Catalytic method for synthesis of benzopyrano[3,2-c]chromene-6,8-dione derivatives by heteropoly acids

Article abstract of DOI:10.1080/00397911.2010.542536

Benzopyrano[3,2-c]chromene-6,8-dione derivatives were prepared by a threecomponent one-pot cyclocondensation of 4-hyroxycoumarin, aldehydes, and 1,3,cyclohexadione using a catalytic amount of heteropolyacids in boiling ethanol in very good yields and rate

Full text of DOI:10.1080/00397911.2010.542536

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Catalytic Method for Synthesis of
Benzopyrano[3,2-c]chromene-6,8-dione
Derivatives by Heteropoly Acids
Radineh Motamedi a , Saeede Baghbani b & Fatemeh F. Bamoharram
c
a Department of Chemistry, School of Sciences, Payam Noor
University (PNU), Delijan, Iran
b Department of Chemistry, School of Sciences, Payam Noor
University (PNU), Tehran, Iran
c Department of Chemistry, Islamic Azad University, Mashhad, Iran
Accepted author version posted online: 17 Nov 2011.Version of
record first published: 03 Feb 2012.
To cite this article: Radineh Motamedi, Saeede Baghbani & Fatemeh F. Bamoharram (2012): Catalytic
Method for Synthesis of Benzopyrano[3,2-c]chromene-6,8-dione Derivatives by Heteropoly Acids,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 42:11, 1604-1612
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Synthetic Communications1, 42: 1604–1612, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.542536
CATALYTIC METHOD FOR SYNTHESIS OF
BENZOPYRANO[3,2-c]CHROMENE-6,8-DIONE
DERIVATIVES BY HETEROPOLY ACIDS
Radineh Motamedi,1 Saeede Baghbani,2 and
Fatemeh F. Bamoharram3
1Department of Chemistry, School of Sciences, Payam Noor University
(PNU), Delijan, Iran
2Department of Chemistry, School of Sciences, Payam Noor University
(PNU), Tehran, Iran
3Department of Chemistry, Islamic Azad University, Mashhad, Iran
GRAPHICAL ABSTRACT
Abstract Benzopyrano[3,2-c]chromene-6,8-dione derivatives were prepared by a three-
component one-pot cyclocondensation of 4-hyroxycoumarin, aldehydes, and 1,3,cyclohexadione
using a catalytic amount of heteropolyacids in boiling ethanol in very good yields and rates.
Keywords Benzopyrano[3,2-c]chromene; catalytic cyclocondensation; catalytic reaction;
heteropolyacid
INTRODUCTION
4-Hydroxycoumarin 3 constitutes the structural nucleus of many natural
products, drugs and pesticides.[1–3] It is the key intermediate for various widely used
oral anticoagulants and rodenticides.[4] Similarly, several derivatives of pyran or
fused pyran ring systems have been shown to possess different types of biological
activities[5] such as antidiabetic[6] and anti-Alzheimer[7] activities. Various other
medical activities have been exhibited by pyran derivatives, including antimicro-
bial,[8] anti tumor,[9] anti fungal, antidepressant,[10] and platelet antiaggregating[11]
activities. They have also been developed as photosensitive drugs,[12] potent and
Received October 13, 2010.
Address correspondence to Radineh Motamedi, Department of Chemistry, School of Sciences,
Payam Noor University (PNU), Tehran, Iran. E-mail: r_motamedi@pnu.ac.ir
1604

BENZOPYRANO[3,2-c]CHROMENE-6,8-DIONE DERIVATIVES
1605
Scheme 1. General synthetic pathway for the preparation of benzopyrano[2,3-c]chromene-6,8-dione deri-
vatives.
selective human dopamine D4 antagonists,[13] nonpentidic HIV protease inhibi-
tors,[14] and antibiotic agents such as novebiocin.[15]
We have recently reported design, synthesis and toxicity effect of novel
benzopyrano[3,2-c]chromene-6,8-diones 4 derivatives (Scheme 1).[16] In continuation
of our attempts to develop selective and preoperatively useful methodology, using
heteropolyacids as green catalysts in various organic reactions,[17] we report a rapid
and convenient method for synthesis of these compounds, catalyzed by heteropolya-
cids (HPAs).
