I
Z. Sipos et al.
Feature
Synthesis
MS: m/z = 342.1 [M+, 100%], 313.1, 281.1, 239.0, 208.0, 184.1, 155.0.
1H NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 7.3 Hz, 1 H, 10-H), 7.83 (d,
J = 7.8 Hz, 2 H, 2′,6′-H), 7.35 (t, J = 7.0 Hz, 1 H, 9-H), 7.32–7.25 (m, 1 H,
8-H), 7.21 (d, J = 6.3 Hz, 1 H, 7-H), 7.00 (d, J = 7.8 Hz, 2 H, 3′,5′-H), 6.72
(s, 1 H, 3-H), 6.61 (s, 1 H, 12-H), 5.19 (s, 2 H, 6-CH2), 4.05 (s, 3 H, 11-
OCH3), 3.88 (s, 3 H, 4′-OCH3).
13C NMR (100 MHz, CDCl3): δ = 177.2 (C-4), 162.1 (C-11), 161.1 (C-2),
160.8 (C-4′), 158.2 (C-4b), 156.7 (C-12a), 130.8 (C-6a), 128.1 (C-8),
127.7 (C-10a), 127.7 (C-4′), 127.6 (C-3′,5′), 127.4 (C-9), 126.0 (C-7),
124.3 (C-10), 123.8 (C-1′), 114.4 (C-2′,6′), 110.3 (C-10b), 109.5 (C-4a),
107.6 (C-3), 93.4 (C-12), 69.4 (C-6), 56.0 (11-OCH3), 55.5 (4′-OCH3).
Anal. Calcd for C22H14O4: C, 77.18; H, 4.12. Found: C, 77.25; H, 4.15.
12-Hydroxy-9-phenyl-5H,11H-benzo[c]pyrano[3,2-g]chromen-11-
one (11b)
Prepared from 2 (0.50 mmol, 0.212 g, 1.0 equiv) with Pd(OAc)2 (11.2
mg, 0.050 mmol), PPh3 (26.6 mg, 0.10 mmol), pivalic acid (2 mL), and
K3PO4 (0.318 g, 1.50 mmol) in anhyd DMF (2 mL) at 130 °C; eluent:
toluene; yield: 144 mg (42%); yellow solid; mp 203–205 °C.
IR (KBr): 3072, 3018, 2921, 2850, 2827, 2769, 2712, 1644, 1587, 1564,
MS: m/z = 409.33 [M + Na+], 388.25, 387.33 [M + H+, 100%], 372.25,
356.25.
1485, 1446, 1420, 1390, 1342, 1255, 1214, 1162, 1133, 1059 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 14.11 (s, 1 H, 5-OH), 8.55 (d, J = 7.9 Hz,
1 H, 1-H), 7.87–7.82 (m, 2 H, 2′,6′-H), 7.54–7.46 (m, 3 H, 3′,4′,5′-H),
7.38 (t, J = 7.6 Hz, 1 H, 2-H), 7.25 (t, J = 7.4 Hz, 1 H, 3-H), 7.12 (d, J = 7.4
Hz, 1 H, 4-H), 6.64 (s, 1 H, 3-H), 6.59 (s, 1 H, 8-H), 5.09 (s, 2 H, 5-CH2).
13C NMR (100 MHz, CDCl3): δ = 182.9 (C-11), 163.8 (C-9), 161.8 (C-
6a), 159.8 (C-12), 156.5 (C-7a), 131.8 (C-4′), 131.0 (C-1′), 130.0 (C-4a),
129.0 (C-3′,5′), 128.5 (C-2), 127.7 (C-12b), 127.2 (C-3), 126.3 (C-1),
126.2 (C-2′,6′), 124.1 (C-4), 107.4 (C-12a), 106.3 (C-11a), 105.6 (C-10),
95.8 (C-7), 69.1 (C-5).
Anal. Calcd for C24H18O5: C, 74.60; H, 4.70. Found: C, 74.67; H, 4.78.
