8
F. S. HOSSEINI ET AL.
OCH3), 3.69 (s, 3H, OCH3), 3.87 (s, 1H, CH), 5.47 (s, 2H, NH2), 6.61 (d, 3JHH = 8.4 Hz,
1H, Ar), 6.67 (s, 1H, Ar), 6.84 (d, 3JHH = 8.4 Hz, 1H, Ar), 7.88 (s, 1H, NH), 8.21 (s, 2H,
NH2). 13C NMR (75.4 MHz, DMSO-d6): δ 22.0 (CH2), 22.6 (CH2), 43.0 (CH), 44.2 (CH2),
54.6 (C-CN), 55.8 (OCH3), 56.0 (OCH3), 77.9 (C-CN), 111.5 (CH of Ar), 112.2 (CH of
Ar), 119.3 (CH of Ar), 123.3 (CN), 125.7 (CN), 140.7 (C of Ar), 147.7 (C-OCH3), 148.8
(C–OCH3), 151.3 (C–S), 164.8 (C–NH2). IR (KBr) (υ¯max /cm–1): 3450 and 3338 and 3201
+
=
(NH2 and NH), 2390–3045 (NH2 ), 2175 (CN), 1601 (C C), 1182 (C–S). MS (EI, 70 eV):
m/z (%) = 313 (21), 312 (100), 297 (18), 280 (28), 267 (13), 251 (26), 237 (13), 145 (32),
84 (4). Anal. Calc. for C20H25N5O2S (399.51): C, 60.13; H, 6.31, N, 17.53. Found: C, 55.83;
H, 6.48, N, 16.47.
4.2.7. Piperidin-1-ium
6-amino-3,5-dicyano-4-(3-fluorophenyl)-1,4-dihydropyridine-2-thiolate (4g)
1
Yellow solid; yield: 0.268 g (75%); m.p. 196–198°C. H NMR (300 MHz, DMSO-d6): δ
1.52–1.55 (m, 2H, CH2), 1.58–1.65 (m, 4H, 2CH2), 2.97–3.00 (m, 4H, 2CH2), 3.95 (s, 1H,
CH), 5.57 (s, 2H, NH2), 6.82 (d, 3JHF = 9.9 Hz, 1H, Ar), 6.93–7.34 (m, 3H, Ar), 8.00 (s, 1H,
NH), 8.21 (s, 2H, NH2). 13C NMR (75.4 MHz, DMSO-d6): δ 22.0 (CH2), 22.6 (CH2), 43.2
(CH), 44.2 (CH2), 53.9 (C–CN), 77.0 (C–CN), 113.2 (CH of Ar, d, 2JCF = 21 Hz), 113.6
(CH of Ar, d, 2JCF = 21 Hz), 123.0 (CH of Ar), 123.3 (CN), 125.4 (CN), 130.5 (CH of Ar),
1
151.1 (C of Ar), 151.6 (C–S), 162.7 (C–F, d, JCF = 243 Hz), 165.7 (C–NH2). IR (KBr)
(υ¯max /cm–1): 3394 and 3325 and 3220 (NH2 and NH), 2390–3157 (NH2+), 2179 (CN),
=
1561 (C C), 1234 (C–S). MS (EI, 70 eV): m/z (%) = 271 (16), 270 (100), 254 (12), 237
(26), 211 (15), 183 (21), 145 (22), 84 (10), 44 (20). Anal. Calc. for C18H20FN5S (357.45):
C, 60.48; H, 5.64, N, 19.59. Found: C, 58.01; H, 5.53, N, 19.78.
4.2.8. Piperidin-1-ium
6-amino-3,5-dicyano-4-(4-trifluoromethylphenyl)-1,4-dihydropyridine-2-thiolate (4h)
1
Yellow solid; yield: 0.334 g (82%); m.p. 183–185°C. H NMR (300 MHz, DMSO-d6): δ
1.53–1.55 (m, 2H, CH2), 1.59–1.61 (m, 4H, 2CH2), 2.96–3.00 (m, 4H, 2CH2), 4.04 (s, 1H,
CH), 5.60 (s, 2H, NH2), 7.30 (d, 3JHH = 8.1 Hz, 2H, Ar), 7.64 (d, 3JHH = 8.1 Hz, 2H, Ar),
8.03 (s, 1H, NH), 8.22 (s, 2H, NH2). 13C NMR (75.4 MHz, DMSO-d6): δ 22.0 (CH2), 22.6
(CH2), 43.5 (CH), 44.2 (CH2), 53.7 (C–CN), 76.6 (C–CN), 123.0 (CN), 125.4 (CN), 125.6
(2CH of Ar), 124.9 (CF3, q, 1JCF = 278 Hz), 127.2 (C–CF3, q, 2JCF = 31 Hz), 128.1 (2CH
of Ar), 151.6 (C–S), 152.5 (C of Ar), 165.9 (C–NH2). IR (KBr) (υ¯max /cm–1): 3402 and
3320 (NH2 and NH), 2390–3145 (NH2+), 2175 (CN), 1556 (C = C), 1175 (C–S). MS (EI,
70 eV): m/z (%) = 321 (27), 320 (48), 259 (100), 237 (19), 222 (22), 207 (18), 193 (17), 177
(29), 154 (19), 134 (60), 119 (33), 84 (30), 56 (33), 41 (32). Anal. Calc. for C19H20F3N5S
(407.46): C, 56.01; H, 4.95, N, 17.19. Found: C, 56.32; H, 4.67, N, 17.01.
4.2.9. Piperidin-1-ium
6-amino-3,5-dicyano-4-(2-nitrophenyl)-1,4-dihydropyridine-2-thiolate (4i)
1
Yellow solid; yield: 0.307 g (80%); m.p. 156–158°C. H NMR (300 MHz, DMSO-d6): δ
1.52–1.55 (m, 2H, CH2), 1.59–1.61 (m, 4H, 2CH2), 2.97–3.00 (m, 4H, 2CH2), 4.71 (s,
1H, CH), 5.64 (s, 2H, NH2), 7.36–7.80 (m, 4H, Ar), 8.10 (s, 1H, NH), 8.25 (s, 2H, NH2).
13C NMR (75.4 MHz, DMSO-d6): δ 22.0 (CH2), 22.6 (CH2), 37.6 (CH), 44.2 (CH2), 53.7
(C–CN), 76.4 (C–CN), 122.5 (CN), 123.8 (CH of Ar), 124.9 (CN), 127.7 (CH of Ar),