1220
S. L E l-D esoky et al. ■Synthesis of Pyrrolo-, Thienopyrrolo-, Benzothienopyrroloquinollines
Rf = 0.38. ’H NMR (250 MHz, CDC13): (3 9.40 (s,
br, 1 H, NH), 9.10 (m, 2 H, 11, 12-H), 8.0 (s, 1 H,
9-H), 7.60-7.20 (m, 13 H, 4,5,7-H, 2Ph), 4.0 (s, 3
H, OCH3).
H, 2Ph), 4.10 (s, 3 H, COOMe), MS: M+ at m/e =
412, two fragment ions at m/e = 354 and 318.
C2,H 17N20 2C1 (412.9)
Calcd
C 72.72 H 4.15 N 6.79%,
Found C 72.76 H 4.20 N6.75%.
a-Amino-N-(2 ',3'-diphenylindole-6 ’-yl)-
dimethylfumarate (7)
Condensation of 9 with different amines
“General procedure ”
A solution of 1 (5.7 g, 0.02 mole) and dimethyla-
cetylenedicarboxylate (3.55 g, 0.025 mol) in 50 ml
methanol was refluxed for 1 h. The precipitate was
formed after cooling, filtered off and crystallized
from methanol to give golden needles, yield 90%,
m.p. 150-152 C. TLC [petroleum ether/ethyl ace-
tate (17:3)]: Rf = 0.62. 'H NMR (250 MHz,
The corresponding amine (3 mmol) was added
to a solution of 9 (0.4 g, 1 mmol) in 10 ml dry tolu-
ene and the reaction mixture was stirred at 100 °C.
When TLC showed complete conversion of the
starting material, the liquids were evaporated in
vacuo and the residue was washed with water and
CDC13): d 9.80 (s, 1 H, NH-enamine), 8.28 (s, 1 H, purified with the suitable method as follows to
NH), 7.54 (d, 1 H, 4-H, J45 = 8.5 Hz), 7.42-7.24
(m, 10 H, 2Ph), 6.98 (d, 1 H, 7-H, J75 = 1.5 Hz),
6.75 (d, 1 H, 5-H, J54 = 8.5 Hz), 5.34 (s, 1 H, ß-H),
3.74, 3.67 (2s, 6 H, 2COOMe).
give compounds lOa-c:
4-Chloro-6,7-diphenyl-2-(N-morpholinocarbonyl)-
pyrrolo[2,3-f]quinoline (10a)
Flash chromatography of the residue [petroleum
ether/ethyl acetate (1 :1 )] gives pale yellow crystals,
yield 77%, m.p. 230-232 C. TLC [petroleum
ether/ethyl acetate (1:1)]: Rf = 0.34, ‘H NMR (250
MHz, CDCU): Ö 10.23 (s, 1 H, NH), 8.09, 7.82 (2d,
2 H, 8,9-H, >89 = 9Hz), 8.00 (s, 1 H, 3-H), 7.57-
7.33 (m, 10 H, 2Ph), 3.98-3.74 (m, 8 H, 4CH2).
C26H22N20 4 (426.5)
Calcd
C 73.21 H 5.20 N 6.57%,
Found C 73.12 H 5.25 N6.60%.
2-Methoxycarbonyl-6,7-diphenylpyrrolo[2,3-f]-
4[1 HJquinolone (8 )
A solution of dimethylfumarate derivative 7
(1 g, 2.35 mmol) in triethyleneglycol dimethyl
ether (triglyme) (10 ml) was refluxed for 1 h. The
solid, formed by cooling, was filtered off, washed
with cold ether and crystallized from chloroform
to give yellow crystals, yield 81%, m.p. 240-243
C. IR (cm -1): 3440, 3360 (2NH), 1740 (COOMe),
1580-1620 (CO, C=C); lH NMR (250 MHz,
CDCI3): (3 11.29 (s, 1 H, NH pyridone), 9.49 (s, 1
H, NH pyrrole), 7.99, 7.20 (2d, 2 H, 8,9-H, / 89 = 9
Hz), 7.54-7.26 (m, 11 H, 3-H, 2Ph), 4.05 (s, 3 H,
COOMe), MS: M+ at m/e = 394.
C28H 22N30 2C1 (468)
Calcd
C 71.85 H 4.74 N 8.98%,
Found C 71.46 H 4.75 N 8.77%.
4-Chloro-6,7-diphenyl-2-(N-thiomorpholinocar-
bonyl)pyrrolo[2, 3-fJquinoline (10b)
Medium pressure chromatography [toluene/ace-
tone (1 2 :1 )] of the residue gave yellow crystals,
yield 62%, m.p. 232-235 C. TLC [toluene/acetone
(12:1)]: Rf = 0.44, 'H NMR (250 MHz, CDC13): 6
10.39 (s, 1 H, NH), 8.11, 7.87 (2d, 2 H, 8 ,9-H, J89 =
9.0 Hz), 7.98 (s, 1 H, 3-H), 7.63-7.38 (m, 10 H,
2Ph), 4.28-4.09 (2 m, 4 H, CH2-S-CH2), 2.98-2.85
(m, 4 H, CH2-N-CH2).
4-Chloro-2-methoxycarbonyl-6,7-
diphenylpyrrolo[2,3-f] quinoline (9)
C28H22N3OClS (484)
A mixture of 8 (1 g, 2.54 mmol), phosphoryl
chloride (6 ml), pyridine (1 ml) and water (0.5 ml)
was boiled for 1 h. The volatile liquids were re-
moved under reduced pressure and the residue
formed was washed with water and purified by
chromatography [petroleum ether/ethyl acetate
(4:1)] to give yellow crystals, m.p. 166-169 C. TLC
Calcd
C 69.48 H 4.58 N 8 .6 8 %,
Found C 69.26 H 4.70 N8.34%.
4-Chloro-6,7-diphenyl-2-(N-piperidinocarbonyl)-
pyrrolo[2,3-f] quinoline (10c)
Medium pressure chromatography of the resi-
[petroleum ether/ethyl acetate (1:1): Rf = 0.66 IR due [toluene/acetone (14:1)] gave colourless crys-
tals, m.p. 118-120 C, TLC (toluene/acetone 14:1)
(cm“1): 3460 (NH), 1724 (CO), 1605 (C=C), ‘H
NMR (250 MHz, CDC13): (3 10.26 (s, 1 H, NH), Rf = 0.30. :H NMR (250 MHz, CDCh): d 10.21 (s,
8.34 (s, 1 H, 3-H), 8.10 (d, 1 H, 9-H, / 98 = 9.0 Hz), 1 H, NH), 8.04, 7.83 (2d, 2 H, 8,9-H, / 89 = 8.9 Hz),
8.02 (d, 1 H, 8-H, / 89 = 9.0 Hz), 7.52-7.33 (m. 10 7.86 (s, 1 H. H-3), 7.52-7.34 (m, 10 H, 2Ph), 3.87-
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 7/26/15 6:15 AM