FeCl3-SiO2 as heterogeneous catalysts for the preparation of dihydropyrano[3,2-b]chromenediones

Article abstract of DOI:10.1135/cccc2011108

FeCl₃-SiO₂ is environment-friendly heterogeneous catalyst for the condensation of kojic acid and aldehydes with dimedone to afford dihydropyrano[3,2-b]chromenediones. The solid acid catalyst is stable and can be easily recovered and

Full text of DOI:10.1135/cccc2011108

Preparation of Dihydropyrano[3,2-b]chromenediones
1793
TABLE I
Synthesis of 2-(hydroxymethyl)-7,7-dimethyl-10-phenyl-7,8-dihydropyrano[3,2-b]chromene-
4,9(6H,10H)-dione (4a) in the presence of a variety of catalystsa
Entry
Catalyst
–
Time, min
Yield, %b
1
2
240
60
60
90
60
60
60
60
90
90
60
60
60
60
60
50
0
I2 (5 mole %)
19
29
11
79
82
80
69
59
68
76
87
93
92
90
93
3
p-TsOH (5 mole %)
H2SO4 (5 mole %)
4
5
FeCl3 (5 mole %)
6
Ce2SO4 (5 mole %)
7
ZnCl2 (5 mole %)
8
Fe(HSO4)3 (5 mole %)
FeCl3–SiO2 (1 mole %)
FeCl3–SiO2 (2 mole %)
FeCl3–SiO2 (3 mole %)
FeCl3–SiO2 (4 mole %)
FeCl3–SiO2 (5 mole %)
FeCl3–SiO2 (6 mole %)
FeCl3–SiO2 (7 mole %)
FeCl3–SiO2 (8 mole %)
9
10
11
12
13
14
15
16
a
Reaction conditions: kojic acid (1 mmol), benzaldehyde (1 mmol), dimedone (1 mmol);
b
100 °C; neat. Isolated yield.
FeCl3–SiO2 as catalyst was isolated from the reaction mixture by simple
filtration. The purified catalyst was achieved through washing the solid res-
idue catalyst by water and ethanol followed by drying in an oven at 100 °C
for 30 min. In every experiment, more than 98% of the FeCl3–SiO2 was
easily recovered from the reaction mixture. Catalytic activity of the recov-
ered catalyst was tested and showed to be the same as FeCl3–SiO2 used for
the first time. The recovered catalyst was reused three times without any
loss of activity (Table II, entry 1).
Collect. Czech. Chem. Commun. 2011, Vol. 76, No. 12, pp. 1791–1797

