Regeneration of aromatic carbonyl compounds from the corresponding oximes using tetrapyridine silver(II) peroxydisulfate in acetonitrile and aqueous media

Article abstract of DOI:10.1080/00397910903013705

The results of the recovery of both aldehyde and ketone carbonyl functionalities from the oxime derivatives in aromatic carbonyl compounds using tetrapyridine silver(II) peroxydisulfate [Ag(py)₄S₂O ₈] as a stable, mild, and efficient oxidizing agent is reported. Yields in excess of 85% were achieved at room temperature in both acetonitrile and aqueous media, making the method versatile and suitable for a wide range of aromatic carbonyl oximes.

Full text of DOI:10.1080/00397910903013705

1
Synthetic Communications , 40: 725–731, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903013705
REGENERATION OF AROMATIC CARBONYL
COMPOUNDS FROM THE CORRESPONDING OXIMES
USING TETRAPYRIDINE SILVER(II) PEROXYDISULFATE
IN ACETONITRILE AND AQUEOUS MEDIA
1
Mohammad Hakimi, Noorallah Feizi, Hassan Hassani,
1
2
1
Hooshang Vahedi, and P. S. Thomas
3
1
Department of Chemistry, Payame Noor University, Mashhad, Iran
Department of Chemistry, Payame Noor University, Birjand, Iran
2
3
Department of Chemistry and Forensic Science, University of Technology,
Sydney, Australia
The results of the recovery of both aldehyde and ketone carbonyl functionalities from the
oxime derivatives in aromatic carbonyl compounds using tetrapyridine silver(II) peroxydi-
4 2 8
sulfate [Ag(py) S O ] as a stable, mild, and efficient oxidizing agent is reported. Yields in
excess of 85% were achieved at room temperature in both acetonitrile and aqueous media,
making the method versatile and suitable for a wide range of aromatic carbonyl oximes.
Keywords: Acetonitrile; carbonyl; oxime; peroxydisulfate ion; water
INTRODUCTION
The protection of functional groups, including aldehydes and ketones, is often
[1]
necessary during total organic synthesis. For aldehydes and ketones, oximes have
been useful derivatives as protecting groups because they are stable under a wide
range of reaction conditions. Additionally, oximes are important mediators for the
[
2]
purification and characterization of aldehydes and ketones. Oximes may also be
[
3]
[4]
used fruitfully as intermediates for the synthesis of amines and nitriles.
Recently, a number of methods for the blocking and recovery of the carbonyl
[
functionalities using the oxime derivative have been reviewed, and they include (a)
5]
[6]
[7]
hydrolysis under the acidic or neutral reaction conditions, (b) oxidation using
[
8]
[9]
chromium(VI), manganese(VII), (IV), (III), thallium(III),
[10]
[11]
cerium(IV),
and
lead(IV), (c) halogenation and halogenated compounds, (d) reduction using
[
12]
[13]
[14]
[
15]
[16]
[17]
[18]
LiAlH , Na S O , Fe(CO)5, TiCl =NaI and VCl2, (e) enzymatic meth-
[19]
4
20]
2
2
4
4
[
[21]
ods, and (f) microwave irradiation. A number of these methods require drastic
reaction conditions or the use of toxic and expensive compounds, making them
undesirable.
Received December 9, 2008.
Address correspondence to P. S. Thomas, Department of Chemistry and Forensic Science,
University of Technology, Sydney, Australia. E-mail: paul.thomas@uts.edu.au
7
25

