Aniline

From Wikipedia, the free encyclopedia

For other uses, see Aniline (disambiguation).

Aniline

IUPAC name[hide]
Phenylamine
Other names[hide]
Aminobenzene
Benzenamine

CAS number
ChemSpider
UNII
DrugBank
KEGG
ChEBI
ChEMBL
Jmol-3D images

Identifiers
62-53-3
5889
SIR7XX2F1K
DB06728
C00292
CHEBI:17296
CHEMBL538
Image 1
Image 2
SMILES

[show]
InChI
[show]
Molecular formula
Molar mass
Appearance

Properties
C6H5NH2
93.13 g/mol
colorless to yellow liquid

Density
Melting point
Boiling point
Solubility in water
Basicity (pKb)
Viscosity
Std enthalpy of
combustion cHo298
MSDS
EU classification

R-phrases
S-phrases

NFPA 704

Flash point
Autoignition
temperature

1.0217 g/mL, liquid

6.3 C; 20.7 F; 266.8 K
184.13 C; 363.43 F; 457.28 K
3.6 g/100 mL at 20 C
9.3
3.71 cP (3.71 mPas at 25 C
Thermochemistry
-3394 kJ/mol
Hazards
External MSDS
Toxic (T)
Carc. Cat. 3
Muta. Cat. 3
Dangerous for
the environment (N)
R23/24/25 R40 R41 R43
R48/23/24/25 R68 R50
(S1/2) S26 S27 S36/37/39 S45 S46
S61 S63

2
3
0
70 C; 158 F; 343 K
770 C; 1,420 F; 1,040 K

Related compounds
Related aromatic
1-Naphthylamine
amines
2-Naphthylamine
Phenylhydrazine
Related compounds Nitrosobenzene
Nitrobenzene
Supplementary data page
Structure and
n, r, etc.
properties
Thermodynamic
Phase behaviour
data
Solid, liquid, gas
Spectral data
UV, IR, NMR, MS
(verify) (what is: / ?)
Except where noted otherwise, data are given for materials in
their standard state (at 25 C (77 F), 100 kPa)
Infobox references

Aniline, phenylamine or aminobenzene is an organic compound with the formula C6H5NH2.

Consisting of a phenyl group attached to an amino group, aniline is the prototypical aromatic
amine. Being a precursor to many industrial chemicals, its main use is in the manufacture of
precursors to polyurethane. Like most volatile amines, it possesses the somewhat unpleasant

odor of rotten fish. It ignites readily, burning with a smoky flame characteristic of aromatic
compounds.

Contents

1 Production
o 1.1 Related aniline derivatives

2 Reactions
o 2.1 Oxidation
o 2.2 Electrophilic reactions at carbon
o 2.3 Reactions at nitrogen

2.3.1 Basicity

2.3.2 Acylation

2.3.3 N-Alkylation

2.3.4 Carbon disulfide derivatives

2.3.5 Diazotization

o 2.4 Other reactions

3 Uses

4 History
o 4.1 Synthetic dye industry
o 4.2 Developments in medicine
o 4.3 Rocket Fuel

5 Toxicology and testing

6 References

7 External links

Production

Aniline is mainly produced in industry in two steps from benzene. First, benzene is nitrated
using a concentrated mixture of nitric acid and sulfuric acid at 50 to 60 C, which gives
nitrobenzene. In the second step, the nitrobenzene is hydrogenated, typically at 200300 C
in presence of various metal catalysts:

Originally, the reduction was effected with a mixture of ferrous chloride and iron metal via
the Bechamp reduction.
As an alternative, aniline is also prepared from phenol and ammonia, the phenol being
derived from the cumene process.[1]
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 (chapps) of the fuchsine fusion.[citation needed]

Related aniline derivatives

Many derivatives of aniline can be prepared in similar fashion from nitrated aromatic
compounds. Nitration followed by reduction of toluene affords toluidines. Nitration of
chlorobenzene and related derivatives and reduction of the nitration products gives aniline
derivatives, e.g. 4-chloroaniline.

Reactions
The chemistry of aniline is rich because the compound has been cheaply available for many
years. Below are some classes of its reactions.

