Efficient one-pot syntheses of 7-alkyl-6H,7H-naphtho[1,2:5,6]pyrano-[3,2-c]chromen-6-ones by 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride

Article abstract of DOI:10.1002/jhet.1658

An efficient synthesis of 7-alkyl-6H,7H-naphtho-[10,20:5,6]pyrano[3,2-c]chromen-6-ones by three-component condensation reaction of β-naphthol, aromatic aldehydes, and 4-hydroxycoumarin catalyzed by 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride

Full text of DOI:10.1002/jhet.1658

Month 2014
Efficient One-Pot Syntheses of 7-Alkyl-6H,7H-naphtho[1,2:5,6]pyrano-
[3,2-c]chromen-6-ones by 1-Methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-
3-ium Chloride
Yu Wan,b Chao Wang,a Hai-ying Wang,a,c Ling-ling Zhao,a,c Xiao-xiao Zhang,a Jing-jing Shi,a Shu-ying Huang,a
Gui-Xiang Liu,a and Hui Wua,b
*
aSchool of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou 221116, People’s Republic of China
bKey Laboratory of Biotechnology on Medical Plant of Jiangsu Province, Xuzhou 221116, People’s Republic of China
cKey Laboratory of Green synthesis of functional material of Jiangsu Province, Xuzhou 221116, People’s Republic of China
*
E-mail: wuhui72@126.com
Received December 27, 2011
DOI 10.1002/jhet.1658
Published online 00 Month 2014 in Wiley Online Library (wileyonlinelibrary.com).
An efficient synthesis of 7-alkyl-6H,7H-naphtho-[10,20:5,6]pyrano[3,2-c]chromen-6-ones by three-
component condensation reaction of b-naphthol, aromatic aldehydes, and 4-hydroxycoumarin catalyzed
by 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride is reported in good to excellent yields and
short reaction times.
J. Heterocyclic Chem, 00, 00 (2014).
INTRODUCTION
(3) in the presence of MSI in [Bpy]BF4 (Table 1). At
80 ꢀC (Table 1, entries 9–12); the reaction proceeded
smoothly and gave short reaction time and high yield. The
increase in temperature did not enhance the yield of the
product. Therefore, we kept the reaction temperature at
80ꢀC. Then, it was shown that when common organic solvents
and water were used as solvents, the yields were very low
(Table 1, entries 1–5). It may be that in these organic
solvents, this reaction could only give some cross-aldol
condensation products, and these low-boiling organic solvents
cannot offer enough energy to afford desired product, which
may be a thermodynamic controlled ones. Meanwhile, water
may be making the equilibrium toward the reactants. How-
ever, when three kinds of ionic liquids were used as reaction
medium, the yield of 4a increased to 85–90% surprisingly
(Table 1, entries 6–8). [Bpy]BF4 gave the highest yield
because of its strongest basicity among these ionic liquids.
According to Table 2, it was found that MSI was the most
efficient catalyst (Table 2, entries 1–7). The important role of
MSI may be attributed to its fitting acidity, stability, and non-
volatility. Then, the study set out to determine the optimal
amount of MSI (Table 2, entries 7–12). The best yield was
obtained when 4 mol% of MSI was loading. Further increas-
ing the amount of MSI had no significant effect on the yield.
Under the optimized reaction condition, the scope and
efficiency of these procedures were explored for the synthesis
of 7-alkyl-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]chromen-
6-ones. As shown in Table 3, the direct three-component
Chromenes constitute a major class of naturally
occurring compounds [1–7], and interest in their chemistry
continues unabated because of their wide range of biological
and therapeutic properties such as antioxidant [8,9],
antibacterial [10,11], cytotoxic [12], anticancer [13,14], and
antihypertensive activity [15]. Considering the aforemen-
tioned reports, development of new and simple synthetic
methods for efficient preparation of new chromenes is an
interesting challenge.
