PAPER
New Synthesis of Dibenzoxocine Derivatives
381
Methyl 3-Hydroxy-2-methylene-3-[(2-phenoxy)phenyl]pro-
panoate (4a)
Reaction time: 24 h; yield: 90%; yellow oil.
Methyl 3-Hydroxy-3-[5-methoxy-2-(p-tolyloxy)phenyl]-2-meth-
ylenepropanoate (4e)
Reaction time: 46 h; yield: 81%; yellow oil.
IR (CH2Cl2): 3438, 1721, 1630, 1583, 1485 cm–1.
IR (CH2Cl2): 3437, 1721, 1612, 1490 cm–1.
1H NMR (CDCl3): d = 3.38 (d, J = 5.8 Hz, 1 H, OH), 3.72 (s, 3 H,
OCH3), 5.78 (s, 1 H, CH), 5.94 (d, J = 5.8 Hz, 1 H, CH), 6.32 (s, 1
H, CH), 6.82–6.85 (m, 1 Harom), 6.95–6.98 (m, 2 Harom), 7.07–7.35
(m, 5 Harom), 7.50–7.54 (m, 1 Harom).
1H NMR (CDCl3): d = 2.31 (s, 3 H, CH3), 3.32 (d, J = 5.8 Hz, 1 H,
OH), 3.73 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3), 5.75 (s, 1 H, CH),
5.85 (d, J = 5.5 Hz, 1 H, CH), 6.31 (s, 1 H, CH), 6.76–6.83 (m, 4
Harom), 7.05–7.10 (m, 3 Harom).
13C NMR (CDCl3): d = 51.9, 68.0, 118.4, 118.6, 123.3, 123.6,
126.3, 128.0, 129.0, 129.7, 131.9, 141.0, 154.2, 156.9, 166.9.
13C NMR (CDCl3): d = 20.6, 52.0, 55.6, 68.0, 112.7, 114.5, 117.5,
120.4, 126.5, 130.1, 132.1, 133.3, 140.8, 147.6, 155.7, 155.8, 166.9.
EIMS: m/z (%) 284 (1, [M+]), 283 (3), 267 (15), 252 (15), 223 (58),
EIMS: m/z (%) 328 (32, [M+]), 296 (17), 267 (14), 225 (46), 221
205 (23), 197 (56), 191 (48), 181 (100), 121 (37).
(100), 151 (41).
Anal. Calcd for C17H16O4: C, 71.82; H, 5.67. Found: C, 71.56; H,
5.40.
Anal. Calcd for C19H20O5: C, 69.50; H, 6.14. Found: C, 69.28; H,
6.05.
Methyl 3-Hydroxy-2-methylene-3-[2-(p-tolyloxy)phenyl]pro-
panoate (4b)
Reaction time: 48 h; yield: 92%; yellow oil.
Methyl 3-[2-(4-Chlorophenoxy)-5-methoxyphenyl]-3-hydroxy-
2-methylenepropanoate (4f)
Reaction time: 48 h; yield: 83%; yellow oil.
IR (CH2Cl2): 3444, 1722, 1630, 1506, 1485 cm–1.
IR (CH2Cl2): 3461, 1720, 1634, 1483 cm–1.
1H NMR (CDCl3): d = 2.33 (s, 3 H, CH3), 3.39 (d, J = 6.1 Hz, 1 H,
OH), 3.73 (s, 1 H, OCH3), 5.79 (s, 1 H, CH), 5.95 (d, J = 5.5 Hz, 1
H, CH), 6.33 (s, 1 H, CH), 6.78–6.89 (m, 3 Harom), 7.06–7.24 (m, 4
1H NMR (CDCl3): d = 3.23 (d, J = 5.5 Hz, 1 H, OH), 3.73 (s, 3 H,
OCH3), 3.81 (s, 3 H, OCH3), 5.73 (s, 1 H, CH), 5.80 (d, J = 5.5 Hz,
1 H, CH), 6.30 (s, 1 H, CH), 6.79–6.86 (m, 4 Harom), 7.07–7.08 (m,
1 Harom), 7.21–7.25 (m, 2 Harom).
Harom), 7.48–7.52 (m, 1 Harom).
13C NMR (CDCl3): d = 20.7, 51.9, 68.2, 117.8, 118.9, 123.2, 126.3,
128.0, 128.9, 130.2, 131.5, 133.0, 141.1, 154.4, 154.8, 167.0.
13C NMR (CDCl3): d = 52.0, 55.6, 67.8, 112.9, 114.7, 118.5, 121.0,
126.7, 127.5, 129.6, 133.8, 140.8, 146.6, 156.4, 156.7, 166.9.
EIMS: m/z (%) = 298 (1, [M+]), 297 (2), 281 (8), 266 (13), 238 (15),
EIMS: m/z (%) = 350 (10), 348 (29, [M+]), 318 (8), 316 (21), 289
221 (19), 211 (40), 195 (100), 177 (13), 121 (66)
(7), 287 (14), 247 (13), 245 (35), 221 (100), 189 (34), 151 (39).
Anal. Calcd for C18H18O4: C, 72.47; H, 6.08. Found: C, 72.36; H,
6.27.
Anal. Calcd for C18H17ClO5: C, 61.99; H, 4.91. Found: C, 60.77; H,
4.83.
Methyl 3-[2-(4-Chlorophenoxy)phenyl]-3-hydroxy-2-methyl-
enepropanoate (4c)
Reaction time: 63 h; yield: 75%; yellow oil.
