International Journal of ChemTech Research

CODEN( USA): IJCRGG ISSN : 0974-4290

Vol.1, No.3 , pp 539-543, July-Sept 2009

I2-Al2O3: A suitable heterogeneous catalyst for the

synthesis of flavones under microwave irradiation
Swapnil R. Sarda1, Wamanrao N. Jadhav2 and Rajendra P. Pawar3*
1
Department of Chemistry, J. E. S. College, Jalna-431 203,(MS), India.
2
Organic Chemistry Synthesis Laboratory, Dnyanopasak College,
Parbhani-431 401, (MS), India.
3
Department of Chemistry, Deogiri College, Aurangabad-431 005.(MS) India.

*E-mail: rppawar@yahoo.com

Abstract: A simple method for the synthesis of flavones is reported using heterogeneous catalyst molecular iodine loaded
neutral alumina under microwave irradiations.
Key Words: Chalcones, flavones, molecular iodine, microwave irradiations etc.

Graphical abstract
OH OH
Al2O3/NaOH
+ ArCHO Ar
R MW R
O O
3(a-h)
1(a-h) 2(a-h)

MW I2-Al2O3

O Ar

R
O
4(a-h)
R Ar
4a =2-OH 4-Cl
4b =2-OH 4-OCH 3
4c =2-OH 4-CH3
4d =2-OH Ar
4e =2-OH 4,5-OCH 3
4f ==2-OH 4-NO 2
4g =2-OH Furan ring
4h =2-OH,3-CH3 Ar

