M. Rostami et al. / Applied Catalysis A: General 397 (2011) 27–34
29
CDCl ) ı (ppm): 71.00, 112.00, 114.20, 127.30, 127.50, 127.65,
3
1
1
5
27.73, 128.87, 129.05, 129.25, 129.89, 131.23, 131.64, 141.40,
59.90, 161.12, 167.05, Mass (m/z): 355.25, 149.04, 115.10, 76.99,
6.97.
(
4Z)-4-(4-nitrobenzylidene)-2-phenyloxazol-5(4H)-one
(3f)
20]: mp 237–239 C; IR (KBr): ꢀ (cm ) 3063, 1795, 1661, 1559,
513, 1450, 1345, 1284, 11167, 979, 865, 684; 1H NMR (500 MHz,
◦
−1
[
1
CDCl ) ı (ppm): 7.28 (1H, s), 7.60–7.63 (2H, t, J = 7.5), 7.7–7.73 (1H,
3
t, J = 7.5), 8.25–8.27 (2H, m), 8.35–8.37 (2H, d, J = 8.8), 8.40–8.42
(
2H, d, J = 8.8); Mass (m/z): 294.06, 105.11, 77.12.
4Z)-4-(4-fluorobenzylidene)-2-phenyloxazol-5(4H)-one (3g)
(
◦
−1
[
26]: mp 177–179 C; IR (KBr): ꢀ (cm ) 3059, 1796, 1662, 1596,
506, 1450, 124, 1242, 1157, 1094, 984, 834, 696; 1H NMR
500 MHz, CDCl ) ı (ppm): 7.19–7.23 (2H, t, J = 8.5), 7.25 (1H,
1
(
3
s), 7.56–7.59 (2H, t, J = 7.3), 7.65–7.68 (1H, t, J = 7.3), 8.21–8.22
2H, d, J = 7.5), 8.25–8.28 (2H, m); Mass (m/z): 267.04, 105,
7.11.
4Z)-4-(2-bromobenzylidene)-2-phenyloxazol-5(4H)-one (3h)
(
7
(
◦
−1
[
1
5]: mp 141–143 C; IR (KBr): ꢀ (cm ) 3054, 1793, 1650, 1551,
325, 1292, 1167, 863, 763, 696; 1H NMR (500 MHz, CDCl3)
ı (ppm): 7.37–7.69 (6H, m), 7.8 (1H, s), 8.22–8.24 (2H, d,
J = 7.3), 8.96–8.97 (1H, d, J = 7.8); Mass (m/z): 326.99, 104.97,
7
7.01.
4Z)-4-(3-bromobenzylidene)-2-phenyloxazol-5(4H)-one (3i)
(
◦
−1
[
25]: mp 147–149 C; IR (KBr): ꢀ (cm ) 3052, 1795, 1656, 1597,
1
449, 1326, 1294, 1163, 982, 873, 776, 678; 1H NMR (500 MHz,
CDCl ) ı (ppm): 7.19 (1H, s), 7.37–7.40 (1H, t, J = 7.8), 7.58–7.62 (3H,
3
m), 7.66–7.69 (1H, t, J = 7.3), 8.10–8.12 (1H, d, J = 7.8), 8.22–8.24 (2H,
m), 8.47 (1H, s); Mass (m/z): 326.99, 194.06, 105.12, 77.08.
(
4Z)-4-(2-chlorobenzylidene)-2-phenyloxazol-5(4H)-one (3j)
◦
−1
[
1
20,21]: mp 162–163 C; IR (KBr): ꢀ (cm ) 3056, 1793, 1652,
554, 1328, 1294, 1169, 865, 764, 694, 565; 1H NMR (500 MHz,
CDCl ) ı (ppm): 7.37–7.69 (6H, m), 7.8 (1H, s), 8.22–8.24 (2H,
3
d, J = 7.3), 8.96–8.97 (1H, d, J = 7.8); Mass (m/z): 283.25, 105.06,
7
7.06.
4Z)-4-(3-nitrobenzylidene)-2-phenyloxazol-5(4H)-one (3k)
(
◦ −1
4,21]: mp 174–176 C; IR (KBr): ꢀ (cm ) 3073, 1717, 1647, 1532,
[
1
7
480, 1351, 1260, 1026, 691; 1H NMR (500 MHz, CDCl ) ı (ppm):
3
Fig. 1. TG-DTG analysis of: (A) [bmim]3PW12O40 and (B) [bmim]4W10O32.
.32 (1H, s), 7.4–7.8 (4H, m), 8.12–8.55 (4H, m), 9.3 (1H, s); Mass
(
m/z): 294.06, 105, 76.95.
