Month 2014
Synthesis of N-Aryl-5-(pyridin-3-yl)-4-(cyano/alkoxycarbonyl)-1,2,3-triazoles
H), 7.67 (t, J = 7.9 Hz, 1H, Ar-H), 7.72 (d, J = 7.7 Hz, 1H, Ar-H),
7.75 (d, J= 7.9 Hz, 1H, Ar-H), 7.85 (s, 1H, Ar-H), 8.21 (dd,
J = 2.4, 8.3 Hz, 1H, Pyridine-H), 8.60 (d, J = 2.4 Hz, 1H, Pyridine-
H); IR (KBr) cmÀ1: 2239 (C≡N), 1596 (C═N), 1185, 1118 (C–F);
ESI-MS m/z [(M + H)+] 350. HRMS Calcd for C15H8N5ClF3
[(M + H)+]: 350.0414. Found: 350.0417.
7.7 Hz, 1H, Pyridine-H), 7.73–7.79 (m, 1H, Ar-H), 8.10 (dd, J=1.8,
7.7 Hz, 1H, Pyridine-H), 8.97 (dd, J= 1.8, 4.7 Hz, 1H, Pyridine-H);
13C-NMR (75 MHz, CDCl3): δ = 105.9 (d, JC–F = 22.7 Hz, SP2-
carbon ortho to –F), 106.2 (d, JC–F = 22.7 Hz, SP2-carbon
ortho to –F), 107.6, 109.6, 119.2 (dd, JC–F = 3.6, 12.7 Hz,
SP2-carbon ortho to –F), 122.6, 123.5, 128.8 (d, JC–
F = 10.8 Hz, SP2-carbon meta to –F), 140.3, 148.6, 149.7,
151.3, 156.1 (dd, JC–F = 12.7, 257.4 Hz, SP2-carbon attached
to –F), 164.3 (dd, JC–F = 10.8, 257.4 Hz, SP2-carbon attached
to –F); IR (KBr) cmÀ1: 2241 (C≡N), 1605 (C═N); ESI-MS
m/z [(M + H)+] 318. HRMS Calcd for C14H7N5ClF2
[(M + H)+]: 318.0352. Found: 318.0358.
Ethyl 3-(3-chloro-4-fluorophenyl)-5-(6-chloropyridin-3-yl)-
3H-1,2,3-triazole-4-carboxylate (11a).
Colorless solid; m.p.
1
100–101°C; H-NMR (300 MHz, CDCl3): δ = 1.20 (t, J = 7.1 Hz,
3H, –CH3), 4.26 (q, J = 7.1 Hz, 2H, –CH2), 7.35 (d, J = 8.3 Hz,
1H, Pyridine-H), 7.41–7.44 (m, 2H, Ar-H), 7.62 (dd, J = 2.4,
6.2 Hz, 1H, Ar-H), 8.18 (dd, J = 2.2, 8.3 Hz, 1H, Pyridine-H),
8.84 (d, J = 2.2 Hz, 1H, Pyridine-H); 13C-NMR (75 MHz,
CDCl3): δ = 13.6, 62.6, 116.9 (d, JC–F = 23.6 Hz, SP2-carbon
ortho to –F), 121.7, 123.8, 124.7, 125.8 (d, JC–F = 7.7 Hz, SP2-
carbon meta to –F), 126.3, 128.3, 139.1, 145.9, 149.8, 152.1,
157.8, 159.4 (d, JC–F = 253.0 Hz, SP2-carbon attached to –F),
164.3; IR (KBr) cmÀ1: 1720 (CO2Et), 1594 (C═N), 1232
(CO2Et); ESI-MS m/z [(M + H)+] 381. HRMS Calcd for
C16H12O2N4Cl2F [(M + H)+]: 381.0315. Found: 381.0324.
3-(3-Chloro-4-fluorophenyl)-5-(2-chloropyridin-3-yl)-3H-1,2,3-
triazole-4-carbonitrile (11b). Colorless solid; m.p. 127–129°C;
1H-NMR (300 MHz, CDCl3): δ =7.12–7.16 (m, 1H, Ar-H),
7.23–7.25 (m, 1H, Ar-H), 7.42 (dd, J= 4.7, 7.9 Hz 1H, Pyridine-H),
7.46–7.49 (m, 1H, Ar-H), 7.81 (dd, J= 1.8, 7.9 Hz, 1H, Pyridine-
H), 8.82 (dd, J= 1.8, 4.7 Hz 1H, Pyridine-H); IR (KBr) cmÀ1: 2231
(C≡N), 1597 (C═N); ESI-MS m/z [(M + H)+] 335. HRMS Calcd
for C14H7N5Cl2F [(M + H)+]: 335.0057. Found: 335.0061.