Recently, 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium
chloride (MSI) was emerged as a promising catalyst for an acid
catalyzed in our lab, such as 14-aryl or alkyl-14H-dibenzo[a,j]
xanthenes [16]. This catalyst is safe, easy to handle, and environ-
mentally benign, and presents fewer disposal problems.
To research its new application, herein we describe an
MSI-catalyzed facile synthesis of 7-alkyl-6H,7H-naphtho
[1,2:5,6]pyrano-[3,2-c]chromen-6-ones via a three-component
reaction of b-naphthol, aromatic aldehydes, and 4-hydroxy-
coumarin (Scheme 1).
RESULTS AND DISCUSSION
To choose optimum conditions, the effect of temperature
and solvent on the rate of the reaction was studied for the
preparation of 7-phenyl-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-one (4a) by three-component condensation reaction
of b-naphthol (1), benzaldehyde(2a), and 4-hydroxycoumarin
© 2014 HeteroCorporation

Y. Wan, C. Wang, H. Wang, L. Zhao, X. Zhang, J. Shi, S. Huang, G. Liu and H. Wu
Vol 000
Scheme 1. One-pot synthesis of 7-alkyl-6H,7H-naphtho[1,2:5,6]pyrano-[3,2-c]chromen-6-ones catalyzed by 1-methyl-3-(2-(sulfooxy)ethyl)-1H-
imidazol-3-ium chloride.
groups such as Me, Cl, F, CN, and NO2 worked well (Table 3,
entries 4d, 4f, 4b, 4j, and 4p).
Table 1
Optimization of reaction conditions.a
We also investigated the reusability of catalyst together
with [Bpy]BF4. The result indicated that the combination
of catalyst and solvent was successfully reused for four
cycles without significant loss of activity (Table 3, entry 4a).
The suggested mechanism of the MSI-catalyzed trans-
formations is shown in Scheme 2. The reaction likely pro-
ceeds initial formation of ortho-quinone methide 5. The
oxonium species 6 is then formed on reaction with 4-
hydroxycoumarin, which then undergoes dehydration to af-
ford the desired product 4. In b-naphthol, the electron den-
sity at the benzylic C-1 position (which is in conjugation
with the aromatic ring) is higher than that at the C-3 posi-
tion. Thus, regioselective formation of the ortho-quinone
methide from this compound involving the C-1 and C-2
positions is favored. In simple phenolic compounds and 1-
naphthol (which are weaker nucleophiles compared with
b-naphthol), the electron density at the ortho-position of
the hydroxyl group is not sufficient for the reaction of
these compounds with the aldehydes, leading to the for-
mation of the corresponding ortho-quinone methides.
In summary, an efficient protocol for one-pot preparation of
7-alkyl-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]chromen-6-ones
by three-component condensation reaction of b-naphthol (1),
aromatic aldehydes (2), and 4-hydroxycoumarin (3) using
MSI as catalyst is described; 19 products were synthesized.
The reactions were carried out under [Bpy]BF4 in short
reaction time and produced the corresponding products in
good to excellent yields. Also, the [Bpy]BF4 and MSI could
be successfully recovered and recycled at least for three runs
without significant loss in activity.
Entry
Solvent
X (mol%)
T (ꢀC)
Yield (%)
1
2
3
4
5
6
7
8
C2H5OH
THF
DMF
4
4
4
4
4
4
4
4
4
4
4
4
80
66
100
95
80
80
80
80
90
100
70
30
NP
42
NP
NP
85
81
90
90
85
75
52
H2O
Ethyl acetate
[Bmim]BF4
[Bpy]Br
[Bpy]BF4
[Bpy]BF4
[Bpy]BF4
[Bpy]BF4
[Bpy]BF4
9
10
11
12
60
aAll reactions were carried out in the scale of 2.0 mmol of b-naphthol
(1), 2.0 mmol of aromatic aldehyde (2), and 2.0 mmol of 4-hydroxycoumarin
(3) in 2 h.
