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1579
I. Damljanovic et al. / Journal of Organometallic Chemistry 694 (2009) 1575–1580
POCl3 (2.25 mL, 27.22 mmol) was added drop-wise under argon.
3.5.2. 1H-4-(Butyliminomethyl)-3-(m-ferrocenyl)-1-phenylpyrazol
(6b)
After 30 min the bath was removed and the reaction mixture
was stirred for 18 h at r.t. The mixture was poured into a beaker
containing ice (30 g) and H2O (30 mL), the resulting solution was
hydrolyzed with Na2CO3 (40 g) in H2O (100 mL) and stirred for
3 h at r.t. Crude aldehyde was extracted with toluene
(3 Â 100 mL), washed with water and brine. After drying (anhy-
drous Na2SO4), the solvent was evaporated and the residue purified
on silica (toluene), yielding deep orange solids.
Dark orange oil; yield: 0.106 g (94%); m.p.: 190–191 °C (Dec.);
1H NMR (200 MHz, CDCl3): 0.96 (t, 3H, J = 7.20 Hz, CH3); 1.40 (m,
2H, CH2); 1.68 (m, 2H, CH2); 3.59 (t, 2H, J = 6.80 Hz, CH2); 4.07 (s,
5H, Fc); 4.33 (t, 2H, J = 1.80 Hz, Fc); 4.69 (t, 2H, J = 1.80 Hz, Fc);
7.28–7.57 (m, 6H, Ar); 7.78–7.84 (m, 3H, Ar); 8.38 (s, 1H,
CH = N); 8.53 (s, 1H, Pz); 13C NMR (200 MHz, CDCl3): 13.87,
20.45, 33.05, 61.81, 66.60, 69.00, 69.59, 84.94, 119.22, 119.80,
126.19, 126.32, 126.43, 126.90, 126.97, 128.65, 129.49, 132.46,
139.61, 139.81, 153.17, 153.48. IR (KBr, cmÀ1): 3052, 2963, 2874,
1637, 1566, 1503, 1412, 1013, 755.
3.4.1. 1H-3-(o-Ferrocenylphenyl)-1-phenylpyrazole-4-carboxaldehyde
(5a)
Yield: 21%; m.p. 189 °C; IR (KBr, cmÀ1): 3122, 2842, 2819, 1678,
1598, 1533, 1500, 1205, 761, 692; 1H NMR (200 MHz, CDCl3):
d = 4.04 (s, 5H, Fc), 4.14 (t, 2H, J = 1.9 Hz, Fc), 4.19 (t, 2H
J = 1.9 Hz, Fc), 7.32–7.52 (m, 6H, Ar), 7.75–7.79 (m, 2H, Ar), 7.91
(dd, 1H, J = 7.3 Hz and 2.0 Hz, Ar), 8.38 (s, 1H, Pz), 9.18 (s, 1H,
CHO); 13C NMR (200 MHz, CDCl3): d = 68.47, 69.61, 69.99, 85.45,
119.41, 119.63, 122.66, 126.19, 127.62, 128.39, 128.87, 129.55,
130.63, 130.75, 138.92, 138.99, 155.56, 185.11.
3.5.3. 1H-4-(Butyliminomethyl)-3-(p-ferrocenyl)-1-phenylpyrazol
(6c)
Dark orange oil; yield: 0.107 g (95%); m.p.: 190–191 °C (Dec.);
1H-NMR (200 MHz, CDCl3): 0.94 (t, 3H, J = 7.20 Hz, CH3); 1.41 (m,
2H, CH2); 1.68 (m, 2H, CH2); 3.59 (t, 2H, J = 6.80 Hz, CH2); 4.06 (s,
5H, Fc); 4.34 (t, 2H, J = 1.80 Hz, Fc); 4.69 (t, 2H, J = 1.80 Hz, Fc);
7.29–7.65 (m, 7H, Ar–H); 7.80 (d, 2H, J = 7.80 Hz, Ar–H); 8.38 (s,
1H, CH@N); 8.50 (s, 1H, Pz); 13C NMR (200 MHz, CDCl3): 13.84,
20.39, 33.05, 61.74, 66.47, 69.11, 69.61, 84.52, 119.15, 119.64,
126.19, 126.88, 126.94, 128.59, 129.43, 129.89, 139.57, 139.79,
152.91, 153.48. IR (KBr, cmÀ1): 3064, 2963, 2875, 1632, 1565,
1503, 1465, 1411, 1084, 1014, 956, 746, 655.
3.4.2. 1H-3-(m-Ferrocenylphenyl)-1-phenylpyrazole-4-
carboxaldehyde (5b)
Yield: 60%; m.p. 124 °C; IR (KBr, cmÀ1): 3119, 2922, 2856, 1682,
1597, 1524, 1500, 1204, 765; 1H NMR (200 MHz, CDCl3): d = 4.07
(s, 5H, Fc), 4.34 (t, 2H, J = 1.8 Hz, Fc), 4.71 (t, 2H J = 1.8 Hz, Fc),
7.37–7.66 (m, 6H, Ar), 7.80 (dd, 2H, J = 7.3 Hz and 1.5 Hz, Ar),
7.93 (t, 1H, J = 1.6 Hz, Ar), 8.55 (s, 1H, Pz), 10.09 (s, 1H, CHO); 13C
NMR (200 MHz, CDCl3): d = 66.69, 69.12, 69.66, 84.79, 119.72,
122.65, 126.43, 126.59, 127.02, 127.92, 128.70, 129.64, 131.06,
131.35, 139.02, 140.07, 154.77, 185.04.
4. Supplementary material
CCDC 690780 contains the supplementary data for this paper.
These data can be obtained free of charge from the Cambridge
3.4.3. 1H-3-(p-Ferrocenylphenyl)-1-phenylpyrazole-4-
carboxaldehyde (5c)
Acknowledgements
Yield: 68%; m.p. 181 °C; IR (KBr, cmÀ1): 3137, 2855, 2831, 1680,
1596, 1517, 1208, 762; 1H NMR (200 MHz, CDCl3): d = 4.06 (s, 5H,
Fc), 4.35 (t, 2H, J = 1.8 Hz, Fc), 4.70 (t, 2H J = 1.8 Hz, Fc), 7.37–7.61
(m, 5H, Ar), 7.75–7.81 (m, 4H, Ar), 8.52 (s, 1H, Pz), 10.08 (s, 1H,
CHO); 13C NMR (200 MHz, CDCl3): d = 66.58, 69.25, 69.66, 84.31,
119.64, 122.49, 126.20, 127.81, 128.69, 128.82, 129.58, 131.14,
138.99, 140.78, 154.50, 184.98.
This work was supported by the Ministry of Science of the
Republic of Serbia (Grant 142042).
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3.5.1. 1H-4-(Butyliminomethyl)-3-(o-ferrocenyl)-1-phenylpyrazol
(6a)
Dark orange oil; yield: 0.104 g (92%); m.p.: 1H NMR (200 MHz,
CDCl3): 0.86 (t, 3H, J = 7.20 Hz, CH3); 1.21 (m, 2H, CH2); 1.44 (m,
2H, CH2); 3.20 (t, 2H, J = 6.80 Hz, CH2); 4.03 (s, 5H, Fc); 4.12 (t,
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