3-(2,4,5-Trifluorophenyl)-1,5-diphenyl-4,5-dihydro-1H-pyrazole
(8a). Synthesized from chalcone 17 ◦ and phenylhydrazine
1,3-Bis(3-fluorophenyl)-5-phenyl-4,5-dihydro-1H-pyrazole (3c).
Synthesized from chalcone 12 and 3◦-fluorophenylhydrazine
1
1
(method B). Yield: 40%. M.p. 124–126 C. H NMR (CDCl3,
(method B). Yield: 41%. M.p. 145–147 C. H NMR (CDCl3,
400 MHz) d 3.15 (ddd, J = 17.9, 7.5, 3.0 Hz, 1H), 3.83 (ddd, J =
17.9, 12.6, 3.0 Hz, 1H), 5.22 (dd, J = 12.6, 7.4 Hz, 1H), 6.74 (tt,
J = 7.3, 1.1 Hz, 1H), 6.84 (td, J = 10.2, 6.5 Hz, 1H), 6.95–6.98
(m, 2H), 7.08–7.14 (m, 2H), 7.17–7.22 (m, 3H), 7.25–7.29 (m, 2H),
7.83 (ddd, 11.2, 9.0, 6.9 Hz, 1H). 13C NMR (CDCl3, 100 MHz) d
400 MHz) d 3.05 (dd, J = 17.2, 6.9 Hz, 1H), 3.76 (dd, J = 17.2,
12.4 Hz, 1H), 5.21 (dd, J = 12.4, 6.9 Hz, 1H), 6.40 (td, J = 8.3,
1.8 Hz, 1H), 6.64 (dd, J = 8.3, 1.5 Hz, 1H), 6.79 (dt, J = 11.8,
2.3 Hz, 1H), 6.96 (tdd, J = 8.3, 2.5, 0.9 Hz, 1H), 7.01 (td, J =
8.2, 6.7 Hz, 1H), 7.18–7.29 (m, 6H), 7.35–7.40 (m, 2H). 13C NMR
(CDCl3, 100 MHz) d 43.5, 64.4, 100.8 (d, JCF = 26.9 Hz), 105.8 (d,
JCF = 21.6 Hz), 108.8 (d, JCF = 2.3 Hz), 112.4 (d, JCF = 22.9 Hz),
115.6 (d, JCF = 21.5 Hz), 121.5 (d, JCF = 2.8 Hz), 125.7, 127.8,
129.3, 130.0 (d, JCF = 9.9 Hz), 130.1 (d, JCF = 8.3 Hz), 134.6 (d,
45.3, (d, JCF = 7.9 Hz), 64.7 (d, JCF = 2.8 Hz), 106.1 (dd, JCF
=
28.5, 21.1 Hz), 113.5, 115.4 (dd, JCF = 20.7, 5.4 Hz), 117.5 (m),
119.7, 125.8, 127.7, 129.0, 129.2, 141.3 (m), 142.1, 144.2, 147.0
(ddd, JCF = 245.0, 12.9, 3.0 Hz), 149.9 (ddd, JCF = 254.1, 14.9,
12.2 Hz), 155.3 (ddd, JCF = 248.3, 9.2, 2.1 Hz). MS (70 eV) 352
(M+, 100), 275 (50), 91 (48), 77 (28). EI HRMS m/z calcd for [M]+
C21H15F3N2 352.1187, found 352.1182.
JCF = 8.3 Hz), 141.7, 145.9 (d, JCF = 10.8 Hz), 146.3 (d, JCF
=
3.1 Hz), 162.9 (d, 245.7 Hz), 163.6 (d, JCF = 242.7 Hz). MS (70 eV)
334 (M+, 100), 257 (40), 230 (12), 109 (50), 95 (18). EI HRMS m/z
calcd for [M]+ C21H16F2N2 334.1282, found 334.1265.
