Organic & Biomolecular Chemistry
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Yield of 6gj using basic conditions: 224 mg (0.70 mmol, 93%). (EI) calcd for C20H12O4 [M]+: 324.1362, found: 324.1366; IR
+
Yield of 6gj using base free conditions: 96 mg (0.30 mmol, (KBr-disc) ν 2954 (w), 1716 (m), 1512 (m), 1251 (s), 1172 (s).
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40%). Mp 202–203 °C; H NMR (300 MHz, acetone-d6) δ 9.37
(E)-Methyl-3-(5-methoxy-2-((E)-4-chlorostyryl)-phenyl)-acrylate
(s, 1H), 8.22 (d, J = 8.9, 2H), 7.84 (d, J = 2.1, 1H), 7.81 (d, J = (6dk). Following the general procedures, 6dk was obtained
8.8, 2H), 7.52 (dd, J = 8.5, 2.1, 1H), 7.42 (d, J = 16.4, 1H), 7.27 from 5k (100 mg, 0.33 mmol) and 4d (45 mg, 0.33 mmol) as a
(d, J = 16.4, 1H), 7.05 (d, J = 8.4, 1H); 13C NMR (75 MHz, yellow solid. Yield of 6dk using base free conditions: 80 mg
acetone-d6) δ 155.5 (0), 147.5 (0), 145.3 (0), 132.7 (1), 132.6 (1), (0.25 mmol, 75%). Mp 216–218 °C; 1H NMR (300 MHz, DMSO-
131.1 (0), 128.6 (1), 127.8 (1), 125.8 (1), 124.8 (1), 117.6 (1), d6) δ 8.03 (d, J = 15.8, 1H), 7.65–7.57 (m, 3H), 7.48 (d, J = 16.2,
111.0 (0); MS (EI) m/z 165 (100%), 194 (40%), 319 ([M]+, 43%); 1H), 7.42 (d, J = 8.5, 2H), 7.26 (d, J = 2.6, 1H), 7.03 (dd, J = 8.7,
HRMS (EI) calcd for C14H10NO3Br [M]+: 318.9844, found: 2.6, 1H), 6.97 (d, J = 16.1, 1H), 6.60 (d, J = 15.8, 1H), 3.82 (s,
318.9840; IR (KBr-disc) ν 3445 (s), 1588 (s), 1496 (s), 1341 (s); 3H), 3.74 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ 166.5, 159.0,
Anal. calcd for C14H10NO3Br: C, 52.5; H, 3.1; N, 4.4. Found C, 141.5, 136.0, 133.3, 131.9, 129.7, 129.2, 128.6, 128.3, 128.2,
52.4; H, 2.9; N, 4.6.
125.6, 120.2, 117.2, 111.3, 55.3, 51.5; MS (EI) m/z 59 (100%),
189 (64%), 269 (74%), 328 ([M]+, 46%); HRMS (EI) calcd for
C19H17O3Cl [M]+: 328.0866, found: 328.0877; IR (KBr-disc) ν
Analytical data for coupling products of 5k
(E)-Methyl-3-(5-methoxy-2-((E)-4-methylstyryl)-phenyl)-acry- 2949 (w), 1714 (s), 1495 (s), 1318 (m), 1171 (s); Anal. calcd for
late (6ak). Following the general procedures, 6ak was obtained C19H17ClO3: C, 69.4; H, 5.2. Found: C, 69.3; H, 5.2.
from 5k (100 mg, 0.33 mmol) and 4a (39 mg, 0.33 mmol) as a
(E)-Methyl-3-(5-methoxy-2-(E)-styrylphenyl)acrylate
(6fk).
yellow oil. Yield of 6ak using base free conditions: 45 mg Following the general procedures, 6fk was obtained from 5k
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(0.15 mmol, 45%). H NMR (300 MHz, DMSO-d6) δ 8.03 (d, J = (100 mg, 0.33 mmol) and 4f (34 mg, 0.33 mmol) as a yellow
15.8, 1H), 7.62 (d, J = 8.7, 1H), 7.49 (d, J = 8.1, 2H), 7.40 (d, J = oil. Yield of 6fk using base free conditions: 83 mg (0.28 mmol,
16.1, 1H), 7.26 (d, J = 2.6, 1H), 7.19 (d, J = 8.0, 2H), 7.03 (dd, J = 86%). 1H NMR (300 MHz, DMSO-d6) δ 8.04 (d, J = 15.8, 1H),
8.8, 2.6, 1H), 6.94 (d, J = 16.1, 1H), 6.60 (d, J = 15.8, 1H), 3.82 7.65 (d, J = 8.7, 1H), 7.61 (d, J = 7.3, 2H), 7.47 (d, J = 16.2, 1H),
(s, 3H), 3.73 (s, 3H), 2.31 (s, 3H); 13C NMR (75 MHz, DMSO-d6) 7.39 (dd, J = 7.4, 7.4, 2H), 7.33–7.25 (m, 2H), 7.05 (dd, J = 8.7,
δ 166.5, 158.7, 141.6, 137.1, 134.3, 133.0, 130.6, 130.1, 129.2, 2.6, 1H), 6.98 (d, J = 16.1, 1H), 6.61 (d, J = 15.8, 1H), 3.83 (s,
128.2, 126.4, 123.7, 120.0, 117.2, 111.2, 55.3, 51.4, 20.8; MS (EI) 3H), 3.74 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ 167.4, 159.8,
m/z 105 (100%), 234 (44%), 249 (73%), 308 ([M]+, 44%); HRMS 142.5, 137.9, 134.1, 131.6, 130.9, 129.6, 129.3, 128.6, 127.4,
(EI) calcd for C20H20O3 [M]+: 308.1412, found: 308.1421; IR 125.7, 121.0, 118.1, 112.2, 56.3, 52.4; MS (EI) m/z 294 ([M]+,
(KBr-disc) ν 2950 (w), 1719 (m), 1603 (m), 1169 (m), 752 (s).
