1
(1.2 mmol) of hexane-2,4-dione in the presence of 26 mg (0.1
mmol) of iodine to afford 238 mg (88%) of pure 1-(1-anthryl)-
2,4-dimethyl pyrrole. Mp: 182-183 °C. H NMR (300 MHz): δ
1.93 (6H, s), 6.06 (2H, s), 7.38-7.55 (4 H, m), 7.71 (1H, s), 7.90
(1H, d, J ) 7.95 Hz), 8.01 (1H, d, J ) 7.98 Hz), 8.09 (1H, d, J )
8.55 Hz) 8.51 (1H, s). Anal. Calcd for C20H17N: C, 88.52; H, 6.31;
N, 5.16. Found: C, 88.61; H, 6.21; N, 5.01.
1,5-Dip h en yl-2-m eth ylp yr r ole (3k ). Yield: 91%. H NMR
(300 MHz, CDCl3): δ 2.13 (3H, s), 6.08 (1H, dd, J ) 0.9, 3.6
Hz), 6.34 (1H, d, J ) 3.3 Hz), 7.03-7.16 (H, m), 7.30-7.34 (3H,
m). 13C NMR (75 MHz, CDCl3): δ 13.7, 107.9, 109.1, 126.0,
127.82, 128.2, 128.3, 128.9, 129,20, 129.3, 132.1, 133.9, 134.6,
139.8. Anal. Calcd for C17H17N: C, 86.76; H, 7.28; N, 5.95.
Found: C, 86.57; H, 7.00; N, 6.12.
1
1-(9-P h en a n th r en yl)-2,5-d im eth ylp yr r ole (3e). A 193 mg
(1 mmol) portion of 1-aminophenanthrene was reacted with
138.8 mg (1.2 mmol) of hexane-2,4-dione in the presence of 26
mg (0.1 mmol) of iodine to afford 247 mg (91%) of pure 1-(9-
phenanthrenyl)-2,4-dimethyl pyrrole. Mp: 154-156 °C. 1H NMR
(300 MHz): δ 1.94 (6H, s), 6.03 (2H, s), 7.11 (1H, d, J ) 8.06
Hz), 7.53-7.75 (5H, m), 7.92 (1H, d, J ) 7.50 Hz), 8.73 (2H, d,
J ) 8.30 Hz). Anal. Calcd for C20H17N: C, 88.52; H, 6.31; N,
5.16. Found: C, 88.43; H, 6.12; N, 4.99.
1-Ben zyl-2-m eth yl-5-p h en ylp yr r ole (3l). Yield: 89%. 1H
NMR (300 MHz, CDCl3): δ 2.12 (3H, s), 5.11 (2H, s), 6.03 (1H,
dd, J ) 0.9. 3.3 Hz), 6.22 (1H, d, J ) 3.6 Hz), 6.92 (2H, m), 7.20-
7.30 (8H, m). 13C NMR (75 MHz, CDCl3) δ 13.0, 48.1, 107.7,
108.4, 126.1, 127.1, 127.4, 127.7, 128.8, 129.11, 129.2, 130.8,
134.2, 135.1, 139.4. Anal. Calcd for C18H17N: C, 87.40; H, 6.92;
N, 5.66. Found: C, 87.30; H, 6.75; N, 5.48.
1-(1-Bu tyl)-2-m eth yl-5-p h en ylp yr r ole (3m ). Yield: 93%.
1H NMR (300 MHz, CDCl3): δ 0.79 (3H, t, J ) 6 Hz), 1.18 (2H,
m), 1.52 (2H, m), 2.30 (3 H, s), 3.82 (2H, m), 5.93 (1H, d, J ) 3.3
Hz), 6.08 (1H, d, J ) 3.3 Hz), 7.23-7.30 (1H, m), 7.36 (4H, m).
Anal. Calcd for C15H19N: C, 84.45; H, 8.97; N, 6.56. Found: C,
84.40; H, 8.81; N, 6.42.
1-(1-P yr en yl)-2,5-d im eth ylp yr r ole (3f). A 217 mg (1 mmol)
portion of 1-aminopyrene was reacted with 138.8 mg (1.2 mmol)
of hexane-2,4-dione in the presence of 26 mg (0.1 mmol) of iodine
to afford 257 mg (87%) of pure 1-(1-pyrenyl)-2,4-dimethylpyrrole.
Mp: 145 °C. IR (CH2Cl2): 3043, 1602, 1489, 1510, 1458, 1409
cm-1 1H NMR (300 MHz): δ 1.92 (6H, s), 6.08 (2 H, s), 7.39
.
(1H, d, J ) 9.10 Hz), 7.90 (1H, d, J ) 8.01 Hz), 8.04-8.27 (7H,
m). Anal. Calcd for C22H17N: C, 89.45; H, 5.80; N, 4.74. Found:
C, 89.17; H, 5.70; N, 4.69.