3-(2,3,4,5-Tetrafluorophenyl)-1,5-diphenyl-4,5-dihydro-1H -
pyrazole (9a). Synthesized from chalcone 18 and phenylhy-
drazine (method B). Yield: 44%. M.p. 126–128 ◦C. 1H NMR
(CDCl3, 400 MHz) d 3.16 (ddd, J = 17.9, 7.4, 2.9 Hz, 1H), 3.84
(ddd, J = 17.9, 12.6, 2.9 Hz, 1H), 5.27 (dd, J = 12.6, 7.4 Hz,
1H), 6.76 (tt, J = 7.3, 1.0 Hz, 1H), 6.96–6.99 (m, 2H), 7.09–7.14
(m, 2H), 7.18–7.22 (m, 3H), 7.25–7.29 (m, 2H), 7.61 (dddd, J =
11.0, 8.5, 6.4, 2.5 Hz, 1H). 13C NMR (CDCl3, 100 MHz) d 44.9
(d, JCF = 7.4 Hz), 64.8 (d, JCF = 2.0 Hz), 108.4 (ddd, JCF = 20.9,
2.8, 2.8 Hz), 113.6, 117.4 (m), 120.0, 125.7, 127.8, 128.9, 129.2,
140.1 (dd, JCF = 243.5, 19.2 Hz), 140.2, 141.1 (dddd, JCF = 250.0,
12.4, 10.3, 4.4 Hz), 141.8, 143.8, 145.5 (ddd, JCF = 252.0, 11.6,
3.0 Hz), 147.1 (dddd, JCF = 246.9, 10.6, 2.5, 2.5 Hz). MS (70 eV)
370 (M+, 100), 293 (46), 91 (35), 77 (19). EI HRMS m/z calcd for
[M]+ C21H14F4N2 370.1093, found 370.1073.
1-(3,5-Difluorophenyl)-3-(3-fluorophenyl)-5-phenyl-4,5-dihydro-
1H-pyrazole (3g). Synthesized from chalcone 12 and 3,5-
difluorophenylhydrazine (method B). Yield: 33%. M.p. 164–
166 ◦C. 1H NMR (CDCl3, 400 MHz) d 3.07 (dd, J = 17.3, 6.6 Hz,
1H), 3.78 (dd, J = 17.3, 12.4 Hz, 1H), 5.18 (dd, 12.4, 6.6 Hz, 1H),
6.14 (tt, J = 9.1, 2.3 Hz, 1H), 6.44–6.51 (m, 2H), 6.98 (tdd, J =
8.3, 2.5, 0.9 Hz, 1H), 7.18–7.31 (m, 6H), 7.35–7.40 (m, 2H). 13C
NMR (CDCl3, 100 MHz) d 43.6, 64.3, 94.2 (t, JCF = 26.4 Hz),
96.4 (dd, JCF = 20.8, 9.2 Hz), 112.6 (d, JCF = 22.9 Hz), 116.0
(d, JCF = 21.5 Hz), 121.7 (d, JCF = 2.5 Hz), 125.6, 128.1, 129.4,
130.1 (d, JCF = 8.3 Hz), 134.2 (d, JCF = 8.3 Hz), 141.2, 146.2 (t,
JCF = 13.7 Hz), 147.2 (d, JCF = 3.1 Hz), 162.9 (d, JCF = 245.8 hz),
163.6 (dd, JCF = 244.1, 15.7 Hz). MS (70 eV) 352 (M+, 100), 275
(36), 248 (13), 127 (30). EI HRMS m/z calcd for [M]+ C21H15F3N2
352.1187, found 352.1170.
3-(Perfluorophenyl)-1,5-diphenyl-4,5-dihydro-1H -pyrazole
(10a). Synthesized from chalcone 19◦ and phenylhydrazine
3-(3,5-Difluorophenyl)-1-(3-fluorophenyl)-5-phenyl-4,5-di-
hydro-1H-pyrazole (7c). Synthesized from chalcone 16 and 3-
fluorophenylhydrazine (method B). Yield: 42%. M.p. 188–190 ◦C.
1H NMR (CDCl3, 400 MHz) d 3.03 (dd, J = 17.1, 6.8 Hz, 1H),
3.73 (dd, J = 17.1, 12.6 Hz, 1H), 5.25 (dd, J = 12.6, 6.8 Hz, 1H),
6.42 (td, J = 8.3, 2.4 Hz, 1H), 6.65 (dd, J = 8.3, 2.1 Hz, 1H), 6.70
(tt, J = 8.8, 2.2 Hz, 1H), 6.78 (dt, J = 11.7, 2.1 Hz, 1H), 7.02 (td,
J = 7.9, 6.9 Hz, 1H), 7.11–7.23 (m, 5H), 7.26–7.30 (m, 2H). 13C
NMR (CDCl3, 100 MHz) d 43.3, 64.6, 100.9 (d, JCF = 26.9 Hz),
103.9 (t, JCF = 25.8 Hz), 106.2 (d, JCF = 21.5 Hz), 108.3, 108.5 (d,
JCF = 11.7 Hz), 108.6, 108.9 (d, JCF = 2.5 Hz), 125.6, 128.0, 129.3,
130.1 (d, JCF = 9.9 Hz), 135.6 (t, JCF = 9.9 Hz), 141.4, 145.2 (t,
JCF = 3.5 Hz), 145.6 (d, JCF = 10.8 Hz), 163.1 (dd, JCF = 248.1,
12.9 Hz), 163.5 (d, JCF = 243.0 Hz). MS (70 eV) 352 (M+, 100), 275
(38), 109 (28). EI HRMS m/z calcd for [M]+ C21H15F3N2 352.1187,
found 352.1184.
