See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/229120295

Three component, one-pot synthesis of dihydropyrano[3,2-c]chromene

derivatives in the presence of H6P2W18O62·18H2O as a green and recyclable
catalyst

Article in Catalysis Communications · December 2008

DOI: 10.1016/j.catcom.2008.08.023

CITATIONS READS

185 313

5 authors, including:

Majid M. Heravi Behnoush alimadadi Jani

Alzahra University Alzahra University
1,057 PUBLICATIONS 22,786 CITATIONS 9 PUBLICATIONS 449 CITATIONS

SEE PROFILE SEE PROFILE

Fatemeh Derikvand Fatemeh F. Bamoharram

42 PUBLICATIONS 1,821 CITATIONS

Islamic Azad University Mashhad Branch
253 PUBLICATIONS 6,747 CITATIONS
SEE PROFILE
SEE PROFILE

All content following this page was uploaded by Behnoush alimadadi Jani on 07 December 2019.

The user has requested enhancement of the downloaded file.

 Catalysis Communications 10 (2008) 272–275

Contents lists available at ScienceDirect

Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Three component, one-pot synthesis of dihydropyrano[3,2-c]chromene

derivatives in the presence of H6P2W18O62
18H2O as a green
and recyclable catalyst
Majid M. Heravi a,*, Behnoush Alimadadi Jani a, Fatemeh Derikvand a,*,
Fatemeh F. Bamoharram b, Hossein A. Oskooie a
a
Department of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran 1234, Iran
b
Department of Chemistry, Islamic Azad University-Mashhad Branch, Mashhad, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The three-component one-pot synthesis of 2-amino-5-oxo-dihydropyrano[3,2-c]chromene derivatives by

Received 5 July 2008 condensing 4-hydroxycoumarin, aldehydes and alkylnitriles using a catalytic amount of
Received in revised form 14 August 2008 H6P2W18O62
18H2O in aqueous ethanol under heating conditions is reported.
Accepted 22 August 2008
Ó 2008 Elsevier B.V. All rights reserved.
Available online 2 September 2008

Keywords:
Pyrano[3,2-c]chromene
H6[P2W18O62]
18H2O
Solid acid catalysts
Multi-component one-pot reactions
On water reactions

1. Introduction sive and anti-ischemic behavior [6–8]. Also, a number of 2-amino-

Green chemistry is a quickly developing new field that provides
us a proactive path for the sustainable progress of future science
and technologies [1]. Green chemistry uses highly efficient and
environmental benign synthetic procedures to deliver life saving
medicines, accelerating guide optimization processes in drug dis-
covery, with reduced needless environmental impact. Green chem-
istry also offers enhanced chemical process economics
concomitant with a reduced environmental burden. From this view
of points, it is desirable to use water as a safe, abundant and envi-
ronmentally benign solvent instead of organic solvents [2].
Pyrano [3,2-c]chromene derivatives are a class of important
heterocycles with a wide range of biological properties [3] such
as spasmolytic, diuretic, anticoagulant, anti-cancer, and anti-ana-
phylactic activity [4]. Moreover they can be used as cognitive
enhancers, for the treatment of neurodegenerative diseases,
including Alzheimer’s disease, amyotrophic lateral sclerosis, Par-
kinson’s disease, Huntington’s disease, AIDS associated dementia
and Down’s syndrome as well as for the treatment of schizophrenia
and myoclonus [5]. In addition, aminochromene derivatives exhi-
bit a wide spectrum of biological activities including antihyperten-
* Corresponding authors. Tel.: +98 6614202750; fax: +98 2188047861.
E-mail addresses: mmh1331@yahoo.com (M.M. Heravi), f_derikvand@yahoo.-
com (F. Derikvand).
4H-pyrans are useful as photoactive materials [9].
Despite their importance from pharmacological, industrial and
synthetic point of views, comparatively few methods for the prep-
aration of pyrano[3,2-c]chromene derivatives have been reported
[10,11]. 2-Amino-4-aryl-5-oxo-4H,5H-pyrano-[3,2-c]chromene-3-
carbonitriles have already been prepared in the presence of organic
bases like piperidine or pyridine in an organic solvent i.e. ethanol
and pyridine [10]. They are also prepared in the presence of Diam-
monium hydrogen phosphate in aqueous ethanol [11] and K2CO3
under microwave irradiation [12]. Three-component synthesis of
spirooxindoles in aqueous medium is as well reported [13].
Some of the reported procedures require long reaction times,
multi-step reactions and complex synthetic pathways, afford prod-
ucts with only modest yields, and non-reusability of the catalyst
[14–25]. Therefore, the development of more effective methods
for their preparation is still necessary.
Recently, there has been considerable interest in the use of het-
eropolyacids as environmentally benign catalysts due to their un-
ique properties such as high thermal stability, low cost, ease of
preparation and ease of recyclability [26]. Wells-Dawson type het-
eropolyacids posses super-acidity and remarkable stability both in
solution and in the solid state [26]. Many typical acid-catalyzed
reactions are effective in the presence of an appropriate Wells-
Dawson type heteropolyacid catalyst [27–30]. In continuation of
our work on catalytic properties of heteropolyacids [31–34] here

1566-7367/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2008.08.023
 M.M. Heravi et al. / Catalysis Communications 10 (2008) 272–275 273

NH2 Table 2
R Synthesis of 2-amino-4-aryl-3-cyano-5-oxo-4H,5H-pyrano-[3,2-c]chromenes in
OH O aqueous ethanol using a catalytic amount of H6P2W18O62
18H2O in refluxing
H6[P2W18O62]. 18H2O
(1mol%) Ar EtOH:H2O (50:50)
ArCHO + R CN +
H2O:EtOH, 1:1 Entry Ar R Product Time (min) Yield (%)a Conversion (%)b
O ref. O O
O
R=CN or CO2Et 1 C6H5 CN 1a 30 89 98
2 4-BrC6H4 CN 1b 60 87 96
Scheme 1. 3 4-ClC6H4 CN 1c 75 89 98
4 3-O2NC6H4 CN 1d 45 80 95
5 4-O2NC6H4 CN 1e 85 90 99
we wish to report the catalytic activity of H6P2W18O62
18H2O as 6 2,4-Cl2C6H3 CN 1f 75 86 96
7 4-CH3OC6H4 CN 1g 60 80 95
a Wells-Dawson type HPA in the one-pot synthesis of pyrano[3,2-
8 2,3-Cl2C6H3 CN 1h 50 90 99
c]chromenes by condensing 4-hydroxycoumarin, aldehydes and 9 4-BrC6H4 CO2Et 2a 16h 87 97
alkylnitriles in aqueous ethanol under refluxing conditions 10 3-O2NC6H4 CO2Et 2b 15h 90 99
(Scheme 1). 11 4-O2NC6H4 CO2Et 2c 16h 90 99
a
Yields are related to isolated pure products.
2. Results and discussion b
Conversions were analyzed by GC.

