J. Chil. Chem. Soc., 63, Nº 4 (2018)
12-(4-Bromophenyl)dibenzo[i,b]pyrano[4,3-b]chromen-11(12H)-one
(4f):
White solid. mp 211-213 °C; FT-IR (KBr): ν 3064, 2941, 1712, 1641, 1461,
1508, 564, 1174, 1240, 811 cm-1. 1H NMR (400 MHz, CDCl3): δ = 3.35 (s, 3H),
5.92 (s, 1H), 6.77 (t, J = 8.8 Hz, 2H), 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, 3H) ppm. 13C NMR
(CDCl , 100 MHz): δ = 35.8, 62.2, 105.8, 113.8, 115.5, 116.5, 117.8, 118.1,
118.7, 3121.4, 123.0, 124.4, 125.0, 127.5, 128.5, 129.9, 130.7, 132.6, 133.9,
138.1, 146.3 (C-O), 154.5 (C-O), 155.6 (C-O), 160.3 (C-O), 175.5 (C=O) ppm.
Anal. calcd for C H O : C, 79.79; H, 4.46. Found: C, 79.85; H, 4.41.
12-(3, 4, 275-1T8ri4methoxyphenyl)dibenzo[i,b]pyrano[4,3-b]chromen-
11(12H)-one (4n):
White solid. mp 287-289 °C; FT-IR (KBr): ν 3072, 1708, 1635, 1463,
1546, 1226, 1267 cm-1. 1H NMR (400 MHz, CDCl3): δ = 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) ppm. 13C NMR (CDCl3, 100 MHz): δ = 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 (C-Br), 152.5 (C-O), 153.9 (C-
O), 160.1 (C-O), 176.0 (C=O) ppm. Anal. calcd for C26H15BrO3: C, 68.59; H,
3.32. Found: C, 68.65; H, 3.26.
12-(4-Fluorophenyl)dibenzo[i,b]pyrano[4,3-b]chromen-11(12H)-one
(4g)|:
White solid. mp 201-203 °C; FT-IR (KBr): ν 3054, 1704, 1639, 1538,
1
1472, 1352, 1242 cm-1. H NMR (400 MHz, CDCl3): δ = 3.56 (s, 3H), 3.61
White solid. mp 241-243 °C; FT-IR (KBr): ν 3132, 1700, 1600, 1650,
1481, 1508, 1564, 1240, 1255 cm-1. 1H NMR (400 MHz, CDCl ): δ = 6.11 (s,
1H), 6.88-6.92 (m, 2H), 7.41-7.50 (m, 7H), 7.64-7.69 (m, 1H),37.85-7.90 (m,
(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 (CDCl , 100 MHz): δ = 35.4, 56.25, 56.8, 56.3, 98.9, 115.3,
116.5, 117.5, 121.2, 122.35, 123.4, 125.6, 127.2, 128.9, 129.0, 130.2, 131.4,
134.5, 135.1, 145.3 (C-O), 146.7 (C-O), 147.1 (C-O), 152.9 (C-O), 159.2 (C-
O), 175.4 (C=O) ppm. Anal. calcd for C29H22O6: C, 74.67; H, 4.75. Found: C,
74.78; H, 4.83.
2H), 7.97 (d, 1H, J = 8.0 Hz), 8.22 (dd, 1H, J = 8.0 Hz, J = 1.2 Hz) ppm. 13
C
NMR (CDCl , 100 MHz): δ = 35.5, 115.1, 115.3, 116.5, 117.3, 122.7, 123.9,
125.3, 125.5,3125.9, 127.5, 128.6, 129.7, 129.9, 130.0, 130.9, 131.8, 141.4 (C-
O), 145.5 (C-O), 148.3 (C-F), 152.9 (C-O), 176.9 (C=O) ppm. Anal. calcd for
C26H15FO3: C, 79.18; H, 3.83. Found: C, 79.13; H, 3.79.
12-(4-Dimethylaminophenyl)dibenzo[i,b]pyrano[4,3-b]chromen-
11(12H)-one (4o):
12-Phenyldibenzo[i,b]pyrano[4,3-b]chromen-11(12H)-one (4i):
White solid. mp 276-278 °C; FT-IR (KBr): ν 3056, 3022, 2920, 1718,
1641, 1463, 1575, 1610, 1222, 1271, 746 cm-1. 1H NMR (400 MHz, CDCl ): δ
= 6.0 (s, 1H), 7.10 (t, 1H, J = 7.2 Hz), 7.22 (t, 2H, J = 7.6 Hz), 7.49 (dd,32H,
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) ppm. 13C NMR (CDCl3, 100
MHz): δ = 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 (C-
O), 153.4 (C-O), 160.2 (C-O), 173.2 (C=O) ppm. Anal. calcd for C26H16O3: C,
82.96; H, 4.28. Found: C, 83.02; H, 4.21.
