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F.-P. Ma et al. / Applied Catalysis A: General 457 (2013) 34–41
1-(3-Chloro-4-methylphenyl)-1H-pyrrole (3s). IR (KBr): 1610,
1510, 1473, 1380, 1334, 1251, 1076, 1047, 1028, 937, 858,
819 cm−1 1H NMR (CDCl3, 500 MHz) ␦: 2.38 (s, 3H), 6.34 (t,
J = 2.0 Hz, 2H), 7.04 (t, J = 2.0 Hz, 2 H), 7.19 (dd, J = 8.5, 2.5 Hz, 1H),
7.26 (d, J = 8.5 Hz,1H), 7.40 (d, J = 2.5 Hz, 1H) ppm; 13C NMR (CDCl3,
125 MHz) ␦: 19.5, 110.8, 118.6, 119.3, 121.1, 131.7, 132.2, 135.1,
139.7 ppm; ESI-MS: m/z = 192 (M + 1)+; Anal. Calcd. for C11H10ClN:
C, 68.93; H, 5.26; N, 7.31. Found: C, 69.10; H, 5.08; N, 7.49.
125 MHz) ␦: 24.4, 108.2, 111.1, 111.6, 118.2, 119.6, 138.6, 150.8,
158.0 ppm; ESI-MS: m/z = 159 (M + 1)+; Anal. Calcd. for C10H10N2:
C, 75.92; H, 6.37; N, 17.71. Found: C, 76.10; H, 6.55; N, 17.53.
6-Methyl-2-(1H-pyrrol-1-yl)benzo[d]thiazole (3al). IR (KBr):
3012, 1606, 1544, 1521, 1509, 1471, 1338, 1276, 1110, 1072, 1049,
;
999, 869, 817, 729 cm−1 1H NMR (CDCl3, 500 MHz) ␦: 2.47 (s, 3H),
;
6.38 (s, 2H), 7.27 (d, J = 8.5 Hz, 1H), 7.44 (s, 2H), 7.58 (s, 1H), 7.75
(d, J = 8.5 Hz, 1H) ppm; 13C NMR (CDCl3, 125 MHz) ␦: 21.5, 112.5,
120.0, 121.2, 121.6, 128.1, 132.1, 134.6, 149.1, 158.7 ppm; ESI-MS:
m/z = 215 (M + 1)+; Anal. Calcd. for C12H10N2S: C, 67.26; H, 4.70; N,
13.07. Found: C, 67.08; H, 4.86; N, 12.90.
1-(3-Chloro-4-fluorophenyl)-1H-pyrrole (3t). IR (KBr): 3132,
1598, 1514, 1419, 1269, 1245, 1076, 1055, 1022, 939, 860, 815,
727 cm−1 1H NMR (CDCl3, 500 MHz) ␦: 6.35 (s, 2H), 7.01 (s,
;
2H), 7.20 (t, J = 9.0 Hz, 1H), 7.24–7.26 (m, 1H), 7.44 (dd, J = 6.0,
2.5 Hz, 1H) ppm; 13C NMR (CDCl3, 125 MHz) ␦: 111.0, 117.2 (d,
2JFC = 22.3 Hz), 120.1 (d, 3JFC = 7.0 Hz), 121.8 (d, 2JFC = 18.6 Hz), 122.8,
N-(1H-pyrrol-1-yl)benzamide (3am). IR (KBr): 3246, 1661,
1527, 1489, 1448, 1278, 1066, 970, 914, 711 cm−1 1H NMR (CDCl3,
;
500 MHz) ␦: 6.23 (J = 2.0 Hz, 2H), 6.76 (t, J = 2.0 Hz, 2H), 7.50 (t,
J = 7.5 Hz, 2H), 7.60 (t, J = 7.5 Hz, 1H), 7.86 (d, J = 7.5 Hz, 2H), 8.55
(br s, 1H) ppm; 13C NMR (CDCl3, 125 MHz) ␦: 108.0, 121.8, 127.4,
128.9, 131.6, 132.7, 163.3 ppm; ESI-MS: m/z = 187 (M + 1)+; Anal.
Calcd. for C11H10N2O: C, 70.95; H, 5.41; N, 15.04. Found: C, 71.12;
H, 5.58; N, 15.20.
1
137.6, 156.1(d, JFC = 246.3 Hz) ppm; ESI-MS: m/z = 196 (M + 1)+;
Anal. Calcd. for C10H7ClFN: C, 61.40; H, 3.61; N, 7.16. Found: C,
61.21; H, 3.80; N, 6.98.
1-(2,4,5-Trichlorophenyl)-1H-pyrrole (3u). 1H NMR (CDCl3,
500 MHz) ␦: 6.36 (t, J = 2.0 Hz, 2H), 6.89 (t, J = 2.0 Hz, 2H), 7.46 (s, 1H),
7.63 (s, 1H) ppm; 13C NMR (CDCl3, 125 MHz) ␦: 110.2, 121.9, 128.2,
128.8, 131.6, 131.7, 138.0 ppm; ESI-MS: m/z = 246 (M + 1)+; Anal.
Calcd. for C10H6Cl3N: C, 48.72; H, 2.45; N, 5.68. Found: C, 48.90; H,
2.62; N, 5.50.
