6
İ. ÇAPAN AND S. SERVI
6.08 mmol) of triethylamine and 3.04 mmol of compound 4 (or compound 6) were added
consecutively to the cold solution. The reaction mixture turned light yellow. The solution
was stirred at 0 °C for 1 h. The mixture was allowed to warm to room temperature and
stirred under an argon atmosphere for 24 h. The resulting white solid was filtered and
the solvent was evaporated under reduced pressure. The crude product was dissolved in
10 mL of methanol and precipitated by dropwise addition of methanol solution to
200 mL of water. The obtained solid was filtered, dried, and then crystallized from benzene
(methanol for compound 10).
8,13-Dihydro-6H-8,13-[1,2]benzenobenzo[4,5]imidazo[1,2-a]naphtho[2,3-e][1,3]
diazepin-7,14-dione (7)
Yield 82.8%, yellow powder, mp: 238–240 °C; IR (ATR, cm−1): 3376, 3061, 3026, 2923,
1
2851, 1634, 1546, 1457, 1370, 1274, 744; H NMR: (400 MHz, DMSO-d6) δ 12.16 (1H,
br), 7.51–7.31 (6H, m), 7.07 (2H, dd, J ¼ 5.4 and 2.9 Hz), 7.02 (4H, dd, J ¼ 5.1 and 3.2 Hz),
6.13 (1H, s), 5.99 (1H, s); 13C NMR: (100 MHz, DMSO-d6) δ (ppm): 167.95–164.64
=
(C O), 154.57 (Cipso-benzimidazole), 148.04–143.86 (Cipso-benzimidazole), 145.68–145.51
(Cipso-DBB), 125.21, 124.11, 123.78, 122.37, 121.53, 111.99 (CH-aromatic), 55.41–
51.67 (CH-bridgehead), 46.24–9.11 (triethylamine salt); Anal. calc. for C25H15N3O2
(389,41): C, 77.11; H, 3.88, N, 10.79; found C, 77.29; H, 3.96; N, 11.03.
General synthesis of 13-(1H-benzimidazol-2-yl)-9,10-dihydro-9,10-[3,4]
epipyrroloanthracene-12,14-dione (8) (Method B)
A total of 0.405 g of compound 9 3.04 mmol of compound 9 (0.405 g) was dissolved in
anhydrous THF (50 mL) and cooled at 0 °C in an ice bath under an argon atmosphere.
Then, 0.243 g of NaH (60%, 6.08 mmol) and 3.04 mmol of compound 4 were added to
the cold solution, respectively. The color of the reaction mixture turned red. The solution
was stirred for 1 h at 0 °C. The mixture was allowed to warm to room temperature and stir-
red under the argon atmosphere for 24 h. The mixture was filtered and the solvent was eva-
porated under reduced pressure. The crude product was dissolved in 10 mL of methanol.
The crude product was precipitated by dropwise addition of methanol solution to 200 mL
of water. The crude product was dried, filtered, and then crystallized from methanol.
13-(1H-benzimidazol-2-yl)-9,10-dihydro-9,10-[3,4]epipyrroloanthracene-12,14-dione (8)
Yield 74.3%, colorless powder, mp: 281–282 °C; IR (ATR, cm−1): 3316, 3066, 2951, 2922,
1
2851, 1683, 1633, 1537, 1456, 1362, 1272, 742; H NMR: (400 MHz, DMSO-d6) δ 12.36
(1H, br), 7.38 (4H, dd, J ¼ 5.3 and 3.2 Hz), 7.34 (2H, dd, J ¼ 5.9 and 3.2 Hz), 7.20 (2H,
dd, J ¼ 5.9 and 3.2 Hz), 6.98 (4H, dd, J ¼ 5.3 and 3.1 Hz), 5.97 (2H, s); 13C NMR: (100
=
=
MHz, DMSO-d6) δ 166.08 (C O), 151.31 (Cipso-benzimidazole), 150.00 (C C), 145.55
=
(Cipso-DBB), 130.94 (C C, Ar-benzimidazole), 125.11–123.96 (CH-DBB), 123.18–111.82
(CH-benzimidazole), 53.53 (CH-bridgehead). Anal. calc. for C25H15N3O2 (389,41): C,
77.11; H, 3.88, N, 10.79; found C, 77.44; H, 3.89; N, 10.84.
Synthesis of N11,N12-di(imidazolidin-2-ylidene)-9,10-dihydro-9,
10-ethenoanthracene-11,12-dicarboxamide (12) (Method C)
A total of 0.100 g Na (4.35 mmol) was dissolved in anhydrous methanol (10 mL) and the
mixture was stirred at room temperature for 10 min. To the resulting sodium methoxide