6706
H. Lee, B.H. Kim / Tetrahedron 69 (2013) 6698e6708
GCeMS m/z (rel intensity) 221 (Mþ, 100), 204 (32), 180 (3), 165 (11),
127 (16), 102 (9), 77 (5), 51 (3).
1H, J¼3.4 Hz), 2.90e2.80 (m, 1H), 2.06 (s, 3H), 1.18 (d, 6H, J¼6.8 Hz);
13C NMR (100 MHz, CDCl3)
148.0, 136.9, 134.1, 133.6, 131.8, 128.1,
d
127.8, 127.7, 126.8, 125.5, 108.4, 107.2, 33.7, 23.9, 13.3; IR (KBr) 3036,
2961, 2926, 1512, 1456, 1396 cmꢂ1; GCeMS m/z (rel intensity) 275
(Mþ, 100), 260 (15), 232 (10), 191 (10), 115 (9); Anal. Calcd for
C20H21N: C, 87.23; H, 7.69; N, 5.09. Found: C, 87.25; H, 7.83; N, 4.87.
4.2.22. 1-Phenyl-1,4-pentanedione (24).14f Yield 75%. White liquid.
TLC (20% ethyl acetate/hexane) Rf 0.40; 1H NMR (400 MHz, CDCl3)
d
7.98 (d, 2H, J¼7.1 Hz), 7.58e7.54 (m,1H), 7.46 (t, 2H, J¼7.6 Hz), 3.28
(t, 2H, J¼6.3 Hz), 2.89 (t, 2H, J¼6.3 Hz), 2.26 (s, 3H); 13C NMR
(100 MHz, CDCl3)
d
207.3, 198.5, 136.6, 133.1, 128.5, 127.9, 36.9, 32.4,
4.2.29. 2-Methyl-5-phenyl-1-(2-propylphenyl)-1H-pyrrole
30.0; IR (KBr) 3422, 3061, 2914, 1702, 1686, 1597, 1448, 1358,
1211 cmꢂ1; GCeMS m/z (rel intensity) 176 (Mþ, 5), 161 (21), 133
(12), 105 (100), 77 (43), 51 (12).
(31). Yield 97%. Orange liquid. TLC (20% ethyl acetate/hexane) Rf
0.81; 1H NMR (400 MHz, CDCl3)
d 7.26e7.20 (m, 4H), 7.04e6.99 (m,
5H), 6.35 (d, 1H, J¼3.5 Hz), 6.05 (d, 1H, J¼3.5 Hz), 2.11e2.04 (m, 1H),
1.96e1.91 (m, 4H),1.33e1.12 (m, 2H), 0.68 (t, 3H, J¼7.3 Hz); 13C NMR
4.2.23. 2-Methyl-1,5-diphenyl-1H-pyrrole (25).14g Yield 86%. Pale
yellow solid, mp 71e72 ꢀC. TLC (20% ethyl acetate/hexane) Rf 0.51;
(100 MHz, CDCl3) d 140.9, 138.1, 134.1, 133.6, 131.6, 129.7, 129.6,
128.3, 127.9, 126.9, 126.3, 125.5, 107.9, 107.1, 32.4, 22.1, 14.0, 12.9; IR
(KBr) 3070, 3033, 2960, 2933, 1602, 1514, 1491, 1394 cmꢂ1; GCeMS
m/z (rel intensity) 275 (Mþ, 100), 260 (81), 230 (27), 198 (12), 129
(11), 115 (16), 91 (9), 77 (9), 51 (6); Anal. Calcd for C20H21N: C, 87.23;
H, 7.69; N, 5.09. Found: C, 86.74; H, 8.09; N, 4.89.
1H NMR (400 MHz, CDCl3)
d
7.34e7.30 (m, 3H), 7.16e7.10 (m, 5H),
7.06e7.05 (m, 2H), 6.35 (d, 1H, J¼3.4 Hz), 6.09 (d, 1H, J¼3.4 Hz), 2.13
(s, 3H); 13C NMR (100 MHz, CDCl3)
139.4, 134.1, 133.5, 131.7, 128.9,
d
128.4, 127.9, 127.7, 127.3, 125.6, 108.6, 107.5, 13.3; IR (KBr) 3107,
3064, 2924, 1596, 1495, 1398 cmꢂ1; GCeMS m/z (rel intensity) 233
(Mþ, 100), 217 (9), 191 (9), 115 (14), 77 (14), 51 (8).
4.2.30. 1-(4-Methoxyphenyl)-2-methyl-5-phenyl-1H-pyrrole
(32).14n Yield 92%. White solid, mp 89e90 ꢀC. TLC (20% ethyl ace-
4.2.24. 1-(2-Ethylphenyl)-2-methyl-5-phenyl-1H-pyrrole (26). Yield
86%. Yellow liquid. TLC (20% ethyl acetate/hexane) Rf 0.69; 1H NMR
tate/hexane) Rf 0.60; 1H NMR (400 MHz, CDCl3)
d 7.05e7.04 (m, 2H),
7.00e6.99 (m, 5H), 6.79 (d, 2H, J¼8.8 Hz), 6.26 (d, 1H, J¼3.4 Hz),
(400 MHz, CDCl3)
d 7.29e7.16 (m, 4H), 7.04e6.94 (m, 5H), 6.33 (d,
5.99 (d, 1H, J¼3.4 Hz), 3.73 (s, 3H), 2.04 (s, 3H); 13C NMR (100 MHz,
1H, J¼3.4 Hz), 6.03 (d, 1H, J¼3.4 Hz), 2.09e1.95 (m, 2H), 1.92 (s, 3H),
CDCl3) d 158.6, 134.2, 133.6, 132.2, 131.9, 129.4, 127.9, 127.7, 125.5,
0.83 (t, 3H, J¼7.6 Hz); 13C NMR (100 MHz, CDCl3)
d
142.3, 137.9,
114.1, 108.3, 107.1, 55.4, 13.2; IR (KBr) 3069, 3002, 2937, 2835, 1601,
1514, 1445, 1247 cmꢂ1; GCeMS m/z (rel intensity) 263 (Mþ, 100),
248 (20), 207 (23), 115 (9), 77 (4).
134.1, 133.6, 131.6, 129.4, 129.0, 128.5, 127.9, 126.9, 126.3, 125.5,
107.9, 107.1, 23.3, 13.4, 12.9; IR (KBr) 3101, 3067, 2970, 2934, 1515,
1494, 1394 cmꢂ1; GCeMS m/z (rel intensity) 261 (Mþ, 100), 246
(80), 230 (20), 184 (15), 115 (12), 77 (8); Anal. Calcd for C19H19N: C,
87.31; H, 7.33; N, 5.36. Found: C, 87.30; H, 7.51; N, 5.73.
4.2.31. 1-(3-Methoxyphenyl)-2-methyl-5-phenyl-1H-pyrrole
(33).14n Yield 98%. Yellow solid, mp 77e78 ꢀC. TLC (20% ethyl ace-
tate/hexane) Rf 0.64; 1H NMR (400 MHz, CDCl3)
d 7.17 (t, 1H,
4.2.25. 2-Methyl-5-phenyl-1-o-tolyl-1H-pyrrole (27).14m Yield 94%.
Yellow solid, mp 60e61 ꢀC. TLC (20% ethyl acetate/hexane) Rf 0.67;
J¼8.0 Hz), 7.08e6.97 (m, 5H), 6.80e6.77 (m, 1H), 6.68 (dt, 1H, J¼8.0,
1.5 Hz), 6.61 (t, 1H, J¼1.5 Hz), 6.27 (d, 1H, J¼3.4 Hz), 6.01 (d, 1H,
J¼3.4 Hz), 3.62 (s, 3H), 2.08 (s, 3H); 13C NMR (100 MHz, CDCl3)
1H NMR (400 MHz, CDCl3)
d
7.27e7.24 (m, 3H), 7.20e7.18 (m, 1H),
7.10e7.04 (m, 5H), 6.39 (d, 1H, J¼3.4 Hz), 6.10 (d, 1H, J¼3.4 Hz), 1.99
(s, 3H), 1.84 (s, 3H); 13C NMR (100 MHz, CDCl3)
138.6, 136.9, 133.9,
d
159.8, 140.4, 134.1, 133.5, 131.6, 129.5, 127.9, 127.6, 125.6, 120.8,
d
114.1, 113.2, 108.6, 107.4, 55.3, 13.3; IR (KBr) 3066, 2921, 2835, 1601,
1514, 1489, 1223 cmꢂ1; GCeMS m/z (rel intensity) 263 (Mþ, 100),
218 (8), 115 (9), 77 (6).
133.6, 131.2, 130.8, 129.3, 128.3, 127.9, 126.9, 126.5, 125.6, 107.9,
107.2, 17.3, 12.8; IR (KBr) 3070, 3029, 2920, 1601, 1514, 1497,
1394 cmꢂ1; GCeMS m/z (rel intensity) 247 (Mþ, 100), 232 (48), 170
(13), 115 (16), 91 (10), 65 (8).
4.2.32. 1-(2-Methoxyphenyl)-2-methyl-5-phenyl-1H-pyrrole
(34).14n Yield 94%. Yellow solid, mp 68e69 ꢀC. TLC (20% ethyl ace-
4.2.26. 2-Methyl-5-phenyl-1-m-tolyl-1H-pyrrole (28). Yield 94%.
