3,3-(Butane-1,4-diyl)bis(1,2-dimethyl-1H-imidazole-3-ium)bromide–cerium(IV) ammonium nitrate: A novel reagent for mild synthesis of 12-aryldibenzo[i,b]pyrano[4,3-b]chromenone of benzyl alcohols

Article abstract of DOI:10.1134/S1070363216120379

A novel and efficient procedure for the synthesis of pyrano[4,3-b]chromene derivatives via three-component condensation reaction of benzyl alcohol, β-naphthol, and 4-hydroxycoumarin using a catalytical amount of cerium(IV) ammonium nitrate (CAN) and a reu

Full text of DOI:10.1134/S1070363216120379

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 87, No. 12, pp. 2759–2767. © Pleiades Publishing, Ltd., 2016.
3,3-(Butane-1,4-diyl)bis(1,2-dimethyl-1H-imidazole-
3-ium)bromide–Cerium(IV) Ammonium Nitrate:
A Novel Reagent for Mild Synthesis
of 12-Aryldibenzo[i,b]pyrano[4,3-b]chromenone of Benzyl Alcohols1
Z. Gharib and M. Nikpassand*
Department of Chemistry, Rasht Branch, Islamic Azad University, Rasht, Iran
*e-mail: Nikpassand@iaurasht.ac.ir
Received January 22, 2016
Abstract—A novel and efficient procedure for the synthesis of pyrano[4,3-b]chromene derivatives via three-
component condensation reaction of benzyl alcohol, β-naphthol, and 4-hydroxycoumarin using a catalytical
amount of cerium(IV) ammonium nitrate (CAN) and a reusable ionic liquid as a catalyst at room temperature is
presented. The method provides several advantages such as simple work-up, environmental friendliness and
shorter reaction time along with high yields. All synthesized compounds were elucidated by comparison with
authentic samples, IR, 1H, and 13C NMR spectroscopy, and elemental analysis.
Keywords: pyrano[4,3-b]chromene, 4-hydroxycoumarin, β-naphthol, benzyl alcohol
DOI: 10.1134/S1070363216120379
INTRODUCTION
RESULTS AND DISCUSSION
Chromenes attract close attention as biologically
active compounds [1, 2] and reagents in organic
synthesis [3, 4]. Fused chromenes demonstrate anti-
tumor [5], anti-cancer [6], anti-coagulant [6], anti-
Alzheimer [7], anti-bacterial [8, 9], anti-malaria [10],
diuretic [11], and spasmolytic [12–14] activities.
Following the earlier studies of synthesis of
heterocyclic pharmaceutically sound compounds [22–
26], we present herein the experimental data on the
synthesis of pyrano[4,3-b]chromenes, using various
benzyl alcohols, 2-naphthol and 4-hydroxycoumarin in
the presence of bis ionic liquid, 3,3-(butane-1,4-diyl)-
bis(1,2-dimethyl-1H-imidazole-3-ium)bromide
([BDBDMIm]Br), and CAN at room temperature
(Scheme 1).
The typical approach to pyrano[4,3-b]chromene
involves a one-pot reaction of tetrahydro-chromeno
[4,3-b]chromene-6,8-dione with tetrahydropyrano[4,3-
b]chromene-1,9-dione derivatives under solvent-free
conditions [15]. Recently some original approaches to
new chromenes were presented [16–18]. Among those
were 7-tetrahydropyran-2-yl chromanes: β-site amyloid
precursor protein cleaving enzyme 1 (BACE1) inhi-
bitors that reduced amyloid β-protein (Aβ) in the
central nervous system [18].
The effect of various acidic catalysts was tested in
the model reaction (Table 1).
The ionic liquid [BDBDMIm]Br was determined to
be the most efficient for the synthesis of pyrano[4,3-b]-
chromenes (Table 1).
Efficiency of the reaction was tested by using
various benzyl alcohols combined with 2-naphthol and
4-hydroxycoumarin in the presence of [BDBDMIm]Br–
CAN at room temperature (Table 2). According to the
experimental data the electron withdrawing substi-
tuents could facilitate the reaction by decreasing
reaction time and increasing yields in comparison with
benzyl alcohols that contained electron donating
substituents.
