Synthesis of coumarin derivatives using glutamic acid under solvent-free conditions

Article abstract of DOI:10.13005/ojc/300265

An efficient,simple and one-pot protocol for synthesis of coumarin derivatives on the basis condensation reaction of phenols with ethyl acetoacetate employing glutamic acid as a novel catalyst is described.

Full text of DOI:10.13005/ojc/300265

ISSN: 0970-020 X
CODEN: OJCHEG
014, Vol. 30, No. (2):
Pg. 863-865
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
2
www.orientjchem.org
Synthesis of Coumarin Derivatives using
Glutamic Acid under Solvent-free Conditions
SETAREH SABETPOOR and FARHAD HATAMJAFARI*
Department of Chemistry, Faculty of Science,
Islamic Azad University-Tonekabon Branch, Tonekabon, Iran.
*
Corresponding author E-mail: hatamjafari@yahoo.com
http://dx.doi.org/10.13005/ojc/300265
(Received: March 05, 2014; Accepted: March 31, 2014)
ABSTRACT
An efficient,simple and one-pot protocol for synthesis of coumarin derivatives on the basis
condensation reaction of phenols with ethyl acetoacetate employing glutamic acid as a novel
catalyst is described.
Key words: One-pot,Glutamic acid, Coumarins, Solvent-Free Conditions.
INTRODUCTION
functionalized gland known as antibiotics agents,
and receptor antagonists have emerged. In
addition, several flavonoid containing the coumarin
core unit have been isolated from natural sources
also show interesting biological properties.
However, Thesereactions often require harsh
conditions and was happened long reaction time
and low efficiency. Kinds of phenols used to replace
Multicomponent reactions are efficient
methods in thesynthesis of heterocycles. In
Multicomponent reactions synthesis to produce
massive amounts of waste,according to the isolation
of the complex, toxic and hazardous solvent at each
step andwill discovered, economically and
environmentallyfriendly. Multicomponent reactions
advantages, synthesized of heavy compound
2
-9
for synthesiscoumarins . Although numerous
methods are capable of affecting these synthesis
has been previously reported. Glutamic acidhas
been used previously as a catalyst for synthesis of
1
molecules by the reaction of small molecule .
1
0
Coumarins derivatives are heterocyclic
units in the field of natural and synthetic organic
chemistry due to their wide range of biological and
therapeutic properties such asanti-inflammatory,
anti-tumor, antioxidant,anti-viral and anti-bacterial
activities.Recently, coumarin appropriate analogue
organic compound ,Previously, we have
1
1-
synthesized a number of heterocyclic compounds
23
. Herein we report glutamic acida new catalyst for
the synthesis of Coumarins at one pot reaction,
environmentally friendly easy separation with high
yields(Scheme 1).

8
64
SABETPOOR & HATAMJAFARI, Orient. J. Chem., Vol. 30(2), 863-865 (2014)
Scheme 1:
All chemicals were obtained from Merck 5,7-dihydroxy-4-methyl-2H-chromen-2-one (S3)
0
or Flukawithout further purification. Silica gel SILG/
White powder, yield (87%), mp:281-282 C
-
1
UV 254 plates were used for TLC. IR spectra were IR (max/cm )(KBr): 3498, 3440(2OH), 1674(C=O),
measured on Shimadzu IR-470 1602(C=C)
a
1
Spectrophotometer. H NMR spectra were
determined on Bruker400 DRX AVANCE instrument
at 400 MHz, respectively.
1
H NMR(DMSO) = 2.47(3H ,s, CH ),
3
5.82(1H, s, CH), 6.16(1H, d, J=2.4 Hz, H ), 6.26(1H,
a
d, J=2.4 Hz, H ), 10.37(2H, brs, 2OH).
b
Typical procedure adopted for the synthesis of 7-
hydroxy-4-methyl-2H-chromen-2-one (S1)
A mixture of resorsinol (1 mmol), ethyl
7-hydroxy-4,8-dimethyl-2H-chromen-2-one (S4)
0
White powder, yield (89%), mp: 261-263 C
-
1
acetoacetate (1 mmol), and glutamic acid (20 mol%) IR (max/cm )(KBr): 3494(OH), 1670(C=O), 1606
was stirred at 110°C for a 15 min. The progress of (C=C)
the reaction was monitored by using TLC. After
completion of the reaction, the solid catalyst
1
HNMR(DMSO): ä =2.27, 2.54(6H, s,
(
glutamic acid) was washed with water, and finally 2CH ), 6.03(1H, s, CH), 6.56(1H, d, J=0.8 Hz, H ),
3
a
purified by recrystallization in ethanol/water.
Data of compounds (S1-S5)
6.60(1H, d, J=0.8 Hz, H ).
b
4
-methyl-2H-chromen-2-one (S5)
0
7
-hydroxy-4-methyl-2H-chromen-2-one (S1)
White powder, Yield: (83%), mp: 80-82 C
0
-1
-1
White powder,Yield:(93%), mp:187-189 C IR (max/cm )(KBr): 1683(C=O), 1604(C=C)cm
-
1
IR (max/cm )(KBr): 3440(OH), 1683(C=O),
1
-
1
1
604(C=C)cm
H NMR (400MHz; DMSO-d )  = 2.34 (3H,
6
s, CH ), 6.10 (1H, s, CH), 6.68(1H, d, J=2.0 Hz, H ),
3
c
1
H NMR (400MHz; DMSO-d )  = 2.34 (3H, 6.79(1H, d, J=2.0 Hz, H ), 7.76(1H, d, J=8.8 Hz, H ).
6
b
a
s, CH ), 6.10 (1H, s, CH), 6.68(1H, d, J=2.0 Hz, H ),
3
c
6
.79(1H, d, J=2.0 Hz, H ), 7.76(1H, d, J=8.8 Hz,
RESULTSAND DISCUSSION
b
H ),8.85(1H, brs, OH).
a
Herein, we report glutamic acid ascatalyst
which could provide high yield, an efficient,
environmentally friendly, easy separationand simple
dihydroxy-4-methyl-2H-chromen-2-one (S2)7,8
0
White powder, Yield: (90%), mp: 241-243 C route for thesynthesis of coumarins.
-
1
IR (max/cm )(KBr): 3444(OH), 1677(C=O),
-
1
1
600(C=C)cm
ACKNOWLEDGEMENTS
1
H NMR(DMSO)  = 2.34(3H, s, CH ),
We gratefully acknowledge the
3
6.11(1H, s, CH), 6.83-7.09(1H, m, Harom), 6.82(1H, financialsupport from the Research Council of
d, J=8.0 Hz, H ), 7.09(1H, d, J=8.0 Hz, H ), 9.30(1H, TonekabonBranch Islamic Azad University.
a
b
brs, OH), 10.0(1H, brs, OH).

SABETPOOR & HATAMJAFARI, Orient. J. Chem., Vol. 30(2), 863-865 (2014)
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