A new application of N-bromosaccharin as a selective and efficient oxidative reagent for regeneration of carbonyl compounds from oximes

Article abstract of DOI:10.1080/10426500490485471

A new method for the direct conversion of various oximes into aldehydes and, ketones by treatment with N-bromosaccharin is described. N-bromosaccharin can be used for an effective, selective and mild oxidizing agent for the regeneration of carbonyl compounds from oximes in good yield.

Full text of DOI:10.1080/10426500490485471

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Phosphorus, Sulfur, and Silicon
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A NEW APPLICATION OF N-
BROMOSACCHARIN AS A
SELECTIVE AND EFFICIENT
OXIDATIVE REAGENT FOR
REGENERATION OF CARBONYL
COMPOUNDS FROM OXIMES
Ardeshir Khazaei a , Abbas Amini Manesh a & Amin
Rostami a
a Department of Chemistry, Faculty of Sciences, Bu-
Ali Sina University , Hamadan, Iran
Published online: 16 Aug 2010.
To cite this article: Ardeshir Khazaei , Abbas Amini Manesh & Amin Rostami (2004)
A NEW APPLICATION OF N-BROMOSACCHARIN AS A SELECTIVE AND EFFICIENT
OXIDATIVE REAGENT FOR REGENERATION OF CARBONYL COMPOUNDS FROM OXIMES,
Phosphorus, Sulfur, and Silicon and the Related Elements, 179:12, 2483-2486, DOI:
10.1080/10426500490485471
To link to this article: http://dx.doi.org/10.1080/10426500490485471
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Phosphorus, Sulfur, and Silicon, 179:2483–2486, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490485471
A NEW APPLICATION OF N-BROMOSACCHARIN
AS A SELECTIVE AND EFFICIENT OXIDATIVE
REAGENT FOR REGENERATION OF CARBONYL
COMPOUNDS FROM OXIMES
Ardeshir Khazaei, Abbas Amini Manesh, and Amin Rostami
Department of Chemistry, Faculty of Sciences, Bu-Ali Sina
University, Hamadan, Iran
(Received March 23, 2004; accepted April 13, 2004)
A new method for the direct conversion of various oximes into alde-
hydes and ketones by treatment with N-bromosaccharin is described.
N-bromosaccharin can be used for an effective, selective and mild oxi-
dizing agent for the regeneration of carbonyl compounds from oximes
in good yield.
Keywords: Aldehydes; ketones; N-bromosaccharin; oximes
Regeneration of carbonyl compounds from the corresponding oximes is
a very important reaction because oximes are the preferred deriva-
tives for purification and characterization of carbonyl compounds.
Oximes are also useful as protecting group.1 So far a good num-
ber of methods based on hydrolytic,2 reductive,3 and oxidative4 re-
actions have been developed for deoximation. The methods based on
oxidative reactions make use of several oxidizing agents. These in-
clude Chromium reagents such as pyridinium chlorochromate,5 pyri-
dinium chlorochromate-H2O2,6 trimethyl ammonium chlorochromate,7
and others such as periodic acid,8 dinitrogen tetroxide,9 dimethyl
dioxirane,10 manganese triacetate,11 and N-haloamines.12 In spite
of the many reagents available, there is still a need for newer
reagents, because the existing oxidative methods suffer from one or
the other disadvantages such as long reaction times,13 need for reflux-
ing temperature,11 difficulties in isolation of products,5–7 and forma-
tion of over oxidation products leading to low yields. In this article, we
Address correspondence to Ardeshir Khazaei, Department of Chemistry, Faculty
of Sciences, Bu-Ali Sina University, P.O. Box 65178-4111, Hamadan, Iran. E-mail:
a Khazaei@basu.ac.ir
2483

2484
A. Khazaei et al.
report a new oxidative method for deoximation using N-bromosaccharin
(N.B.Sa.) as an oxidizing agent, which overcomes the disadvantages as-
sociated with oxidative methods developed so far (Scheme 1).
SCHEME 1
RESULTS AND DISCUSSION
The results of the conversion of various oximes to their corresponding
carbonyl compounds are presented in Table I.
Dissolution of oximes in acetone with the addition of a small amount
of water and subsequent reaction with N.B.Sa. under stirring at room
temperature or reflux gave the corresponding carbonyl compounds
in good yields. Even the sterically hindered ketone oxime (Table I,
TABLE I Deoximation with N.B.Sa. at Room Temperature
Entry
Substrate
Product
Time (h) Yield (%)a,b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Cyclohexanone oxime
Acetophenone oxime
Benzaldehyde oxime
4-Chloro benzaldehyde oxime 4-Chloro benzaldehyde
Benzophenone oxime Benzophenone
4-Methyl acetophenone oxime 4-Methyl acetophenone
Isobutyraldehyde oxime Isobutyraldehyde
Isobutyl methyl ketone oxime Isobutyl methyl ketone
Diisopropyl ketone oxime Diisopropyl ketone
2-Chloro benzaldehyde oxime 2-Chloro benzaldehyde
Cyclohexanone
Acetophenone
Benzaldehyde
1.5
1.5
1.5
1.5
1.5
1.6
2
96.52
94.7
94.5
94
93.5
93
92
91
91
2
2.2
2.6
2.2
2.6
3.8
2.5
90.8c
90.3
90c
86c
82
Ethyl methyl ketone oxime
Benzoin oxime
Camphor oxime
Ethyl methyl ketone
Benzoin
Camphor
Cyclopentanone oxime
Cyclopentanone
aProducts were characterized by their physical constants, comparison with authentic
samples and melting points of 2,4-dinitro phenyl hydrazone derivatives, and by their IR
and NMR spectra.
bIsolated yields.
cUnder reflux conditions.

Deprotection of Oximes
2485
entry 13) was succesfully oxidatively cleaved to the corresponding ke-
tone in good yield. The aldoximes were converted to the corresponding
aldehydes, and no acid was formed due to overoxidation of the regener-
ated aldehyde (Table I, entries 3, 4, 7, 10). This procedure is also useful
for the chemoselective oxidative deoximation of oximes in the presence
of alcohols or for oximes that contain OH functional group (Table I,
entry 12). Thus, when equimolar mixtures of cyclohexanone oxime and
benzyl alcohol in acetone and water were allowed to react with N.B.Sa.
at room temperature, the ketone oxime underwent chemoselectively ox-
idative deoximation, giving (95%) cyclohexanone, whereas the benzyl
alcohol was recovered unchanged (Scheme 2).
SCHEME 2 Selective deoximation in the presence of alcohol.
On the other hand, in this reaction (according to Scheme 1) N-
bromosaccharin(I) converted to the saccharin(II), which can be isolated,
brominated, and reused as a new deoximating reagent.
CONCLUSION
In conclusion, the striking features of our method are the reaction oc-
curs at room temperature, no formation of overoxidation products due
to high chemoselectivity and the mild nature of N-bromosaccharin, easy
workup procedure, high yields, and the oxidative reagent (N.B.Sa.) can
be recovered and reused many times.
EXPERIMENTAL: GENERAL PROCEDURE
A mixture of the oxime (3 mmol) and N.B.Sa. (3.5 mmol) in acetone
(10 ml) and water (1 ml) was stirred at the temperature given in Table I
for the specified time. After the reaction was completed (thin layer chro-
matography (TLC)), the solvent was removed under reduced pressure
and 20 ml of diethyl ether was added to the mixture. It was then stirred

2486
A. Khazaei et al.
for 10 min, and then the saccharin was removed by filteration and the
product was purified by column chromatography (CCl4/methanol).
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