An environmentally benign method for oxidation of oximes with potassium permanganate supported on kieselguhr under solvent-free conditions

Article abstract of DOI:10.1007/s11164-012-0948-4

A rapid and highly efficient procedure for oxidative cleavage of oximes to their parent aldehydes and ketones by grinding with potassium permanganate supported on kieselguhr at room temperature under solvent-free conditions with yields between 82 and 96 % is described. This method has advantages over previous methods used with potassium permanganate oxidation.

Full text of DOI:10.1007/s11164-012-0948-4

Res Chem Intermed
DOI 10.1007/s11164-012-0948-4
An environmentally benign method for oxidation
of oximes with potassium permanganate supported
on kieselguhr under solvent-free conditions
Li-Yun Zhu
Wenjin Zheng
•
Zhiyuan Lou
•
•
Jianan Lin
Ji-Dong Lou
•
Changhe Zhang
•
Received: 14 October 2012 / Accepted: 22 November 2012
Ó Springer Science+Business Media Dordrecht 2012
Abstract A rapid and highly efficient procedure for oxidative cleavage of oximes
to their parent aldehydes and ketones by grinding with potassium permanganate
supported on kieselguhr at room temperature under solvent-free conditions with
yields between 82 and 96 % is described. This method has advantages over previous
methods used with potassium permanganate oxidation.
Keywords Kieselguhr Á Oxidation Á Oximes Á Potassium permanganate Á
Solvent-free
Introduction
Oximes are useful as protecting groups in organic syntheses [1] and have found
extensive application in the isolation, purification, and characterization of carbonyl
compounds [2, 3]. Oximes have been used as intermediates for many synthetic
products and have been also proved to be important and useful reagents in organic
synthesis [4–6]. Several procedures, for example, hydrolytic [7], oxidative [7–12],
L.-Y. Zhu Á J. Lin Á W. Zheng Á J.-D. Lou
College of Life Sciences, China Jiliang University, Hangzhou 310018, Zhejiang, China
Z. Lou
Department of Nutrition & Food Science, University of Maryland, College Park, MD 20742, USA
C. Zhang
Centre for the Research and Technology of Agro-Environmental and Biological Sciences
(
(
CITAB)/Department of Biology and Environment, Universidade de Tr a´ s-os-Montes e Alto Douro
UTAD), Apartado 1013, 5001-801 Vila Real, Portugal
J.-D. Lou (&)
Sirnaomics, Inc., 401 Professional Drive, Gaithersburg, MD 20879, USA
e-mail: jidonglou@sirnaomics.com
123

L. Zhu et al.
and reductive [13–15] reactions, have been reported for regeneration of carbonyl
compounds, for example, aldehydes and ketones, from their corresponding oximes.
Sometimes the deoximation process can be undertaken under both homogeneous
and heterogeneous conditions. Oxidative cleavage is one of the most important
reactions for this transformation in synthetic organic chemistry. Although some of
the known methods or reagents are used under mild reaction conditions, most
require drastic conditions, high temperature, long reaction times, reagents that are
not readily available, and tedious work-up procedures. Therefore, the development
of mild and efficient methods for selective cleavage of derivatives containing
carbon–nitrogen double bonds, such as oximes, to afford carbonyl compounds
continues to be a significant aspect of organic chemistry.
Results and discussion
Several potassium permanganate or potassium permanganate-based reagents have
been used as oxidants for deoximation, for example, potassium permanganate–
manganese(II) sulfate [16], potassium permanganate–manganese dioxide [16],
potassium permanganate–wet silica gel [17], potassium permanganate–montmo-
rillonite K-10 [18], potassium permanganate–alumina [19, 20], potassium
permanganate–zeolite [21], potassium permanganate–graphite [22, 23], potassium
permanganate–kieselguhr [24], and potassium permanganate–silica gel [25], all of
which have achieved good results.
Because potassium permanganate is a relatively environmentally friendly agent
26, 27], we are interested in seeking newer or improved procedures with this
[
reagent for oxidative cleavage of oximes to their parent aldehydes and ketones. We
recently reported this oxidative transformation with potassium permanganate
adsorbed on inorganic solids, for instance, graphite [22], kieselguhr [24], and silica
gel [25] under heterogeneous conditions. In continuation of previous investigations,
we now report here a rapid and highly efficient procedure for oxidation of oximes
(
1) to the corresponding aldehydes and ketones (2) with potassium permanganate
supported on kieselguhr under solvent-free conditions at room temperature
Scheme 1). It is well known that the main advantages of organic reactions
performed with solid-supported reagents [28–30] and under solvent-free conditions
31–33] are enhanced selectivity, milder reaction conditions, much improved
(
[
reaction rates, formation of cleaner products, and associated ease of manipulation.
In this procedure the finely powdered oximes were converted to the correspond-
ing carbonyl compounds in a mortar with grinding by a pestle in the presence of
OH
N
KMnO - kieselguhr
O
4
R1
R2
solvent-free, RT, grind
R1
R2
(1)
(2)
Scheme 1 Oxidation of oximes
1
23

