A novel synthesis of biscoumarin derivatives catalyzed by ZnCl2under solvent-free coditions

Article abstract of DOI:10.13005/ojc/300263

Zinc chloride (ZnCl₂) is used as an efficient catalyst condensation of 4-hydroxycoumarin and with various aromatic aldehydes leading to the formation of biscoumarin derivatives. Easy isolation of the products, short reaction times, excellent yi

Full text of DOI:10.13005/ojc/300263

ISSN: 0970-020 X
CODEN: OJCHEG
2014, Vol. 30, No. (2):
Pg. 853-855
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
A Novel Synthesis of Biscoumarin Derivatives
Catalyzed by ZnCl2 under Solvent-Free Coditions
VAHID VAHABI 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/300263
(Received: February 12, 2014; Accepted: March 04, 2014)
ABSTRACT
Zinc chloride (ZnCl2) is used as an efficient catalyst condensation of 4-hydroxycoumarin
and with various aromatic aldehydes leading to the formation of biscoumarin derivatives. Easy
isolation of the products, short reaction times, excellent yields and reusability of catalyst was
theadvantage of thismethod.
Key words: Bis-coumarins , ZnCl2, Aromatic Aldehydes, Solvent-free Conditions.
INTRODUCTION
trifluoroacetic acid are employed 5-6, molecular
iodine 7, [bmim][BF4] 8, tetrabutylammonium bromide
9
Biscoumarin and its derivatives are of
considerable interest due to their biological
activities such as urease inhibitors1, HIV inhibitory
(TBAB) , Zn(Proline)210, sodium dodecyl sulfate
(SDS) 11.Previously, we have synthesized a number
of heterocyclic compounds12-22
.
2
3
activity , anticoagulant activity , treatment of
4
thrombosis .
Herein, we report an efficient method for
the synthesis of somebiscoumarin derivatives from
aromatic aldehydes and 4-hydroxycoumarin
catalyzed by Zinc chloride under solvent-free
conditions (Scheme 1).
From among various catalyst for synthesis
of Biscoumarins, the following catalysts can be
referred such as sulfuric acid, phosphorus
pentoxide, aluminumchloride, iodine, and
Scheme 1:

854
VAHABI & HATAMJAFARI, Orient. J. Chem., Vol. 30(2), 853-855 (2014)
EXPERIMENTAL
3,3'-[(2-Chlorophenyl)methylene]bis(4-hydroxy-
2H-chromen-2-one) (H3)
White crystals, Yield: (90%), mp225-223
All chemicals were obtained from Merck
or Flukawithout further purification. Silica gel SILG/ oC.IR (max/cm-1) (VBr): 3120(arom. CH Str.); 1660,
UV 254 plates were used for TLC. IR spectra were 1620 (C=O Str.); 1490(C=CStr.). H-NMR (400.13
1
measured on a Shimadzu IR-470 Spectrophotometer. MHz CDCl3): =6.16(H, s, CH); 7.24-7.39(5H, m,
1H NMR spectra were determined on Bruker400 5CH); 7.41(2H, d,3J=8.0 Hz, 2CH); 7.49(1H, d,3J=8.0
3
DRX AVANCE instrument at 400 MHz, respectively. Hz, CH); 7.64(2H, t, J=7.6 Hz, 2CH); 8.04(2H,
m,2CH); 10.95(H, s, OH); 11.67(H, s, OH).
General procedure for preparation of H1-H4
3,3'-[(2-Fluorophenyl)methylene]bis(4-hydroxy-
A mixture of aldehyde (1 mmol), 4-hydroxycoumarin 2H-chromen-2-one) (H4)
(1 mmol), ammonium acetate (3 mmol) and
White crystals, Yield: (85%), mp 215-
ZnCl2(15mol %) as a catalyst was stirred at 110 oC 217oC. IR (max/cm-1) (VBr): 3130(arom. CH Str.);
1
for 35 min. The progress of reaction was monitored 1675, 1605 (C=O Str.); 1510(C=C Str.). H-NMR
by TLC. After finishing, recrystallized from ethanol (400.13 MHz CDCl3): =6.13(H, s, CH); 7.18-
95% to give pure products (H1-H4)
7.37(8H, m, 8CH); 7.43(1H, d,3J=8.2 Hz, CH);
3
7.65(2H, d,3J=8.2 Hz, 2CH); 8.03(2H, dd, J=28.0
3
3,3'-[(3-Nitrophenyl)methylene]bis(4-hydroxy-2H- Hz, J=8.0 Hz, 2CH); 11.33(H, s, OH); 11.56(H, s,
chromen-2-one) (H1)
White crystals, Yield: (89%), mp 233-
OH).
235oC. IR (max/cm-1) (VBr): 3120(arom. CH Str.);
1680,1630 (C=O Str.); 1540 , 1340 (NO2 Str.) ;
1490(C=C Str.).1H-NMR (400.13 MHz CDCl3):
RESULTSAND DISCUSSION
We have been able to introduce an efficient
=6.15(H, s, CH); 7.40-7.61(6H, m, 6CH); 7.69(2H, method for the synthesis of biscoumarin derivatives
t,3J=7.6 Hz, 2CH); 8.03(H, d, 3J=7.6 Hz, CH); 8.09(H, via condensation of 4-hydroxycoumarin with various
s, CH); 8.12( H, t, 3J=7.6 Hz, CH); 8.17(H, d, 3J=8.0 aromatic aldehydes. Therefore, reported ZnCl2as
Hz, CH); 11.40(H, s, OH); 11.60(H, s, OH).
catalyst which could provide an efficient, cheap,
easy separationunder solvent-free condition for the
3,3'-[(4-Nitrophenyl)methylene]bis(4-hydroxy-2H- synthesis of biscoumarins with high yield.
chromen-2-one) (H2)
White crystals, Yield: (87%), mp230-
232oC.IR (max/cm-1) (VBr): 3140(arom. CH Str.);
ACKNOWLEDGEMENTS
1670,1610 (C=O Str.); 1580 , 1370 (NO2 Str.) ;
We gratefully acknowledge the financial
1
1480(C=C Str.). H-NMR (400.13 MHz CDCl3): support from the Research Council of Tonekabon
=6.13(H, s, CH); 7.41-7.47(6H, m, 6CH); 7.69(2H, Branch Islamic Azad University.
t,3J=8.0 Hz, 2CH); 8.02(H, d, 3J=7.6 Hz, CH); 8.10(H,
3
3
d, J=7.8 Hz CH); 8.20( 2H, d, J=8.8 Hz, 2CH);
11.39(H, s, OH); 11.59(H, s, OH).
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