Table 2
Optimization of the catalyst for the synthesis of 7-phenyl-6H,7H-naphtho
[1,2:5,6]pyrano[3,2-c]chromen-6-one.a
Entry
Catalyst
X (mol%)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
H2SO4
SSA
TsOH
HCl
SiO2
HOAc
MSI
MSI
MSI
MSI
MSI
4
4
4
4
4
4
1
2
3
4
5
6
2
2
2
2
2
2
2
2
2
2
2
2
14
31
70
17
NP
24
64
72
83
90
90
88
9
10
11
12
MSI
EXPERIMENTAL
SSA, silica sulfuric acid; MSI, 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-
3-ium chloride.
aAll reactions were carried out in the scale of 2.0 mmol of b-naphthol (1),
2.0 mmol of aromatic aldehyde (2), and 2.0 mmol of 4-hydroxycoumarin
(3) in 2 h.
General information.
Commercial solvents and reagents
were used as received. Melting points are uncorrected. IR
spectra were recorded on Varian F-1000 spectrometer in KBr
1
with absorptions in cmÀ1. H NMR were determined on Varian
400-MHz spectrometer in DMSO-d6 (J values are in Hz).
Chemical shifts are expressed in parts per million downfield
from internal standard TMS.
The synthesis of methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-
ium chloride was followed by literature method [16].
reaction worked well with a variety of aromatic aldehydes.
The electronic and steric effects of substituents in aromatic
aldehydes had no significant effect on the yields. Aromatic
aldehydes bearing electron-withdrawing or electron-donating
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
Efficient One-Pot Syntheses of 7-Alkyl-6H,7H-naphtho[1,2:5,6]pyrano-
[3,2-c]chromen-6-ones by 1-Methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium Chloride
Table 3
Preparation of 7-alkyl-6H,7H-naphtho[1,2:5,6]pyrano-[3,2-c]chromen-6-one.a
Mp (ꢀC)
Entry
R
Time (h)
Yield (%)
Found
Reported
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4p
4q
4r
4s
C6H5
3-FC6H4
2
2
2
2
3
2
3
2
2
1
1
3
2
2
2
1
1
2
3
90(90, 90, 89)b
199–200
216–217
298–299
267–268
266–267
239–240
196–197
281–282
262–263
241–242
282–283
242–243
211–212
245–246
206–207
237–238
240–241
211–212
299–300
281–282 [17]
87
89
90
88
86
84
88
90
91
92
85
90
91
90
87
85
91
90
4-OH-3-NO2C6H3
2,3-(CH3)2C6H3
2,3-(OCH3)2C6H3
2,4-Cl2C6H4
3,4,5-(OCH3)3C6H2
4-BrC6H4
4-ClC6H4
4-CNC6H4
4-IC6H4
4-CHOC6H4
4-OCH3C6H4
4-FC6H4
3-BrC6H4
3-NO2C6H4
2-ClC6H4
267–268 [17]
267–268 [17]
253–254 [17]
249–250 [17]
2-OCH3C6H4
4-OHC6H4
aAll reactions were carried out in the scale of 2.0 mmol of b-naphthol (1), 2.0 mmol of aromatic aldehyde (2), and 2.0 mmol of 4-hydroxycoumarin (3).
bYields after recovery of [Bpy]BF4.
Scheme 2. Proposed mechanism for the synthesis of 7-alkyl-6H,7H-naphtho[10,20:5,6]pyrano-[3,2-c]chromen-6-one.
Procedure for the synthesis of 7-alkyl-6H,7H-naphtho
[1,2:5,6]pyrano[3,2-c]chromen-6-ones. A mixture of aldehyde
(2 mmol), b-naphthol (2 mmol), 4-hydroxycoumarin (2 mmol), ionic
liquid [Bpy]BF4 (2 mL), and MSI (0.06 mmol) was stirred at 80ꢀC
for 1–3 h (monitored by TLC). The resulting solid was washed with
water and dried in vacuum. The crude product was purified by
recrystallization from ethanol and DMF to give target products.
The spectral data of new products are given as follows.