The use of ionic liquids as reaction media and catalysts
[19–21] could solve the problems of the earlier
approaches to pyrano[4,3-b]chromenes: solvents emis-
sion and catalysts recycling.
1 The text was submitted by the authors in English.
2759

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GHARIB, NIKPASSAND
Scheme 1. Synthesis of pyrano[4,3-b]chromenes using [BDBDMIm]Br.
HO
O
2
[BDBDMIm]Br−CAN
+
room temperature
OH
O
O
R
HOH2C
4a−4p
O
O
R
3
1a−1p
On the basis of the above data a possible me-
chanism for the synthesis of pyrano[4,3-b]chromene
derivatives was proposed (Scheme 2) according to
which the reaction started with full activation by
polarization of benzyl alcohols with [BDBDMIm]Br
forming the intermediate 5 which was followed by
benzyl alcohols conversion to benzaldehydes 6 by
oxidation with CAN [(NH4)2Ce(NO3)6]. The nucleo-
philic addition of 4-hydroxycoumarin to intermediate 6
led to 7. Finally, nucleophilic attack of 2-naphthol in
compound 7 and dehydration led to compound 4.
0.05 g of CAN at room temperature in the absence of
another reagent. 4-Nitrobenzaldehyde was isolated in
15 min with the yield 99%. The ionic liquid was easily
recovered by separation from the reaction medium by
washing with distilled H2O after which it could be
reuse in subsequent reactions. In five successive runs
the recycled ionic liquid demonstrated nearly no loss
of activity (Table 3).
EXPERIMENTAL
Materials and measurements. Chemicals were
purchased from Merck and Fluka and used without
further purification. Elemental analysis was carried out
on a Carlo-Erba EA1110CNNO-S analyzer. Melting
The proposed mechanism was supported by the
experiment in which 4-nitrobenzyl alcohol (1 mmol)
was treated with 4 mmol % of [BDBDMIm]Br and
Table 1. Effect of catalysts on the synthesis of 4aa,b
Entry
no.
Time,
Catalyst
Catalyst amount/1 mmol of aldehyde
Reaction condition
Reflux
Yield, %
min
840
360
240
210
720
360
180
170
175
90
1
HCl
4 drops
52
65
71
68
48
63
80
79
82
87
96
96
2
SiO2
0.2 mmol
0.2 g
Reflux
3
Montmorillonite K10
Montmorillonite KSF
Fe3O4
Reflux
4
0.2 g
Reflux
5
0.2 mmol
0.2 mmol
0.04 mmol
0.04 mmol
0.04 mmol
0.02 mmol
0.04 mmol
0.06 mmol
Reflux
6
ZnCl2
Reflux
7
[BMIm]Br
Neat, room temperature
Neat, room temperature
Neat, room temperature
Neat, room temperature
Neat, room temperature
Neat, room temperature
8
[BMIm]OH
9
[BMIm]HSO4
[BDBDIm]Br
[BDBDIm]Br
[BDBDIm]Br
10
11
12
60
60
a The solvent in entries 1–6 was water b 0.05 g of CAN was used in all reactions.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 12 2016

3,3-(BUTANE-1,4-DIYL)BIS(1,2-DIMETHYL-1H-IMIDAZOLE-3-IUM)BROMIDE
Table 2. Synthesis of pyrano[4,3-b]chromenes 4a–4p using [BDBDIm]Br
2761
mp, °C
calculated
Comp. no.
Product
Time, min Yield, %a
found
4a
60
96
258–260 257–258 [12]
O
O
O
O
NO2
NO2
4b
4c
75
60
91
89
231–233 237–238 [14]
267–269 267–268 [12]
O
O
O
O
O
Cl
4d
120
89
238–240 240–241 [14]
O
Cl
Cl
O
O
O
4e
4f
120
92
92
267–269 267–268 [12]
287–289 281–282 [14]
Cl
O
O
O
75
Br
O
O
O
4g
60
92
241–243 245–246 [14]
O
F
O
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GHARIB, NIKPASSAND
Table 2. (Contd.)
mp, °C
calculated
Comp. no.