(HPAs) are considered to be environmentally benign catalysts because of their
unique properties such as high thermal stability, low cost, ease of preparation, and
ease of recyclability.[18,19] Many organic reactions, including oxygenation, estrifica-
tion, and polymerization[20–23] can be catalyzed effectively by HPAs because of their
high oxidation capatibility, strong acidity, and unique pseudo-liquid-phase
behavior.[24]
RESULTS AND DISCUSSION
We have previously described synthesis of novel 7-aryl benzopyrano[3,2-c]
chromene-6,8-dione 4 derivatives by one-pot, three-component cyclocondensation
of 4-hydroxy coumarin, 1,3-cyclohexadione, and aryl aldehyde after 5 h refluxing
in acetic acid in yields of 60–78% (Scheme 1).[16]
The structures of compounds 4 were deduced from their infrared (IR)16] Armed
with our experiences using various HPAs as green catalysts in acidic catalytic
reactions,[17] we were persuaded to study the use of these catalysts for synthesis of
compounds 4. Initially the coupling reaction of 4-hydroxy coumarine 3, 4-nitro-
benzaldehyde 2a, and 1,3-cyclohexadione 1 in ethanol with different catalytic
amounts of H6P2Mo18O62 and at room temperature and refluxing condition was
investigated to optimize the reaction conditions. The best yield was obtained in pres-
ence of 10% molar ratio of the catalyst in boiling ethanol. Then using the optimized
reaction conditions, the coupling reaction was examined in different solvents such as
methanol, ethanol and acetic acid to find the best solvent. The yields in all cases were
the same. Therefore, ethanol was selected as a suitable solvent.
In the next step, using the optimized conditions, the one-pot coupling reactio-
nof a series of aryl aldehyde in the presence of H6P2Mo18O62(10%) was investigated,

1606
R. MOTAMEDI, S. BAGHBANI, AND F. F. BAMOHARRAM
Table 1. Catalytic synthesis of 7-aryl-benzopyrano[3,2-c]chromene-6,8-dione derivatives in ethanol was
refluxed by H6P2Mo18O62 (10%)
Compound
R
Yield (%)
Time (min)
Mp
4a
4b
4c
4d
4e
4f
4-Nitro
3-Nitro
2-Nitro
90
90
90
80
79
80
85
84
85
86
87
88
4
4
4
4
4
4
4
4
4
4
4
4
196 (195–197)
219 (218–220)
222 (222–223)
170 (170–171)
265 (265–264)
238 (238–239)
244 (244–245)
247 (247–248)
294 (294–295)
196 (196–197)
188 (188–189)
246 (245–246)
4-Bromo
3-Bromo
2-Bromo
4-Chloro
3-Chloro
2-Chloro
4-Methoxy
3-Methoxy
2-Methoxy
4g
4h
4i
4j
4k
4l
and the obtained results are summarized in Table 1. All the aforementioned cata-
lyzed reactions delivered excellent product yields and reaction times compared to
those without catalyst. All products were identified by comparison with authentic
samples.[16]
These results demonstrate that both the yields and the reaction time are rela-
tively independent of the position of the substituent in aryl aldehyde. However,
nitrobenzaldehyde had relatively better yields. To show the effect of the different cat-
alysts, the one-pot coupling reaction of 4-hydroxylcoumarine 3, 4-nitrobenzaldehyde
2a, and 1,3-cyclohexadione 1 was examined in presence of 10% molar ratio of differ-
ent HPA catalysts such as H6P2Mo18O62, H6P2W18O62, K7PWMo11O39,
H14[NaP5W29MoO110], and K3PW12O40. The results are presented in Table 2. As
shown in Table 2, however, both H14[NaP5W29MoO110] and H6P2W18O62 showed
the best yield. The rates of reactions were two to 10 times faster in the presence of
Preyssler-type HPA H14[NaP5W29MoO110]. Among HPA and Preyssler structures
used in the present study, H14[NaP5W29MoO110] showed more activity and yields
because of the it has more acidic protons, which is in a good agreement with the find-
ings of earlier work.[17]
HPA were separated by filtration, and the products were purified by recrysta-
lizing from ethyl acetate. The reactions were monitored by thin-layer chromato-
graphy (TLC), and subsequent workup afforded a single compound (by TLC) in
Table 2. Catalytic synthesis of 4-nitro-benzopyrano[3,2-c]chromene-6,8-
dione derivatives in ethanol was refluxed by heteropolyacids
Yield (%)
Time (min)
H6P2Mo18O62
H6P2W18O62
K7PWMo11O39
90
98
80
98
85
4
30
7
H14[NaP5W29MoO110
]
2
K3PW12O40
5

BENZOPYRANO[3,2-c]CHROMENE-6,8-DIONE DERIVATIVES
1607
Scheme 2. Possible mechanism of formation of 4 in reaction pathway.