(Scheme-1)
Rajendra P. Pawar et al /Int.J. ChemTech Res.2009,1(3)
Introduction
Environmental pressure to reduce waste and re-
use materials has driven studies into ‘Green’ chemistry.
Chemical and pharmaceutical industries are always under
pressure to develop more environmentally friendly
organic reaction methodologies using nonhazardous
catalysis. Microwave irradiation is used for a variety of
organic reactions due to short reaction time, cleaner
reactions, easier work-up and better yield. Thus the
microwave oven procedure is now well established in
MORE chemistry [1]. More recently, the emphasis has
shifted in favour of microwaves-assisted methods under
solvent-free conditions, providing an opportunity to work
in open vessels, thus avoiding the risk of the development
of high pressure. Inorganic solid support organic
transformations are gaining much attention due to
simplified product isolation, mild reaction conditions,
high selectivity etc. Solvent free microwave assisted
chemical reactions in combination of solid supported
reagents, were used to carry out a wide range of reaction
in shorter time as compare to other conventional reaction
methods [2]. The use of solvent free conditions with
heterogeneous catalysts represents one of the more
powerful green chemical procedures [3], Alumina is a
particularly interesting metal oxide widely used
industrially as filler, adsorbent, drying agent, catalyst,
solid support and reagent [4].
In the continuation of our work [5-6] herein, we
describe a simple and convenient method for the
synthesis flavones using I2-Al2O3 catalyst under
microwave irradiation in excellent yields. (Scheme-1)
Inexpensive and nontoxic molecular iodine has
received considerable attention in organic
transformations, affording the corresponding products in
excellent yields with high selectivity. I2-Al2O3 catalyzed
synthesis of dihydropyrimidine under microwave
irradiation has been recently reported [7]. The mild lewis
acidity associated with iodine enhanced its usage in
organic synthesis using stoichiometric levels to catalytic
amounts. Owing to numerous advantages associated with
this eco-friendly element, iodine has been explored as a
powerful catalyst for various organic transformations [8],
such as synthesis of benzothiophenes, bis-indoles,
deprotection of acetals, transesterification, Michael
addition, β-ketoenol ethers and multicomponent
dihydropyrimidinone synthesis. Recently, we reported the
use of iodine for the synthesis of tetrahydrobenzo [b]
pyrans and imidazole [9].
Chalcones and its derivatives display many
biological activities [10] and used as on starting materials
in the synthesis of various heterocyclic compounds [11].
Flavones occupy a special place in the realm of natural
and synthetic organic chemistry owing to their useful
biological activities such as anti-inflammatory and
antioxidant. Substituted flavones like amino flavones
have been studied as tyrosine kinaes inhibitors and as
antimitotic agents [12].
540
Various methods have been reported for the
synthesis of flavones, includes Baker-Venkatraman
rearrangement [13], HTIB (Koser’s reagent), FeCl3 [14],
SeO2 [15], DMSO-I2 [16], Br2/CHCl3, NaOAc/AcOH,
EtOH/HCl, clay [17], H2SO4, Palladium-Thiourea [18],
Wells-Dawson heteropolyacid [19] had been reported.
Recently we synthesized flavones by using EAN ionic
liquid [5] under microwave irradiation and [bmim]BF4
ionic liquid at 100 OC temperature [6].
Experimental
Materials and methods
Melting points were measured in open glass
capillaries on a Perfit Electrothermal melting-point
apparatus and are uncorrected. 1H NMR and 13C NMR
spectra were recorded at room temperature on a 300
MHz. Varian Inova Spectrometer in CDCl3 using TMS as
internal standard. A Samsung domestic microwave oven
was used at 400W power level for all the experiments.
The reactions were monitored by TLC using pre-coated
plates (Merck). Column chromatography was performed
using Acme silica gel (100–200 mesh). All reagents were
obtained from commercial sources and used without
further purification. Solvents for chromatography were
distilled before use. The products were also characterized
by comparison of their melting point with literature
values.
Synthesis of heterogeneous catalyst I2-Al2O3:
Dissolve 2.538 g (10 mmol) iodine in minimum
quantity of solvent dichloro methane. Adsorb this iodine
solution on 25 g neutral alumina and stirred with glass
rod. The mixture was air dried and stored in glass bottle
until use.
Synthesis of 1-phenyl-3-(4-chlorophenyl)-prop-2-en-1-
one
Mixtures of 2-Hydroxy acetophenone (1mmol,
0.136 g, 1a) 4-chlorobenzaldehyde (1mmol, 0.140 g, 2a)
and sodium hydroxide (2mmol, 0.08 g) were dissolved in
minimum quantity of dichloromethane (2 mL). The
solution was adsorbed on neutral alumina (1.5 g), air-
dried and irradiate in a microwave oven (400W) for
appropriate time (4 to 5 min). After completion of
reaction as monitored by TLC, the mixture was cooled,
diluted with ethanol and filtered to separate insoluble
Al2O3. The filtrate was poured on crushed ice and
neutralized with dilute HCl. The isolated crude was
purified by column chromatography using n-hexane:
acetone (7:1) eluent to afford pure 1-phenyl-3-(4-
chlorophenyl)-prop-2-en-1-one (3a). The products were
identified by comparison with standard physical and
spectral data given in the literature (Table-1).
Synthesis of 2-(4-chlorophenyl)-4H-chromen-4-one
(4a)
Rajendra P. Pawar et al /Int.J. ChemTech Res.2009,1(3) 541

A mixture of 1-phenyl-3-(4-chlorophenyl)-prop- Spectral Analysis

2-en-1-one (1mmol, 0.258 g, 1a) and 0.25 g of I2-Al2O3
catalyst was irradiated in a microwave oven (400W) for
appropriate time (3 to 5 min). After completion of
reaction as monitored by TLC, the mixture was cooled,
diluted with ethyl acetate and filtered to separate
insoluble Al2O3. The filtrate was washed with a dilute
solution of sodium thiosulfate to remove iodine and
subsequently with water. After evaporation of ethyl
acetate, the crude was purified by column
chromatography hexane: ethyl acetate (9:1) eluent to
afford pure 2-(4-chlorophenyl)-4H-chromen-4-one (4a).
The products obtained were characterized by comparison
of IR, 1H NMR and melting point with literature values
(Table-1).
2-(4-chlorophenyl)-4H-chromen-4-one (4a): 1H NMR
(300 MHz, CDCl3) δ: 6.79 (s, 1H, pyrone ring), 7.05 (2H,
dd, J=2.6 and 7.6 Hz, Ar-H), 7.32-7.48 (4H, m , Ar-H),
7.54 (2H, dd, J=7.8 and 2.6 Hz, Ar-H).
2-(4-methylphenyl)-4H-chromen-4-one (4b): 1H NMR
(300 MHz, CDCl3) δ: 2.41 (3H, s, Ar-CH3), 6.61 (s, 1H,
pyrone ring), 6.95 (2H, dd, J=2.6 and 7.6 Hz, Ar-H),
7.17-7.22 (4H, m , Ar-H), 7.48 (2H, dd, J=7.8 and 2.6
Hz, Ar-H).
2-(4-methoxylphenyl)-4H-chromen-4-one (4b): 1H
NMR (300 MHz, CDCl3) δ: 3.85 (3H, s, Ar-OCH3), 6.76
(s, 1H, pyrone ring), 7.12 (2H, dd, J=2.6 and 7.6 Hz, Ar-
H), 7.17-7.42 (4H, m , Ar-H), 7.48 (2H, dd, J=7.8 and 2.6
Hz, Ar-H).