Oxidation
The oxidation of aniline has been heavily investigated, and can result in reactions localized at
nitrogen or more commonly results in the formation of new C-N bonds. In alkaline solution,
azobenzene results, whereas arsenic acid produces the violet-coloring 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 gives 4-aminophenol and para-amino diphenylamine. Oxidation with
persulfate affords a variety of polyanilines compounds. These polymers exhibit rich redox
and acid-base properties.

Polyanilines can form upon oxidation of aniline.

Electrophilic reactions at carbon

Like phenols, aniline derivatives are highly susceptible to electrophilic substitution reactions.
Its high reactivity reflects that it is an enamine, which enhances the electron-donating ability
of the ring. For example, reaction of aniline with sulfuric acid at 180 C produces sulfanilic
acid, H2NC6H4SO3H, which can be converted to sulfanilamide. Sulfanilamide is one of the
sulfa drugs, which were widely used as antibacterials in the early 20th century. The largest
scale industrial reaction of aniline involves its alkylation with formaldehyde. . An idealized
equation is shown:
2 C6H5NH2 + CH2O CH2(C6H4NH2)2 + H2O
The resulting diamine is the precursor to 4,4'-MDI and related diisocyanates.

Reactions at nitrogen
Basicity
Aniline is a weak base. Aromatic amines such as aniline are, in general, much weaker bases
than aliphatic amines because of the electron-withdrawing effect of the phenyl group. Aniline
reacts with strong acids to form anilinium (or phenylammonium) ion (C6H5-NH3+).[2]
Although aniline is weakly basic, it precipitates zinc, aluminium, and ferric salts, and, on
warming, expels ammonia from its salts. The weak basicity is due to both an inductive effect
from the more electronegative sp2 carbon and to a resonance effect, as the lone pair on the
nitrogen is partially delocalized into the pi system of the benzene ring.
Acylation
Aniline reacts with carboxylic acids[3] 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-CO-NH-C6H5 is acetanilide. Antifebrin (acetanilide), an anti-pyretic and
analgesic,[4] is obtained by the reaction of acetic acid and aniline.
N-Alkylation
N-Methylation of aniline with methanol at elevated temperatures over acid catalysts gives Nmethylaniline and dimethylaniline:
C6H5NH2 + 2 CH3OH C6H5N(CH3)2 + 2H2O
N-Methylaniline and dimethylaniline are colorless liquids with boiling points of 193195 C
and 192 C, respectively. These derivatives are of importance in the color industry. Aniline
combines directly with alkyl iodides to form secondary and tertiary amines.

Carbon disulfide derivatives

Boiled with carbon disulfide, it gives sulfocarbanilide (diphenylthiourea) (CS(NHC6H5)2),
which may be decomposed into phenyl isothiocyanate(C6H5CNS), and triphenyl guanidine
(C6H5N=C(NHC6H5)2).
Diazotization
Aniline and its ring-substituted derivatives react with nitrous acid to form diazonium salts.
Through these intermediates, aniline can be conveniently converted to -OH, -CN, or a halide
via Sandmeyer reactions. This diazonium salt can also be reacted with NaNO2 and phenol
which produces a dye which is benzeneazophenol, this process is called coupling.

Other reactions
It reacts with nitrobenzene to produce phenazine in the Wohl-Aue reaction. Hydrogenation
gives cyclohexylamine.
Being a standard reagent in laboratories, aniline is used for many niche reactions. Its acetate
is used in the Aniline acetate test for carbohydrates, identifying pentoses by conversion to
furfural. It is used to stain neural RNA blue in the Nissl stain.[citation needed]

Uses
The largest application of aniline is for the preparation of methylene dianiline and related
compounds by condensation with formaldehyde as discussed above). The diamines are
condensed with phosgene to give Methylene diphenyl diisocyanate, a precursor to urethane
polymers.[1] Other uses include rubber processing chemicals (9%), herbicides (2%), and dyes
and pigments (2%).[5] As additives to rubber, aniline derivatives such as phenylenediamines
and diphenylamine, are antioxidants. Illustrative of the drugs prepared from aniline is
paracetamol (acetaminophen, Tylenol). The principal use of aniline in the dye industry is as a
precursor to indigo, the blue of blue jeans.[1]

Cake of indigo dye, which is prepared from aniline.