(100 MHz, DMSO-d6) d 175.64, 162.41, 162.28, 152.32,
151.98, 141.08, 133.89, 132.01, 130.46, 128.96, 128.80,
128.65, 127.90, 127.16, 126.59, 123.89, 123.51, 123.23,
122.78, 122.60, 118.70, 116.12, 112.54, 98.65, 35.67; IR (KBr,
n, cmÀ1): 3023, 2938, 1680, 1605, 1533, 1436, 1374, 1246,
1026, 942, 806, 739; HRMS (ESI) m/z: Calcd for [M + H]+
C26H15FO3: 395.1101; found: 395.1161.
7-(4-Hydroxy-3-nitrophenyl)-6H,7H-naphtho[1,2:5,6]pyrano
[3,2-c]chromen-6-ones(4c).
mp 298–299ꢀC, yellow solid; 1H
7-(3-Fluorophenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
mp 216–217ꢀC, white solid; 1H NMR
NMR (400 MHz, DMSO-d6) d 10.84 (s, 1H), 7.98–8.11 (m, 5H),
7.82 (t, J= 8.0 Hz, 1H), 7.71 (d, J= 8.0 Hz, 1H), 7.64 (d, J=9.2Hz,
1H), 7.49–7.57 (m, 4H), 6.96 (d, J= 8.8 Hz, 1H), 6.01 (s, 1H); 13C
NMR (100 MHz, DMSO-d6) d 175.01, 165.09, 164.71, 152.16,
148.50, 147.08, 132.16, 131.82, 123.83, 123.72, 118.84, 117.90,
chromen-6-ones (4b).
(400 MHz, DMSO-d6) d 7.98 (t, J= 7.2 Hz, 1H), 7.91 (d, J=8.0Hz,
1H), 7.81 (d, J= 7.6 Hz, 1H), 7.75 (d, J= 8.0 Hz, 1H), 7.60
(t, J=7.6Hz, 1H), 7.55 (d, J= 8.0 Hz, 1H), 7.34–7.42 (m, 2H),
7.24–7.34 (m, 4H), 7.09–7.15 (m, 2H), 6.58 (s, 1H); 13C NMR
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Y. Wan, C. Wang, H. Wang, L. Zhao, X. Zhang, J. Shi, S. Huang, G. Liu and H. Wu
Vol 000
115.94, 111.57, 111.32, 104.38, 99.10, 35.59; IR (KBr, n, cmÀ1):
3123, 3042, 1716, 1640, 1572, 1468, 1304, 1277, 1071, 926, 834,
744, 674; HRMS (ESI) m/z: Calcd for [M+ H]+ C26H15NO6:
438.1069; found: 438.1057.
122.98, 122.07, 121.82, 117.85, 116.81, 115.80, 112.76, 98.51,
35.33; IR (KBr, n, cmÀ1): 3023, 2229, 1680, 1617, 1571, 1466,
1264, 1171, 1070, 926, 810, 761, 685; HRMS (ESI) m/z: Calcd
for [M+ H]+ C27H15NO3: 402.1167; found: 402.1178.
7-(2,3-Dimethylphenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-ones(4d).
7-(4-Iodophenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]chromen-
1
mp 267–268ꢀC, white solid; 1H
6-ones(4k). mp 282–283ꢀC, white solid; H NMR (400 MHz,
NMR (400 MHz, DMSO-d6) d 8.09 (d, J = 8.4 Hz, 1H), 7.90
(d, J= 8.0 Hz, 1H), 7.84 (d, J= 7.6 Hz, 1H), 7.77 (d, J=9.2Hz, 1H),
7.62 (t, J= 8.0 Hz, 1H), 7.47 (t, J=8.0Hz, 1H), 7.40 (d, J=8.0
Hz, 1H), 7.31–7.36 (m, 2H), 7.09 (d, J= 8.8 Hz, 1H), 7.02–7.04
(m, 3H), 6.59 (s, 1H), 2.18 (s, 3H), 1.72 (s, 3H); 13C NMR
(100 MHz, DMSO-d6) d 176.73, 162.95, 151.80, 139.13, 136.45,
134.11, 133.69, 132.19, 129.09, 128.77, 127.89, 126.93, 125.22,
124.06, 123.35, 122.94, 122.60, 119.34, 118.40, 116.15, 116.07,
112.72, 105.59, 98.79, 36.08, 20.40, 15.04; IR (KBr, n,
cmÀ1): 3058, 3027, 1689, 1630, 1573, 1539, 1488, 1344,
1271, 1075, 942, 819, 754; HRMS (ESI) m/z: Calcd for
[M + H]+ C28H20O3: 404.1410; found: 404.1414.
