4/27/2018 Nitro compound - Wikipedia

Nitro compound
Nitro com pounds are organic compounds that contain one or more nitro
functional groups (−NO2 ). The nitro group is one of the most common explosophores
(functional group that makes a compound explosiv e) used globally . The nitro group is
also strongly electron-withdrawing. Because of this property , C−H bonds alpha
(adjacent) to the nitro group can be acidic. For similar reasons, the presence of nitro
groups in aromatic compounds retards electrophilic aromatic substitution but
facilitates nucleophilic aromatic substitution. Nitro groups are rarely found in nature,
being almost inv ariably produced by nitration reactions starting with nitric acid.
The structure of the nitro
group

Contents
Production and occurrence
Preparation of aromatic nitro compounds
Preparation of aliphatic nitro compounds
Ter Meer Reaction
Occurrence in nature
Reactions of aliphatic nitro compounds
Reduction
Acid-base reactions
Condensation reactions
Biochemical reactions
Reactions of aromatic nitro compounds
Explosions
See also
References

Production and occurrence

Preparation of aromatic nitro compounds

Aromatic nitro compounds are ty pically sy nthesized by nitration. Nitration is achiev ed using a mixture of nitric acid
and sulfuric acid, which produce the nitronium ion (NO2 + ), which the electrophile:

H+
+

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The nitration product produced on the largest scale, by far, is nitrobenzene. Many explosiv es are produced by
nitration including trinitrophenol (picric acid), trinitrotoluene (TNT), and trinitroresorcinol (sty phnic acid). [1]
Another but more specialized method for making ary l-NO2 group starts from halogenated phenols, is the Zinke
nitration.

Preparation of aliphatic nitro compounds

Aliphatic nitro compounds can be sy nthesized by v arious methods; notable examples include:

Free radical nitration of alkanes.[2] The reaction produces fragments from the parent alkane, creating a diverse mixture
of products; for instance, nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane are produced by treating
propane with nitric acid in the gas phase (e.g. 350–450 °C and 8–12 atm).
Nucleophilic substitution reactions between halocarbons[3] or organosulfates[4] with silver or alkali nitrite salts.
Nitromethane can be produced in the laboratory by treating sodium chloroacetate with sodium nitrite.[5]
Oxidation of oximes[6] or primary amines.[7]
By decarboxylation of α-nitro carboxylic acids formed from nitriles and ethyl nitrate.[8][9]

Ter Meer Reaction

In nucleophilic aliphatic substitution, sodium nitrite (NaNO2 ) replaces an alky l halide. In the so-called Ter Meer
reaction (187 6) named after Edmund ter Meer, [10] the reactant is a 1,1-halonitroalkane:

The reaction mechanism is proposed in which in the first slow step a proton is abstracted from nitroalkane 1 to a
carbanion 2 followed by protonation to a nitronate 3 and finally nucleophilic displacement of chlorine based on an
experimentally observ ed hy drogen kinetic isotope effect of 3.3. [11] When the same reactant is reacted with
potassium hy droxide the reaction product is the 1,2-dinitro dimer. [12]

Occurrence in nature
Chloramphenicol is a rare example of a naturally occurring nitro compound. At least some naturally occurring nitro
groups arose by the oxidation of amino groups. [13] 2-Nitrophenol is an aggregation pheromone of ticks.

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Examples of nitro compounds are rare in nature. 3-Nitropropionic acid found in fungi and plants (Indigofera).
Nitropentadecene is a defense compound found in termites. Nitropheny lethane is found in Aniba canelilla. [14]
Nitropheny lethane is also found in members of the Annonaceae, Lauraceae and Papav eraceae. [15]

Reactions of aliphatic nitro compounds

Reduction
Nitro compounds participate in sev eral organic reactions, the most important being their reduction to the
corresponding amines:

RNO2 + 3 H2 → RNH2 + 2 H2O

Acid-base reactions
Nitroalkanes are somewhat acidic. The pKa s of nitromethane and isopropy l nitrate, are 17 .2 and 16.9 in dimethy l
sulfoxide (DMSO) solution. These v alues suggest aqueous pKa s of around 11. [16] In other words, these carbon acids
can be deprotonated in aqueous solution. The conjugate base is called nitronate. Nitronates protonate at oxy gen to
giv e a tautomer of nitroalky l precursor. This process is the start of a reaction that conv erts nitronates to aldehy des
or ketones, called the Nef reaction.

Condensation reactions
Nitromethane undergoes base-cataly zed additions to aldehy des in 1,2-addition in the nitroaldol reaction. Similarly ,
it adds to alpha-beta unsaturated carbony l compounds as a 1,4-addition in the Michael reaction as a Michael donor.
Nitroalkenes are Michael acceptors in the Michael reaction with enolate compounds. [17][18]

Biochemical reactions
Many flav in-dependent enzy mes are capable of oxidizing aliphatic nitro compounds to less-toxic aldehy des and
ketones. Nitroalkane oxidase and 3-nitropropionate oxidase oxidize aliphatic nitro compounds exclusiv ely , whereas
other enzy mes such as glucose oxidase hav e other phy siological substrates. [19]

Reactions of aromatic nitro compounds

Reduction of aromatic nitro compounds with hy drogen ov er metal cataly sts giv es anilines. Virtually all aromatic
amines (anilines) are deriv ed from nitroaromatics. A v ariation is formation of a dimethy laminoarene with palladium
on carbon and formaldehy de:[20]

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The Leimgruber–Batcho, Bartoli and Baey er–Emmerling indole sy ntheses begin with aromatic nitro compounds.
Indigo can be sy nthesized in a condensation reaction from ortho-nitrobenzaldehy de and acetone in strongly basic
conditions in a reaction known as the Baey er–Drewson indigo sy nthesis.

Explosions
Explosiv e decomposition of organo nitro compounds are redox reactions, wherein both the oxidant (nitro group)
and the fuel (hy drocarbon substituent) are bound within the same molecule. The explosion process generates heat
by forming highly stable products including molecular nitrogen (N2 ), carbon dioxide, and water. The explosiv e
power of this redox reaction is enhanced because these stable products are gases at mild temperatures. Many
contact explosiv es contain the nitro group.

See also
Functional group
Reduction of nitro compounds
Nitration
Nitrite (also an NO2 group, but bonds differently)
Nitroalkene
Nitroglycerin

References
1. Gerald Booth, "Nitro Compounds, Aromatic", in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH,
Weinheim. doi:10.1002/14356007.a17_411 (https://doi.org/10.1002%2F14356007.a17_411)
2. Markofsky, Sheldon; Grace, W.G. (2000). "Nitro Compounds, Aliphatic". Ullmann's Encyclopedia of Industrial
Chemistry. doi:10.1002/14356007.a17_401 (https://doi.org/10.1002%2F14356007.a17_401). ISBN 3527306730.
3. Kornblum, N.; Ungnade, H. E. (1963). "1-Nitroöctane". Organic Syntheses. 4: 724. doi:10.15227/orgsyn.038.0075 (http
s://doi.org/10.15227%2Forgsyn.038.0075).
4. Walden, P. (1907). "Zur Darstellung aliphatischer Sulfocyanide, Cyanide und Nitrokörper". Berichte der deutschen
chemischen Gesellschaft. 40 (3): 3214–3217. doi:10.1002/cber.19070400383 (https://doi.org/10.1002%2Fcber.19070400
383).
5. Whitmore, F. C.; Whitmore, Marion G. (1923). "Nitromethane". Organic Syntheses. 1: 401.
doi:10.15227/orgsyn.003.0083 (https://doi.org/10.15227%2Forgsyn.003.0083).
6. Olah, George A.; Ramaiah, Pichika; Chang-Soo, Lee; Prakash, Surya (1992). "Convenient Oxidation of Oximes to Nitro
Compounds with Sodium Perborate in Glacial Acetic Acid". Synlett. 4 (4): 337–339. doi:10.1055/s-1992-22006 (https://d
oi.org/10.1055%2Fs-1992-22006).
7. Ehud, Keinan; Yehuda, Mazur (1977). "Dry ozonation of amines. Conversion of primary amines to nitro compounds".
The Journal of Organic Chemistry. 42 (5): 844–847. doi:10.1021/jo00425a017 (https://doi.org/10.1021%2Fjo00425a017).
8. Wislicenus, Wilhelm; Endres, Anton (1902). "Ueber Nitrirung mittels Aethylnitrat [Nitrification by means of ethyl
nitrate]". Berichte der deutschen chemischen Gesellschaft. 35 (2): 1755–1762. doi:10.1002/cber.190203502106 (https://
doi.org/10.1002%2Fcber.190203502106).
9. Weygand, Conrad (1972). Hilgetag, G.; Martini, A., eds. Weygand/Hilgetag Preparative Organic Chemistry (4th ed.).
New York: John Wiley & Sons, Inc. p. 1007. ISBN 0471937495.
10. Edmund ter Meer (1876). "Ueber Dinitroverbindungen der Fettreihe". Justus Liebigs Annalen der Chemie. 181 (1): 1–22.
doi:10.1002/jlac.18761810102 (https://doi.org/10.1002%2Fjlac.18761810102).
11. Hawthorne, M. Frederick (1956). "Aci-Nitroalkanes. I. The Mechanism of the ter Meer Reaction1". Journal of the
American Chemical Society. 78 (19): 4980. doi:10.1021/ja01600a048 (https://doi.org/10.1021%2Fja01600a048).

