Bernd Schmidt et al.
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8.8 Hz, 2H), 6.30 (d, J=16.0 Hz, 1H), 3.82 (s, 3H), 3.78 (s,
3H); 13C NMR (75 MHz, CDCl3): d=167.6 (0), 161.3 (0),
144.4 (1), 129.6 (1), 127.1 (0), 115.2 (1), 114.3 (1), 55.3 (3),
270.9970; anal. calcd. for C11H11O3Br: C 48.7, H 4.1; found:
C 48.6, H 3.9.
(E)-Methyl 3-(3-bromo-4-hydroxyphenyl)acrylate (4i):
Product 4i was obtained as a colourless solid; yield: 102 mg
(0.40 mmol, 80%); mp 109–1148C. 1H NMR (300 MHz,
CDCl3): d=7.63 (d, J=2.0 Hz, 1H), 7.54 (d, J=16.0 Hz,
1H), 7.38 (dd, J=8.5, 2.0 Hz, 1H), 7.00 (d, J=8.5 Hz, 1H),
6.28 (d, J=16.0 Hz, 1H), 5.86 (s, 1H), 3.78 (s, 3H);
13C NMR (75 MHz, CDCl3): d=167.6, 154.2, 143.2, 132.0,
˜
51.5 (3); IR (KBr disc): n=2949 (m), 1716 (s), 1637 (s),
1601 (s), 1511 (s), 1432 (s), 1329 (s), 1301 (s), 1287 (s),
1255 cmÀ1 (s); MS (ESI): m/z=193 ([M+H]+, 44), 161
(100), 147 (25); HR-MS (ESI): m/z=193.0870, calcd. for
C11H13O3 [M+H]+: 193.0865; anal. calcd. for C11H12O3: C
68.7, H 6.3; found: C 68.6, H 6.3.
(E)-Methyl 3-[4-(benzyloxy)pheny])acrylate (4b): Product
4b was obtained under base-free conditions as a colourless
solid; yield: 71 mg (52%); mp 134–1368C (reported in the
literature:[61] 1368C). 1H NMR (300 MHz, CDCl3): d=7.65
(d, J=16.0 Hz, 1H), 7.47 (d, J=8.7 Hz, 2H), 7.45–7.30
(5H), 6.98 (d, J=8.8 Hz, 2H), 6.32 (d, J=16.0 Hz, 1H), 5.10
(s, 2H), 3.80 (s, 3H); 13C NMR (75 MHz, CDCl3): d=167.7
(0), 160.5 (0), 144.4 (1), 136.5 (0), 129.7 (1), 128.6 (1), 128.1
(1), 127.4 (1), 127.4 (0), 115.4 (1), 115.2 (1), 70.1 (2), 51.5
˜
129.3, 128.9, 117.0, 116.7, 111.0, 51.9; IR (KBr): n=3312
(m), 1688 (s), 1631 (s), 1600 (s), 1430 cmÀ1 (s); MS (ESI):
m/z=257 ([M+H]+, 16), 225 (100), 146 (41); HR-MS
(ESI); m/z=256.9813, calcd. for C10H10O3Br [M+H]+:
256.9807; anal. calcd. for C10H9O3Br: C 46.7, H 3.5; found:
C 46.6, H 3.4.
(E)-2-Methoxy-5-(3-methoxy-3-oxoprop-1-enyl)benzoic
acid (4j): Product. 4j was obtained from 1l under base-free
conditions with concomitant ester hydrolysis as a colourless
solid; yield: 56 mg (0.24 mmol, 48%); mp 139–1428C.
