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J. Wei et al. / Journal of Fluorine Chemistry 133 (2012) 146–154
1
3
4.2.1. Methyl 1-benzyl-5-(trifluoromethyl)-1H-1,2,3-triazole-4-
CDCl3) d 53.48, 53.69, 119.85 (q, JC–F = 267.5 Hz), 126.31 (q, JC–
2
carboxylate (3aa) [14]
F = 2.5 Hz), 129.26, 129.85, 132.42, 135.08, 140.08 (q, JC–
F = 39.58 Hz), 157.41 ppm. MS (EI) m/z 319 (M+). IR (KBr) 3018,
2962, 1736, 1475, 1377, 832 cmꢀ1. Anal. Calcd. for C12H9ClF3N3O2:
C, 45.09; H, 2.84; N, 13.14. Found: C, 45.11; H, 2.81; N, 13.17.
White solid; mp: 40.2–41.0 8C; 1H NMR (500 MHz, CDCl3)
d 3.94
(s, 3H, OCH3), 5.94 (s, 2H, CH2), 7.33–7.37 (m, 5H, ArH) ppm. 19F
NMR (470 MHz, CDCl3)
d
ꢀ56.61 (s, CF3) ppm. MS (EI) m/z 270 (M+).
4.2.2. Methyl 3-benzyl-5-(trifluoromethyl)-3H-1,2,3-triazole-4-
4.2.9. Methyl 1-(4-nitrobenzyl)-5-(trifluoromethyl)-1H-1,2,3-
carboxylate (4aa) [14]
triazole-4-carboxylate (3ae)
White solid; mp: 63.0–63.9 8C; 1H NMR (500 MHz, CDCl3)
d
3.97
White solid; mp: 101.2–102.6 8C; 1H NMR (500 MHz, CDCl3)
d
(s, 3H, OCH3), 5.76 (s, 2H, CH2), 7.20–7.35 (m, 5H, ArH) ppm. 19F
NMR (470 MHz, CDCl3)
3.95 (s, 3H, OCH3), 5.88 (s, 2H, CH2), 7.37 (d, J = 8.5 Hz, 2H, ArH),
d
ꢀ61.12 (s, CF3) ppm. MS (EI) m/z 270 (M+).
8.19 (d, J = 8.5 Hz, 2H, ArH) ppm. 19F NMR (470 MHz, CDCl3)
d
ꢀ56.63 (s, CF3) ppm. 13C NMR (125 MHz, CDCl3)
d 53.09, 54.08,
4.2.3. Methyl 1-(4-methylbenzyl)-5-(trifluoromethyl)-1H-1,2,3-
119.02 (q, 1JC–F = 270 Hz), 124.39, 128.42, 128.92 (q, 2JC–F = 45 Hz),
139.64, 140.13, 148.30, 159.12 ppm. MS (EI) m/z 330 (M+). IR (KBr)
3020, 2964, 1740, 1531, 1479, 1347, 1321, 825 cmꢀ1. Anal. Calcd.
for C12H9F3N4O4: C, 43.65; H, 2.75; N, 16.97. Found: C, 43.84; H,
2.73; N, 16.91.
triazole-4-carboxylate (3ab)
White solid; mp: 37.4–39.1 8C; 1H NMR (500 MHz, CDCl3)
d 2.32
(s, 3H, CH3), 3.97 (s, 3H, OCH3), 5.72 (s, 2H, CH2), 7.12 (d, J = 8.5 Hz,
2H, ArH), 7.20 (d, J = 8.5 Hz, 2H, ArH) ppm. 19F NMR (470 MHz,
CDCl3)
d
ꢀ56.60 (s, CF3) ppm. 13C NMR (125 MHz, CDCl3)
d 21.13,
52.88, 54.92, 55.28, 114.26, 119.16 (q, 1JF–C = 268.75 Hz), 128.66 (q,
2JF–C = 42.5 Hz), 129.83, 130.37, 139.05, 159.42 ppm. MS (EI) m/z
299 (M+). IR (KBr) 3038, 2956, 1744, 1470, 1354, 818 cmꢀ1. Anal.
Calcd. for C13H12F3N3O2: C, 52.18; H, 4.04; N, 14.04. Found: C,
52.37; H, 4.03; N, 14.12.