2-(3,4-Dimethoxyphenyl)-11-methoxy-4H,6H-benzo[c]pyra-
no[2,3-h]chromen-4-one (12c)
Prepared from 9c (0.149 g, 0.3 mmol, 1.0 equiv) with Pd(OAc)2 (6.7
mg, 0.030 mmol), PPh3 (15.7 mg, 0.060 mmol), pivalic acid (9 mg,
0.090 mmol), and K3PO4 (0.191 g, 0.90 mmol) in anhyd DMF (1 mL) at
140 °C; conversion = 91%; eluent: hexane/acetone (2:1); yield: 54 mg
(43%); off-white solid; mp 217–220 °C.
MS: m/z = 342.1 [M+, 100%], 313.1, 281.0, 258.1, 239.1, 207.0, 171.1,
139.1, 115.1.
IR (KBr): 2956, 2923, 2853, 1731, 1638, 1598, 1573, 1518, 1494, 1465,
1440, 1423, 1361, 1271, 1250, 1109, 1021 cm–1
.
Anal. Calcd for C22H14O4: C, 77.18; H, 4.12. Found: C, 77.23; H, 4.14.
1H NMR (400 MHz, CDCl3): δ = 8.20 (d, J = 6.1 Hz, 1 H, 10-H), 7.49 (d,
J = 7.1 Hz, 1 H, 6′-H), 7.38–7.27 (m, 3 H, 2′-H, 8-H, 9-H), 7.20 (s, 1 H, 7-
H), 6.94 (d, J = 7.1 Hz, 1 H, 5′-H), 6.70 (s, 1 H, 3-H), 6.61 (s, 1 H, 12-H),
5.18 (s, 2 H, 6-CH2), 4.04 (s, 3 H, 11-OCH3), 3.97, 3.94 (2 s, 3 H each, 3′-
OCH3, 4′-OCH3).
13C NMR (100 MHz, CDCl3): δ = 177.1 (C-4), 161.1 (C-11), 160.8 (C-2),
158.2 (C-4b), 156.6 (C-12a), 151.7 (C-4′), 149.2 (C-3′), 130.7 (C-6a),
128.0 (C-8), 127.6 (C-10a), 127.4 (C-9), 126.0 (C-7), 124.3 (C-10),
123.8 (C-1′), 119.5 (C-6′), 111.0 (C-5′), 110.3 (C-10b), 109.4 (C-4a),
108.5 (C-2′), 107.8 (C-3), 93.4 (C-12), 69.4 (C-6), 56.0 (11-OCH3), 55.9
(3′-OCH3, 4′-OCH3).
11-Methoxy-2-phenyl-4H,6H-benzo[c]pyrano[2,3-h]chromen-4-
one (12a)
Prepared from 9a (0.144 g, 0.33 mmol, 1.0 equiv) with Pd(OAc)2 (7.4
mg, 0.033 mmol), PPh3 (17.3 mg, 0.066 mmol), pivalic acid (10 mg,
0.099 mmol), and K3PO4 (0.210 g, 0.99 mmol) in anhyd DMF (1 mL) at
120 °C, conversion = 89%; eluent: hexane/EtOAc (2:1); yield: 40 mg
(34%); brown solid; mp 176–178 °C.
IR (KBr): 3061, 3034, 2924, 2852, 1726, 1656, 1601, 1577, 1492, 1451,
1434, 1419, 1352, 1233, 1195, 1130, 1105 cm–1
.
1H NMR (360 MHz, CDCl3): δ = 8.21 (d, J = 6.6 Hz, 1 H, 10-H), 7.89 (m,
2 H, 2′,6′-H), 7.51 (m, 3 H, 3′,4′,5′-H), 7.40–7.33 (m, 1 H, 9-H), 7.32–
7.26 (m, 1 H, 8-H), 7.20 (s, 1 H, 7-H), 6.89 (s, 1 H, 3-H), 6.76 (s, 1 H, 12-
H), 5.18 (s, 2 H, 6-CH2), 4.07 (s, 3 H, 11-OCH3).
MS: m/z = 439.33 [M + Na+], 418.33, 417.33 [M + H+, 100%], 401.25,
400.33, 386.33, 373.25.
Anal. Calcd for C25H20O6: C, 72.11; H, 4.84. Found: C, 72.02; H, 4.73.
