Regeneration of aldehydes and ketones by the oxidation of oximes using potassium permanganate-graphite with grinding under solvent-free conditions

Article abstract of DOI:10.1134/S1070427217080225

A facile and efficient procedure for the oxidative cleavage of oximes to their parent aldehydes and ketones by grinding with potassium permanganate-graphite at room temperature under solvent-free conditions in the yields between 80 and 94% is described. All reactions are complete in 5 min.

Full text of DOI:10.1134/S1070427217080225

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2017, Vol. 90, No. 8, pp. 1326−1329. © Pleiades Publishing, Ltd., 2017.
VARIOUS TECHNOLOGICAL
PROCESSES
Regeneration of Aldehydes and Ketones by the Oxidation
of Oximes Using Potassium Permanganate-Graphite
with Grinding under Solvent-Free Conditions1
a,b
b,c
d
b,c
Li-Yun Zhu *, Lin-zhen Song , Wei Chen , Yong-sheng Gao ,
b,c
b,c
a
Chunmiao Zhang , Jiaping Wang , Jun-qing Qian *
a
College of Biology and Environment, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China
*
e-mail: qjq@zjut.edu.cn
b
National & Local United Engineering Lab of Quality Controlling Technology and Instrumentation for Marine Food,
China Jiliang University, Hangzhou 310018, China
e-mail: zly@cjlu.edu.cn
c
Key Laboratory of Marine Food Quality and Hazard Controlling Technology of Zhejiang Province,
China Jiliang University, Hangzhou 310018, China
College of Life Sciences, Zhejiang Sci-Tech University, Hangzhou 310018, China
d
Received April 19, 2017
Abstract—A facile and efficient procedure for the oxidative cleavage of oximes to their parent aldehydes and
ketones by grinding with potassium permanganate-graphite at room temperature under solvent-free conditions
in the yields between 80 and 94% is described. All reactions are complete in 5 min.
DOI: 10.1134/S1070427217080225
AIMS AND BACKGROUND
EXPERIMENTAL
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]. Likewise, 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]. Regeneration of carbonyl compounds,
such as aldehydes and ketones, from the oxime derivatives
is an important process in synthetic organic chemistry,
for instance, regeneration by the way of hydrolytic,
reductive, and oxidative reactions [7]. However, only a
limited number of methods or reagents are available for
the conversion of oximes to the corresponding carbonyl
compounds under mild reaction conditions. Therefore,
there has been considerable interest in the development
of mild techniques for this transformation.
Oxidation of benzaldehyde oxime to benzaldehyde:
(typical procedure). Potassium permanganate (190 mg,
1.2 mmol) and graphite (760 mg) were mixed with a pestle
and mortar. Benzaldehyde oxime (121 mg, 1 mmol) was
added. The reaction mixture was well ground at room
temperature using a pestle. The progress of the reaction
was monitored by TLC (Aluminum-backed silica gel
GF254) using hexane : ethyl acetate (7 : 3) as eluent.
After 5 min the reaction was complete. The solid was
filtered and washed with dichloromethane (3 × 5 mL).
The combined filtrates were evaporated to give crude
product, which was purified by preparative TLC (silica
gel GF254) with hexane : ethyl acetate (7 : 3) to afford
1
02 mg (94%) benzaldehyde.
RESULTS AND DISCUSSION
The oxidative cleavage reaction is one of the most
important procedures for regeneration of carbonyl
1
The text was submitted by the authors in English.
1
326

