618
K. J. Jeon and K.-J. Lee
Vol 45
vacuo. The resulting mixture was chromatographed on silica gel
eluting with hexane/ethyl acetate (6:1) to produce 2.53 g (66%)
of 2e as an oil; ir (potassium bromide): 3500, 1731, 1601, 1505,
1434 cm-1; 1H nmr (deuteriochloroform): δ 2.55 (d, J = 5.2 Hz, 1
H), 3.72 (s, 3 H), 5.79 (d, J = 3.7 Hz, 1 H), 6.52-6.53 (m, 1 H),
7.07 (d, J = 1.8 Hz, 1 H), 7.31-7.40 (m, 3 H), 7.46-7.51 (m, 3
H); 13C nmr (deuteriochloroform): δ 52.0, 72.4, 87.1, 111.7,
124.0, 127.0, 128.0, 128.5, 130.3, 132.1, 137.4, 140.1, 143.0,
145.5, 166.4. Anal. Calcd. for C15H13IO4: C, 46.90; H, 3.41.
Found: C, 46.67; H, 3.37.
122.4, 125.0, 125.6, 127.9 (two), 137.9, 141.5, 143.1, 146.8,
148.0, 166.8. Anal. Calcd. for C15H11IO2S: C, 47.14; H, 2.90; S,
8.39. Found: C, 47.30; H, 2.78; S, 8.12.
Methyl 2-(4H-Indeno[1,2-b]thiophen-4-yl)propenoate (3b).
To a stirred solution of 2b (0.55 g, 2 mmoles) in carbon
tetrachloride (5 mL) was added 95% sulfuric acid (0.11 mL, 2
mmoles) at room temperature. After 5 hours, the mixture was
neutralized with saturated sodium bicarbonate solution and
extracted with dichloromethane (5 × 10 mL). The combined
organic layers were dried over anhydrous magnesium sulfate
and the solvent was evaporated in vacuo. The resulting mixture
was chromatographed on silica gel eluting with hexane/ethyl
acetate (6:1) to produce 0.31 g (61%) of 3b as a solid; mp 42-43
℃; ir (potassium bromide): 1723, 1626, 1605, 1455, 1438 cm-1;
1H nmr (deuteriochloroform): δ 3.86 (s, 3 H), 4.93 (s, 1 H), 5.44
(s, 1 H), 6.16 (s, 1 H), 7.02 (d, J = 4.9 Hz, 1 H), 7.16-7.21 (m, 1
H), 7.30 (d, J = 4.9 Hz, 1 H), 7.32-7.48 (m, 3 H); 13C nmr
(deuteriochloroform): δ 47.1, 52.2, 119.0, 122.7, 125.0, 125.2,
125.3, 127.5 (two), 138.1, 139.0, 142.7, 148.3, 149.7, 167.4.
Anal. Calcd. for C15H12O2S: C, 70.29; H, 4.72; S, 12.51. Found:
C, 69.98; H, 4.50; S, 12.29.
Methyl (Z)-2-(8H-Indeno[2,1-b]thiophen-8-yl)-3-iodoprop-
enoate (3c). To a stirred solution of 2c (0.80 g, 2 mmoles) in
carbon tetrachloride (5 mL) was added 95% sulfuric acid (0.11
mL, 2 mmoles) at room temperature. After 2 hours, the mixture
was neutralized with saturated sodium bicarbonate solution and
extracted with dichloromethane (5 × 10 mL). The combined
organic layers were dried over anhydrous magnesium sulfate
and the solvent was evaporated in vacuo. The resulting mixture
was chromatographed on silica gel eluting with hexane/ethyl
acetate (6:1) to produce 0.49 g (65%) of 3c as an oil; ir
(potassium bromide): 1728, 1606, 1588, 1487, 1453, 1436 cm-1;
1H nmr (deuteriochloroform): δ 3.90 (s, 3 H), 5.04 (s, 1 H), 7.06
(d, J = 0.9 Hz, 1 H), 7.18-7.23 (m, 1 H), 7.24 (d, J = 4.9 Hz, 1
H), 7.32-7.36 (m, 2 H), 7.38 (d, J = 4.9 Hz, 1 H), 7.50-7.53 (m,
1 H); 13C nmr (deuteriochloroform): δ 51.1, 52.2, 87.1, 118.6,
119.7, 125.1, 125.2, 127.9, 129.8, 138.7, 140.9, 145.6, 146.4,
147.1, 166.3. Anal. Calcd. for C15H11IO2S: C, 47.14; H, 2.90; S,
8.39. Found: C, 47.05; H, 2.78; S, 8.17.
Methyl 2-[1-{2-(Furan-3-yl)phenyl}-1-hydroxymethyl]
propenoate (2f). A mixture of 1c (1.72 g, 10 mmoles), methyl
acrylate (2.70 mL, 30 mmoles), DABCO (1.12 g, 10 mmoles)
and triethanolamine (0.93 mL, 8 mmoles) without solvent was
stirred at room temperature for 14 days. The reaction mixture
was diluted with water (20 mL) and extracted with dichloro-
methane (3 × 40 mL). The combined organic layers were dried
over anhydrous magnesium sulfate and the solvent was
evaporated in vacuo. The resulting mixture was chromato-
graphed on silica gel eluting with hexane/ethyl acetate (6:1) to
produce 1.57 g (61%) of 2f as an oil; ir (potassium bromide):
3437, 1722, 1631, 1506, 1439 cm-1; 1H nmr (deuterio-
chloroform): δ 2.77 (d, J = 4.3 Hz, 1 H), 3.72 (s, 3 H), 5.70 (s, 1
H), 5.83 (s, 1 H), 6.38 (s, 1 H), 6.56-6.57 (m, 1 H), 7.33-7.38
(m, 3 H), 7.47-7.52 (m, 3 H); 13C nmr (deuteriochloroform): δ
52.0, 69.3, 111.8, 124.3, 126.5, 126.9, 127.8, 128.0, 130.1,
132.2, 138.4, 140.1, 142.3, 142.8, 166.8. Anal. Calcd. for
C15H14O4: C, 69.76; H, 5.46. Found: C, 69.55; H, 5.24.