Ethyl 5-(6-chloropyridin-3-yl)-3-phenyl-3H-1,2,3-triazole-4-
carboxylate (11g).
Colorless solid; m.p. 80–81°C; 1H-NMR
(300 MHz, CDCl3): δ = 1.10 (t, J = 7.1 Hz, 3H, –CH3), 4.22
(q, J = 7.1 Hz, 2H, –CH2), 7.44 (d, J = 8.3 Hz, 1H, Pyridine-H),
7.49–7.53 (m, 2H, Ar-H), 7.54–7.59 (m, 3H, Ar-H), 8.24 (dd,
J = 2.4, 8.3 Hz, 1H, Pyridine-H), 8.90 (d, J = 2.4 Hz, 1H,
Pyridine-H); 13C-NMR (75 MHz, CDCl3): δ = 14.9, 62.4, 121.4,
123.8, 125.5, 129.1, 130.2, 134.5, 136.4, 137.9, 139.0, 149.8,
152.2, 159.7; IR (KBr) cmÀ1: 1723 (CO2Et), 1597 (C═N),
1226 (CO2Et); ESI-MS m/z [(M + H)+]: 329. HRMS Calcd for
C16H14O2N4Cl [(M + H)+]: 329.0799. Found: 329.0803.
5-(6-Chloropyridin-3-yl)-3-(2,4-difluorophenyl)-3H-1,2,3-
triazole-4-carbonitrile (11h). Colorless solid; m.p. 120–122°C;
1H-NMR (300 MHz, CDCl3): δ = 7.16–7.23 (m, 2H, Ar-H), 7.50
(d, J = 8.3 Hz, 1H, Pyridine-H), 7.63–7.71 (m, 1H, Ar-H), 8.36
(dd, J = 2.3, 8.3 Hz, 1H, Pyridine-H), 9.14 (d, J = 2.3 Hz, 1H,
Pyridine-H); 13C-NMR (75 MHz, CDCl3): δ = 105.9 (d, JC–
F = 22.7 Hz, SP2-carbon ortho to –F), 106.3 (d, JC–F = 22.7Hz,
SP2-carbon ortho to –F), 108.4, 109.6, 119.0 (dd, JC–F = 4.5,
12.7Hz, SP2-carbon ortho to –F), 124.9, 127.5, 128.7 (d, JC–
F = 10.8 Hz, SP2-carbon meta to –F), 136.3, 147.7, 148.5, 153.3,
156.2 (dd, JC–F = 12.7, 257.9 Hz, SP2-carbon attached to –F),
164.1 (dd, JC–F = 10.8, 257.9 Hz, SP2-carbon attached to –F); IR
(KBr) cmÀ1: 2233 (C≡N), 1604 (C═N); ESI-MS m/z [(M + H)+]
318. HRMS Calcd for C14H7N5ClF2 [(M + H)+]: 318.0352.
Found: 318.0354.
Ethyl 3-(3-chloro-4-fluorophenyl)-5-(furan-2-yl)-3H-1,2,3-
triazole-4-carboxylate (11c). Colorless solid; m.p. 124–126°C;
1H-NMR (300 MHz, CDCl3): δ = 1.21 (t, J = 7.1 Hz, 3H, –CH3),
4.44 (q, J = 7.1 Hz, 2H, –CH2), 6.67 (dd, J = 1.9, 3.4 Hz, 1H,
Furan-H), 7.30 (d, J = 3.4 Hz, 1H, Furan-H), 7.38–7.46 (m, 2H,
Ar-H), 7.51–7.54 (m, 1H, Ar-H), 7.73 (d, 1H, J = 1.9 Hz,
Furan-H); IR (KBr) cmÀ1: 1709, 1262 (CO2Et); ESI-MS m/z
[(M + H)+] 336. HRMS Calcd for C15H12O3N3ClF [(M + H)+]:
336.0545. Found: 336.0550.
3-(3-Chloro-4-fluorophenyl)-5-(6-chloropyridin-3-yl)-3H-1,2,3-
triazole-4-carbonitrile (11d). Colorless solid; m.p. 126–128°C;
1H-NMR (300 MHz, CDCl3): δ = 7.42–7.47 (m, 2H, Ar-H), 7.49
(d, J= 8.3 Hz, 1H, Pyridine-H), 7.69–7.73 (m, 1H, Ar-H), 8.33
(dd, J= 2.2, 8.3Hz, 1H, Pyridine-H), 9.13 (d, J= 2.2 Hz, 1H,
Pyridine-H); 13C-NMR (75 MHz, CDCl3): δ = 109.1, 118.2 (d, JC–
F = 23.0 Hz, SP2-carbon ortho to –F), 122.4, 123.0 (d, JC–
F =7.7Hz, SP2-carbon meta to –F), 124.0, 124.4, 124.9, 126.0,
131.1, 136.3, 147.3, 149.3, 153.4, 158.8 (d, JC–F = 255.3 Hz, SP2-
carbon attached to –F); IR (KBr) cmÀ1: 2235 (C≡N), 1594
(C═N); ESI-MS m/z [(M + H)+] 335. HRMS Calcd for
C14H7N5Cl2F [(M + H)+]: 335.0057. Found: 335.0063.