Product
Time, min Yield, %a
found
4h
60
94
88
85
83
276–278 282–283 [14]
276–278 280–282 [12]
225–227 230–231 [12]
257–258 267–268 [14]
O
I
O
O
4i
4j
75
O
O
O
120
120
O
O
O
Me
4k
O
O
O
Me
Me
4l
4m
4n
135
150
120
82
80
83
211–213 214–215 [12]
214–216 211–212 [14]
201–203 196–197 [14]
O
O
O
OMe
O
O
MeO
O
O
O
OMe
O
OMe
OMe
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3,3-(BUTANE-1,4-DIYL)BIS(1,2-DIMETHYL-1H-IMIDAZOLE-3-IUM)BROMIDE
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Table 2. (Contd.)
Comp. no.
4o
mp, °C
calculated
255–257 257–258 [12]
Product
Time, min Yield, %a
found
135
150
84
85
O
O
O
NMe2
4p
298–300 299–300 [14]
O
O
O
OH
a Isolated yield.
points were measured on an Electro-thermal 9100
apparatus. FT-IR spectra were recorded (KBr discs) on
a Shimadzu FT-IR-8400S spectrophotometer. H and
13C NMR spectra were measured on a Bruker DRX
500 Avance spectrometer in CDCl3 or DMSO-d6 with
TMS as the internal standard.
1
Scheme 2. A possible mechanism of synthesis of pyrano[4,3-b]chromene.
4
N
N
N
N
I.L. H3C
CH3
CH2OH
CH2
CH3
2(NH4)2Ce(NO3)6
R
Br
OH
Br
1
CH2
[BDBDMIm]Br
I.L.
O
C−H
R
O
5
R
6
O
O
R
I.L.
4
2(NH4)2Ce(NO3)5 + 2HNO3
OH
O
O
OH
R
O
O
7
O
O
2
3
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GHARIB, NIKPASSAND
Table 3. Evaluation of reusability of ionic liquid for the
synthesis of 4a
12-(3-Nitrophenyl)dibenzo[i,b]pyrano[4,3-b]chro-
men-11(12H)-one (4b). White solid, mp 251–253°C.
IR spectrum, ν, cm–1: 3070, 2931, 1714, 1485, 1573,
1269, 1523, 1350 cm–1. 1H NMR spectrum (CDCl3), δ,
ppm: 6.23 s (1H), 7.41–7.54 m (6H), 7.70 m (1H),
7.88 d (1H, J = 1.2 Hz), 7.92 d (2H, J = 4.8 Hz), 7.94 d
Run no.
1
Time, min
60
Yield, %
96
2
3
60
60
96
96
13
(2H, J = 8.4 Hz), 8.19 d (2H, J = 1.6 Hz). C NMR
spectrum (CDCl3), δ, ppm: 36.2, 99.1, 115.9, 116.7,
117.5, 122.0, 122.9, 123.1, 123.3, 125.5, 125.7, 125.9,
127.8, 128.8, 129.2, 130.4, 130.6, 131.9, 133.7, 134.9,
145.7, 147.5, 148.4,153.0, 160.0, 176.8. Found,%: C
74.18; H 3.62; N 3.27. C26H15NO5. Calculated, %: C
74.10; H 3.59; N 3.32.
4
5
60
60
95
92
Synthesis of [BDBDMIm]Br. A mixture of 1,4-
dibromobutane (10 mmol) or 1,4-dibromopentane
(10 mmol) and 1,2-dimethylimidazole (20 mmol) was
loaded in a pressure tube and mixed well. The sealed
pressure tube was irradiated at 180W and 75°C under
3–4 psi pressure for 2 min three times in a microwave
oven with intervals of 2 min. Upon completion of the
reaction (TLC) the ionic liquid was separated from the
reaction mixture by extraction with 2×15 cm3 of water.