4.2.10. Methyl 3-(4-nitrobenzyl)-5-(trifluoromethyl)-3H-1,2,3-
triazole-4-carboxylate (4ae)
White solid; mp: 114.9–115.7 8C; 1H NMR (500 MHz, CDCl3)
d
3.95 (s, 3H, OCH3), 6.03 (s, 2H, CH2), 7.51 (d, J = 8.5 Hz, 2H, ArH),
8.19 (d, J = 8.5 Hz, 2H, ArH) ppm. 19F NMR (470 MHz, CDCl3)
d
ꢀ61.14 (s, CF3) ppm. 13C NMR (125 MHz, CDCl3)
d 53.51, 53.65,
4.2.4. Methyl 3-(4-methylbenzyl)-5-(trifluoromethyl)-3H-1,2,3-
119.74 (q, 1JC–F = 268 Hz), 124.26, 126.49 (d, 3JC–F = 2.5 Hz), 129.26,
140.17 (q, 2JC–F = 39.2 Hz), 140.70, 148.24, 157.33 ppm. MS (EI) m/z
330 (M+). IR (KBr) 3026, 2966, 1741, 1522, 1473, 1351, 1329,
825 cmꢀ1. Anal. Calcd. for C12H9F3N4O4: C, 43.65; H, 2.75; N, 16.97.
Found: C, 43.82; H, 2.74; N, 16.92.
triazole-4-carboxylate (4ab)
White solid; mp: 68.5–69.2 8C; 1H NMR (500 MHz, CDCl3)
d 2.35
(s, 3H, CH3), 3.97 (s, 3H, OCH3), 5.92 (s, 2H, CH2), 7.18 (d, J = 8.0 Hz,
2H, ArH), 7.27 (d, J = 8.0 Hz, 2H, ArH) ppm. 19F NMR (470 MHz,
CDCl3)
d
ꢀ61.10 (s, CF3) ppm. 13C NMR (125 MHz, CDCl3)
d 21.24,
1
53.36, 54.24, 119.95 (q, JF–C = 267.5 Hz), 126.33, 128.32, 129.71,
131.07, 138.96, 140.01 (q, 2JF–C = 39.2 Hz), 157.47 ppm. MS (EI) m/z
299 (M+). IR (KBr) 3030, 2959, 1739, 1470, 1374, 815 cmꢀ1. Anal.
Calcd. for C13H12F3N3O2: C, 52.18; H, 4.04; N, 14.04. Found: C,
52.35; H, 4.01; N, 14.07.
4.2.11. Methyl 5-(trifluoromethyl)-1-((naphthalen-2-yl)methyl)-1H-
1,2,3-triazole-4-carboxylate (3af)
Yellow oil; 1H NMR (500 MHz, CDCl3)
d
3.97 (s, 3H, OCH3), 5.90 (s,
2H, CH2), 7.31 (d, J = 8.5 Hz, 1H, ArH), 7.47–7.50 (m, 2H, ArH), 7.65 (s,
1H, ArH), 7.78–7.82 (m, 3H, ArH) ppm. 19F NMR (470 MHz, CDCl3)
d
ꢀ56.58 (s, CF3) ppm. 13C NMR (125 MHz, CDCl3)
d 52.94, 55.23,
1
4.2.5. Methyl 1-(4-methoxybenzyl)-5-(trifluoromethyl)-1H-1,2,3-
60.41, 119.17 (q, JC–F = 269.2 Hz), 124.48, 126.84, 126.92, 127.80,
2
triazole-4-carboxylate (3ac) [15]
128.06, 128.86 (q, JC–F = 42.5 Hz), 129.17, 130.68, 133.10, 133.26,
White solid; mp: 77.4–78.5 8C; 1H NMR (500 MHz, CDCl3)
d
3.75
139.44, 159.39 ppm. MS (EI) m/z 335 (M+). IR (KBr) 3027, 2956, 1745,
1473, 1353 cmꢀ1. Anal. Calcd. for C16H12F3N3O2: C, 57.32; H, 3.61; N,
12.53. Found: C, 57.22; H, 3.60; N, 12.52.
(s, 3H, OCH3), 3.94 (s, 3H, OCH3), 5.66 (s, 2H, CH2), 6.83 (d,
J = 9.0 Hz, 2H, ArH), 7.17 (d, J = 9.0 Hz, 2H, ArH) ppm. 19F NMR
(470 MHz, CDCl3)
d
ꢀ56.63 (s, CF3) ppm. MS (EI) m/z 315 (M+).
