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J.C. Sloop et al. / Journal of Fluorine Chemistry 118 (2002) 135–147
1-Phenyl-3,5-ditrifluoromethylpyrazole (3g): This com-
pound was obtained as a pale yellow liquid 3g, bp 110 8C
Anal. Calc. for C14H13F3N2O: C, 64.15, H, 4.11, N, 8.80.
Found: C, 64.49, H, 4.03, N, 8.95.
1
(28 mmHg). NMR: H: d 7.0 (1H, s), 7.4 (5H, m). 13C: d
5-(4-Cyanophenyl)-1-phenyl-3-trifluoromethylpyrazole
(3o): This compound was obtained as a yellow solid (EtOH),
3o, mp 77 8C. NMR: d 1H: 6.9 (1H, s), 7.1 (2H, m), 7.25 (5H,
m), 7.4 (2H, m). 13C: d 106, 117 (CF3, q, 1JCÀF ¼ 269 Hz),
1
1
107, 117 (CF3, q, JCÀF ¼ 273 Hz), 122 (CF3, q, JCÀF
¼
2
272 Hz), 125, 128, 129, 130, 134 (C–CF3, q, JCÀF
¼
35 Hz), 138, 143 (CF3, q, JCÀF ¼ 36 Hz). 19F: d À58.7
(3F, s), À63.1 (3F, s). Anal. Calc. for C11H16F6N4: C, 49.64,
H, 2.16, N, 10.00. Found: C, 50.01, H, 1.98, N, 10.32.
1,3-Diphenyl-5-trifluoromethylpyrazole (2h) and 1,5-
diphenyl-3-trifluoromethyl-pyrazole (3h): These compounds
were obtained as an 18:82 mixture of 2h:3h, which on
recrystallization (EtOH) gave a white crystalline solid, 3h,
mp 87–88 8C [19] (mp 95 8C). Anal. Calc. for C16H11F3N2:
C, 66.66, H, 3.85, N, 9.72. Found: C, 66.41, H, 3.85, N, 9.86.
5-(2-Fluorophenyl)-1-phenyl-3-trifluoromethylpyrazole
(3i): This compound was obtained as a pale purple solid
2
2
137, 143 (C–CF3, q, JCÀF ¼ 36 Hz). 19F: d À62.5 (3F, s).
Anal. Calc. for C17H10F3N3: C, 64.98, H, 3.50, N, 13.37.
Found: C, 64.49, H, 3.87, N, 13.29.
5-(4-Nitrophenyl)-1-phenyl-3-trifluoromethylpyrazole (3p):
This compound was obtained as a yellowish-brown solid
(EtOH), 3p, mp 56 8C. NMR: 1H: d 6.7 (1H, s), 7.3 (9H, m).
13C: d 107, 122 (CF3, q, 1JCÀF ¼ 270 Hz), 137, 142 (C–CF3,
2
q, JCÀF ¼ 36 Hz). 19F: d À62.0 (3F, s). Anal. Calc. for
C16H10F3N3O2: C, 57.66, H, 3.02, N, 12.61. Found: C,
58.00, H, 3.11, N, 12.86.
1
(EtOH), 3i, mp 80–83 8C. NMR: H: d 6.8 (1H, s), 7.4
3-(2-Naphthyl)-1-phenyl-5-trifluoromethylpyrazole (2q)
and 5-(2-naphthyl-1-phenyl-3-trifluoromethylpyrazole (3q):
These compounds were obtained as a 93:7 mixture of 3q:2q,
and recrystallization (EtOH) yields orange–brown crystals,
3q, mp 48–50 8C. NMR: 2q: 19F: d À57.8 (3F, s). 3q: 1H: d
6.8 (1H, s), 7.1 (2H, d, J ¼ 5:3 Hz), 7.3 (2H, d, J ¼ 3:9 Hz),
7.4 (3H, t, J ¼ 5:3 Hz), 7.7 (2H, d, J ¼ 4:0 Hz), 7.8 (3H, t,
J ¼ 3:9 Hz). 13C: d 106, 121 (CF3, q, 1JCÀF ¼ 272 Hz), 139,
141 (C–CF3, q, 2JCÀF ¼ 35 Hz). 19F: d À62.3 (3F, s). Anal.
Calc. for C20H13F3N2: C, 71.00, H, 3.42, N, 7.31. Found: C,
70.75, H, 3.39, N, 6.96.
(9H, m). 13C: d 106, 121 (CF3, q, 1JCÀF ¼ 264 Hz), 137, 142
(C–CF3, q, 2JCÀF ¼ 35 Hz), 158 (Ar–F, d, 1JCÀF ¼ 248 Hz).
19F: d À62.3 (3F, s), À113, (1F, s). Anal. Calc. for
C16H10F4N2: C, 62.76, H, 3.29, N, 9.15. Found: C, 62.33,
H, 3.60, N, 8.89.
5-(2-Methylphenyl)-1-phenyl-3-trifluoromethylpyrazole
(3j): This compound was obtained as yellow crystals
1
(EtOH), 3j, mp 56–58 8C. NMR: H: d 2.3 (3H, s), 6.5
(1H, s), 7.45 (9H, m). 13C: d 38, 106, 121 (CF3, q,
2
1JCÀF ¼ 269 Hz), 137, 142 (C–CF3, q, JCÀF ¼ 34 Hz).
19F: d À62.6 (3F, s). Anal. Calc. for C17H13F3N2: C,
67.61, H, 4.34, N, 9.28. Found: C, 67.95, H, 4.01, N, 8.95.