The aqueous phase was evaporated under vacuum to
give the desired ionic liquid.
12-(4-Cholorophenyl)dibenzo[i,b]pyrano[4,3-b]-
chromen-11(12H)-one (4c). White solid, mp 267–
269°C. IR spectrum, ν, cm–1: 3072, 1708, 1637, 1488,
1506, 1577, 1267, 1226, 1093, 813. 1H NMR spectrum
(CDCl3), δ, ppm: 6.10 s (1H), 7.20 d.d (2H, J = 8.8,
2.8 Hz), 7.42–7.50 m (6H), 7.67 t (1H, J = 8.4 Hz),
7.86–7.98 m (3H), 8.10 d (1H, J = 8.4 Hz), 8.20 d.d
13
(1H, J = 8.0, 6.4 Hz). C NMR spectrum (CDCl3), δ,
ppm: 35.9, 99.8, 117.0, 117.4, 122.7, 123.3, 123.4,
124.3, 125.4, 125.6, 126.0, 127.5, 128.6, 129.8, 130.0,
130.9, 131.8, 132.5, 133.5, 142.2, 147.4, 153.0, 160.0,
176.9. Found, %: C 76.05; H 3.71. C26H15ClO3.
Calculated, %: C 76.01; H 3.68.
General procedure for synthesis of pyrano[4,3-b]-
chromenes. A mixture containing benzyl alcohol
(1 mmol), β-naphthol (1 mmol), 4-hydroxycoumarin
(1 mmol), 4 mmol % of [BDBDMIm]Br, and 0.05 g of
CAN was stirred at room temperature for the required
reaction times. Progress of the reaction was monitored
by TLC (EtOAc : petroleum ether, 1 : 3). Upon
completion of the process the product was extracted
with CHCl3/H2O. The organic phases was separated
and the solvent evaporated. Crystallization of the
residue gave the pure product. The aqueous phase was
concentrated under reduced pressure, washed with
Et2O, and evaporated under reduced pressure to
recover the ionic liquid for subsequent use.
12-(2-Cholorophenyl)dibenzo[i,b]pyrano[4,3-b]-
chromen-11(12H)-one (4d). White solid, mp 238–
240°C. IR spectrum, ν, cm–1: 3056, 2929, 1714, 1643,
1465, 1560, 1612, 1224, 1035, 742. 1H NMR spectrum
(CDCl3), δ, ppm: 6.40 s (1H), 7.05–7.12 m (2H), 7.35–
7.57 m (7H), 7.67 t (1H, J = 9.2 Hz), 7.82–7.88 m
(12H), 8.20 d.d (1H, J = 8.0, 1.2 Hz), 8.27 d (1H, J =
8.4 Hz). 13C NMR spectrum (CDCl3), δ, ppm: 34.6,
99.5, 116.5, 117.3, 123.2, 123.8, 124.1, 125.3, 125.4,
126.0, 127.1, 127.5, 128.1, 128.6, 129.8, 130.1, 131.3,
131.6, 133.4, 141.1, 147.2, 152.9, 160.3, 176.7. Found,
%: C 75.93; H 3.61. C26H15ClO3. Calculated, %: C
76.01; H 3.68.
12-(4-Nitrophenyl)dibenzo[i,b]pyrano[4,3-b]chro-
men-11(12H)-one (4a). White solid, mp 258–260°C.
IR spectrum, ν, cm–1: 3016, 1729, 1480, 1538, 1250,
1341. 1H NMR spectrum (CDCl3), δ, ppm: 6.24 s (1H),
7.34–7.51 m (5H), 7.61–7.70 m (3H), 7.81–7.92 m
(3H), 8.09 d (2H, J = 8.6 Hz), 8.19 d (1H, J = 8.2 Hz).
13C NMR spectrum (CDCl3), δ, ppm: 36.9, 98.3, 116.2,
116.7, 117.5, 123.3, 123.4, 123.8, 125.8, 125.9, 126.7,
127.3, 128.5, 129.8, 130.2, 130.7, 131.6, 133.5, 146.6,
148.0, 150.7, 153.2, 160.4, 177.3. Found, %: C 74.03;
H 3.65; N 3.21. C26H15NO5. Calculated, %: C 74.10; H
3.59; N 3.32.
