Efficient oxidative cleavage of oximes to their corresponding carbonyl compounds with chromic acid supported on kieselguhr under heterogeneous conditions

Article abstract of DOI:10.1080/15533174.2011.594840

An efficient oxidative cleavage of oximes to their corresponding carbonyl compounds with chromic acid supported on kieselguhr reagent under heterogeneous conditions at reflux with a yield between 86 and 96% is described. In these reaction conditions, deoximation of aldoximes required a longer reaction time than that of ketoximes, and the conditions are not suitable for deoximation of aliphatic aldoximes. Copyright Taylor & Francis Group, LLC.

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Efficient Oxidative Cleavage of Oximes to Their
Corresponding Carbonyl Compounds with Chromic
Acid Supported on Kieselguhr Under Heterogeneous
Conditions
a c
a
a
b
c
Ji-Dong Lou , Xiu Lian Lu , Li-Hong Huang , Changhe Zhang , Qiang Wang
&
a
Xiao-Nan Zou
a
College of Life Sciences , China Jiliang University , Hangzhou, Zhejiang, P. R. China
Center for the Research and Technology of Agro-Environmental and Biological Sciences
b
(CITAB)/Department of Biology and Environment , Universidade de Trás-os-Montes e Alto
Douro (UTAD) , Vila Real, Portugal
c
Sirnaomics, Inc. , Gaithersburg, Maryland, USA
Published online: 02 Dec 2011.
To cite this article: Ji-Dong Lou , Xiu Lian Lu , Li-Hong Huang , Changhe Zhang , Qiang Wang & Xiao-Nan Zou (2011)
Efficient Oxidative Cleavage of Oximes to Their Corresponding Carbonyl Compounds with Chromic Acid Supported on
Kieselguhr Under Heterogeneous Conditions, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal
Chemistry, 41:10, 1278-1281, DOI: 10.1080/15533174.2011.594840
To link to this article: http://dx.doi.org/10.1080/15533174.2011.594840
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:1278–1281, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.594840
Efficient Oxidative Cleavage of Oximes to Their
Corresponding Carbonyl Compounds with Chromic Acid
Supported on Kieselguhr Under Heterogeneous Conditions
1
,3
1
1
2
3
Ji-Dong Lou, Xiu Lian Lu, Li-Hong Huang, Changhe Zhang, Qiang Wang,
1
and Xiao-Nan Zou
College of Life Sciences, China Jiliang University, Hangzhou, Zhejiang, P. R. China
Center for the Research and Technology of Agro-Environmental and Biological Sciences
1
2
(
CITAB)/Department of Biology and Environment, Universidade de Tr a´ s-os-Montes e Alto Douro
UTAD), Vila Real, Portugal
Sirnaomics, Inc., Gaithersburg, Maryland, USA
(
3
the mixture is magnetically stirred. A solution of benzophe-
An efficient oxidative cleavage of oximes to their corresponding none oxime (197 mg, 1 mmol) in dichloromethane (5 mL) is
carbonyl compounds with chromic acid supported on kieselguhr added, and after 2 h at reflux the solid is filtered and washed
reagent under heterogeneous conditions at reflux with a yield be-
tween 86 and 96% is described. In these reaction conditions, deox-
evaporated to give crude product, which is purified by prepara-
imation of aldoximes required a longer reaction time than that of
ketoximes, and the conditions are not suitable for deoximation of
aliphatic aldoximes.
with dichloromethane (3 × 5 mL). The combined filtrates are
tive thin-layer chromatography (TLC) with hexane:ethyl acetate
(7:3) to afford 174 mg (96%) benzophenone.
Keywords carbonyl compounds, chromic acid, kieselguhr, oxidative
cleavage, oximes
RESULTS AND DISCUSSION
So far, many methods and reagents have been reported
for regeneration of carbonyl compounds like aldehydes
and ketones from oxime derivatives, for instance, mainly,
hydrolytic, reductive, and oxidative reactions, and the de-
oximation process can be undertaken in both homogeneous
and heterogeneous conditions. It is well known that one
of the most important procedures for this transformation is
oxidation with hexavalent chromium derivatives, such as Jones
INTRODUCTION
Oxime compounds are useful protecting groups in organic
syntheses[ and have found extensive application in the iso-
lation, purification, and characterization of carbonyl com-
pounds.[ Oximes have been used as intermediates for a num-
ber of synthetic products, and have proved to be important and
1]
[8]
2,3]
[
4–6]
useful reagents in organic syntheses as well.
The develop-
[9]
[10]
reagent, , methylammonium chlorochromate–alumina,
ment of mild and efficient methods for the selective cleavage
of derivatives containing a carbon–nitrogen double bond like
oximes to afford carbonyl compounds continues to be a signifi-
cant aspect of organic chemistry.
chromium trioxide–silica gel,[11] pyridinium fluorochro-
[12]
[14]
[13]
mate,
mate,
quinolinium dichromate,
potassium dichro-
[15]
pyridinium fluorochromate–hydrogen peroxide,
[16]
2
,6-dicarboxypyridinium chlorochromate,
γ -picolinium
benzyltriphenylphosphonium chlorochro-
[
16]
chlorochromate,
mate,[
16]
quinolinium fluorochromate,
[19]
tetramethylam-
benzyltrimethylammonium
EXPERIMENTAL
[
20]
monium fluorochromate(VI),
Oxidative Cleavage of Benzophenone Oxime to
Benzophenone: Typical Procedure
The chromium trioxide-kieselghur reagent (450 mg) is
placed in a flask together with dichloromethane (30 mL) and
fluorochromate(VI),[
carboxypyridinium
21]
imidazolium dichromate,
[22]
di-
fluorochromate,[
chromic
23]
tetrabutylam-
chromium
[
7]
[24]
acid,[25]
monium
chromate,
[26]
trioxide–NaHSO4•H2O,
glycinium chlorochromate-silica
gel,[ ammonium chlorochromate–montmorillonite K10,
etc. Although some of the reported reactions with chromium(VI)
or chromium(VI)-based reagents are carried out under mild con-
ditions, most of these methods are often hazardous, expensive,
or use reagents not readily available or reagents that need to be
27]
[28]
Received 17 April 2011; accepted 30 May 2011.
Address correspondence to Ji-Dong Lou, College of Life Sciences,
China Jiliang University, Hangzhou, Zhejiang 310018, P. R. China.
E-mail: lou@cjlu.edu.cn
1278

