Javad SAFARI et al. / Chinese Journal of Catalysis, 2011, 32: 1850–1855
į 26.8, 29.8, 33.1, 36.1, 41.2, 51.8, 106.9, 108.5, 110.4, 112.8,
1H), 5.62 (d, J = 4.4 Hz, 1H), 5.58 (s, 1H, NH), 7.06 (d, J = 8.1
Hz, 1H), 7.11 (dd, J = 7.9 Hz, J = 7.3 Hz, 1H), 7.14 (d, J = 7.3
Hz, 1H), 7.27 (dd, J = 8.1 Hz, J = 7.9 Hz, 1H), 7.36–7.50 (m,
5H); 13C NMR (100 MHz, CDCl3): į 27.4, 29.4, 32.7, 37.9,
41.9, 50.7, 57.4, 108.3, 110.6, 122.7, 125.3, 125.9, 126.4,
126.8, 127.3, 128.2, 131.6, 132.7, 138.3, 140.2, 197.9; Anal.
Calcd. for C24H25NO2: C, 80.19; H, 7.01, N, 3.90. Found: C,
80.07; H, 6.98; N, 3.86.
125.1, 127.3, 128.4, 129.4, 129.5, 130.4, 135.7, 136.4, 149.1,
156.2, 196.3; Anal. Calcd. for C23H22BrNO: C, 67.65; H, 5.43;
N, 3.43. Found: C, 67.49; H, 5.40; N, 3.39.
4-(3-chloroyphenyl)-7,7-dimethyl-2-phenyl-4,6,7,8-tetra-
hydro-5(1H)-quinolinone (4i): mp 214–217 ºC; IR (KBr, cm–1)
3341, 1664, 1732; 1H NMR (400 MHz, CDCl3): į 1.16 (s, 3H),
1.17 (s, 3H), 2.22–2.45 (m, 4H), 4.55 (d, J = 4.8 Hz, 1H), 5.23
(d, J = 4.8 Hz, 1H), 5.72 (s, 1H, NH), 7.0–7.40 (m, 5H), 7.42 (s,
1H), 7.47 (d, J = 7.2 Hz, 1H), 7.52 (d, J = 7.8 Hz, 1H), 7.74 (dd,
J = 7.8 Hz, J = 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3): į
26.1, 29.4, 33.7, 35.4, 42.5, 52.1, 107.5, 108.7, 111.1, 112.2,
125.5, 126.7, 128.8, 129.1, 130.5, 131.1, 134.1, 136.8, 150.8,
157.1, 197.4; Anal. Calcd. for C23H22ClNO: C, 75.92; H, 6.09;
N, 3.85. Found: C, 75.90; H, 5.35; N, 3.35.
2
Results and discussion
We had the opportunity to further explore the catalytic ac-
tivity of Co NPs for the synthesis of 1,4-DHPs. The crystallite
size of the Co NPs was determined by XRD and the results are
presented in Fig. 1(a). The XRD peaks were FCC (111), (200),
and (220) for the sample synthesized at 200 °C in an ethanol
hydrazine alkaline system and were assigned using JCPDS
15-806 for the cubic lattice. An examination of the sample by
SEM (Fig. 1(b)) reveals that the diameters of the nanoparticles
are less than 90 nm, which agrees with the size calculated from
the XRD pattern using the Scherrer equation.
4-(4-bromophenyl)-7,7-dimethyl-2-phenyl-4,6,7,8-tetra-
hydro-5(1H)-quinolinone (4j): mp 217–220 ºC; IR (KBr, cm–1)
3344, 1679, 1731; 1H NMR (400 MHz, CDCl3): į 1.11 (s, 3H),
1.13 (s, 3H), 2.20–2.50 (m, 4H), 4.74 (d, J = 4.7 Hz, 1H), 5.34
(d, J = 4.7 Hz, 1H), 5.79 (s, 1H, NH), 7.0–7.25 (m, 5H), 7.36
(d, J = 7.9 Hz, 2H), 7.45 (d, J = 7.9 Hz, 2H); 13C NMR (100
MHz, CDCl3): į 27.4, 29.4, 32.7, 37.9, 41.9, 50.7, 107.1, 108.3,
125.2, 126.1, 127.9, 128.3, 128.7, 128.8, 134.2, 135.8, 147.7,
151.0, 195.5; Anal. Calcd. for C23H22BrNO: C, 67.65; H, 5.43;
N, 3.43. Found: C, 67.49; H, 5.40; N, 3.39.
