2354
D. C. Flores et al.
PAPER
1H NMR (400 MHz, CDCl3): d = 1.23 (t, 3JHH = 6.80 Hz, 3 H, Me),
2.63 (m, 2 H, CH2), 2.99 (m, 2 H, CH2), 3.16 (dd, 2JHH = 17.2 Hz,
1H NMR (400 MHz, CDCl3): d = 2.28 (s, 3 H, 5-aryl Me), 2.47 (s,
3 H, styryl Me), 3.0 (dd, 2JHH = 16.9 Hz, 3JHH = 5.5 Hz, 1 H, Pyr H-
4 trans), 3.69 (dd, 2JHH = 16.9 Hz, 3JHH = 12.2 Hz, 1 H, Pyr H-4 cis),
5.85 (dd, JHH = 12.2 Hz, JHH = 5.5 Hz, 1 H, Pyr H-5), 6.87 (d,
2JHH = 16.3 Hz, 1 H, styryl), 7.05–7.32 (m, 13 H, aryl, styryl CH,
Pyrim H-5), 7.69 (m, 2 H, Pyrim 6-Ph).
13C NMR (100 MHz, CDCl3): d = 19.5 (Me), 19.8 (Me), 40.2 (Pyr
C-4), 59.3 (Pyr C-5), 103.3 (3JCF = 2.4 Hz, Pyrim C-5), 120.7
(1JCF = 275.5 Hz, CF3), 122.6 (styryl CH), 124.6, 125.6, 126.5,
126.8, 127.3, 127.4, 128.6, 128.7, 130.3, 130.6, 131.3, 133.5 (aryl,
styryl CH), 134.3, 134.8, 136.0, 136.3, 140.6, 154.8 (aryl, Pyr C-3),
157.3 (2JCF = 34.4 Hz, Pyrim C-4), 158.2 (Pyrim C-2), 167.4 (Pyrim
C-6).
2
3JHH = 4.8 Hz, 1 H, Pyr H-4 trans), 3.69 (dd, JHH = 17.2 Hz,
3
3
3
3JHH = 11.9 Hz, 1 H, Pyr H-4 cis), 4.09 (m, JHH = 6.8 Hz, 2 H,
CH2), 5.65 (dd, 3JHH = 11.9 Hz, 3JHH = 4.8 Hz, 1 H, Pyr H-5), 6.73
(d, 3JHH = 16.4 Hz, 1 H, styryl CH), 6.79 (s, 1 H, Pyrim H-5), 7.26–
7.47 (m, 11 H, Ar, styryl CH).
13C NMR (100 MHz, CDCl3): d = 14.0 (Me), 31.5 (CH2), 32.4
(CH2), 40.9 (Pyr C-4), 60.4 (CH2), 62.3 (Pyr C-5), 106.5 (Pyrim C-
5, 3JCF = 2.2 Hz), 120.5 (CF3, 1JCF = 275.5 Hz), 121.4 (styryl CH),
126.2, 127.0, 127.5, 128.6, 128.9, 136.0 (Ar), 136.4 (styryl CH),
142.1 (Ar), 155.0 (Pyr C-3), 156.4 (2JCF = 35.4 Hz, Pyrim C-4),
157.6 (Pyrim C-2), 172.3 (CO2Et), 172.4 (Pyrim C-6).
19F NMR (376.5 MHz, CDCl3): d = –70.46.
MS (EI, 70 eV): m/z (%) = 498 (50) [M+], 483 (38), 407 (20), 342
(44), 223 (22), 157 (27), 130 (49), 115 (100), 91 (52).
MS (EI, 70 eV): m/z (%) = 494 (90) [M+], 449 (22), 306 (39), 278
(100), 230 (40), 143 (80), 115 (25).
Anal. Calcd for C28H21F3N4: C, 72.28; H, 5.05; N, 11.24. Found: C,
72.5; H, 5.1; N, 11.1.
Anal. Calcd for C27H25F3N4O2: C, 65.58; H, 5.10; N, 11.33. Found:
C, 65.58; H, 5.10; N, 11.33.
6-(2-Furyl)-2-[3-(2-methylstyryl)-5-(2-tolyl)-4,5-dihydro-1H-
pyrazol-1-yl]-4-(trifluoromethyl)pyrimidine (10)
Mp 245–246 °C.
6-Phenyl-2-(5-phenyl-3-styryl-4,5-dihydro-1H-pyrazol-1-yl)-4-
(trifluoromethyl)pyrimidine (7)
Mp 164–167 °C.