1
each case. The product was identified by its H NMR, mass, and IR spectra, which
were compared to those reported previously.[16]
Generally, reactions catalyzed by HPAs may be represented by the conven-
tional mechanisms of Brønsted acid catalysis. A plausible mechanism for the forma-
tion of compounds 4 is given in Scheme 2. It is reasonable to assume that in the first
step aldol condensation between arylaldehydes and 1,3-cyclohexadione affords com-
pound 5. In the second step Michael addition of 4-hydroxycoumarine to compound
5 led to the formation of the intermediates 6, which undergo cyclization followed by
dehydration to give the desired compounds 4 (Scheme 2). The proton can catalyze all
three steps.
Catalysts based on HPAs have many advantages over acid catalyzsts. They are
not corrosive, are environmetally benign, present fewer disposals problem, and sepa-
rates easily and have thermal stability. These catalysts are not soluble in ethanol,
which enables easy separation and recovery by filtering for immediate reuse without
any important decrease of the catalyst reactivity.
EXPERIMENTAL
General Procedure for the Synthesis of 7-Aryl-9,10-dihydro-7h,11h-
benzopyrano[3,2-c]chromene-6,8-dione Derivatives
4-Hydroxyl coumarin 3 (0.162 g, 1 mmol), 1,3 cyclohexadione 1 (0.112 g,
1 mmol) and arylaldehydes (1 mmol), and the appropriate HPA (0.04 mmol) were
refluxed in ethanol (50 ml) for the indicated time (Table 1).
The catalyst was removed by filtration and washed with warm ethanol (the
catalyst is not soluble in ethanol). The catalyst was further washed with diethyl ether
after filtration. It could be reused for a second run of the reaction. The yields of

1608
R. MOTAMEDI, S. BAGHBANI, AND F. F. BAMOHARRAM
product were almost identical to those obtained using fresh catalyst. The filtrate was
cooled, and the precipitated solid was collected by filtration, washed with cold ethyl
acetate, dried, and recrystallized from ethyl acetate to give the pure product 4
1
(Table 1). All products were identified by their mass and H NMR spectra by com-
parison with authentic samples.[16]
9,10-Dihydro-7-(4-nitrophenyl)-7h,11 h-benzopyrano[3,2c]chromene-6,
=
8-dione 4a. IR (KBr) n: 3068 (C-H aromatic), 2914 (C-H aliphatic), 1721 (C O),
1
1526, 1362 (NO2) cmꢀ1. H NMR (CDCl3) d: 2.08–2.21 (m, 2H, H10), 2.44–2.47
(m, 2H, H11), 2.79–2.84 (m, 1H, H9), 2.89–2.90 (m, 1H, H9), 5.08 (s, 1H, H7), 7.36
(dd, 1H, J ¼ 8.0, 1.0 Hz, H4), 7.40 (td, 1H, J ¼ 8.0, 1.0 Hz, H2), 7.57 (d, 2H,
J ¼ 8.5 Hz, H14, H18), 7.62 (td, 1H, J ¼ 8.0, 1.5 Hz, H3), 7.91 (dd, 1H, J ¼ 8.0,
1.5 Hz, H1), 8.13 (d, 2H, J ¼ 8.5 Hz, H15, H17). MS: m=z (%), 389 (Mþ, 11), 372
(47), 342 (22), 267 (100), 149 (17), 122 (13), 83 (23), 55 (40). Anal. calcd. for
C22H15NO6: C, 67.86; H, 3.88; N, 3.60. Found: C, 67.69; H, 3.70; N, 3.82.
9,10-Dihydro-7-(3-nitrophenyl)-7h,11h-benzopyrano[3,2-c]chromene-6,
=
8-dione (4b). IR (KBr) n: 3100 (C-H aromatic), 2934 (C-H aliphatic), 1731 (C O),
1526, 1362 (NO2) cmꢀ1. 1H NMR (CDCl3) d: 2.08–2.21 (m, 2H, H10), 2.40–2.50 (m,
2H, H11), 2.77–2.85 (m, 1H, H9), 2.92–2.99 (m, 1H, H9), 5.09 (s, 1H, H7), 7.36 (d, 1H,
J ¼ 8.0 Hz, H4), 7.41 (t, 1H, J ¼ 8.0 Hz, H2), 7.48 (t, 1H, J ¼ 8.0 Hz, H17), 7.62 (t, 1H,
J ¼ 8.0 Hz, H3), 7.94 (m, 2H, H18, H1), 8.05–8.08 (m, 2H, H14, H16). MS: m=z (%),
390 (Mþ þ 1, 29), 389 (Mþ, 8), 373 (86), 343 (16), 267 (100). Anal. calcd. for
C22H15NO6: C, 67.86; H, 3.88; N, 3.60. Found: C, 68.15; H, 3.65; N, 3.85.
9,10-Dihydro-7-(2-nitrophenyl)-7h,11h-benzopyrano[3,2-c]chromene-6,
=
8-dione (4c). IR (KBr) n: 3078 (C-H aromatic), 2950 (C-H aliphatic), 1731 (C O),
1526, 1357 (NO2) cmꢀ1. 1H NMR (CDCl3) d: 2.05–2.14 (m, 2H, H10), 2.40–2.42 (m,
2H, H11), 2.72–2.79 (m, 1H, H9), 2.83–2.89 (m, 1H, H9), 5.75 (s, 1H, H7), 7.31 (t, 1H,
J ¼ 7.5 Hz, H16), 7.34 (d, 1H, J ¼ 8.0 Hz, H4), 7.38 (t, 1H, J ¼ 8.0 Hz H2), 7.47 (t, 1H,
J ¼ 7.5 Hz, H17), 7.54 (d, 1H, J ¼ 7.5 Hz, H18), 7.59 (t, 1H, J ¼ 8.0 Hz, H3), 7.78 (d,
1H, J ¼ 7.5 Hz, H15), 7.91 (d, 1H, J ¼ 8.0 Hz H1). MS: m=z (%), 389 (Mþ, 33), 342
(40), 267 (100), 149 (23), 122 (57), 83 (31), 55 (91). Anal. calcd. for C22H15NO6:
C, 67.86; H, 3.88; N, 3.60. Found: C, 67.63; H, 4.15; N, 3.89.
7-(4-Bromophenyl)-9,10-dihydro-7h,11h-benzopyrano[3,2-c]chromene-6,
=
8-dione (4d). IR (KBr) n: 3080 (C-H aromatic), 2939 (C-H aliphatic), 1716 (C O)
cmꢀ1 1H NMR (CDCl3) d: 2.07–2.18 (m, 2H, H10), 2.42–2.46 (m, 2H, H11),
.
2.78–2.80 (m, 1H, H9), 2.85–2.90 (m, 1H, H9), 4.94 (s, 1H, H7), 7.25 (d, 2H,
J ¼ 8.5 Hz, H14, H18), 7.34 (dd, 1H, J ¼ 8.0, 1.0 Hz, H4), 7.36 (td, 1H, J ¼ 8.0,
1.0 Hz, H2), 7.37 (d, 2H, J ¼ 8.5 Hz, H15, H17),7.59 (td, 1H, J ¼ 8.0, 1.5 Hz, H3),
7.88 (dd, 1H, J ¼ 8.0, 1.5 Hz, H1). MS: m=z (%), 424 (Mþ þ 2, 18), 422 (Mþ, 16),
342 (40), 267 (100), 154 (25), 122 (18), 93 (38), 74 (42). Anal. calcd. for C22H15BrO4:
C, 62.43; H, 3.57. Found: C, 62.67; H, 3.81.
7-(3-Bromophenyl)-9,10-dihydro-7h,11h-benzopyrano[3,2-c]chromene-6,
=
8-dione (4e). IR (KBr) n: 3050 (C-H aromatic), 2950 (C-H aliphatic), 1731 (C O)
cmꢀ1 1H NMR (CDCl3) d: 2.18–2.09 (m, 2H, H10), 2.50–2.30 (m, 2H, H11),
.
2.74–2.80 (m, 1H, H9), 2.88–2.93 (m, 1H, H9), 4.95 (s, 1H, H7), 7.15 (t, 1H,

BENZOPYRANO[3,2-c]CHROMENE-6,8-DIONE DERIVATIVES
1609
J ¼ 8.0 Hz, H17), 7.29 (dt, 1H, J ¼ 8.0, 1.0 Hz,H18), 7.34 (d, 1H, J ¼ 8.0 Hz, H4), 7.38
(t, 1H, J ¼ 8.0 Hz, H2),7.39 (t, 1H, J ¼ 1.0 Hz,H14), 7.41 (dt, 1H, J ¼ 8.0, 1.0 Hz, H16),
7.58 (td, 1H, J ¼ 8.0, 1.0 Hz H3), 7.90 (dd, 1H, J ¼ 8.0, 1.0 Hz, H1). MS: m=z (%), 424
(Mþ þ 2, 10), 422 (Mþ, 10), 343 (50), 267 (41), 249 (100), 122 (23), 93 (10). Anal.
calcd. for C22H15BrO4: C, 62.43; H, 3.57. Found: C, 62.68; H, 3.82.
7-(2-Bromophenyl)-9,10-dihydro-7h,11h-benzopyrano[3,2-c]chromene-6,
=
8-dione (4f). IR (KBr) n: 3052 (C-H aromatic), 2919 (C-H aliphatic), 1726 (C O)
cmꢀ1 1H NMR (CDCl3) d: 2.05–2.157 (m, 2H, H10), 2.36–2.45 (m, 2H, H11),
.
2.72–2.78 (m, 1H, H9), 2.82–2.88 (m, 1H, H9), 5.25 (s, 1H, H7), 7.06 (t, 1H,
J ¼ 7.5 Hz, H16), 7.24 (t, 1H, J ¼ 7.5 Hz, H17), 7.33 (d, 1H, J ¼ 8.0 Hz, H4), 7.35 (t,
1H, J ¼ 8.0 Hz, H2),7.49-7.46 (m, 2H, H15, H18), 7.57 (td, 1H, J ¼ 8.0, 1.0 Hz, H3),
7.90 (dd, 1H, J ¼ 8.0, 1.0 Hz, H1). MS: m=z (%), 424 (Mþ þ 2, 10), 422 (Mþ, 10),
343 (100), 267 (22). Anal. calcd. for C22H15BrO4: C, 62.43; H, 3.57. Found: C,
62.71; H, 3.38.
7-(4-Chlorophenyl)-9,10-dihydro-7h,11h-benzopyrano[3,2-c]chromene-6,
=
8-dione (4g). IR (KBr) n: 3100 (C-H aromatic), 2939 (C-H aliphatic), 1716 (C O)
cmꢀ1 1H NMR (CDCl3) d: 2.05–2.16 (m, 2H, H10), 2.42–2.46 (m, 2H, H11),
.
