[(NO3)3Ce]3.H2IO6: As a versatile and efficient reagent for cleavage of carbon-nitrogen double bonds under heterogeneous and non-aqueous conditions

Article abstract of DOI:10.1081/SCC-100108227

Oximes, hydrazones and semicarbazones of benzylic aldehydes and ketones undergo facile cleavage to the corresponding carbonyl compounds by tris[tri-nitratocerium(IV)]paraperiodate, [(NO₃)₃Ce]₃.H₂IO₆, in good to high yields.

Full text of DOI:10.1081/SCC-100108227

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[
NO ) Ce] .H IO : AS A VERSATILE AND EFFICIENT
3 3 3 2 6
REAGENT FOR CLEAVAGE OF CARBON–NITROGEN
DOUBLE BONDS UNDER HETEROGENEOUS AND NON-
AQUEOUS CONDITIONS
a
a
F. Shirini & M. R. Azadbar
a
Department of Chemistry, Faculty of Science , Gulian University , Rasht, Iran
Published online: 09 Nov 2006.
To cite this article: F. Shirini & M. R. Azadbar (2001) [NO ) Ce] .H IO : AS A VERSATILE AND EFFICIENT REAGENT FOR
3
3
3
2
6
CLEAVAGE OF CARBON–NITROGEN DOUBLE BONDS UNDER HETEROGENEOUS AND NON-AQUEOUS CONDITIONS, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:24, 3775-3779,
DOI: 10.1081/SCC-100108227
To link to this article: http://dx.doi.org/10.1081/SCC-100108227
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SYNTHETIC COMMUNICATIONS, 31(24), 3775–3779 (2001)
[
(NO ) Ce] .H IO : AS A VERSATILE AND
3 3 3 2 6
EFFICIENT REAGENT FOR CLEAVAGE
OF CARBON–NITROGEN DOUBLE
BONDS UNDER HETEROGENEOUS
AND NON-AQUEOUS CONDITIONS
F. Shirini* and M. R. Azadbar
Department of Chemistry, Faculty of Science,
Gulian University, Rasht, Iran
ABSTRACT
Oximes, hydrazones and semicarbazones of benzylic aldehy-
des and ketones undergo facile cleavage to the corresponding
carbonyl compounds by tris[tri-nitratocerium(IV)]paraperio-
date, [(NO ) Ce] .H IO , in good to high yields.
3
3
3
2
6
Derivatives of carbonyl compounds such as oximes, hydrazones and
semicarbazones are highly crystalline and very useful for the characteriza-
tion and purification of carbonyl compounds. Regeneration of carbonyl
compounds from their derivatives under mild conditions is an important
process in synthetic organic chemistry.
The classical method for the cleavage of oximes to aldehydes and
ketones includes acid hydrolysis which is not suitable for acid sensitive
*
Corresponding author.
3
775
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

ORDER
REPRINTS
3
776
SHIRINI AND AZADBAR
1
compounds. Several oxidative deoximation methods have been developed
2
–5
which have found some advantages over the classical hydrolysis methods.
Little attention has been paid to the oxidative cleavage of hydrazones
and semicarbazones and only a few reports are available dealing with
the conversion of these derivatives to their corresponding carbonyl
6
–8
compounds.
In this communication we wish to report that tris[trinitrato Ce(IV)]-
9
–11
paraperiodate, [(NO ) Ce] .H IO , a previously reported oxidizing agent,
3
3
3
2
6
is able to perform the cleavage of carbon–nitrogen double bonds of
benzylic oximes, hydrazones and semicarbazones in refluxing acetonitrile.
Our experiments show that benzylic oximes, hydrazones and semicar-
bazones are converted to their corresponding aldehydes and ketones in low
reaction times and in good to high yields (Table 1). In Table 2 the results of
our experiments are compared with some of those reported in literature. This
methodology is not recommended for the cleavage of aliphatic carbon–
nitrogen double bonds (Table 1, entries 23, 24).
In summary, tris[trinitratocerium(IV)]paraperiodate is an effective and
convenient reagent for converting benzylic oximes, hydrazones and semi-
carbazones to their corresponding carbonyl compounds. A full research,
based on this method, conserning cleavage of carbon–nitrogen double
bonds in other classes of organic compounds is under way.
EXPERIMENTAL
Chemicals were purchased from Merck, Fluka, BDH and Aldrich
chemical companies. All oximes, hydrazones and semicarbazones were pre-
1
2,13
pared using standard synthetic methods.
Products were separated and
purified by different chromatography techniques, and were also identified by
the comparison of their mp, IR, NMR, bp and refractive index with those
reported for authentic samples.
General Procedure
A solution of the substrate (1 mmol) in acetonitrile (3 mL) was
treated with 0.5–1 molar equivalent of reagent and the mixture was
refluxed for 5–90 min. The progress of the reaction was monitored by
TLC or GLC. The reaction mixture was filtered and the solid residue
was washed by acetonitrile (9 mL). Evaporation of the solvent followed

ORDER
REPRINTS
[
(NO
3
)
3
Ce]
3
.H
2
IO
6
3777

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778
SHIRINI AND AZADBAR
Table 2. Comparison of Some of the Results Obtained from [(NO ) Ce] .H IO (1)
3
3
3
2
6
and Some of Those Reported with Methyl Ammonium Chlorochromate Adsorbed
3
4
5
on Alumina (2), Sodium Perbromate (3), Pyridinium Chlorochromate (4), and
5
Ozone (5)
Yield (%)
Entry
Substrate
Product
1
2
3
4
5
1
2
3
4
Acetophenone oxime
Benzophenone oxime
Benzaldehyde phenylhydrazone Benzaldehyde
Acetophenone 93 76 88 55 96
Benzophenone 95 61 87 55 95
75
–
–
–
–
65
15
–
–
Acetophenone semicarbazone Acetophenone 85
by column chromatography on silica gel, gave the corresponding carbonyl
compounds in good to high yields.
ACKNOWLEDGMENTS
We are thankful to Gulian University Research Council for the partial
support of this work.
REFERENCES
1. Hersberg, E.B. J. Org. Chem. 1948, 13, 542.
2. Maloney, J.R.; Lyle, R.E. Synthesie 1978, 212.
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1998, 28, 607.
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5
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8
. Bandgar, B.P.; Shaikh, S.I.; Iyer, S. Synth. Commun. 1996, 26, 1163.
. Yang, Y.-T.; Li, T.-S.; Li, Y.-L. Synth. Commun. 1993, 23, 1121.
. Ranu, B.C.; Sarkar, D.C. J. Org. Chem. 1988, 53, 878.
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9. Firouzabadi, H.; Iranpoor, N.; Hajipour, G.; Toofan, J. Synth.
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1
1
0. Iranpoor, N.; Salehi, P.; Shirini, F. Org. Prep. and Procedure Int. 1995,
7, 216.
1. Firouzabadi, H.; Shirini, F. Synth. Commun. 1996, 26, 423.
2

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REPRINTS
[
(NO
3
)
3
Ce]
3
.H
2
IO
6
3779
1
1
2. Vogel, A.I. A Text Book of Practical Organic Chemistry, ELBS 3rd
Ed., Longman Group Limited, London, 1975, p. 721.
3. Mino, T.; Masuda, S.; Nishio, M.; Yamashita, M. J. Org. Chem. 1997,
62, 2633.
Received in the UK September 20, 2000

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