1198
M. A. P. Martins, C. M. P. Pereira, S. Moura, C. P. Frizzo, P. Beck,
N. Zanatta, H. G. Bonacorso and A. F. C. Flores
Vol 44
1H NMR (CDCl3) ꢀ (J, Hz) 2h: 3.10 (d, 1H, J = 19, H4a), 3.40
(d, 1H, J = 19, H4b), 6.90 (t, 1H, H3), 7.34 (m, 5H, Ph); 3h:
6.82 (d, 1H, H4) 7.90 (d, 1H, H3), 7.73 (m, 5H, Ph). 13C NMR
3-Ethyl-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-
phenyl pyrazole (2b). This compound was obtained as an oil.
1H NMR (CDCl3) ꢀ (J, Hz) 1.12 (t, 3H, CH3), 2.28 (q, 2H, CH2),
2.84 (d, 1H, J = 16, H4a), 3.20 (d, 1H, J = 16, H4b), 7.27 (m,
5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz) 154.0 (C3), 45.9 (C4),
2
(CDCl3) ꢀ (JC-F, Hz) 2h: 148.2 (C3), 47.8 (C4), 92.5 (q, J = 32,
1
C5), 124.0 (q, J = 282, CF3), 125.6, 129.0, 129.2, 140.1 (N-
2
1
93.0 (q, J = 31, C5), 123.9 (q, J = 283, CF3), 10.7 (CH3), 23.0
(CH2), 125.2, 128.5, 129.0 141.5 (N-Ph). MS (m/z, %) 240 (M+ -
H2O, 100), 225 (45), 77 (Ph, 57). Anal. Calcd. for C12H13F3N2O
(258.24): C, 55.81; H, 5.07; N, 10.85%. Found: C, 55.50; H,
5.05; N, 10.78%.
Ph); 3h: 139.9 (C3), 109.2 (C4), 132.9 (q, 2J = 39, C5),120.2 (q,
1J = 269, CF3), 125.6, 129.0, 129.2, 138.0 (N-Ph).
3(5)-Methyl-1-phenyl-5(3)-trifluoromethylpyrazole (3a +
4a). The data listed refers to a mixture of 3a and 4a, with molar
ratio of 1:1. The mixture of compounds was obtained as an oil.
3a: 1H NMR (CDCl3) ꢀ 2.29 (s, 3H, CH3), 6.52 (s, 1H, H4), 7.50
(m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz) 149.0 (C3), 108.5
5-Hydroxy-3-propyl-5-trifluoromethyl-4,5-dihydro-1H-
phenylpyrazole (2c). This compound was obtained as an oil. 1H
NMR (CDCl3) ꢀ (J, Hz) 0.97 (t, 3H, CH3), 1.65 (m, 2H, CH2),
2.30 (t, 2H, CH2), 2.91 (d, 1H, J = 18, H4a), 3.22 (d, 1H, J = 18,
H4b), 7.31 (m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz) 153.2
(C3), 46.0 (C4), 93.0 (q, 2J = 31, C5), 122.0 (q, 1J = 284, CF3),
13.6 (CH3), 19.8 (CH2), 31.6 (CH2), 124.5, 128.7, 128.8, 141.2
(N-Ph). MS (m/z, %) 254 (M+ - H2O, 62), 239 (100), 77 (Ph,
43). Anal. Calcd. for C13H15F3N2O (272.27): C, 57.35; H, 5.55;
N, 10.29%. Found: C, 56.99; H, 5.52; N, 10.22%.
1
(C4), 125.0–139.0 (N-Ph), 132.9 (q, 2J = 39, C5), 120.1 (q, J =
267, CF3), 13.2 (CH3). MS (m/z, %) 226 (M+, 100), 77 (Ph, 70).
4a: 1H NMR (CDCl3) ꢀ 2.31 (s, 3H, CH3), 6.44 (s, 1H, H4), 7.33
(m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz) 149.6 (C3), 109.4
1
(C4), 125.0–139.0 (N-Ph), 132.7 (q, 2J = 39, C5), 118.4 (q, J =
259, CF3), 12.2 (CH3). MS (m/z, %) 226 (M+, 100), 77 (Ph, 45).
Anal. Calcd. for (mixture of 3a + 4a) C11H9F3N2 (226.20): C,
58.41; H, 4.01; N, 12.31%. Found: C, 58.02; H, 3.98; N,
12.30%.
5-Hydroxy-3-(1-methylethyl)-5-trifluoromethyl-4,5-dihydro-
1H-phenylpyrazole (2d). This compound was obtained as an
3-Ethyl-1-phenyl-5-trifluoromethylpyrazole (3b). This
compound was obtained as a white solid, mp 73-75°C. 1H NMR
(CDCl3) ꢀ 1.32 (t, 3H, CH3), 2.71 (q, 2H, CH2), 6.62 (s, 1H, H4),
7.46 (m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz) 154.8 (C3),
107.1 (C4), 125.5, 128.8, 128.9, 139.1, (N-Ph), 132.8 (q, 2J = 39,
C5), 119.8 (q, 1J = 259, CF3), 13.5 (CH3), 21.2 (CH2). MS (m/z,
%) 240 (M+, 100), 77 (Ph, 57). Anal. Calcd. for C12H11F3N2
(240.23): C, 60.00; H, 4.62; N, 11.66%. Found: C, 59.83; H,
4.60; N, 11.63%.
1
oil. H NMR (CDCl3) ꢀ (J, Hz) 1.15 (d, 6H, 2CH3), 2.65 (m,
1H, CH), 2.91 (d, 1H, J = 18, H4a), 3.23 (d, 1H, J = 18, H4b),
7.25 (m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz) 157.0 (C3),
1
44.0 (C4), 93.2 (q, 2J = 31, C5), 123.9 (q, J = 283, CF3), 19.9
(CH3), 20.1 (CH3), 29.4 (CH), 125.1, 128.6, 128.8, 141.5 (N-
Ph). MS (m/z, %) 254 (M+ - H2O, 62), 239 (100), 77 (Ph, 43).
Anal. Calcd. for C13H15F3N2O (272.27): C, 57.35; H, 5.55; N,
10.29%. Found: C, 56.96; H, 5.50; N, 10.21%.
1-Phenyl-3-propyl-5-trifluoromethylpyrazole (3c). This
compound was obtained as a white solid, mp 69-71°C. 1H NMR
(CDCl3) ꢀ 0.99 (t, 3H, CH3), 1.65 (m, 2H,CH2), 2.65 (t, 2H,
CH2), 6.60 (s, 1H, H4), 7.42 (m, 5H, Ph). 13C NMR (CDCl3) ꢀ
(JC-F, Hz) 153.5 (C3), 107.7 (C4), 125.6, 128.6, 128.9, 139.2, (N-
Ph), 132.8 (q, 2J = 38, C5), 122.8 (q, 1J = 268, CF3), 13.7 (CH3),
21.5, 31.6 (2CH2). MS (m/z, %) 254 (M+, 29), 226 (100), 77 (Ph,
47). Anal. Calcd. for C13H13F3N2 (254.26): C, 61.41; H, 5.15; N,
11.02%. Found: C, 61.30; H, 5.14; N, 11.00%.
3-Butyl-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-
phenylpyrazole (2e). This compound was obtained as an oil. 1H
NMR (CDCl3) ꢀ (J, Hz) 0.92 (t, 3H, CH3), 1.36 (m, 4H, 2CH2),
2.30 (t, 2H, CH2), 2.86 (d, 1H, J = 18, H4a), 3.18 (d, 1H, J = 18,
H4b), 7.33 (m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz) 153.1
2
1
(C3), 46.2 (C4), 93.2 (q, J = 31, C5), 122.0 (q, J = 285, CF3),
13.8 (CH3), 21.4 (CH2), 27.6 (CH2), 29.5 (CH2), 124.5, 128.5,
129.0, 141.8 (N-Ph). MS (m/z, %) 268 (M+ - H2O, 10), 226
(100), 77 (Ph, 33). Anal. Calcd. for C14H17F3N2O (286.30): C,
58.74; H, 5.99; N, 9.78%. Found: C, 58.46; H, 5.96; N, 9.73%.
5-Hydroxy-3-(2-methylpropyl)-5-trifluoromethyl-4,5-dihydro-
1H-phenylpyrazole (2f). This compound was obtained as an oil.
