H
ELVETICA
CHIMICA
ACTA – Vol. 88 (2005)
2835
698 (25), 669 (9), 668 (18), 667 (18), 614 (10), 602 (13), 601 (48), 600 (77), 403 (15), 392 (24), 391 (81), 390 (100),
373 (12), 179 (15), 83 (27). HR-MS: 875.5540 (C57H71N4Oþ4 ; calc. 875.5475). Anal. calc. for C57H72N4O4 (877.2): C
78.04, H 8.27, N 6.39; found C 77.31, H 7.69, N 6.81.
2,9-Bis[1-heptyl-2-(1H-imidazol-1-yl)octyl]anthra[2,1,9-def:6,5,10-d’e’f’]diisoquinoline-1,3,8,10-tetrone (4):
13 mg (0.1%). Rf (silica gel, CHCl3/EtOH 10 : 1) 0.04. UV (CHCl3): 528.5 (1.00), 491 (0.649), 461.5 (0.288),
436.5 (0.122). Fluorescence (CHCl3): 536 (1.00), 578 (0.587), 626 (0.174), 689 (0.029). Fluorescence quantum
yield (lexc. 490 nm, E528.5 =0.0482/l cm in CHCl3): 85%. MS (70 eV): 943 (3, M+), 942 (7), 874 (6), 858 (12),
778 (10), 777 (16), 764 (11), 763 (18), 679 (12), 668 (13), 667 (15), 600 (7), 487 (7), 455 (19), 454 (14), 404
(13), 403 (24), 392 (28), 391 (100), 390 (88), 373 (15), 276 (12), 179 (26), 165 (20), 128 (12), 95 (13), 69 (22),
68 (57), 55 (13).
10-Heptyl-2-(1-heptyloctyl)-11-hexyl-10,11-dihydroimidazo[2,1-a]anthra[2,1,9-def:6,5,10-d’e’f’]diisoquino-
line-1,3,8(2H)-trione (5): 3 mg (0.03%). Rf (silica gel, CHCl3) 0.09. Rf (silica gel, CHCl3/EtOH 10 : 1) 0.95. Rf
(silica gel, CH2Cl2/acetone 20 : 1) 0.77. UV (CHCl3): 538 (1.00), 500 (0.683), 469.5 (0.281), 439 (0.099). Fluores-
cence (CHCl3): 550 (1.00), 593 (0.590), 642 (sh, 0.151). Fluorescence quantum yield (lexc. 490 nm, E538 =0.0516/l
cm in CHCl3): 87%. IR (KBr): 2956m, 2924s, 2855m, 1697s, 1657s, 1620w, 1595w, 1462w, 1344m, 808w, 744w. 1H-
NMR (CDCl3): 0.80–0.86 (m, 4 Me); 1.19–1.35 (m, 38 H, CH2); 1.40–1.70 (m, 2 H, CH2); 1.70–1.90 (m, 1 H,
CH2); 1.90–2.10 (m, 2 H, CH2); 2.10–2.30 (m, 3 H, CH2); 4.05–4.20 (m, 1 H, CH); 4.30–4.50 (m, 1 H, CH);
5.12 –5.30 (m, 1 H, CH); 8.53–8.64 (m, 8 H, perylene). MS (70 eV): 809 (12), 808 (22, M+), 807 (10), 806
(12), 725 (11), 724 (46), 723 (96), 711 (11), 710 (52), 709 (100), 625 (5), 604 (14), 603 (6), 602 (17), 512 (10),
498 (10), 414 (13), 338 (6), 337 (20), 335 (25), 210 (13), 111 (9), 98 (6), 97 (22), 85 (6), 84 (11), 83 (28), 82 (7),
71 (11), 70 (19), 69 (32), 67 (10), 57 (23), 56 (21), 55 (34), 44 (94), 43 (24), 41 (22). HR-MS: 807.5319 (C54H69-N3Oþ3 ;
calc. 807.5338).
Reaction of 1 with 1-(Hexylheptyl)amine and 1H-Imidazole. According to [2], 1-(hexylheptyl)amine (24.7,
124 mmol), 1 (20.7 g, 52.8 mmol), and 1H-imidazole (30 g) were allowed to react for 4 h at 1608 under Ar: 39.3 g
(ca. 98%) of dye material. Column chromatography (silica gel, CHCl3) gave a yellow forerun, 2,9-bis(1-hexyl-
heptyl)anthra[2,1,9-def:6,5,10-d’e’f’]diisoquinoline-1,3,8,10-tetrone [11] (32.7 g, 82%; anal. pure), and 740 mg of
a dye mixture. The latter was separated by means of a chromatotron [5] (rotatory chromatograph, silica gel,
CH2Cl2/acetone 20 :1). Some material was firmly adsorbed, a forerun was discarded, and the two following frac-
tions were collected.