Aniline is also used at a smaller scale in the production of the intrinsically conducting
polymer polyaniline.

History
Aniline was first isolated by destructive distillation of indigo by Otto Unverdorben,[6] who
named it Crystallin. In 1834, Friedlieb Runge isolated from coal tar a substance that turned a
beautiful blue color when treated with chloride of lime, and he named it kyanol or cyanol.[7]
In 1840, Carl Julius Fritzsche (18081871) treated indigo with caustic potash and obtained an
oil that he named aniline, after an indigo-yielding plant, Ail (Indigofera suffruticosa).[8][9] In
1842, Nikolay Nikolaevich Zinin reduced nitrobenzene and obtained a base that he named
benzidam.[10] In 1843, August Wilhelm von Hofmann showed that all of these substances are
the same substance thereafter known as phenylamine or aniline.[11]

Synthetic dye industry

In 1856, von Hofmann's student William Henry Perkin discovered mauveine and went into
industry producing the first synthetic dye. Other aniline dyes followed, such as fuchsine,
safranine, and induline. At the time of mauveine's discovery, aniline was expensive. Soon
thereafter, applying a method reported in 1854 by Antoine Bchamp,[12] it was prepared "by
the ton".[13] The Bchamp reduction enabled the evolution of a massive dye industry in
Germany. Today, the name of BASF, originally Badische Anilin- und Soda-Fabrik, now
among the largest chemical suppliers, echoes the legacy of the synthetic dye industry, built
via aniline dyes and extended via the related azo dyes. The first azo dye was aniline yellow.
[14]

Developments in medicine
In the late 19th century, aniline emerged as an analgesic drug, its cardiac-suppressive side
effects countered with caffeine.[15] During the first decade of the 20th century, while trying to
modify synthetic dyes to treat African sleeping sickness, Paul Ehrlich who had coined the
term chemotherapy for his magic bullet approach to medicine failed and switched to
modifying Bchamp's atoxyl, the first organic arsenical drug, and serendipitously obtained a
treatment for syphilis salvarsan the first successful chemotherapy agent. Salvarsan's
targeted microorganism, not yet recognized as a bacterium, was still thought to be a parasite,
and medical bacteriologists, believing that bacteria were not susceptible to the
chemotherapeutic approach, overlooked Alexander Fleming's report in 1928 on the effects of
penicillin.[16]
In 1932, Bayer sought medical applications of its dyes. Gerhard Domagk identified as an
antibacterial a red azo dye, introduced in 1935 as the first antibacterial drug, prontosil, soon
found at Pasteur Institute to be a prodrug degraded in vivo into sulfanilamide a colorless
intermediate for many, highly colorfast azo dyes already with an expired patent,
synthesized in 1908 in Vienna by the researcher Paul Gelmo for his doctoral research.[16] By
the 1940s, over 500 related sulfa drugs were produced.[16] Medications in high demand during
World War II (193945), these first miracle drugs, chemotherapy of wide effectiveness,
propelled the American pharmaceutics industry.[17] In 1939, at Oxford University, seeking an
alternative to sulfa drugs, Howard Florey developed Fleming's penicillin into the first
systemic antibiotic drug, penicillin G. (Gramicidin, developed by Ren Dubos at Rockefeller

Institute in 1939, was the first antibiotic, yet its toxicity restricted it to topical use.) After
World War II, Cornelius P. Rhoads introduced the chemotherapeutic approach to cancer
treatment.[18]

Rocket Fuel
In the 1940's and early 1950's, aniline was used with nitric acid as rocket fuel for small
missiles and jet assisted take-off (JATO). The two fuel components are hypergolic, producing
a violent reaction on contact.[19]

Toxicology and testing

Aniline is toxic by inhalation of the vapour, ingestion, or percutaneous absorption.[20][21] The
IARC lists it in Group 3 (not classifiable as to its carcinogenicity to humans) due to the
limited and contradictory data available. The early manufacture of aniline resulted in
increased incidents of bladder cancer, but these effects are now attributed to naphthylamines,
not anilines.[1]
Many methods exist for detection of aniline.[22] It is metabolized to p-aminophenol and pacetamidophenol, which are excreted in urine as sulfate and glucuronide conjugates. On
hydrolysis of urine, p-aminophenol is reformed, and can be detected using the o-cresol test.

References
This article incorporates text from a publication now in the public
domain: Chisholm, Hugh, ed. (1911). Encyclopdia Britannica (11th ed.). Cambridge
University Press
1. ^ Jump up to: a b c d Thomas Kahl, Kai-Wilfrid Schrder, F. R. Lawrence, W. J.
Marshall, Hartmut Hke, Rudolf Jckh "Aniline" in Ullmann's Encyclopedia of
Industrial Chemistry 2007; John Wiley & Sons: New
York.doi:10.1002/14356007.a02_303
2. Jump up ^ McMurry, John E. (1992), Organic Chemistry (3rd ed.), Belmont:
Wadsworth, ISBN 0-534-16218-5
3. Jump up ^ Carl N. Webb (1941), "Benzanilide", Org. Synth.; Coll. Vol. 1: 82
4. Jump up ^ No longer in common medicinal use.
5. Jump up ^ "Aniline". The Chemical Market Reporter. Retrieved 2007-12-21.
6. Jump up ^ Otto Unverdorben (1826). "Ueber das Verhalten der organischen Krper
in hheren Temperaturen" [On the behaviour of organic substances at high
temperatures]. Annalen der Physik und Chemie 8 (11): 397410.
Bibcode:1826AnP....84..397U. doi:10.1002/andp.18260841109.

7. Jump up ^ F. F. Runge (1834) "Ueber einige Produkte der Steinkohlendestillation"

(On some products of coal distillation), Annalen der Physik und Chemie, 31 : 6577
(see page 65), 513524; and 32 : 308332 (see page 331).
8. Jump up ^ J. Fritzsche (1840) "Ueber das Anilin, ein neues Zersetzungsproduct des
Indigo" (On aniline, a new decomposition product of indigo), Bulletin Scientifique
[publi par l'Acadmie Impriale des Sciences de Saint-Petersbourg], 7 (12) : 161
165. Reprinted in:
o J. Fritzsche (1840) "Ueber das Anilin, ein neues Zersetzungsproduct des
Indigo," Justus Liebigs Annalen der Chemie, 36 (1) : 8490.
o J. Fritzsche (1840) "Ueber das Anilin, ein neues Zersetzungsproduct des
Indigo", Journal fr praktische Chemie, 20 : 453457. In a postscript to this
article, Erdmann (one of the journal's editors) argues that aniline and the
"cristallin", which was found by Unverdorben in 1826, are the same
substance ; see pages 457459.
9. Jump up ^ synonym I anil, ultimately from Sanskrit "nla", dark-blue.
10. Jump up ^ N. Zinin (1842). "Beschreibung einiger neuer organischer Basen,
dargestellt durch die Einwirkung des Schwefelwasserstoffes auf Verbindungen der
Kohlenwasserstoffe mit Untersalpetersure" (Description of some new organic bases,
produced by the action of hydrogen sulfide on compounds of hydrocarbons and
hyponitric acid [H2N2O3]), Bulletin Scientifique [publi par l'Acadmie Impriale des
Sciences de Saint-Petersbourg], 10 (18) : 272285. Reprinted in: N. Zinin (1842)
"Beschreibung einiger neuer organischer Basen, dargestellt durch die Einwirkung des
Schwefelwasserstoffes auf Verbindungen der Kohlenwasserstoffe mit
Untersalpetersure," Journal fr praktische Chemie, 27 (1): 140153. Benzidam is
named on page 150. Fritzsche, Zinin's colleague, soon recognized that "benzidam"
was actually aniline. See: Fritzsche (1842) Bulletin Scientifique, 10 : 352. Reprinted
as a postscript to Zinin's article in: J. Fritzsche (1842) "Bemerkung zu vorstehender
Abhandlung des Hrn. Zinin" (Comment on the preceding article by Mr. Zinin),
Journal fr praktische Chemie, 27 (1) : 153.
See also: (Anon.) (1842) "Organische Salzbasen, aus Nitronaphtalose und Nitrobenzid
mittelst Schwefelwasserstoff entstehend" (Organic bases originating from
nitronaphthalene and nitrobenzene via hydrogen sulfide), Annalen der Chemie und
Pharmacie, 44 : 283287.
11. Jump up ^ August Wilhelm Hofmann (1843) "Chemische Untersuchung der
organischen Basen im Steinkohlen-Theerl" (Chemical investigation of organic bases
in coal tar oil), Annalen der Chemie und Pharmacie, 47 : 3787. On page 48,
Hofmann argues that krystallin, kyanol, benzidam, and aniline are identical.
12. Jump up ^ A. Bchamp (1854) "De l'action des protosels de fer sur la nitronaphtaline
et la nitrobenzine. Nouvelle mthode de formation des bases organiques artificielles
de Zinin" (On the action of iron protosalts on nitronaphthaline and nitrobenzene. New
method of forming Zinin's synthetic organic bases.), Annales de Chemie et de
Physique, 3rd series, 42 : 186 196. (Note: In the case of a metal having two or more
distinct oxides (e.g., iron), a "protosalt" is an obsolete term for a salt that is obtained

