Conversion of oximes into carbonyl compounds with thalium(III) nitrate supported onto HZSM-5 zeolite under microwave irradiation in solventless system

Article abstract of DOI:10.1080/10426500307816

Oximes are oxidatively deprotected by thalium(III) nitrate supported onto HZSM-5 zeolite to the parent carbonyl compounds in high yields upon exposure to microwave irradiation.

Full text of DOI:10.1080/10426500307816

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Phosphorus, Sulfur, and Silicon and the Related
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Conversion of Oximes into Carbonyl Compounds with
Thalium(III) Nitrate Supported onto HZSM-5 Zeolite
Under Microwave Irradiation in Solventless System
a
b
Majid M. Heravi & Mitra Ghassemzadeh
a
Azzahra University , Vanak, Tehran, Iran
b
Chemistry and Chemical Engineering Research Center of Iran , Tehran, Iran
Published online: 27 Oct 2010.
To cite this article: Majid M. Heravi & Mitra Ghassemzadeh (2003) Conversion of Oximes into Carbonyl Compounds with
Thalium(III) Nitrate Supported onto HZSM-5 Zeolite Under Microwave Irradiation in Solventless System, Phosphorus, Sulfur, and
Silicon and the Related Elements, 178:1, 119-123, DOI: 10.1080/10426500307816
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Phosphorus, Sulfur and Silicon, 2003, Vol. 178:119–123
Copyright �C 2003 Taylor & Francis
1
042-6507/03 $12.00 + .00
DOI: 10.1080/10426500390170255
CONVERSION OF OXIMES INTO CARBONYL
COMPOUNDS WITH THALIUM(III) NITRATE
SUPPORTED ONTO HZSM-5 ZEOLITE
UNDER MICROWAVE IRRADIATION
IN SOLVENTLESS SYSTEM
a
b
Majid M. Heravi and Mitra Ghassemzadeh
a
Azzahra University, Vanak, Tehran, Iran and Chemistry and
Chemical Engineering Research Center of Iran, Tehran, Iran
b
(
Received June 20, 2002)
Oximes are oxidatively deprotected by thalium(III) nitrate supported
onto HZSM-5 zeolite to the parent carbonyl compounds in high yields
upon exposure to microwave irradiation.
Keywords: Carbonyl compounds; deoximation; microwave irradiation;
thalium nitrate; zeolite
INTRODUCTION
Oximes frequently are used to protect carbonyl compounds and
hence much attention has been paid to develop methods for their
1
deprotection. Since oximes can be prepared from noncarbonyl com-
pounds, its conversion to carbonyl compounds can be considered a use-
2,3
ful method for the synthesis of the latter.
The classical recovery of aldehydes or ketones from oximes con-
sists of acid hydrolysis which removes the hydroxylamine from the
4
equilibrium and often results in low yields. Although a large number
of reagents are found in the literature for cleavage of oximes to carbonyl
5
compounds, there still appears a need either to improve the existing
methods or to introduce newer reagents to permit better selectivity with
easy work up procedures.
M. M. Heravi is thankful for the partial financial support from Azzahra University
Research Council.
Address correspondence to Majid M. Heravi, Department of Chemistry, School of
Sciences, Azzahra University, Vanak, Tehran, Iran. E-mail: mmheravi@azzahra.ac.ir
1
19

1
20
M. M. Heravi and M. Ghassemzadeh
6
Thalium(III) nitrate has been used as an oxidizing agent and
7
Willgerodth-Kindler reaction. Recently, there has been growing inter-
est in the application of microwave irradiation in chemical reaction
8
enhancement, the salient features being improved reaction rates and
formation of cleaner products.
When this technique is combined with solvent-free conditions, it
would be especially appealing as it provides an opportunity to work
with open vessels, thus avoiding the risk of high pressure development,
and a possibility of carrying out the reaction on a preparative scale in
9
addition to the associated selectivity and ease of manipulation. The mi-
crowave enhanced chemical reactions on mineral supports have gained
1
0
much attention.
In continuation of our ongoing program to develop environ-
mentally benign reactions under solvent-free conditions using sup-
ported reagent combined with microwave,11 in this article we re-
port the deoximation reaction using thalium(III) nitrate supported
onto HZSM-5 zeolite under microwave irradiation in solventless
system.
RESULTS AND DISCUSSION
Recently, we reported12 on the use of HZSM-5 zeolite as a support for
the oxidation of alcohols. Among various mineral supports examined
such as alumina, clay, silica, and Na-zeolite, we found that HZSM-5
zeolite gives the best results. A weight equivalent of HZSM-5 zeo-
lite and thalium(III) nitrate were crushed using pestle and mortar to
give an intimate pair. Two equivalents of this mixture were crushed
with the equivalent of neat benzaldoxime and exposed to microwave
irradiation.
The progress of the reaction was monitored by TLC using petroleum
ether-ethyl acetate, 8:2, as eluents. After 2 min deoximation of ben-
zaldoxime was complete to afford benzaldehyde almost in quantitative
yield.
To assess the generality of this deoximation method a variety of
aldoximes and ketoximes were reacted under these conditions which
yielded to excellent yields (Table I). The interesting feature of this
method is the successful deoximation of ketones. As with some other
13
reagents it results in the formation of Beckmann rearrangement
products. However, this method is unsuccessful when applied to aryl al-
doximes and ketoximes which contain strong electron donating groups
such as � NH2 or � OH at ortho or para position most probably due

