G.T. Cin et al. / Journal of Organometallic Chemistry 696 (2011) 613e621
619
7.23 (d, 2H, J ¼ 8.7 Hz), 7.12 (d,1H, J ¼ 7.8 Hz), 6.83 (d, 2H, J ¼ 8.7 Hz),
6.82 (d, 1H, J ¼ 7.8 Hz), 6.60 (s, 1H), 4.79 (t, 2H, J ¼ 1.6 Hz), 4.32
(t, 2H, J ¼ 1.6 Hz), 4.14 (s, 5H), 3.81 (br s, 2H), 3.78 (s, 3H); 13C-NMR
3H); 13C-NMR (CDCl3),
d
: 151.9 (C), 144.5 (C), 141.0 (C), 137.6 (C),
136.9 (C), 133.1 (C), 130.3 (CH), 130.2 (CH), 130.0 (CH), 129.9 (CH),
129.5 (CH), 127.7 (CH), 123.7 (CH), 119.1 (CH), 116.4 (CH), 115.1 (C),
105.8 (CH), 22.6 (CH3) Anal. Calcd for C22H19N3: C, 81.20; H, 5.89; N,
12.91; Found: C, 81.41; H, 5.76; N, 13.05.
(CDCl3), d:152.7 (C), 151.5 (C), 148.1 (C), 146.3 (C), 132.0 (C), 130.1
(CH), 125.7 (CH), 122.6 (CH), 118.3 (CH), 116.2 (CH), 113.5 (CH), 112.8
(C), 106.8 (CH), 77.6 (C), 69.6 (CH), 68.6 (CH), 66.9 (CH), 55.3 (CH3).
Anal. Calcd for C26H23N3OFe: C, 66.50; H, 5.16; N, 9.35; Found: C,
66.63; H, 5.26; N, 9.23.
4.7. General procedure for the synthesis of ferrocenyl-containing
pyrazolo [4,3-c] quinolines (11e12)
4.6.5. 2-(1,3-Diphenyl-1H-pyrazol-5-yl)-phenylamine (10a)
Yield 68%; yellow oil; IR (KBr) nmax: 3470 (NeH asym.), 3381
Compound (9e10) (1 mmol), ferrocenylcarboxaldehyde (1 mmol,
214.1 mg) and p-tolylsulphonic acid (p-TsOH) (0.1 mmol, 19.0 mg)
were dissolved in toluene (8 ml) and refluxed for 9e11 h under
nitrogen atmosphere. The mixture was purified by flash column
chromatography on silica gel using hexane/EtOAc (8/1) as eluent to
afford 11e12. For all the compounds (11e12) data related to percent
yields, melting points (m.p) and elemental analyses are reported in
Table 2.
(NeH sym.), 1598 (C]N); 1H-NMR (CDCl3),
d: 7.96 (d, 2H,
J ¼ 7.8 Hz), 7.49e7.43 (m, 3H), 7.39e7.28 (m, 5H), 7.19 (td,1H, J ¼ 7.3,
1.6 Hz), 7.01 (dd, 1H, J ¼ 7.6, 1.2 Hz), 6.86 (s, 1H), 6.73 (td, 2H, J ¼ 7.0,
1.0 Hz), 3.85 (br s, 2H); 13C-NMR (CDCl3),
d: 152.1 (C), 144.7 (C),141.1
(C), 140.1 (C), 133.0 (C), 131.1 (CH), 130.1 (CH), 128.7 (CH), 128.1 (CH),
127.1 (CH), 125.8 (CH), 123.8 (CH), 118.3 (CH), 116.0 (CH), 115.6 (CH),
114.8 (C), 106.0 (CH). Anal. Calcd for C21H17N3: C, 81.00; H, 5.50;
N, 13.49; Found: C, 81.23; H, 5.66; N, 13.32.
4.7.1. 3,4-Diferrocenyl-1- phenyl-1H-pyrazolo[4,3-c]quinoline
(11a)
4.6.6. 2-[1-(2-Chlorophenyl)-3-phenyl-1H-pyrazol-5-yl]-
phenylamine (10b)
Yellow solid; IR (KBr) nmax: 1595 (C]N), 1562, 1506, 1447 (C]
C); 1H-NMR (CDCl3),
d
: 8.14 (d, 1H, J ¼ 7.9 Hz), 7.66e7.63 (m, 2H),
Yield 74%; yellow oil; IR (KBr) nmax: 3465 (NeH asym.), 3378
7.62e7.47 (m, 5H), 7.21e7.17 (m, 1H), 4.54 (t, 2H, J ¼ 1.8 Hz) 4.27
(NeH sym.), 1615 (C]N), 762 (CeCl); 1H-NMR (CDCl3),
d: 7.94 (d,
(t, 2H, J ¼ 1.8 Hz), 4.07 (t, 2H, J ¼ 1.8 Hz), 4.03 (t, 2H, J ¼ 1.8 Hz),
2H, J ¼ 7.5 Hz), 7.48 (d, 2H, J ¼ 7.5 Hz), 7.33e7.28 (m, 4H), 7.23
(td, 2H, J ¼ 7.3, 1.5 Hz), 6.95 (dd, 1H, J ¼ 7.3, 1.5 Hz), 6.87 (dd, 2H,
J ¼ 7.3, 1.5 Hz), 6.84 (s, 1H), 3.84 (br s, 2H); 13C-NMR (CDCl3),
4.02 (s, 5H), 4.01 (s, 5H); 13C-NMR (CDCl3),
d: 156.0 (C), 146.2
(C), 145.9 (C), 141.3 (C), 140.1 (C), 129.7 (CH), 129.6 (CH), 129.4
(CH), 128.6 (CH), 127.2 (CH), 124.9 (C), 121.4 (CH), 115.0 (C), 85.9
(C), 79.0 (CH), 72.0 (CH), 71.4 (CH), 69.8 (CH), 69.7 (CH), 68.0 (CH),
67.6 (CH).