During initial exploratory reactions, we studied the synthesis of

2-Amino-4-(4-bromo-phenyl)-3-cyano-4H,5H-pyrano[3,2-c]chro- The reactions which occur in this pseudoliquid, are accelerated
mene-5-one from the condensation of 4-hydroxycoumarine, 4- due to the participation of all bulk protons of the heteropolyanion
bromo-benzaldehde and malononitrile in the presence of a variety and have good yields [38].
of solvents and catalysts to optimize the reaction conditions (Table Using these optimized reaction conditions, the scope and effi-
1). ciency of this aqueous approach was explored for the synthesis
First the reaction was tested with a catalytic amount of of a wide variety of substituted pyrano[3,2-c]chromene-5-ones
H6P2W18O62
18H2O under heating conditions in different sol- and the obtained results are summarized in Table 2.
vents and the best results were obtained in a mixture of ethanol All the aforementioned reactions (Table 2) delivered excellent
and water (50:50). The acidic properties of heteropolyacids in solu- product yields and accommodated a wide range of aromatic alde-
tions have been characterized in terms of dissociation constants hydes bearing both, electron-donating and electron-withdrawing
and Hammett acidity function [35]. Since heteropolyacids have dif- substituents. These three-component condensation reactions also
ferent dissociation constants and Hammett acidity in different sol- proceeded with ethyl caynoacetate (Table 2, entries 9–11); in these
vents [35], therefore, they show different behaviors for dissociation cases the reaction times are longer. It may be due to the less activ-
of protons in different solvents [29,30]. ity of ethyl caynoacetate than malononitrile. In all cases, the ob-
In compared to H6P2W18O62
18H2O, using H14[NaP5W30O110] tained product was isolated by a simple filtration, washed with
or NH2SO3H as catalyst in the model reaction under refluxing con- water and aqueous ethanol and purified by recrystallization from
ditions in aqueous ethanol (50:50) afforded fewer yields (Table 1). ethanol.
It is clear that many properties of the heteropoly compounds in A possible mechanism for these reactions is given in Scheme 2.
solution depend on the concentration, the pH value of the solution, It is noteworthy to mention that the catalyst is recyclable and
the reaction temperature, hydration water, and other factors. At could be reused without significant loss of activity. It could be
present, it is impossible to take all of these possible factors into ac- recovered by filtration of product, evaporation of solvent and
count in this study. Generally, solid heteropolyanions form ionic washing with diethyl ether. The recycled catalyst could subject
crystals composed of heteropolyanions, counteractions and hydra- to a second or even another reaction. In the model reaction the re-
tion water. In solid heteropolyanions, the protons take part in the sults of the first experiment and the subsequent were almost con-
formation of the heteropolyanion crystal structure and link the sistent in yield after five runs (87%, 87%, 85%, 83%, 80%; Table 3).
neighboring heteropolyanions via the hydrated water molecules
[36].
Polar molecules such as H2O, NH3, amines and alcohols are not
only adsorbed on the external surface of the heteropolyanion crys- +
H +
tallites, but also penetrate the bulk, where they interact with the H
O O
loosely bonded protons (hydrogen bonding), thus forming proton- H6P2W18O62 RCH2CN OH R
ated monomers or protonated clusters. Generally, such absorption Ar H H
Ar H H
and desorption processes are fast, indicating that at least a fraction Ar CN
of the absorbed molecules exhibits mobility, remembering to some
OH +
extent the mobility of solute molecules in concentrated liquid solu- H
tion. Such behavior has been called ‘‘pseudoliquid behavior” [37]. N R
Ar O
-H2O R O O
Ar
H CN H6P2W18O62 H
Table 1 O O
Optimization of the reaction conditions under refluxing conditions +
NH H
Entry Catalyst (mol%) Solvent Time (min) Yield (%)a R NH2
O H
1 H6[P2W18O62]
18H2O(1) EtOH 120 72 -H+ R
Ar O
2 H6[P2W18O62]
18H2O(1) H2O 140 82
3 H6[P2W18O62]
18H2O(1) H2O:EtOH 60 87 Ar
O O
4 NH2SO3H(10) H2O:EtOH 100 76
5 H14[NaP5W30O110](1) H2O:EtOH 90 74 O O
a
Yields are related to isolated pure products. Scheme 2. Suggested mechanism.
274 M.M. Heravi et al. / Catalysis Communications 10 (2008) 272–275
Table 3
Reusability of the catalysts in the model reaction (in 60 min)
Entry Number of recycle
1 First
2 1
3 2
4 3
5 4
a
Yields are related to isolated pure products.
In summary, we have demonstrated an elegant protocol for the
synthesis of substituted pyrano[3,2-c]chromene-5-ones using
H6P2W18O62.18H2O, which proceeds efficiently in aqueous ethanol
under heating conditions. Also the use of green, non toxic, inexpen-
sive and reusable catalyst, H6P2W18O62
18H2O, renders this
method eco-friendly, with a very simple isolation procedure that
entails the filtration of the precipitated products.
3. Experimental
Melting points were measured by using the capillary tube
method with an electro thermal 9200 apparatus. 1HNMR spectra
were recorded on a Bruker AQS AVANCE-500 MHz spectrometer
using TMS as an internal standard (DMSO solution). IR spectra
were recorded from KBr disk on the FT–IR Bruker Tensor 27. The
reactions were monitored by TLC. All solvents and reagents were
purchased from Aldrich and Merck with high-grade quality, and
used without any purification. All products were characterized by
their spectra and physical data.
3.1. General procedure
A solution of an aromatic aldehyde (1 mmol), alkylnitril
(1.2 mmol), 4-hydroxycoumarin (1 mmol) and H6P2W18O62