12-(4-Bromophenyl)dibenzo[i,b]pyrano[4,3-b]-
chromen-11(12H)-one (4f). White solid, mp 287–
289°C. IR spectrum (KBr), ν, cm–1: 3072, 1708, 1635,
1
1463, 1546, 1226, 1267. H NMR spectrum (CDCl3),
δ, ppm: 6.02 s (1H), 7.41 s (4H), 7.47–7.57 m (3H),
7.64 d (1H, J = 8.8 Hz), 7.71–7.74 m (1H), 7.80–7.86
m (1H), 8.0–8.09 m (4H). 13C NMR spectrum
(CDCl3), δ, ppm: 35.8, 105.2, 113.4, 116.1, 116.9,
117.0, 117.1, 118.3, 120.9, 123.8, 125.2, 125.5, 128.0,
129.2, 130.9, 131.0, 131.6, 131.9, 133.8, 141.3, 152.5,
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3,3-(BUTANE-1,4-DIYL)BIS(1,2-DIMETHYL-1H-IMIDAZOLE-3-IUM)BROMIDE
2765
153.9, 160.1, 176.0. Found, %: C 68.65; H 3.26.
C26H15BrO3. Calculated, %: C 68.59; H 3.32.
8.2 Hz). 13C NMR spectrum (CDCl3), δ, ppm: 15.2,
20.6, 36.5, 98.8, 105.7, 112.9, 116.1, 116.3, 118.7,
119.6, 122.9, 122.3, 123.6, 124.2, 125.6, 126.0, 127.6,
128.1, 129.5, 132.6, 133.2, 134.2, 136.6, 139.5, 151.3,
162.6, 176.9. Found, %: C 83.03; H 5.06. C28H20O3.
Calculated, %: C 83.15; H 4.98.
12-(4-Fluorophenyl)dibenzo[i,b]pyrano[4,3-b]-
chromen-11(12H)-one (4g). White solid, mp 241–
243°C. IR spectrum, ν, cm–1: 3132, 1700, 1600, 1650,
1
1481, 1508, 1564, 1240, 1255. H NMR spectrum
(CDCl3), δ, ppm: 6.11 s (1H), 6.88-6.92 m (2H), 7.41–
7.50 m (7H), 7.64–7.69 m (1H), 7.85–7.90 m (2H),
7.97 d (1H, J = 8.0 Hz), 8.22 d.d (1H, J = 8.0, 1.2 Hz).
13C NMR spectrum (CDCl3), δ, ppm: 35.5, 115.1,
115.3, 116.5, 117.3, 122.7, 123.9, 125.3, 125.5, 125.9,
127.5, 128.6, 129.7, 129.9, 130.0, 130.9, 131.8, 133.4,
139.5, 147.3, 152.9, 176.9. Found, %: C 79.13; H 3.79.
C26H15FO3. Calculated, %: C 79.18; H 3.83.
12-(4-Methoxyphenyl)dibenzo[i,b]pyrano[4,3-b]-
chromen-11(12H)-one (4l). White solid, mp 211–213°C.
IR spectrum, ν, cm–1: 3064, 2941, 1712, 1641, 1461,
1508, 564, 1174, 1240, 811. 1H NMR spectrum
(CDCl3), δ, ppm: 3.35 s (3H), 5.92 s (1H), 6.77 t (2H,
J = 8.8 Hz), 7.29–7.32 m (2H), 7.48–7.55 m (3H), 7.60
d (1H, J = 9.2 Hz), 7.68–7.72 m (2H), 7.96–8.09 m
13
(3H). C NMR spectrum (CDCl3), δ, ppm: 35.8, 62.2,
105.8, 113.8, 115.5, 116.5, 117.8, 118.1, 118.7, 121.4,
123.0, 124.4, 125.0, 127.5, 128.5, 129.9, 130.7, 132.6,
133.9, 138.1, 146.3, 154.5, 155.6, 160.3, 175.5. Found,
%: C 79.85; H 4.41. C27H18O4. Calculated, %: C 79.79;
H 4.46.
