Molecules 2011, 16
9630
OCH3), 5.03 (s, 1H, H4), 7.44 (d, J = 7.9 Hz, 2H, Ar), 8,12 (d, J = 7.9 Hz, 2H, Ar), 9,67 (s, 1H, CHO),
10.48 (s, 1H, NH); 13C-NMR (DMSO-d6) ppm 18.7 (CH3), 39.2 (C4), 51.2 (OCH3), 104.6 (C5),
111.1 (C3), 124.4 (C3′,C5′), 129.6 (C2′,C6′), 141.1 (C2), 147.1 (C4′), 146.9 (C6), 153.7 (C1′), 166.6
(COOCH3), 187.4 (CHO); ESI-MS: m/z 337 [M+H]+.
Methyl
6-chloro-5-formyl-4-(4-methoxycarbonylphenyl)-2-methyl-l,4dihydropyridine-3-carboxylate
(IId). White solid; mp 202–204 °C; yield: 63%; 1H-NMR (DMSO-d6) 2.34 (s, 3H, CH3), 3.53 (s, 3H,
OCH3), 3.79 (s, 3H, OCH3), 5.00 (s, 1H, CH), 7.29 (d, J = 7.9 Hz, 2H, Ar), 7.84 (d, J = 7.9 Hz, 2H,
Ar), 9.67 (s, 1H, HCO), 10.46 (s, 1H, NH); 13C-NMR (DMSO-d6) 17.8 (CH3), 38.0 (C4), 51.1
(OCH3), 103.8 (C3), 110.5 (C5), 127.6 (C3′,C5′), 129.3 (C2′,C6′), 143.1 (C2),146.1 (C6), 150.7 (C1′),
166.4 (COOCH3), 186.5 (CHO); ESI-MS: m/z 350 [M+H]+.
Methyl 4-(2′,3′-dihidroxyphenyl)-6-chloro-5-formyl-2-methyl-l,4dihydropyridine-3-carboxylate (IIe).
1
White solid; mp 239–241 °C; yield: 70%; H-NMR (DMSO-d6) 2.24 (s, 3H, CH3), 3,77 (s, 3H,
OCH3), 4.98 (s, 1H, H4), 5.40 (brs, 2H, OH), 6.62(m, 3H, Ar) 9.71 (s, 1H, HCO), 10.38 (s, 1H, NH);
13C-NMR (DMSO-d6) 17.8 (CH3), 38.2 (C4), 51.3 (OCH3), 103.7 (C3), 110.3 (C5), 114.3 (C4′),
122.2 (C5′), 123.2 (C6′), 124.1 (C1′), 145.2 (C3′), 147 (C2′), 143.1 (C2), 146.5 (C6), 150.3 (C1′),
166.6 (COOCH3), 186.8 (CHO); ESI-MS: m/z 324 [M+H]+.
Methyl
6-chloro-4-(4′-dimethylaminophenyl)-5-formyl-2-methyl-1,4-dihydropyridine-3-carboxylate
1
(IIf). Yellow solid; m.p. 290–292 °C; yield: 60%; H-NMR (DMSO-d6) 2.34 (s, 3H, CH3), 3.10 (s,
6H, CH3), 3,52 (s, 3H, OCH3), 5.00 (s, 1H, H4), 7.39 (d, J = 7.9 Hz, 2H, Ar), 8,08 (d, J = 7.9 Hz, 2H,
Ar), 9,77 (s, 1H, CHO), 10.48 (s, 1H, NH); 13C-NMR (DMSO-d6) 18.7 (CH3), 39.2 (C4), 41.7
(2CH3), 51.2 (OCH3), 104.4 (C5), 110.9 (C3), 124.2 (C3′,C5′), 129.8 (C2′,C6′), 141.1 (C2), 147.2
(C4′), 146.7 (C6), 153.5 (C1′), 166.8 (COOCH3), 187.2 (CHO). ESI-MS: m/z 335 [M+H]+.
Ethyl 6-chloro-5-formyl-2-methyl-4-phenyl-1,4-dihydropyridine-3-carboxylate (IIg). White solid; m.p.
201–202 °C; yield: 62%; 1H-NMR (DMSO-d6) 1.10 (t, J = 7.1 Hz, 3H, CH3), 2.33 (s, 3H, CH3), 4.02
(q, J = 7.1 Hz, 2H, OCH2), 4.93 (s, 1H, H4), 7.09 (d, J = 7.8 Hz, 2H, Ar), 7.31–7.11 (m, 3H, Ar), 9.72
13
(s, 1H, CHO), 10.35 (s, 1H, NH); C-NMR (DMSO-d6) 14.6 (CH3), 18.3 (CH3), 38.1 (C4), 59.8
(OCH2), 103.9 (C5), 109.3 (C3), 126.1 (C4′), 126.6 (C2′,C6′), 128.2 (C3′,C5′), 144.3 (C2), 146.9 (C1′),
147.9 (C6), 166.2 (COOCH2CH3), 187.4 (CHO); ESI-MS: m/z 306 [M+H]+.
Ethyl 6-chloro-5-formyl-2-methyl-4-(2′-nitrophenyl)-1,4-dihydropyridine-3-carboxylate (IIh). Yelow
solid; m.p. 198–200 °C; yield: 65%; 1H-NMR (DMSO-d6) 1.10 (t, J =7.1 Hz, 3H, CH3), 2.35 (s, 3H,
CH3), 3.99 (q, J =7.1 Hz, 2H, OCH2), 5.03 (s, 1H, H4), 7.64–7.53 (s, 2H, Ar), 7.96 (t, J = 2.0 Hz, 1H,
Ar), 8.02 (dt, J = 7.7 Hz, J = 2.0 Hz, 1H, Ar), 9.68 (s, 1H, CHO), 10.52 (1H, s, NH); 13C-NMR
(DMSO-d6) 14.8 (CH3), 18.6 (CH3), 39.0 (C4), 60.6 (OCH2), 104.8 (C5), 111.3 (C3), 122.4 (C3′),
122.7 (C5′), 130.7 (C4′), 135.0 (C6′), 144.1 (C2), 147.1 (C6), 148.4 (C2′), 148,6 (C1′), 166.5
(COOCH2CH3), 187.4 (CHO); ESI-MS: m/z 351 [M+H]+.
Ethyl 4-(2′,3′-dihidroxyphenyl)-6-chloro-5-formyl-2-methyl-l,4dihydropyridine-3-carboxylate (IIi).
1
White solid; mp 248–250 °C; yield: 63%; H-NMR (DMSO-d6) 1.28 (t, 3H, CH3), 4,17 (q, 2H,