482 JOURNAL OF CHEMICAL RESEARCH 2013
NMR (CDCl3, 75 MHz) δ 37.31, 108.08, 122.85, 128.00, 128.00,
129.14, 129.14, 131.34, 131.34, 131.46, 139.93, 186.18; MS m/z:
208.1([M+Na]+, 100%).
128.54, 128.54, 128.61, 129.38, 130.28, 130.46, 130.46, 137.17,
137.17, 138.30, 141.89, 185.92; HRMS calcd for C19H18NO [M+H]+:
276.1388, found: 276.1390.
(4-Chlorophenyl)(1-methyl-1H-pyrrol-2-yl)methanone (4c): White
(1-Benzyl-1H-pyrrol-2-yl)(3-chlorophenyl)methanone (5e): Pale
yellow oil. IR (KBr) ν: 3064, 3031, 2926, 1627, 1566, 1524, 1464,
1410, 1333, 1253, 1143, 1084, 737 cm−1; 1H NMR (CDCl3, 500 MHz)
δ 5.63 (s, 2H), 6.21(dd, J = 2.6, 4 Hz, 1H), 6.75(dd, J = 1.6, 4 Hz, 1H),
7.01 (m, 1H), 7.16 (d, J = 7.4 Hz, 2H), 7.22 (m, 1H), 7.27–7.36
(m, 3H), 7.43–7.46 (m, 1H), 7.62 (d, J = 7.7 Hz, 1H), 7.73 (s, 1H);
13C NMR (CDCl3, 75 MHz) δ 52.40, 108.87, 123.69, 127.11, 127.18,
127.49, 127.60, 128.58, 129.08, 129.25, 129.53, 131.21, 131.34,
132.90, 134.10, 137.97, 141.50, 184.22; HRMS calcd for C18H15NOCl
[M+H]+: 296.0843, found: 296.0842.
1
solid; m.p. 70–71 °C, (lit.23 69–71 °C). H NMR (CDCl3, 300 MHz)
δ 4.03 (s, 3H), 6.15–6.17 (m, 1H), 6.70–6.71 (m, 1H), 6.93 (s, 1H),
7.41–7.44 (d, J = 8.28 Hz, 2H), 7.73–7.76 (d, J = 8.31 Hz, 2H); 13C
NMR (CDCl3, 75 MHz) δ 37.32, 108.29, 122.77, 128.33, 128.33,
130.22, 130.22, 130.55, 131.75, 137.63, 138.25, 188.30; MS m/z:
220.0([M+H]+, 100%).
(4-(Chloromethyl)phenyl)(1-methyl-1H-pyrrol-2-yl)methanone
(4d): Colourless oil. IR (KBr) ν: 3108, 2951, 2867, 1717, 1626, 1571,
1525, 1461, 1412, 1402, 1378, 1329, 1256, 1152, 1092, 1061, 918,
877, 850, 806, 743, 723, 679, 606 cm−1; 1H NMR (CDCl3, 300 MHz)
δ 4.03 (s, 3H), 4.63 (s, 2H), 6.15–6.17 (m, 1H), 6.72–6.73 (m, 1H),
6.92 (s, 1H), 7.45–7.48 (m, 2H), 7.78–7.80 (m, 2H); 13C NMR (CDCl3,
75 MHz) δ 37.32, 45.54, 108.19, 122.88, 128.16, 128.47, 129.54,
129.95, 130.35, 131.64, 139.85, 140.55, 185.37; HRMS calcd for
C13H13NOCl [M+H]+: 234.0686, found: 234.0688.
1-(1-Methyl-1H-pyrrol-2-yl)-2-phenylethanone (4e): Colourless oil,
(lit.24 colourless oil). 1H NMR (CDCl3, 300 MHz) δ 3.88 (s, 3H), 4.04–
4.10 (m, 2H), 6.11–6.13 (m, 1H), 6.78 (s, 1H), 7.06–7.07 (m, 1H),
7.21–7.22 (m, 1H); 7.24–7.30 (m, 4H);13C NMR (CDCl3, 75 MHz)
δ 37.55, 45.84, 107.96, 119.78, 126.54, 126.98, 128.13, 128.37,
129.09, 129.30, 131.35, 135.47, 188.17; MS m/z: 222.1([M+Na]+,
100%).
2-Chloro-1-(1-methyl-1H-pyrrol-2-yl)ethanone (4f): White solid;
m.p. 46–47 °C, (lit.27 m.p. 47 °C). 1H NMR (CDCl3, 300 MHz) δ 3.96
(s, 3H), 4.49 (s, 2H), 6.16–6.18 (m, 1H), 6.89 (s, 1H), 6.98–7.00 (m,
1H);13C NMR (CDCl3, 75 MHz) δ 37.64, 45.67, 108.67, 119.88,
128.12, 132.27, 178.17; MS m/z: 180.1([M+H]+, 8%).