1H NMR (400 MHz, CDCl3): d = 2.35 (s, 3 H, 5-aryl Me), 2.57 (s,
2
3
3 H, styryl Me), 3.07 (dd, JHH = 16.9 Hz, JHH = 5.5 Hz, 1 H, Pyr
H-4 trans), 3.75 (dd, 2JHH = 16.9 Hz, 3JHH = 12.0 Hz, 1 H, Pyr H-4
cis), 5.89 (dd, 3JHH = 12.0 Hz, 3JHH = 5.5 Hz, 1 H, Pyr H-5), 6.51 (d,
3JHH = 1.8 Hz, 1 H, Furyl H-4), 6.93 (d, 2JHH = 16.2 Hz, 1 H, styryl),
1H NMR (400 MHz, CDCl3): d = 3.19 (dd, JHH = 17.2 Hz,
2
3JHH = 5.2 Hz, 1 H, Pyr H-4 trans), 3.72 (dd, JHH = 17.2 Hz,
2
3JHH = 12.0 Hz, 1 H, Pyr H-4 cis), 5.76 (dd, JHH = 12.0 Hz,
3
3JHH = 5.2 Hz, 1 H, Pyr H-5), 6.74 (d, 3JHH = 16.4 Hz, 1 H, styryl),
7.23–7.50 (m, 14 H, Ar, styryl CH, Pyrim H-5), 7.82 (m, 2 H, Pyrim
6-Ph).
2
7.10–7.25 (m, 9 H, Ar, Pyrim H-5), 7.34 (d, JHH = 16.2 Hz, 1 H,
styryl), 7.55 (s, 1 H, Furyl H-3), 7.58 (1 H, Furyl H-5).
13C NMR (100 MHz, CDCl3): d = 19.4 (Me), 19.7 (Me), 40.3 (Pyr
C-4), 59.0 (Pyr C-5), 101.5 (Pyrim C-5), 112.5 (Furyl), 113.4 (Fur-
yl), 120.5 (1JCF = 275.5 Hz, CF3), 122.6 (styryl CH), 124.6, 125.7,
126.5, 126.8, 127.3, 128.6, 130.3, 130.6, 133.5, 134.3, 134.8 (Ar),
136.0 (styryl CH), 140.6 (Furyl), 145.3 (Furyl), 151.4 (Ar), 154.8
(Pyr C-3), 157.1 (2JCF = 37.8 Hz, Pyrim C-4), 158.1 (Pyrim C-2),
158.3 (Pyrim C-6).
13C NMR (100 MHz, CDCl3): d = 41.1 (Pyr C-4), 62.6 (Pyr C-5),
103.2 (3JHH = 2.2 Hz, Pyrim C-5), 120.7 (1JCF = 275.5 Hz, CF3),
121.6 (styryl CH), 126.0, 126.9, 127.3, 127.6, 127.5, 128.7, 128.7,
128.8, 131.3, 136.0 (Ar), 136.1 (styryl CH), 136.2, 142.5 (Ar),
154.6 (Pyr C-3), 157.3 (2JCF = 35.1 Hz, Pyrim C-4), 158.3 (Pyrim
C-2), 167.3 (Pyrim C-6).
MS (EI, 70 eV): m/z (%) = 470 (70) [M+], 365 (23), 340 (100), 328
(83), 264 (25), 128 (56), 115 (45), 103 (59).
MS (EI, 70 eV) m/z (%) = 488 (84) [M+], 473 (59), 397 (35), 332
(100), 244 (30), 213 (23), 157 (80), 115 (95).
Anal. Calcd for C28H19Cl2F3N4: C, 62.35; H, 3.55; N, 10.39. Found:
C, 62.50; H, 3.75; N, 10.70.
Anal. Calcd for C28H23F3N4O: C, 68.84; H, 4.75; N, 11.47. Found:
C, 68.6; H, 4.60; N, 11.50.
6-Methyl-2-[3-(4-methylstyryl)-5-(4-tolyl)-4,5-dihydro-1H-
pyrazol-1-yl]-4-(trifluoromethyl)pyrimidine (8)
Mp 176–178 °C.
2-[3-(2-Methylstyryl)-5-(2-tolyl)-4,5-dihydro-1H-pyrazol-1-yl]-
6-(2-thienyl)-4-(trifluoromethyl)pyrimidine (11)
Mp 261–263 °C.
