10.1002/ejoc.201900584
European Journal of Organic Chemistry
ARTICLE
35.97 (C5); IR: 3058, 2836, 1637, 1565, 1492, 1312, 1300, 1216, 1175,
1093, 798; ESI-MS: 208.0 (100%) [M+H]+, 209.9 (32.8%) [M+H]+; HRMS
(APCI): m/z = 208.0525 ([M+H]+, calc. 208.0524).
(m, 2H, H6), 2.97 (d, J = 4.8 Hz, 3H, CH3), 2.68–2.62 (m, 2H, H5); 13C-
NMR, HSQC, HMBC (101 MHz, Chloroform-d) δ 192.11 (C4), 167.15 (CO),
148.55 (C2), 147.22 (C1‘), 129.96 (C4‘), 128.73 (C3‘, C5‘), 117.26 (C2‘,
C6‘), 103.44 (C3), 47.26 (C6), 35.99 (C5), 26.95 (CH3); IR: 1636, 1563,
1504, 1409, 1304, 1277, 1218, 1178, 767, 728; ESI-MS: 231.2 (100%)
[M+H]+, 253.2 (47.5%) [M+Na]+, 483.1 (19.9%) [M+Na]+; HRMS (ESI): m/z
= 231.1130 ([M+H] +, calc. 231.1128).
1-(4-bromophenyl)-2,3-dihydropyridin-4(1H)-one (2f): Yield: 24.8 mg,
33%, yellow solid; Rf = 0.17 (cHex/EtOAc = 2:3); mp: 122.6–124.5 °C; 1H-
NMR, COSY (400 MHz, Chloroform-d) δ 7.50–7.46 (m, 2H, H3‘, H5‘), 7.38
(d, J = 7.8 Hz, 1H, H2), 7.00–6.94 (m, 2H, H2‘, H6‘), 5.24 (d, J = 7.8 Hz,
1H, H3), 3.97 (dd, J = 8.0, 7.1 Hz, 2H, H6), 2.66 (dd, J = 8.0, 7.1 Hz, 2H,
H5); 13C-NMR, HSQC, HMBC (101 MHz, Chloroform-d) δ 191.93 (C4),
149.02 (C2), 144.30 (C1‘), 132.72 (C3‘, C5‘), 119.77 (C2‘, C6‘), 117.22
(C4‘), 102.93 (C3), 47.66 (C6), 36.02 (C5); IR: 1644, 1596, 1567, 1491,
1311, 1266, 1217, 1177, 821, 800; ESI-MS: 252.2 (99.5%), 254.0 (100%)
[M+H]+, 274.0 (9.2%), 276.0 (8.6%) [M+Na]+; HRMS (APCI): m/z =
252.0019 ([M+H] +, calc. 252.0019).
1-(m-tolyl)-2,3-dihydropyridin-4(1H)-one (2k): Yield: 34.3 mg, 0.183
mmol, 62%, yellow oil; Rf = 0.25 (cHex/EtOAc = 2:3); 1H-NMR, COSY (400
MHz, Chloroform-d) δ 7.43 (d, J = 7.8 Hz, 1H, H2), 7.25 (td, J = 7.6, 0.7
Hz, 1H, H5’), 6.94–6.98 (m, 1H, H6’), 6.92–6.87 (m, 2H, H2’, H4’), 5.20 (d,
J = 7.8 Hz, 1H, H3), 4.03–3.94 (m, 2H, H6), 2.68–2.59 (m, 2H, H5), 2.37
(s, 3H, CH3); 13C-NMR, HSQC, HMBC (101 MHz, Chloroform-d) δ 192.11
(C4), 149.86 (C2), 145.23 (C1’), 139.79 (C3’), 129.53 (C5’), 125.31 (C6’),
119.07 (C4’), 115.42 (C2’), 101.89 (C3), 47.70 (C6), 36.03 (C5), 21.65
(CH3); IR: 1647, 1572, 1494, 1467, 1309, 1274, 1228, 1184, 778, 696; ESI-
MS: 188.1 (100%) [M+H]+, 210.0.1 (8.4%) [M+Na]+, 397.1 (8.6%)
[2M+Na]+; HRMS (APCI): m/z = 188.1071 ([M+H] +, calc. 188.1070).
