Paper
NJC
Experimental
Methods and materials
(d, 1H, J = 8.4); 13C NMR (DMSO-d6, 100 MHz): d 177.0, 173.9,
159.1, 158.1, 152.9, 141.0, 134.9, 128.4, 125.8, 124.3, 116.6,
110.6, 90.9, 56.7, 46.8; anal. calcd. For C15H8ClN5O3S: C,
48.20; H, 2.16; N, 18.74; S, 8.58. Found: C, 48.42; H, 2.26; N,
18.65; S, 8.50.
Chemicals were purchased from Merck and Aldrich. IR spectra
were recorded on a FT-IR JASCO-680 and the H-NMR spectra
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were obtained on a Bruker DPX-400 or 300 MHz Avance 2
instrument. The varioEl CHNS was also used for elemental
analysis. Powder X-ray diffraction measurements were made on
a Philips X’pert diffractometer, using filtered Cu Ka radiation.
The images of CuFe2O4 nanocrystals were obtained using a
JEOL-JFM-1200 EX transmission electron microscope (TEM).
Compound 8c. Mp. 276–278; FT-IR (KBr, cmÀ1): 3352, 3280,
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3160, 2197, 1690, 1590, 1500, 1378, 1342, 1186, 1130; H NMR
(DMSO-d6, 400 MHz): d 12.60 (s, 1H), 7.49 (s, 2H), 7.38 (d, 3H,
J = 8.0 Hz), 7.28 (t, 1H, J = 7.6 Hz), 7.23 (t, 2H, J = 7.6), 7.06 (t, 2H,
J = 7.6 Hz), 6.82 (d, 1H, J = 8.0 Hz); 13C NMR (DMSO-d6,
100 MHz): d 175.3, 173.9, 159.2, 158.1, 143.4, 137.6, 134.5,
129.8, 129.7, 128.8, 126.7, 126.5, 123.17, 116.6, 110.6, 108.5,
91.5, 57.0, 47.8; anal. calcd. For C21H13N5O3S: C, 60.71; H, 3.15;
N, 16.86; S, 7.72. Found: C, 60.77; H, 3.10; N, 16.90; S, 7.68.
Compound 8d. Mp. 280–282; FT-IR (KBr, cmÀ1): 3516, 3351,
3175, 2207, 1688, 1652, 1594, 1403, 1344, 1190, 1117, 755, 577;
1H NMR (DMSO-d6, 400 MHz): d 12.53 (s, 1H), 7.49 (s, 2H), 7.30
(d, 1H, J = 7.6 Hz), 7.27 (d, 1H, J = 7.6 Hz), 7.01 (t, 2H, J = 7.6 Hz),
3.14 (s, 1H); 13C NMR (DMSO-d6, 100 MHz): d 175.6, 173.8,
158.9, 158.8, 158.1, 152.6, 143.6, 132.0, 128.7, 123.7, 122.5,
116.6, 106.2, 91.4, 56.9, 46.2, 28.4; anal. calcd. For C16H11N5O3S:
C, 54.38; H, 3.14; N, 19.82; S, 9.07. Found: C, 54.61; H, 3.06; N,
19.88; S, 9.00.
Preparation of the catalyst
Appropriate stoichiometric amounts of initial materials were
used for two microemulsions. The amounts of aqueous phase
and organic phase are the same as those used in ref. 20. The
first microemulsion was prepared at ambient temperature by
adding 5 ml of 0.05 M K2Cu(CN)4 and 5 ml of 0.1 M K3[Fe(CN)6]
into 80 ml of octanol that was used as an organic phase and
also a co-surfactant at the same time. Furthermore, 10 ml of an
aqueous solution of cetyl trimethylammonium bromide (CTAB)
was added and stirred at 1200 rpm. The second microemulsion
was prepared by the same method just using HCHO and
CH3COONa instead of metals, then two microemulsions were
mixed together and left for 3 h at room temperature. The pH of
the solution was about 8. Finally, the resulting precipitate was
separated by centrifugation and washed thoroughly with absolute
EtOH and hot H2O several times to remove impurities. The
product was dried at 120 1C in an air oven and calcined at 700 1C
for 2 h to obtain nano-CuFe2O4.
Compound 8e. Mp. 298–300; FT-IR (KBr, cmÀ1): 3433, 3302,
3166, 2200, 1486, 1411, 1657, 1570, 1486, 1399, 1342, 1184,
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1124, 571, 539; H NMR (DMSO-d6, 400 MHz): d 13.8 (br, 1H),
12.55 (s, 1H), 10.57 (s, 1H), 7.49 (s, 2H), 7.24 (dd, 1H, J = 8.4, 2.4
Hz), 7.01 (td, 1H, J = 8.8, 2.4 Hz), 6.79 (dd, 1H, J = 7.2, 2.0 Hz);
13C NMR (DMSO-d6, 100 MHz): d 177.2, 173.9, 159.1, 158.1,
157.0, 152.8, 138.2, 134.6, 116.6, 114.9, 112.09, 109.8, 91.1, 56.9,
47.07; anal. calcd. For C15H8FN5O3S: C, 50.42; H, 2.26; N, 19.60;
S, 8.97. Found: C, 50.65; H, 2.20; N, 19.69; S, 8.91.
General procedure for the synthesis of compounds 7–10
Compound 9b. Mp. 285–287; FT-IR (KBr, cmÀ1): 3321, 3214,
2203, 1743, 1705, 1674, 1608, 1364, 1341, 1214, 1100, 763;
1H NMR (DMSO-d6, 400 MHz): d 11.44 (s, 1H), 8.37 (s, 1H),
8.23 (dd, 1H, J = 8.4, 2.4 Hz), 7.96 (dd, 1H, J = 8.4, 2.4 Hz), 7.85
(s, 2H), 7.81–7.77 (m, 1H), 7.59–7.50 (m, 2H); 13C NMR (DMSO-
d6, 100 MHz): d 177.8, 158.7, 158.6, 155.7, 152.1, 148.5, 148.4,
133.9, 133.7, 126.2, 125.0, 122.7, 120.5, 116.6, 112.6, 109.6,
100.1, 90.9, 55.5, 47.7; anal. calcd. For C20H10N4O6: C, 59.71;
H, 2.51; N, 13.93. Found: C, 59.90; H, 2.49; N, 14.04.
Isatine 1 (1 mmol), malononitrile (2) (1.1 mmol), compounds
3–6 (1 mmol), and CuFe2O4 NPs (0.07 mmol) were added to a
10 mL mixture of EtOH/H2O (1/1) and refluxed for an appropriate
time (Table 2). The reaction progress was monitored by TLC
(hexane/AcOEt, 10 : 7). After completion of the reaction, the
solvent was removed under reduced pressure and the crude
products 7–10 were obtained after recrystalization from EtOH.
The catalyst was separated by simple filtration or an external
magnetic field, washed with EtOH, and dried at 80 1C.
Compound 9c. Mp. 304–306; FT-IR (KBr, cmÀ1): 3463, 3346,
Spectral data for new compounds
2198, 1713, 1674, 1614, 1498, 1362, 1217, 1172, 1107, 1078, 747,
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Compound 7b. Mp. 255–257; FT-IR (KBr, cmÀ1): 3376, 3172, 702; H NMR (DMSO-d6, 400 MHz): d 7.99 (d, 1H, J = 7.6 Hz),
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2205, 1722, 1695, 1610, 1501, 1376, 1330, 1113, 754; H NMR 7.83–7.78 (m, 2H), 7.65–7.51 (m, 6H), 7.41 (d, 3H, J = 8 Hz), 7.28
(DMSO-d6, 400 MHz): d 12.42 (s, 1H), 11.23 (s, 1H), 7.53 (s, 2H), (t, 1H, J = 8.0 Hz), 7.09 (t, 1H, J = 8.0 Hz), 6.73 (d, 1H, J = 7.6 Hz);
7.36 (d, 3H, J = 8.0 Hz), 7.28 (t, 1H, J = 7.6 Hz), 7.21 (t, 2H, J = 7.6 13C NMR (DMSO-d6, 100 MHz): d 175.2, 158.5, 158.4, 155.2,
Hz), 7.06 (t, 2H, J = 7.6 Hz), 6.82 (d, 1H, J = 8.0 Hz); 13C NMR 152.1, 143.3, 134.3, 133.8, 131.9, 129.8, 129.2, 128.3, 126.5,
(DMSO-d6, 100 MHz): d 175.8, 161.53, 158.3, 137.6, 134.6, 132.3, 125.0, 124.5, 123.4, 122.7, 116.83, 116.80, 116.7, 112.4, 108.7,
129.8, 129.6, 126.6, 125.7, 123.9, 123.0, 110.6, 108.5, 86.8, 57.3, 101.2, 56.6; anal. calcd. For C26H15N3O4: C, 72.05; H, 3.49; N,
43.2; anal. calcd. For C21H13N5O4: C, 63.16; H, 3.28; N, 17.54. 9.70. Found: C, 72.25; H, 3.42; N, 9.66.
Found: C, 63.27; H, 3.20; N, 17.44.
Compound 10b. Mp. 298–300; FT-IR (KBr, cmÀ1): 3353, 3292,
Compound 8b. Mp. 299–301; FT-IR (KBr, cmÀ1): 3359, 3285, 3102, 2196, 1707, 1670, 1608, 1485, 1352, 1312, 1216, 1013; 1H NMR
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3157, 2199, 1683, 1572, 1478, 1398, 1341, 1170, 1113; H NMR (DMSO-d6, 400 MHz): d 10.43 (s, 1H), 7.29 (s, 2H), 7.00–6.94
(DMSO-d6, 400 MHz): d 12.54 (s, 1H), 10.68 (s, 1H), 7.51 (s, 2H), (m, 2H), 6.77 (dd, 1H, J = 8.4, 4.4 Hz), 2.70–2.58 (m, 2H), 2.29–
7.42 (d, 1H, J = 1.6 Hz), 7.23 (dd, 1H, J = 8.2, 1.6 Hz), 6.81 2.19 (m, 2H), 197–1.92 (m, 2H); 13C NMR (DMSO-d6, 100 MHz):
New J. Chem.
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