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3H), 4.66 (s, 1H), 5.29 (s, 2H, –NH2), 6.37–6.40 (m, 2H), 6.99 (d, 3.72–3.79 (m, 2H), 3.91–3.94 (m, 2H), 4.87 (s, 1H), 5.50 (s, 2H,
J ¼ 8.5 Hz, 1H), 7.07–7.11 (m, 2H), 7.29 (d, J ¼ 7.5 Hz, 1H), 7.35 –NH2), 7.11 (d, J ¼ 3 Hz, 1H), 7.36–7.37 (m, 2H), 7.41 (d, J ¼ 3 Hz,
(t, J ¼ 8 Hz, 1H), 9.61 (s, 1H, –OH). 13C NMR (125 MHz, DMSO- 1H), 7.50–7.51 (m, 3H), 9.79 (s, 1H, –OH). 13C NMR (125 MHz,
d6/TMS): d 20.7, 33.0, 51.7, 52.1, 54.9, 59.6, 101.5, 103.5, 104.3, DMSO-d6/TMS): d 13.1, 13.6, 34.8, 57.8, 60.4, 61.4, 102.4, 120.9,
121.3, 123.9, 127.1, 129.1, 129.2, 130.4, 130.6, 135.7, 139.1, 121.7, 122.9, 127.4, 127.6, 129.5, 130.0, 130.7, 135.3, 135.7,
142.2, 151.0, 155.9, 159.0, 163.3, 165.5. MS m/z (ESI) for 142.8, 149.9, 151.5, 162.3, 164.5. MS (ESI) for C24H21Cl2N3O5: m/
C
24H23N3O6: m/z 450.2 [M + H]+. Elemental analyses: calc.: C, z 502.6 [M + H]+. Elemental analyses: calc.: C, 57.38; H, 4.21; N,
64.13; H, 5.16; N, 9.35. Found: C, 64.10; H, 5.18; N, 9.36%.
8.36. Found: C, 57.36; H, 4.22; N, 8.37%.
Dimethyl 6-amino-4-(5-bromo-2-hydroxyphenyl)-5-cyano-1,4-
Diethyl 6-amino-4-(5-bromo-2-hydroxyphenyl)-1-(4-bromo-
dihydro-1-m-tolylpyridine-2,3-dicarboxylate (5g). White solid. phenyl)-5-cyano-1,4-dihydropyridine-2,3-dicarboxylate
(5k).
Yield: 78%. Rf: 0.25 (2 : 3 EtOAc–hexane); mp: 195–197 ꢁC. IR White solid. Yield: 79%. Rf: 0.25 (2 : 3 EtOAc–hexane); mp: 207–
(KBr): 3444, 3354, 2945, 2192, 1736, 1725, 1645, 1582, 1423, 209 ꢁC. IR (KBr): 3452, 3350, 2981, 2150, 1770, 1704, 1669, 1584,
1326, 1262, 1178, 1022, 783, 700, 623 cmꢀ1. 1H NMR (400 MHz, 1421, 1335, 1282, 1181, 1025, 795, 719, 582 cmꢀ1. 1H NMR (500
CDCl3/TMS): d 2.32 (s, 3H), 3.34 (s, 3H), 3.48 (s, 3H), 4.70 (s, 1H), MHz, DMSO-d6/TMS): d 0.88 (t, J ¼ 7 Hz, 3H), 1.03 (t, J ¼ 7 Hz,
5.42 (s, 2H, –NH2), 6.80 (d, J ¼ 8.4 Hz, 1H), 7.04–7.06 (m, 2H), 3H), 3.74–3.96 (m, 2H), 4.00–4.22 (m, 2H), 4.66 (s, 1H), 5.60 (s,
7.19–7.23 (m, 2H), 7.29 (d, J ¼ 7.6 Hz, 1H), 7.36 (t, J ¼ 8 Hz, 1H), 2H, –NH2), 6.78 (d, J ¼ 8.5 Hz, 1H), 7.19–7.24 (m, 4H), 7.71 (d,
10.16 (s, 1H, –OH). 13C NMR (100 MHz, DMSO-d6/TMS): d 21.2, J ¼ 8.5 Hz, 2H), 9.99 (s, 1H, –OH). 13C NMR (125 MHz, DMSO-d6/
34.1, 52.3, 52.8, 58.8, 103.4, 110.4, 118.3, 121.5, 127.3, 129.8, TMS): d 13.2, 13.7, 35.0, 59.8, 60.3, 61.4, 102.7, 109.8, 117.9,
130.7, 130.9, 131.1, 133.8, 135.8, 139.9, 143.3, 152.1, 154.9, 121.1, 123.3, 130.4, 131.6, 132.5, 132.7, 133.2, 135.0, 142.3,
163.6, 165.6. MS (ESI) for C23H20BrN3O5: m/z 498.2 [M + H]+. 151.4, 155.0, 162.5, 164.6. MS m/z (ESI) for C24H21Br2N3O5: m/z
Elemental analyses: calc.: C, 55.43; H, 4.05; N, 8.43. Found: C, 589.7 [M + H]+. Elemental analyses: calc.: C, 48.75; H, 3.58; N,
55.45; H, 4.04; N, 8.42%.