REGENERATION OF ALDEHYDES AND KETONES BY THE OXIDATION
1327
Scheme 1. Oxidation of oximes.
Table 1. Oxidative cleavage of oximes to their corresponding
carbonyl compounds with potassium permanganate-graphite
under solvent-free conditions
Yieldb,
%
Entry
Oxime
Producta
compounds from oximes. So far, several potassium
1
94
permanganate (KMnO ) or potassium permanganate-
4
based reagents have been used as oxidants for deoximation,
for example, potassium permanganate-manganese(II)
sulphate [8], potassium permanganate-manganese
dioxide [8], potassium permanganate-wet silica gel [9],
potassium permanganate-montmorillonite K-10 [10],
potassium permanganate-alumina [11, 12], potassium
permanganate-zeolite [13], potassium permanganate-
graphite [14, 15], potassium permanganate-kieselguhr
2
84
3
4
86
90
[
16, 17], potassium permanganate-silica gel [18], and
potassium permanganate-aluminum silicate [19], etc.
most of which have achieved good results.
Potassium permanganate-based reagents have been
extensively used as oxidants for the oxidation of a
variety of organic functional groups, either in aqueous
or non-aqueous media [20, 21]. Because potassium
permanganate is a relatively environmentally friendly
agent, we are interested in seeking newer or improved
procedures with this reagent for oxidative cleavage of
oximes to their parent aldehydes and ketones. We have
reported this oxidative transformation using potassium
permanganate assisted with inorganic solids, for
instance, graphite [14, 15], kieselguhr [16, 17], silica gel
5
94
80
6
a
All products were identified by comparison of their physical and
spectral data with those of authentic samples.
b Isolated yields.
[18], and aluminum silicate [19], under heterogeneous
conditions or under solvent-free conditions.
In continuation of previous investigations [14–19],
we now report here a facile and efficient procedure for
the oxidation of oximes (1) to the corresponding aldehydes
and ketones (2) using potassium permanganate-graphite
at room temperature under solvent-free conditions with
grinding (Scheme 1).
The oxidized products are all known compounds and
identified by spectroscopic comparison with authentic
samples. Our results are listed in the Table 1.
Because the present reaction is performed under
solvent-free conditions with solid-supported reagents,
the main advantages of the present oxidation are
of enhanced selectivity and reactivity, mild reaction
conditions, and straightforward work-up procedure
In this procedure the oximes are converted to the
corresponding carbonyl compounds in a mortar with
grinding by a pestle in the presence of potassium
permanganate-graphite at room temperature under
solvent-free conditions. Under our experiments, a 1 to
[22–27]. Furthermore, since the present method avoids
the use of toxic reagents such as hexavalent chromium
derivatives, it may be carried out on a large scale.
1.2 molar ratio of the substrate to the oxidant is employed.
The progress of the reaction is monitored with TLC, and
the corresponding aldehydes and ketones is purified by
preparative TLC. All reactions are complete in 5 min.
Some data for the oxidation of benzaldehyde oxime
to benzaldehyde with supported potassium permanga-
nate reagents under different reaction conditions are
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 8 2017

1328
LI-YUN ZHU et al.
Table 2. Comparison of oxidation of benzaldehyde oxime to benzaldehyde with potassium permanganate under different reaction
conditions
Molar ratio substrate
Reaction Yield,
Entry
Supports
Reaction conditions
to potassium
References
time
%
permanganate
1
2
Graphite
Solvent-free/RT/grind
Solvent-free/RT/grind
1 : 1.2
1 : 1.2
5 min
5 min
94
92
Present work
17
Kieselguhr
Montmorillonite
K-10
3
Solvent-free/RT/grind
Solvent-free/50OC/grind
CH Cl /RT
1 : 2
1 : 1.4
1 : 2
5 min
40 min
20 min
1 h
85
78
86
92
10
11
16
18
4
5
6
Alumina
Kieselguhr
Silica gel
2
2
CH Cl /RT
1 : 2
2
2
listed in Table 2. By comparing the current procedure
with the most of others (Table 2), the amount of potas-
sium permanganate used is decreased, the reactions are
milder, or the time of the oxidation is shorter. Therefore,
the advantages of the present route are over most of
those of previous potassium permanganate oxidation
methods.
5. Sandler, S.R. and Karo, W., Organic Functional Group
Preparations, vol. 3, 2nd Ed., San Diego:Academic Press,
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6
. Haines, H., Methods for The Oxidation of Organic
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CONCLUSIONS
7. Sahu, S., Sahu, S., Patel, S., Dash, S., and Mishra, B.K.,
Indian J. Chem., 2008, vol. 47B, p. 259.
Afacile and efficient procedure for oxidative cleavage
of oximes to their parent aldehydes and ketones by
grinding with potassium permanganate-graphite at room
temperature under solvent-free conditions in the yields
between 80 and 94% is described. All reactions are
complete in 5 min. The main advantages of the present
oxidation are of enhanced selectivity and reactivity,
mild reaction conditions, and straightforward work-up
procedure.
8
9
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