DMSO-d6) d 7.98–8.06 (m, 4H), 7.82 (t, J = 8.4 Hz, 1H), 7.71
(d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.0Hz, 1H), 7.48–7.57 (m, 5H),
7.24 (d, J = 8.0 Hz, 2H), 5.95 (s, 1H); 13C NMR (100MHz,
DMSO-d6) d 174.51, 159.37, 152.64, 146.26, 143.37, 134.49,
131.25, 130.20, 129.66, 128.17, 128.11, 127.58, 126.72, 125.89,
125.01, 123.43, 122.87, 117.41, 116.73, 101.43, 98.34; IR
(KBr, n, cmÀ1): 3077, 3042, 1715, 1640, 1571, 1468, 1304, 1276,
1005, 926, 815, 754, 674; HRMS (ESI) m/z: Calcd for [M + H]+
C26H15IO3: 503.0219; found: 503.0229.
7-(4-Formylphenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-ones(4l).
mp 242–243ꢀC, white solid; 1H NMR
(400MHz, DMSO-d6) d 9.85 (s, 1H), 8.07–8.10 (m, 2H), 8.00
(t, J = 8.4 Hz, 2H), 7.82 (t, J = 8.0Hz, 1H), 7.75 (t, J =8.0 Hz, 3H),
7.65–7.71 (m, 3H), 7.48–7.56 (m, 3H), 6.10 (s, 1H); 13C NMR
(100MHz, DMSO-d6) d 175.50, 159.47, 152.47, 146.69, 143.70,
136.99, 134.18, 131.41, 130.73, 130.18, 130.03, 128.71, 127.60,
125.77, 125.56, 125.02, 123.70, 122.50, 117.82, 116.74, 116.44,
98.92, 92.69, 35.12; IR (KBr, n, cmÀ1): 3031, 1698, 1638, 1573,
1466, 1304, 1235, 1071, 926, 819, 748, 687; HRMS (ESI) m/z:
Calcd for [M+ H]+ C27H16O4: 405.1170; found: 405.1189.
7-(2,3-Dimethoxyphenyl)-6H,7H-naphtho[1,2:5,6]pyrano
[3,2-c]chromen-6-ones(4e).
mp 266–267ꢀC, white solid; 1H
NMR (400 MHz, DMSO-d6) d 8.59 (s, 1H), 8.36 (d, J = 7.6 Hz,
1H), 8.17 (d, J = 8.0 Hz, 1H), 7.93–7.98 (m, 3H), 7.71
(t, J = 7.2Hz, 1H), 7.65 (d, J = 8.8 Hz, 1H), 7.44–7.53 (m, 4H),
6.81 (d, J = 7.6 Hz, 1H), 5.97 (s, 1H), 3.70 (s, 3H), 3.35 (s, 3H);
13C NMR (100 MHz, DMSO-d6) d 175.37, 162.59, 152.49,
146.72, 143.28, 134.20, 131.43, 131.14, 130.59, 130.18, 130.06,
128.72, 127.62, 125.78, 125.58, 125.03, 123.73, 119.74, 117.83,
116.76, 116.48, 112.72, 98.93, 56.86, 55.26, 35.21; IR
(KBr, n, cmÀ1): 3012, 2932, 1716, 1651, 1576, 1483, 1372,
1251, 1035, 932, 818, 759, 660; HRMS (ESI) m/z: Calcd for
[M + H]+ C28H20O5: 437.1344; found: 437.1354.
