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New Journal of Chemistry
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ARTICLE
Journal Name
source. X-ray fluorescence (XRF) spectroscopy was recorded by Calcd. for C19H10ClFN2O3: C, 61.89; H, 2.73; N, 7.60%. Found: C,
DOI: 10.1039/C5NJ01302J
X-Ray Fluorescence Analyzer, Bruker, S4 Pioneer, Germany. The 61.90; H, 2.55; N, 7.72%.
varioEl CHNS Isfahan Industrial University was used for
Compound 6k. IR (KBr): 3391, 3180, 2196, 1712, 1674,
1
elemental analysis. Transmission electron microscopy (TEM) 1608, 1381, 1240, 1054 cm-1. H NMR (DMSO, 400 MHz): δ
images of the electrocatalyst were recorded using a Philips 7.90 (dd, 1H, J = 8.0 Hz), 7.73–7.69 (m, 1H), 7.44–7.38 (m, 7H),
CM-10 TEM microscope operated at 100 kV.
7.18 (d, 2H, J = 8.8 Hz), 6.95 (d, 2H, J = 8.8 Hz), 5.06 (s, 2H),
4.40 (s, 1H). 13C NMR (DMSO, 100 MHz): δ 159.51, 157.87,
General procedure for the preparation of nanosilica molybdic 157.45, 153.09, 152.06, 137.05, 135.60, 132.83, 128.76,
acid 2 128.40, 127.79, 127.64, 124.63, 122.41, 119.30, 116.53,
To an oven-dried (125 °C, vacuum) sample of silica–gel 60 (10 114.61, 112.97, 104.19, 69.17, 58.09, 36.13 ppm. Anal. Calcd.
g) in a round bottomed flask (250 mL) equipped with a for C26H18N2O4: C, 73.92; H, 4.29; N, 6.63%. Found: C, 74.15; H,
condenser and a drying tube, thionyl chloride (40 mL) was 4.15; N, 6.79%.
added and the mixture in the presence of CaCl2 as a drying
Compound 6l. IR (KBr): 3340, 3312, 2188, 1697, 1669,
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agent was refluxed for 48 h. The resulting white-grayish 1598, 1379, 1066 cm-1. H NMR (DMSO, 400 MHz): δ 8.44(d,
powder was filtered and stored in a tightly capped bottle.22 1H, J = 6.4 Hz), 7.96 (d, 2H, J = 8.0 Hz), 7.83 (d, 1H, J = 8.0 Hz),
0.1g of silica chloride
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was dissolved in toluene (10 ml) and 7.76–7.33 (m, 8H), 5.48 (s, 1H). 13C NMR (DMSO, 100 MHz): δ
stirred for 30 min. The solution of 0.084 g sodium molybdate 159.55, 157.83, 153.80, 152.07, 133.26, 132.93, 130.93,
in 10 ml toluene was added to the first solution and stirred for 128.47, 127.43, 126.10, 126.00, 125.85, 125.75, 124.74,
10 min. The resulting mixture was sonicated in ultrasonic bath 123.43, 122.43, 119.15, 116.61, 112.96, 104.65, 58.49 ppm.
for 1h at room temperature. The mixture was transferred to a Anal. Calcd. for C23H14N2O3: C, 75.40; H, 3.85; N, 7.65%. Found:
70 ml autoclave, heated at 140 °C for 4 h. White precipitate C, 75.65; H, 3.70; N, 7.53%.
obtained, washed with distilled water and then separated by
Compound 6m. IR (KBr): 3389, 3310, 2201, 1713, 1671,
filtration, dried at 22 ˚C for 0 h. The white powder was 1606, 1374, 1049 cm-1. 1H NMR (DMSO, 400 MHz): δ 7.90 (dd,
dissolved in HCl (0.1 N) and stirred for 1h. The white powder 1H, J = 6.5, 1.3 Hz), 7.73–7.69 (m, 1H), 7.51–7.44 (m, 2H), 7.38
was separated by filtration, washed with distilled water and (s, 2H), 7.19–7.15 (m, 4H), 4.41 (s, 1H), 2.84 (m, 1H, 6.92 Hz),
dried at 22 ˚C for 0 h.