4.2.12. Methyl 5-(trifluoromethyl)-1-((naphthalen-2-yl)methyl)-3H-
4.2.6. Methyl 1-(4-methoxybenzyl)-5-(trifluoromethyl)-1H-1,2,3-
triazole-4-carboxylate (4ac) [16]
1,2,3-triazole-4-carboxylate (4af)
Yellow oil; 1H NMR (500 MHz, CDCl3)
d
3.93 (s, 3H, OCH3), 6.09
White solid; mp: 113.6–115.1 8C; 1H NMR (500 MHz, CDCl3)
d
(s, 2H, CH2), 7.45 (d, J = 8.5 Hz, 1H, ArH), 7.49–7.52 (m, 2H, ArH),
3.78 (s, 3H, OCH3), 3.95 (s, 3H, OCH3), 5.86 (s, 2H, CH2), 6.85 (d,
7.81–7.84 (m, 4H, ArH) ppm. 19F NMR (470 MHz, CDCl3)
d
ꢀ61.02
J = 8.5 Hz, 2H, ArH), 7.31 (d, J = 8.5 Hz, 2H, ArH) ppm. 19F NMR
(s, CF3) ppm. 13C NMR (125 MHz, CDCl3)
d
53.38, 54.57, 60.48,
1
3
(470 MHz, CDCl3)
d
ꢀ61.10 (s, CF3) ppm. MS (EI) m/z 315 (M+).
119.93 (q, JC–F = 269.2 Hz), 125.42, 126.46 (q, JC–F = 1.25 Hz),
126.75, 126.85, 127.78, 127.82, 128.15, 128.99, 131.35, 133.17,
2
4.2.7. Methyl 1-(4-chlorobenzyl)-5-(trifluoromethyl)-1H-1,2,3-
140.05 (q, JC–F = 39.58 Hz), 157.41 ppm. MS (EI) m/z 335 (M+). IR
triazole-4-carboxylate (3ad)
(KBr) 3027, 2958, 1740, 1469, 1373 cmꢀ1
.
Anal. Calcd. for
16H12F3N3O2: C, 57.32; H, 3.61; N, 12.53. Found: C, 57.45; H,
3.59; N, 12.49.
White solid; mp: 44.4–45.8 8C; 1H NMR (500 MHz, CDCl3)
d
3.94
(s, 3H, OCH3), 5.71 (s, 2H, CH2), 7.14 (d, J = 8.5 Hz, 2H, ArH), 7.30 (d,
J = 8.5 Hz, 2H, ArH) ppm. 19F NMR (470 MHz, CDCl3)
ꢀ56.65 (s,
CF3) ppm. 13C NMR (125 MHz, CDCl3) 52.98, 54.36, 119.10 (q, 1JC–
C
d
d
4.2.13. Methyl 1-(4-methoxybenzyl)-5-(pentafluoroethyl)-1H-1,2,3-
F = 268.75 Hz), 128.67 (q, 2JC–F = 41.25 Hz), 129.09, 129.38, 131.79,
135.22, 139.48, 159.28 ppm. MS (EI) m/z 319 (M+). IR (KBr) 3009,
2957, 1744, 1474, 1357, 814 cmꢀ1. Anal. Calcd. for C12H9ClF3N3O2:
C, 45.09; H, 2.84; N, 13.14. Found: C, 45.12; H, 2.82; N, 13.16.
triazole-4-carboxylate (3bc)
White solid; mp: 40.9–42.5 8C; 1H NMR (500 MHz, CDCl3)
d 3.76
(s, 3H, OCH3), 3.94 (s, 3H, OCH3), 5.62 (s, 2H, CH2), 6.84 (d,
J = 8.5 Hz, 2H, ArH), 7.21 (d, J = 8.5 Hz, 2H, ArH) ppm. 19F NMR
(470 MHz, CDCl3)
d
ꢀ83.63 (t, J = 4.7 Hz, CF3), ꢀ108.57 to ꢀ108.54
3
4.2.8. Methyl 3-(4-nitrobenzyl)-5-(trifluoromethyl)-3H-1,2,3-
(m, CF2) ppm. 13C NMR (125 MHz, CDCl3)
d
52.93, 54.91 (t, JC–
1
2
triazole-4-carboxylate (4ad)
F = 2.5 Hz), 55.34, 111.49 (tq, JC–F = 285.83 Hz, JC–F = 41.39 Hz),
1
2
White solid; mp: 67.1–67.7 8C; 1H NMR (500 MHz, CDCl3)
d
3.95
114.36, 118.26 (qt, JC–F = 303.75 Hz, JC–F = 37.19 Hz), 125.46,
2
(s, 3H, OCH3), 5.89 (s, 2H, CH2), 7.28–7.32 (m, 4H, ArH) ppm. 19F
126.67 (t, JC–F = 31.25 Hz), 132.48, 140.56, 159.28, 160.13 ppm.
NMR (470 MHz, CDCl3)
d
ꢀ61.13 (s, CF3) ppm. 13C NMR (125 MHz,
MS (EI) m/z 365 (M+). IR (KBr) 3007, 2959, 1747, 1465, 1358,