Article
Naeimi et al.
3
benzene (3e). yellow solid; (found m.p. = 204-206 °C m.p in lit.
cm ). Then, the solvent removed by rotary and colored solid
product was obtained. The crude product was purified by re-
crystallization from petroleum ether. The pure Schiff base was
obtained and characterized by physical and spectroscopic data.
2,2’-[1,2-ethandiylbis-(nitrilomethylidine)]-bis-(3-nitro-
4
06-207 °C ); IR (KBr)/u (cm ): 3427 (OH), 1666 (CHO), 1613
2
-1
2
1
1
460 (C=C), 1522 (N=N), 1146, 842, 758; H NMR (CDCl
3
, 400
MHz)/d ppm: 11.36 (s, 1H, O-H), 10.05 (s, 1H aldehyde), 8.21 (d,
1
H), 8.18 (dd, 1H), 7.79 (d, 2H), 7.66 (d, 2H), 7.14 (d, 1H); C
3
1
NMR/(CDCl
3
, 100 MHz)/d ppm: 192.2, 164.5, 151.2, 136.8,
f
phenylazo) phenol (4a). yellow solid; m.p. = 218-220 °C; R =
-
0.47; IR (KBr)/u (cm ): 3440 (OH), 1633 (C=N), 1526 (N=N),
1
1
3
32.9, 130.0, 129.7, 124.6, 123.1, 119.8, 117.6; UV/lmax (nm):
+
2
+
44, 242; MS: m/z: 306 (M +2, 94), 304 (M , 94), 155 (90), 121
1
), 1284 (C-O), 1110, 860 and 703; H
1488 (C=C), 1352 (NO
2
(
100), 91 (58), 65 (97); Anal. Calcd. For C13
H
9
O
2
N
2
Br: C, 51.17;
NMR (DMSO, 400 MHz)/d ppm: 13.95 (s, 1H, O-H), 8.71 (s,
H, 2.97; N, 9.18; Found: C, 51.20; H, 2.94; N, 9.22. 1-(3-
Formyl-4-hydroxyphenylazo)-4-methoxybenzene (3f). white
1CH imine), 8.45 (s, 1H), 8.3 (d, 1H), 8.22 (dd, 1H), 8.12 (d, 1H)
1
3
7.93 (dd, 1H), 7.83 (t, 1H), 6.93 (d, 1H), 4.04 (s, 2H); C NMR/
(DMSO, 100 MHz)/d ppm: 173.6, 172.0, 157.7, 153.7, 148.4,
136.0, 135.5, 134.2, 131.4, 129.1, 124.6, 122.4, 120.4, 61.7;
4
solid; (found m.p. = 98-100 °C m.p in lit. 98-100 °C ); IR
3
-
KBr)/u (cm ): 3443 (OH), 1660 (CHO), 1613, 1477 (C=C),
1
(
1
524 (N=N), 1283 (C-O), 1141 and 840; H NMR (CDCl
+
UV/lmax (nm): 362, 268, 253; MS: m/z: 505 (M +1, 5), 504 (M ,
+
1
3
, 400
+
10), 368 (30), 97 (30), 57 (90) 43 (100); MS: m/z: 567 (M +1, 3),
+
566 (M , 7), 368 (27), 266 (49), 91 (46), 83 (67), 69 (41), 57 (70)
MHz)/d ppm: 11.31 (s, 1H, O-H), 10.04 (s, 1H aldehyde), 8.2 (d,
H), 8.18 (dd, 1H), 7.82 (d, 2H), 7.33 (d, 2H), 7.13 (d, 1H), 2.45
1
1
s, 3H); C NMR/(CDCl
3
(
3
, 100 MHz)/d ppm: 191.3, 166.1, 161.8,
22 6 8
43 (100); Anal. Calcd. For C28H O N : C, 59.36, H, 3.91; N,
1
46.6, 141.1, 129.3, 124.7, 124.5, 123.1, 120.1, 114.9, 56.0;
19.78. Found: C, 59.40, H, 3.94: N, 19.75. 2,2’-[1,2-ethan-
+
+
UV/lmax (nm): 345, 242; MS: m/z: 257 (M +1, 48), 256 (M ,
4), 149 (73), 121 (83), 107 (59) 91 (100), 65 (63); Anal. Calcd.
: C, 65.62; H, 4.72; N, 10.93. Found: C, 65.66; H,
diylbis-(nitrilomethylidine)]-bis-(4-chlorophenylazo) phenol
9
f
(4b). yellow solid; m.p. = 264-266 °C; R = 0.59; IR (KBr)/u
-
1
(cm ): 3432 (OH), 1633 (C=N), 1579 (N=N), 1482 (C=C), 1283
For C14
H
12
O
3
N
2
1
(C-O), 1145, 1103 and 856; H NMR (DMSO, 400 MHz)/d ppm:
4
.69; N, 10.89.
Preparation of nanocrystalline MgO: Nanocrystalline
14.04 (s, 1H, O-H), 8.70 (s, 1CH imine), 8.03 (d, 1H), 7.90 (dd,
13
4
4
MgO was prepared by means of a procedure reported elsewhere.
1H), 7.88 (d, 2H), 7.35 (d, 2H), 6.96 (d, 1H), 4.01 (s, 2H);
C
In short, poly (vinyl alcohol) (PVA, MW70,000) was dissolved in
NMR/(DMSO, 100 MHz)/d ppm: 167.1, 164.3, 151.3, 144.4,
135.7, 131.3, 128.9, 124.5, 124.3, 118.8, 117.6, 60.1; UV/lmax
water at 90 °C under vigorous stirring to form a transparent solu-
+
(nm): 358, 278, 242; MS: m/z: 549 (M +4, <1), 547 (M +2, <1),
4
+2
tion. Mg(NO
3
)
2
. 6H
2
O was dissolved in water containing PVA.
+
545 (M +1, <1), 266 (58), 91 (39), 83 (41), 57 (87) 43 (100);
The metal ion-to-PVA monomer unit molar ratio (M/PVA) was
chosen as 1:3. Aqueous ammonia (25% w/w) was added drop
wise at room temperature to the resulting viscous liquid mixture,
with rapid stirring, to achieve careful pH adjustment to 10.5. Af-
ter precipitation, the slurry was stirred for another 30 min and
then heated under reflux at 80 °C for 20 h under continuation of
stirring. The mixture was cooled to room temperature, filtered-
off, and washed with hot deionized water for effective removal of
the poly (vinyl alcohol). The final product was dried at 80 °C for
22 2 6 2
Anal. Calcd. For C28H O N Cl : C, 61.66; H, 4.07; N, 15.41;
Found: C, 61.70, H, 4.09; N, 15.39. 2,2’-[1,2-ethandiylbis-(ni-
trilomethylidine)]-bis-(4-methylphenylazo) phenol (4c). golden
-
1
f
solid, m.p. = 248-250 °C; R = 0.64; IR (KBr)/u (cm ); 3433
(OH), 1633 (C=N), 1488 (N=N), 1463 (C=C), 1284 (C-O), 1148
1
and 845; H NMR (DMSO, 400 MHz)/d ppm: 13.72 (s, 1H, O-H),
8.51 (s, 1CH imine), 7.96 (d, 1H), 7.89 (dd, 1H), 7.77 (d, 2H),
1
3
7.30 (d, 2H), 7.06 (d, 1H), 4.03 (s, 2H), 2.43 (s, 2H); C NMR/
(DMSO, 100 MHz)/d ppm: 166.4, 164.2, 152.7, 145.4, 139.1,
131.3, 128.9, 127.1,122.7, 120.2, 118.1, 59.3, 21.3; UV/lmax
2
4 h and calcined at 700 °C.
General procedure for the synthesis of Schiff bases con-
+
(nm): 352, 276, 242; MS: m/z: 505 (M +1, 5), 504 (M , 10), 368
+
taining diazo groups (4a–f): In this reaction, measured quanti-
ties of nanocrystalline MgO (0.025 g, 0.6 mmol) and salicylal-
dehyde containing diazo functional groups (4 mmol) (3a-f) were
poured into mortar and thoroughly mixing together. Then ethyl-
(30), 266 (63), 91 (38), 83 (75), 69 (45), 57 (90) 43 (100); Anal.
Calcd. For C30
71.44; H, 5.57; N, 16.69.
2,2’-[1,2-ethandiylbis-(nitrilomethylidine)]-bis-(3-methyl-
phenylazo) phenol (4d). orange solid, m.p. = 190-192 °C; R
28 2 6
H O N : C, 71.41; H, 5.59; N, 16.66. Found: C,
3
enediamine (0.12 cm , 2 mmol) was added to the reaction mix-
ture. The resulting mixture was placed in a flask and mechani-
cally stirred. The progress of the reaction was monitored by TLC.
After completion of the reaction, the desired product was sepa-
rated by washing the reaction mixture with chloroform (2 ´ 10
f
=
-
0.61; IR (KBr)/u (cm ); 3433 (OH), 1633 (C=N), 1487 (N=N),
1
1
1286 (C-O), 1126 and 846; H NMR (DMSO, 400 MHz)/d ppm:
13.76 (S, 1H, O-H), 8.51 (s, 1CH imine), 7.98 (d, 1H), 7.96 (dd,
956
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J. Chin. Chem. Soc. 2015, 62, 951-958