79%), 235 (100%), 220 (38%), 191 (26%); HRMS (EI) calcd for
(E)-Methyl-3-(5-methoxy-2-((E)-3-methylstyryl)-phenyl)-acry- C19H18O3 [M]+: calcd 294.1256, found: 294.1251; IR (KBr-disc)
late (6bk). Following the general procedures, 6bk was obtained ν 2947 (w), 1710 (m), 1316 (m), 1166 (s); Anal. calcd for
from 5k (100 mg, 0.33 mmol) and 4b (39 mg, 0.33 mmol) as a C19H18O3: C, 77.5; H, 6.2. Found: C, 77.0; H, 6.2.
yellow oil. Yield of 6bk using base free conditions: 71 mg
(E)-Methyl-3-(5-methoxy-2-((E)-4-nitrostyryl)-phenyl)-acrylate
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(0.23 mmol, 70%). H NMR (300 MHz, DMSO-d6) δ 8.69 (d, J = (6gk). Following the general procedures, 6gk was obtained
15.8, 1H), 8.12 (d, J = 8.7, 1H), 7.92–7.78 (m, 4H), 7.67 (d, J = from 5k (100 mg, 0.33 mmol) and 4g (49 mg, 0.33 mmol) as a
7.7, 1H), 7.62 (d, J = 2.6, 1H), 7.53 (dd, J = 8.7, 2.6, 1H), 7.44 (d, yellow solid. Yield of 6gk using base free conditions: 91 mg
J = 16.0, 1H), 6.95 (d, J = 16.0, 1H), 4.41 (s, 3H), 4.40 (s, 3H), (0.27 mmol, 83%). Mp 142–145 °C; 1H NMR (300 MHz,
2.97 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ 167.4, 159.7, DMSO-d6) δ 8.23 (d, J = 8.9, 2H), 8.09 (d, J = 15.8, 1H), 7.89 (d,
142.5, 138.7, 137.9, 134.0, 131.8, 131.0, 129.5, 129.3, 127.9, J = 8.9, 2H), 7.76 (d, J = 16.2, 2H), 7.73 (d, J = 8.8, 1H), 7.30 (d,
125.5, 124.6, 120.9, 118.1, 112.2, 56.3, 52.4, 21.9; MS (EI) m/z J = 2.6, 1H), 7.17 (d, J = 16.1, 1H), 7.08 (dd, J = 8.8, 2.6, 1H),
234 (44%), 249 (100%), 308 ([M]+, 71%); HRMS (EI) calcd for 6.63 (d, J = 15.8, 1H), 3.85 (s, 3H), 3.75 (s, 3H); 13C NMR
C20H20O3 [M]+: 308.1412, found: 308.1425. IR (KBr-disc) ν 2947 (75 MHz, DMSO-d6) δ 166.4, 159.6, 146.2, 144.0, 141.3, 134.1,
(w), 1712 (m), 1493 (m), 1166 (s); Anal. calcd for C20H20O3: C, 129.5, 129.1, 128.6, 128.2, 127.4, 124.0, 120.8, 117.2, 111.5,
77.9; H, 6.5. Found: C, 77.4; H, 6.6.
55.5, 51.6; MS (EI) m/z 59 (100%), 189 (79%), 280 (87%), 339
(E)-Methyl-3-(5-methoxy-2-((E)-4-methoxystyryl)-phenyl)-acry- ([M]+, 36%); HRMS (EI) calcd for C19H17O5N [M]+: 339.1107,
late (6ck). Following the general procedures, 6ck was obtained found; 339.1114; IR (KBr-disc) ν 2953 (w), 1716 (m), 1515 (m),
from 5k (100 mg, 0.33 mmol) and 4c (44 mg, 0.33 mmol) as a 1339 (s); Anal. calcd for C19H17O5N: C, 67.2; H, 5.1; N, 4.1.
yellow oil. Yield of 6ck using base free conditions: 15 mg Found C, 66.8; H, 5.3; N, 4.0.
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(0.05 mmol, 14%). H NMR (300 MHz, DMSO-d6) δ 8.13 (d, J =
15.8, 1H), 7.55 (d, J = 8.7, 1H), 7.47 (d, J = 8.6, 2H), 7.24 (d, J =
16.0, 1H), 7.05 (d, J = 2.6, 1H), 6.97 (dd, J = 8.6, 2.7, 1H), 6.93
General procedure and analytical data for Suzuki coupling
products of phenol diazonium salts
(d, J = 8.7, 1H), 6.86 (d, J = 16.0, 1H), 6.38 (d, J = 15.8, 1H), 3.86 To a solution of the corresponding phenol diazonium salt 5
(s, 3H), 3.85 (s, 3H), 3.84 (s, 3H); 13C NMR (75 MHz, DMSO-d6) (0.5 mmol) in methanol (5.0 mL) was added Pd(OAc)2 (3 mg,
δ 167.2, 159.5, 158.9, 142.4, 133.7, 130.9, 130.5, 130.3, 128.1, 2.5 mol%) and organotrifluoroborate 13 (101 mg, 0.5 mmol).
127.8, 122.9, 119.9, 116.7, 114.2, 111.4, 55.4, 55.3, 51.7; MS (EI) The suspension was stirred for 12 h at ambient temperature.
m/z 324 ([M]+, 11%), 262 (22%), 231 (27%), 49 (100%); HRMS After this time, activated charcoal was added to absorb the
This journal is © The Royal Society of Chemistry 2013
Org. Biomol. Chem., 2013, 11, 3674–3691 | 3689