7-(4-Methoxyphenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-ones(4m).
mp 211–212ꢀC, white solid; 1H NMR
(400 MHz, DMSO-d6) d 8.03 (d, J = 8.0 Hz, 1H), 7.98–8.05
(m, 3H), 7.80 (t, J = 8.4 Hz, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.63
(d, J = 8.0 Hz, 1H), 7.48–7.55 (m, 3H), 7.32 (d, J = 8.0 Hz, 2H),
6.76 (d, J = 8.4 Hz, 2H), 5.94 (s, 1H), 3.63 (s, 3H); 13C NMR
(100 MHz, DMSO-d6) d 175.51, 159.57, 152.38, 146.65, 143.75,
137.02, 134.81, 131.93, 131.13, 130.22, 130.04, 128.61, 127.62,
126.77, 125.76, 125.03, 123.74, 122.55, 117.61, 116.47, 116.12,
101.87, 99.56, 35.62; IR (KBr, n, cmÀ1): 3074, 1708, 1632,
1510, 1408, 1304 1264, 1032, 923, 812, 753, 686; HRMS (ESI)
m/z: Calcd for [M + Na]+ C27H18O4: 429.1160; found: 429.1162.
7-(3-Bromophenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
7-(3,4,5-Trimethoxyphenyl)-6H,7H-naphtho[1,2:5,6]pyrano
[3,2-c]chromen-6-ones(4g).
mp 196–197ꢀC, white solid; 1H
NMR (400 MHz, DMSO-d6) d 8.20 (t, J = 8.0 Hz, 2H), 8.07
(d, J = 9.2 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.72–7.77 (m, 2H),
7.48–7.56 (m, 4H), 6.67 (d, J = 9.6 Hz, 2H), 5.78 (s, 1H), 3.64
(s, 6H), 3.54 (s, 3H); 13C NMR (100 MHz, DMSO-d6)
d 175.58, 159.60, 152.53, 147.62, 146.87, 145.76, 135.06,
134.24, 131.45, 130.45, 129.76, 128.76, 127.79, 125.79, 123.75,
122.97, 121.81, 117.83, 116.79, 115.78, 98.49, 56.88, 56.34,
56.25, 35.89; IR (KBr, n, cmÀ1): 3080, 2958, 1721, 1646, 1573,
1465, 1304, 1265, 1067, 923, 842, 755, 686; HRMS (ESI) m/z:
Calcd for [M + Na]+ C29H22O6: 489.1416; found: 489.1406.
7-(4-Bromophenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-ones(4o).
mp 206–207ꢀC, white solid; 1H NMR
(400 MHz, DMSO-d6) d 8.05–8.11 (m, 3H), 8.01 (t, J=8.4Hz,
1H), 7.82 (d, J = 8.4 Hz, 1H), 7.70 (t, J= 8.4 Hz, 2H), 7.64
(d, J= 8.4 Hz, 1H), 7.57 (t, J = 7.2 Hz, 1H), 7.51 (t, J=8.4Hz, 2H),
7.36 (d, J= 8.4 Hz, 1H), 7.30 (d, J= 8.4 Hz, 1H), 7.18 (t,
J= 8.4 Hz, 1H), 6.02 (s, 1H); 13C NMR (100 MHz, DMSO-d6) d
175.97, 156.02, 153.22, 147.45, 144.07, 135.10, 131.41, 129.61,
128.26, 127.72, 126.87, 125.30, 125.09, 123.79, 122.82, 118.18,
117.53, 116.46, 101.75, 35.89; IR (KBr, n, cmÀ1): 3067, 1711,
1644, 1568, 1461, 1265, 1066, 926, 808, 742, 684; HRMS (ESI)
m/z: Calcd for [M+ H]+ C26H15BrO3: 454.0215; found: 454.0232.
7-(2-Chlorophenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-ones(4h).
