The rapid synthesis of β-nitrostyrenes under microwave irradiation without solvent

Article abstract of DOI:10.1081/SCC-120014781

The β-nitrostyrenes (3a-l) were prepared by condensation of benzaldehydes with nitromethane in the presence of K₂CO₃/Al₂O₃ under microwave irradiation without solvent. They were characterized by IR, ¹H-NMR, and elemental analysis.

Full text of DOI:10.1081/SCC-120014781

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THE RAPID SYNTHESIS OF β-NITROSTYRENES UNDER
MICROWAVE IRRADIATION WITHOUT SOLVENT
a
a
Cunde Wang & Song Wang
a
Department of Chemistry, Yangzhou University, Yangzhou, 225002, P.R. China
Version of record first published: 22 May 2009.
To cite this article: Cunde Wang & Song Wang (2002): THE RAPID SYNTHESIS OF β-NITROSTYRENES UNDER MICROWAVE
IRRADIATION WITHOUT SOLVENT, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 32:22, 3481-3486
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 22, pp. 3481–3486, 2002
THE RAPID SYNTHESIS OF
b-NITROSTYRENES UNDER
MICROWAVE IRRADIATION
WITHOUT SOLVENT
Cunde Wang* and Song Wang
Department of Chemistry, Yangzhou University,
Yangzhou 225002, P.R. China
ABSTRACT
The b-nitrostyrenes (3a–l) were prepared by condensation
of benzaldehydes with nitromethane in the presence of
K CO /Al O under microwave irradiation without solvent.
2
3
2
3
1
They were characterized by IR, H-NMR, and elemental
analysis.
Many reports dealing with the biological activity of b-nitrostyrene
stated that it had a detrimental effect on sects and on the growth of fungi
and that it could be used for the protective treatment of textiles, leather, and
other organic materials. Generally, b-nitrostyrenes were synthesized by con-
densation with benzaldehydes and nitromethane. And the condensation was
usually been catalyzed by (a) bases such as alcoholic potassium hydroxide,
[
1]
aqueous sodium hydroxide or alcoholic methylamine ; (b) buffer solutions
containing a conjugate acid–base pair such as ammonium acetate in
*
Corresponding author. E-mail: wcd640918@163.com
481
3
DOI: 10.1081/SCC-120014781
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
482
WANG AND WANG
[2]
acetic acid ; (c) salts such as zinc chloride or potassium fluoride in the
[
3]
presence of dimethylammonium chloride in refluxing toluene solution.
Recently many studies have shown that some organic reactions are faster
and more efficient under microwave irradiation in the solid state than in
[4,5]
solution.
To develop a more reliable procedure for b-nitrostyrenes, we
have found that b-nitrostyrenes were conveniently obtained under mild con-
ditions by the reaction between benzaldehydes and nitromethane in the
presence of potassium carbonate under microwave irradiation without
solvent (Sch. 1). The optimum proportions of the reagents involved
Scheme 1.
Table 1. Preparation of Compounds 3
Microwave Irrad.
Power
(W)
a
Time Yield
(min)
ꢀ ꢀ
M.P. ( C) [Lit. C]
Compound
Formula
(%)
[
2]
3
3
3
3
3
3
3
3
3
3
3
3
a
b
c
d
e
f
g
h
i
C
C
C
8
8
8
H
H
H
7
7
5
NO
NO
NO
2
3
2
175
200
200
225
225
200
225
225
175
225
175
175
5
5
4
4
4
5
5
4
6
5
6
6
86
91
95
94
90
92
94
89
90
91
74
71
57–58 (59–59)
167–169 (168–169)
109–110 (110)
94–96
165–166
[
2]
[
1,6]
Cl
2
C H N O
8
9
8
6
7
6
2
4
C
C
H
H
NO
NO
4
2
4
3
2
3
2
2
[
[
7]
4]
Cl
113–114 (113–114)
167–168 (167–168)
C H NO
9
9
[
3]
C
C
8
H
7
NO
133–134 (134.5–135)
[
186–188 (187–188)
[
8]
10
H
12
N
O
2
2]
j
C H NO
9
85–87 (86–87)
[
9
9]
k
l
C
C
15
H
H
12
N
N
O
O
5
140–141 (141)
144–146 (144–147)
[
10]
17
14
7
a
Isolated yield.

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b-NITROSTYRENES
3483

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3
484
WANG AND WANG

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b-NITROSTYRENES
3485
have been experimentally determined. The best reaction time and microwave
power have been selected also under microwave irradiation without solvent
(Table 1). All the products have been fully characterized on the basis of their
microanalytical and spectral data (Table 2).
In conclusion, we developed a procedure for the efficient preparation
of b-nitrostyrenes (3) from benzaldehydes and nitromethane with excellent
yields (71–95%). The final products were easily isolated and purified directly
by silica gel chromatography. The simplicity of the experimental procedure,
direct conversion of benzaldehydes to b-nitrostyrenes (3) in the presence of
the catalyst K CO /Al O , quick reaction times (4–6 min) and lower power
2
3
2
3
(175–225 W) made this method more attractive than others known in
literature.
EXPERIMENTAL
Melting points were uncorrected, elemental analytical data were
obtained using a model 240 elementary instrument. IR spectra were mea-
1
sured using a model 408 infrared spectrometer, H NMR spectra were
recorded on a JNM-90Q spectrometer using TMS as internal standard
(
CDCl solutions).
3
General Procedure for the Preparation of b-Nitrostyrenes (3a–l)
A mixture of 5 mmol benzaldehyde, 1.53 g (25 mmol) nitromethane
and 0.35 g potassium carbonate was finely ground by agate mortar and
pestle and was mixed with 5 g aluminum oxide (150 mesh). The mixture
was then put in a 25 mL beaker and introduced into a Galan WP750A
domestic microwave oven. Microwave irradiation was carried out for the
appropriate time and at the power indicated (see Table 1). The mixture was
cooled to ambient temperature, then water and nitromethane were removed
by reduced pressure. The residue was purified by silica gel chromatography
ꢀ
(petroleum ether [60–90 C]/ethyl acetate/dichloromethane, 1 : 1 : 0.3) to give
the product (3a–l). The structures of all products were identified on the basis
1
of elemental analytical data, IR, and H NMR data (see Table 2).
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3
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Received in Japan July 10, 2001