1H NMR (400 MHz, CDCl3): d = 2.29 (s, 3 H, 4-Me), 2.42 (s, 3 H,
1H NMR (400 MHz, CDCl3): d = 2.36 (s, 3 H, Ar Me), 2.59 (s, 3 H,
2
Pyrim 6-Me), 2.47 (s, 3 H, 4-Me), 3.02 (dd, JHH = 17.0 Hz,
2
3
styryl Me), 3.04 (dd, JHH = 16.8 Hz, JHH = 5.2 Hz, 1 H, Pyr H-4
2
3JHH = 5.2 Hz, 1 H, Pyr H-4 trans), 3.66 (dd, JHH = 17.0 Hz,
trans), 3.76 (dd, 2JHH = 16.8 Hz, 3JHH = 12.0 Hz, 1 H, Pyr H-4 cis),
3
3JHH = 12.1 Hz, 1 H, Pyr H-4 cis), 5.81 (dd, JHH = 12.1 Hz,
3
3
5.93 (dd, JHH = 12.0 Hz, JHH = 5.2 Hz, 1 H, Pyr H-5), 6.94 (d,
3JHH = 16.2 Hz, 1 H, styryl), 7.06–7.25 (m, 9 H, Ar, Pyrim H-5),
3JHH = 5.2 Hz, 1 H, Pyr H-5), 6.68 (s, 1 H, Pyrim H-5), 6.88 (d,
3JHH = 16.3 Hz, 1 H, styryl), 7.01–7.16 (m, 7 H, Ar), 7.26 (d,
3JHH = 16.3 Hz, 1 H, styryl), 7.49 (m, 1 H, Ar).
7.32 (d, 3JHH = 16.2 Hz, 1 H, styryl), 7.46 (d, JHH = 4.8 Hz, 1 H,
3
thienyl H-3), 7.58 (dd, 1 H, thienyl H-4), 7.63 (d, 1 H, thienyl H-5).
13C NMR (100 MHz, CDCl3): d = 19.3 (Me), 19.8 (Me), 24.8 (Py-
rim 6-Me), 40.4 (Pyr C-4), 58.6 (Pyr C-5), 106.9 (Pyrim C-5), 120.5
(1JCF = 275.5 Hz, CF3), 122.6, 124.7, 125.6, 126.5, 126.7, 127.3,
128.6, 130.2, 130.7, 133.5, 134.8 (Ar), 136.0 (styryl CH), 140.7
(Ar), 154.8 (Pyr C-3), 155.9 (2JCF = 35.2 Hz, Pyrim C-4), 157.9 (Py-
rim C-2), 171.3 (Pyrim C-6).
13C NMR (100 MHz, CDCl3): d = 19.7 (Me), 19.8 (Me), 40.2 (Pyr
C-4), 59.3 (Pyr C-5), 101.8 (Pyrim C-5), 120.6 (1JCF = 275.5 Hz,
CF3), 122.6 (styryl CH), 124.4, 125.7, 126.5, 126.7, 127.2, 128.2
(Ar), 128.4 (thienyl), 128.7 (Ar), 130.5 (thienyl), 130.6 (Ar), 130.9
(thienyl), 133.6 (Ar), 134.1 (thienyl), 134.8 (Ar), 136.1 (styryl CH),
140.4, 142.0 (Ar), 155.0 (Pyr C-3), 157.1 (2JCF = 36.8 Hz, Pyrim
C-4), 158.0 (Pyrim C-2), 161.8 (Pyrim C-6).
MS (EI, 70 eV): m/z (%) = 436 (100) [M+], 421 (81), 345 (61), 303
(26), 280 (95), 258 (36), 215 (14), 157 (92), 128 (37), 115 (83).
MS (EI, 70 eV): m/z (%) = 504 (5) [M+], 491 (58), 475 (65), 399
(23), 357 (15), 334 (50), 244 (22), 157 (66), 128 (42), 115 (100).
Anal. Calcd for C25H23F3N4: C, 68.79; H, 5.31; N, 12.84. Found: C,
68.90; H, 5.35; N, 12.80.
Anal. Calcd for C28H23F3N4S: C, 66.65; H, 4.59; N, 11.10. Found:
C, 66.60; H, 4.55; N, 10.96.
2-[3-(2-Methylstyryl)-5-(2-tolyl)-4,5-dihydro-1H-pyrazol-1-yl]-
6-phenyl-4-(trifluoromethyl)pyrimidine (9)
Mp 199–201 °C.
Synthesis 2006, No. 14, 2349–2356 © Thieme Stuttgart · New York