A facile method for the conversion of oximes and tosylhydrazones to carbonyl compounds with Cr-MCM-41 zeolite under microwave irradiation

Article abstract of DOI:10.1081/SCC-120005429

Cr-MCM-41 zeolite supported on silica gel can be used as an effective and mild oxidizing agent for the direct conversion of oximes and tosylhydrazones to carbonyl compounds under microwave irradiation in good yield. The procedure is applicable to the variety of oximes and tosylhydrazones and the zeolite can be recycled.

Full text of DOI:10.1081/SCC-120005429

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A FACILE METHOD FOR THE CONVERSION OF OXIMES
AND TOSYLHYDRAZONES TO CARBONYL COMPOUNDS
WITH CR-MCM-41 ZEOLITE UNDER MICROWAVE
IRRADIATION*
a
a
a
Lingaiah Nagarapu , Narender Ravirala & Dattatray Akkewar
a
Organic Chemistry Division-II, Indian Institute of Chemical Technology, Hyderabad, 500 007,
India
Published online: 18 Oct 2011.
To cite this article: Lingaiah Nagarapu , Narender Ravirala & Dattatray Akkewar (2002) A FACILE METHOD FOR THE
CONVERSION OF OXIMES AND TOSYLHYDRAZONES TO CARBONYL COMPOUNDS WITH CR-MCM-41 ZEOLITE UNDER MICROWAVE
IRRADIATION*, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
32:14, 2195-2202, DOI: 10.1081/SCC-120005429
To link to this article: http://dx.doi.org/10.1081/SCC-120005429
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 14, pp. 2195–2202, 2002
A FACILE METHOD FOR THE
CONVERSION OF OXIMES AND
TOSYLHYDRAZONES TO CARBONYL
COMPOUNDS WITH Cr-MCM-41 ZEOLITE
UNDER MICROWAVE IRRADIATION*
y
Lingaiah Nagarapu, Narender Ravirala,
and Dattatray Akkewar
Organic Chemistry Division-II, Indian Institute of
Chemical Technology, Hyderabad-500 007, India
ABSTRACT
Cr-MCM-41 zeolite supported on silica gel can be used as an
effective and mild oxidizing agent for the direct conversion of
oximes and tosylhydrazones to carbonyl compounds under
microwave irradiation in good yield. The procedure is applic-
able to the variety of oximes and tosylhydrazones and the
zeolite can be recycled.
[
1]
Oximes are useful protecting groups and are extensively used for
purification and characterization of carbonyl compounds. Oximes also
served as intermediates for many reactions such as the preparation
*
IICT Communication No. 4767.
Corresponding author. E-mail: nagarapu@iict.ap.nic.in
y
2
195
DOI: 10.1081/SCC-120005429
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

2
196
NAGARAPU, RAVIRALA, AND AKKEWAR
[
of amides via the Beckmann rearrangement. Their synthesis from non-
2]
[3]
carbonyl compounds provides an alternative pathway to aldehydes and
ketones. The hydrolytic stability of oximes has inspired the development of
[
several deoximation reagents such as trimethylammonium chlorochro-
4]
[
5]
[6]
[7]
mate, dinitrogen tetraoxide, pyridinium chloro chromate (PCC), chro-
[
8]
[9]
mium trioxide-chlorotrimethyl silane,
[11]
titanium silicate-1, tert-butylhydroperoxide, N-haloamides, manga-
nese triacetate,
Even among the new reagents, the use of dimethyl dioxirane is restricted
to ketoximes whereas PCC-H O suffers from the disadvantage of overox-
idation of resulting aldehydes.
[18–20]
Cr-MCM-41 zeolite
clay-supported ferric nitrate,
[10]
[12]
[13]
[14]
[15]
Dess-Martin periodinane (DMP)
and Cu(NO ).
3
[
16]
2
[
2
17]
has received wide recognition as a mild selec-
tive reagents for the oxidation reactions of saturated heterocyclics like
piperidine and pyrrolidine to piperidone and pyrrolidone. We now wish to
report a simple and efficient new method for the direct conversion of oximes
and tosylhydrazones to their corresponding carbonyl compounds by
Cr-MCM-41 zeolite as an oxidizing agent supported on silica gel under
microwave irradiation for accelerating the rate of chemical process
(
Scheme 1). Silica gel is essential for efficient oxidation. Because solid sup-
ports are rather poor thermal conductors (with consequently an important)
gradient in temperature inside the materials), whereas they behave as strong
microwave absorbents (and therefore with a better homogeneity in tempera-
[21]
ture). The salient features of the reaction is that the Cr-MCM-41 zeolite is
recovered and recycled for four cycles without substantial loss in the yield of
product.
Scheme 1.
Several examples illustrating this method are summarized in Tables 1
and 2. It is noteworthy that, unlike other oxidative hydrolytic methods, the
major drawback of overoxidation of the ensuring aldehydes, is not observed
under the reaction conditions. Even the sterically hindered camphor oxime
has been successfully converted to camphor in good yield. Interestingly, the
ꢀ
,ꢁ-unsaturated oxime underwent deoximation very efficiently without
affecting the C¼C bond and the reaction is essentially chemoselective.

