456 JOURNAL OF CHEMICAL RESEARCH 2016
161.9 (C=O), 140.5 (C), 139.0 (C), 136.8 (C), 133.0 (C), 130.3 (CH),
125.4 (CH), 61.3 (CH2), 21.4 (CH3), 14.6 (CH3), 10.3 (CH3); HRESIMS
m/z for C13H16N3O2 [M + H]+ calcd 246.1243; found: 246.1222.
(cm–1) ν: 3050 (CAr–H), 1688 (C=O), 1517 (N=N), 950 (N–N=N);
1H NMR (500 MHz, CDCl3) δ (ppm): 7.35 (d, J = 8.9 Hz, 2H), 7.06
1
(d, J = 8.9 Hz, 2H), 3.89 (s, 3H), 2.75 (s, 3H), 2.55 (s, 3H); H NMR
Ethyl 5-methyl-1-(3-nitrophenyl)-1H-1,2,3-triazole-4-carboxylate
(3f): Yellow solid; m.p.: 146–148 °C (lit.32 144–146 °C); IR (cm–1) ν:
3095, 3002 (CAr–H), 1732 (C=O), 1590 (N=N), 1534, 1351 (Ar–NO2),
(500 MHz, DMSO-d6) δ (ppm): 7.53 (d, J = 8.9 Hz, 2H), 7.16 (d,
J = 8.9 Hz, 2H), 3.85 (s, 3H), 2.62 (s, 3H), 2.47 (s, 3H); 13C NMR (126
MHz, CDCl3) δ (ppm): 194.6 (C=0), 160.8 (C), 143.7 (C), 137.7 (C),
128.3 (C), 126.8 (CH), 114.9 (CH), 55.8 (CH3), 28.0 (CH3), 10.2 (CH3);
13C NMR (126 MHz, DMSO-d6) δ (ppm): 193.3 (C=O), 160.2 (C),
142.6 (C), 137.7 (C), 127.7 (C), 126.9 (CH), 114.8 (CH), 55.6 (CH3),
27.5 (CH3), 9.6 (CH3); HRESIMS m/z for C12H14N3O2 [M + H]+ calcd
232.1086; found: 232.1085.
1-(1-(2-Bromophenyl)-5-methyl-1H-1,2,3-triazol-4-yl)ethanone
(3n): White solid; m.p.: 110–111 °C; IR (cm–1) ν: 3065, 3003 (CAr–H),
1679 (C=O), 1553 (N=N), 951 (N–N=N); 1H NMR (500 MHz, CDCl3)
δ (ppm): 7.81–7.71 (m, 1H), 7.51 (td, J = 7.5, 1.7 Hz, 1H), 7.51–7.38 (m,
1H), 7.37 (dd, J = 7.3, 2.2 Hz, 1H), 2.73 (s, 3H), 2.41 (s, 3H); 13C NMR
(126 MHz, CDCl3) δ (ppm): 194.3 (C=O), 143.2 (C), 139.1 (C), 134.6
(C), 133.9 (CH), 132.4 (CH), 129.2 (CH), 128.8 (CH), 121.5 (C), 27.9
(CH3), 9.7 (CH3); HRESIMS m/z for C11H10BrN3ONa [M + Na]+ calcd
301.9899; found: 301.9902.
1
1217 (CO–O), 973 (N–N=N), H NMR (500 MHz, CDCl3) δ (ppm):
8.41 (dd, J = 8.1, 1.4 Hz, 1H), 8.35 (t, J = 1.6 Hz, 1H), 7.87 (d, J = 8.0
Hz, 1H), 7.81 (t, J = 8.0 Hz, 1H), 4.44 (q, J=7.1 Hz, 2H), 2.65 (s, 3H),
1.42 (t, J = 7.1 Hz, 3H); 13C NMR (126 MHz, CDCl3) δ (ppm): 161.4
(C=O), 148.8 (C), 139.0 (C), 137.3 (C), 136.4 (C), 131.1 (CH), 131.0
(CH), 124.8 (CH), 120.4 (CH), 61.4 (CH2), 14.4 (CH3), 10.2 (CH3);
HRESIMS m/z for C12H13N4O4 [M + H]+ calcd 277.0937; found:
277.0897.
Ethyl 1-(3,4-dichlorophenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate
(3g): Pale orange solid; m.p.: 118–120 °C; IR (cm–1) ν: 3101, 3092
(CAr–H), 1732 (C=O), 1577 (N=N), 1216 (CO–O), 1028 (Ar–Cl), 975
(N–N=N); 1H NMR (500 MHz, CDCl3) δ (ppm): 7.61 (d, J = 8.1 Hz, 1H),
7.57 (s, 1H), 7.31 (d, J = 7.9 Hz, 1H), 4.37 (q, J = 7.0 Hz, 2H), 2.55 (s,
3H), 1.37 (t, J = 7.0 Hz, 3H); 13C NMR (126 MHz, CDCl3) δ (ppm): 161.3
(C=O), 138.8 (C), 136.9 (C), 134.6 (C), 134.5 (C), 133.8 (C), 131.4 (CH),
127.2 (CH), 124.4 (CH), 61.2 (CH2), 14.3 (CH3), 10.0 (CH3); HRESIMS
m/z for C12H12Cl2N3O2 [M + H]+ calcd 300.0307; found: 300.0279.
Ethyl 1-(3,4-dimethylphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate
(3h): White solid; m.p.: 118–120 °C; IR (cm–1) ν: 3085, 3055 (CAr–H),
1710 (C=O), 1564 (N=N), 1248 (CO–O), 985 (N–N=N); 1H NMR (500
MHz, CDCl3) δ (ppm): 7.26 (d, J = 7.8 Hz, 1H), 7.18 (s, 1H), 7.10 (d,
J = 7.8 Hz, 1H), 4.42 (q, J = 7.1 Hz, 2H), 2.53 (s, 3H), 2.31 (s, 3H), 2.30
(s, 3H), 1.41 (t, J = 7.1 Hz, 3H); 13C NMR (126 MHz, CDCl3) δ (ppm):
161.9 (C=O), 139.0 (C), 138.9 (C), 138.4 (C), 136.5 (C), 133.1 (C), 130.6
(CH), 126.4 (CH), 122.6 (CH), 61.1 (CH2), 19.9 (CH3), 19.6 (CH3),
14.4 (CH3), 10.1 (CH3); HRESIMS m/z for C14H18N3O2 [M + H]+ calcd
260.1399; found: 260.1399.
Ethyl 1-(3-chloro-4-methoxyphenyl)-5-methyl-1H-1,2,3-triazole-
4-carboxylate (3i): Pale purple solid; m.p.: 120–121 °C; IR (cm–1) ν:
3073 (CAr–H), 1725 (C=O), 1582 (N=N), 1214 (CO–O), 1019 (Ar–Cl),
977 (N–N=N); 1H NMR (500 MHz, CDCl3) δ (ppm): 7.43 (s, 1H), 7.28
(d, J = 7.5 Hz, 1H), 7.04 (d, J = 8.3 Hz, 1H), 4.39 (q, J = 7.0 Hz, 2H),
3.93 (s, 3H), 2.51 (s, 3H), 1.38 (t, J = 7.1 Hz, 3H); 13C NMR (126 MHz,
CDCl3) δ (ppm): 161.6 (C=O), 156.3 (C), 139.0 (C), 136.6 (C), 128.3
(C), 127.3 (CH), 125.0 (CH), 123.4 (C), 112.2 (CH), 61.1 (CH2), 56.6
(CH3), 14.4 (CH3), 9.9 (CH3); HRESIMS m/z for C13H15ClN3O3 [M +
H]+ calcd 296.0802; found: 296.0810.
1-(1-(4-Nitrophenyl)-5-phenyl-1H-1,2,3-triazol-4-yl)ethanone (3o):
White solid; m.p.: 172–174 °C; IR (cm–1) ν: 3088, 3062 (CAr–H), 1687
1
(C=O), 1555 (N=N), 853 (N–N=N); H NMR (500 MHz, CDCl3) δ
(ppm): 8.23 (d, J = 9.2 Hz, 2H), 7.47 (d, J = 9.3 Hz, 2H), 7.45–7.36 (m,
3H), 7.31–7.25 (m, 2H), 2.74 (s, 3H); 13C NMR (126 MHz, CDCl3) δ
(ppm): 192.6 (C=O), 147.8 (C), 143.9 (C), 140.6 (C), 139.3 (C), 130.7
(CH), 130.2 (CH), 128.9 (CH), 125.7 (CH), 125.1 (C), 124.9 (CH), 28.5
(CH3); HRESIMS m/z for C16H12N4O3Na [M + Na]+ calcd 331.0802;
found: 331.0808.
Hex-5-yn-1-yl
5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-
carboxylate (3p): Yellow solid; m.p.: 137–139 °C; IR (cm–1) ν: 3293
(Csp–H), 3118, 3075 (CAr–H), 2953–2917 (Csp3–H), 1719 (C=O),
1550 (N=N), 1210 (CO–O), 907 (N–N=N); 1H NMR (500 MHz,
CDCl3) δ (ppm): 8.47 (d, J = 9.0 Hz, 2H), 7.73 (d, J = 9.0 Hz, 2H),
4.45 (t, J = 6.6 Hz, 2H), 2.69 (s, 3H), 2.29 (td, J = 7.0, 2.6 Hz, 2H),
2.05–1.89 (m, 3H), 1.80–1.63 (m, 2H); 13C NMR (126 MHz, CDCl3) δ
(ppm): 161.4 (C=O), 148.3 (C), 140.3 (C), 138.9 (C), 137.4 (C), 126.0
(CH), 125.3 (CH), 83.8 (C, C≡CH), 68.9 (CH, C≡CH), 64.8 (CH2),
27.8 (CH2), 25.0 (CH2), 18.2 (CH2), 10.3 (CH3); HRESIMS m/z for
C16H16N4O4Na [M + Na]+ calcd 351.1064; found: 351.1062.
(5-Methyl-1-(4-nitrophenyl)-1H-1,2,3-triazol-4-yl)(morpholino)
methanone (3q): Yellow solid; m.p.: 182–183 °C; IR (cm–1) ν: 3118,
3088 (CAr–H), 2977, 2937 (Csp3–H), 1612 (C=O), 1568 (N=N), 859
(N–N=N); 1H NMR (500 MHz, CDCl3) δ (ppm): 8.44 (d, J = 9.1 Hz,
2H), 7.72 (d, J = 9.0 Hz, 2H), 4.18–4.12 (m, 2H), 3.79 (s, 6H), 2.61 (s,
3H); 13C NMR (126 MHz, CDCl3) δ (ppm): 160.8 (C=O), 148.2 (C),
140.6 (C), 140.3 (C), 138.3 (C), 125.8 (CH), 125.3 (CH), 67.3 (CH2),
67.0 (CH2), 47.9 (CH2), 42.9 (CH2), 10.5 (CH3); HRESIMS m/z for
C14H16N5O4 [M + H]+ calcd 318.1197; found: 318.1200.
1-(3-Chloro-4-fluorophenyl)-5-methyl-1H-1,2,3-triazole-4-
carboxylate (3j): Colourless crystals (toluene); m.p.: 98–99 °C;
IR (cm–1) ν: 3084, 3010 (CAr–H), 1722 (C=O), 1562 (N=N), 1255
1
(CO–O), 1026 (Ar–Cl), 974 (N–N=N); H NMR (500 MHz, CDCl3)
δ (ppm): 7.51 (dd, J = 6.2, 2.0 Hz, 1H), 7.33 (m, 1H), 7.30 (t, J = 8.5 Hz,
1H), 4.35 (q, J = 7.1 Hz, 2H), 2.51 (s, 3H), 1.34 (t, J = 7.1 Hz, 3H);
13C NMR (126 MHz, CDCl3) δ (ppm): 161.3 (C=O), 158.7 (d,
J = 253.8 Hz, C), 138.9 (C), 136.7 (C), 131.8 (d, J = 2.5 Hz, C), 127.9
(CH), 125.4 (d, J = 7.8 Hz, CH), 122.4 (d, J = 19.1 Hz, C), 117.6 (d,
J = 22.7 Hz, CH), 61.1 (CH2), 14.2 (CH3), 9.9 (CH3); HRESIMS m/z for
C12H12ClFN3O2 [M + H]+ calcd 284.0602; found: 284.0604.
1-(4-Nitrophenyl)-5-phenyl-1H-1,2,3-triazole-4-carbonitrile
(3r):
Yellow solid; m.p.: 162–165 °C (lit.31,32 162–165 °C); IR (cm–1) ν: 3088
(CAr–H), 2240 (C≡N), 1532 (N=N), 854 (N–N=N); 1H NMR (500
MHz, CDCl3) δ (ppm): 8.32 (d, J = 9.2 Hz, 2H), 7.58 (d, J = 8.7 Hz, 2H),
7.55–7.46 (m, 3H), 7.38–7.32 (m, 2H); 13C NMR (126 MHz, CDCl3) δ
(ppm): 148.3 (C), 143.5 (C), 139.9 (C), 131.8 (CH), 129.9 (CH), 129.0
(CH), 125.8 (CH), 125.3 (CH), 122.7 (C), 121.4 (C), 111.5 (C, C≡N);
HRESIMS m/z for C15H10N5O2 [M + H]+ calcd 292.0829; found: 292.0827.
1-(5-Methyl-1-(4-nitrophenyl)-1H-1,2,3-triazol-4-yl)ethanone (3l):
White crystals (THF); m.p.: 139–40 °C (lit.30 148 °C); IR (cm–1) ν: 3077,
3004 (CAr–H); 2852 (Csp3–H), 1681 (C=O), 1598 (N=N), 1598 (CAr–CAr),
1
951 (N–N=N), 1518–1344 (Ar–NO2); H NMR (500 MHz, CDCl3) δ
We acknowledge the European ChemBioFight project (grant
agreement 269301) for financial support.
(ppm): 8.38 (d, J = 8.15 Hz, 2H), 7.88 (d, J = 8.14 Hz, 2H), 3.23 (s, 3H),
2.55 (s, 3H); 1H NMR (500 MHz, DMSO-d6) δ (ppm): 8.47 (d, J = 8.9
Hz, 2H), 7.97 (d, J = 9.0 Hz, 2H), 2.64 (s, 3H), 2.59 (s, 3H); 13C NMR
(126 MHz, CDCl3) δ (ppm): 193.2 (C=O), 147.9 (C), 143.1 (C), 139.8
(C), 138.2 (C), 126.5 (CH), 125.1 (CH), 27.6 (CH3), 9.8 (CH3); 13C NMR
(126 MHz, DMSO-d6) δ (ppm): 193.2 (C=O), 147.9 (C), 143.1 (C),
139.9 (C), 138.2 (C), 126.5 (CH), 125.1 (CH), 27.6 (CH3), 9.8 (CH3);
HRESIMS m/z for C11H11N4O3 [M + H]+ for 247.0831; found: 247.0828.
1-(1-(4-Methoxyphenyl)-5-methyl-1H-1,2,3-triazol-4-yl)ethanone
(3m): White crystals (THF); m.p.: 120–122 °C (lit.30,36 120 °C); IR
Received 27 April 2016; accepted 12 May 2016
Published online: 22 July 2016
References
1
Beena, N. Kumar, R.K. Rohilla, N. Roy and D.S. Rawat, Bioorg. Med.
Chem. Lett., 2009, 19, 1396.