1-Cyclopen tyl-2-m eth yl-5-ph en ylpyr r ole (3n ). Yield: 76%.
1H NMR (300 MHz, CDCl3): δ 1.58 (2H, m), 1.82 (2H, m), 1.99
(4 H, m), 2.42 (3H, s), 4.65(1 H, m), 5.96 (1H, d, J ) 3.3 Hz),
6.01 (1H, d, J ) 3.3 Hz), 7.35 (5H, m). Anal. Calcd for C16H19N:
C, 85.28; H, 8.49; N, 6.21. Found: C, 85.24; H, 8.66; N, 6.11.
1, 2, 3, 5-Tetr a p h en ylp yr r ole (3o). Yield: 15%. 1H NMR
(300 MHz, CDCl3): δ 6.0 (1H, s), 6.96-7.05 (4H, m), 7.10-7.21
(13H, m), 7.22-7.25 (3H, m).
1-(6-Ch r ysen yl)-2,5-d im eth ylp yr r ole (3g). A 243 mg (1
mmol) portion of 6-aminochrysene was reacted with 138.8 mg
(1.2 mmol) of hexane-2,4-dione in the presence of 26 mg (0.1
mmol) of iodine to afford 257 mg (80%) of pure 1-(6-chrysenyl)-
2,4-dimethylpyrrole. Mp: 225-226 °C. 1H NMR (300 MHz): δ
1.97 (6H, s), 5.99 (2H, s), 7.25 (1 H, m), 7.58-7.74 (4H, m), 8.03
(1H, m), 8.08 (1 H, d, J ) 9.09 Hz), 8.69 (2H, m), 8.76 (1H, d, J
) 9.10 Hz), 8.84 (1H, d, J ) 8.20 Hz). Anal. Calcd for C24H19N:
C. 89.68; H, 5.95; N, 4.35. Found: C, 89.49; H, 6.12; N, 4.10.
1-(4-Meth oxyp h en yl)-2,5-d im eth ylp yr r ole (3b). A 123 mg
(1 mmol) portion of p-anisidine was reacted with 138.8 mg (1.2
mmol) of hexane-2,4-dione in the presence of 26 mg (0.1 mmol)
of iodine to afford 169 mg (84%) of pure 1-(4-methoxyphenyl)-
2,4-dimethylpyrrole. 1H NMR (300 MHz): δ 2.02 (6H, s), 3.85
(3H, s), 5.88 (2 H, s), 6.97 (2H, d, J ) 8.89 Hz), 7.13 (2H, d, H
) 8.90 Hz). Anal. Calcd for C13H15NO: C, 77.58; H, 7.51; N, 6.95.
Found: C, 77.46; H, 7.43; N, 6.83.
1-(2-Am in op yr id yl)-2,5-d im eth ylp yr r ole (3j). A 94 mg (1
mmol) portion of 2-aminopyridine was reacted with 138.8 mg
(1.2 mmol) of hexane-2,4-dione in the presence of 26 mg (0.1
mmol) of iodine to afford 175 mg of crude product. It was purified
by column chromatography using 10% ethyl acetate and 90%
hexane to afford 134 mg (78%) of pure 1-(2-aminopyridyl)-2,4-
dimethyl pyrrole. 1H NMR (300 MHz): δ 2.12 (6H, s), 5.90 (2 H,
s), 7.29 (2H, d, m), 7.82 (1H, m), 8.60 (1H, m). Anal. Calcd for
Bis-p yr r ole (3h ). A 60 mg (1 mmol) portion of ethylenedi-
amine was reacted with 278 mg (2.4 mmol) of hexane-2,4-dione
in the presence of 26 mg (0.1 mmol) of iodine to afford 192 mg
(89%) of pure 1-(4-methoxyphenyl)-2,4-dimethylpyrrole as an oil.
1H NMR (300 MHz): δ 2.00 (12H, s), 3.92 (4H, s), 5.80 (4H, s).
Anal. Calcd for C14H20N2: C, 77.72; H, 9.31; N, 12.95. Found:
C, 77.48; H, 9.11; N, 12.79.
Ack n ow led gm en t. We gratefully acknowledge the
funding support from the University of Texas, M. D.
Anderson Cancer Center. We are thankful to NIH
Cancer Center Support Grant, 5-P30-CA16672-25, in
particular the shared resources of the Pharmacology and
Analytical Center Facility. We are grateful to Dr.
Swapan Dasgupta for taking some melting points of the
compounds described here.
C
11H12N2: C, 76.71; H, 7.02; N, 6.95. Found: C, 76.80; H, 6.95;
N, 6.83.
J O035200I
216 J . Org. Chem., Vol. 69, No. 1, 2004