Solid state synthesis of substituted coumarin-3-carboxylic acids via the knoevenagel condensation under microwave irradiation

Article abstract of DOI:10.1080/10426500490466814

Synthesis of substituted coumarin-3-carboxylic acids using the Knovenagel reaction of malonic acid and O-hydroxyaryl aldehydes supported onto HZSM-5 zeolite under microwave irradiation is described.

Full text of DOI:10.1080/10426500490466814

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SOLID STATE SYNTHESIS OF SUBSTITUTED COUMARIN-3-
CARBOXYLIC ACIDS VIA THE KNOEVENAGEL
CONDENSATION UNDER MICROWAVE IRRADIATION
a
a
a
Majid M. Heravi , Rahim Hekmatshoar & Maryam Emamgholizadeh
a
Department of Chemistry, Faculty of Science, Alzahra University, Vanak, Tehran, Iran
Published online: 16 Aug 2010.
To cite this article: Majid M. Heravi , Rahim Hekmatshoar & Maryam Emamgholizadeh (2004): SOLID STATE SYNTHESIS OF
SUBSTITUTED COUMARIN-3-CARBOXYLIC ACIDS VIA THE KNOEVENAGEL CONDENSATION UNDER MICROWAVE IRRADIATION,
Phosphorus, Sulfur, and Silicon and the Related Elements, 179:9, 1893-1896
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Phosphorus, Sulfur, and Silicon, 179:1893–1896, 2004
Copyright ꢀC Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490466814
SOLID STATE SYNTHESIS OF SUBSTITUTED
COUMARIN-3-CARBOXYLIC ACIDS VIA THE
KNOEVENAGEL CONDENSATION UNDER
MICROWAVE IRRADIATION
Majid M. Heravi, Rahim Hekmatshoar,
and Maryam Emamgholizadeh
Department of Chemistry, Faculty of Science,
Alzahra University, Vanak, Tehran, Iran
(
Received January 22, 2004; accepted February 20, 2004)
Synthesis of substituted coumarin-3-carboxylic acids using the
Knovenagel reaction of malonic acid and O-hydroxyaryl aldehydes sup-
ported onto HZSM-5 zeolite under microwave irradiation is described.
Keywords: Coumarin; Knoevenage; microwave irradiation; solid state;
zeolite
INTRODUCTION
Coumarins are widespread in nature as physiologically active con-
stituent plants.1 Moreover, coumarins have a broad range of appli-
cation in the pharmaceutical, perfumes, cosmetic, and food industries.4
The synthesis of coumarins and their derivatives has attracted consid-
erable attraction from organic and medicinal chemists for many years,
−3
5
as a large number of natural products contain this reterocyclic system.
Coumarins have been synthesized by many different routes, includ-
6
7
ing traditional Pechmann reaction and Knoevenagel condensation
8
of hydroxyl aldehydes with maleic acid, malonic ester or cyanoacetic
ester. For Knoevenagel condensation of coumarin synthesis, a series of
developments and modifications have been also reported. The meth-
ods have their own merits and drawbacks.
1
0
1
1
The microwave-enhanced chemical reactions in solventless system
have gained popularity as they can be conducted efficiently and rapidly
to afford pure products in high yield.12 Recently there has been a shift
Address correspondence to Majid M. Heravi, Department of Chemistry, Faculty of
Science, Alzahra University, Vanak, Tehran, Iran. E-mail: mmheravi@azzahra.ac.ir
1
893

1
894
M. M. Heravi et al.
in emphasis in chemistry, with the desire to develop more environmen-
tally friendly routes to a myriad of materials. This shift is most ap-
parent in the growth of green chemistry. Green chemistry approaches
not only hold significant potential for omitting undesirable by-product,
avoiding use of toxic, expensive, and flammable solvents, reduction in
waste disposal, and lowering energy costs, but also for the develop-
ment of new methodologies toward previously unobtainable materials
13
using existing technologies. We have recently reported on a solvent-
free synthesis of coumarins,1 on the microwave assisted Pechmann
reaction on P2O5/moleculare sieves application for the preparation of
4b
4
-substituted coumarins.14a In continuation of our interest on reactions
under microwave irradiation in solvent-free conditions, in this commu-
nication we report the soli-state synthesis of substituted coumarin-3-
carboxylic acids via Knoevenagel condensation under microwave irra-
diation. In an effort to find suitable mineral support, traditional sup-
ports such as alumina, silica gel montmorilonitrile K-10, HY-zeolite,
and HZSM-5 zeolite were examined. The latter gave the best result re-
garding yields, rate of reaction, and ease of workup procedure. We have
found that coumarin-3-carboxylic acids can be readily prepared from
the reaction of 2-hydroxybenzaldehydes and hydroxynaphthaldehyde
supported onto HZSM-5 zeolite to microwave irradiation. Most of the
hydroxyaldehyde disappeared within the first 2 min as determined by
TLC (Scheme 1). It is notable that in the absence of solid support the
reactions are sluggish, and considerable amounts of starting materials
are recovered unchanged even after prolonged exposure to microwave
irradiation.
SCHEME 1

Coumarins
1895
In conclusion we have developed a very simple and fast synthesis
of coumarin-3-carboxylic acids utilizing the Knoevenagel condensation
between 2-hydroxybenzaldehydes and 2-hydroxynaphthaldehyde with
malonic acid supported onto HZSM-5 zeolite under microwave irradi-
ation in solventless system. The ease of this synthesis, along with its
eco-friendly nature, make it suitable a methodology in oganic synthesis.
EXPERIMENTAL
Melting points were determined with an electrothermal 9100 apparatus
and are uncorrected. The infrared spectra were obtained on Philips PU
1
9
800 Fourier transform infrared (FTIR) spectrometer. H NMR spec-
tra were recorded Brucker 80 MHz. TLC analysis were performed on
Merck 60 PF 256 silica gel plates using mixture of hexane-ethyl acetate
4
0:60. HZSM-5 zeolite was prepared following a previously described
1
7
method. Some products (entries 1–3, 5) were brown, and their physical
and spectroscopic data were compared with those of authentic samples.
General Procedure
Malonic acid (1.5 mmol) was mixed thoroughly with HZSM-5 zeolite
(
0.15 g) using pistal and mortar. The mixture was transferred to a
beaker and mixed with a selected 2-hydroxybenzaldehyde (1 mmol). The
beaker was placed in a house hold microwave oven for the specified time.
The progress of reaction was monitored by TLC using hexane:ethyl ac-
etate 40:60. Dichloromethane (20 ml) was added to the crude product
and filtered. Water (20 ml) was added and the organic layer was sepa-
rated. The solvent was distilled and the crude product was purified if
necessary by crystallization (Table I).
TABLE I Knoevenagel Synthesis of Coumarin-3-carboxylic Acids under
Microwave Irradiation in Solventless System
Reaction
time (min)
Entry
R1
R2
Mp
190(MeOH)
aYield (%)
1
1
1
6
6
6
1
2
3
4
5
H
OMe
H
H
H
OMe
H
4
6
3
4
15
190–191
194–196
194–195
87
89
97
93
75
192–193
194(EtOAc)
185(EtOAc)
NO2
235–236(EtOAc) 236–23716
aYields refer to isolated products.

1
896
M. M. Heravi et al.
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