Efficient solvent free deoximation and dehydrazonation with HIO3 in the presence of wet SiO2

Article abstract of DOI:10.1081/SCC-120002113

This paper is a report of an efficient and convenient method for deoximation and dehydrazonation of benzylic oximes and hydrazones with HIO₃ in the presence of wet SiO₂.

Full text of DOI:10.1081/SCC-120002113

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EFFICIENT SOLVENT FREE DEOXIMATION AND
DEHYDRAZONATION WITH HIO3 IN THE PRESENCE OF
WET SiO2
F. Shirini a , M. A. Zolfigol b & M. R. Azadbar a
a Department of Chemistry , Faculty of Science , Guilan University , Rasht, Iran
b Department of Chemistry , Faculty of Science , Bu-Ali Sina University , Hamadan, Iran
Published online: 16 Aug 2006.
To cite this article: F. Shirini , M. A. Zolfigol & M. R. Azadbar (2002) EFFICIENT SOLVENT FREE DEOXIMATION AND
DEHYDRAZONATION WITH HIO3 IN THE PRESENCE OF WET SiO2 , Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 32:3, 315-318
To link to this article: http://dx.doi.org/10.1081/SCC-120002113
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SYNTHETIC COMMUNICATIONS, 32(3), 315–318 (2002)
EFFICIENT SOLVENT
FREE DEOXIMATION AND
DEHYDRAZONATION WITH HIO3
IN THE PRESENCE OF WET SiO2
F. Shirini,1, M. A. Zolfigol,2 and M. R. Azadbar1
*
1Department of Chemistry, Faculty of Science,
Guilan University, Rasht, Iran
2Department of Chemistry, Faculty of Science,
Bu-Ali Sina University, Hamadan, Iran
ABSTRACT
This paper is a report of an efficient and convenient method
for deoximation and dehydrazonation of benzylic oximes and
hydrazones with HIO3 in the presence of wet SiO2.
Synthesis of oximes and hydrazones from carbonyl compounds, is of
great interest to synthetic chemists, as they are readily prepared and highly
stable compounds. Oximes and hydrazones are also extensively used for
purification and characterisation of carbonyl compounds. Since oximes
can be prepared from non-carbonyl compounds,1,2 the generation of carbo-
nyl compounds from oximes provides an alternative method for the pre-
paration of aldehydes and ketones. Some of the methods reported for
deoximation invariably require high temperature, longer reaction time,
*Corresponding author.
315
Copyright & 2002 by Marcel Dekker, Inc.
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SHIRINI, ZOLFIGOL, AND AZADBAR
and the formation of over-oxidized products leading to low yields.3–8 Little
attention has been paid to the cleavage of carbon–nitrogen double bond of
hydrazones and only a few reports are available dealings with the conversion
of the derivatives to their corresponding carbonyl compounds.9,10
In this communication we introduce a simple and efficient method of
deoximation and dehydrazonation of benzylic oximes and hydrazones for
regeneration of aldehydes and ketones by using HIO3 in the presence of wet
SiO2 under solvent free conditions (Table 1).
Our experiments show that benzylic oximes and hydrazones are con-
verted to their corresponding carbonyl compounds from good to high
yields. Further oxidation of aldehydes to their corresponding carboxylic
acids are not observed.
In order to show the efficiency of this method we have compared some
of the results with relevant ones reported in the literature4,5,11 (Table 2).
On the basis of what we have already said, we can conclude that the
present procedure of deoximation and dehydrazonation with HIO3
in the presence of wet SiO2 provides a very convenient and efficient
method for the generation of carbonyl compounds from benzylic oximes
Table 1. Deoximation and Dehydrazonation with HIO3 in the Presence of Wet SiO2
Time
(min)
Yield
(%)
Entry
Substrate
Product
1
2
3
4
5
6
7
8
4-Nitrobenzaldoxime
3-Nitrobenzaldoxime
4-Methoxybenaldoxime
Acetophenone oxime
Benzophenone oxime
Benzoin oxime
Benzaldehyde hydrazone
4-Nitrobenzaldehyde
hydrazone
3-Nitrobenzaldehyde
hydrazone
4-Methoxybenzaldehyde-
hydrazone
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
4-Methoxybenzaldehyde
Acetophenone
Benzophenone
Benzoin
Benzaldehyde
15
15
10
45
40
45
10
90
92
82
90
87
80
90
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
4-Methoxybenzaldehyde
30
30
5
89
85
95
9
10
11
4-Chlorobenzaldehyde-
hydrazone
Acetophenone hydrazone
4-Methylacetophenone-
hydrazone
4-Chlorobenzaldehyde
Acetophenone
30
10
82
70
12
13
4-Methylacetophenone
10
73
All reactions performed on a steam bath.