OXIDATIVE CLEAVAGE OF OXIMES
1279
TABLE 1
Oxidative cleavage of oximes to their corresponding carbonyl compounds with chromic acid supported on kieselguhr reagent
under heterogeneous conditions
b
Entry
1
Oxime
Time (h)
2
Producta
Yield (%)
96
OH
N
O
OH
2
2
92
N
O
Cl
Cl
Cl
Cl
OH
3
4
5
2.5
2.5
2.5
90
92
87
N
O
OH
N
O
OH
N
N
O
OH
N
6
7
3
3
86
92
O
OH
CHO
N
8
9
3
90
OH
CHO
OCH3
OCH3
N
3
5
92
86
OH
CHO
CHO
10
N
OH
a
b
All products were identified by comparison of their physical and spectral data with those of authentic samples.
Isolated yields.
freshly prepared. Furthermore, some of these methods require a procedure for the oxidative cleavage of oximes (1) to their
long reaction times with poor yields of the products, or have te- corresponding carbonyl compounds (2) with this reagent under
dious work-up procedures. Therefore, some existing procedures heterogeneous conditions (Scheme 1). This procedure offers a
may be modified to more modern, elegant, and safe versions.
simple and efficient deoximation method for the preparation of
As a part of our ongoing program related to developing new aldehydes and ketones, and is an extension of our previous work
oxidation methods and based on our previous investigations for as well.
oxidation of alcohols and α-hydroxy ketones with chromic acid
In this procedure, the mixture of oximes and chromic acid
supported on kieselguhr reagent,[
7,29–31]
we wish to report here supported on kieselguhr reagent is heated under reflux in

1280
J.-D. LOU ET AL.
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N
CrO - kieselguhr
O
3
2
R1
R1
R2
CH Cl Reflux
2
2,
(
1)
(2)
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SCH. 1.
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compounds under mild condition. Synth. Commun. 2000, 30(4), 665–
oxidant is employed. The progress of the reaction is monitored
with thin-layer chromatography (TLC), and the corresponding
6
69.
aldehydes and ketones are purified by preparative TLC in good
yields. In the case of ketoxime, the starting materials are con-
sumed in less than 3 h, and deoximation of aldoximes requires a
slightly longer reaction time. However, these reaction conditions
are not suitable for deoximation of aliphatic aldoximes.
1
2. Bhandari, A.; Mishra, P.; Banerji, K.K. Kinetics and mechanism of the
oxidative regeneration of carbonyl compounds from oximes by pyridinium
fluorochromate. React. Kinet. Catal. Lett. 2000, 71, 343–347.
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Regeneration of carbonyl compounds from oximes, phenylhydrazones,
p-nitrophenylhydrazones, and semicarbazones by quinolinium dichro-
mate under nonaqueous conditions. Synth. Commun. 2001, 31, 435–
438.
1
Compared with some of the previous procedures for the ox-
idative cleavage of oximes to their corresponding carbonyl com-
pounds with hexavalent chromium derivatives cited earlier, the 14. Mohammadpoor-Baltork, I.; Sadeghi, M.M.; Adibi, A.-H. Efficient,
solvent-free oxidation of organic compounds with potassium dichromate
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of the products is relatively higher and the reaction time of the
oxidation is comparatively shorter. The oxidized products are all
known compounds and identified by spectroscopic comparison
with authentic samples. Our results are listed in the Table 1.
1
5. Ganguly, N.C.; Sukai, A.K.; De, S.; De, P. Oxidative deprotection of oximes
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CONCLUSION
1
7. Salehi, P.; Khodaei, M.M.; Goodarzi, M. A mild and selective deoxima-
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An efficient oxidative cleavage of oximes to their correspond-
ing carbonyl compounds with chromic acid supported on kiesel-
guhr under heterogeneous conditions at reflux with a yield be-
tween 86 and 96% is described. In case of ketoxime, the starting
materials are consumed in less than 3 h, and deoximation of al-
doximes requires a slightly longer reaction time. However, these
reaction conditions are not suitable for deoximation of aliphatic
aldoximes.
2
002, 32, 1259–1263.
1
8. Hajipour, A.R.; Mallakpour, S.E.; Mohammadpoor-Baltork, I.; Backnejad,
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