d:152.7 (C), 144.8 (C), 144.2 (C), 140.1 (C), 133.2 (C), 132.3 (C), 130.0
(CH), 129.7 (CH), 129.4 (CH), 128.7 (CH), 128.2 (CH), 127.6 (CH),
127.4 (CH), 121.5 (CH), 119.4 (CH), 116.1 (CH), 115.3 (C), 106.1 (CH).
Anal. Calcd for C21H16ClN3: C, 72.93; H, 4.66; N, 12.15; Found: C,
73.10; H, 4.52; N, 12.01.
4.7.2. 1- (2-Chlorophenyl)-3,4-diferrocenyl-1H-pyrazolo[4,3-c]
quinoline (11b)
Yellow solid; IR (KBr) nmax: 1596 (C]N),1560,1506,1446 (C]C);
4.6.7. 2-[1-(4-Chlorophenyl)-3-phenyl-1H-pyrazol-5-yl]-
phenylamine (10c)
1H-NMR (CDCl3),
d
: 8.24 (d, 1H, J ¼ 7.7 Hz), 7.78e7.72 (m, 2H),
7.66e7.60 (m, 1H), 7.37e7.19 (m, 4H), 4.83 (t, 2H, J ¼ 1.6 Hz), 4.51 (t,
Yield 79%; yellow oil; IR (KBr) nmax: 3468 (NeH asym.), 3375
2H, J ¼ 1.6 Hz), 4.26 (t, 2H, J ¼ 1.6 Hz), 4.17 (t, 2H, J ¼ 1.6 Hz), 4.11 (s,
(NeH sym.), 1617 (C]N), 765 (CeCl); 1H-NMR (CDCl3),
d
: 7.93 (d,
5H), 4.09 (s, 5H); 13C-NMR (CDCl3),
d: 159.3 (C), 146.8 (C), 144.3 (C),
2H, J ¼ 7.2 Hz), 7.45 (t, 2H, J ¼ 7.2 Hz), 7.37 (d, 2H, J ¼ 7.3 Hz), 7.27 (d,
2H, J ¼ 7.3 Hz), 7.20 (td, 2H, J ¼ 7.2, 1.5 Hz), 6.98 (dd, 1H, J ¼ 7.4,
1.3 Hz), 6.84 (s, 1H), 6.73 (td, 2H, J ¼ 7.4, 1.3 Hz), 3.83 (br s, 2H); 13C-
143.4 (C), 138.7 (C), 135.5 (C), 131.1 (CH), 130.9 (CH), 130.3 (CH),
129.9 (CH), 129.8 (CH), 128.0 (CH), 125.0 (CH), 124.3 (C), 121.6 (CH),
115.7 (C), 86.3 (C), 81.9 (C), 72.3 (CH), 71.8 (CH), 70.1 (CH), 69.9 (CH),
68.2 (CH), 67.7 (CH).
NMR (CDCl3), d: 152.4 (C), 144.7 (C), 141.1 (C), 138.6 (C), 132.8
(C), 131.0 (CH), 130.4 (CH), 129.7 (CH), 129.2 (C), 128.6 (CH), 128.1
(CH), 127.7 (CH), 125.8 (CH), 118.4 (CH), 115.6 (CH), 115.2 (C), 106.2
(CH). Anal. Calcd for C21H16ClN3: C, 72.93; H, 4.66; N, 12.15; Found:
C, 73.15; H, 4.52; N, 12.34.