7.11. Found: C, 48.77; H, 3.57; N, 7.10%.
Dimethyl 6-amino-5-cyano-4-(3-ethoxy-2-hydroxyphenyl)-1,4-
Diethyl 6-amino-5-cyano-4-(3-ethoxy-2-hydroxyphenyl)-1,4-
dihydro-1-m-tolylpyridine-2,3-dicarboxylate (5h). White solid. dihydro-1-m-tolylpyridine-2,3-dicarboxylate (5l). White solid.
Yield: 81%. Rf: 0.25 (2 : 3 EtOAc–hexane); mp: 199–201 ꢁC. IR Yield: 80%. Rf: 0.20 (2 : 3 EtOAc–hexane); mp: 198–200 ꢁC. IR
(KBr): 3435, 3368, 2900, 2187, 1745, 1720, 1645, 1500, 1423, (KBr): 3400, 3310, 2982, 2118, 1777, 1713, 1645, 1567, 1408,
1369, 1209, 1153, 1000, 789, 721, 598 cmꢀ1. 1H NMR (500 MHz, 1362, 1229, 1110, 1011, 795, 710, 545 cmꢀ1. 1H NMR (500 MHz,
DMSO-d6/TMS): d 1.38 (t, J ¼ 7 Hz, 3H), 2.34 (s, 3H), 3.33 (s, 3H), DMSO-d6/TMS): d 0.83 (t, J ¼ 7 Hz, 3H), 1.01 (t, J ¼ 7 Hz, 3H),
3.47 (s, 3H), 4.04 (q, J ¼ 7 Hz, 2H), 4.80 (s, 1H), 5.33 (s, 2H, 1.38 (t, J ¼ 7 Hz, 3H), 2.34 (s, 3H), 3.72–3.83 (m, 2H), 3.90 (q, J ¼
–NH2), 6.72–6.76 (m, 2H), 6.81–6.83 (m, 1H), 7.13–7.16 (m, 2H), 7 Hz, 2H), 4.04 (q, J ¼ 7 Hz, 2H), 4.80 (s, 1H), 5.30 (s, 2H, –NH2),
7.30 (d, J ¼ 7.5 Hz, 1H), 7.37 (t, J ¼ 7.5 Hz, 1H), 8.50 (s, 1H, -OH). 6.74–6.76 (m, 2H), 6.81–6.83 (m, 1H), 7.17 (d, J ¼ 8.5 Hz, 2H),
13C NMR (125 MHz, DMSO-d6/TMS): d 14.7, 20.7, 33.3, 51.7, 7.30 (d, J ¼ 8.5 Hz, 1H), 7.37 (t, J ¼ 8.5 Hz, 1H), 8.48 (s, 1H, –OH).
52.2, 59.1, 63.9, 103.2, 111.0, 118.6, 120.2, 121.2, 127.2, 129.2, 13C NMR (125 MHz, DMSO-d6/TMS): d 13.2, 13.7, 14.7, 20.7,
130.4, 130.7, 131.4, 135.5, 139.1, 142.4, 144.0, 146.6, 151.2, 33.6, 58.9, 60.1, 61.1, 64.0, 103.3, 111.1, 113.5, 120.6, 121.3,
163.2, 165.4. MS (ESI) for C25H25N3O6: m/z 464.7 [M + H]+. 127.6, 129.2, 130.4, 131.1, 131.5, 135.5, 139.1, 142.2, 144.2,
Elemental analyses: calc.: C, 64.79; H, 5.44; N, 9.07. Found: C, 146.5, 151.2, 162.7, 164.9. MS (ESI) for C27H29N3O6: m/z 492.8 [M
67.80; H, 5.42; N, 9.08%.
+ H]+. Elemental analyses: calc.: C, 65.97; H, 5.95; N, 8.55.