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DEOXIMATION AND DEHYDRAZONATION WITH HIO3
317
Table 2. Comparison of Some of the Results Obtained by the Deoximation with
HIO3 in the Presence of Wet SiOa2 (1) with Some of Those Obtained by N-Butyl-
triphenylphosphonium Dichromate (2),4 Sodium Perbromate (3)5, and ozone (4)11
(Reagent/Substrate)a
(h)
(3)
Yield (%)
(4)
Entry
1
Substrate
(1)
(2)
4-Nitrobenzaldoxime
(5) (0.25)
(90)
(1) (0.5)
(70)
(4) (12)
(40)
(–) (1)
(61)
2
Acetophenone oxime
(5) (0.75)
(90)
–
(4) (6.5)
(88)
(–) (2)
(96)
aWet SiO2 : substrate (0.4 g : 1 mmol).
and hydrazones. Afull research, based on this method, concerning the
cleavage of carbon–nitrogen double bonds in other classes of organic com-
pounds is under way.
EXPERIMENTAL
Chemicals were purchased from Merck, Fluka, BDH and Aldrich
chemical companies. All oximes and hydrazones were prepared using stan-
dard synthetic method.12 Products were separated and purified by different
chromatography techniques, and were also identified by the comparison of
their, mp, IR, NMR, bp, refractive index with those reported for the authen-
tic samples.
General Procedure: To a mixture of HIO3 (0.88 g, 5 mmol) and
wet SiO2 [(SiO2/H2O: 20% ww), 0.4 g], was added oxime or hydrazone
(1 mmol). The resulting mixture was shacked on a steam bath for the definite
time (Table 1). The reaction was monitored by TLC. After completion of the
reaction, CH2Cl2 (5 ml) and sodium thiosulfate (0.5 g) were added to the
mixture and the resultant mixture was filtered after 15 min. Anhydrous
MgSO4 was added to the filterate and filtered. Evaporation of the solvent,
being followed by column chromatography on silica gel, gave the corre-
sponding carbonyl compounds from good to high yields.
ACKNOWLEDGMENT
We greatly acknowledge the Research Councils of Guilan and Bu-Ali
Sina Universities for their financial support.

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SHIRINI, ZOLFIGOL, AND AZADBAR
REFERENCES
1. Kabalk, G.W.; Pace, R.D.; Wadgaonkar, P.P. Synth. Commun. 1990,
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2. Stiver, S.; Yates, P. J. Chem. Soc., Chem. Commun. 1983, 2, 50.
3. Bandgar, B.P.; Shaikh, S.I.; Iyer, S. Synth. Commun. 1996, 26, 1163.
4. Mohammadpoor-Baltork, I.; Sadeghi, M.M.; Mahmoodi, N.;
Kharamesh, B. Indian J. Chem. 1997, 36B, 438.
5. Olah, G.A.; Aravanaghi, M.; Parakash, G.K.S. Synthesis 1980, 220.
6. Kamal, A.; Rao, V.M.; Meshram, H.M. J. Chem. Soc., Perkin Trans.
1, 1991, 2056.
7. Maloney, J.R.; Lyle, R.E. Synthesis 1978, 212.
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9. Barton, D.H.R.; Lester, D.J.; Ley, S.V. J. Chem. Soc., Chem.
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Received in the UK May 16, 2000

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