Benign method for oxidation of oximes
Table 1 Oxidative cleavage of oximes to their corresponding carbonyl compounds with potassium
permanganate supported on kieselguhr under solvent-free conditions
a
b
Yield (%)
Entry
1
Oxime
Time (min)
5
Product
90
92
OH
OH
O
O
N
N
2
5
Cl
Cl
Cl
Cl
3
4
5
10
10
10
90
86
82
OH
O
N
OH
OH
O
O
N
N
6
7
10
5
82
92
OH
N
O
N
CHO
CHO
OH
OH
8
5
96
84
N
OCH
3
OCH
3
9
10
CHO
N
OH
a
All products were identified by comparison of their physical and spectral data with those of authentic
samples
b
Isolated yields
123

L. Zhu et al.
potassium permanganate supported on kieselguhr at room temperature under
solvent-free conditions. In our experiments, a 1:1.2 molar ratio of substrate to the
oxidant was used. The progress of the reaction was monitored with TLC, and
the corresponding aldehydes and ketones were purified by preparative TLC. The
oxidized products are all known compounds and were identified by comparison of
spectra with those of authentic samples. Our results are listed in the Table 1. It is
noteworthy that in the absence of kieselguhr the reactions are slow, substantial
amounts of the starting materials are recovered unchanged from the reaction
mixture, and the work-up of the reaction mixture is rather difficult.
Data for oxidation of benzaldehyde oxime to benzaldehyde with potassium
permanganate or supported potassium permanganate reagents under different
reaction conditions are listed in Table 2. It can be seen from this table that when
potassium permanganate supported on kieselguhr under solvent-free conditions at
room temperature was used the time required for completion of the oxidation was
only 5 min and the yield was 92 % (entry 1); under heterogeneous conditions,
however, it was completed in 20 min and the yield was 86 % (entry 4). In addition,
comparison of this procedure with the others (Table 2) reveals the amount of
manganese dioxide used is reduced (entries 2–5), the reactions are milder (entry 3),
or the time required for oxidation is shorter (entries 3–5). Therefore, this method has
benefits over previous potassium permanganate oxidation methods.
Experimental
Oxidation of benzaldehyde oxime to benzaldehyde: typical procedure
Potassium permanganate (190 mg, 1.2 mmol) and kieselguhr (570 mg, purchased
from Tianjin Fu Chen Chemical Reagent Factory) were mixed with a pestle and
mortar. Benzaldehyde oxime (121 mg, 1 mmol) was added. The reaction mixture
was well ground at room temperature by use of a pestle. The progress of the reaction
was monitored by TLC (silica gel GF254) using hexane–ethyl acetate (7:3) as eluent.
After 5 min the reaction was complete. The solid was isolated by filtration and
Table 2 Comparison of methods for oxidation of benzaldehyde oxime to benzaldehyde with potassium
permanganate under different reaction conditions
Entry Support
Reaction
conditions
Molar ratio substrate to
potassium permanganate
Reaction Yield Ref.
(%)
time
1
2
3
Kieselguhr
Solvent-free/
RT/grind
1:1.2
1:2
5 min
92
This
work
Montmorillonite Solvent-free/
RT/grind
5 min
85
78
[18]
K-10
Alumina
Solvent-free/
5
1:1.4
40 min
[19]
0 °C/grind
CH Cl /RT
4
5
Kieselguhr
Silica gel
2
2
1:2
1:2
20 min
1 h
86
92
[24]
[25]
CH Cl
2
2
/RT
1
23

Benign method for oxidation of oximes
washed with dichloromethane (3 9 5 mL). The combined filtrates were evaporated
to give the crude product, which was purified by preparative TLC (silica gel GF254
with hexane–ethyl acetate (7:3) to afford 100 mg (92 %) benzaldehyde.
)
Conclusion
A rapid and highly efficient procedure for oxidative cleavage of oximes to their
parent aldehydes and ketones by grinding with potassium permanganate supported
on kieselguhr at room temperature under solvent-free conditions with yields
between 82 and 96 % is described. Comparison of this procedure with others reveals
that the amount of manganese dioxide used is reduced, the reaction conditions are
milder, or the time required for oxidation is shorter. Therefore, this method has
benefits over previous methods used with potassium permanganate oxidation.
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