have been clearly linked by epidemiological and analytic chemical studies to the toxic oil syndrome that hit Spain in the spring and summer of 1981, in which 20,000 became acutely ill, 12,000 were hospitalized, and more than 350 died in the first year of the epidemic. The precise etiology though remains unknown.

Some authorities class aniline as a carcinogen, although the IARC lists it in Group 3 (not classifiable as to its carcinogenicity to humans) due to the limited and contradictory data available.