1H NMR (300 MHz, CDCl3): d=8.34 (d, J=2.3 Hz, 1H),
7.72 (dd, J=8.6, 2.3 Hz, 1H), 7.65 (d, J=16.1 Hz, 1H), 7.10
(d, J=8.7 Hz, 1H), 6.43 (d, J=16.0 Hz, 1H), 4.11 (s, 3H),
3.82 (s, 3H); 13C NMR (75 MHz, CDCl3): d=167.1, 159.3,
˜
(3); IR (KBr disc): n=2948 (w), 1717 (s), 1634 (m), 1602
(m), 1510 (s), 1285 (s), 1250 (m), 1203 (m), 1170 cmÀ1 (s);
MS (EI): m/z=268 ([M]+, 48), 218 (54), 91 (100); HR-MS
(EI): m/z=268.1092, calcd. for C17H16O3 [M]+: 268.1099;
anal. calcd. for C17H16O3: C 76.1, H 6.0; found: C 76.0, H
5.8.
142.6, 134.3, 133.2, 128.5, 118.0, 112.3, 56.9, 51.7; IR (neat):
À1
˜
n=2952 (w), 1712 (s), 1606 (m), 1264 cm (s); MS (ESI):
(E)-Methyl 3-(4-hydroxyphenyl)acrylate (4c): Product 4c
was obtained in either methanol or acetonitrile under basic
conditions as a colourless solid; yield: 89 mg (99%); mp
134–1368C (reported in the literature:[62] 135–1378C).
1H NMR (300 MHz, CDCl3): d=7.64 (d, J=16.0 Hz, 1H),
7.42 (d, J=8.5 Hz, 2H), 6.86 (d, J=8.6 Hz, 2H), 6.30 (d, J=
16.0 Hz, 1H), 6.06 (s, 1H), 3.81 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=168.2 (0), 158.0 (0), 144.9 (1), 130.0 (1), 127.0
m/z=237 ([M+H]+, 30); 219 (100); HR-MS (ESI): m/z=
237.0751, calcd. for C12H13O5 [M+H]+: 237.0763.
(E)-2-Hydroxy-5-(3-methoxy-3-oxoprop-1-enyl)benzoic
acid (4k): Product 4k was obtained under base-free condi-
tions as a colourless solid; yield: 60 mg (0.27 mmol, 54%);
1
mp 213–2148C. H NMR (300 MHz, DMSO-d6): d=8.06 (s,
1H), 7.93 (d, J=8.7 Hz, 1H), 7.64 (d, J=16.0 Hz, 1H), 7.00
(d, J=8.7 Hz, 1H), 6.51 (d, J=16.0 Hz, 1H), 3.71 (s, 3H);
13C NMR (75 MHz, DMSO-d6): d=171.4 (0), 166.7 (0),
162.6 (0), 143.5 (1), 134.5 (1), 131.3 (1), 125.4 (1), 117.9 (1),
˜
(0), 115.9 (1), 115.0 (1), 51.7 (3); IR (neat): n=3472 (s),
1687 (s), 1432 (s), 1176 (s), 984 cmÀ1 (s); MS (ESI): m/z=
179 ([M+H]+, 100), 147 (28), 116 (30); HR-MS (ESI):
m/z=179.0724, calcd. for C10H11O3 [M+H]+: 179.0708; anal.
calcd. for C10H10O3: C 67.4, H 5.7; found: C 67.4, H 5.5.
(E)-Methyl 3-(4-hydroxy-3-nitrophenyl)acrylate (4e):
Product 4e was obtained as a colourless solid; yield: 89 mg
(0.40 mmol, 80%); mp 1448C (reported in the literature:[63]
˜
116.0 (1), 113.5 (0), 51.3 (3); IR (KBr disc): n=2966 (m),
2855 (m), 1631 (s), 1594 (s), 1491 (s), 1432 (s), 1369 (m),
1339 (s), 1301 (s), 1263 (s), 1204 cmÀ1 (s); MS (ESI): m/z=
223 ([M+H]+, 90); 205 (100); HR-MS (ESI): m/z=
223.0622, calcd. for C11H11O5 [M+H]+: 223.0606; anal.
calcd. for C11H10O5: C 59.5, H 4.5; found: C 59.2, H 4.4.