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12. 3-Hexene, 3,4-dinitro- D. E. Bisgrove, J. F. Brown, Jr., and L. B. Clapp. Organic Syntheses, Coll. Vol. 4, p.372 (1963);
Vol. 37, p.23 (1957). (Article (http://www.orgsynth.org/orgsyn/pdfs/CV4P0372.pdf))
13. Zocher, Georg; Winkler, Robert; Hertweck, Christian; Schulz, Georg E (2007). "Structure and Action of the N-oxygenase
AurF from Streptomyces thioluteus". Journal of Molecular Biology. 373 (1): 65–74. doi:10.1016/j.jmb.2007.06.014 (http
s://doi.org/10.1016%2Fj.jmb.2007.06.014). PMID 17765264 (https://www.ncbi.nlm.nih.gov/pubmed/17765264).
14. José Guilherme S. Maia, Eloísa Helena A. Andrade "Database of the Amazon aromatic plants and their essential oils"
Quim. Nova, (2009) 32(3), 595–622, 2009 [1] (http://www.scielo.br/pdf/qn/v32n3/a06v32n3.pdf)
15. Klaus Kubitzki, Jens G. Rohwer, Volker Bittrich "Flowering Plants · Dicotyledons: Magnoliid, Hamamelid and
Caryophyllid Families" 1993, Springer-Verlag, Berlin
16. Bordwell, Frederick G; Satish, A. V (1994). "Is Resonance Important in Determining the Acidities of Weak Acids or the
Homolytic Bond Dissociation Enthalpies (BDEs) of Their Acidic H-A Bonds?". Journal of the American Chemical
Society. 116 (20): 8885. doi:10.1021/ja00099a004 (https://doi.org/10.1021%2Fja00099a004).
17. Ranganathan, Darshan; Rao, Bhushan; Ranganathan, Subramania; Mehrotra, Ashok & Iyengar, Radha (1980).
"Nitroethylene: a stable, clean, and reactive agent for organic synthesis" (http://pubs.acs.org/doi/abs/10.1021/jo01295a0
03). The Journal of Organic Chemistry. 45 (7): 1185–1189. doi:10.1021/jo01295a003 (https://doi.org/10.1021%2Fjo01295
a003). Retrieved 5 January 2014.
18. Jubert, Carole & Knochel, Paul (1992). "Preparation of polyfunctional nitro olefins and nitroalkanes using the copper-zinc
reagents RCu(CN)ZnI" (http://pubs.acs.org/doi/abs/10.1021/jo00046a027). The Journal of Organic Chemistry. 57 (20):
5431–5438. doi:10.1021/jo00046a027 (https://doi.org/10.1021%2Fjo00046a027). Retrieved 5 January 2014.
19. Nagpal, Akanksha; Valley, Michael P.; Fitzpatrick, Paul F.; Orville, Allen M. (2006). "Crystal Structures of Nitroalkane
Oxidase: Insights into the Reaction Mechanism from a Covalent Complex of the Flavoenzyme Trapped during Turnover"
(https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1855086). Biochemistry. 45 (4): 1138–50. doi:10.1021/bi051966w (http
s://doi.org/10.1021%2Fbi051966w). PMC 1855086 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1855086)  .
PMID 16430210 (https://www.ncbi.nlm.nih.gov/pubmed/16430210).
20. Organic Syntheses, Coll. Vol. 5, p.552 (1973); Vol. 47, p.69 (1967). http://orgsynth.org/orgsyn/pdfs/CV5P0552.pdf

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