Nitration

Nitration is a general class of a chemical process for the

introduction of a nitro group into an organic chemical compound.
More loosely the term also is applied incorrectly to the different
process of forming nitrate esters between alcohols and nitric
acid, as occurs in the synthesis of nitroglycerin. The difference
between the resulting structure of nitro compounds and nitrates
is that the nitrogen atom in nitro compounds is directly bonded to
a non-oxygen atom, typically carbon or another nitrogen atom,
whereas in nitrate esters, also called organic nitrates, the nitrogen
is bonded to an oxygen atom that in turn usually is bonded to a
carbon atom (nitrito group).

There are many major industrial applications of nitration in the

strict sense; the most important by volume are for the production
of Nitroaromatic compounds such as nitrobenzene. Nitration
reactions are notably used for the production of explosives, for
example the conversion of guanidine to nitroguanidine and the
conversion of toluene to trinitrotoluene. However, they are of wide
importance as chemical intermediates and precursors. Millions of
tons of nitroaromatics are produced annually.[1]

Aromatic nitration
Typical nitration syntheses apply so-called "mixed acid", a mixture
of concentrated nitric acid and sulfuric acids.[2] This mixture
produces the nitronium ion (NO2+), which is the active species in
aromatic nitration. This active ingredient, which can be isolated in
the case of nitronium tetrafluoroborate,[3] also effects nitration
without the need for the mixed acid. In mixed-acid syntheses
sulfuric acid is not consumed and hence acts as a catalyst as
well as an absorbent for water. In the case of nitration of benzene,
the reaction is conducted at a warm temperature, not exceeding
50 °C. [4] The process is one example of electrophilic aromatic
substitution, which involves the attack by the electron-rich
benzene ring:
Alternative mechanisms have also been proposed, including one
involving single electron transfer (SET).[5][6]

Scope
Selectivity can be a challenge in nitrations because as a rule more
than one compound may result but only one is desired, so
alternative products act as contaminants or are simply wasted.
Accordingly, it is desirable to design syntheses with suitable
selectivity; for example, by controlling the reaction conditions,
fluorenone can be selectively trinitrated[7] or tetranitrated.[8]

The substituents on aromatic rings affect the rate of this

electrophilic aromatic substitution. Deactivating groups such as
other nitro groups have an electron-withdrawing effect. Such
groups deactivate (slow) the reaction and directs the electrophilic
nitronium ion to attack the aromatic meta position. Deactivating
meta-directing substituents include sulfonyl, cyano groups, keto,
esters, and carboxylates. Nitration can be accelerated by
activating groups such as amino, hydroxy and methyl groups also
amides and ethers resulting in para and ortho isomers.

The direct nitration of aniline with nitric acid and sulfuric acid,
according to one source,[9] results in a 50/50 mixture of para- and
meta-nitroaniline isomers. In this reaction the fast-reacting and
activating aniline (ArNH2) exists in equilibrium with the more
abundant but less reactive (deactivated) anilinium ion (ArNH3+),
which may explain this reaction product distribution. According to
another source,[10] a more controlled nitration of aniline starts
with the formation of acetanilide by reaction with acetic anhydride
followed by the actual nitration. Because the amide is a regular
activating group the products formed are the para and ortho
isomers. Heating the reaction mixture is sufficient to hydrolyze
the amide back to the nitrated aniline.

In the Wolffenstein–Böters reaction, benzene reacts with nitric

acid and mercury(II) nitrate to give picric acid.

Ipso nitration
With aryl chlorides, triflates and nonaflates ipso substitution can
take place as well in so-called ipso nitration.[11] The phrase was
first used by Perrin and Skinner in 1971 in an investigation into
chloroanisole nitration [12] In one protocol 4-chloro-n-butylbenzene
is reacted with sodium nitrite in t-butanol in presence of 0.5 mol%
Pd2(dba)3, a biarylphosphine ligand and a phase-transfer catalyst
to 4-nitro-n-butylbenzene [13]

See also
Menke nitration

Zincke nitration
Reactive nitrogen species

References
1. Gerald Booth (2007). "Nitro Compounds, Aromatic". Ullmann's
Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH.
doi:10.1002/14356007.a17_411 .

2. John McMurry Organic Chemistry 2nd Ed.

3. George A. Olah and Stephen J. Kuhn. "Benzonitrile, 2-methyl-

3,5-dinitro-" . Organic Syntheses.; Collective Volume, 5, p. 480

4. https://www.chemguide.co.uk/organicprops/arenes/nitration
.html

5. Esteves, P. M.; Carneiro, J. W. M.; Cardoso, S. P.; Barbosa, A. G.

H.; Laali, K. K.; Rasul, G.; Prakash, G. K. S.; e Olah, G. A. (2003).
"Unified Mechanism Concept of Electrophilic Aromatic
Nitration Revisited: Convergence of Computational Results
and Experimental Data". J. Am. Chem. Soc. 125 (16): 4836–
49. doi:10.1021/ja021307w . PMID 12696903 .

6. Queiroz, J. F.; Carneiro, J. W. M.; Sabino A. A.; Sparapan, R.;

Eberlin, M. N.; Esteves, P. M. (2006). "Electrophilic Aromatic
Nitration: Understanding Its Mechanism and Substituent
Effects". J. Org. Chem. 71 (16): 6192–203.
doi:10.1021/jo0609475 . PMID 16872205 .
 7. E. O. Woolfolk and Milton Orchin. "2,4,7-Trinitrofluorenone" .
Organic Syntheses.; Collective Volume, 3, p. 837

8. Melvin S. Newman and H. Boden. "2,4,5,7-

Tetranitrofluorenone" . Organic Syntheses.; Collective Volume,
5, p. 1029

9. Web resource: warren-wilson.edu

10. Mechanism and synthesis Peter Taylor, Royal Society of

Chemistry (Great Britain), Open University

11. Prakash, G.; Mathew, T. (2010). "Ipso-Nitration of Arenes".

Angewandte Chemie International Edition in English. 49 (10):
1726–1728. doi:10.1002/anie.200906940 . PMID 20146295 .

12. Perrin, C. L.; Skinner, G. A. (1971). "Directive effects in

electrophilic aromatic substitution ("ipso factors"). Nitration of
haloanisoles". Journal of the American Chemical Society. 93
(14): 3389. doi:10.1021/ja00743a015 .

13. Fors, B.; Buchwald, S. (2009). "The Pd-Catalyzed Conversion of

Aryl Chlorides, Triflates, and Nonaflates to Nitroaromatics" .
Journal of the American Chemical Society. 131 (36): 12898–
12899. doi:10.1021/ja905768k . PMC 2773681 .
PMID 19737014 .
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