Deoximation
121
TABLE I Deoximation Reaction Using Thalium(III) Nitrate Under
Microwave Irradiation in a Solventless System
Reaction time
Yieldb
(%)
Entry
1
Substrate
(sec)
Producta
120
98
2
3
120
80
83
85
4
5
180
240
82
80
6
7
240
180
85
92
8
9
240
240
83
90
aAll products were known and identified by comparison of their physical data with
those of authentic sample.
b
Yields are based on isolated product.

1
22
M. M. Heravi and M. Ghassemzadeh
to concomitant oxidation of the aromatic ring to quinone derivatives
Scheme 1).
(
SCHEME 1
This phenomenon has been noticed previously.14 This limitation,
however, can be circumvented by acetylation of the OH and NH2 groups
1
4
before the formation of oximes.
In conclusion we have developed a rapid and solventless method for
cleavage of oxime compounds. This high yielding method is manipu-
latively simple and a selective protocol when compared to the conven-
tional solution phase or heterogeneous reactions.
EXPERIMENTAL SECTION
All substrates were synthesized by a known literature procedure. All
products were characterized by comparison of their physical and spec-
troscopic data with those of authentic samples.
Deprotection of Oximes. Typical Procedure.
Thalium(III) nitrate (4 mmol) and benzylaldoxime (2 mmol) were
crushed using a pestle and mortar. This mixture was transferred to
a beaker and exposed to microwave irradiation. The progress of the
reaction was monitored by TLC using petroleum ether: ethyl acetate
8
:2. After completion of the reaction, the product was extracted with
dichloromethane and filtered. The filtrate was evaporated to dryness to
afford benzaldehyde. Yield 98%.
Caution: Although this reaction worked safely in our hand, using a
microwave oven in an efficient hood is highly recommended.

Deoximation
123
REFERENCES
[
[
[
1] T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis (John Wiley
and Sons, New York, 1999), 3rd ed.
2] D. H. R. Barton, J. M. Beaton, L. E. Geller, and M. M. Pechel, J. Am. Chem. Soc.,
8
3, 4076 (1961).
3] A. R. Katritzky, O. Meth-Cohn, and C. W. Rees, eds., Comprehensive Organic Func-
tional Groups Transformations (Pergamon, New York, 1995), 1st ed., vol. 3.
4] E. B. Hersberg, J. Org. Chem., 13, 542 (1948).
[
[
5] a) N. B. Barhate, A. S. Gajare, R. D. Wakarkar, and A. Sudalai, Tetrahedron Lett.,
3
8, 653 (1997); b) Y. S. Yadav, P. K. Sasmal, and P. K. Chand, Synth. Commun., 29,
3
667 (1999); c) B. A. Nattier, K. J. Eash, and R. S. Mohan, Synthesis, 1010 (2001);
d) A. Carsaro, A. Chiacchio, and V. Pistara, Synthesis, 13, 1903 (2001).
[
[
6] A. McKillop, J. D. Hunt, R. D. Naylor, and F. C. Taylor, J. Am. Chem. Soc., 93, 4918
(
1971).
7] A. McKillop, J. D. Hunt, R. D. Naylor, and F. C. Taylor, J. Am. Chem. Soc., 93, 4919
1971).
(
[
[
8] R. A. Abramivoch, Org. Prep. Proced. Int., 23, 683 (1991).
9] R. S. Varma, R. Dahija, and R. K. Saini, Tetrahedron Lett., 38, 8819 (1997).
[
[
10] R. S. Varma and R. Dahija, Tetrahedron Lett., 38, 2043 (1997).
11] a) M. M. Heravi, D. Ajami, M. Ghassemzadeh, and M. M. Mojtahedi, Tetrahedron
Lett., 40, 561 (1999); b) M. M. Heravi, D. Ajami, and M. Ghassemzadeh, Synthesis,
3
, 393 (1999); c) M. M. Heravi, D. Ajami, K. Aghapoor, and M. Ghassemzadeh,
J. Chem. Soc., Chem. Commun., 833 (1999); d) M. M. Heravi, D. Ajami, and M. M.
Mojtahedi, J. Chem. Res., 126 (2000).
[
12] M. M. Heravi, D. Ajami, K. Tabar-Hydar, and M. Ghassemzadeh, J. Chem. Res., 334
(1999).
[
[
13] A. Bosch, P. Cruz, A. Diez-Barra, A. Loupy, and F. Langa, Synlett., 1259 (1995).
14] A. McKillop, B. P. Swann, and E. C. Taylor, Tetrahedron Lett., 26, 4031 (1970).