Razieh FAZAELI et al. / Chinese Journal of Catalysis, 2012, 33: 237–246
146.7. IR (KBr) ꢂmax = 1123, 1495, 1598 cm–1.
2 Results and discussion
5-(3-Chlorophenyl)-1,3-diphenyl-2-pyrazoline (3e). 1H
NMR (CDCl3): ꢁ 3.08 (dd, J = 6.8 Hz, 17.0 Hz, 1H), 3.43 (dd, J
= 12.2 Hz, 17.2 Hz, 1H), 5.63 (dd, J = 6.9 Hz, 12.4 Hz, 1H)
6.85–7.81 (m, 14H). Anal. calcd. for C21H17N2Cl: C, 85.85; H,
5.72; N, 9.43; found C, 85.79; H, 5.70; N, 9.41. 13C NMR
(CDCl3): ꢁ 42.37, 61.54, 113.58, 119.60, 124.44, 127.79,
128.07, 128.92, 129.18, 129.48, 130.67, 132.53, 133.04,
135.04, 139.67, 144.84, 147.53. IR (KBr) ꢂmax = 1127, 1501,
1593 cm–1.
2.1 Characterization of the CsHPW
FT-IR spectroscopy is a convenient method for the charac-
terization of the Keggin structure of heteropolyanions. The
infrared spectrum of the Cs2.5H0.5PW12O40 nanocasts (Fig. 4(c))
gave strong vibrations at 1081 (ꢁas(P–Oa)), 986 (ꢁas(W–Oa)),
892 (ꢁas(W–O–W)), and 800 cmꢀ1 (ꢁas(W–Oc–W)) while
bulk-Cs2.5H0.5PW12O40 gave vibrations at 1080, 986, 891, and
801 cm–1 (Fig. 4(a)). In addition, the observed band at 523 cmꢀ1
may be attributed to the ꢂ(P–O) vibration [45]. Moreover, the
band located at 1622 cmꢀ1 may be characteristic of the O–H
stretching vibration (Fig. 4(c)).
The chemical composition of the bulk CsHPW samples and
their nanocasts were estimated by averaging the results of
energy dispersive X-ray spectroscopy (EDS) experiments at
five different positions in the samples. EDS results indicate that
the as-prepared CsHPW nanocast samples contain Cs, W, P,
and O (Fig. 5 and Table 1). The percentage of silica matrix
removed from the CsHPW/SBA composite was about 99%.
The Cs content in the CsHPW materials was characterized by
Cs/W12 further defined as the Cs/W12 ratio and this was calcu-
lated from the atomic percentages of Cs and W in the samples
5-(2-Chlorophenyl)-1,3-diphenyl-2-pyrazoline (3f). 1H
NMR (CDCl3): ꢁ 3.06 (dd, J = 4.8 Hz, 17.6 Hz, 1H), 3.96 (dd, J
= 11.2 Hz, 17.7 Hz, 1H), 5.64 (dd, J = 4.7 Hz, 11.0 Hz, 1H),
6.76–7.74 (m, 14H); Anal. Calcd. for C21H17ClN2: C, 75.78; H,
5.15; N, 8.41. Found: C, 75.83; H, 5.23; N, 8.38%.13C NMR
(CDCl3): ꢁ 41.9, 61.5, 113.3, 119.2, 125.9, 127.5, 127.9, 128.3,
128.5, 128.8, 129.3. 129.8, 131.4, 132.2, 139.5, 144.6, 147.4.
IR (KBr) ꢂmax = 1120, 1497, 1595 cm–1.
5-(2,4-Dichlorophenyl)-1,3-diphenyl-2-pyrazoline (3g).
1H NMR (CDCl3): ꢁ 3.02 (dd, J = 6.6 Hz, 17.6 Hz, 1H), 3.97
(dd, J = 12.5 Hz, 17.5 Hz, 1H), 5.59 (dd, J = 6.6 Hz, 12.2 Hz,
1H), 6.69–7.71 (m, 13H); Anal. Calcd. for C21H16Cl2N2: C,
68.67; H, 4.39; N, 7.62. Found: C, 68.73; H, 4.39; N, 7.71%.
13CNMR (CDCl3): ꢁ 41.5, 60.9, 113.5, 119.5, 124.3, 125.6,
127.4, 127.7, 128.6, 128.5, 128.5, 129.2, 129.5, 132.1, 133.9,
137.7, 144.4, 147.5. IR (KBr) ꢂmax = 1118, 1503, 1589 cm–1.
5-(3-Bromophenyl)-1,3-diphenyl-2-pyrazoline (3h). 1H
NMR (CDCl3): ꢁ 3.08 (dd, J = 7.1 Hz, 17.0 Hz, 1H), 3.35 (dd, J
= 12.1 Hz, 16.9 Hz, 1H), 5.68 (dd, J = 6.9 Hz, 12.7 Hz, 1H)
6.80–7.75 (m, 14H). Anal. calcd. for C21H17N2Br: C, 85.85; H,
5.72; N, 9.43; found C, 85.78; H, 5.69; N 9.43. 13C NMR
(CDCl3): ꢁ 42.35, 60.47, 113.35, 119.50, 124.23, 127.94,
128.05, 129.06, 129.16, 129.35, 130.59, 132.41, 133.18,
139.66, 145.25, 147.14. IR (KBr) ꢂmax = 1126, 1502, 1598
cm–1.
(a)
100
80
60
40
120
(b)
100
1
80
60
40
20
0
5-(4-Methoxyphenyl)-1,3-diphenyl-2-pyrazoline (3i). H
NMR (CDCl3): ꢁ 3.12 (dd, J = 7.1 Hz, 17.1 Hz, 1H), 3.82 (s,
3H, OCH3), 3.87 (dd, J = 12.1 Hz, 16.9 Hz, 1H), 5.24 (dd, J =
7.2 Hz, 12 Hz, 1H) 6.75–7.85 (m, 14H). Anal. calcd. for
C22H20N2O: C, 84.62; H, 6.41; N, 8.97; found C, 84.56; H,
6.40; N, 8.93. 13C NMR (CDCl3): ꢁ 44.08, 55.64, 64.14,
113.72, 114.46, 119.54, 126.42, 127.91, 128.47, 128.89,
129.19, 130.56, 133.21, 135.03, 145.34, 147.17. FT-IR (KBr)
ꢂmax = 1120, 1261, 1512, 1597 cm–1.
-20
(c)
100
80
60
40
3-(4-Chlorophenyl)-1,5-diphenyl-2-pyrazoline (3j). 1H
NMR (DMSO): ꢁ 3.15 (dd, J = 7.1 Hz, 17.0 Hz, 1H), 3.87 (dd,
J = 12.2 Hz, 17.1 Hz, 1H), 5.33 (dd, J = 7.3 Hz, 12.4 Hz, 1H)
6.83–7.67 (m, 14H). Anal. calcd. for C21H17N2Cl: C, 84.85; H,
5.72; N, 9.43; found C, 84.81; H, 5.77; N, 9.47. 13C NMR
(DMSO): ꢁ 42.39, 61.31, 113.53, 117.26, 126.83, 126.94,
128.64, 129.16, 129.39, 130.55, 132.17, 132.19, 136.05,
139.61, 143.73, 147.39. IR (KBr) ꢂmax = 1121, 1509, 1599
cm–1.
20
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cmꢃ1)
Fig. 4. FT-IR spectra of Bulk-CsHPW (a), CsHPW/SBA-15 (b), and
CsHPW nanocrystals (c).