White solid. mp 255-257 °C; FT-IR (KBr): ν 3074, 2914, 1656, 1521,
1
1560, 1660, 1346, 1191, 810 cm-1. H NMR (400 MHz, CDCl ): δ = 2.10 (s,
6H), 5.60 (s, 1H), 7.22-7.39 (m, 8H), 7.50-7.52 (m, 1H), 7.633-7.68 (m, 1H),
7.80-7.84 (m, 3H), 8.01 (d, 1H, J = 8.2 Hz) ppm.13C NMR (CDCl3, 100 MHz):
δ = 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 (C-N),
154.2 (C-O), 155.0 (C-O), 158.5 (C-O), 173.4 (C=O) ppm. Anal. calcd for
C28H21NO : C, 80.17; H, 5.05; N, 3.34. Found: C, 80.24; H, 4.99; N, 3.29.
12-(43-Hydroxyphenyl)dibenzo[i,b]pyrano[4,3-b]chromen-11(12H)-
one (4p):
12-(4-Methylphenyl)dibenzo[i,b]pyrano[4,3-b]chromen-11(12H)-one
(4j):
White solid. mp 298-300 °C; FT-IR (KBr): ν 3281, 3012, 1706, 1635,
1
White solid. mp 225-227 °C; FT-IR (KBr): ν 3018, 2920, 1714, 1639,
1551, 1462, 1301, 1203 cm-1. H NMR (400 MHz, CDCl3): δ = 5.72 (s, 1H),
1
1463, 1510, 1566, 1224 cm-1. H NMR (400 MHz, CDCl3): δ = 2.16 (s, 3H),
7.60 (d, 1H, J = 8.6 Hz), 7.63–7.70 (m, 3H), 7.87 (t, J = 8.6 Hz, 1H), 7.90 (d,
3H, J = 8.4 Hz), 8.05 (d, 3H, J = 8.2 Hz), 8.13 (t. 2H, J = 8.2 Hz), 8.21 (d, 1H,
J = 8.2 Hz), 9.31 (s, 1H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 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, 152.0 (C-O), 152.5 (C-O),
156.0 (C-O), 162.3 (C-O), 175.2 (C=O) ppm. Anal. calcd for C26H16O4: C,
79.58; H, 4.11;. Found: C, 79.66; H, 4.03.
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 (dd, 1H, J =7.6 Hz, J = 0.8 Hz) ppm.
13C NMR (CDCl , 100 MHz): δ = 31.2, 34.6, 105.9, 114.2, 116.0, 117.1, 117.3,
117.4, 118.0, 1230.0, 122.1, 124.3, 125.0, 127.2, 128.8, 130.0, 130.5, 131.4,
132.0, 135.0, 140.2, 153.3 (C-O), 154.4 (C-O), 161.4 (C-O), 174.7 (C=O) ppm.
Anal. calcd for C H18O3: C, 83.06; H, 4.65. Found: C, 83.12; H, 4.61.
12-(2,3-Dim2e7thylphenyl)dibenzo[i,b]pyrano[4,3-b]chromen-11(12H)-
one (4k):
RESULTS AND DISCUSSION
White solid. mp 257-258 °C; FT-IR (KBr): ν 3018, 1682, 1636, 1543,
1
1452, 1319, 1242 cm-1. H NMR (400 MHz, CDCl ): δ = 1.78 (s, 3H), 2.32
In continuation of our ongoing studies to synthesize heterocyclic and
pharmaceutical compounds by mild and practical protocols 25-28, herein we wish
to report our experimental results on the synthesis of pyrano[4,3-b]chromenes,
using various aromatic aldehydes, 2-naphthol and 4-hydroxycoumarin in the
presence of POImD in aqueous media at room temperature (Scheme 1).
The reaction between 4-nitrobenzaldehyde, 2-naphthol and
4-hydroxycoumarin in the presence of different catalysts was carried out as a
model. All the reactions were carried out with catalytic amounts of catalysts. As
described in Table 1, the higher yield, shorter reaction time and milder reaction
condition gained with 0.01mmol of POImD (Table 1; Entry 13).
(s, 3H), 6.63 (s, 1H), 7.06–7.08 (m, 3H), 7.11 (d, J 3= 8.6 Hz, 1H), 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, J = 8.2 Hz, 1H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 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, 147.5 (C-
O), 151.3 (C-O), 162.6 (C-O), 176.9 (C=O) ppm. Anal. calcd for C28H20O3: C,
83.15; H, 4.98. Found: C, 83.03; H, 5.06.
12-(4-Methoxyphenyl)dibenzo[i,b]pyrano[4,3-b]chromen-11(12H)-
one (4l):
Scheme 1. Synthesis of pyrano[4,3-b]chromenes using POImD
4196