4
.2. Procedure for synthesis of NaY/SA/Cu(II)
To a mixture of NaY zeolite in toluene (20 mL), trimethoxysilyl propylamine (2 mL) was added and stirred for 24 h under reflux
o
conditions. Then zeolite was separated by filtration and dried at 60 C. For sulfonation, chlorosulfonic acid (2 mL) and triethylamine
(
0.2 mL) was added to a mixture of functionalized zeolite (1 g) in toluene (20 mL) and stirred at reflux conditions for 24 h. Finally, the
o
participated solid was filtrated, washed with water and dried over 60 C to obtain the NaY-SA compound. A pH analysis of NaY-SA
showed 1.5 mmol/g loading of SO H. In the next step, NaY-SA (1 g) was reacted with 100 mL of a 0.001 mol/L solution of Cu(OAc)
in toluene for 24 h at room temperature. After sonication (2 × 3 min) the NaY/SA/Cu(II) product was filtered, and dried at 60 C
Scheme 4). Then the loading of copper in NaY/SA/Cu(II) was determined to be 2% by atomic absorption spectroscopy.
3
2
o
(
Scheme 4. Step by step synthesis of NaY/SA/Cu(II).
4
.3. General procedure for formylation of amines
To a mixture of amine (1 mmol) and NaY/SA/Cu(II) (0.01 g), formic acid (5 mmol, 0.19 mL) was added and stirred for appropriate
time at room temperature. After completion of the reaction as monitored by TLC (n-hexane/ EtOAc = 8/2), NaY/SA/Cu(II) catalyst
was filtered and organic layer evaporated under reduced pressure to give pure product. The structure of the products was established
1
13
from their physical properties and spectral ( H NMR, C NMR and IR) analysis and were compared with the data reported in the
literature and are available as the Supporting information.
Physical and spectroscopic characterization data of selected new compounds (9, 13, 14 and 16) are shown below, and others were
given in Supporting information.
o
-1
N-(2,4-Dichlorophenyl) formamide (9): Mp: 154-157 C. IR (KBr pellet, cm ): νmax 3244, 3090, 3034, 2986, 2899, 1695, 1664,
1
1
585, 1529, 1398, 1298, 1103, 1049, 817, 752, 700, 381. H NMR (DMSO-d
6
, 300 MHz): δ 9.74 (s, 1H, CHO). 7.37-8.14 (m, 3H, Ar-
, 75 MHz): δ 161.03, 133.88, 129.29, 128.79, 128.14, 124.73, 124.43. Elemental analysis for
2
NO, Calcd. C, 44.25; H, 2.65; N, 7.37. Found: C, 44.00; H, 2.80; N, 7.37.
1
3
H), 7.15 (s, 1H, NH), C NMR (DMSO-d
Cl
N-(Pyridin-2-yl)formamide (13): Mp: 130-132 C. IR (KBr pellet, cm ): νmax 3319, 3157, 2876, 1668, 1624, 1589, 1454, 1369, 1327,
6
C
7
H
5
o
-1
1
, 300 MHz): δ 7.67-7.94 (m, 1H, CHO), 6.01-7.15 (m, 4H, Ar-H), 5.78 (s, 1H, NH). 13
O calcd. C, 59.01; H,
1
248, 1134, 765, 387. H NMR (DMSO-d
NMR (DMSO-d , 75 MHz): δ 160.08, 155.91, 149.63, 136.91, 120.72, 105.79. Elemental analysis for C
.95; N, 22.94. Found: C: 59.20, H: 5.15, N: 23.00.
N-(4,6-Dimethylpyrimidin-2-yl)formamide (14): Mp: 145-148 C. IR (KBr pellet, cm ): νmax 3325, 3182, 3094, 2930, 2858, 2735,
6
C
6
6 6 2
H N
4
o
-1
1
1
682, 1662, 1635, 1574, 1589, 1373, 1323, 1136, 935, 553, 387. H NMR (DMSO-d
6
, 300 MHz): δ 7.90 (s, 1H, CHO), 6.11 (m, 2H,
1
3
NH and Ar-H), 1.92 (s, 6H, CH
3
). C NMR (DMSO-d
6
, 75 MHz): δ 164.06, 159.63, 156.81, 137.39, 18.21. Elemental analysis for
7 9 3
C H N O: calcd. C, 55.62; H, 6.00; N, 27.80. Found: C: 56.00, H: 5.86, N: 27.81.
o
-1
N,N'-(1,2-Phenylene)diformamide (16): Mp: 180-182 C. IR (KBr pellet, cm ): νmax 3101, 2922, 2856, 2808, 2696, 1682, 1620,
1
1
(
560, 1485, 1452, 1398, 1249, 1120, 1035, 802, 605, 624, 426. H NMR (DMSO-d
6
, 300 MHz): δ 8.22-8.34 (m, CHO, 2 H), 7.62-7.65
m, Ar-H, 2 H), 7.20-7.23 (m, Ar-H, 2 H), 6.89 (NH, 2 H). C NMR (75 MHz, DMSOd ): δ 163.62, 130.12, 124.64, 122.58. Elemental
analysis for C : Calcd. C, 58.53; H, 4.91; N, 17.06. Found: C: 59.19, H: 5.00, N: 17.39.
1
3
6
8
8 2 2
H N O
Acknowledgment
We thank Arak University for financial support for this work.
References
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