Clinoptilolite-supported Iron(III) nitrate as a powerful and efficient deoximation catalyst. Fast regeneration of carbonyl compounds from oximes

Article abstract of DOI:10.1134/S1070428009060104

Clinoptilolite-supported iron(III) nitrate (clinofen) ensures fast and efficient regeneration of carbonyl compounds from the corresponding oximes Pleiades Publishing, Ltd., 2009.

Full text of DOI:10.1134/S1070428009060104

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 6, pp. 863–864. © Pleiades Publishing, Ltd., 2009.
Published in Russian in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 6, pp. 876–877.
Clinoptilolite-Supported Iron(III) Nitrate as a Powerful
and Efficient Deoximation Catalyst. Fast Regeneration
of Carbonyl Compounds from Oximes*
M. M. Heravi, K. Bakhtiari, H. A. Oskooie, and R. Hekmatshoar
Department of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran, Iran
Received May 15, 2006
Abstract—Clinoptilolite-supported iron(III) nitrate (clinofen) ensures fast and efficient regeneration of car-
bonyl compounds from the corresponding oximes.
DOI: 10.1134/S1070428009060104
Oximes are crystalline substances which are widely
used for the isolation, purification, and identification
of parent carbonyl compounds [1]. Protection of car-
bonyl functionality via conversion into the correspond-
ing oximes attract considerable attention of organic
chemists, taking into account that such derivatives can
readily be obtained and are highly stable [2].
pounds remains an important problem. We recently
reported on solvent-free deoximation of oximes using
zeofen under microwave irradiation [14]. In the present
communication we report on a very convenient and
highly effective procedure for oxidative deoximation
of ketone and aldehyde oximes to the corresponding
carbonyl compounds using clinoptilolite-supported
iron(III) nitrate (clinofen) [15] as nontoxic hetero-
geneous reagent in an organic solvent under moderate
conditions (no aqueous media were needed).
Regeneration of carbonyl compounds from their
oximes is a quite important problem. In the recent
years, numerous reagents have been proposed to effect
deoximation (for review, see [3]). Some other reagents,
such as thallium(III) nitrate on HZSM-5 zeolite [4],
ammonium chlorochromate applied to clay [5], Oxone
over wet alumina [6], silica-supported prolinium
chlorochromate [7], 2,6-dicarboxypyridinium chloro-
chromate [8], silica-supported bismuth(III) nitrate in
the presence of DABCO [9], etc. [10, 11] were also
reported.
Fe(NO ) ·9H O/clinoptilolite
3
3
2
NOH
O
CHCl , reflux
3
R
R'
R
R'
R = Ar, Alk; R′ = H, Alk (see table).
As far as we know, this is the first report on the use
of clinoptilolite in organic synthesis. Our results (see
table) demonstrate such advantages of the proposed
procedure as high rate of oxidative deoximation, no
formation of overoxidation products, simple experi-
ment, and high yields.
Most known methods for the recovery of car-
bonyl compounds from their oximes have some limita-
tions, including long reaction times, tedious work-up
and isolation procedures, and expensive, hazardous, or
very toxic reagents. In addition, some procedures
require the use of difficultly accessible reagents which
must be freshly prepared. Many reagents are not selec-
tive for oximes in the presence of unsaturated C=C
bonds [12]. In some cases, side overoxidation proc-
esses led to reduction of the yield of the target products
EXPERIMENTAL
All initial oximes were prepared by known meth-
ods. The physical and spectral properties of the ob-
tained carbonyl compounds were identical to those
reported for authentic samples [16].
[
13]. Therefore, search for mild, selective, safe, low-
Regeneration of carbonyl compounds from the
corresponding oximes using clinofen. A mixture of
expensive, and effective oxidants for the transforma-
tion of oximes into the corresponding carbonyl com-
1
mol of oxime, 1 g of clinoptilolite, and 1 mmol of
*
The text was submitted by the authors in English.
iron(III) nitrate in 10 ml of chloroform was heated un-
8
63

8
64
HERAVI et al.
Deoximation of aldehyde and ketone oximes using iron(III)
nitrate supported onto clinoptilolite (chloroform, reflux)
4. Heravi, M.M. and Ghasemzadeh, M., Phosphorus,
Sulfur Silicon Relat. Elem., 2003, vol. 178, p. 119.
5
. Heravi, M.M., Beheshtiha, Y.S., Ghasemzadeh, M.,
Hekmatshoar, R., and Sarmad, N., Monatsh. Chem.,
2000, vol. 131, p. 187.
mp (bp), °C
Time, Yield, %
min (GLC data)
R
R′
this published
work data [16]
6. Bigdeli, M.A., Alavi Nikje, M.M., and Heravi, M.M.,
Phosphorus, Sulfur Silicon Relat. Elem., 2002, vol. 177,
p. 15.
3
4
4
2
-O
2
NC
6
H
4
H
10
02
99
94
92
96
96
94
97
95
97
96
56
56–59
-MeC
-ClC
-MeOC
6
H
4
H
H
H
H
(204) (204–205)
7
. Shirini, F., Mamaghani, M., Parsa, F., and Mohammad-
Baltork, I., Bull. Korean Chem. Soc., 2002, vol. 23,
p. 1683.
6
H
4
12
46
47
6
H
4
05
(238)
(253)
(158)
79
(238)
(253)
(156)
80–82
PhCH=CH
CH
15
8. Tajbakhsh, M., Hosseinzadeh, R., and Shakoori, A.,
Tetrahedron Lett., 2004, vol. 45, p. 1889.
(
2
)
5
0.01.5
15
9. Khazaei, A., Ghorbani-Vaghei, R., and Tajbakhsh, M.,
4
-O
2
NC
6
H
4
Me
H
Tetrahedron Lett., 2001, vol. 42, p. 5099.
Me(CH
Me(CH
2
)
8
6
05
(209) (208–209)
1
0. Niaki, T.T., Oskooiee, H.A., Heravi, M.M., and
2
)
H
02
(171)
44
(171)
Miralaee, B., J. Chem. Res., 2004, no. 7, p. 488.
2
-O
2
NC
6
H
4
H
10
43.4–44.0
1
1. Li, D., Shi, F., Guo, Sh., and Deng, Y., Tetrahedron
Lett., 2004, vol. 45, p. 265.
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Int., 1998, vol. 39, p. 713; Hajipour, A.R. and Mah-
boubhgah, N., Org. Prep. Proced. Int., 1999, vol. 31,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009