Synthesis of New Thiophene-Substituted 3,3-Diphenyl-3H-naphtho[2,1-b]pyrans
FULL PAPER
1489, 1445, 1341, 1276, 1212, 1195, 1132, 1089, 1051, 1002, 949,
907, 877, 836, 805, 764, 741, 696 cmϪ1 1H NMR (400 MHz, 8.8 Hz, 1 H) ppm. 13C NMR (100 MHz, [D5]pyridine): δ ϭ 83.3
[D5]pyridine): δ ϭ 6.55 (d, J ϭ 10.0 Hz, 1 H), 7.10 (dd, J ϭ 3.6, (C), 115.5 (C), 119.9 (ϪCHϭ), 120.3 (ϪCHϭ), 123.4 (ϪCHϭ),
(dd, J ϭ 2.0, 8.8 Hz, 1 H), 8.11 (d, J ϭ 1.8 Hz, 1 H), 8.16 (d, J ϭ
.
5.1 Hz, 1 H), 7.16 (d, J ϭ 3.7 Hz, 1 H), 7.28 (m, 2 H), 7.37 (d, J ϭ 124.8 (ϪCHϭ), 125.2 (ϪCHϭ), 125.4 (ϪCHϭ), 125.6 (ϪCHϭ),
3.7 Hz, 1 H), 7.40 (m, 4 H), 7.40 (dd, J ϭ 1.1, 3.6 Hz, 1 H), 7.41 125.8 (ϪCHϭ), 125.9 (ϪCHϭ), 127.8 (4 ϫ ϪCHϭ), 128.4 (2 ϫ
(ddd, J ϭ 1.1, 6.7, 8.6 Hz, 1 H), 7.43 (dd, J ϭ 1.1, 5.1 Hz, 1 H), ϪCHϭ), 129.1 (5 ϫ ϪCHϭ), 129.3 (ϪCHϭ), 130.1 (C), 130.3 (C),
7.58 (s, 1 H), 7.58 (d, J ϭ 10.0 Hz, 1 H), 7.56 (ddd, J ϭ 1.3, 6.9,
130.6 (C), 131.0 (ϪCHϭ), 137.3 (C), 138.2 (C), 143.8 (C), 146.0 (2
8.3 Hz, 1 H), 7.75 (m, 4 H), 8.20 (br. d, J ϭ 8.4 Hz, 1 H), 8.28 (br. ϫ C), 151.7 (C) ppm. C33H22OS2: C 79.48, H 4.45, S 12.8; found
d, J ϭ 8.4 Hz, 1 H) ppm. 13C NMR (100 MHz, [D5]pyridine): δ ϭ
83.5 (C), 115.5 (C), 120.2 (ϪCHϭ), 120.7 (ϪCHϭ), 122.9
(ϪCHϭ), 125.00 (ϪCHϭ), 125.2 (ϪCHϭ), 125.3 (ϪCHϭ), 126.0
(ϪCHϭ), 127.0 (ϪCHϭ), 127.8 (4 ϫ ϪCHϭ), 127.9 (ϪCHϭ),
128.4 (C), 128.5 (2 ϫ ϪCHϭ), 129.1 (5 ϫ ϪCHϭ), 129.5 (ϪCHϭ),
129.6 (ϪCHϭ), 131.4 (C), 134.5 (C), 137.9 (C), 138.7 (C), 140.7
(C), 146.0 (2 ϫ C), 150.6 (C) ppm. C33H22OS2: C 79.48, H 4.45, S
12.8; found C 79.38, H 4.48, S 13.0.
C 79.38, H 4.51, S 12.6.
9-(2,2Ј-Bithien-5-yl)-3,3-diphenyl-3H-naphtho[2,1-b]pyran
(XV):
This compound was obtained by General Procedure (5), from III
(482 mg, 1.00 mmol) and 2 (333 mg, 1.20 mmol). Purification by
column chromatography (SiO2; n-pentane/CH2Cl2, gradient 100:0
to 50:50) afforded the pure compound XV (414 mg, 0.83 mmol,
83%) as a yellow solid after recrystallization (heptane/benzene).
This compound was also prepared by General Procedure (7), from
23 (3.08 mg, 10 mmol). The reaction mixture was stirred under re-
flux for six days. Purification of the concentrate by column chroma-
tography and recrystallization carried out as mentioned above, af-
forded XV (2.69 g, 5.39 mmol, 54%) as a yellow solid, m.p. 211 °C.