(400MHz, DMSO-d6)
mp 281–282ꢀC, white solid; 1H NMR
8.18 (d, J = 8.0 Hz, 1H), 7.94
d
(d, J = 8.4 Hz, 1H), 7.84–7.89 (m, 2H), 7.66 (t, J = 8.0 Hz, 1H),
7.45–7.52 (m, 4H), 7.40 (t, J = 7.6 Hz, 1H), 7.30–7.36
(m, 4H), 6.08 (s, 1H); 13C NMR (100 MHz, DMSO-d6)
d 175.50, 159.62, 152.51, 149.14, 146.78, 134.26, 132.23,
131.43, 130.31, 129.50, 128.75, 127.71, 125.82, 125.02, 123.66,
122.44, 118.55, 117.84, 116.79, 115.87, 109.50, 98.46, 35.69; IR
(KBr, n, cmÀ1): 3058, 3027, 1692, 1634, 1554, 1482, 1361, 1259,
1027, 966, 875, 776; HRMS (ESI) m/z: Calcd for [M+ H]+
C26H15BrO3: 454.0205; found: 454.0212.
chromen-6-ones(4q).
mp 240–241ꢀC, white solid; 1H NMR
(400 MHz, DMSO-d6) d 8.00 (d, J = 8.4Hz, 2H), 7.76–7.87
(m, 3H), 7.68 (d, J = 8.0 Hz, 1H), 7.47–7.54 (m, 3H), 7.39
(d, J = 7.6 Hz, 1H), 7.31–7.36 (m, 3H), 7.23 (t, J = 8.8 Hz, 1H),
6.34 (s, 1H); 13C NMR (100MHz, DMSO-d6) d 174.20, 165.64,
162.28, 156.39, 152.96, 149.09, 142.38, 140.25, 135.61, 133.58,
131.11, 130.54, 129.00, 128.71, 127.38, 126.60, 125.89, 123.72,
122.52, 121.44, 116.13, 112.99, 99.86, 35.22; IR (KBr, n, cmÀ1):
3071, 1711, 1639, 1573, 1466, 1352, 1237, 1072, 983, 827, 759,
683; HRMS (ESI) m/z: Calcd for [M + H]+ C26H15ClO3:
411.0850; found: 411.0855.
7-(4-Cyanophenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-ones(4j).
mp 241–242ꢀC, white solid; 1H NMR
(400MHz, DMSO-d6) d 8.07 (t, J = 8.8 Hz, 2H), 8.01 (t
J = 8.4 Hz, 2H), 7.83 (t, J = 8.0 Hz, 1H), 7.64–7.83 (m, 6H), 7.49–
7.57 (m, 3H), 6.11 (s, 1H); 13C NMR (100 MHz, DMSO-d6) d
174.89, 158.63, 152.55, 147.63, 146.88, 145.77, 135.07, 134.26,
131.46, 130.08, 129.77, 128.77, 127.80, 125.81, 125.05, 123.77,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
Efficient One-Pot Syntheses of 7-Alkyl-6H,7H-naphtho[1,2:5,6]pyrano-
[3,2-c]chromen-6-ones by 1-Methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium Chloride
REFERENCES AND NOTES
7-(2-Methoxyphenyl)-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-ones(4r).
mp 211–212ꢀC, white solid; 1H NMR
[1] Jang, K. H.; Lee, B. H.; Choi, B. W.; Lee, H.-S.; Shin, J. J Nat
(400 MHz, DMSO-d6) d 8.12 (d, J= 8.8 Hz, 1H), 7.88 (d,
J= 8.0 Hz, 1H), 7.81 (d, J= 8.0 Hz, 1H), 7.73 (d, J= 8.8 Hz, 1H),
7.60 (t, J= 8.4 Hz, 1H), 7.37–7.44 (m, 2H), 7.27–7.34 (m, 2H), 7.20
(t, J=7.2Hz, 1H), 7.10 (d, J= 8.8 Hz, 1H), 7.03 (d, J=7.6Hz, 1H),
6.94 (d, J=8.0Hz, 1H), 6.92 (t, J=8.8Hz, 1H), 6.68 (s, 1H), 3.35
(s, 3H); 13C NMR (100 MHz, DMSO-d6) d 175.73, 159.77, 156.21,
152.48, 146.57, 143.36, 137.10, 134.49, 131.35, 130.25, 130.00,
128.14, 127.29, 125.33, 125.12, 125.02, 123.64, 122.32, 117.08,
116.84, 116.61, 112.49, 98.89, 35.80; IR (KBr, n, cmÀ1): 3023,
2939, 1681, 1632, 1578, 1489, 1388, 1251, 1032, 949, 819, 755;
HRMS (ESI) m/z: Calcd for [M + Na]+ C27H18O4: 429.1168; found:
429.1160.