Preparation of Dihydropyrano[3,2-b]chromenediones
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Preparation of FeCl3–SiO2 Catalyst
In a 250 ml flask, chromatographic grade silica gel (50 g; 70–230 mesh) and anhydrous fer-
ric chloride (4 g; 8% of the weight of SiO2) were vigorously stirred under solvent-free condi-
tions at room temperature for 24 h to achieve a homogeneous adsorption. A pale yellowish-
green powder (2.0 g, equiv. to 2 mmol of FeCl3) was obtained.
Preparation of 4. General Procedure
A mixture of kojic acid (1 mmol), aldehyde (1 mmol), dimedone (1 mmol) and FeCl3–SiO2
(0.05 mmol) was heated at 100 °C for appropriate time (TLC). After completion, ethyl
acetate (2 × 20 ml) was added, and the solid catalyst was removed by filtration. The solvent
was evaporated and the crude product was puried by silica gel column chromatography
using ethyl acetate–hexane (7:3) as an eluent.
2-(Hydroxymethyl)-7,7-dimethyl-10-phenyl-7,8-dihydropyrano[3,2-b]chromene-4,9(6H,10H)-dione
(4a). IR (KBr): 3362, 3080, 2952, 2890, 1667, 1637, 1441, 1378, 1219, 1193, 1078, 990, 950,
712. 1H NMR (CDCl3, 400 MHz): 7.32–7.21 (m, 5 H), 6.50 (s, 1 H), 4.87 (s, 1 H), 4.43–4.32
(m, 2 H), 2.71–2.59 (m, 2 H), 2.29–2.19 (m, 2 H), 1.11 (s, 3 H), 1.04 (s, 3 H). 13C NMR
(CDCl3, 100 MHz): 196.2, 171.3, 167.3, 163.9, 151.7, 140.5, 137.5, 128.8, 128.1, 127.8,
112.3, 112.2, 60.6, 50.4, 40.9, 38.4, 32.3, 29.0, 27.4. MS (ESI): m/z 353 [M + H]+. For
C
21H20O5 (352.13) calculated: 71.58% C, 5.72% H; found: 71.65% C, 5.68% H.
2-(Hydroxymethyl)-7,7-dimethyl-10-(4-chlorophenyl)-7,8-dihydropyrano[3,2-b]chromene-
4,9(6H,10H)-dione (4b). IR (KBr): 3325, 2961, 2930, 2870, 1672, 1640, 1600, 1490, 1442,
1377, 1218, 1190, 1076, 1014, 952, 850. 1H NMR (CDCl3, 400 MHz): 7.28–7.18 (m, 4 H),
6.52 (s, 1 H), 4.87 (s, 1 H), 4.41–4.37 (m, 2 H), 2.66–2.60 (m, 2 H), 2.30–2.21 (m, 2 H), 1.11
(s, 3 H), 1.03 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 196.3, 171.4, 168.3, 164.1, 151.2, 138.9,
137.5, 133.6, 129.4, 129.0, 112.0, 111.9, 60.4, 50.3, 40.8, 37.8, 32.3, 28.9, 27.4. MS (ESI):
m/z 387 [M + H]+. For C21H19ClO5 (386.09) calculated: 65.20% C, 4.95% H; found: 65.12%
C, 4.88% H.
2-(Hydroxymethyl)-7,7-dimethyl-10-(4-florophenyl)-7,8-dihydropyrano[3,2-b]chromene-
4,9(6H,10H)-dione (4c). IR (KBr): 3363, 2953, 2930, 2853, 1675, 1638, 1601, 1509, 1443,
1378, 1219, 1192, 1157, 1075, 962, 845, 683. 1H NMR (CDCl3, 400 MHz): 7.24–7.20 (m,
2 H), 6.99–6.95 (m, 2 H), 6.52 (s, 1 H), 4.87 (s, 1 H), 4.40–4.36 (m, 2 H), 2.65–2.61 (m, 2 H),
2.25–2.22 (m, 2 H), 1.10 (s, 3 H), 1.03 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 196.4, 171.5,
168.3, 164.0, 160.9, 151.5, 137.4, 136.2, 129.7, 129.6, 115.8, 115.6, 112.2, 112.0, 60.4, 50.3,
40.8, 37.7, 32.3, 28.9, 27.4. MS (ESI): m/z 371 [M + H]+. For C21H19FO5 (370.12) calculated:
68.10% C, 5.17% H; found: 68.20% C, 5.12% H.
2-(Hydroxymethyl)-7,7-dimethyl-10-(4-nitrophenyl)-7,8-dihydropyrano[3,2-b]chromene-
4,9(6H,10H)-dione (4d). IR (KBr): 3334, 2960, 2928, 2855, 1675, 1633, 1596, 1520, 1375,
1347, 1216, 1123, 1058, 1003, 946, 867, 622. 1H NMR (CDCl3, 400 MHz): 8.18 (d, 2 H, J =
8.8), 7.47 (d, 2 H, J = 8.4), 6.53 (s, 1 H), 5.03 (s, 1 H), 4.42–4.37 (m, 2 H), 2.69–2.65 (m,
2 H), 2.27–2.23 (m, 2 H), 1.13 (s, 3 H), 1.04 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 196.0,
170.8, 167.0, 164.4, 150.0, 147.4, 137.9, 129.1, 124.1, 112.6, 111.5, 60.6, 50.3, 40.9, 38.4,
32.3, 28.9, 27.5. MS (ESI): m/z 398 [M + H]+. For C21H19NO7 (397.12) calculated: 63.47% C,
4.82% H, 3.52% N; found: 63.35% C, 4.85% H, 3.57% N.
2-(Hydroxymethyl)-7,7-dimethyl-10-(3-nitrophenyl)-7,8-dihydropyrano[3,2-b]chromene-
4,9(6H,10H)-dione (4e). IR (KBr): 3393, 2955, 2922, 2851, 1669, 1637, 1599, 1530, 1448,
1377, 1350, 1213, 1143, 1080, 678. 1H NMR (CDCl3, 400 MHz): 8.11–8.09 (m, 2 H), 7.63 (d,
Collect. Czech. Chem. Commun. 2011, Vol. 76, No. 12, pp. 1791–1797

Preparation of Dihydropyrano[3,2-b]chromenediones
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1219, 1193, 1120, 1029, 950, 860, 629. 1H NMR (CDCl3, 400 MHz): 7.18–7.16 (m, 2 H),
6.83–6.80 (m, 2 H), 6.50 (s, 1 H), 4.83 (s, 1 H), 4.40–4.35 (m, 2 H), 3.75 (s, 3 H), 2.65–2.61
(m, 2 H), 2.23–2.22 (m, 2 H), 1.10 (s, 3 H), 1.04 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 196.4,
171.5, 168.0, 16.7, 159.0, 152.0, 137.3, 132.7, 129.1, 114.2, 112.5, 129.1, 60.5, 55.2, 50.4,
40.8, 37.5, 32.2, 29.0, 27.4. MS (ESI): m/z 383 [M + H]+. For C22H22O6 (382.14) calculated:
69.10% C, 5.80% H; found: 69.20% C, 5.72% H.
We are pleased to acknowledge the financial support from Xinxiang Medical University.
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