7-(2,2Ј-Bithien-5-yl)-3,3-diphenyl-3H-naphtho[2,1-b]pyran
(XIII):
This compound was obtained by General Procedure (7), from 30
(3.08 g, 10 mmol). The reaction mixture was stirred under reflux
for six days. The residue was purified by column chromatography
(SiO2; n-pentane/CH2Cl2, gradient 100:0 to 60:40) to afford the IR (KBr): ν˜ ϭ 3076, 3064, 3022, 1630, 1614, 1589, 1504, 1447,
pure compound XIII (3.19 mg, 6.39 mmol, 64%) as a pale-yellow 1425, 1375, 1243, 1230, 1201, 1086, 1051, 1020, 975, 952, 838, 801,
solid after recrystallization (heptane/benzene), m.p. 155 °C. IR
(KBr): ν˜ ϭ 3102, 3063, 3023, 2954, 2923, 2853, 1630, 1602, 1583,
729, 700 cmϪ1 1H NMR (400 MHz, [D5]pyridine): δ ϭ 6.58 (d,
.
J ϭ 10.0 Hz, 1 H), 7.11 (dd, J ϭ 3.7, 5.0 Hz, 1 H), 7.29 (m, 2 H),
1516, 1491, 1458, 1447, 1409, 1373, 1355, 1321, 1255, 1219, 1202, 7.35 (d, J ϭ 3.8 Hz, 1 H), 7.38 (d, J ϭ 8.8 Hz, 1 H), 7.39 (m, 4 H),
1157, 1093, 1071, 1052, 1031, 907, 822, 805, 767, 760, 696 cmϪ1
.
7.41 (dd, J ϭ 1.1, 5.0 Hz, 1 H), 7.43 (dd, J ϭ 1.1, 3.7 Hz, 1 H),
7.57 (d, J ϭ 3.8 Hz, 1 H), 7.68 (d, J ϭ 10.0 Hz, 1 H), 7.70 (d, J ϭ
8.8 Hz, 1 H), 7.72 (br. d, J ϭ 8.6 Hz, 1 H), 7.73 (m, 4 H), 7.79 (d,
1H NMR (400 MHz, [D5]pyridine): δ ϭ 6.56 (d, J ϭ 10.0 Hz, 1
H), 7.06 (d, J ϭ 3.8 Hz, 1 H), 7.10 (dd, J ϭ 3.6, 5.1 Hz, 1 H), 7.12
(dd, J ϭ 1.7, 3.5 Hz, 1 H), 7.28 (m, 2 H), 7.37 (dd, J ϭ 1.1, 3.6 Hz, J ϭ 8.6 Hz, 1 H), 8.43 (br. s, 1 H) ppm. 13C NMR (100 MHz,
1 H), 7.38 (m, 4 H), 7.43 (dd, J ϭ 1.1, 5.1 Hz, 1 H), 7.46 (dd, J ϭ [D5]pyridine): δ ϭ 83.4 (C), 115.4 (C), 118.7 (ϪCHϭ), 119.3
2.3, 7.1 Hz, 1 H), 7.48 (d, J ϭ 9.3 Hz, 1 H), 7.50 (t, J ϭ 7.1 Hz, 1 (ϪCHϭ), 120.5 (ϪCHϭ), 122.8 (ϪCHϭ), 124.9 (ϪCHϭ), 125.9
H), 7.58 (d, J ϭ 10.0 Hz, 1 H), 7.72 (m, 4 H), 8.14 (dd, J ϭ 2.3,
(3 ϫ ϪCHϭ), 127.8 (4 ϫ ϪCHϭ), 128.4 (2 ϫ ϪCHϭ), 129.08 (5
7.1 Hz, 1 H), 8.21 (d, J ϭ 9.3 Hz, 1 H) ppm. 13C NMR (100 MHz, ϫ ϪCHϭ), 129.1 (ϪCHϭ), 129.7 (C), 130.3 (ϪCHϭ), 130.7
[D5]pyridine): δ ϭ 83.3 (C), 115.5 (C), 119.4 (ϪCHϭ), 120.7 (ϪCHϭ and C), 133.2 (C), 137.9 (C), 138.1 (C), 144.0 (C), 146.0
(ϪCHϭ), 122.8 (ϪCHϭ), 125.9 (ϪCHϭ), 126.9 (C), 127.07 (2 ϫ C), 152.1 (C) ppm. C33H22OS2: C 79.48, H 4.45, S 12.8; found
(ϪCHϭ), 127.09 (ϪCHϭ), 127.8 (4 ϫ ϪCHϭ), 128.38 (ϪCHϭ),
128.43 (3 ϫ ϪCHϭ), 128.48 (ϪCHϭ), 128.50 (C), 128.54 (ϪCHϭ),
129.1 (4 ϫ ϪCHϭ), 129.3 (ϪCHϭ), 129.4 (ϪCHϭ), 131.4 (C),
133.2 (C), 138.5 (C), 141.5 (C), 145.9 (2 ϫ C), 151.6 (C) ppm.
C33H22OS2: C 79.48, H 4.45, S 12.8; found C 79.55, H 4.43, S 12.7.
C 79.41, H 4.53, S 12.8.
