Vol. 22, No. 8, 2011
Bonacorso et al.
1435
2
2
(q, J 31 Hz, C-4), 130.3 (d, 4J 3 Hz, 2 C-FPh), 129.1
(C-10a), 128.3 (d,3J 8 Hz, 4 C-FPh), 122.2 (C-6), 123.4 (q,
1J 275 Hz, CF3), 121.4 (q, 1J 275 Hz, CF3), 117.6 (q, 3J 5 Hz,
147.8 (C-6a), 147.4, 143.9 (4 C-Ph), 134.3 (q, J 31 Hz,
C-4), 131.4 (C-10a), 130.0 (4 C-Ph), 126.5 (C-6), 125.2 (q,
4J 3 Hz, C-5), 124.5 (4 C-Ph), 123.4 (q, 1J 275 Hz, CF3),
121.5 (q, 1J 275 Hz, CF3), 121.6 (q, 3J 5 Hz, C-3), 120.9
2
C-5), 115.4 (C-4a), 114.4 (d, J 22 Hz, 4 C-FPh), 114.2
(C-3), 112.8 (C-9); GC-MS (EI, 70 eV, m/z) 503 (M+, 100),
485 (7), 435 (18), 409 (16%); Anal. calcd. for C26H12F8N2
(504.09): C, 61.91; H, 2.40; N, 5.55%. Found: C, 61.95;
H, 2.53; N, 5.64%.
(C-4a), 118.4 (q, J 5 Hz, C-9); GC-MS (EI, 70 eV, m/z)
3
558 (M+, 100), 539 (18), 489 (30), 69 (10%); Anal. calcd.
for C26H12F6N4O4 (558.08): C, 55.92; H, 2.17, N; 10.03%.
Found: C, 55.88; H, 2.28; N, 10.21%.
2,10-di(4-Chlorophenyl)-4,8-bis(trifluoromethyl)-
1,7-phenanthroline (3g)
4-Trifluoromethyl-2-methyl-7-aminoquinoline (4b)32
Brown solid (0.18 g, 40% yield); mp 174-176 °C;
1H NMR (CDCl3) d 7.87 (dq, 1H, J1 2, J2 9 Hz, H-5),
7.30 (s, 1H, H-3), 7.21 (d, 1H, J 2 Hz, H-8), 7.02 (dd, 1H,
J1 2, J2 9 Hz, H-6), 4.18 (s, 2H, NH), 2.72 (s, 3H, CH3);
13C NMR (DMSO-d6) d 158.1 (C-2), 150.7 (C-8a), 150.6
(C-7), 132.2 (q, 2J 30 Hz, C-4), 123.6 (C-5), 119.5 (C-6),
118.3 (q, 1J 275 Hz, CF3), 113.5 (q, 3J 5 Hz, C-3), 112.2
(C-4a), 106.8 (C-8), 24.7 (CH3); 19F NMR (376 MHz,
CDCl3) d −61.25 (CF3-4); GC-MS (EI, 70 eV, m/z) 226
(M+, 100), 210 (7), 199 (31), 157 (8), 142 (7), 69 (6%);
Anal. calcd. for C11H9F3N2 (226.07): C, 58.41; H, 4.01; N,
12.38%. Found: C, 58.04; H, 4.01; N, 12.01%.
Yellow solid (0.37 g, 35% yield); mp 236-238 °C;
1H NMR (CDCl3) d 8.39 (dq, 1H, J1 2, J2 8 Hz, H-5), 8.34
(d, 1H, J 2 Hz, H-6), 8.23 (s, 1H, H-3), 7.76 (s, 1H, H-9),
7.49-7.46 (m, 2H, Ph), 7.37-7.35 (m, 4H, Ph), 7.24-7.21
(m, 2H, Ph); 13C NMR (CDCl3) d 153.2 (C-10), 152.5
2
(C-2), 151.6 (C-10b), 151.1 (q, J 34 Hz, C-8), 148.2
2
(C-6a), 137.8, 135.3 (4 C-Ph), 134.1 (q, J 31 Hz, C-4),
131.5 (C-10a), 130.9, 169.7 (8 C-Ph), 128.0 (C-6), 126.4
(C-5), 123.6 (q, 1J 275 Hz, CF3), 121.5 (q, 1J 275 Hz, CF3),
3
3
119.5 (q, J 5 Hz, C-3), 119.3 (C-4a), 118.1 (q, J 5 Hz,
C-9); 19F NMR (CDCl3) d −60.59 (CF3-4), −67.57 (CF3-8);
GC-MS (EI, 70 eV, m/z) 535 (M+, 100), 501 (20), 467 (12),
425 (12), 232.6 (14), 198 (14), 138 (5%); Anal. calcd. for
C26H14F6N2 (536.02): C, 58.12; H, 2.25; N, 5.21%. Found:
C, 58.21; H, 2.32; N, 5.18%.
