Regeneration of aldehydes from bisulfite addition products in the solid state using montmorillonite KSF clay under microwave irradiation

Article abstract of DOI:10.1039/a900309f

Microwave irradiation of bisulfite addition products with montmorillonite KSF clay under solvent-free conditions provides a fast, efficient and simple method for regeneration of aldehydes in excellent yields.

Full text of DOI:10.1039/a900309f

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5
60 J. CHEM. RESEARCH (S), 1999
J. Chem. Research (S),
Regeneration of Aldehydes from Bisulfite
Addition Products in the Solid State using
Montmorillonite KSF Clay under Microwave
Irradiation�
1
999, 560^561y
Alok Kumar Mitra,* Aparna De and Nilay Karchaudhuri
Department of Chemistry, University of Calcutta, 92, Acharya Prafulla Chandra Road,
Calcutta-700 009, India
Microwave irradiation of bisulfite addition products with montmorillonite KSF clay under solvent-free conditions
provides a fast, efficient and simple method for regeneration of aldehydes in excellent yields.
Protection of aldehydes as bisul¢te addition products is of
great interest to organic chemists as they are easily prepared
by treatment with sodium bisul¢te. The bisul¢te addition
Table 1 Microwave-assisted regeneration of aldehydes from
bisulfite addition products using montmorillonite KSF clay
1
products are extensively used for puri¢cation of aldehydes.
Although the regeneration of the aldehyde can be performed
a
Entry
1
Aldehyde
t/s
Yield (%)
96
2
by treatment of the addition product with mineral acid or
CHO
3
base, these methods are hazardous. Such reagents are also
10
corrosive and detrimental to the environment.
OH
The use of inorganic supports as reaction media in
organic synthesis is increasingly widespread owing to
CHO
4
improved e¤ciency of many surface bound reagents.
2
3
4
14
12
15
95
90
92
Further, with the advent of microwave dielectric heating,
the rate of several reactions can be promoted to a¡ord
MeO
MeO
CHO
CHO
5
faster and cleaner conversion. Microwave heating tech-
niques in solvent-free organic reactions have been developed
recently. Thus, by the choice of suitable solid supports such
as silica, alumina or clays, several organic reactions are car-
ried out successfully in the solid state in an ordinary dom-
6
Cl
estic microwave oven.
O2N
CHO
CHO
5
6
18
20
87
85
Ar
Ar
OH
Montmorillonite KSF
microwave
O
H
SO3Na
H
85–98%
O2N
MeO
CHO
Scheme 1
7
8
5
97
96
HO
HO
Montmorillonite KSF clay has been extensively used in
CHO
CHO
7
8
various organic reactions viz. alkylation, acylation,
9
15
Beckmann rearrangement etc. and also under microwave
1
0
MeO
MeO
irradiation in Fischer indole synthesis, ortho-ester Claisen
1
1
12
13
rearrangement, acetal formation, anhydride formation,
etc. In continuation of our ongoing programme to develop
9
9
10
16
95
92
98
synthetic protocols utilising microwave irradiation under
MeO
O
1
4
solvent-free conditions, we report a simple synthetic pro-
cedure for regeneration of aldehydes from bisul¢te addition
products in the solid state using montmorillonite KSF clay
CHO
CHO
1
0
O
(
Scheme 1). The reaction proceeds e¤ciently in excellent
yields at ambient pressure within a few seconds (Table
). To the best of our knowledge, this is the ¢rst report
MeO
1
1
1
BnO
BnO
of the regeneration of aldehydes from their bisul¢te addition
products using montmorillonite KSF under microwave
irradiation. The reaction remains incomplete if the amount
of clay used is less than the optimum amount found exper-
imentally or if the reaction is carried out at room tempera-
ture for several hours. Montmorillonite KSF was
regenerated easily by washing with ethanol, followed by
drying at 110 8C for 12 h, and could be reused.
CHO
1
2
11
97
MeO
a
Yields refer to pure products.
Experimental
*
To receive any correspondence (e-mail: akmitra@cucc.ernet.in).
This is a Short Paper as de¢ned in the Instructions for Authors,
�
The IR spectra were run on Perkin-Elmer 782 spectrometer.
H NMR spectra were recorded in CDCl3 solution on a Bruker
1
Section 5.0 [see J. Chem. Research (S), 1999, Issue 1]; there is
therefore no corresponding material in J. Chem. Research (M).
AM 300L NMR spectrometer operating at 300 MHz using