1
(method B). Yield: 90%. M.p. 138–140 C. H NMR (CDCl3,
400 MHz) d 3.14 (dd, J = 17.7, 7.3 Hz, 1H), 3.83 (dd, J = 17.6,
12.6 Hz, 1H), 5.22 (dd, J = 17.6, 12.6 Hz, 1H), 5.22 (dd, J = 12.6,
7.3 Hz, 1H), 6.5 (t, J = 7.3 Hz, 1H), 6.97 (dd, J = 8.8, 1.0 Hz,
2H), 7.08–7.12 (m, 2H), 7.16–7.21 (m, 3H), 7.24–7.28 (m, 2H). 13
C
NMR (CDCl3, 100 MHz) d 45.9 (t, JCF = 4.3 Hz), 63.8, 109.0 (td,
JCF = 13.6, 4.1 Hz), 113.7, 120.2, 125.7, 127.8, 128.9, 129.2, 135.7
(m), 137.9 (dm, JCF = 251.6 Hz), 140.2 (dm, JCF = 251.3 Hz),
141.5, 143.7, 144.7 (dm, JCF = 254.6 Hz). MS (70 eV) 388 (M+,
100), 311 (45), 91 (36), 77 (25). EI HRMS m/z calcd for [M]+
C21H13F5N2 388.0999, found 388.1000.
1,3-Bis(perfluorophenyl)-5-phenyl-4,5-dihydro-1H -pyrazole
(10j). Synthesized from chalcone 19 an◦d perfluorophenylhy-
drazine (method B). Yield: 3%. M.p. 83–85 C. 1H NMR (CDCl3,
400 MHz) d 3.34 (dd, J = 17.6, 8.9 Hz, 1H), 3.76 (dd, 17.6,
3-(3,5-Difluorophenyl)-5-phenyl-1-(2,3,5,6-tetrafluorophenyl)-
4,5-dihydro-1H-pyrazole (7i). Synthesized from chalcone 16 and
2,3,5,6-te◦trafluorophenylhydrazine (method B). Yield: 72%. M.p.
11.5 Hz, 1H), 5.33 (dd, 11.5, 8.9 Hz, 1H), 7.19–7.25 (m, 5H). 13
C
NMR (CDCl3 100 MHz) d 45.1 (t, JCF = 3.9 Hz), 68.0, 108.3 (td,
JCF = 14.2, 4.1 Hz), 119.4 (td, JCF = 11.9, 3.8 Hz), 126.6, 128.8,
129.0, 137.8 (dm, JCF = 250.4 Hz), 137.9 (dm, JCF = 251.2 hz),
138.7 (dtt, JCF = 252.0, 13.7, 4.5 Hz), 139.1, 139.5 (m), 141.1 (dtt,
JCF = 252.0, 13.7, 4.5 Hz), 141.1 (dtt, JCF = 256.8, 13.6, 4.7 Hz),
145.1 (dm, JCF = 254.6 Hz). MS (70 eV) 478 (M+, 100), 401 (30),
374 (20), 296 (72), 181 (50), 103 (25), 77 (23). EI HRMS m/z calcd
for [M]+ C21H8F10N2 478.0528, found 478.0511.
1
112–114 C. H NMR (CDCl3, 400 MHz) d 3.19 (dd, J = 17.0,
7.5 Hz, 1H), 3.66 (dd, J = 17.0, 12.0 Hz, 1H), 5.50 (dd, J = 12.0,
7.5 Hz), 6.62 (tt, J = 9.8, 7.1 Hz, 1H), 6.73 (tt, J = 8.7, 2.2 Hz,
1H), 7.11–7.33 (m, 7H). 13C NMR (CDCl3, 100 MHz) d 42.2, 67.8
(t, JCF = 3.3 Hz), 100.5 (t, JCF = 23.1 Hz), 104.2 (t, JCF = 25.5 Hz),
108.6 (dd, JCF = 19.2, 7.4 Hz), 124.2 (tt, JCF = 10.9, 2.9 Hz), 126.4,
128.5, 129.0, 135.3 (t, JCF = 9.9 Hz), 140.0, 141.3 (dtt, JCF = 249.1,
1544 | Org. Biomol. Chem., 2009, 7, 1536–1546
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The Royal Society of Chemistry 2009
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