Cr-MCM-41 ZEOLITE AS OXIDIZING AGENT
2197
Table 1. Oxidative Cleavage of Oximes with Cr-MCM-41-SiO Under Microwave
2
Irradiation
a
b
c
Entry
1
Substrate
Product
Time (min)
5
Yield (%)
98
2
3
5
5
98
97
4
5
6
5
98
95
6
5
87
7
8
10
10
72
75
9
10
8
77
85
1
0
(
continued )

2
198
NAGARAPU, RAVIRALA, AND AKKEWAR
Table 1. Continued
a
b
c
Entry
Substrate
Product
Time (min)
5
Yield (%)
90
1
1
1
1
1
2
3
4
6
5
6
90
96
92
1
1
1
5
6
7
5
6
7
98
97
88
1
1
8
9
8
6
86
88
2
0
1
8
86
2
6
82
a
All the substrates were prepared by known literature procedures.
1
All the products were characterized by comparison of their m.p. IR and H NM R
b
spectra with those of authentic samples.
c
Yields refer to isolated pure product.

Cr-MCM-41 ZEOLITE AS OXIDIZING AGENT
2199
Table 2. Oxidative Cleavage of Tosylhydrozaones with Cr-MCM-41-SiO Under
2
Microwave Irradiation
a
b
c
Entry
1
Substrate
Product
Time (min)
6
Yield (%)
96
2
3
5
5
93
92
4
5
5
6
90
95
6
6
95
7
8
7
8
86
82
9
10
9
85
98
1
0
(
continued )

2
200
NAGARAPU, RAVIRALA, AND AKKEWAR
Table 2. Continued
a
b
c
Entry
Substrate
Product
Time (min)
8
Yield (%)
77
1
1
1
1
1
2
3
4
6
7
5
98
98
78
1
1
1
5
6
7
6
6
76
80
82
10
1
8
9
7
8
88
86
1
2
0
10
72
2
1
6
75
a
All the substrates were prepared by known literature procedures.
1
All the products were characterized by comparison of their m.p. IR and H NM R
b
spectra with those of authentic samples.
c
Yields refer to isolated pure product.

Cr-MCM-41 ZEOLITE AS OXIDIZING AGENT
2201
In addition, it appears that electron withdrawing and electron donating
groups do not significantly affect the rate of reaction.
To show the dramatic acceleration in the rate of deprotection due to
microwave irradiation, under the same experimental conditions, several
oximes and tosylhydrazones were heated just by conventional heating.
However, only low yields of products were obtained in very long reaction
times. E.g., benzaldehyde was isolated from benzaldoxime at (10–18%,
ꢀ ꢀ ꢀ
6
(
5 C, 4 min), (77%, 65 C, 8 h), (88%, 100 C, 4 h), and tosylhydrazone at
ꢀ
ꢀ
ꢀ
8–15%, 65 C, 4 min), (62%, 65 C, 8 h), (78%, 100 C, 4 h).
In summary, we have developed a mild method for the regeneration
of carbonyl compounds from a variety of aromatic, aliphatic, polynuclear
and heterocyclic oximes and tosylhydrazones that possesses significant
advantages. The application of microwave offers a very quick and clean
method for this conversion. The optional simplicity, selectivity, high yields,
shorter reaction times, mild conditions and easy work-up, can make this
procedure a useful and attractive alternative to the currently available
methods.
Representative procedure: A mixture of oxime or tosylhydrazone
1.65 mmol) and Cr-MCM-41-SiO (0.15 g; 5.0 mmol/g of SiO ) was thor-
2 2
(
oughly ground in a mortor for a few minutes. The mixture was irradiated at
50 W for specified time (Tables 1 and 2). The reaction is monitored by TLC
the mixture was cooled to room temperature, water (50 mL) is added, (zeo-
6
lite was filtered and washed thoroughly with CCl and activated for recycle)
4
and the residue was extracted with CCl (2 ꢁ 5 mL). The combined organic
4
phase was washed with brine, dried (Na SO ) and the solvent was removed
2
4
in vacuo to afford the crude product which was purified by column chroma-
tography on silica gel eluted with ethyl acetate–hexane (1 : 5).
1
H NMR (CDCl , 200 MHz) of Entry 11 (Table 1, oxime): ꢂ 6.88 (d,
3
1
-
1
(
H, Ph-CH¼), 6.55 (dd, 1H, ¼CH-), 9.85 (d, 1H, CH¼N), 8.01 (brs, 1H,
OH), and 7.33–7.71 (m, 5H, Ar-H). Benzaldehyde (product): ꢂ 6.78 (d,
H, Ph-CH¼), 6.56 (dd, 1H, ¼CH-), 9.88 (d, 1H, -CHO) and 7.36–7.66
m, 5H, Ar-H).
Entry 15 (Table-1, oxime): ꢂ 1.32 (t, 3H, -CH ), 2.55 (q, 2H, -CH -),
3
2
8
2
.62 (s, 1H, CH¼), 10.55 (brs, 1H, -OH) and 7.26–8.65 (m, 3H, Ar-H).
-Ethyl-4-pyridinaldehyde (product): ꢂ 1.25 (t, 3H, -CH ), 2.78 (q, 2H,
3
-
CH -), 10.38 (s, 1H, -CHO) and 7.22–8.31 (m, 3H, Ar-H).
2
Entry 11 (Table-2, tosylhydrazone): ꢂ: 2.25 (s, 3H, -CH ), 7.17 (d, 1H,
3
Ph-CH¼), 7.07 (dd, 1H, ¼CH-), 7.09 (d, 1H, CH¼N), 7.60 (brs, 1H, -NH)
and 6.92–7.66 (m, 9H, Ar-H).
Entry 15 (Table-2, tosylhydrazone): ꢂ 2.89 (s, 3H, -CH ), 7.83 (brs, 1H,
3
-
NH), 6.58–7.33 (m, 5H, Ar-H). Ketone (substrate): ꢂ 2.56 (s, 3H, -CH ) and
3
6.45–7.20 (m, 5H, Ar-H).

2
202
NAGARAPU, RAVIRALA, AND AKKEWAR
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Received in Japan April 20, 2001