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J. CHEM. RESEARCH (S), 1999 561
tetramethylsilane as the internal standard. Montmorillonite KSF was
purchased from Aldrich. The reactions were carried out in a domestic
microwave oven (BPL-SANYO, BMO-700T, 1200 W).
3
4
5
M. D. So¡er, M. P. Bellis, H. E. Gellerson and R. A. Stewart,
Org. Synth., Coll. Vol. 4, John Wiley & Sons, New York, 1992,
p. 903.
A. McKillop and D. W. Young, Synthesis, 1979, 481; J. M.
Riego, Z. Sedin, J. M. Zaldivar, N. C. Marziazo and C.
Tortalo, Tetrahedron Lett., 1996, 37, 513.
General Procedure.öA mixture of bisul¢te addition product
(
1 mmol) and montmorillonite KSF (300 mg) was taken in a 25 ml
Erlenmeyer £ask and kept over an alumina bath (heat sink) inside
a domestic microwave oven and irradiated for 5^20 s and the reaction
was monitored by TLC. The product was extracted with ethyl acetate
S. Caddick, Tetrahedron, 1995, 51, 10403; S. A. Galema,
Chem. Soc. Rev., 1997, 26, 233; F. Langa, P. D. L. Cruz,
A. D. L. Hoz, A. Diaz-Ortiz and E. Diez-Barra, Contemp. Org.
Synth., 1997, 4, 373; A. K. Bose, B. K. Banik, N. Lavlinskaia,
M. Jayaraman and M. S. Manhas, CHEMTECH, 1997, 27, 18;
A. K. Mitra, A. De and N. Karchaudhuri, Synth Commun.,
1999, in press.
(
2 Â 5 ml), washed with brine and dried over anhydrous sodium
sulfate. Evaporation of the solvent a¡orded the products in excellent
yield (Table 1). All the products were characterised by 1H NMR
spectroscopy and by comparison with IR spectra of authentic
samples.
6
V. K. Ahluwalia, B. Goyal and U. Das, J. Chem. Res (S),
1
997, 266; H. M. Sampath Kumar, P. K. Mohanty, M. Suresh
In conclusion, we have developed a solvent-free method
for the facile regeneration of aldehydes from their bisul¢te
addition products in the solid state using montmorillonite
KSF clay under microwave irradiation.
Kumar and J. S. Yadav, Synth. Commun., 1997, 27, 1327;
R. S. Varma, R. Dahiya and S. Kumar, Tetrahedron Lett.,
1
997, 38, 2039; G.-S. Zhang, D-H. Yang, M-F. Chen and
K. Cai, Synth. Commun., 1998, 28, 2221; R. S. Varma, K.
P. Naicker and P. J. Liesen, Tetrahedron Lett., 1998, 39, 3977.
P. Laszlo and A. Mathy, Helv. Chim. Acta, 1987, 70, 577.
A. Cornelis, A. Gerstmans, P. Laszlo, A. Mathy and I. Zieba,
Catal. Lett., 1990, 6, 103.
We thank the CSIR, the UGC, New Delhi and the Uni-
versity of Calcutta for ¢nancial support.
7
8
9
0
H. M. Meshram, Synth. Commun., 1990, 20, 3253.
D. Villemin, B. Labiad and Y. Ouhilal, Chem. Ind., 1989, 607.
Received, 11th January 1999; Accepted, 1st June 1999
Paper E/9/00309F
1
11 R. S. Huber and G. B. Jones, J. Org. Chem., 1992, 57, 5778;
G. B. Jones, R. S. Huber and S. Chau, Tetrahedron, 1993,
4
9, 369.
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2