4-Trifluoromethyl-2-phenyl-7-aminoquinoline (4c)
Brown solid (0.22 g, 38% yield); mp 139-141 °C;
1H NMR (DMSO-d6) d 8.25 (dd, 2H, J1 2, J2 8 Hz, Ph), 7.95
(s, 1H, H-3), 7.79 (dq, 2H, J1 2, J2 8 Hz, H-5), 7.57-7.51 (m,
3H, Ph), 7.21 (d, 1H, J 2 Hz, H-6), 7.16 (s, 1H, H-8), 6.15
(s, 2H, NH2); 13C NMR (DMSO-d6) d 155.4 (C-2), 151.0
(C-8a), 150.9 (C-7), 138.1 (C-Ph), 130.7 (q, 2J 30 Hz, C-4),
2,10-di(4-Bromophenyl)-4,8-bis(trifluoromethyl)-
1,7-phenanthroline (3h)
Yellow solid (0.43 g, 33% yield); mp 262-264 °C;
1H NMR (CDCl3) d 8.35 (s, 1H, H-3), 8.22 (s, 1H, H-9),
7.95 (dq, 1H, J1 2, J2 8 Hz, H-5), 7.78 (d, 1H, J 2 Hz, H-6),
7.58 (dd, 4H, J1 2, J2 8 Hz, Ph), 7.21 (dd, 4H, J1 2, J2 8 Hz,
Ph); 13C NMR (CDCl3) d 152.8 (C-10), 152.2 (C-2), 151.2
1
129.6, 128.7, 127.0 (5 C-Ph), 123.8 (q, J 275 Hz, CF3),
123.7 (C-5), 120.5 (C-6), 113.0 (C-4a), 110.0 (q, 3J 5 Hz,
C-3), 107.3 (C-8); 19F NMR (CDCl3) d −61.28 (CF3-4);
GC-MS (EI, 70 eV, m/z) 288 (M+, 100), 273 (5), 219 (20),
203 (5%); Anal. calcd. for C16H11F3N2 (288.09): C, 66.66;
H, 3.85; N, 9.72%. Found: C, 66.32; H, 3.75; N, 9.64%.
2
(C-10b), 149.3 (q, J 34 Hz, C-8), 137.5 (C-6a), 134.9
(2 C-Ph), 133.8 (q, 2J 31 Hz, C-4), 132.0 (C-10a), 131.2,
130.6, 129.3 (10 C-Ph), 127.7 (C-6), 125.6 (C-5), 123.5
1
1
(q, J 275 Hz, CF3), 121.5 (q, J 275 Hz, CF3), 119.4 (q,
3J 5 Hz, C-3), 118.9 (C-4a), 117.8 (q, 3J 5 Hz, C-9); GC-MS
(EI, 70 eV, m/z) 625 (M+, 100), 554 (23), 468 (5), 69 (8%);
Anal. calcd. for C26H12Br2F6N2 (623.93): C, 49.87; H, 1.93;
N, 4.47%. Found: C, 49.83; H, 2.01; N, 4.58%.
4-Trifluoromethyl-2-(4-methylphenyl)-7-aminoquinoline
(4d)
Yellow brown (0.14 g, 24% yield); mp 156-158 °C;
1H NMR (CDCl3) d 8.03 (d, 2H, J 8 Hz, Ph), 7.91 (dq, 2H,
J1 2, J2 9 Hz, H-5), 7.86 (s, 1H, H-3), 7.34 (d, 2H, J 2 Hz,
Ph), 7.31 (s, 1H, H-8), 7.04 (dd, 1H, J1 2, J2 9 Hz, H-6), 4.16
(s, 2H, NH2), 2.43 (s, 3H, 2 CH3); 13C NMR (DMSO-d6)
d 156.9 (C-2), 150.9 (C-8a), 148.2 (C-7), 139.8, 136.0
(2 C-Ph), 134.5 (q, 2J 31 Hz, C-4), 129.5, 127.2 (4 C-Ph),
124.8 (C-5), 123.7 (q, 1J 275 Hz, CF3), 119.4 (C-6), 115.2
(C-4a), 112.1 (q, 3J 5 Hz, C-3), 110.0 (C-8), 21.2 (CH3);
GC-MS (EI, 70 eV, m/z) 302 (M+, 100), 233 (23), 69 (10%);
Anal. calcd. for C17H13F3N2 (302.10):C, 67.54; H, 4.33; N,
9.27%. Found: C, 67.14; H, 4.19; N, 8.90%.
4,8-bis(Trifluoromethyl)-2,10-di(4-nitrophenyl)-
1,7-phenanthroline (3i)
Yellow solid (0.29 g, 23% yield); mp 249-251 °C;
1H NMR (CDCl3) d 8.37 (dd, 4H, J1 2, J2 8 Hz, Ph), 8.12
(dd, 4H, J1 2, J2 8 Hz, Ph), 7.97 (dq, 1H, J1 2, J2 8 Hz,
H-5), 7.90 (s, 1H, H-3), 7.37 (s, 1H, H-9), 7.13 (dd, 1H,
J1 2, J2 8 Hz, H-6); 13C NMR (CDCl3) d 155.5 (C-10),
2
153.9 (C-2), 152.0 (C-10b), 150.4 (q, J 34 Hz, C-8),