1.17 (d, 6H, 6.92 Hz). 13C NMR (DMSO, 100 MHz): δ 159.54,
158.00, 157.95, 153.28, 152.08, 147.11, 140.70, 132.88,
General procedure for the preparation of pyrano[2,3- 127.45, 126.42, 124.65, 122.41, 119.29, 116.54, 112.95,
c]coumarin derivatives 6
Malononitrile (1.1 mmol), aromatic aldehyde
hydroxycoumarin (1 mmol), and SMA
added to a 10 mL mixture EtOH/H2O (50/50) in a 25-mL pyrex
104.18, 58.03, 38.85, 36.50, 33.23, 23.79 ppm. Anal. Calcd. for
(1 mmol), 4- C22H18N2O3: C, 73.74; H, 5.03; N, 7.82%. Found: C, 73.45; H,
(5 mol %) were 5.12; N, 7.74%.
Compound 6n. IR (KBr): 3427, 3280, 2188, 1720, 1669,
3
4
5
2
flask and refluxed for an appropriate time (Table 3). The 1594, 1389, 1048 cm-1. 1H NMR (DMSO, 400 MHz): δ 7.82 (dd,
reaction progress was controlled by thin layer chromatography 1H, J = 6.44, 1.36 Hz), 7.72–7.67 (m, 1H), 7.48–7.43 (m, 2H),
(TLC) using hexane/EtOAc (1:1). After completion of the 7.35 (s, 2H), 4.43 (s, 1H), 1.74 (m, 1H), 1.63-1.57 (m, 4H), 1.38-
reaction, the solvent was removed under vacuum, the crude 1.32 (m, 2H), 1.18-0.94 (m, 4H). 13C NMR (DMSO, 100 MHz): δ
products
6
were obtained after recrystalization from EtOH.
160.64, 160.06, 154.63, 152.02, 132.67, 124.56, 122.05,
116.53, 116.00, 113.00, 104.60, 52.48, 43.18, 36.66, 30.51,
27.52, 26.11, 25.85, 25.52 ppm. Anal. Calcd. for C19H18N2O3: C,
Spectral data
Compound 6i. IR (KBr): 3396, 3321, 3195, 2202, 1706, 70.80; H, 5.59; N, 8.69%. Found: C, 70.53; H, 5.22; N, 8.38%.
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1671, 1607, 1381, 1053 cm-1. H NMR (DMSO, 400 MHz): δ
7.90 (dd, 1H, J = 7.8, 1.2 Hz), 7.75–7.70 (m, 1H), 7.52–7.43 (m,
6H), 7.30–7.28 (m, 2H), 4.50 (s, 1H) ppm. 13C NMR (DMSO, 100
MHz): δ 159.55, 157.94, 153.70, 152.18, 146.02, 132.99,
130.69, 130.39, 130.05, 126.94, 124.65, 122.54, 121.68,
119.05, 116.57, 112.98, 103.15, 57.31, 36.59 ppm. Anal. Calcd.
for C19H11BrN2O3: C, 57.74; H, 2.81; N, 7.09%. Found: C, 58.05;
H, 2.68; N, 7.16%.
Results and discussion
Nanosilica molybdic acid was synthesized and characterized by
X-ray fluorescence (XRF), X-ray diffraction pattern (XRD),
Fourier transform infrared spectroscopy (FT-IR) and
transmission electron microscopy (TEM).
In continuation of our previous studies on the
development of various catalysts in synthesis of organic
compounds,20-22 as can be seen in Scheme 1, from the reaction
of readily available materials such as silica gel and thionyl
Compound 6j. IR (KBr): 3408, 3280, 3175, 2203, 1705,
1
1674, 1602, 1381, 1055 cm-1. H NMR (DMSO, 400 MHz): δ
7.90 (dd, 1H, J = 7.8, 1.2 Hz), 7.76–7.72 (m, 1H), 7.55–7.48 (m,
4H), 7.55–7.19 (m, 3H), 5.19 (d, 1H, J = 1.6 Hz). 13C NMR
(DMSO, 100 MHz): δ 159.38, 158.77, 152.11, 133.14 (d, J = 8.9
Hz), 129.88 (d, J = 10.4 Hz), 124.84, 124.68 (d, J = 4.2 Hz),
122.29, 118.73, 116.68, 115.25, 112.56, 38.83 ppm. Anal.
chloride, silica chloride
found that anhydrous sodium molybdate can react with
give silica molybdic acid (and subsequently nano SMA) . From
1
has been prepared.35 Accordingly, we
to
1
2
the synthetic point of view, the nucleophilic substitution at
silicon is also attractive.
2 | J. Name., 2012, 00, 1-3
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