1-(4-iodophenyl)-2,3-dihydropyridin-4(1H)-one (2g): Yield: 20.0 mg,
0.0669 mmol, 22%, orange solid; Rf = 0.19 (cHex/EtOAc = 2:3); mp: 158.5–
1
161.6 °C; H-NMR, COSY (400 MHz, Chloroform-d) δ 7.70–7.64 (m, 2H,
H3‘, H5‘), 7.38 (d, J = 7.8 Hz, 1H, H2), 6.88–6.83 (m, 2H, H2‘, H6‘), 5.25
(d, J = 7.8 Hz, 1H, H3), 3.97 (dd, J = 8.0, 7.1 Hz, 2H, H6), 2.66 (dd, J =
8.0, 7.1 Hz, 2H, H5); 13C-NMR, HSQC, HMBC (101 MHz, Chloroform-d) δ
191.94 (C4), 148.84 (C2), 144.97 (C1‘), 138.67 (C3‘, C5‘), 120.05 (C2‘,
C6‘), 103.10 (C3), 87.57 (C4‘), 47.55 (C6), 36.04 (C5); IR: 1649, 1594,
1572, 1488, 1312, 1299, 1264, 1247, 1218, 1177, 817; ESI-MS: 300.0
(100%) [M+H]+, 322.0 (9.9%) [M+Na]+; HRMS (APCI): m/z = 299.9878
([M+H] +, calc. 299.9880).
1-(3-methoxyphenyl)-2,3-dihydropyridin-4(1H)-one (2l): Yield: 39.8 mg,
0.196 mmol, 65%, orange solid; Rf = 0.18 (cHex/EtOAc = 2:3); mp: 67.3–
68.8 °C; 1H-NMR, COSY (400 MHz, Chloroform-d) δ 7.43 (d, J = 7.8 Hz,
1H, H2), 7.27 (t, J = 8.2 Hz, 1H, H5‘), 6.69–6.65 (m, 2H, H4‘, H6‘), 6.60 (t,
J = 2.3 Hz, 1H, H2‘), 5.21 (d, J = 7.8 Hz, 1H, H3), 3.97 (dd, J = 8.1, 7.1 Hz,
2H, H6), 3.81 (s, 3H, CH3), 2.64 (dd, J = 8.1, 7.1 Hz, 2H, H5); 13C-NMR,
HSQC, HMBC (101 MHz, Chloroform-d) δ 192.20 (C4), 160.71 (C3‘),
149.66 (C2), 146.43 (C1‘), 130.53 (C5), 110.56, 109.37 (C4‘, C6‘), 104.76
(C2‘), 102.15 (C3), 55.52 (CH3), 47.62 (C6), 35.99 (C5); IR: 1646, 1572,
1497, 1310, 1280, 1251, 1237, 1202, 1173, 1051; ESI-MS: 204.1 (100%)
[M+H]+, 226.1 (21.3%) [M+Na]+, 429.3 (20.1%) [2M+Na]+. The analytical
data are consistent with those reported in the literature.[10o]
1-(4-(trifluoromethyl)phenyl)-2,3-dihydropyridin-4(1H)-one (2h): Yield:
20.7 mg, 0.0858 mmol, 29%, yellow solid; Rf = 0.19 (cHex/EtOAc = 2:3);
mp: 119.2–121.8 °C; 1H-NMR, COSY (400 MHz, Chloroform-d) δ 7.66–
7.62 (m, 2H, H3’, H5’), 7.47 (d, J = 7.8 Hz, 1H, H2), 7.19–7.16 (m, 2H, H2’,
H6’), 5.32 (d, J = 7.8 Hz, 1H, H3), 4.07–4.01 (m, 2H, H6), 2.74–2.67 (m,
2H, H5); 13C-NMR, HSQC, HMBC (101 MHz, Chloroform-d) δ 192.04 (C4),
148.27 (C2), 147.72 (C1’), 127.10 (q, J = 3.7 Hz, C3’, C5’), 125.97 (q, J =
33.1 Hz, C4’)*, 124.07 (q, J = 271.5 Hz, CF3)*, 117.54 (C2’, C6’), 104.08
(C3), 47.35 (C6), 36.08 (C5); *Outer quartet signals can hardly be seen
due to their low intensity; IR: 1642, 1563, 1519, 1313, 1283, 1219, 1196,
1173, 1103, 1068; ESI-MS: 242.1 (100%) [M+H]+, 264.0 (5.6%) [M+Na]+;
HRMS (APCI): m/z = 242.0793 ([M+H] +, calc. 242.0787).