13C NMR (90 MHz, CDCl3): δ = 177.3 (C-4), 161.7 (C-11), 161.6 (C-2),
158.3 (C-4b), 156.7 (C-12a), 131.6 (C-4′), 131.1 (C-1′), 130.7 (C-6a),
129.0 (C-3′,5′), 128.1 (C-8), 127.6 (C-9), 127.4 (C-10a), 126.2 (C-2′,6′),
126.0 (C-7), 124.4 (C-10), 110.7 (C-10b), 108.9 (C-4a), 108.2 (C-3),
93.5 (C-12), 69.4 (C-6), 56.3 (11-OCH3).
MS: m/z = 379.17 [M + Na+], 358.17, 357.17 [M + H+, 100%], 343.33,
342.17, 340.17, 326.17, 325.25.
11-Methoxy-2-(3,4,5-trimethoxyphenyl)-4H,6H-benzo[c]pyra-
no[2,3-h]chromen-4-one (12d)
Prepared from 9d (0.125 g, 0.237 mmol, 1.0 equiv) with Pd(OAc)2 (5.0
mg, 0.024 mmol), PPh3 (12.4 mg, 0.047 mmol), pivalic acid (7.3 mg,
0.071 mmol), and K3PO4 (0.150 g, 0.711 mmol) in anhyd DMF (1 mL)
at 120 °C; conversion = 92%; eluent: hexane/acetone (2:1); yield: 17
mg (16%); white solid; mp 245–247 °C.
Anal. Calcd for C23H16O4: C, 77.52; H, 4.53. Found: C, 77.55; H, 4.56.
IR (KBr): 3447, 3053, 2946, 2920, 2836, 1645, 1598, 1507, 1461, 1423,
1357, 1251, 1203, 1182, 1129, 1071 cm–1
.
11-Methoxy-2-(4-methoxyphenyl)-4H,6H-benzo[c]pyrano[2,3-
h]chromen-4-one (12b)
1H NMR (400 MHz, CDCl3): δ = 8.23 (d, J = 7.8 Hz, 1 H, 10-H), 7.38 (t,
J = 7.4 Hz, 1 H, 9-H), 7.31 (t, J = 7.3 Hz, 1 H, 8-H), 7.22 (d, J = 7.2 Hz, 1
H, 7-H), 7.09 (s, 2 H, 2′,6′-H), 6.74 (s, 1 H, 3-H), 6.66 (s, 1 H, 12-H), 5.21
(s, 2 H, 6-CH2), 4.09 (s, 3 H, 11-OCH3), 3.97 (s, 6 H, 3′,5′-OCH3), 3.93 (s,
3 H, 4′-OCH3).
13C NMR (100 MHz, CDCl3): δ = 177.1 (C-4), 161.2 (C-11), 160.7 (C-2),
158.2 (C-4b), 156.7 (C-12a), 153.5 (C-3′,5′), 140.8 (C-4′), 130.7 (C-6a),
128.1 (C-8), 127.5 (C-9), 126.7 (C-10a), 126.0 (C-7), 124.4 (C-10),
110.5 (C-10b), 109.9 (C-1′), 109.5 (C-4a), 108.8 (C-3), 103.4 (C-2′,6′),
93.4 (C-12), 69.5 (C-6), 61.0 (4′-OCH3), 56.4 (3′-OCH3, 5′-OCH3), 56.1
(11-OCH3).
Prepared from 9b (0.154 g, 0.33 mmol, 1.0 equiv) with Pd(OAc)2 (7.4
mg, 0.033 mmol), PPh3 (17.3 mg, 0.066 mmol), pivalic acid (10 mg,
0.099 mmol), and K3PO4 (0.210 g, 0.99 mmol) in anhyd DMF (1 mL) at
120 °C; conversion = 71%; eluent: hexane/EtOAc (2:1); yield: 70 mg
(55%); white solid; mp 182–184 °C.
IR (KBr): 3038, 3003, 2828, 2835, 1639, 1599, 1574, 1512, 1493, 1462,
1425, 1354, 1301, 1260, 1179, 1130, 1033 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–K