Ethyl 5-(6-chloropyridin-3-yl)-3-(3-trifluoromethylphenyl)-
3H-1,2,3-triazole-4-carboxylate (11i).
Colorless solid; m.p.
85–86°C; 1H-NMR (300 MHz, CDCl3): δ = 1.13 (t, J = 7.1 Hz,
3H, –CH3), 4.24 (q, J = 7.1 Hz, 2H, –CH2), 7.44 (d,
J = 8.3 Hz,1H, Pyridine-H), 7.68–7.75 (m, 2H, Ar-H), 7.77 (s,
1H, Ar-H), 7.84–7.86 (m, 1H, Ar-H), 8.20 (dd, J = 2.4, 8.3 Hz,
1H, Pyridine-H), 8.88 (d, J = 2.4 Hz, 1H, Pyridine-H); IR (KBr)
cmÀ1: 1730 (CO2Et), 1603 (C═N), 1229 (CO2Et), 1170, 1129
(C–F); ESI-MS m/z [(M + H)+] 397. HRMS Calcd for
C17H13O2N4ClF3 [(M + H)+]: 397.0679. Found: 397.0682.
5-(2-Chloropyridin-3-yl)-3-(3-trifluoromethylphenyl)-3H-1,2,3-
Ethyl 5-(6-chloropyridin-3-yl)-3-(2,4-difluorophenyl)-3H-1,2,3-
triazole-4-carbonitrile (11j).
Colorless solid; m.p. 138–139°C;
triazole-4-carboxylate (11e). Colorless solid; m.p. 85–87°C; 1H-
NMR (300 MHz, CDCl3): δ =1.20 (t, J= 7.1 Hz, 3H, –CH3), 4.26
(q, J= 7.1 Hz, 2H, –CH2), 7.06 (t, J= 7.2 Hz, 1H, Ar-H), 7.12
(t, J= 7.2 Hz, 1H, Ar-H), 7.43 (d, J= 8.2 Hz, 1H, Pyridine-H),
7.58–7.62 (m, 1H, Ar-H), 8.22 (dd, J= 2.2, 8.2 Hz, 1H, Pyridine-
H), 8.89 (d, J= 2.2 Hz, 1H, Pyridine-H); IR (KBr) cmÀ1: 1719
(CO2Et), 1609 (C═N), 1222 (CO2Et); ESI-MS m/z [(M + H)+] 365.
HRMS Calcd for C16H12O2N4ClF2 [(M + H)+]: 365.0617. Found:
365.0620.
1H-NMR (300 MHz, CDCl3): δ = 7.46 (dd, J = 4.7, 7.5 Hz, 1H,
Pyridine-H), 7.84 (t, J= 7.9 Hz, 1H, Ar-H), 7.92 (d, J = 7.7 Hz, 1H,
Ar-H), 8.07 (dd, J= 1.8, 7.5 Hz, 1H, Pyridine-H), 8.09–8.14 (d,
J = 7.9 Hz, 1H, Ar-H), 8.18 (s, 1H, Ar-H), 8.60 (dd, J= 1.8,
4.7 Hz, 1H, Pyridine-H); 13C-NMR (75 MHz, CDCl3): δ = 106.4,
108.3, 112.9, 121.2, 122.7, 123.5, 124.7, 126.2, 127.7, 131.0,
133.4, (q, JC–F = 237.7 Hz, –CF3), 135.3, 140.4, 151.5, 159.2; IR
(KBr) cmÀ1: 2239 (C≡N), 1594 (C═N), 1167, 1126 (C–F); ESI-
MS m/z [(M + H)+] 350. HRMS Calcd for C15H8N5ClF3
[(M + H)+]: 350.0414. Found: 350.0419.
5-(2-Chloropyridin-3-yl)-3-(2,4-difluorophenyl)-3H-1,2,3-triazole-
4-carbonitrile (11f). Colorless solid; m.p. 147–149°C; 1H-NMR
(300MHz, CDCl3): δ = 7.16–7.24 (m, 2H, Ar-H), 7.31 (dd, J = 4.7,
Propan-2-yl 5-(6-chloropyridin-3-yl)-3-(3-trifluoromethylphenyl)-
3H-1,2,3-triazole-4-carboxylate (11k).
Colorless solid; m.p.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet