10.1002/ejoc.201700300
European Journal of Organic Chemistry
FULL PAPER
afford 1a (352 mg, 45 % yield) as a white solid. mp: 128-131 °C (lit. 124-
125 °C). 1H NMR (300 MHz, CDCl3), δ (ppm): 7.52 - 7.60 (m, 5 H); 4.00 (s,
3 H); 3.91 (s, 3 H). 13C NMR (91 MHz, CDCl3), δ (ppm): 160.1 (Cq), 159.4
(Cq), 138.7 (Cq), 135.5 (Cq), 132.5 (Cq), 130.5 (CH), 129.6 (2 CH), 124.2
(2 CH), 53.8 (CH3), 52.7 (CH3). IR (neat), ν (cm-1): 2956, 1721, 1557, 1498,
1355, 1292, 1239, 1201, 1170, 1093, 1067, 1005, 962, 828, 761, 687.
HRMS (ESI+): calcd for C12H12N3O4 [M+H]+ 262.0822, found 262.0823.
HRMS (ESI+): calcd for C17H13F3N3O2 [M+H]+ 348.0954, found 348.0953.
ε 254nm (MeCN): 34.14 l/mol.cm.
Methyl 5-(4-methoxyphenyl)-1-phenyl-1H-1,2,3-triazole-4-carboxylate
(1e) and methyl 4-(4-methoxyphenyl)-1-phenyl-1H-1,2,3-triazole-5-
carboxylate (1e’): azidobenzene (650 mg, 5.46 mmol), methyl 3-(4-
methoxyphenyl)propiolate (692 mg, 3.64 mmol) were dissolved in toluene
(10 mL) and heated for 48 h at reflux. The solvent was removed under
reduce pressure and purified by chromatography (Silica gel,
hexane/EtOAc, 2:1) to afford 1e (298 mg, 26 %) and 1e’ (184 mg, 16 %)
as off-white solid. 1e’: mp: 100-102 °C. Rf = 0.28 (Hexane/EtOAc 2/1). 1H
NMR (360 MHz, CDCl3), δ (ppm): 7.84 (d, J = 8.63 Hz, 2 H); 7.46 - 7.62
(m, 5 H); 7.02 (d, J = 8.63 Hz, 2 H); 3.89 (s, 3 H); 3.74 (s, 3 H). 13C NMR
(91 MHz, CDCl3), δ (ppm): 160.3 (Cq), 160.0 (Cq), 149.5 (Cq), 137.0 (Cq),
130.3 (2 CH), 129.8 (CH), 129.1 (2 CH), 125.2 (2 CH), 124.8 (Cq), 122.0
(Cq), 113.8 (2 CH), 55.3 (CH3), 52.5 (CH3). IR (neat), ν (cm-1): 1718, 1612,
1497, 1438, 1356, 1248, 1221, 1111, 1017, 989, 846, 760. HRMS (ESI+):
+ calcd for C17H16N3O3 [M+H]+ 310.1186, found 310.1181. ε 254nm (MeCN):
37.48 l/mol.cm. 1e: mp: 98-100 °C. Rf = 0.12 (Hexane/EtOAc 2:1). 1H NMR
(360 MHz, CDCl3), δ (ppm): 7.36 - 7.49 (m, 3 H); 7.28 - 7.34 (m, 2 H); 7.24
(d, J = 8.6 Hz, 2 H); 6.90 (d, J = 8.6 Hz, 2 H); 3.93 (s, 3 H); 3.83 (s, 3 H).
13C NMR (91 MHz, CDCl3), δ (ppm): 161.4 (Cq), 160.6 (Cq), 140.8 (Cq),
136.1 (Cq), 135.8 (Cq), 131.6 (2 CH), 129.3 (CH), 129.2 (2 CH), 125.1 (2
CH), 117.1 (Cq), 113.8 (2 CH), 55.1 (CH3), 52.0 (CH3). IR (neat), ν (cm-1):
1726, 1499, 1441, 1380, 1289, 1217, 1145, 1091, 1008, 839, 776, 696,
614. HRMS (ESI+): calcd for C17H16N3O3 [M+H]+ 310.1186, found
310.1182. ε 254nm (MeCN): 35.9 l/mol.cm.
Dimethyl
1-(4-chlorophenyl)-1H-1,2,3-triazole-4,5-dicarboxylate
(1b):[20] 1-azido-4-chlorobenzene (216 mg, 1.69 mmol) and dimethyl but-
2-ynedioate (0.312 mL, 2.54 mmol were dissolved in MeCN (4 mL) in
microwave vial. The mixture was stirred for 6 days at rt, concentrated in
vacuo and recrystallized in MeOH to afford 1b (203 mg, 40 %) as a white
solid. mp: 135-137°C (lit. 135 °C). 1H NMR (360 MHz, CDCl3), δ (ppm):
7.49 - 7.56 (m, 4 H); 4.02 (s, 3 H); 3.94 (s, 3 H). 13C NMR (91 MHz, CDCl3),
δ (ppm): 160.0 (Cq), 159.2 (Cq), 138.9 (Cq), 136.7 (Cq), 133.9 (Cq), 132.3
(Cq), 129.9 (2 CH), 125.6 (2 CH), 53.9 (CH3), 52.8 (CH3). IR (neat), ν (cm-
1): 1718, 1496, 1440, 1305, 1241, 1077, 1000, 829, 535. HRMS (ESI+):
calcd for C12H11ClN3O4 [M+H]+ 296.0432, found 296.0432.
Methyl 1,5-diphenyl-1H-1,2,3-triazole-4-carboxylate (1c) and methyl
1,4-diphenyl-1H-1,2,3-triazole-5-carboxylate
(1c’):[21]
methyl
3-
phenylpropiolate (642 mg, 4.01 mmol) and azidobenzene (716 mg,
6.01mmol) were dissolved in benzene (10 mL) and heated for 48 h at reflux.
The crude mixture was concentrated in vacuo and purified by
chromatography (Silica gel, pentane/EtOAc, 3:1) to afford the desired
product 1c (320 mg, 29 %) and 1c’ (135 mg, 12 %) as white solids. 1c:
mp: 132-134 °C (lit. 130 °C). Rf = 0.15 (Hexane/EtOAc 3:1). 1H NMR (360
MHz, CDCl3), δ (ppm): 7.28 - 7.48 (m, 9 H); 3.93 (s, 3 H). 13C NMR (91
MHz, CDCl3) , δ (ppm): 161.3 (Cq), 140.9 (Cq), 136.5 (Cq), 135.6 (Cq),
130.1 (2 CH), 129.9 (CH), 129.4 (CH), 129.2 (2 CH), 128.3 (2 CH), 125.4
(Cq), 125.1 (2 CH), 52.0 (CH3). IR (neat), ν (cm-1): 3063, 1725, 1500, 1442,
1432, 1224, 1141, 1070, 998, 925, 819, 762, 691. HRMS (ESI+): calcd for
C16H14N3O2 [M+H]+ 280.1080, found 280.1079. 1c’: mp: 108-110 °C (lit.
135 °C). Rf = 0.37 (Hexane/EtOAc 3:1). 1H NMR (360 MHz, CDCl3), δ
Methyl 1-(4-methoxyphenyl)-5-phenyl-1H-1,2,3-triazole-4-carboxylate
(1f) and methyl 1-(4-methoxyphenyl)-4-phenyl-1H-1,2,3-triazole-5-
carboxylate (1f’): 1-azido-4-methoxybenzene (0.905 g, 6.07 mmol) and
methyl 3-phenylpropiolate (0.597 mL, 4.05 mmol) were dissolved in 10 mL
of benzene in a microwave vial and heated to 100 °C for 50 h. The mixture
was concentrated in vacuo and purified by chromatography (Silica gel,
pentane/EtOAC, 1:0 to 2:1) to afford 1f (436 mg, 35 %) as a yellow solid
and 1f’ (245 mg, 20 %) as a pink solid. 1f’: mp: 100-102 °C. Rf = 0.38
(Pentane/EtOAc 3:1). 1H NMR (360 MHz, CDCl3), δ (ppm): 7.85 (d, J =
6.8 Hz, 2 H); 7.37 - 7.57 (m, 5 H); 7.04 (d, J = 8.6 Hz, 2 H); 3.90 (s, 3 H);
3.75 (s, 3 H). 13C NMR (75 MHz, CDCl3), δ (ppm): 160.6 (Cq), 159.9 (Cq),
149.3 (Cq), 129.9 (Cq), 129.8 (Cq), 129.1 (CH), 128.8 (2 CH), 128.3 (2
CH), 126.6 (2 CH), 125.5 (Cq), 114.2 (2 CH), 55.6 (CH3), 52.6 (CH3). IR
(neat), ν (cm-1): 3006, 2953, 2838, 1727, 1511, 1487, 1450, 1230, 1224,
1113, 1106, 1017, 836, 768, 699. HRMS (ESI+):calcd for C17H16N3O3
[M+H]+ 310.1186, found 310.1179. ε 254nm (MeCN): 41.4 l/mol.cm. 1f: mp:
122-124 °C. Rf = 0.13 (Pentane/EtOAc 3:1). 1H NMR (360 MHz, CDCl3),
δ (ppm): 7.35 - 7.48 (m, 3 H); 7.28 - 7.34 (m, 2 H); 7.19 (d, J = 9.1 Hz, 2
H); 6.88 (d, J = 9.1 Hz, 2 H); 3.92 (s, 3 H); 3.82 (s, 3 H). 13C NMR (75 MHz,
CDCl3), δ (ppm): 161.4 (Cq), 160.1 (Cq), 140.9 (Cq), 136.3 (Cq), 130.1 (2
CH), 129.8 (CH), 128.6 (Cq), 128.3 (2 CH), 126.5 (2 CH), 125.6 (Cq), 114.3
(2 CH), 55.4 (CH3), 52.0 (CH3). IR (neat), ν (cm-1): 3062, 2949, 2841, 1717,
1515, 1370, 1252, 1223, 1084, 994, 838, 765, 698. HRMS (ESI+):calcd for
(ppm): 7.87 (d, J = 6.36 Hz, 2 H); 7.39 - 7.65 (m, 8 H); 3.74 (s, 3 H). 13
C
NMR (91 MHz, CDCl3), δ (ppm): 159.8 (Cq), 149.4 (Cq), 136.9 (Cq), 129.9
(CH), 129.6 (CH), 129.1 (2 CH), 128.8 (2 CH), 128.3 (2 CH), 125.4 (Cq),
125.2 (2 CH), 52.6 (CH). IR (neat), ν (cm-1): 3058, 2953, 2923, 2852, 1721,
1554, 1495, 1440, 1297, 1263, 1225, 1150, 993, 764, 697. HRMS (ESI+):
calcd for C16H14N3O2 [M+H]+ 280.1080, found 280.1080.
Methyl
carboxylate (1d) and methyl 1-phenyl-4-(4-(trifluoromethyl)phenyl)-
1H-1,2,3-triazole-5-carboxylate (1d’): methyl 3-(4-
1-phenyl-5-(4-(trifluoromethyl)phenyl)-1H-1,2,3-triazole-4-
(trifluoromethyl)phenyl)propiolate (1.76 g, 7.71 mmol) and azidobenzene
(1.38 g, 11.56 mmol) were dissolved in toluene (20 mL) and heated at
reflux for 62 h. The solution was concentrated in vacuo and purified by
chromatography (Silica gel, pentane/EtOAc, 3:1) to afford 1d and 1d’ in a
3:2 ratio (2.05 g, 77 %) as pale yellow solids. 1d’: mp: 115-117 °C. Rf =
0.4 (Pentane/EtOAc 3:1). 1H NMR (360 MHz, CDCl3), δ (ppm): 8.02 (d, J
= 8.17 Hz, 2 H); 7.76 (d, J = 8.17 Hz, 2 H); 7.42 - 7.64 (m, 5 H); 3.76 (s, 3
H). 13C NMR (91 MHz, CDCl3), δ (ppm): 159.4, 148.0, 136.7, 133.2, 131.42,
131.0, 130.7, 130.3, 130.1, 129.1, 128.5, 126.0, 125.4, 125.3, 125.25,
125.20, 125.16, 125.13, 122.4, 119.4, 52.7. IR (neat), ν (cm-1): 1724, 1497,
1440, 1326, 1300, 1268, 1228, 1201, 1153, 1105, 1066, 1038, 1023, 994,
852, 815, 785, 773, 696. HRMS (ESI+): calcd for C17H13F3N3O2 [M+H]+
348.0954, found 348.0955. ε 254nm (MeCN): 38.86 l/mol.cm. 1d: mp: 128-
130 °C. Rf = 0.17 (Pentane/EtOAc 3:1). 1H NMR (360 MHz, CDCl3), δ
(ppm): 7.66 (d, J = 7.72 Hz, 2 H); 7.36 - 7.50 (m, 5 H); 7.27 - 7.33 (m, 3
H); 3.94 (s, 3 H). 13C NMR (91 MHz, CDCl3), δ (ppm): 161.0, 139.4, 136.8,
135.2, 132.2, 131.9, 131.5, 131.1, 130.7, 129.8, 129.4, 129.2, 128.0, 125.3,
125.2, 125.18, 125.14, 125.11, 125.0, 121.9, 118.9, 52.1. IR (neat), ν (cm-
1): 1727, 1500, 1441, 1326, 1221, 1123, 1067, 998, 846, 763, 690, 618.
C17H16N3O3 [M+H]+ 310.1186, found 310.1180. ε
l/mol.cm.
(MeCN): 42.94
254nm
Methyl 1,5-bis(4-methoxyphenyl)-1H-1,2,3-triazole-4-carboxylate (1g)
and methyl 1,4-bis(4-methoxyphenyl)-1H-1,2,3-triazole-5-carboxylate
(1g’): 1-azido-4-methoxybenzene (895 mg, 6.00 mmol) and methyl 3-(4-
methoxyphenyl)propiolate (761 mg, 4mmol) were dissolved in benzene
(10 mL) and heated at reflux for 26 h. The solvent was removed under
reduced pressure and the residue was purified by chromatography (Silica
gel, pentane/EtOAC, 3:1) to afford 1g (202 mg, 15 %) and 1g’ (101 mg,
7 %) as brown solids. 1g’: mp: 148-150 °C. Rf = 0.25 (Pentane/EtOAc 3:1).
1H NMR (360 MHz, CDCl3), δ (ppm): 7.81 (d, J = 8.6 Hz, 2 H); 7.43 (d, J =
8.6 Hz, 2 H); 6.87 - 7.12 (m, 4 H); 3.90 (s, 3 H); 3.89 (s, 3 H); 3.74 (s, 3 H).
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