Methyl 3-[(5-Chloro-2-phenoxy)phenyl]-3-hydroxy-2-methyl-
enepropanoate (4g)
Reaction time: 48 h; yield: 83%; reddish oil.
IR (CH2Cl2): 3415, 1719, 1630, 1582, 1483 cm–1.
IR (CH2Cl2): 3438, 1720, 1630, 1588, 1476 cm–1.
1H NMR (CDCl3): d = 3.27 (d, J = 5.8 Hz, 1 H, OH), 3.73 (s, 3 H,
OCH3), 5.76 (s, 1 H, CH), 5.91 (d, J = 5.8 Hz, 1 H, CH), 6.32 (s, 1
H, CH), 6.74–6.92 (m, 3 Harom), 7.16–7.29 (m, 4 Harom), 7.52–7.55
(m, 1 Harom).
1H NMR (CDCl3): d = 3.35 (d, J = 5.8 Hz, 1 H, OH), 3.75 (s, 3 H,
OCH3), 5.77 (s, 1 H, CH), 5.90 (d, J = 5.5 Hz, 1 H, CH), 6.34 (s, 1
H, CH), 6.75–6.77 (m, 1 Harom), 6.93–6.96 (m, 2 Harom), 7.09–7.21
(m, 2 Harom), 7.31–7.37 (m, 2 Harom), 7.52–7.53 (m, 1 Harom).
13C NMR (CDCl3): d = 52.0, 67.9, 118.6, 119.8, 124.1, 126.5,
128.1, 129.2, 129.4, 129.7, 132.0, 140.9, 153.9, 155.6, 166.9.
13C NMR (CDCl3): d = 52.1, 67.7, 118.7, 119.5, 123.7, 126.8,
128.0, 128.7, 128.9, 129.9, 133.6, 140.5, 152.8, 156.5, 166.8.
EIMS: m/z (%) = 318 (2, [M+]), 317 (6), 301 (5), 286 (17), 257 (35),
215 (100), 205 (42), 191 (59), 121 (78).
EIMS: m/z (%) = 318 (1, [M+]), 317 (3), 286 (15), 285 (10), 259
(14), 258 (12), 257 (31), 227 (32), 226 (13), 225 (100), 223 (57),
217 (31), 215 (92), 205 (27), 157 (21), 155 (61).
Anal. Calcd for C17H15ClO4: C, 64.06; H, 4.74. Found: C, 63.85; H,
4.59.
Anal. Calcd for C17H15ClO4: C, 64.06; H, 4.74. Found: C, 64.18; H,
4.51.
Methyl 3-Hydroxy-3-[(5-methoxy-2-phenoxy)phenyl]-2-meth-
ylenepropanoate (4d)
Reaction time: 48 h; yield: 78%; yellow oil.
Methyl 3-[(5-Fluoro-2-phenoxy)phenyl]-3-hydroxy-2-methyl-
enepropanoate (4h)
Reaction time: 9 h; yield: 82%; yellow oil.
IR (CH2Cl2): 3449, 1720, 1631, 1589, 1484 cm–1.
IR (CH2Cl2): 3437, 1721, 1631, 1589, 1486 cm–1.
1H NMR (CDCl3): d = 3.31 (d, J = 5.8 Hz, 1 H, OH), 3.72 (s, 3 H,
OCH3), 3.81 (s, 3 H, OCH3), 5.75 (s, 1 H, CH), 5.84 (d, J = 5.5 Hz,
1 H, CH), 6.31 (s, 1 H, CH), 6.79–6.98 (m, 4 Harom), 7.01–7.08 (m,
2 Harom), 7.26–7.32 (m, 2 Harom).
13C NMR (CDCl3): d = 52.0, 55.6, 67.9, 112.8, 114.5, 117.3, 120.9,
122.6, 126.6, 129.6, 133.6, 140.8, 147.0, 156.1, 158.0, 166.9.
1H NMR (CDCl3): d = 3.36 (d, J = 5.8 Hz, 1 H, OH), 3.74 (s, 3 H,
OCH3), 5.75 (s, 1 H, CH), 5.86 (d, J = 5.8 Hz, 1 H, CH), 6.32 (s, 1
H, CH), 6.80–6.85 (m, 1 Harom), 6.89–6.97 (m, 3 Harom), 7.06–7.11
(m, 1 Harom), 7.25–7.35 (m, 3 Harom).
13C NMR (CDCl3): d = 52.0, 67.7, 114.8 (d, J = 24.5 Hz), 115.6 (d,
J = 23.7 Hz), 118.0, 120.3 (d, J = 8.3 Hz), 123.3, 126.8, 129.8,
134.3 (d, J = 7.1 Hz), 140.5, 149.7 (d, J = 2.6 Hz), 157.3, 158.9 (d,
J = 242.7 Hz), 166.8.
EIMS: m/z (%) = 314 (24, [M+]), 282 (22), 253 (18), 227 (18), 221
(100), 211 (45), 189 (16), 151 (30).
Anal. Calcd for C18H18O5: C, 68.78; H, 5.77. Found: C, 68.48; H,
5.62.
EIMS: m/z (%) = 302 (2, [M+]), 301 (2), 285 (13), 270 (17), 241
(56), 226 (21), 215 (40), 209 (64), 199 (100), 139 (37).
Synthesis 2011, No. 3, 377–386 © Thieme Stuttgart · New York