12-Phenyldibenzo[i,b]pyrano[4,3-b]chromen-
11(12H)-one (4i). White solid, mp 276–278°C. IR
spectrum, ν, cm–1: 3056, 3022, 2920, 1718, 1641,
1463, 1575, 1610, 1222, 1271, 746. 1H NMR spectrum
(CDCl3), δ, ppm: 6.0 s (1H), 7.10 t (1H, J = 7.2 Hz),
7.22 t (2H, J = 7.6 Hz), 7.49 d.d (2H, J = 7.2 Hz,), 7.52–
7.57 m (4H), 7.62 d (1H, J = 9.2 Hz), 7.72 d (1H, J =
9.2 Hz), 7.82 t (1H, J = 6.8 Hz), 7.99–8.12 m (3H). 13C
NMR spectrum (CDCl3), δ, ppm: 36.7, 106.0, 113.6,
116.7, 117.0, 117.3, 117.4, 118.2, 119.0, 120.2, 122.3,
124.2, 124.5, 127.5, 129.5, 130.0, 130.1, 131.2, 133.7,
138.8, 152.7, 153.4, 160.2, 173.2. Found, %: C 83.02;
H 4.21. C26H16O3. Calculated, %: C 82.96; H 4.28.
12-(3,4,5-Trimethoxyphenyl)dibenzo[i,b]pyrano-
[4,3-b]chromen-11(12H)-one (4n). White solid, mp
201–203°C. IR spectrum, ν, cm–1: 3054, 1704, 1639,
1
1538, 1472, 1352, 1242. H NMR spectrum (CDCl3),
δ, ppm: 3.56 s (3H), 3.61 s (6H), 5.75 s (1H), 6.69 d
(2H, J = 8.6 Hz), 7.42–7.58 m (4H), 7.70–7.76 m (2H),
8.02 d (1H, J = 8.2 Hz), 8.11 d (1H, J = 8.6 Hz), 8.24 t
(2H, J = 8.4 Hz). 13C NMR spectrum (CDCl3), δ, ppm:
35.4, 56.25, 56.8, 56.3, 98.9, 115.3, 116.5, 117.5, 121.2,
122.5, 123.4, 125.6, 127.2, 128.9, 129.0, 130.2, 131.4,
134.5, 135.1, 145.3, 146.7, 147.1, 152.9, 159.2, 175.4.
Found, %: C 74.78; H 4.83. C29H22O6. Calculated, %:
C 74.67; H 4.75.
12-(4-Methylphenyl)dibenzo[i,b]pyrano[4,3-b]-
chromen-11(12H)-one (4j). White solid, mp 225–
227°C. IR spectrum, ν, cm–1: 3018, 2920, 1714, 1639,
1
1463, 1510, 1566, 1224. H NMR spectrum (CDCl3),
δ, ppm: 2.16 s (3H), 5.73 s (1H), 7.0–7.04 m (2H), 7.27–
7.30 m (2H), 7.46–7.55 m (4H), 7.74 d (2H, J =
9.2 Hz), 8.01–8.08 m (3H), 8.17 d.d (1H, J = 7.6,
0.8 Hz). 13C NMR spectrum (CDCl3), δ, ppm: 31.2,
34.6, 105.9, 114.2, 116.0, 117.1, 117.3, 117.4, 118.0,
120.0, 122.1, 124.3, 125.0, 127.2, 128.8, 130.0, 130.5,
131.4, 132.0, 135.0, 140.2, 153.3, 154.4, 161.4, 174.7.
Found, %: C 83.12; H 4.61. C27H18O3. Calculated, %:
C 83.06; H 4.65.