Yellow solid, mp 72e73 ꢀC. TLC (20% ethyl acetate/hexane) Rf 0.72;
tate/hexane) Rf 0.64; 1H NMR (400 MHz, CDCl3)
d 7.26e7.22 (m,1H),
7.03e7.00 (m, 6H), 6.86e6.83 (m, 2H), 6.28 (d, 1H, J¼3.4 Hz), 6.02
1H NMR (400 MHz, CDCl3)
d 7.23e7.21 (m, 1H), 7.13e7.11 (m, 3H),
(d, 1H, J¼3.4 Hz), 3.59 (s, 3H), 1.98 (s, 3H); 13C NMR (100 MHz,
7.07e7.06 (m, 3H), 6.97e6.94 (m, 2H), 6.34 (d,1H, J¼3.4 Hz), 6.08 (d,
CDCl3) d 155.7, 134.5, 133.8, 132.0, 130.3, 129.2, 128.1, 127.8, 125.6,
1H, J¼3.4 Hz), 2.31 (s, 3H), 2.12 (s, 3H); 13C NMR (100 MHz, CDCl3)
120.6, 111.9, 107.94, 107.93, 106.9, 55.5, 12.6; IR (KBr) 3069, 2922,
1601, 1506, 1460, 1024 cmꢂ1; GCeMS m/z (rel intensity) 263 (Mþ,
100), 248 (27), 232 (13), 217 (11), 115 (13), 77 (8), 51 (5).
d
139.3, 138.8, 134.1, 133.5, 131.7, 128.9, 128.6, 128.1, 127.9, 127.6,
125.51, 125.52, 108.5, 107.3, 21.3, 13.3; IR (KBr) 3095, 3036, 2920,
1603, 1516, 1491, 1395 cmꢂ1; GCeMS m/z (rel intensity) 247 (Mþ,
100), 230 (9), 191 (8), 115 (11), 91 (7), 65 (5); Anal. Calcd for
C18H17N: C, 87.41; H, 6.93; N, 5.66. Found: C, 86.90; H, 7.02; N, 5.19.
4.2.33. 1-(4-Fluorophenyl)-2-methyl-5-phenyl-1H-pyrrole
(35).14o Yield 80%. Yellow solid, mp 99e100 ꢀC. TLC (20% ethyl ac-
etate/hexane) Rf 0.63; 1H NMR (400 MHz, CDCl3)
d
7.07e7.02 (m,
4H), 6.98e6.96 (m, 5H), 6.26 (d,1H, J¼3.4 Hz), 6.01 (d,1H, J¼3.4 Hz),
2.05 (s, 3H); 13C NMR (100 MHz, CDCl3)
4.2.27. 2-Methyl-5-phenyl-1-p-tolyl-1H-pyrrole (29).14m Yield 93%.
Pale yellow solid, mp 73e74 ꢀC. TLC (20% ethyl acetate/hexane) Rf
d
161.6 (d, J¼247.5 Hz),
0.73; 1H NMR (400 MHz, CDCl3)
d
7.14e7.12 (m, 4H), 7.06e7.04 (m,
5H), 6.34 (d, 1H, J¼3.4 Hz), 6.07 (d, 1H, J¼3.4 Hz), 2.36 (s, 3H), 2.12
(s, 3H); 13C NMR (100 MHz, CDCl3)
137.1, 136.7, 134.1, 133.6, 131.7,
135.4 (d, J¼2.9 Hz), 134.3, 133.3, 131.7, 129.9 (d, J¼8.7 Hz), 127.9 (d,
J¼21.1 Hz), 125.8, 116.0, 115.8, 108.7, 107.6, 13.2; IR (KBr) 3109, 3070,
2921, 1509, 1396, 1219 cmꢂ1; GCeMS m/z (rel intensity) 251 (Mþ,
100), 235 (8), 209 (10), 115 (12), 95 (10), 75 (7).
d
129.5, 128.1, 127.9, 127.7, 125.5, 108.4, 107.3, 21.1, 13.3; IR (KBr) 3034,
2922, 1601, 1516, 1445, 1398 cmꢂ1; GCeMS m/z (rel intensity) 247
(Mþ, 100), 191 (13), 129 (9), 115 (12), 91 (9), 65 (10).
4.2.34. 1-(4-Chlorophenyl)-2-methyl-5-phenyl-1H-pyrrole
(36).14p Yield 83%. Yellow solid, mp 102e103 ꢀC (lit.14p mp
105e106 ꢀC). TLC (20% ethyl acetate/hexane) Rf 0.70; 1H NMR
4.2.28. 1-(4-Isopropylphenyl)-2-methyl-5-phenyl-1H-pyrrole
(30). Yield 85%. White solid, mp 78e79 ꢀC. TLC (20% ethyl acetate/
(400 MHz, CDCl3)
(m, 5H), 6.34 (d, 1H, J¼3.4 Hz), 6.09 (d, 1H, J¼3.4 Hz), 2.13 (s, 3H);
13C NMR (100 MHz, CDCl3)
137.9, 134.2, 133.2, 133.1, 131.5, 129.6,
d 7.34e7.31 (m, 2H), 7.18e7.14 (m, 2H), 7.12e7.03
hexane) Rf 0.68; 1H NMR (400 MHz, CDCl3)
7.05e7.04 (m, 2H), 6.99e6.97 (m, 5H), 6.27 (d,1H, J¼3.4 Hz), 6.00 (d,
d
7.12 (d, 2H, J¼8.3 Hz),
d