Methyl 2-[1-Hydroxy-1-{2-(pyridin-4-yl)phenyl}methyl]
propenoate (2g). A mixture of 1d (1.85 g, 10 mmoles), methyl
acrylate (2.70 mL, 30 mmoles), DABCO (1.12 g, 10 mmoles)
and triethanolamine (0.93 mL, 8 mmoles) without solvent was
stirred at room temperature for 11 days. The reaction mixture
was diluted with water (20 mL) and extracted with
dichloromethane (3 × 40 mL). The combined organic layers
were dried over anhydrous magnesium sulfate and the solvent
was evaporated in vacuo. The resulting mixture was chromato-
graphed on silica gel eluting with hexane/ethyl acetate (6:1) to
produce 2.10 g (78%) of 2g as a white solid; mp 116-117 ℃; ir
(potassium bromide): 3190, 1712, 1628, 1598, 1541, 1478,
Methyl 2-(8H-Indeno[2,1-b]thiophen-8-yl)propenoate (3d).
To a stirred solution of 2d (0.55 g, 2 mmoles) in carbon
tetrachloride (5 mL) was added 95% sulfuric acid (0.11 mL, 2
mmoles) at room temperature. After 2 hours, the mixture was
neutralized with saturated sodium bicarbonate solution and
extracted with dichloromethane (5 × 10 mL). The combined
organic layers were dried anhydrous magnesium sulfate and the
solvent was evaporated in vacuo. The resulting mixture was
chromatographed on silica gel eluting with hexane/ethyl acetate
(6:1) to produce 0.32 g (64%) of 3d as an oil; ir (potassium
1
1437, 1152, 1045 cm-1; H nmr (deuteriochloroform): δ 3.65 (s,
3 H), 3.68 (br s, 1 H), 5.61 (s, 1 H), 5.89 (s, 1 H), 6.40 (s, 1 H),
7.21-7.24 (m, 1 H), 7.35-7.52 (m, 5 H), 8.52-8.54 (m, 2 H); 13C
nmr (deuteriochloroform): δ 51.9, 68.7, 124.4, 126.1, 127.1,
128.1, 128.9, 129.6, 138.1, 138.9, 142.3, 149.0, 149.3, 166.4.
Anal. Calcd. for C16H15NO3: C, 71.36; H, 5.61; N, 5.20. Found:
C, 71.12; H, 5.39; N, 5.07.
Methyl (Z)-2-(4H-Indeno[1,2-b]thiophen-4-yl)-3-iodoprop-
enoate (3a). To a stirred solution of 2a (0.80 g, 2 mmoles) in
carbon tetrachloride (5 mL) was added 95% sulfuric acid (0.11
mL, 2 mmoles) at room temperature. After 3 hour, the mixture
was neutralized with saturated sodium bicarbonate solution and
extracted with dichloromethane (5 × 10 mL). The combined
organic layers were dried over anhydrous magnesium sulfate
and the solvent was evaporated in vacuo. The resulting mixture
was chromatographed on silica gel eluting with hexane/ethyl
acetate (6:1) to produce 0.54 g (71%) of 3a as a solid; mp: 83-84
°C; ir (potassium bromide): 1731, 1605, 1581, 1455, 1433 cm-1;
1H nmr (deuteriochloroform): δ 3.85 (s, 3 H), 4.91 (s, 1 H), 6.91
(d, J = 0.9 Hz, 1 H), 7.02 (d, J = 4.9 Hz, 1 H), 7.18-7.24 (m, 1
H), 7.32 (d, J = 4.9 Hz, 1 H), 7.34-7.39 (m, 2 H), 7.45-7.48 (m,
1 H); 13C nmr (deuteriochloroform): δ 50.7, 52.1, 85.4, 119.2,
1
bromide): 1716, 1629, 1607, 1488, 1454, 1437 cm-1; H nmr
(deuteriochloroform): δ 3.90 (s, 3 H), 5.03 (s, 1 H), 5.53 (s, 1
H), 6.19 (s, 1 H), 7.16-7.22 (m, 1 H), 7.25 (d, J = 4.9 Hz, 1 H),
7.30-7.33 (m, 1 H), 7.35 (d, J = 4.9 Hz, 1 H), 7.38-7.41 (m, 1
H), 7.51-7.54 (m, 1 H); 13C nmr (deuteriochloroform): δ 47.8,
52.3, 118.5, 119.5, 124.8, 125.2, 125.3, 127.4, 129.3, 138.9,
139.2, 146.0, 147.0, 148.3, 167.2. Anal. Calcd. for C15H12O2S: C,
70.29; H, 4.72; S, 12.51. Found: C, 70.11; H, 4.50; S, 12.39.
Methyl (Z)-2-(8H-Indeno[1,2-c]furan-8-yl)-3-iodopropen-
oate (3e). To a stirred solution of 2e (0.77 g, 2 mmoles) in
carbon tetrachloride (5 mL) was added 95% sulfuric acid (0.11
mL, 2 mmoles) at room temperature. After 4 hours, the mixture
was neutralized with saturated sodium bicarbonate solution and