O. Talaz, N. Saracoglu / Tetrahedron 66 (2010) 1902–1910
1909
(603 mg, 2.66 mmol) in THF (15 mL). The reaction mixture was
stirred in an ice-bath for 3 h, and then the solvent was evaporated
to dryness. The residue was dissolved by EtOAc (200 mL) and
washed with saturated NaHCO3 (2ꢁ100 mL), water (100 mL). The
EtOAc solution was decanted and the precipitate was dried to give
the product 43 in quantitative yield (pale yellow powder from ac-
etone/hexane, 487 mg, 94%, mp 345–346 ꢀC); 1H NMR (400 MHz,
EtOH. The mixture was stirred at 95 ꢀC for 16 h. After the solvent
was evaporated, the residue was dissolved by CH2Cl2 (100 mL).
Organic layer was washed with water (2ꢁ50 mL), dried over
MgSO4, and the solvent was evaporated. The crude product was
eluted by silica gel (20 g) column chromatography with EtOAc/
hexane (20:80) (120 mL). The solvent was removed under reduced
pressure and tetramer 37 (144 mg, 82%) was obtained.
Acetone-d6):
d 11.22 (m, NH, 1H), 11.03 (m, NH, 1H), 10.91 (m, NH,
1H), 8.59 (d, J¼7.7 Hz,]CH, 1H), 8.14 (d, J¼8.1 Hz,]CH, 1H), 7.80 (d,
J¼7.6 Hz,]CH, 1H), 7.67 (d, J¼8.1 Hz,]CH, 1H), 7.54 (d,
J¼8.1 Hz,]CH, 1H), 7.51 (d, J¼8.1 Hz,]CH, 1H), 7.34 (td, J¼7.5 Hz,
1.0 Hz,]CH, 1H), 7.29–7.20 (m,]CH, 1H), 7.19–7.09 (m,]CH, 4H),
3.88 (d, J¼12.3 Hz, A part of AB system, CH2, 1H), 3.85 (d, J¼12.3 Hz,
B part of AB system, CH2, 1H). 13C NMR (100 MHz, Acetone-d6):
Acknowledgements
We are greatly indebted to Atatu¨rk University, Faculty of Sci-
ences and Department of Chemistry for financial supports of this
work.
d
205.5, 189.1, 141.5, 137.5, 136.8, 136.3, 135.9, 135.7, 128.9, 127.5,
Supplementary data
126.1, 123.1, 123.0, 122.4, 122.3, 121.5, 120.7, 120.4, 120.1, 118.9, 114.2,
111.8, 111.1, 105.8, 105.4, 41.6. (KBr, cmꢂ1) 3261, 1704, 1602, 1544,
1411, 1228, 746. Anal. Calcd for C26H17N3O: C, 80.60; H, 4.42; N,
10.85. Found: C, 80.77; H, 4.50; N, 10.82.
Supplementary data includes 1H and 13C NMR spectra of com-
pounds. Supplementary data associated with this article can be
4.18. 5,10,15,20-Tetrahydrotriindolo[20,30:3,4:20,-
30:5,6:20,30:7,8]cycloocta[1,2-b]indole (37)
References and notes
A solution of 43 (100 mg, 0.26 mmol) and phenylhydrazine
(28 mg, 0.26 mmol) was stirred at 95 ꢀC for 2 h. Then, to this so-
lution was added ZnCl2 (150 mg, 1.10 mmol) and 10 mL of absolute
EtOH. The mixture was stirred at 95 ꢀC for 16 h. The solvent was
then evaporated, the residue was dissolved by CH2Cl2 (100 mL) and
washed with water (2ꢁ50 mL), dried over MgSO4, and the solvent
was evaporated. The crude product was eluted by silica gel (15 g)
column chromatography with EtOAc/hexane (20:80) (100 mL). The
solvent was removed under reduced pressure and tetramer 37 was
obtained in quantitative yield (light yellow powder from EtOAc/
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hexane, 95 mg, 80%, mp>350 ꢀC); 1H NMR (400 MHz, CDCl3):
(m, NH, 4H), 7.70 (d, J¼7.7 Hz,]CH, 4H), 7.43 (bd, J¼7.3 Hz,]CH,
d 8.45
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d 137.3,
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3249, 3053, 2919, 2852, 1718, 1606, 1491, 1452, 1373, 1315, 1284,
1236, 1046, 744. Anal. Calcd for C32H20N4: C, 83.46; H, 4.38; N, 12.17.
Found: 83.29; H, 4.25; N, 12.21.
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4.19. 5,6,12,13-Tetrahydroindolo[20,30:5,6]cycloocta
[1,2-b]indole-7,14-dione (44)
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To a solution of 10 (400 mg, 1.39 mmol) in THF (20 mL, 90%
aqueous) cooled with ice-bath for 1 h was added a solution of DDQ
(634 mg, 2.79 mmol) in THF (10 mL). The reaction mixture was
stirred at ice-bath at 4 h, and then the solvent was evaporated to
dryness. The residue was dissolved by EtOAc (200 mL), washed
with saturated NaHCO3 (2ꢁ100 mL), and water (100 mL). The EtOAc
solution was decanted and the precipitate was dried to give the
product 44 in quantitative yield (light yellow powder from acetone/
hexane, 395 mg, 90%, mp 280–281 ꢀC); 1H NMR (400 MHz, DMSO-
d6):
d
12.32 (m, NH, 2H), 8.09 (bd, J¼7.7 Hz,]CH, 2H), 7.36 (dd,
J¼7.0, 1.5 Hz,]CH, 2H), 7.15–7.11 (m,]CH, 4H), 5.42 (d, J¼13.9 Hz, A
part of AX system, CH2, 1H), 3.91 (d, J¼13.9 Hz, X part of AX system,
CH2, 1H). 13C NMR (100 MHz, DMSO-d6):
d 188.8, 143.3, 135.4, 127.8,
123.6, 122.8, 121.9, 112.1, 111.0, 44.5. IR (KBr, cmꢂ1) 3014, 2975, 1739,
1432, 1366, 1217, 1032, 901, 778, 710. Anal. Calcd for C20H14N2O2: C,
76.42; H, 4.49; N, 8.91. Found: C, 76.60; H, 4.58; N, 8.99.
4.20. Synthesis of tetramer 37 from 44
A solution of 44 (120 mg, 0.38 mmol) and phenylhydrazine
(82 mg, 0.76 mmol) was stirred at 95 ꢀC for 2 h. Then, to this so-
lution was added ZnCl2 (150 mg, 1.10 mmol) and 10 mL of absolute