from the oxide containing the lowest proportion of oxygen to metal; e.g., in the case
of iron, which has two oxides iron (II) oxide (FeO) and iron (III) oxide (Fe2O3)
FeO is the "protoxide" from which protosalts can be made. See: Wiktionary:
protosalt.)
13. Jump up ^ Perkin, William Henry. 1861-06-08. "Proceedings of Chemical Societies:
Chemical Society, Thursday, May 16, 1861." The Chemical News and Journal of
Industrial Science. Retrieved on 2007-09-24.
14. Jump up ^ Auerbach G, "Azo and naphthol dyes", Textile Colorist, 1880
May;2(17):137-9, p 138.
15. Jump up ^ Wilcox RW, "The treatment of influenza in adults", Medical News, 1900
Dec 15;77():931-2, p 932.
16. ^ Jump up to: a b c D J Th Wagener, The History of Oncology (Houten: Springer,
2009), pp 1501.
17. Jump up ^ John E Lesch, The First Miracle Drugs: How the Sulfa Drugs
Transformed Medicine (New York: Oxford University Press, 2007), pp 2023.
18. Jump up ^ "Medicine: Spoils of war", Time, 15 May 1950.
19. Jump up ^ "Hypergolic propellant", Wikipedia
20. Jump up ^ Muir, GD (ed.) 1971, Hazards in the Chemical Laboratory, The Royal
Institute of Chemistry, London.
21. Jump up ^ The Merck Index. 10th ed. (1983), p.96, Rahway: Merck & Co.
22. Jump up ^ Basic Analytical Toxicology (1995), R. J. Flanagan, S. S. Brown, F. A. de
Wolff, R. A. Braithwaite, B. Widdop: World Health Organization

External links
Wikimedia Commons has media related to Aniline.

International Chemical Safety Card 0011

CDC - NIOSH Pocket Guide to Chemical Hazrds

Aniline electropolymerisation

Aniline in the ChemIDplus database

Categories:

Anilines

Dyes

Hazardous air pollutants

IARC Group 3 carcinogens

Navigation menu

Create account

Log in

Article

Talk

Read

Edit

View history

Main page

Contents

Featured content

Current events

Random article

Donate to Wikipedia

Interaction

Help

About Wikipedia

Community portal

Recent changes

Contact page

Tools
Print/export
Languages

Catal

etina

Dansk

Deutsch

Eesti

Espaol

Euskara

Franais

Gaeilge

Ido

Italiano

Latvieu

Magyar

Nederlands

Norsk bokml

Polski

Portugus

Romn

Slovenina

Slovenina

/ srpski

Suomi

Svenska

Trke

Ting Vit

Edit links

This page was last modified on 5 January 2014 at 04:24.

Text is available under the Creative Commons Attribution-ShareAlike License;

additional terms may apply. By using this site, you agree to the Terms of Use and
Privacy Policy.
Wikipedia is a registered trademark of the Wikimedia Foundation, Inc., a non-profit
organization.

Privacy policy

About Wikipedia

Disclaimers

Contact Wikipedia

Developers

Mobile view