726
M. HAKIMI ET AL.
An alternate method for the regeneration of the protected carbonyl functionality
À2
from the oxime derivative is oxidation with the peroxydisulfate ion, S2O8 . The perox-
odisulfate ion is a strong oxidizing agent with a standard redox potential of 2.01V in
[22]
aqueous solution.
derivatives have been reported using tetrabutyl ammonium peroxydisulfate,
The reactions of organic compounds using peroxydisulfate
[
23]
[
bis(1-benzyl)-4-aza-1-azoniabicyclo [2.2.2] octane peroxodisulfate, benzyl triphenyl
24]
[25]
[26]
phosphonium peroxodisulfate,
[27]
supported peroxodisulfate,
polymer-supported-peroxydisalfate,
and n-butyl phenyl phosphonium peroxodisulfate.
Amberlyst-
[28]
However, little attention has been paid to the oxidative cleavage of oximes by
peroxodisulfates and, in particular, to the conversion of oxime derivatives to their
[23–28]
corresponding carbonyl compounds.
This article reports on the oxidation of
[
29]
a variety of aromatic oximes using tetrapyridine silver(II) peroxydisulfate, produc-
ing the corresponding carbonyl compounds in good yield and using mild reaction
conditions, because the reactions were carried out at room temperature in both acet-
onitrile and aqueous media (Scheme 1). The oxidizing agent, tetrapyridine silver(II)
peroxydisulfate, was selected because it is easily prepared in good yield (95%) from
an aqueous solution of silver nitrate, pyridine, and potassium peroxodisulfate.
The yields and the times required for the reaction are listed in Table 1 for the oxi-
dation of a range of aromatic oximes containing both electron-releasing and
electron-withdrawing groups. In each case, the reaction regenerated the carbonyl
derivative in good yield (85–90%), although the yield of product was found to depend
on the nature of the substrate and reaction medium. For the aldehyde oximes examined,
the reagent was found to be more reactive toward those containing the electron-
releasing groups (entries 2 and 3). To achieve similar yields (85–90%) for oximes
containing strong electron-withdrawing groups (entry 6), a longer reaction time was
required (90–180 min). To assess the efficiency of the reagent for the regeneration of
aromatic ketone-oximes, a series of reactions (entries 9 and 10) was carried out at room
temperature, producing similarly good yields (85–95%) and further demonstrating the
efficiency of this reagent. The reaction was carried out in both acetonitrile and aqueous
media for each of the carbonyl–oximes systems. Good yields were achieved (>85%) in
both media, although acetonitrile required longer reaction times to achieve these yields.
In summary, tetrapyridine silver(II) peroxydisulfate has been demonstrated to
be an efficient reagent for the regeneration of carbonyl functionalities in aromatic
compounds in yields of 80–95% from their corresponding oximes in both acetonitrile
and aqueous media. Additionally, the reagent is cost-effective, readily available, and
simple to prepare. The good yields of products from the range of oximes investigated
in both aqueous and polar organic media with the further advantage of mild reaction
conditions suggest that this novel method for the recovery of carbonyl functionalities
from oximes has general applicability.
Scheme 1. Conversion of oximes to carbonyls.

CARBONYL REGENERATION FROM OXIME INTERMEDIATES
727
Table 1. Deoximation by tetrapyridine silver(II) peroxodisulfate
H
2
O
3
CH CN
a
Time (min) Yield (%) Time (min) Yield (%)
a
Entry
1
Substrate
Product
30
30
90
85
60
60
95
93
2
3
4
5
6
30
40
40
90
88
85
90
80
50
100
120
180
90
88
85
85
90
7
8
30
40
90
85
60
20
85
(
Continued )

728
M. HAKIMI ET AL.
Table 1. Continued
H
2
O
3
CH CN
a
a
Time (min) Yield (%) Time (min) Yield (%)
Entry
9
Substrate
Product
30
30
90
90
15
15
95
95
10
a
Yields refer to the isolated products and 2,4-dinitrophenyl-hydrazine derivatives. Structures were con-
1 13
firmed by IR, H NMR, C NMR, and mp=bp.
EXPERIMENTAL
Tetrapyridine silver(II) peroxodisulfate was prepared according to a reported
[
method. All the other reagents were purchased from Aldrich and used as supplied.
29]
1
The products were characterized by IR and H NMR. The yields refer to the isolated
regenerated carbonyl products or to the corresponding 2,4-dinitrophenyl-hydrazine
derivatives.
General Procedure
Tetrapyridine silver(II) peroxodisulfate (3 mmol) was added to a solution of
oxime (1 mmol) in acetonitrile (8 ml) or water (8 ml). The mixture was stirred at room
temperature. The progress of the reaction was followed by thin-layer chromato-
graphy. When the reaction was complete, silica gel (6 g) was added, and the solvent
was evaporated under the reduced pressure. The resulting powder was added to the
top of a short silica-gel column and purified using n-hexane–EtOAc in a 5:1 ratio as
the eluent. Recovery of the pure carbonyl compounds was then achieved by evapor-
ation of the solvent under the reduced pressure.
ACKNOWLEDGMENT
The investigation has enjoyed the support of the Payam Noor University of
Fariman and Mashhad.
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