18H2O (1 mol%) in H2O (5 ml) and EtOH (5 ml) was stirred under
heating conditions for appropriate time. After completion of the
reaction which was monitored by TLC, the mixture was cooled to
room temperature. The solid product was collected by filtration,
washed with water and aqueous ethanol and purified by recrystal-
lization from ethanol.
3.2. Recycling of the catalyst
After completing the model reactions, the products were re-
moved by filtration. The catalyst was recovered by evaporation of
solvent and washing with diethyl ether. In the model reaction
the catalyst was recycled for five times and reused. As shown in Ta-
ble 3 the obtained results of the first experiment and the subse-
quent were almost consistent in yield after five runs.
3.3. Selected spectroscopic data
Hydrogens of aryl substituents are shown by Hn’.
3.3.1. 2-Amino-4-(3-nitrophenyl)-3-cyano-4H,5H-pyrano[3,2-c]
chromene-5-one 1d
White Solid, m.p. = 258–260 °C; IR (KBr): tmax = 3404, 3322,
3194, 2202, 1703, 1672, 1531, 1349 cm 1, 1HNMR (DMSO-d6,
500 MHz): dH = 4.74 (1H, s, H-4), 7.44 (1H, d, J = 6.7 Hz, H7), 7.51
(1H, t, J = 7.6 Hz, H9), 7.56 (2H, br s, NH2), 7.64 (1H, t, J = 7.6 Hz,
H5’), 7.73 (1H, dt, J = 7.5, 1.3 Hz, H8), 7.82 (1H, d, J = 6.8 Hz, H2’),
7.92 (1H, dd, J = 6.8, 1.2 Hz, H10), 8.12 (1H, dd, J = 8.4, 1.4 Hz, H4’),
8.14 (1H, s, H6’) ppm.
3.3.2. 2-Amino-4-(4-nitrophenyl)-3-cyano-4H,5H-pyrano[3,2-c]
chromene-5-one1e
Yield(%)a Pale Yellow Solid, m.p. = 260–262 °C; IR (KBr): tmax = 3482,
87 3432, 3371, 3335, 2195, 1718, 1673, 1607, 1506, 1374,1306 cm
1 1
87 ; HNMR (DMSO-d6, 500 MHz): dH = 4.68 (1H, s, H-4), 7.47 (1H,
85 d, J = 8.3 Hz, H7), 7.52 (1H, t, J = 7.7 Hz, H9), 7.57 (2H, br s, NH2),
83 7.60 (2H, d, J = 8.0 Hz, H2’,6’), 7.74 (1H, t, J = 7.8 Hz, H8), 7.91 (1H,
80
d, J = 7.8 Hz, H10), 8.18 (2H, d, J = 8.3 Hz, H3’,5’) ppm.
3.3.3. 2-Amino-4-(2,4-dichlorophenyl)-3-cyano-4H,5H-pyrano[3,2-c]
chromene-5-one1f
White Solid m.p. = 255–257 °C; IR (KBr): tmax = 3463, 3295,
3163, 3070, 2198, 1715, 1674, 1590 cm 1; 1HNMR (DMSO-d6,
500 MHz): dH = 4.99 (1H, s, H-4), 7.36 (1H, dd, J = 8.3, 1.9 Hz, H5’),
7.40 (1H, d, J = 8.3 Hz, H7), 7.41 (2H, br s, NH2), 7.46 (1H, d,
J = 8.3 Hz, H3’), 7.51 (1H, t, J = 7.7 Hz, H9), 7.56 (1H, d, J = 2.1 Hz,
H6’), 7.73 (1H, t, J = 8.2 Hz, H8), 7.92 (1H, d, J = 8.9 Hz, H10) ppm.
3.3.4. 2-Amino-4-(2,3-dichlorophenyl)-3-cyano-4H,5H-pyrano[3,2-c]
chromene-5-one 1h
White Solid, m.p. = 280–282 °C; IR (KBr): tmax = 3403, 3294,
3179, 2198, 1710, 1672, 1601 cm 1; 1HNMR (DMSO-d6,
500 MHz): dH = 5.09 (1H, s, H-4), 7.29-7.35 (2H, m, H4’,5’), 7.47–
7.55 (5H, m, H7,8,9 & NH2), 7.72–7.75 (1H, m, H6’), 7.92 (1H, dd,
J = 7.8, 1.3 Hz, H10) ppm.
3.3.5. 2-Amino-4-(3-nitrophenyl)-3-carboethoxy-4H,5H-pyrano[3,2-c]
chromene-5-one2b
Pale Yellow Solid, m.p. = 247–250 °C; IR (KBr): tmax = 3433,
3315, 1710, 1687, 1657, 1609, 1579 cm 1; 1HNMR (DMSO-d6,
500 MHz): dH = 1.09 (3H, t, J = 7.0 Hz, CH3), 3.98 (2H, m, CH2),
4.83 (1H, s, H-4), 7.46 (1H, d, J=8.1 Hz, H7), 7.50–7.57 (2H, m,
H9,5’), 7.24 (2H, d, J = 7.2 Hz, H8,10), 7.95 (2H, s, NH2), 8.00 (1H, d,
J = 7.7 Hz, H2’), 8.04–8.06 (2H, m, H4’,6’) ppm.
Acknowledgments
The authors are thankful from Azzahra Research Council for the
partial financial support.
References
[1] R.S. Varma, Green Chem. 1 (1999) 43.
[2] C.-J. Li, L. Chen, Chem. Soc. Rev. 5 (2006) 68.
[3] G.R. Green, J.M. Evans, A.K. Vong, in: A.R. Katritzky, C.W. Rees, E.F. Scriven
(Eds.), In Comprehensive Heterocyclic Chemistry II, 5, Pergamon Press, Oxford,
1995, p. 469.
[4] W.O. Foye, Principi Di Chemico Frmaceutica, Piccin, Padova, Italy, 1991.
[5] C.S. Konkoy, D.B. Fick, S.X. Cai, N.C. Lan, J.F.W. Keana, PCT Int Appl WO 0075123
(2000), Chem. Abstr. 134 (2001) 29313a.
[6] A. Burgard, H.-J. Lang, U. Gerlach, Tetrahedron 55 (1999) 7555.
[7] J.M. Evans, C.S. Fake, T.C. Hamilton, R.H. Poyser, G.A. Showell, J. Med. Chem. 27
(1984) 1127.
[8] J.M. Evans, C.S. Fake, T.C. Hamilton, R.H. Poyser, E.A. Watts, J. Med. Chem. 26
(1983) 1582.
[9] D. Arnesto, W.M. Horspool, N. Martin, A. Ramos, C. Seaone, J. Org. Chem. 54
(1989) 3069.
[10] R.M. Shaker, Pharmazie 51 (1996) 148.
[11] Sh. Abdolmohammadi, S. Balalaie, Tetrahedron Lett. 48 (2007) 3299.
[12] M. Kidwai, S. Saxena, Synth. Commun. 36 (2006) 2737.
[13] S.-L. Zhu, Sh.-J. Ji, Y. Zhang, Tetrahedron 63 (2007) 9365.
[14] C. Wiener, C.H. Schroeder, B.D. West, K.P. Link, J. Org. Chem. 27 (1962) 3086.
[15] T. Kuwada, K. Harada, J. Nobuhiro, T. Choshi, Heterocycles 57 (2002) 2081.
[16] P. Srivastava, A.S. Saxena, V.J. Ram, Synthesis (2000) 541.
[17] A.D. Broom, J.L. Shim, G.L. Anderson, J. Org. Chem. 41 (1976) 1095.
[18] H.C. Scarborough, J. Org. Chem. 29 (1964) 19.
[19] J.L. Shim, R. Niess, A.D. Broom, J. Org. Chem. 37 (1972) 578.
[20] B.H. Rizkalla, A.D. Broom, J. Org. Chem. 37 (1972) 3980.
[21] F. Shönfeld, R. Troschütz, Heterocycles 55 (2001) 1679.
[22] E.C. Taylor, K. Lee, Heterocycles 45 (1997) 2229.
[23] E.V. Stoyanov, I.C. Ivanov, D. Heber, Molecules 5 (2000) 19.
[24] V.K. Ahluwalia, R. Kumar, A. Khurana, R. Bhatla, Tetrahedron 46 (1990) 3953.
[25] Y.-M. Ren, Ch. Cai, Catal. Commun. 9 (2008) 1017.
 M.M. Heravi et al. / Catalysis Communications 10 (2008) 272–275 275