12-(4-Dimethylaminophenyl)dibenzo[i,b]pyrano-
[4,3-b]chromen-11(12H)-one (4o). White solid, mp
255–257°C. IR spectrum, ν, cm–1: 3074, 2914, 1656,
1521, 1560, 1660, 1346, 1191, 810. 1H NMR spectrum
(CDCl3), δ, ppm: 2.10 s (6H), 5.60 s (1H), 7.22–7.39
m (8H), 7.50–7.52 m (1H), 7.63–7.68 m (1H), 7.80–
7.84 m (3H), 8.01 d (1H, J = 8.2 Hz). 13C NMR
spectrum (CDCl3), δ, ppm: 35.0, 52.4, 105.7, 113.0,
115.2, 116.1, 117.2, 117.9, 118.2, 121.9, 123.4, 125.0,
126.8, 128.6, 129.0, 132.1, 133.0, 133.6, 136.2, 137.0,
142.3, 154.2, 155.0, 158.5, 173.4. Found, %: C 80.24;
H 4.99; N 3.29. C28H21NO3. Calculated, %: C 80.17; H
5.05; N 3.34.
12-(2,3-Dimethylphenyl)dibenzo[i,b]pyrano[4,3-b]-
chromen-11(12H)-one (4k). White solid, mp 257–
258°C. IR spectrum, ν, cm–1: 3018, 1682, 1636, 1543,
1452, 1319, 1242. 1H NMR spectrum (CDCl3), δ, ppm:
1.78 s (3H), 2.32 s (3H), 6.63 s (1H), 7.06–7.08 m
(3H), 7.11 d (1H, J = 8.6 Hz), 7.32–7.37 m (2H), 7.42
d (1H, J = 8.2 Hz), 7.51 t (1H, J = 8.2 Hz), 7.65 t (1H,
J = 8.4 Hz), 7.79 d (1H, J = 8.4 Hz), 7.89 d (1H, J =
8.4 Hz), 7.92 d (1H, J = 8.2 Hz), 8.11 d (1H, J =
12-(4-Hydroxyphenyl)dibenzo[i,b]pyrano[4,3-b]-
chromen-11(12H)-one (4p). White solid, mp 298–
300°C. IR spectrum, ν, cm–1: 3281, 3012, 1706, 1635,
1
1551, 1462, 1301, 1203. H NMR spectrum (CDCl3),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 12 2016

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GHARIB, NIKPASSAND
δ, ppm: 5.72 s (1H), 7.60 d (1H, J = 8.6 Hz), 7.63–7.70
m (3H), 7.87 t (1H, J = 8.6 Hz), 7.90 d (J = 8.4 Hz,
3H), 8.05 d (J = 8.2 Hz, 3H), 8.13 t (2H, J = 8.2 Hz),
8.21 d (1H, J = 8.2 Hz), 9.31 s (1H). 13C NMR
spectrum (CDCl3), δ, ppm: 35.8, 98.4, 112.5, 116.2,
118.4, 122.5, 123.3, 123.7, 126.2, 127.8, 128.5, 128.9,
130.4, 130.8, 131.3, 131.9, 135.0, 140.3, 140.4, 149.6,
151.98, 152.5, 156.0, 162.3, 175.2. Found, %: C 79.66;
H 4.03. C26H16O4. Calculated, %: C 79.58; H 4.11.
3,3-(butane-1,4-diyl)bis(1,2-dimethyl-1H-imidazole-3-
ium)bromide–CAN.
ACKNOWLEDGMENTS
Financial support from the Research Council of
Islamic Azad University of Rasht branch is sincerely
acknowledged.
REFERENCES
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3-ium)bromide ([BDBDMIm]Br). IR spectrum, ν,
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CONCLUSIONS
We have developed an efficient, green, fast, and con-
venient procedure for the multicomponent synthesis of
pyrano[4,3-b]chromenes via a tandem reaction, in
which benzyl alcohols were converted to benzal-
dehydes using the novel oxidant system [BDBDMIm]
Br–CAN followed by cyclocondensation reaction of β-
naphthol, aldehydes and 4-hydroxycoumarin. To the
best of our knowledge, that was the first report on
synthesis of pyrano[4,3-b]chromenes derivatives using
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