Table-1: I2-Al2O3 catalyzed novel synthesis of flavones under microwave irradiation

Entry Chalcone (3a–h) Product (4a–h) Time Yield M. P.

(min.) (%)a (0C)b

OH Cl
a Cl
4 90 187-188
(185-187)5
O

O O

OH OCH3
b OCH3
4.5 85 155-156
(155-156)5
O

O
O

OH
c 4 88 78-80
O
(108-109)17
O

OH
d 3.5 92 100
O
(97-98)19
O
O
OCH3

OH O
e OCH3 OCH3 5 80 160-162
OCH3 (154)5
O
O
NO2

OH
f NO 2 O
5 85 276-278
(277)5
O
O
O O
Cl OH Cl O
g 3.5 90 130-132
(134-135)19
O
O

h OH O

4 85 126-128
O (122-124)19
O
a
Isolated yield
b
Reported melting points
Rajendra P. Pawar et al /Int.J. ChemTech Res.2009,1(3)
Results and Discussion
Synthesis of flavones using the heterogeneous
catalyst I2-Al2O3 under microwave irradiation has been
reported. Excellent yield was obtained in shorter reaction
time (Scheme-1). As these reactions were carried out
under microwave irradiation, it reduces the cost and time
period of reaction. α-β-unsaturated carbonyl compounds
were prepared by well-known Claisen-Schimdt
condensation process using NaOH-Al2O3 under
microwave irradiation. Most of the reaction was
completed within 3-4 minutes giving 90-95% yield of
products.
For a synthesis of flavones, the 2-hydroxy
chalcone and I2-Al2O3 was irradiated in a microwave
oven for a specified time. After completion of reaction as
monitored by TLC, aqueous work-up afforded pure
flavones. Synthesis of flavones using molecular iodine
catalyst was completed within 5-to7 min by
dehydrogenative cyclisation of 2-hydroxy chalcone,
afforded 80 to 95 % flavones (Table-1). However, in
absence of iodine the reaction does not proceed even after
long time (30 minutes). It indicates that the oxidation of
2-hydroxy chalcone into flavones is only due to
molecular iodine and not because of air O2. The reactions
can be faster, the reaching substantial completion in
several minutes compared to hours in organic solvents.
The result showed that efficiency and yield of the
reaction is high as compared to other conventional
methods. The use of 10-mol % of the catalyst was
sufficient to promote the reaction; higher amount of the
catalyst did not improve the yield of product. The
reaction proceeds cleanly at 400 W and no undesirable
side product were observed. At higher power level
Table-2: synthesis of 1-(2-hydroxyphenyl)-3-p-tolylprop-2-en-1-one (4a) catalyzed by iodine
under different condition
Entry Catalyst Solvent Reaction
conditionb
1 I2 DMSO Reflux18
2 I2 DMSO MW19
3 I2 DMF Reflux
4 I2 Solvent free MW
5 Al2O3- I2 Solvent free 80 OC
6 Al2O3- I2 Solvent free MW
a
Isolated yield
b
Reported method
References
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542
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The 1HNMR spectra of flavones showed a
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to flavones in the presence I2-Al2O3 under microwave
irradiation. Shorter reaction time, simple reaction
conditions, and higher yield render this method superior.
Acknowledgements
The authors are thankful to the Principal Dr. P.
L. More, Dnyanopasak College, Parbhani, and Principal
Dr. R. S. Agrawal, J. E. S. College, Jalna, for
encouragement during the process of carrying out this
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Commission for funding under Minor Research Project to
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