Dimethyl
6-amino-5-cyano-1,4-dihydro-4-(2-hydroxy-4- Found: C, 65.99; H, 5.94; N, 8.54%.
methoxyphenyl)-1-(4-methoxyphenyl)pyridine-2,3-dicarboxylate
Diethyl 6-amino-5-cyano-1,4-dihydro-4-(2-hydroxy-4-methoxy-
(5i). White solid. Yield: 85%. Rf: 0.25 (2 : 3 EtOAc–hexane); mp: phenyl)-1-(4-methoxyphenyl)pyridine-2,3-dicarboxylate
(5m).
203–205 ꢁC. IR (KBr): 3475, 3323, 2967, 2163, 1740, 1709, 1680, White solid. Yield: 81%. Rf: 0.25 (2 : 3 EtOAc–hexane); mp: 183–
1575, 1443, 1329, 1220, 1175, 1036, 726, 712, 589 cmꢀ1. 1H NMR 185 ꢁC. IR (KBr): 3444, 3326, 2987, 2120, 1725, 1702, 1654, 1523,
(500 MHz, DMSO-d6/TMS): d 3.35 (s, 3H), 3.48 (s, 3H), 3.68 1469, 1355, 1230, 1110, 1026, 770, 759, 530 cmꢀ1. 1H NMR (500
(s, 3H), 3.79 (s, 3H), 4.65 (s, 1H), 5.29 (s, 2H, –NH2), 6.36–6.39 MHz, DMSO-d6/TMS): d 0.86 (t, J ¼ 7 Hz, 3H), 1.03 (t, J ¼ 7 Hz,
(m, 2H), 6.97–7.02 (m, 3H), 7.20 (d, J ¼ 9 Hz, 2H), 9.61 (s, 1H, 3H), 3.68 (s, 3H), 3.72–3.84 (m, 5H), 3.86–3.92 (m, 2H), 4.65 (s,
–OH). 13C NMR (125 MHz, DMSO-d6/TMS): d 32.8, 51.7, 52.2, 1H), 5.27 (s, 2H, –NH2), 6.36–6.41 (m, 2H), 7.00 (t, J ¼ 8.5 Hz,
54.9, 55.5, 59.3, 101.5, 103.2, 104.3, 108.7, 114.6, 121.4, 124.0, 3H), 7.22 (d, J ¼ 8.5 Hz, 2H), 9.59 (s, 1H, –OH). 13C NMR (125
128.0, 129.0, 131.5, 142.6, 151.3, 155.8, 159.0, 159.8, 163.4, MHz, DMSO-d6/TMS): d 13.3, 13.8, 33.1, 54.9, 55.5, 59.1, 60.1,
165.5. MS (ESI) for C24H23N3O7: m/z 466.3 [M + H]+. Elemental 61.1, 100.2, 101.4, 103.3, 104.2, 114.5, 121.5, 124.2, 128.0, 129.4,
analyses: calc.: C, 61.93; H, 4.98; N, 9.03. Found: C, 61.95; H, 131.8, 142.4, 151.4, 155.9, 159.0, 159.9, 162.9, 164.9. MS (ESI) for
4.97; N, 9.02%.
Diethyl 6-amino-4-(3,5-dichloro-2-hydroxyphenyl)-5-cyano- 63.28; H, 5.51; N, 8.51. Found: C, 63.29; H, 5.49; N, 8.52%.
C
26H27N3O7: m/z 494.3 [M + H]+. Elemental analyses: calc.: C,
1,4-dihydro-1-phenylpyridine-2,3-dicarboxylate (5j). White
Diethyl 6-amino-4-(5-bromo-2-hydroxyphenyl)-5-cyano-1,4-
solid. Yield: 84%. Rf: 0.25 (2 : 3 EtOAc–hexane); mp: 210–212 ꢁC. dihydro-1-m-tolylpyridine-2,3-dicarboxylate (5n). White solid.
IR (KBr): 3422, 3356, 2989, 2178, 1750, 1725, 1667, 1422, 1369, Yield: 84%. Rf: 0.25 (2 : 3 EtOAc–hexane); mp: 206–208 ꢁC. IR
1232, 1156, 1023, 777, 712, 533 cmꢀ1 1H NMR (500 MHz, (KBr): 3420, 3318, 2999, 2164, 1755, 1729, 1697, 1568, 1473,
.
DMSO-d6/TMS): d 0.82 (t, J ¼ 7 Hz, 3H), 1.01 (t, J ¼ 7 Hz, 3H), 1333, 1215, 1148, 1098, 795, 726, 569 cmꢀ1. 1H NMR (500 MHz,
3764 | RSC Adv., 2014, 4, 3758–3767
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