Ghashang & Shaterian
FULL PAPER
Preparation of 1,5-diaryl-3-(arylamino)-1H-pyr-
rol-2(5H)-ones
130.3, 132.3, 132.8, 135.3, 136.9, 137.5, 139.5, 158.1,
160.3, 167.4; IR (KBr) ν: 3315, 2990, 1677, 1647, 1609,
1584, 1526, 1497, 1451, 1424, 1376, 1266, 1212, 1175,
1114, 1089, 1045, 873, 851, 809, 768 cm . Anal. calcd
for C28H30N2O3: C 75.99, H 6.83, N 6.33; found C 76.07,
H 6.92, N 6.42.
General procedure To a mixture of aldehyde (1
mmol), aromatic amine (2 mmol) and ethyl pyruvate
(1.5 mmol) was added SiO2-FeCl3 (0.01 g) as catalyst
and the mixture was stirred for appropriate time at am-
bient condition (until a pasty mixture was formed). In
the second step the reaction mixture was heated at 100
℃. The progress of the reaction was monitored by TLC.
After completion of the reaction, the mixture was dis-
solved in CH2Cl2 and filtered. Catalyst was recovered
and filtrate solution was evaporated and the corre-
sponding pure product was obtained by recrystallization
procedure in aqueous ethanol (80%).
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1-(3,4-Dimethylphenyl)-3-(3,4-dimethylphenyla-
mino)-5-(3,4,5-trimethoxyphenyl)-1H-pyrrol-2(5H)-
one (Table 2, Entry 8) 1H NMR (CDCl3, 400 MHz) δ:
2.22 (s, 3H), 2.24 (s, 3H), 2.25 (s, 3H), 2.27 (s, 3H),
3.81 (s, 6H), 3.82 (s, 3H), 5.57 (d, J=2.4 Hz, 1H), 6.02
(d, J=2.4 Hz, 1H), 6.43 (s, 2H), 6.58 (s, 1H), 6.86—
6.90 (m, 2H), 7.06—7.09 (dd, J=2.8, 8.0 Hz, 2H), 7.15
—7.18 (dd, J=2.0, 8.0 Hz, 1H), 7.36 (d, J=2.0 Hz,
1H); 13C NMR (CDCl3, 100 MHz) δ: 18.9, 19.2, 20.0,
56.2, 60.8, 64.8, 103.7, 107.0, 114.1, 118.3, 119.7,
123.6, 129.5, 130.0, 130.3, 132.3, 133.4, 133.8, 134.9,
137.2, 137.6, 137.7, 139.2, 153.6, 167.3; IR (KBr) ν:
3309, 3014, 2937, 1683, 1649, 1612, 1539, 1455, 1422,
1336, 1321, 1231, 1187, 1126, 1009, 830, 776, 744, 679
1-(3,4-Dimethylphenyl)-3-(3,4-dimethylphenyl-
amino)-5-phenyl-1H-pyrrol-2(5H)-one (Table 2, En-
try 5) 1H NMR (CDCl3, 400 MHz) δ: 2.20 (s, 3H),
2.23 (s, 3H), 2.24 (s, 3H), 2.27 (s, 3H), 5.65 (d, J=2.4
Hz, 1H), 6.03 (d, J=2.4 Hz, 1H), 6.57 (s, 1H), 6.85—
6.88 (dd, J=2.4, 8.0 Hz, 1H), 6.90 (s, 1H), 7.04 (d, J=
8.0 Hz, 1H), 7.07 (d, J=8.0 Hz, 1H), 7.15—7.18 (dd, J
=2.4, 8.2 Hz, 1H), 7.23—7.31 (m, 5H), 7.39 (d, J=1.6
Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ: 18.9, 19.2,
20.0 (2C), 64.4, 107.2, 114.2, 118.3, 119.4, 123.4, 126.9,
128.0, 128.9, 129.4, 129.9, 130.3, 132.5, 133.5, 134.9,
137.1, 137.6, 137.9, 139.2, 167.3; IR (KBr) ν: 3317,
33064, 2957, 2915, 1674, 1612, 1590, 1539, 1504, 1454,
1323, 1267, 1218, 1187, 1157, 1097, 1020, 867, 834,
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cm . Anal. calcd for C29H32N2O4: 73.70, H 6.83, N
5.93; found C 73.79, H 6.91, N 5.99.
1-(4-Methoxyphenyl)-3-(4-methoxyphenylamino)-
5-nonyl-1H-pyrrol-2(5H)-one (Table 2, Entry 9) 1H
NMR (CDCl3, 400 MHz) δ: 0.89 (t, J=7.2 Hz, 3H),
1.22—1.29 (m, 15H), 1.42—1.47 (m, 1H), 3.83 (s, 3H),
3.86 (s, 3H), 4.65—4.67 (m, 1H), 5.97 (d, J=2.0 Hz,
1H), 6.47 (s, 1H), 6.92 (d, J=8.8 Hz, 2H), 6.98 (d, J=
8.8 Hz, 2H), 7.08 (d, J=8.8 Hz, 2H), 7.29 (s, 1H), 7.39
(d, J=8.8 Hz, 2H); 13C NMR (CDCl3, 100 MHz) δ:
14.1, 21.5, 22.7, 23.9, 29.2, 29.4, 29.5, 31.8, 31.9, 55.5,
55.6, 60.2, 62.0, 104.4, 114.4, 114.7, 118.3, 118.7,
124.7, 128.2, 129.8, 133.9, 166.3; IR (KBr) ν: 3306,
3077, 2996, 2923, 1673, 1644, 1592, 1546, 1513, 1440,
1300, 1245, 1177, 1114, 1035, 921, 834, 815, 779, 727
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778, 715, 698 cm . Anal. calcd for C26H26N2O: C
81.64, H 6.85, N 7.32; found C 81.75, H 6.92, N 7.43.
5-(2,4-Dimethoxyphenyl)-1-(3,4-dimethylphenyl)-
3-(3,4-dimethylphenylamino)-1H-pyrrol-2(5H)-one
(Table 2, Entry 6) 1H NMR (CDCl3, 400 MHz) δ:
2.20 (s, 3H), 2.23 (s, 3H), 2.26 (s, 3H), 2.27 (s, 3H),
3.76 (s, 3H), 3.93 (s, 3H), 6.04 (d, J=2.8 Hz, 1H), 6.15
(d, J=2.4 Hz, 1H), 6.35—6.38 (dd, J=2.4, 8.4 Hz, 1H),
6.48 (d, J=2.4 Hz, 1H), 6.53 (s, 1H), 6.85—6.88 (m,
3H), 7.06 (t, J=8.4 Hz, 1H), 7.26—7.28 (dd, J=2.0,
8.0 Hz, 1H), 7.49 (d, J=2.0 Hz, 1H); 13C NMR (CDCl3,
100 MHz) δ: 18.9, 19.2, 20.0, 20.1, 55.3, 55.6, 56.8,
98.5, 105.1, 107.3, 113.9, 117.7, 118.2, 118.5, 122.4,
127.5, 129.1, 129.8, 130.3, 132.3, 132.8, 135.3, 136.9,
137.5, 139.5, 158.1, 160.3, 167.4; IR (KBr) ν: 3330,
2995, 1686, 1648, 1611, 1584, 1538, 1501, 1457, 1388,
1258, 1204, 1170, 1114, 1040, 863, 822, 786
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cm . Anal. calcd for C27H36N2O3: C 74.28, H 8.31, N
6.42; found C 74.35, H 8.40, N 6.49.
Results and discussion
To choose optimum conditions, first we tried to pre-
pare 3-(p-toluidino)-5-phenyl-1-p-tolyl-1H-pyrrol-
2(5H)-one from the reaction of benzaldehyde, 4-methyl
aniline, and ethyl pyruvate as a model in the presence of
SiO2-FeCl3 as catalyst under ambient conditions (Table
1, Scheme 2).
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cm . Anal. calcd for C28H30N2O3: C 75.99, H 6.83, N
To optimize the reaction conditions, the reaction was
carried out by the using of different solvents (Table 1,
Entries 1—6) or solvent-free conditions (Table 1, En-
tries 9—20), varying amount of the catalyst (Table 1,
Entries 17—20), different amount of ethyl pyruvate
(Table 1, Entries 1—20) and the using of an additive
such as Na2SO4 for the removal of water (Table 1, En-
tries 7, 8, 13—20). Unfortunately all efforts prepared
the desired product in low yield (less than 50%). The
yield could be improved slightly by increasing the tem-
perature to 100 ℃ (Table 1, Entry 12) and also when
the reaction was occurred under reflux conditions
6.33; found C 76.08, H, 6.91, N 6.40.
5-(2,5-Dimethoxyphenyl)-1-(3,4-dimethylphenyl)-
3-(3,4-dimethylphenylamino)-1H-pyrrol-2(5H)-one
(Table 2, Entry 7) 1H NMR (CDCl3, 400 MHz) δ:
2.20 (s, 3H), 2.23 (s, 3H), 2.26 (s, 3H), 2.29 (s, 3H),
3.63 (s, 3H), 3.92 (s, 3H), 6.05 (d, J=2.4 Hz, 1H), 6.20
(d, J=2.4 Hz, 1H), 6.50—6.52 (m, 2H), 6.71—6.74 (dd,
J=3.2, 8.8 Hz, 1H) 6.84—6.88 (m, 3H), 7.06 (t, J=7.6
Hz, 2H), 7.25—7.29 (dd, J=2.4, 8.0 Hz, 1H), 7.49 (d,
J=2.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ: 18.9,
19.2, 20.0, 20.1, 55.3, 55.6, 56.9, 98.6, 105.1, 107.3,
113.9, 117.7, 118.2, 118.5, 122.4, 127.5, 129.1, 129.8,
1852
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1851— 1855