[26] N. Mizuno, M. Misono, Chem. Rev. 98 (1998) 199.
[27] L.E. Briand, G.T. Baronetti, H.J. Thomas, Appl. Catal. A: Gen. 256 (2003)
37.
[28] G.P. Romanelli, G. Baronetti, H.J. Thomas, J.C. Autino, Tetrahedron Lett. 43
(2002) 7589.
[29] G.P. Romanelli, H.J. Thomas, G.T. Baronetti, J.C. Autino, Tetrahedron Lett. 44
(2003) 1301.
[30] G. Baronetti, L. Briand, U. Sedran, H. Thomas, Appl. Catal. A: Gen. 172 (1998)
265.
[31] M.M. Heravi, M. Khorasani, F. Derikvand, H.A. Oskooie, F.F. Bamoharram, Catal.
Commun. 8 (2007) 1886.
[32] M.M. Heravi, L. Ranjbar, F. Derikvand, F.F. Bamoharram, Catal. Commun. 8
(2007) 289.
[33] M.M. Heravi, F. Derikvand, L. Ranjbar, H.A. Oskooie, F.F. Bamoharram, J. Mol.
Catal. A: Chem. 261 (2007) 156.
[34] M.M. Heravi, F. Derikvand, F.F. Bamoharram, J. Mol. Catal. A: Chem. 263 (2007)
112.
[35] I.V. Kozhevnikov, Russ. Chem. Rev. 56 (1987) 811.
[36] I.V. Kozhevnikov, Chem. Rev. 98 (1998) 171.
[37] A. Bielański, A. Lubańska, A. Micek-Ilnica, J. Poźniczek, Coord. Chem. Rev. 249
(2005) 2222.
[38] F. Cavani, Catal. Today 41 (1998) 73.

View publication stats