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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.
Structure and synthesis
Consisting of a phenyl group
attached to an amino group
, aniline is usually produced in industry in two steps 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.
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
(échappés) of the fuchsine
Aniline is colourless, it slowly oxidizes
and resinifies in air, giving a red-brown tint to aged samples. The oxidation of aniline has been carefully investigated. In alkaline solution, azobenzene
results, whereas arsenic acid
produces the violet-colouring matter violaniline. Chromic acid
converts it into quinone
, whereas chlorates
, in the presence of certain metallic salts (especially of vanadium
), give aniline black
. Hydrochloric acid and potassium chlorate give chloranil. Potassium permanganate
in neutral solution oxidizes it to nitrobenzene
, in alkaline solution to azobenzene
, ammonia and oxalic acid
, in acid solution to aniline black. Hypochlorous acid
and para-amino diphenylamine
Aniline is a weak base
. Aromatic amines
such as aniline are, in general, much weaker bases than aliphatic
amines. Aniline reacts with strong acids to form anilinium
(or phenylammonium) ion (C6
). The sulfate
forms beautiful white plates. Although aniline is weakly basic, it precipitates zinc
, and ferric
salts, and, on warming, expels ammonia
from its salts.
Aniline reacts with carboxylic acids or more readily with acyl chlorides
such as acetyl chloride
to give amides
. The amides formed from aniline are sometimes called anilides
, for example CH3
. Antifebrin (acetanilide
), an anti-pyretic and analgesic, is obtained by the reaction of acetic acid
Aniline combines directly with alkyl iodides
to form secondary and tertiary amines. Monomethyl and dimethyl aniline are colourless liquids prepared by heating aniline, aniline hydro-chloride and methyl alcohol
in an autoclave
at 220 °C. They are of great importance in the colour industry. Monomethyl aniline boils at 193-195 °C, dimethyl aniline at 192 °C.
Boiled with carbon disulfide
, it gives sulfocarbanilide (diphenyl thiourea
, which may be decomposed into phenyl isothiocyanate
CNS, and triphenyl guanidine
Like phenols, aniline derivatives are highly susceptible to electrophilic substitution reactions. For example, reaction of aniline with sulfuric acid at 180 °C produces sulfanilic acid, NH2C6H4SO3H, which can be converted to sulfanilamide. Sulfanilamide is one of the sulfa drugs that were widely used as antibacterials in the early 20th century.
Aniline and its ring-substituted derivatives react with nitrous acid
to form diazonium salts
. Through these, the -NH2
group of aniline can be conveniently converted to -OH, -CN, or a halide
via Sandmeyer reactions
It reacts with nitrobenzene to produce phenazine
in the Wohl-Aue reaction
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
, 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
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.
Aniline was first isolated from the destructive distillation of indigo
in 1826 by Otto Unverdorben
, who named it crystalline. In 1834, Friedrich Runge
, 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 nīla
, dark-blue, and nīlā
, 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.
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.