5-(2-Methoxyphenyl)-1-phenyl-3-trifluoromethylpyrazole
(3k): This compound was obtained as a pale yellow liquid,
3k, bp 159 8C (28 mmHg). NMR: 1H: d 4.1 (3H, s), 7.0 (1H,
s), 7.15 (2H, m), 7.6 (2H, m). 13C: d 56, 106, 122 (CF3, q,
1JCÀF ¼ 270 Hz), 137, 142 (C–CF3, q, 2JCÀF ¼ 34 Hz). 19F:
d À62.0 (3F, s). Anal. Calc. for C17H13F3N2O: C, 64.15, H,
4.11, N, 8.80. Found: C, 63.79, H, 4.10, N, 8.87.
3-(2-Pyridyl)-1-phenyl-5-trifluoromethylpyrazole (2r)
and 5-(2-pyridyl)-1-phenyl-3-trifluoromethylpyrazole (3r):
These compounds were obtained as a 90:10 mixture of
3r:2r, which reduced on distillation to a 42:58 mixture
1
of 3r:2r, bp 207–210 8C (25 mmHg). NMR: 2r: H: d 7.1
(1H, s), 7.4 (5H, m), 8.0 (2H, d, J ¼ 10:9 Hz), 8.6 (2H, q,
J ¼ 5:9 Hz). 13C: d 108, 118 (CF3, q, 1JCÀF ¼ 280 Hz), 137,
137 (C–CF3, q, 2JCÀF ¼ 39 Hz). 19F: À57.8 (3F, s). 3r: 1H: d
6.9 (1H, s), 7.3 (m, 5H), 7.8 (t, J ¼ 5:9 Hz, 2H), 8.5 (q,
J ¼ 5:9 Hz, 2H). 13C: d 107, 122 (CF3, q, 1JCÀF ¼ 280 Hz),
5-(4-Fluorophenyl)-1-phenyl-3-trifluoromethylpyrazole
(3l): This compound was obtained as a yellow solid (EtOH),
3l, mp 101 8C. NMR: 1H: d 6.8 (1H, s), 7.35 (9H, m). 13C: d
2
137, 144 (C–CF3, q, JCÀF ¼ 39 Hz). 19F: d À62. (3F, s).
Anal. Calc. for C15H10F3N3: C, 62.08, H, 3.79, N, 14.48.
Found: C, 62.39, H, 3.83, N, 14.20.
1
106, 121 (CF3, q, JCÀF ¼ 264 Hz), 137, 142 (C–CF3, q,
1
2JCÀF ¼ 36 Hz), 158 (Ar–F, d, JCÀF ¼ 248 Hz). 19F: d
5-(2-Pyrrolyl)-1-phenyl-3-trifluoromethylpyrazole (3s):
This compound was obtained as brown crystals (EtOH),
À62.1 (3F, s), À113 (1F, s). Anal. Calc. for C16H10F4N2:
C, 62.76, H, 3.29, N, 9.15. Found: C, 62.26, H, 3.69, N, 9.08.
5-(4-Methylphenyl)-1-phenyl-3-trifluoromethylpyrazole
(3m): This compound was obtained as a yellow liquid, 3m,
bp 165 8C (28 mmHg). NMR: 1H: d 2.3 (3H, s), 6.5 (1H, s),
7.5 (9H, m). 13C: d 38, 106, 121 (CF3, q, 1JCÀF ¼ 269 Hz),
1
3s, mp 103–105 8C. NMR: H: d 5.9 (d, J ¼ 3:4 Hz, 1H),
6.0 (d, J ¼ 3:3 Hz, 1H), 6.67 (1H, s), 6.71 (s, 1H), 7.3
(m, 5H), 8.7 (bs, 1H). 13C: d 103, 109, 110, 113, 120, 122
1
(CF3, q, JCÀF ¼ 271 Hz), 125, 129, 137, 142 (C–CF3, q,
2JCÀF ¼ 36 Hz). 19F: d À62.4 (3F, s). Anal. Calc. for
C14H10F3N3: C, 60.65, H, 3.63, N, 15.15. Found: C,
60.65, H, 3.64, N, 15.16.
2
137, 142 (C–CF3, q, JCÀF ¼ 34 Hz). 19F: d À62.2 (3F, s).
Anal. Calc. for C17H13F3N2: C, 67.61, H, 4.34, N, 9.28.
Found: C, 67.50, H, 4.12, N, 9.22.
5-(2-Furyl)-1-phenyl-3-trifluoromethylpyrazole (3t): This
compound was obtained as gray–green crystals (EtOH),
5-(4-Methoxyphenyl)-1-phenyl-3-trifluoromethylpyrazole
(3n): This compound was obtained as a pale yellow liquid,
1
3t, mp 42–43 8C. NMR: H: d 5.9 (1H, s), 6.3 (1H, s),
1
3n, bp 159 8C (28 mmHg). NMR: H: d 4.2 (3H, s), 7.0
6.9 (1H, s), 7.45 (m, 6H). 13C: d 104, 110, 111, 121 (CF3, q,
1JCÀF ¼ 269 Hz, 121), 139, 143 (C–CF3, q, 2JCÀF ¼ 36 Hz).
19F: d À62.5 (3F, s). Anal. Calc. for C14H9F3N2O: C, 60.43,
H, 3.26, N, 10.06. Found: C, 60.60, H, 3.51, N, 10.23.
(1H, s), 7.15 (2H, m, J ¼ 7:8 Hz), 7.4 (5H, m), 7.6 (2H, m,
J ¼ 7:7 Hz). 13C: d 56, 106, 122 (CF3, q, 1JCÀF ¼ 270 Hz),
2
137, 142 (C–CF3, q, JCÀF ¼ 34 Hz). 19F: d À62 (3F, s).