9-(1-Hexylheptyl)-2-[1-hexyl-2-(1H-imidazol-1-yl)heptyl]anthra[2,1,9-def:6,5,10-d’e’f’]diisoquinoline-1,3,8,
10-tetrone: 300 mg (0.7%). M.p. 275–2788. Rf (silica gel, toluene/acetone 4 : 1) 0.15. Rf (silica gel, CHCl3/EtOH
10 : 1) 0.36. Rf (silica gel, CHCl3/AcOH 10 : 1) 0.14. Rf (silica gel, CH2Cl2/acetone 20 : 1) 0.27. UV (CHCl3): 528
(83200), 491 (48600), 459 (16500), 434 (3600). Fluorescence (CHCl3): 536, 576. Solid-state fluorescence: 626. IR
(KBr): 2955m, 2927s, 2857m, 1698s, 1658s, 1594s, 1578w, 1495w, 1458w, 1435w, 1405m, 1339s, 1258w, 1174w,
1126w, 1107w, 854w, 810w, 748w. 1H-NMR (CDCl3): 0.81 (t, 4 Me); 1.21–1.32 (m, 30 H, CH2); 1.70–1.95 (m,
4 H, a-CH2); 1.95–2.10 (m, 1 H, a-CH2); 2.10–2.29 (m, 2 H, a-CH2); 2.30–2.48 (m, 1 H, a-CH2); 4.98–5.09
(m, 1 H, CH); 5.09–5.19 (m, 1 H, CH); 5.38–5.50 (m, 1 H, CH); 6.75 (s, 1 H, im.); 6.88 (s, 1 H, im.); 7.32 (s,
1 H, im.); 8.50–8.67 (m, 8 H, perylene). 13C-NMR (CDCl3): 14.5 (q); 22.9 (t); 23.0 (t); 26.4 (t); 26.8 (t); 27.1
(t); 27.3 (t); 29.3 (t); 29.6 (t); 32.0 (t); 32.2 (t); 32.8 (t); 33.9 (t); 55.2 (d); 57.8 (d); 59.4 (d); 117.1, 122.4,
123.1, 123.3, 123.6, 126.8, 129.3, 129.8, 131.8, 132.5, 134.6, 135.3, 137.7 (13 s); 164.2 (s, C=O); 164.6 (s, C=O).
MS (70 eV): 822 (10), 821 (36, [M+H]+), 820 (61, M+), 752 (5, [Mꢀimidazole]+), 749 (3, [MꢀC5H11]+), 735
(2, [MꢀC6H13]+), 670 (6), 669 (13), 656 (12), 655 (24), 640 (8), 639 (17), 638 (5, [MꢀC13H26]+), 586 (6), 585
(15), 574 (12), 573 (42), 572 (67, [M+ ꢀC13H26 ꢀimidazole]+), 473 (5), 404 (11), 403 (24), 393 (6), 392 (29),
391 (98), 390 (100), 374 (8), 373 (27), 346 (8), 345 (15), 248 (8), 166 (5), 165 (19), 151 (11), 109 (9), 95 (11),
85 (9), 83 (13), 69 (11), 55 (17). ESI-MS: 2463 (2, [3 (M+H)]+), 1713 (20), 1712 (31), 1711 (23), 1643 (13),
1642 (42, [2 (M+H)]+), 822 (70, [M+2 H]+), 821 (100, [M+H]+), 753 (13). HR-MS: 820.4955 (C53H64N4Oþ4 ;
calc. 820.4927).
2,9-Bis[1-hexyl-2-(1H-imidazol-1-yl)heptyl]anthra[2,1,9-def:6,5,10-d’e’f’]diisoquinoline-1,3,8,10-tetrone: 34
mg (0.07 %). Rf (silica gel, CHCl3/EtOH 10 : 1) 0.09. MS (70 eV): 886 (1, M+), 822 (7), 821 (22), 820 (39, [Mꢀ
C3H2N2]+), 753(6), 752 (7, [MꢀC3H2N2 ꢀimidazole]+), 670 (8), 669 (15), 656 (7), 655 (13), 640 (6), 639 (12), 585
(10), 574 (10), 573 (33), 572 (51, [MꢀC13H26 –2 C3H2N2]+), 404 (9), 403 (17), 393 (5), 392 (24), 391 (84), 390
(100), 374 (6), 373 (19), 346 (7), 345 (11), 248 (7), 165 (8), 151 (8), 69 (5), 55 (7).