1H NMR (CDCl3) ꢀ (J, Hz) 0.92 (d, 6H, 2CH3), 1.85 (m, 1H,
CH), 2.01 (d, 2H, CH2), 2.82 (d, 1H, J = 20, H4a), 3.16 (d, 1H, J
= 20, H4b), 7.27 (m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz)
3-(1-Methylethyl)-1-phenyl-5-trifluoromethylpyrazole (3d).
1
This compound was obtained as a white solid, mp 45-47°C. H
NMR (CDCl3) ꢀ 1.31 (d, 3H, 2CH3), 1.28 (m, 1H, CH), 6.60 (s,
1H, H4), 6.63 (m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz) 159.3
(C3), 105.9 (C4), 126.0, 128.9, 129.0, 139.2, (N-Ph), 132.3 (q, 2J
= 40, C5), 119.9 (q, 1J = 269, CF3), 22.5 (2CH3), 30.3 (CH). MS
(m/z, %) 254 (M+, 57), 239 (100), 77 (Ph, 47). Anal. Calcd. for
C13H13F3N2 (254.26): C, 61.41; H, 5.15; N, 11.02%. Found: C,
61.24; H, 5.13; N, 10.99%.
3-Butyl-1-phenyl-5-trifluoromethylpyrazole (3e). This
compound was obtained as an oil. 1H NMR (CDCl3) ꢀ 0.99 (t, 3H,
CH3), 1.4 (m, 2H, CH2), 1.70 (m, 2H, CH2), 2.67 (m, 2H, CH2),
6.67 (s, 1H, H4), 7.50 (m, 5H, Ph). 13C NMR (CDCl3) ꢀ (JC-F, Hz)
153.7 (C3), 107.6 (C4), 125.5, 128.7, 128.9, 139.1, (N-Ph), 132.8
(q, 2J = 39, C5), 122.5 (q, 1J = 269, CF3), 13.8 (CH3), 22.3 (CH2),
27.3 (CH2), 31.5 (CH2). MS (m/z, %) 268 (M+, 9), 226 (100), 77
(Ph, 29). Anal. Calcd. for C14H15F3N2 (268.28): C, 62.68; H, 5.64;
N, 10.44%. Found: C, 62.36; H, 5.61; N, 10.39%.
2
1
152.8 (C3), 46.2 (C4), 93.1 (q, J = 31, C5), 123.9 (q, J = 284,
CF3), 22.2 (CH3), 22.4 (CH3), 26.5 (CH), 38.7 (CH2),124.0,
128.7, 129.1, 141.8 (N-Ph). MS (m/z, %) 268 (M+ - H2O, 5), 226
(100), 77 (Ph, 29). Anal. Calcd. for C14H17F3N2O (286.30): C,
58.74; H, 5.99; N, 9.78%. Found: C, 58.39; H, 5.95; N, 9.73%.
3-Phenyl-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-
phenylpyrazole (2g). This compound was obtained as an oil. 1H
NMR (CDCl3) ꢀ (J, Hz) 3.40 (d, 1H, J =19, H4a), 3.60 (d, 1H, J
= 19, H4b), 6.64-7.88 (m, 10H, N-Ph, C3-Ph). 13C NMR
(CDCl3) ꢀ (JC-F, Hz) 151.2 (C3), 43.7 (C4), 93.0 (q, 2J = 31, C5),
124.3 (q, 1J = 282, CF3), 124 – 128 (N-Ph, C3-Ph). Anal. Calcd.
For C16H13F3N2O (306.29): C, 62.74%; H, 4.28% ; N, 9.15%.
Found: C, 62.45; H, 4.26; N, 9.10%.
3-(2-Methylpropyl)-1-phenyl-5-trifluoromethylpyrazole (3f).
1
This compound was obtained as a white solid, mp 59-60°C. H
NMR (CDCl3) ꢀ 0.92 (d, 6H, 2CH3), 1.92(m, 1H, CH), 1.41 (m,
2H, CH2), 2.5 (d, 2H, CH2), 6.52 (s, 1H, H4), 7.40 (m, 5H, Ph).
13C NMR (CDCl3) ꢀ (JC-F, Hz) 154.8 (C3), 107.8 (C4), 125.1,
5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-phenylpyra-
zole (2h) and 5-trifluoromethylphenylpyrazole (3h). The data
listed refers to a mixture of 2h and 3h, with a molar ratio of 2:1,
respectively. The mixture of compounds was obtained as an oil.