1-(1-Benzyl-1H-pyrrol-2-yl)-2-chloroethanone (5f): Pale yellow
1
solid; m.p. 90–92 °C, (lit.26 89–91 °C). H NMR (CDCl3, 300 MHz)
δ 4.79 (s, 2H), 5.56 (s, 2H), 6.25–6.27 (m, 1H), 7.07–7.09 (d, J = 6.93
Hz, 2H), 7.20–7.31 (m, 4H), 7..42–7.43 (m, 1H); 13C NMR (CDCl3,
75 MHz) δ 46.32, 51.39, 108.97, 121.24, 126.61, 126.89, 127.12,
127.12, 128.33, 128.33, 132.66, 138.54, 181.10; MS m/z: 234.1
([M+H]+, 100%).
We are grateful to the National Basic Research Program of
China (No. 2011CB933503) for financial support.
Received 1 May 2013; accepted 27 May 2013
Published online: 9 August 2013
References
1
J.A. Joule, K. Mills and D.F. Smith, Heterocyclic chemistry, 3rd edn.,
Stanley Thornes: Cheltenham, 1998.
Methyl 2-(1-benzyl-1H-pyrrole-2-carbonyl) benzoate (5a): White
oil. IR (KBr) ν: 2950, 2921, 1721, 1630, 1457, 1397, 1323, 1331,
2
3
4
G.H. Posner, Angew. Chem. Int. Ed. Engl., 1978, 17, 487.
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1
1263, 1122, 1078, 1030, 913, 871, 714 cm−1; H NMR (DMSO-d6,
300 MHz) δ 3.38 (s, 3H), 5.70 (s, 2H), 6.18 (dd, J = 2.52 Hz, 4.05 Hz,
1H), 6.33(dd, J = 1.71 Hz, 4.05 Hz, 1H), 7.23–7.46 (m, 7H), 7.60–
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δ 51.26, 51.98, 108.96, 122.58, 127.18, 128.13, 129.39, 129.43,
129.43, 129.61, 129.70, 129.70, 131.82, 131.82, 132.01, 132.01,
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5
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(1-Benzyl-1H-pyrrol-2-yl)(phenyl)methanone (5b): Colourless oil,
(lit.11 colourless oil). 1H NMR (CDCl3, 500 MHz) δ 5.63 (s, 2H), 6.16–
6.17 (m, 1H), 6.73–6.75 (m, 1H), 6.95–6.96 (m, 1H), 7.14–7.20
(m, 2H), 7.24–7.27 (m, 1H), 7.35–7.38 (m, 2H), 7.42–7.44 (m, 2H),
7.45–7.46 (m, 1H), 7.73–7.74 (m, 2H); 13C NMR (CDCl3, 75 MHz)
δ 52.22, 108.52, 123.32, 127.06, 127.33, 127.33, 127.83, 127.83,
128.47, 128.47, 129.06, 129.06, 130.01, 130.31, 131.22, 138.16,
139.82, 185.95; MS m/z: 180.1([M+H]+, 8%).
(1-Benzyl-1H-pyrrol-2-yl)(4-methoxyphenyl)methanone (5c): White
solid; m.p. 66–68C. IR (KBr) ν: 3106, 2969, 2930, 2840, 1624, 1601,
1506, 1457, 1406, 1390, 1340, 1303, 1256, 1172, 1142, 1088, 1022,
918, 877, 845, 742, 732, 647, 614 cm−1; 1H NMR (CDCl3, 500 MHz)
δ 3.77 (s, 3H), 5.60 (s, 2H), 6.16–6.17 (m, 1H), 6.73–6.74 (m, 1H),
6.86–6.87 (m, 2H), 6.88–6.94 (m, 1H), 7.13–7.15 (m, 2H), 7.17–7.20
(m, 1H), 7.25–7.26 (m, 2H), 7.77 (s, 2H); 13C NMR (CDCl3, 75 MHz)
δ 52.02, 55.18, 108.29, 113.14, 113.14, 122.28, 127.01, 127.01,
127.26, 127.26, 128.42, 130.09, 130.09, 130.18, 131.33, 132.32,
139.30, 162.33, 184.91; HRMS calcd for C19H18NO2 [M+H]+:
292.1338, found: 292.1342.
8
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(1-Benzyl-1H-pyrrol-2-yl)(p-tolyl)methanone (5d): Pale yellow oil.
IR (KBr) ν: 3030, 2922, 1624, 1523, 1495, 1460, 1410, 1333, 1259,
1178, 1083, 915, 876, 744 cm−1; 1H NMR (CDCl3, 500 MHz) δ 2.38
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J = 1.65, 4 Hz, 1H), 6.96–6.97 (m, 2H), 7.16 (d, J = 7.15 Hz, 3H), 7.21
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