3,3-Diphenyl-8-(2,2Ј:5Ј,2ЈЈ-terthien-5-yl)-3H-naphtho[2,1-b]pyran
(XVI): This compound was obtained by General Procedure (5),
from II (482 mg, 1.00 mmol) and 3 (432 mg, 1.20 mmol). Purifi-
cation by column chromatography (SiO2; n-pentane/CH2Cl2, gradi-
ent 100:0 to 50:50) afforded the pure compound XVI (372 mg,
8-(2,2Ј-Bithien-5-yl)-3,3-diphenyl-3H-naphtho[2,1-b]pyran
(XIV):
This compound was obtained by General Procedure (5), from II 0.64 mmol, 64%) as a yellow solid after recrystallization from ben-
(482 mg, 1.00 mmol) and 2 (333 mg, 1.20 mmol). Purification by
column chromatography (SiO2; n-pentane/CH2Cl2, gradient 100:0
to 50:50) afforded the pure compound XIV (439 mg, 0.88 mmol,
zene. This compound was also prepared by General Procedure (5),
from V (413 mg, 1.00 mmol) and 3 (432 mg, 1.20 mmol). Purifi-
cation by column chromatography and recrystallization carried out
88%) as a yellow solid after recrystallization from heptane/benzene. as mentioned above, yielded XVI (314 mg, 0.54 mmol, 54%) as a
This compound was also prepared by General Procedure (5), from
V (413 mg, 1.00 mmol) and 2 (333 mg, 1.20 mmol). Purification by
column chromatography and recrystallization carried out as men-
tioned above, yielded XIV (429 mg, 0.86 mmol, 86%) as a yellow
solid. This compound was also prepared by General Procedure (7),
from 20 (3.08 g, 10 mmol). The reaction mixture was stirred under
reflux for six days. Purification of the concentrate by column chro-
matography and recrystallization carried out as mentioned above,
yellow solid. This compound was also prepared by General Pro-
cedure (7), from 21 (3.90 g, 10 mmol). The reaction mixture was
stirred under reflux for six days. Purification of the concentrate by
column chromatography and recrystallization carried out as men-
tioned above, afforded XVI (522 mg, 0.09 mmol, 9%) as a yellow
solid, m.p. 262 °C. IR (KBr): ν˜ ϭ 3060, 3027, 2925, 2854, 1631,
1588, 1495, 1450, 1378, 1345, 1273, 1244, 1220, 1184, 1094, 1075,
1008, 954, 881, 830, 813, 795, 754, 698 cmϪ1. 1H NMR (400 MHz,
afforded XIV (1.10 g, 2.20 mmol, 22%) as a yellow solid, m.p. 244 [D5]pyridine): δ ϭ 6.53 (d, J ϭ 10.0 Hz, 1 H), 7.09 (dd, J ϭ 3.6,
°C. IR (KBr): ν˜ ϭ 3059, 3024, 1628, 1587, 1493, 1447, 1243, 1219, 5.1 Hz, 1 H), 7.24 (d, J ϭ 3.9 Hz, 1 H), 7.28 (d, J ϭ 3.9 Hz, 1 H),
1094, 1009, 949, 883, 813, 795, 751, 696 cmϪ1. 1H NMR (400 MHz, 7.29Ϫ7.33 (m, 2 H), 7.33 (d, J ϭ 3.8 Hz, 1 H), 7.36 (dd, J ϭ 1.1,
[D5]pyridine): δ ϭ 6.53 (d, J ϭ 10.0 Hz, 1 H), 7.09 (dd, J ϭ 3.6, 3.6 Hz, 1 H), 7.40 (dd, J ϭ 1.1, 5.1 Hz, 1 H), 7.41Ϫ7.46 (m, 4 H),
5.1 Hz, 1 H), 7.28 (m, 2 H), 7.32 (d, J ϭ 3.8 Hz, 1 H), 7.38 (m, 4 7.41 (d, J ϭ 8.8 Hz, 1 H), 7.44 (d, J ϭ 3.8 Hz, 1 H), 7.49 (d, J ϭ
H), 7.39 (dd, J ϭ 1.1, 3.6 Hz, 1 H), 7.41 (dd, J ϭ 1.1, 5.1 Hz, 1 10.0 Hz, 1 H), 7.72Ϫ7.76 (m, 4 H), 7.79 (d, J ϭ 8.8 Hz, 1 H), 7.86
H), 7.44 (d, J ϭ 9.0 Hz, 1 H), 7.48 (d, J ϭ 3.7 Hz, 1 H), 7.53 (d, (dd, J ϭ 1.9, 8.8 Hz, 1 H), 8.09 (d, J ϭ 1.5 Hz, 1 H), 8.13 (d, J ϭ
J ϭ 10.0 Hz, 1 H), 7.71 (m, 4 H), 7.81 (d, J ϭ 9.0 Hz, 1 H), 7.88 9.0 Hz, 1 H) ppm. 13C NMR (100 MHz, [D5]pyridine): δ ϭ 83.9
Eur. J. Org. Chem. 2003, 2799Ϫ2812
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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