4-(1H-Pyrrol-1-yl)benzamide (3an). IR (KBr): 3142, 1645, 1613,
1577, 1525, 1475, 1425, 1394, 1327, 1199, 1120, 1064, 1014, 920,
846, 723 cm−1 1H NMR (CDCl3, 500 MHz) ␦: 6.39 (t, J = 2.0 Hz, 2H),
;
7.16 (t, J = 2.0 Hz, 2H), 7.47(d, J = 8.5 Hz, 2H), 7.89 (d, J = 8.5 Hz, 2H)
ppm; 13C NMR (CDCl3, 125 MHz) ␦: 111.4, 119.1, 119.7, 130.0,
129.1,143.4, 168.2 ppm; ESI-MS: m/z = 187 (M + 1)+; Anal. Calcd. for
1-(4-Bromonaphthalen-1-yl)-1H-pyrrole (3ag). IR (KBr): 1591,
1521, 1473, 1357, 1267, 1155, 1078, 1028, 833, 724 cm−1 1H NMR
;
(CDCl3, 500 MHz) ␦: 6.41 (t, J = 2.0 Hz, 2H), 6.96 (t, J = 2.0 Hz, 2H),
7.31 (d, J = 7.5 Hz, 1H), 7.53 (t, J = 8.0 Hz, 1H), 7.63 (t, J = 7.5 Hz, 1H),
7.72 (d, J = 8.5 Hz,1H), 7.80 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 8.5 Hz, 1H)
ppm; 13C NMR (CDCl3, 125 MHz) ␦: 109.5, 122.3, 123.3, 123.8, 123.9,
124.6, 127.6, 127.8, 128.1, 129.4, 131.1, 132.6, 133.2 ppm; ESI-MS:
m/z = 273 (M + 1)+; Anal. Calcd. for C14H10BrN: C, 61.79; H, 3.70; N,
5.15. Found: C, 61.60; H, 3.89; N, 4.98.
C
11H10N2O: C, 70.95; H, 5.41; N, 15.04. Found: C, 71.12; H, 5.60; N,
14.86.
1,5-Di(1H-pyrrol-1-yl)naphthalene (3ap). 1H NMR (CDCl3,
500 MHz) ␦: 6.43 (t, J = 2.0 Hz, 4H), 7.01 (t, J = 2.0 Hz, 4H), 7.50–7.51
(m, 4H), 7.75 (dd, J = 8.5, 2.5 Hz, 2H) ppm; 13C NMR (CDCl3,
125 MHz) ␦: 109.4, 123.3, 123.4, 124.1, 126.3, 131.0, 138.5 ppm;
ESI-MS: m/z = 259 (M + 1)+; Anal. Calcd. for C18H14N2: C, 83.69; H,
5.46; N, 10.84. Found: C, 83.50; H, 5.65; N, 10.66.
1-(9H-fluoren-2-yl)-1H-pyrrole (3ah). IR (KBr): 1618, 1500,
1473, 1400, 1334, 1305, 1230, 1112, 1064, 1001, 943, 823, 734,
723 cm−1 1H NMR (CDCl3, 500 MHz) ␦: 3.96 (s, 2H), 6.37 (s, 2
;
3. Results and discussion
H), 7.14 (s, 2H), 7.31 (t, J = 7.5 Hz, 1H), 7.38–7.43 (m, 2H), 7.56 (d,
J = 8.0 Hz, 1H), 7.57 (s, 1H), 7.77–7.81 (m, 2H) ppm; 13C NMR (CDCl3,
125 MHz) ␦: 37.1, 110.3, 117.5, 119.6, 119.8, 120.6, 125.1, 126.7,
127.0, 139.5, 139.7, 1141.0, 143.2, 144.8 ppm; ESI-MS: m/z = 232
(M + 1)+; Anal. Calcd. for C17H13N: C, 88.28; H, 5.67; N, 6.06. Found:
C, 88.10; H, 5.82; N, 5.89.
3.1. Preparation and characterization of magnetic
catalyst
Sb-containing immobilized ionic liquid on magnetic nanopar-
ticle catalyst was readily prepared in a three-step as shown
in Scheme 2. 1-Methyl-3-(trimethoxysilylpropyl)-imidazolium
chloride (I) was prepared by reaction of N-methylimidazole
and 3-chloropropyltrimethoxysilane, followed by treatment with
anhydrous SbCl3. Immobilization of complex II in ␥-Fe2O3@SiO2
2-Methyl-6-(1H-pyrrol-1-yl)pyridine (3aj). IR (KBr): 3103,
2923, 1583, 1554, 1485, 1460, 1373, 1342, 1238, 1193, 1168, 1068,
943, 835, 785 cm−1 1H NMR (CDCl3, 500 MHz) ␦: 2.55 (s, 3H),
;
6.35 (t, J = 2.0 Hz, 2H), 6.95 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H),
7.52 (t, J = 2.0 Hz, 2H), 7.61 (t, J = 8.0 Hz, 1H) ppm; 13C NMR (CDCl3,
Scheme 2. Preparation of ␥-Fe2O3@SiO2–Sb-IL.