Solid state cleavage of oximes with potassium permanganate supported on alumina

Article abstract of DOI:10.1081/SCC-120016316

A manipulatively simple and rapid method for conversion of oximes to the corresponding carbonyl compounds is described. The reaction is conducted under solvent-less conditions using alumina-supported permanganate. According to the reaction system and conditions used, different ketones and aldehydes are obtained in moderate and good yields.

Full text of DOI:10.1081/SCC-120016316

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Solid State Cleavage of Oximes with Potassium
Permanganate Supported on Alumina
G. H. Imanzadeh a , A. R. Hajipour b & S. E. Mallakpour b
a College of Chemistry, Mohagheghe Ardabili University, Ardabil, IR. Iran
b College of Chemistry, Isfahan University of Technology, Isfahan, IR. Iran
Published online: 17 Aug 2006.
To cite this article: G. H. Imanzadeh , A. R. Hajipour & S. E. Mallakpour (2003): Solid State Cleavage of Oximes
with Potassium Permanganate Supported on Alumina, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 33:5, 735-740
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 5, pp. 735–740, 2003
Solid State Cleavage of Oximes with Potassium
Permanganate Supported on Alumina
2
G. H. Imanzadeh,1, A. R. Hajipour, and S. E. Mallakpour
*
1College of Chemistry, Mohagheghe Ardabili
University, Ardabil, IR. Iran
2College of Chemistry, Isfahan University of
Technology, Isfahan, IR. Iran
ABSTRACT
A manipulatively simple and rapid method for conversion of oximes
to the corresponding carbonyl compounds is described. The reaction
is conducted under solvent-less conditions using alumina-supported
permanganate. According to the reaction system and conditions
used, different ketones and aldehydes are obtained in moderate and
good yields.
*Correspondence: G. H. Imanzadeh, College of Chemistry, Mohagheghe
Ardabili University, Ardabil 179, IR. Iran; E-mail: imanzad2000@yahoo.com.
735
DOI: 10.1081/SCC-120016316
Copyright & 2003 by Marcel Dekker, Inc.
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736
Imanzadeh, Hajipour, and Mallakpour
Oxidation of organic compounds in organic solvents under mild
conditions is very important in organic synthesis.[1,5] Over the last 15
years, several new oxidizing reagents have been reported for oxidation
of organic compounds. Unfortunately, most of these reagents suffer at
least one of the following disadvantages: (i) cost of preparation, (ii)
longer reaction time, (iii) no selectivity, (iv) tedious work up procedure.
In recent years, the use of solid supports in synthetic organic
chemistry has become more popular.[6,7] The advantages of this method
over conventional homogeneous reactions are that they provide high
selectivity, enhanced reaction rate, and cleaner product.[6,7]
Oximes are very useful for protecting groups in organic synthesis.[8]
These highly crystalline compounds can be prepared from carbonyl
and non carbonyl compounds.[9] Deoximation of such oximes provide
an alternative method for the synthesis of carbonyl compounds.
The classical method for cleavage of oximes to aldehydes and ketones
includes acid hydrolysis which is not suitable for acid sensitive
compounds.[10] Several oxidative deoximation methods have been devel-
oped which have found some advantages over the classical hydrolysis
method.[11–15]
In continuation of our ongoing programto develop environmentally
benign methods using solid supports,[16–21] we now wish to report an
excellent rapid and selective deoximation method by the KMnO4–Al2O3
an inexpensive oxidant. In this simple and efficient method the finely
powdered oximes are converted to the corresponding carbonyl compounds
in a mortar with grinding by a pestle in the presence of supported perman-
ganate on alumina. The reaction has been proceeded under solvent-free
conditions for the time and at the temperature being specified in Table 1.
Interestingly in this method no over oxidation to carboxylic acid was
observed (Table 1, oxime 1).
In order to evaluate the effect of alumina in this reaction, we tried the
reaction of benzophenone oxime with KMnO4 without using alumina.
The reaction was unsuccessful and benzophenone oxime was recovered
after 40 min grinding in a mortar at 50ꢀC. We also observed that in
a,b-unsaturated oxime, only C¼NOH group was selectively oxidized to
corresponding carbonyl compounds and the reagent was ineffective in
oxidizing double bond (Table 1, oxime 12)
Another noteworthy advantage of the reagent lies exclusive cleavage
of ketoxime irrespective of the presence of aldoxime. When a mixture of
finely powdered benzophenone oxime and benzaldehyde oxime was
ground at 50ꢀC for 30 min, only benzophenone oxime was selectively
converted to benzophenone, and benzaldehyde oxime did not react at
all (Sch. 1).

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Solid State Cleavage of Oximes
737
Table 1. Cleavage of oximes with supported permanganate on alumina.
Time
(min)
Temperature
(ꢀC)
Yieldsa
(%)
Entry
R1
R2
1
2
Ph
Ph
Ph
H
40
20
15
10
40
15
40
40
15
40
15
40
10
10
15
25
40
30
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
78
94
99
80
88
84
80
73
93
90
93
90
91
87
95
92
84
97
CH3
Ph
3
4
2-ClC6H4
CH3
H
5
3,4,5(MeO)3C6H2
4-MeOC6H4
4-ClC6H4
6
CH3
H
7
8
3,4(MeO)2C6H3
3,4(MeO)2C6H3
2-MeC6H4
4-MeC6H4
PhCH¼CH
PhCH¼CH
PhCH¼CH
2-naph
H
9
CH3
H
10
11
12
13
14
15
16
17
18
CH3
H
Ph
CH3
CH3
CH3CH2
H
2-naph
4-NO2C6H3CH¼CH
Ph
PhCO
19
10
50
91
20
15
50
87
aYields refer to isolated products.
Pyridiniumchlorochromate (PCC) is a reagent that converts the
oximes to carbonyl compounds.[22] In Table 2 some of the results of
our experiments are compared with those reported with PCC. The results
show that rate and the yields of reactions are higher with KMnO4–Al2O3
than those reported with PCC. In addition, in our method the reactions
took place under solvent-free conditions, therefore is cheaper and safer
than PCC method.

