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H2O, dried over Na2SO4, evaporated, and chromatographed on silica (CHCl3:CH3OH 20:1) to
yield, besides 245 mg of the educt, 150 mg 8a (75%).
M.p.: 65ꢁC; 1H NMR (CD2Cl2, ꢂ, 200 MHz): 11.96, 11.83, 11.75, 11.74 (4s, 4H, OH-1, 10, 8, 80),
9.69 (bs, 1H, OH-3), 7.42 (m, 5H, phenyl-H), 7.33 (s, 1H, H-ar), 7.11 (d, 1H, J 2.5 Hz, H-ar), 7.03
(s, 2H, H-ar), 6.78 (s, 1H, H-ar), 6.61 (d, 1H, J 2.3 Hz, H-ar), 6.53 (d, 1H, J 2.5 Hz, H-ar), 6.22
(d, 1H, J 2.4 Hz, H-ar), 5.08 (s, 2H, CH2-phenyl), 4.44, 4.28 (2s, 2H, CH2-O), 3.73, 3.69, 3.67 (3s,
16H, (OCH2CH2)4-) ppm; 13C NMR (CDCl3, ꢂ, 50.3 MHz): 190.4, 189.6, 181.1, 180.5 (4 C=O),
165.5, 165.0, 164.9 (2 C), 162.4, 162.1, 148.5, 147.7, 135.3 (C-phenyl-1), 134.9, 134.4, 133.0, 132.5,
128.8 (2 phenyl-C-3), 128.5 (C-phenyl-4), 127.6 (2 phenyl-C), 121.8, 121.4, 118.0, 117.4, 114.4,
113.9, 110.2, 109.6, 109.0, 108.9, 108.6, 107.5 (30 C-ar), 71.7, 71.5, 70.8, 70.6, 70.5, 70.3 (11 C,
signal overlap, -CH2-(OCH2CH2-O)4-CH2-, phenyl-CH2) ppm; UV/Vis (ethanol): ꢁmax 362
(14800), 270 (10160), 260 (11070), 219 (25830) nm ("); IR (KBr): ꢃ 3470, 3078, 2867, 1630,
1613 cmꢂ1
.
3-Benzyl-1,8-dihydroxy-6-(10,30,80-trihydroxy-60-(2-(2-(2-(2-methoxyethyl)-ethoxy)-ethoxy)-ethoxy)-
ethoxymethyl-anthracene-90,100-dione-yl)-anthracene-9,10-dione (8b; C47H43O15)
Prepared in analogy to 8a to yield, besides educt 7b, 82% of 8b.
M.p.: 49±51ꢁC; 1H NMR (CDCl3, ꢂ, 200 MHz): 11.95, 11.83, 11.82, 11.78 (4s, 4H, OH-1, 10, 8,
80), 9.17 (s, 1H, OH-3), 7.40 (m, 6H, phenyl-H, 1H-ar), 7.18 (s, 1H, H-ar), 7.12, 6.50 (2d, 1H, J
2.3 Hz, H-ar), 7.04 (s, 1H, H-ar), 6.83 (s, 2H, H-ar), 6.38 (d, 1H, J 2.1 Hz, H-Ar), 5.03 (s, 2H,
phenyl-CH2), 4.45, 4.31 (2s, 2H, CH2O-), 3.6±3.8 (m, 20H, O-(CH2-CH2-O)5-) ppm; 13C NMR
(CDCl3, ꢂ, 50.3 MHz): 190.0, 189.4, 180.8, 180.5 (4 C=O), 165.3, 164.8 (2 C), 164.7, 162.2, 162.0,
148.3, 147.7, 135.2 (C-phenyl-1), 134.6, 134.3, 132.8, 132.4, 128.6 (2 phenyl-C), 128.3 (C-phenyl-4),
127.4 (2 phenyl-C), 121.8, 121.4, 117.9, 117.4, 114.2, 113.8, 109.9, 109.5, 108.8, 108.5, 108.4, 107.2
(30 C, C-ar), 71.6, 71.4, 70.5, 70.4, 70.3, 70.2, 70.1 (13 C, signal overlap, -CH2-(OCH2CH2-O)5-
CH2-, Phenyl-CH2) ppm; UV/Vis (CH3CN): ꢁmax 436 (19950) nm ("); IR (KBr): ꢃ 3470, 3065,
2871, 1628 cmꢂ1
.
Di-(1,3,8-trihydroxy-6-(2-ethoxy)-ethoxymethyl-10H-anthracene-9-one-yl)-ether (9a; C38H34O15)
100 mg (0.12 mmol) 8a were dissolved in 20 ml glacial acetic acid at 100ꢁC and re¯uxed for 20 min
after addition of 540 mg (2.4 mmol) SnCl2 Á 2H2O in 2.5 ml conc. HCl Á 200 ml ice water were added
to the reaction mixture and the mixture was ®ltered. The residue was chromatographed on silica
(CHCl3:CH3OH 20:1) to yield 40 mg (40%) of 9a.
M.p.: 62±64ꢁC; 1H NMR (DMSO-d6, ꢂ, 200 MHz): 12.31, 12.23, 10.85 (3s, 2H, OH), 6.64,
6.72, 6.38, 6.20 (4s, 2H, H-ar), 4.48 (s, 4H, CH2-O), 4.28 (s, 4H, ar-CH2-ar), 3.57 (m, 16H,
(OCH2CH2-)4O) ppm; UV/Vis (ethanol): ꢁmax 361 (17930), 219 (37623) nm ("); IR (KBr):
ꢃ 3220, 2873, 1626, 1603 cmꢂ1
.
1,2-Bis-(1,3,8-trihydroxy-6-(2-oxyethoxy)-ethoxymethyl-10H-anthracene-9-one-yl)-ethane
(9b; C40H38O16)
Prepared in analogy to 9a in a yield of 55%.
1
M.p.: 48±50ꢁC; H NMR (CDCl3:CD3OD 1:2, ꢂ, 200 MHz): 6.65, 6.62, 6.21 (3s, 2H, H-ar),
6.12 (d, 2H, J 2.3 Hz, H-ar), 4.40 (s, 4H, CH2-O), 4.00 (s, 4H, ar-CH2-ar), 3.64 (m, 20H, (O-CH2-
CH2-)5O) ppm; 13C NMR (CDCl3:CD3OD 1:2, ꢂ, 50.3 MHz): 192.3 (2 C=O), 165.9, 165.6, 163.0,
147.7, 145.2, 142.5, 113.8, 109.8 (8.2 C-Ar), 117.7, 115.2, 107.9, 101.9 (4.2 CH-ar), 72.9 (2 CH2O-),
71.3 (-O(CH2CH2O)3-), 70.75 (2 O-CH2), 33.37 (2 ar-CH2-ar) ppm; UV/Vis (ethanol): ꢁmax 361
(18200), 219 (37800) nm ("); IR (KBr): ꢃ 3220, 2923, 2876, 1627, 1605 cmꢂ1
.