methyl 3-(4-oxo-3,4-dihydropyridin-1(2H)-yl)benzoate (2m): Yield:
1
26.3 mg, 0.114 mmol, 38%, yellow oil; Rf = 0.14 (cHex/EtOAc = 2:3); H-
NMR, COSY (400 MHz, Chloroform-d) δ 7.79 (dt, J = 8.0, 1.2 Hz, 1H, H4’),
7.75 (dd, J = 2.6, 1.2 Hz, 1H, H2’), 7.46 (d, J = 7.8, 1H, H2), 7.45 (t, J =
8.0, 1H, H5’), 7.28 (ddd, J = 8.0, 2.6, 1.2 Hz, 1H, H6’), 5.26 (d, J = 7.8 Hz,
1H, H3), 4.03 (dd, J = 8.1, 7.1 Hz, 2H, H6), 3.92 (s, 3H, CH3), 2.67 (dd, J
= 8.1, 7.1 Hz, 2H, H5); 13C-NMR, HSQC, HMBC (101 MHz, Chloroform-d)
δ 192.02 (C4), 166.38 (COOMe), 149.08 (C2), 145.30 (C1’), 131.75 (C3’),
129.88 (C5’), 125.22 (C4’), 122.24 (C6’), 118.93 (C2’), 103.00 (C3), 52.54
(CH3), 47.58 (C6), 36.02 (C5); IR: 1718, 1648, 1570, 1306, 1262, 1242,
1219, 1177, 1108, 755; ESI-MS: 232.1 (100%) [M+H]+, 254.1 (30.2%)
[M+Na]+, 485.1 (18.6%) [2M+Na]+; HRMS (ESI): m/z = 232.0971 ([M+H] +,
calc. 232.0968).
1-(4-nitrophenyl)-2,3-dihydropyridin-4(1H)-one (2i): Yield: 21.6 mg,
0.099 mmol, 33%, yellow solid; Rf = 0.26 (cHex/EtOAc = 1:4); mp: 125–
135 °C; 1H-NMR, COSY (400 MHz, Chloroform-d) δ 8.30–8.22 (m, 2H, H3’,
H5’), 7.52 (d, J = 8.0 Hz, 1H, H2), 7.20–7.13 (m, 2H, H2’, H6’), 5.40 (d, J
= 8.0 Hz, 1H, H3), 4.11–4.06 (m, 2H, H6), 2.76–2.69 (m, 2H, H5); 13C-
NMR, HSQC, HMBC (101 MHz, Chloroform-d) δ 191.96 (C4), 149.75 (C1’),
146.99 (C2), 143.19 (C4’), 125.86 (C3’, C5’), 116.84 (C2’, C6’), 105.71
(C3), 47.22 (C6), 36.04 (C5); IR: 1655, 1573, 1501, 1310, 1284, 1221,
1181, 1113, 854, 751; ESI-MS: 219.1 (100%) [M+H]+. The analytical data
are consistent with those reported in the literature.[25]
3-(4-oxo-3,4-dihydropyridin-1(2H)-yl)benzonitrile (2n): Yield: 23.7 mg,
0.120 mmol, 40%, yellow solid; Rf = 0.11 (cHex/EtOAc = 2:3); mp: 126.1–
1
130.0 °C; H-NMR, COSY (400 MHz, Chloroform-d) δ 7.54–7.45 (m, 1H,
H5‘), 7.42–7.38 (m, 2H, H2, H4‘), 7.36–7.30 (m, 2H, H2‘, H6‘), 5.30 (d, J =
7.9 Hz, 1H, H3), 4.05–3.97 (m, 2H, H6), 2.72–2.66 (m, 2H, H5); 13C-NMR,
HSQC, HMBC (101 MHz, Chloroform-d) δ 191.82 (C4), 148.06 (C2),
145.70 (C1‘), 130.76 (C5‘), 127.34 (C4‘), 122.01 (C6‘), 120.91 (C2‘),
118.16 (CN), 113.89 (C3‘), 104.21 (C3), 47.38 (C6), 35.99 (C5); IR: 2230,
1647, 1570, 1490, 1464, 1311, 1277, 1225, 1178, 1112, 796; ESI-MS:
N-methyl-4-(4-oxo-3,4-dihydropyridin-1(2H)-yl)benzamide (2j): Yield:
34.6 mg, 0.150 mmol, 50%, yellow solid; Rf = 0.19 (EtOAc/MeOH = 10:1);
mp: 177.4–178.8 °C; 1H-NMR, COSY (400 MHz, Chloroform-d) δ 7.85–
7.79 (m, 2H, H3‘, H5‘), 7.46 (d, J = 7.8 Hz, 1H, H2), 7.12–7.07 (m, 2H, H2‘,
H6‘), 6.58 (q, J = 4.8 Hz, 1H, NH), 5.25 (d, J = 7.8 Hz, 1H, H3), 4.03–3.98
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