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738
Imanzadeh, Hajipour, and Mallakpour
Scheme 1.
Table 2. Comparison of oxidation of some oximes with KMnO4–Al2O3
and PCC.
KMnO4–Al2 O3
Yield (min)
PCC[22]
Substrate
Product
Yield (h)
Cyclohexanone oxime
Cyclopentanone oxime
Acetophenone oxime
Benzaloxime
Cyclohexanone
Cyclopentanone
Acetophenone
Benzaldehyde
91 (10)
87 (15)
94 (20)
78 (40)
47 (18)
28 (18)
61 (15)
56 (15)
In conclusion, in this study, we introduced a new method for regen-
eration of carbonyl compounds from oximes using inexpensive alumina
supported potassiumpermanganate. Aldehydes were in high yields without
further oxidation to acid. Our method is simple, safe, low cost, and rapid.
All yields refer to isolated product. Thin layer chromatography
(TLC) was carried out using glass sheets precoated with silica gel 60F.
Melting points were determined on an Electro thermal Gallen Kamp
apparatus and uncorrected. 1H NMR spectra were recorded on a

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Solid State Cleavage of Oximes
739
VarianEM-390(60 MHz).InfraredspectrawereobtainedusingaShimadzu
IR-435 spectrometer. The purity of products was determined by GC and
1H NMR spectroscopy, and comparing with authentic samples.
DEOXIMATION WITH ALUMINA
SUPPORTED PERMANGANATE
General Procedure
Dry powder of benzophenone oxime (1 mmol, 0.197 g) was added to
KMnO4–Al2O3 (1.4 mmol, 1.0 g),[16] and the mixture was ground with a
pestle in a mortar at 50ꢀC for 15 min. After completion of reaction
(monitored by TLC), acetone (15 mL) was added to the reaction mixture
and after vigorous stirring (5 min at room temperature), the mixture was
filtered and acetone was evaporated by rotary evaporator. The residue
was dissolved in the ether (20 mL). The organic layer was washed
with 10% HCl (10 mL) and dried (MgSO4). Evaporation of the solvent
under vacuumgave the benzophenone in pure form(99%). M.p.
47–48ꢀC, lit.[3] 48ꢀC.
ACKNOWLEDGMENTS
We thank Mohagheghe Ardabili University and Isfahan University
of Technology Councils for the partial support of this work.
REFERENCES
1. Firouzabadi, H.; Sardarian, A.R.; Naderi, M.; Vesal, B. Tetrahedron
1984, 23, 5001.
2. Firouzabadi, H.; Mohammadpoor Baltork, I. Bull. Chem. Soc. Jpn.
1992, 64, 1185.
3. Firouzabadi, H.; Mostafavipoor, Z. Bull. Chem. Soc. Jpn. 1983,
56, 914.
4. Firouzabadi, H.; Sardarian, A.R. Synth. Commun. 1983, 13, 863.
5. Mohammadpoor Baltork, I.; Pouranshivani, S. Synth. Commun.
1996, 26, 1.
6. Fatiadi, A.J. Synthesis 1987, 85.
7. Menger, F.M.; Lee, C. J. Org. Chem. 1979, 44, 3446.

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740
Imanzadeh, Hajipour, and Mallakpour
8. Corey, E.J.; Hopkins, P.B.; Kim, S.; Yoo, S.; Nambiar, K.P.;
Falk, J.R. J. Am. Chem. Soc. 1979, 101, 7131.
9. Barton, D.H.R.; Beaton, J.M.; Jeller, L.E.; Pechet, M.M. J. Am.
Chem. Soc. 1961, 83, 4076.
10. Hersberg, E.B. J. Org. Chem. 1984, 49, 542.
11. Satish, S.; Kalyanam, N. Chem. Ind. 1981, 809.
12. Pines, S.H.; Chemerda, J.M.; Kozlowoski, M.A. J. Org. Chem.
1966, 31, 3446.
13. Drabowicz, J. Synthesis 1980, 125.
14. Hajipour, A.R.; Mahboubkhah, N. J. Chem. Research (s) 1998, 123.
15. Rao, C.G.; Radhakrishna, A.S.; Singh, B.B.; Bhatnagar, S.P.
Synthesis 1983, 808.
16. Hajipour, A.R.; Mallakpour, S.E.; Imanzadeh, G.H. Chemistry
Lett. 1999, 99.
17. Hajipour, A.R.; Mallakpour, S.E.; Imanzadeh, G.H. J. Chem.
Research (s) 1999, 228.
18. Hajipour, A.R.; Mallakpour, S.E.; Imanzadeh, G.H. Indian J. Chem.
Sect. B 2001, 40B, 250.
19. Hajipour, A.R.; Mallakpour, S.E.; Imanzadeh, G.H. Indian J. Chem.
Sect. B 2001, 40B, 237.
20. Hajipour, A.R.; Mohammadpoor Baltork, I.; Imanzadeh, G.H.
Synth. Commun. 1999, 29, 1697.
21. Ghiaci, M.; Imanzadeh, G.H. Synth. Commun. 1998, 28, 2275.
22. Maloney, J.R.; Saavedra, J.E. Synthesis 1978, 212.
Received in Japan December 19, 2001