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Nef Reaction

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307 views3 pages

Nef Reaction

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Uploaded by

Subhabrata Mabhai
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© © All Rights Reserved
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Nef reaction

From Wikipedia, the free encyclopedia


The Nef reaction is an organic reaction describing
the acid hydrolysis of a salt of a primary or secondary nitroalkane (1)
to an aldehyde or a ketone (3) and nitrous oxide(4).[1][2][3]

The reaction was reported in 1894 by the chemist John Ulric Nef [4], who
treated the sodium salt of nitroethane with sulfuric acid resulting in a
85-89% yield of nitrous oxide and at least 70% yield of acetaldehyde.
However, the reaction was pioneered a year earlier in 1893 by
Konovalov[5], who converted the potassium salt of 1-phenylnitroethane
with sulfuric acid to acetophenone.
The Nef reaction should not be confused with the Nef synthesis.
[edit]Reaction mechanism
The reaction mechanism starting from the nitro salt as the resonance
structures 1a and 1b is depicted below:

The salt is protonated forming the nitronate 2 (in some cases these
nitronates have been isolated) and once more to the iminium ion 3. This
intermediate is attacked by water in a nucleophilic
addition forming 4 which loses a proton and then water to the
1-nitroso-alkanol 5 which is believed to be responsible for the
deep-blue color of the reaction mixture in many Nef reactions. This
intermediate rearranges to hyponitrous acid 6 (forming nitrous
oxide 6c through 6b) and the oxonium ion 7 which loses a proton to form
the carbonyl compound.
Note that the reaction requires an alpha hydrogen atom and therefore the
reaction fails with tertiary nitro compounds.
[edit]Scope
The Nef reaction is frequently encountered in organic synthesis. It has
been applied in carbohydrate chemistry as a chain-extension method
for aldoses for example in theisotope labeling of C14-D-mannose and
C14-D-glucose from D-arabinose and C14-nitromethane (the first step here
is a Henry reaction):

The opposite reaction is the Wohl degradation.


The reaction is also used in combination with the Michael reaction in
the synthesis of ã-keto-carbonyls such as [6]:

or 2,5-heptanedione [7] Hydrolysis of nitro compounds with strong acid


without the intermediate salt stage results in the formation
of carboxylic acids and hydroxylaminesalts.
The hydrolysis step of the Nef reaction can also be performed with Lewis
acids such as tin(IV) chloride[8], or oxidants such as oxone[9].
[edit]References
^ The NEF Reaction Wayland E. Noland Chem. Rev. 1955, 55(1), 137 - 155.
(Review, doi:10.1021/cr50001a003)
^ Pinnick, H. W. Org. React. 1990, 38, 655-792. (Review)
^ Grierson, D. S.; Husson, H.-P. Comp. Org. Syn. 1991, 6, 937-944.
(Review)
^ Nef, J. U. Liebigs Ann. Chem. 1894, 280.
^ Konovalov.,: J. Russ. Phys. Chem. Soc. 2 1893, 6(I), 509.
^ A convenient synthesis of ã-functionalized cyclopentenones Nour
Lahmar, Taïcir Ben Ayed , Moncef Bellassoued and Hassen Amri Beilstein
Journal of Organic Chemistry2005, 1:11 doi:10.1186/1860-5397-1-11
^ McMurry, J. E.; Melton, J. Organic Syntheses, Coll. Vol. 6, p.648
(1988); Vol. 56, p.36 (1977). (Article)
^ Miyashita, M.; Yanami, T.; Yoshikoshi, A. Organic Syntheses, Coll.
Vol. 7, p.414 (1990); Vol. 60, p.117 (1981). (Article)
^ Ceccherelli, P.; Curini, M.; Marcotullio, M. C.; Epifano, F.; Rosati,
O. Synth. Commun. 1998, 28, 3057-3064.
Categories: Substitution reactions | Name reactions
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This page was last modified on 4 March 2011 at 17:24.
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