Prod 2005, 68, 716.
[2] Malquichagua Salazar, K. J.; Delgado Paredes, G. E.; Lluncor,
L. R.; Young, M. C. M.; Kato, M. J. Phytochemistry 2005, 66, 573. 2005,
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7-(4-Hydroxyphenyl-6H,7H-naphtho[1,2:5,6]pyrano[3,2-c]
chromen-6-ones(4s).
[8] Shanthi, G.; Perumal, P. T.; Rao, U.; Sehgal, P. K. Indian J
Chem Sec B 2007, 48B, 1319.
[9] Foroumadi, A.; Dehghan, G.; Samzadeh-Kermani, A.;
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A.; Kreddan, K. M. Arkivoc 2007 (xvi), 83, 24.
[12] Alizadeh, B. H.; Ostad, S. N.; Foroumadi, A.; Amini,
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(xiii), 45–56.
[13] Gourdeau, H.; Leblond, L.; Hamelin, B.; Desputeau, C.;
Dong, K.; Kianicka, I.; Custeau, D.; Boudreau, C.; Geerts, L.;
Cai, S.-X.; Drewe, J.; Labrecque, D.; Kasibhatla, S.; Tseng, B. Mol
Cancer Ther 2004, 3, 1375.
mp 299–300ꢀC, white solid; 1H NMR
(400MHz, DMSO-d6) d 9.29 (s, 1H), 8.17 (d, J = 8.0 Hz, 1H),
8.08 (t. J = 8.0 Hz, 2H), 8.02 (d, J = 8.0 Hz, 3H), 7.97 (d, J =
8.0 Hz, 3H), 7.81 (t, J = 8.0 Hz, 1H), 7.69–7.73 (m, 3H), 7.61
(d, J = 9.2 Hz, 1H), 5.88 (s, 1H); 13C NMR (100 MHz, DMSO-d6)
d 175.03, 162.41, 156.28, 152.32, 151.98, 149.08, 140.63,
140.11, 135.27, 131.52, 131.01, 130.87, 130.13, 128.57, 128.13,
127.29, 126.88, 123.72, 123.03, 122.82, 118.91, 116.12, 112.53,
98.76, 35.46; IR (KBr, n, cmÀ1): 3293, 3023, 1712, 1648, 1562,
1467, 1311, 1226, 1051, 918, 835, 756, 690; HRMS (ESI) m/z:
Calcd for [M + H]+ C26H16O4: 393.1178; found: 393.1188.
Acknowledgments. We are grateful to the foundation of the
“Priority Academic Program Development of Jiangsu Higher
Education Institutions”, “Qing Lan Project in Jiangsu Province”
(no.08QL001T), “Key Basic Research Project in Jiangsu
University” (no. 10KJA430050), the “Post-graduate Innovation
Project in Jiangsu Province” (no. CXZZ11_0904), and the
“Natural Science Foundation of XuZhou Normal University”
(no. 09XLA17, No. 09XLB05) for financial support.
[14] Reddy, P. N.; Reddy, Y. T.; Rao, M. K.; Rajitha, B. Heterocycl
Commun 2003, 9, 647.
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[17] Ma, W. W.; Wang, X.; Yan, F. L.; Wu, L. Q.; Wang, Y. L.
Monatsh Chem 2011, 142, 163.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet