A novel catalytic method for the regeneration of carbonyl compounds from oximes using aluminum nitrate and NaBr as catalyst

Article abstract of DOI:10.1016/j.cclet.2010.03.019

A wide variety of aldoximes and ketoximes were regenerated to corresponding carbonyl compounds with Al(NO₃)₃·9H₂O in presence of catalytic amounts of NaBr in CH₂Cl₂ at room temperature.

Full text of DOI:10.1016/j.cclet.2010.03.019

Available online at www.sciencedirect.com
Chinese Chemical Letters 21 (2010) 1083–1086
www.elsevier.com/locate/cclet
A novel catalytic method for the regeneration of carbonyl
compounds from oximes using aluminum nitrate
and NaBr as catalyst
*
Arash Ghorbani-Choghamarani , Javad Zeinivand
Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran
Received 25 January 2010
Abstract
A wide variety of aldoximes and ketoximes were regenerated to corresponding carbonyl compounds with Al(NO
3
)
3
Á9H
2
O in
presence of catalytic amounts of NaBr in CH Cl at room temperature.
2010 Arash Ghorbani-Choghamarani. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
2
2
#
Keywords: Deoximation; Aluminum nitrate [Al(NO
3
)
3
2
Á9H O]; NaBr; Oximes
Recently, development of efficient and new catalytic systems for various organic transformations is an active
ongoing research area and the scope for further improvement towards milder reaction conditions [1]. The development
of heterogeneous catalysts for fine chemicals synthesis has become a major area of research [2]. Also important aspect
of clean technology is the use of environmentally friendly catalysts [3].
Developing mild and efficient methods for the selective cleavage of nitrogen-containing derivatives to afford
carbonyl compounds continues to be a significant aspect of organic chemical transformation [4]. Apart from their
usefulness as latent protected forms of aldehydes and ketones, oximes occupy a key position in the chemical space that
correlates carbonyl compounds with nitroalkanes, amines and carboxamides [5]. Oximes are easily prepared. Also
they are highly stable and crystalline compounds, which are used for the isolation, purification and characterization of
carbonyl compounds. Since oximes can be prepared from non-carbonyl compounds, the regeneration of carbonyl
compounds from oximes provides an alternative method for the preparation of aldehydes and ketones [6–8].
Even though various approaches have been reported for deoximation reaction such as silica chromate
[
tert-butyl hypoiodite [13], 2-iodobenzoic acid/b-cyclodextrin/H O [14], tungstate sulfuric acid/NaNO [15],
9], aqueous H PO [10], tungstate sulfuric acid (TSA)/KMnO [11], tetra-n-alkylammonium bromates [12],
3 4 4
2
2
BAcImBF /silica gel [16], H O /montmorillonite-K10 supported CoCl [17], N-bromophthalimide [18], and
2
4
2
2
bispyridine-silver(I) dichromate [19], but these methods suffer from some disadvantages like long reaction times,
expensive reagent and catalyst, difficulties in isolation of products, and formation of over-oxidation products
leading to low yields.
*
Corresponding author.
E-mail addresses: arashghch58@yahoo.com, a.ghorbani@mail.ilam.ac.ir (A. Ghorbani-Choghamarani).
1001-8417/$ – see front matter # 2010 Arash Ghorbani-Choghamarani. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2010.03.019

1084
A. Ghorbani-Choghamarani, J. Zeinivand / Chinese Chemical Letters 21 (2010) 1083–1086
+
Recently we have shown that bromonium ion (Br ) can effectively apply for the oxidation of different types of
+
organic compounds [20–24]. Therefore we wish to examine Br for the regeneration of carbonyl compounds from
oximes. However a mixture of aluminum nitrate in the presence of catalytic amount of NaBr was applied for the in situ
+
generation of Br .
In this communication we report a novel catalytic media for the effective regeneration of carbonyl compounds from
aldoximes and ketoximes using Al(NO ) Á9H O in the presence of catalytic amounts of NaBr.
3
3
2
Therefore, various aldoximes and ketoximes 1 were deoximated with combination of Al(NO ) Á9H O I and
3
3
2
catalytic amounts of NaBr II in dichloromethane at room temperature in good to high yields (Scheme 1 and Table 1).
The deoximation reactions were carried out under completely heterogeneous conditions in dichloromethane at
room temperature. The reaction procedure is very simple and the products are easily isolated from the reaction media
because in this heterogeneous system the reagent and catalyst are insoluble in dichloromethane; therefore products can
be easily obtained by simple filtration and evaporation of CH Cl .
2
2
To approve the catalytic role of NaBr in this catalytic system, para-methyl benzaldehyde oxime (1m), as typical
example, was subjected to deoximation reaction without sodium bromide. Surprisingly, it was observed that the
reaction time increased to 22.5 h (entry 14, Scheme 2).
A possible mechanism of this oxidizing system is shown in Scheme 3.
One of the observed evidence for this mechanism is evolving of NO from the reaction vessel that can be converted
to the nitrogen brown-color oxides, which can be observed on the top of the reaction solution.
In conclusion, we have developed a novel, heterogeneous and catalytic protocol for the selective deoximation of
aldoximes and ketoximes into corresponding carbonyl compounds via combination of aluminum nitrate and catalytic
amount of NaBr. Furthermore, this method exhibits substrate versatility, mild reaction conditions, and easy and clean
work-up of products.
1
. Experimental
All ketoximes and aldoximes were prepared by aldehydes and ketones, which were purchased from Fluka, Merck
and Aldrich chemical companies.
[(Scheme_1)TD$FIG]
Scheme 1.

A. Ghorbani-Choghamarani, J. Zeinivand / Chinese Chemical Letters 21 (2010) 1083–1086
1085
Table 1
Regeneration of carbonyl compounds from oximes using Al(NO
temperature.
3
)
3
Á9H
2
O I in the presence of catalytic amounts of NaBr II in CH
2
Cl
2
at room
a,b
Entry
Substrate
Product
Substrate/reagent/catalyst (mmol)
Time (min)
Yield (%)
I
II
1
2
3
4
5
6
7
8
9
1a
1b
1c
1d
1e
1f
2a
2b
2c
2d
2e
2f
1.2
1.2
1.2
1.2
1.2
1.2
2
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
–
55
98
98
89
97
97
91
79
58
83
96
89
99
90
110
45
160
105
220
190
30.5h
240
6.75h
195
180
210
22.5h
195
1g
1h
1i
2g
2h
2i
4
2
1
1
1
1
1
1
0
1
2
3
4
5
1j
2j
2
1k
1l
2k
2l
2
2
1m
1m
1n
2m
2m
2n
2
c
2
88
2
0.05
94
a
Isolated yields.
1 13
The oxidation products (aldehydes and ketones) were characterized by comparison of their spectral (IR, H NMR, and C NMR) and physical
b
data with authentic samples.
c
Without catalyst.
[(Scheme_2)TD$FIG]
Scheme 2.
[(Scheme_3)TD$FIG]
Scheme 3.

1086
A. Ghorbani-Choghamarani, J. Zeinivand / Chinese Chemical Letters 21 (2010) 1083–1086
1
.1. Deoximation of cyclohexane oxime 1c to cyclohexanone 2c using Al(NO ) Á9H O and NaBr
3
3
2
A mixture of cyclohexane oxime 1c (0.113 g, 1 mmol), Al(NO ) Á9H O (0.344, 1.2 mmol) and NaBr (0.005 g,
3
3
2
0
TLC). After reaction completion, reaction mixture was filtered and the residue was washed with CH Cl (20 mL).
.05 mmol) in CH Cl (5 mL) was stirred at room temperature for 45 min (the reaction progress was monitored by
2 2
2
2
Finally CH Cl was removed and the yield was 0.087 g (89%).
2
2
Acknowledgment
Financial support for this work by the research facilities of Ilam University, Ilam, Iran is gratefully acknowledged.
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