The lattice parameter of the prepared Co NPs was 0.204 nm,
which is in good agreement with JCPDS 15-806. The crystal-
lite sizes were 83.2, 78.8, and 77.4 nm, respectively, calculated
on the (111), (200), and (220) diffraction maxima from the
half-width of the diffraction peak using Scherrer formula.
In addition the surface area was found to be approximately
4-(2-fluorophenyl)-7,7-dimethyl-2-phenyl-4,6,7,8-tetra-
hydro-5(1H)-quinolinone (4k): mp 198–200 ºC; IR (KBr, cm–1)
3337, 1672, 1750; 1H NMR (400 MHz, CDCl3): į 1.08 (s, 3H),
1.12 (s, 3H), 2.25–2.57 (m, 4H), 4.68 (d, J = 4.8 Hz, 1H), 5.29
(d, J = 4.8 Hz, 1H), 5.67 (s, 1H, NH), 6.95 (dd, J = 9.2 Hz, J =
8.4 Hz, 1H), 7.21 (dd, J = 7.6 Hz, J = 7.2 Hz, 1H), 7.32 (d, J =
7.6 Hz, 1H), 7.42 (dd, J = 8.4 Hz, J = 7.2 Hz, 1H), 7.6–7.90 (m,
5H); 13C NMR (100 MHz, CDCl3): į 27.4, 29.4, 32.7, 37.9,
41.9, 50.7 (d, J = 9.2 Hz), 107.1, 108.3, 116.7 (d, J = 21.4 Hz),
125.2, 126.1, 127.9, 127.9 (d, J = 21.7 Hz), 128.3, 129.7 (d, J =
7.9 Hz), 128.8, 134.2, 135.8, 147.7, 161.0 (d, J = 249 Hz),
195.5; Anal. Calcd. for C23H22FNO: C, 69.51; H, 6.38; N, 4.03.
Found: C, 69.46; H, 5.38; N, 3.35.
(a)
(111)
(220)
(200)
30
40
50
60
70
80
4-(4-fluorophenyl)-7,7-dimethyl-2-phenyl-4,6,7,8-tetra-
hydro-5(1H)-quinolinone (4l): mp 210–213 ºC; IR (KBr, cm–1)
3339, 1676, 1735; 1H NMR (400 MHz, CDCl3): į 1.15 (s, 3H),
1.17 (s, 3H), 2.29–2.40 (m, 4H), 4.56 (d, J = 5.1 Hz, 1H), 5.02
(d, J = 5.1 Hz, 1H), 6.13 (s, 1H, NH), 6.80 (dd, J = 8.9 Hz, J =
7.4 Hz, 2H), 7.31 (dd, J = 8.9 Hz, J = 4.2 Hz, 2H), 7.6–8.55 (m,
5H); 13C NMR (100 MHz, CDCl3): į 26.8, 29.9, 32.2, 36.2,
42.4, 49.9, 107.4, 108.8, 123.2 (d, J = 22 Hz), 126.1, 127.9,
128.3 (d, J = 8 Hz), 129.7, 138.8, 139.2, 140.8, 150.6, 163.5 (d,
J = 244 Hz), 194.5; Anal. Calcd. for C23H22FNO: C, 69.51; H,
6.38; N, 4.03. Found: C, 69.46; H, 5.38; N, 3.35.
2T/(o )
(b)
4-(2-methoxyphenyl)-7,7-dimethyl-2-phenyl-4,6,7,8-tetra-
hydro-5(1H)-quinolinone (4m): mp 196–199 ºC; IR (KBr,
1
cm–1) 3343, 1666, 1745; H NMR (400 MHz, CDCl3): į 1.13
Fig. 1. XRD pattern (a) and SEM image (b) of the prepared Co NPs in
an ethanol hydrazine alkaline system.
(s, 3H), 1.19 (s, 3H), 2.21–2.40 (m, 4H), 4.67 (d, J = 4.4 Hz,