4.7.3. 1- (4-Chlorophenyl)-3,4-diferrocenyl-1H-pyrazolo[4,3-c]
quinoline (11c)
Yellow solid; IR (KBr) nmax: 1598 (C]N), 1565, 1510, 1448 (C]C);
1H-NMR (CDCl3),
d
: 8.23 (d, 1H, J ¼ 7.6 Hz), 7.70 (d, 2H, J ¼ 8.4 Hz),
4.6.8. 2-[1-(4-Methoxyphenyl)-3-phenyl-1H-pyrazol-5-yl]-
phenylamine (10d)
7.64 (d, 2H, J ¼ 8.4 Hz), 7.61 (d, 1H, J ¼ 8.4 Hz), 7.35e7.31 (m, 2H),
4.63 (d, 2H, J ¼ 1.6 Hz), 4.35 (d, 2H, J ¼ 1.6 Hz), 4.17 (d, 2H,
J ¼ 1.6 Hz), 4.14 (d, 2H, J ¼ 1.6 Hz), 4.11 (s, 5H), 4.10 (s, 5H); 13C-NMR
Yield 77%; yellow oil; IR (KBr) nmax: 3472 (NeH asym.), 3380
(NeH sym.), 1608 (C]N); 1H-NMR (CDCl3),
d:
7.96 (d, 2H,
(CDCl3), d: 156.2 (C), 146.8 (C), 146.0 (C), 140.1 (C), 139.8 (C), 135.2
J ¼ 7.6 Hz), 7.47 (t, 2H, J ¼ 7.6 Hz), 7.37 (d, 2H, J ¼ 8.8 Hz), 7.34 (d, 2H,
J ¼ 8.8 Hz), 7.20 (td, 1H, J ¼ 7.6, 1.6 Hz), 7.01 (dd, 1H, J ¼ 7.4, 1.2 Hz),
6.73 (td, 2H, J ¼ 7.4, 1.2 Hz), 6.86 (s, 1H), 3.87 (br s, 2H), 3.80 (s, 3H);
(C), 130.0 (CH), 129.9 (CH), 129.8 (CH), 128.8 (CH), 128.4 (CH), 125.1
(C), 121.2 (CH), 114.8 (C), 85.7 (C), 78.8 (C), 72.0 (CH), 71.5 (CH), 69.9
(CH), 69.7 (CH), 68.1 (CH), 67.7 (CH).
13C-NMR (CDCl3),
d: 158.6 (C), 151.8 (C), 144.8 (C), 141.1 (C), 133.3
(C), 133.1 (C), 131.2 (CH), 129.6 (CH), 128.7 (CH), 128.0 (CH), 125.6
(CH), 118.2 (CH), 116.0 (CH), 115.1 (CH), 114.0 (C), 105.5 (CH), 55.4
(CH3). Anal. Calcd for C22H19N3O: C, 77.40; H, 5.61; N, 12.31; Found:
C, 77.53; H, 5.39; N, 12.48.
4.7.4. 3,4-Diferrocenyl-1-(4-methoxyphenyl)-1H-pyrazolo[4,3-c]
quinoline (11d)
Yellow solid; IR (KBr) nmax: 1596 (C]N), 1566, 1510,1444 (C]C);
1H-NMR (CDCl3),
d
: 8.22 (d, 1H, J ¼ 8.4 Hz), 7.68e7.62 (m, 2H), 7.57
(d, 1H, J ¼ 8.2 Hz), 7.31 (d, 2H, J ¼ 8.8 Hz), 7.19 (d, 2H, J ¼ 8.8 Hz),
4.64 (t, 2H, J ¼ 1.6 Hz), 4.37 (t, 2H, J ¼ 1.6 Hz), 4.16 (t, 2H, J ¼ 1.6 Hz),
4.6.9. 2-(3-Phenyl-1-p-tolyl-1H-pyrazol-5-yl)-phenylamine (10e)
Yield 81%; yellow oil; IR (KBr) nmax: 3460 (NeH asym.), 3371
4.13 (t, 2H, J ¼ 1.6 Hz), 4.10 (s, 10H), 4.0 (s, 3H); 13C-NMR (CDCl3),
d:
(NeH sym.),1611 (C]N); 1H-NMR (CDCl3),
d
: 7.94 (d, 2H, J ¼ 7.4 Hz),
160.3 (C), 156.1 (C), 145.9 (C), 140.3 (C), 134.1 (C), 129.6 (C), 128.5
(CH), 128.2 (CH), 124.9 (C), 121.3 (CH), 115.1 (C), 114.9 (CH), 85.9 (C),
79.1(C), 72.0 (CH), 71.4 (CH), 69.8 (CH), 69.7 (CH), 68.0 (CH), 67.6
(CH), 55.7 (CH3).
7.42 (t, 2H, J ¼ 7.2 Hz), 7.36 (d,1H, J ¼ 7.3 Hz), 7.30 (d, 2H, J ¼ 8.2 Hz),
7.19 (t, 1H, J ¼ 7.4 Hz), 7.11 (d, 2H, J ¼ 8.2 Hz), 7.00 (dd, 1H, J ¼ 7.5,
1.1 Hz), 6.72 (t, 2H, J ¼ 7.5 Hz), 6.86 (s, 1H), 3.57 (br s, 2H), 2.35 (s,