2.74–2.80 (m, 1H, H9), 2.85–2.91 (m, 1H, H9), 4.96 (s, 1H, H7), 7.23 (d, 2H,
J ¼ 8.5 Hz, H14, H18), 7.33 (d, 2H, J ¼ 8.5 Hz, H15, H17), 7.34–7.39 (m, 2H, H2,
H4), 7.61 (td, 1H, J ¼ 8.0, 1.5 Hz, H3), 7.88 (dd, 1H, J ¼ 8.0, 1.5 Hz, H1), MS: m=z
(%), 380 (Mþ þ 2, 8), 378 (Mþ, 25), 344 (15), 327 (85), 266 (80), 216 (100), 111
(65), 54 (95). Anal. calcd. for C22H15ClO4: C, 69.75; H, 3.99. Found: C, 69.97;
H, 3.76.
7-(3-Chlorophenyl)-9,10-dihydro-7h,11h-benzopyrano[3,2-c]chromeneꢀ-61,
=
8-dione (4h). IR (KBr) n: (C-H aromatic), 2965 (C-H aliphatic), 1726 (C O) cm
.
1H NMR (CDCl3)d: 2.09–2.17 (m, 2H, H10), 2.38–2.50 (m, 2H, H11), 2.74–2.80 (m,
1H, H9), 2.88–2.92 (m, 1H, H9), 4.96(s, 1H, H7), 7.15 (dt, 1H, J ¼ 7.5, 1.5 Hz, H18),
7.20 (t, 1H, J ¼ 7.5 Hz, H17), 7.26 (t, 1H, J ¼ 1.5, H14), 7.33 (dd, 1H, J ¼ 8.0,
1.0 Hz,H4), 7.36–7.39 (m, 2H, H16, H2), 7.59 (td, 1H, J ¼ 8.0, 1.5 Hz, H3), 7.89
(dd, 1H, J ¼ 8.0, 1.5 Hz, H1), MS: m=z (%), 380 (Mþ þ 2, 3.5), 378 (Mþ, 10), 344
(100), 268 (38), 111(10). Anal. calcd. for C22H15ClO4: C, 69.75; H, 3.99. Found:
C, 69.47; H, 4.28.
7-(2-Chlorophenyl)-9,10-dihydro-7h,11h-benzopyrano[3,2-c]chromene-6,
=
8-dione (4i). IR (KBr) n: 3062 (C-H aromatic), 2955 (C-H aliphatic), 1726 (C O)
cmꢀ1. 1H NMR (CDCl3) d: 1.93 (m, 2H, H10), 2.29–2.33 (m, 2H, H11), 2.82–2.85 (m,
2H, H9), 5.06 (s, 1H, H7), 7.16 (t, 1H, J ¼ 7.6 Hz, H16), 7.24 (t, 1H, J ¼ 7.6 Hz, H17),
7.29 (d, 1H, J ¼ 7.6, H18), 7.34 (d, 1H, J ¼ 8.0 Hz, H4), 7.46 (t, 1H, J ¼ 8.0 Hz, H2),
7.50 (d, 1H, J ¼ 7.6 Hz, H15), 7.7 (td, 1H, J ¼ 8.0, 1.0 Hz, H3), 7.98 (dd, 1H, J ¼ 8.0,
1.0 Hz, H1). MS: m=z (%), 380 (Mþ þ 2, 3), 378 (Mþ, 10), 344 (100), 343 (55), 268
(25). Anal. calcd. for C22H15ClO4: C, 69.75; H, 3.99. Found: C, 69.46; H, 3.70.
9,10-Dihydro-7-(4-methoxyphenyl)-7h,11h-benzopyrano[3,2-c]chromene-
=
6,8-dione (4j). IR (KBr) n: 3080 (C-H aromatic), 2939 (C-H aliphatic), 1726 (C O)
cmꢀ1. 1H NMR (CDCl3) d: 2.07–2.16 (m, 2H, H10), 2.41–2.46 (m, 2H, H11), 2.73–2.79
(m, 1H, H9), 2.85-2.90 (m, 1H, H9), 3.74 (s, 3H, CH3), 4.94 (s, 1H, H7), 6.79 (d, 2H,

1610
R. MOTAMEDI, S. BAGHBANI, AND F. F. BAMOHARRAM
J ¼ 9.0 Hz, H15, H17), 7.30 (d, 2H, J ¼ 9.0 Hz, H14, H18) 7.32 (dd, 1H, J ¼ 8.0,
1.0 Hz,H4), 7.36 (td, 1H, J ¼ 8.0, 1.0 Hz, H2), 7.57 (td, 1H, J ¼ 8.0, 1.5 Hz, H3), 7.87
(dd, 1H, J ¼ 8.0, 1.5 Hz, H1). MS: m=z (%), 374 (Mþ, 18), 343 (10), 300 (10), 267
(100). Anal. calcd. for C23H18O5: C, 73.79; H, 4.05. Found: C, 73.48; H, 3.83.