(E)-Methyl 2-methoxy-5-(3-methoxy-3-oxoprop-1-enyl)-
benzoate (4l): Product 4l was obtained in acetonitrile as a
colourless solid; yield: 65 mg (0.26 mmol, 52%); mp 87–
898C. 1H NMR (300 MHz, CDCl3): d=7.90 (d, J=2.3 Hz,
1H), 7.56 (d, J=16.0 Hz, 1H), 7.55 (dd, J=8.5, 2.1 Hz, 1H),
6.92 (d, J=8.8 Hz, 1H), 6.29 (d, J=16.0 Hz, 1H), 3.86 (s,
3H), 3.84 (s, 3H), 3.72 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=167.1, 165.7, 160.3, 143.1, 132.9, 131.3, 126.4, 120.3, 116.5,
1
142–1488C). H NMR (300 MHz, CDCl3): d=10.70 (s, 1H),
8.23 (d, J=2.2 Hz, 1H), 7.75 (dd, J=8.8, 2.2 Hz, 1H), 7.61
(d, J=16.0 Hz, 1H), 7.19 (d, J=8.8 Hz, 1H), 6.39 (d, J=
16.0 Hz, 1H), 3.80 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
167.0, 156.3, 141.8, 136.1, 133.9, 127.5, 125.1, 121.0, 119.0,
˜
52.1; IR (KBr disc): n=3262 (m), 2924 (m), 1724 (s), 1620
(s), 1533 cmÀ1 (s); MS (ESI): m/z=223 ([M]+, 85), 192
(100), 146 (28); HR-MS (ESI): m/z=223.0491, calcd. for
C10H9NO5 [M]+: 223.0481; anal. calcd. for C10H9NO5: C 53.8,
H 4.1, N 6.3; found: C 54.2, H 4.2, N, 6.2.
˜
112.2, 56.0, 52.0, 51.4; IR (neat): n=2950 (w), 1704 (s), 1605
(m), 1434 (m), 1260 (s), 1166 cmÀ1 (s); MS (ESI): m/z=251
([M+H]+, 47); 219 (100); HR-MS (ESI): m/z=251.0899,
calcd. for C13H15O5 [M+H]+: 251.0919; anal. calcd. for
C13H14O5: C 62.4, H 5.6; found: C 62.3, H 5.5.
(E)-Methyl 3-(3-bromo-4-methoxyphenyl)acrylate (4h):
Product 4h was obtained as a colourless solid; yield: 27 mg
(0.10 mmol, 19%); mp 115–1168C. 1H NMR (300 MHz,
CDCl3): d=7.72 (d, J=2.1 Hz, 1H), 7.55 (d, J=16.0 Hz,
1H), 7.41 (dd, J=8.5, 2.1 Hz, 1H), 6.87 (d, J=8.6 Hz, 1H),
6.29 (d, J=16.0 Hz, 1H), 3.90 (s, 3H), 3.77 (s, 3H);
13C NMR (75 MHz, CDCl3): d=167.5, 157.6, 143.2, 132.8,
(E)-Methyl
2-hydroxy-5-(3-methoxy-3-oxoprop-1-enyl)-
benzoate (4m): Product 4m was obtained under base-free
conditions as a colourless solid; yield: 118 mg (0.5 mmol,
99%); mp 94–968C (reported in the literature:[64] 92–948C).
1H NMR (300 MHz, CDCl3): d=10.94 (s, 1H), 7.94 (d, J=
2.0 Hz, 1H), 7.59 (dd, J=8.6, 2.2 Hz, 1H), 7.57 (d, J=
16.0 Hz, 1H), 6.95 (d, J=8.7 Hz, 1H), 6.29 (d, J=16.0 Hz,
1H), 3.94 (s, 3H), 3.77 (s, 3H); 13C NMR (75 MHz, CDCl3):
129.1, 128.7, 116.9, 112.5, 112.0, 56.6, 51.9. IR (KBr disc):
À1
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n=3438 (m), 1704 (s), 1633 (s), 1497 (s), 1265 cm (s); MS
(ESI): m/z=271 ([M+H]+, 15), 239 (100), 160 (68); HR-MS
(ESI): m/z=270.9984, calcd. for C11H12O3Br [M+H]+:
2470
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 2463 – 2473