4Z)-4-(2,4-dichlorobenzylidene)-2-phenyloxazol-5(4H)-one
(
◦
−1
(5H, m), 8.14–8.19 (2H, m); 13C NMR (125 MHz, CDCl3) ı (ppm):
16.2, 125.6, 125.9, 126.9, 127.6, 128.2, 128.9, 133, 135.95, 136.35,
(
1
3l) [27]: mp 181–183 C; IR (KBr): ꢀ (cm ) 3064, 2922, 2850,
797, 1655, 1558, 1450, 1323, 1168, 1093, 979, 694; 1H NMR
1
51.58, 160.56, 167.3; Mass (m/z): 269.12, 207.11, 105.14, 77.08.
(
500 MHz, CDCl ) ı (ppm): 7.42–7.44 (1H, d, J = 8.6), 7.53 (1H, s),
3
7
8
.57–7.60 (2H, m), 7.67–7.70(2H, m), 8.21–8.23 (2H, d, J = 8.1),
.94–8.95 (1H, d, J = 8.6); Mass (m/z): 318.2, 105.12, 77.06.
3. Results and discussion
(
4Z)-4-((naphthalen-1-yl)methylene)-2-phenyloxazol-5(4H)-
◦
−1
one (3m) [25]: mp 163–165 C; IR (KBr): ꢀ (cm ) 3060, 2923,
792, 1645, 1549, 1488, 1448, 1323, 1167, 978, 874, 694; 1H NMR
500 MHz, CDCl ) ı (ppm): 7.57–7.70 (6H, m), 7.94–7.96 (1H, d,
3.1. Preparation and characterization of catalysts
1
(
The prepared catalysts were characterized by TG-DTG,
XRD, FT-IR and UV–Vis spectroscopic methods and nitrogen
absorption–desorption determination (BET).
3
J = 8), 8.01–8.02 (1H, d, J = 8.1), 8.19 (1H, s), 8.25–8.26 (2H, m),
8
.35–8.37 (1H, d, J = 8.5), 9.07–9.09 (1H, d, J = 7.4); Mass (m/z):
2
99.09, 105, 77.01.
In TG-DTG analysis of [bmim] PW12O40 and [bmim] W10O32 no
3
4
(
4Z)-4-((1H-indol-3-yl)methylene)-2-phenyloxazol-5(4H)-one
important weight loss or major endothermic peak was observed
◦
−1
◦
(
1
3n) [5,21]: mp 209–211 C; IR (KBr): ꢀ (cm ) 3328, 3052, 1730,
644, 1508, 1459, 1288, 1124, 887, 743; H NMR (500 MHz, C D O)
around 100 C (Fig. 1a and b), and both catalysts were thermally
1
◦
stable up to 400 C.
3
6
ı (ppm): 7.32–7.62 (6H, m), 7.7 (1H, s), 8.05 (1H, bs), 8.17–8.19
Fig.
2 shows the FT-IR spectra of [bmim] W10O32 and
4
13
(
1H, dd, J = 9.5, J = 1.5), 8.65 (1H, s), 8.87 (1H, bs);
CNMR
[bmim] PW12O40
.
The characteristic bands of [bmim]Cl,
3
(
125 MHz, C D O) ı (ppm): 112.23, 112.40, 119.62, 121.63, 123.24,
[bmim] W10O32, [bmim] PW12O40, H PW12O40 and K W10O32
3
6
4
3
3
4
1
1
7
25.65, 126.45, 127.08, 127.52, 127.55, 129.13, 132.60, 134.42,
37.02, 160.03, 166.99; Mass (m/z): 288.04, 154.87, 104.88,
6.87.
are shown in Table 1. From these data, it is clear that both catalysts
contain imidazolium cation and anionic Keggin parts.
The UV–Vis spectroscopy, in the diffuse reflectance mode, was
employed for characterization of these heterogeneous catalysts.
The reflectance of these catalysts resembles solution counter-
(
4Z)-4-((5-methylthiophen-2-yl)methylene)-2-phenyloxazol-
◦
−1
5
(4H)-one (3o): mp 145–147 C; IR (KBr): ꢀ (cm ) 3070, 2922,
2
852, 1726, 1639, 1510, 1440, 1375, 1230, 1132, 750; 1H NMR
part spectra and two peaks at 235 and 260 nm for H PW12O40
3
(
500 MHz, CDCl ) ı (ppm): 2.63 (3H, s), 6.89 (1H, s), 7.43–7.63
and a peak at 320 nm for K W10O32 were observed. These
3
4