9,10-Dihydro-7-(3-methoxyphenyl)-7h,11h-benzopyrano[3,2-c]chromene-
6,8-dione ꢀ(14k). IR (KBr) n: 3080 (C-H aromatic), 2939 (C-H aliphatic), 1736
.
1H NMR (CDCl3) d: 2.08–2.16 (m, 2H, H10), 2.41–2.49 (m, 2H,
=
(C O) cm
H11), 2.73–2.79 (m, 1H, H9), 2.85-2.90 (m, 1H, H9), 3.78 (s, 3H, CH3), 4.99 (s,
1H, H7), 6.72 (dd, 1H, J ¼ 8.0, 1.5 Hz, H18), 6.94 (t, 1H, J ¼ 1.5 Hz, H14), 6.99
(dd, 1H, J ¼ 8.0, 1.5 Hz H16), 7.17 (t, 1H, J ¼ 8.0 Hz, H17), 7.32 (d, 1H, J ¼ 8.0 Hz,
H4), 7.36 (t, 1H, J ¼ 8.0 Hz H2), 7.57 (td, 1H, J ¼ 8.0, 1.0 Hz, H3), 7.88 (dd, 1H,
J ¼ 8.0, 1.0 Hz, H1). MS: m=z (%), 374 (Mþ, 70), 343 (65), 267 (100), 93 (90), 76
(95). Anal. calcd. for C23H18O5: C, 73.79; H, 4.05. Found: C, 73.95; H, 3.82.
9,10-Dihydro-7-(2-methoxyphenyl)-7h,11h-benzopyrano[3,2-c]chromene-
=
6,8-dione (4 l). IR (KBr) n: 3067 (C-H aromatic), 2945 (C-H aliphatic), 1721 (C O)
cmꢀ1 1H NMR (CDCl3) d: 2.02–2.13 (m, 2H, H10), 2.34–2.43 (m, 2H, H11),
.
2.70–2.78 (m, 2H, H9), 3.70 (s, 3H, CH3), 5.06 (s, 1H, H7), 6.79 (dd, 1H, J ¼ 8.0,
1.0 Hz, H15), 6.94 (td, 1H, J ¼ 8.0, 1.0 Hz, H17), 7.17 (td, 1H, J ¼ 8.0, 1.5 Hz, H16),
7.32 (dd, 1H, J ¼ 8.0, 1.0 Hz, H4), 7.35 (td, 1H, J ¼ 8.0, 1.0 Hz H2), 7.52 (dd, 1H,
J ¼ 8.0, 1.5 Hz, H18), 7.55 (td, 1H, J ¼ 8.0, 1.5 Hz, H3, 7.94 (dd, 1H, J ¼ 8.0,
1.5 Hz, H1), MS: m=z (%), 374 (Mþ, 55), 344 (30), 319 (18), 268 (100), 122 (25), 56
(12). Anal. calcd. for C23H18O5: C, 73.79; H, 4.05. Found: C, 73.98; H, 4.33.
CONCLUSION
We have developed a method using an ecofriendly and reusable heterogeneous
inorganic catalyst for synthesis of 7-aryl-benzopyrano[3,2-c]chromene-6,8-dione
derivatives
4 using heteropolyacids catalysts. Among the heteropolyacids,
H14[NaP5W30O110] have exhibited high activities for the synthesis of these com-
pounds. The reasonable reaction times, good yields, simple workup procedure,
and environmentally friendly conditions are the main advantages of this method.
All catalysts are not soluble in ethanol, which enabled easy separation and
recovery by filtering for their immediate reuse without any important decrease of
the catalyst reactivity.
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