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Helvetica Chimica Acta Vol. 85 (2002)
2-([(6-Bromohexyl)oxy]anthracene-9,10-dione (8a): Yield 52%. M.p. 91 928. 1H-NMR (CDCl3): 1.52
1.91 (m, 4 CH2); 3.44 (t, J 6.7, CH2Br); 4.15 (t, J 6.3, CH2O); 7.25 (dd, J 8.7, 2.5, HÀC(3)); 7.70 (d, J 2.5,
HÀC(1)); 8.24 (d, J 8.8, HÀC(4)); 7.74 8.30 (m, 4 arom. H). 13C-NMR (CDCl3): 25.21, 27.87, 28.85, 29.70
(CH2); 33.65 (CH2Br); 68.55 (CH2O); 110.50, 121.43, 126.99, 127.11, 129.74, 133.61, 133.70, 134.12, 135.58, 163.85
(arom. C); 182.12, 183.28 (C(9), C(10)). Anal. calc. for C20H19BrO3: C 62.03, H 4.95; found: C 62.01, H 4.97.
2,2'-[Hexane-1,6-diylbis(oxy)]anthracene-9,10-dione (8b): Yield 9%. M.p. 200 2018. 1H-NMR (CDCl3):
1.60 1.93 (m, 4 CH2); 4.19 (t, J 6.3, 2 CH2O); 7.27 (dd, J 8.6, 2.6, 2 H, HÀC(3)); 7.72 (d, J 2.6, 2 H,
HÀC(1)); 8.26 (d, J 8.7, 2 H, HÀC(4)); 7.76 8.31 (m, 8 arom. H). Anal. calc. for C34H26O6 ¥ 2 H2O: C 72.07,
H 5.34; found: C 72.06, H 4.95.
3-(4-Bromobutoxy)-9H-xanthen-9-one (9a): Yield 56%. M.p. 117 1188. 1H-NMR (CDCl3): 1.99 2.15
(m, 2 CH2); 3.51 (t, J 6.4, CH2Br); 4.12 (t, J 5.6, CH2O); 6.86 (d, J 2.4, HÀC(4)); 6.93 (dd, J 8.8, 2.4,
HÀC(2)); 8.24 (d, J 9.2, HÀC(1)); 7.35 8.34 (m, 4 arom. H). 13C-NMR (CDCl3): 27.64, 29.29 (CH2); 33.13
(CH2Br); 67.54 (CH2O); 100.68, 113.46, 115.83, 117.66, 121.96, 123.85, 126.64, 128.29, 134.26, 156.18, 158.01,
164.29 (arom. C); 176.23 (C(9)). Anal. calc. for C17H15BrO3: C 58.81, H 4.35; found: C 58.82, H 4.39.
1
3,3'-[Butane-1,4-diylbis(oxy)]bis[9H-xanthen-9-one] (9b): Yield 13%. M.p. 218 2198. H-NMR (CDCl3):
2.08 2.11 (m, 2 CH2); 4.20 (t, J 5.2, 2 CH2O); 6.88 (d, J 2.4, 2 H, HÀC(4)); 6.95 (dd, J 8.8, 2.4, 2 H,
HÀC(2)); 8.26 (d, J 8.8, 2 H, HÀC(1)); 7.26 8.35 (m, 8 arom. H). Anal. calc. for C30H22O6: C 75.30, H 4.63;
found: C 75.13, H 4.66.
3-[(6-Bromohexyl)oxy]-9H-xanthen-9-one (10a): Yield 43%. M.p. 94 958. 1H-NMR (CDCl3): 1.52 1.92
(m, 4 CH2); 3.44 (t, J 6.7, CH2Br); 4.08 (t, J 6.4, CH2O); 6.86 (d, J 2.3, HÀC(4)); 6.93 (dd, J 8.8, 2.4,
HÀC(2)); 8.24 (d, J 8.8, HÀC(1)); 7.35 8.35 (m, 4 arom. H). 13C-NMR (CDCl3): 25.22, 27.84, 28.81, 32.59
(CH2); 33.71 (CH2Br); 68.41 (CH2O); 100.61, 113.56, 115.67, 117.65, 121.95, 123.82, 126.63, 128.22, 134.23,
156.19, 158.04, 164.54 (arom. C); 176.26 (C(9)). Anal. calc. for C19H19BrO3: C 60.81, H 5.10; found: C 60.80,
H 5.17.
3,3'-[Hexane-1,6-diylbis(oxy)]bis[9H-xanthen-9-one] (10b): Yield 17%. M.p. 197 1988. 1H-NMR (CDCl3):
1.60 1.95 (m, 4 CH2); 4.11 (t, J 6.3, 2 CH2O); 6.87 (d, J 2.3, 2 H, HÀC(4)); 6.94 (dd, J 8.9, 2.3, 2 H,
HÀC(2)); 8.25 (d, J 8.8, 2 H, HÀC(1)); 7.32 8.35 (m, 8 arom. H). Anal. calc. for C32H26O6 ¥ 0.25 H2O:
C 75.21, H 5.23; found: C 75.21, H 5.22.
2-(4-Bromobutoxy)dibenzofuran (11a): Yield 44%. M.p. 57 588. 1H-NMR (CDCl3): 1.96 2.15
(m, 2 CH2); 3.52 (t, J 6.8, CH2Br); 4.08 (t, J 6.0, CH2O); 7.02 (dd, J 8.8, 2.8, HÀC(3)); 7.40 (d, J 2.8,
HÀC(1)); 7.45 (d, J 8.8, HÀC(4)); 7.29 7.91 (m, 4 arom. H). 13C-NMR (CDCl3): 27.99, 29.51 (CH2); 33.46
(CH2Br); 67.81 (CH2O); 104.69, 111.72, 112.08, 115.60, 120.52, 122.41, 124.41, 124.69, 127.10, 150.94, 155.06,
156.90 (arom. C). Anal. calc. for C16H15BrO2: C 60.21, H 4.74; found: C 60.55, H 4.80.
2,2'-[Butane-1,4-diylbis(oxy)]bis[dibenzofuran] (11b): Yield 12%. M.p. 152 1538. 1H-NMR (CDCl3):
2.08 2.11 (m, 2 CH2); 4.18 (m, 2 CH2O); 7.06 (dd, J 8.8, 2.4, 2 H, HÀC(3)); 7.44 (d, J 2.4, 2 H, HÀC(1));
7.46 (d, J 8.8, 2 H, HÀC(4)); 7.29 7.90 (m, 8 arom. H). Anal. calc. for C28H22O4: C 79.60, H 5.5.25; found:
C 79.33, H 5.32.
2-[(6-Bromohexyl)oxy]dibenzofuran (12a): Yield 52%. M.p. 38 398. 1H-NMR (CDCl3): 1.52 1.95
(m, 4 CH2); 3.43 (t, J 6.4, CH2Br); 4.05 (t, J 6.4, CH2O); 7.03 (dd, J 8.8, 2.8, HÀC(3)); 7.41 (d, J 2.4,
HÀC(1)); 7.45 (d, J 8.8, HÀC(4)); 7.29 7.91 (m, 4 arom. H). 13C-NMR (CDCl3): 25.35, 27.95, 29.22, 29.51
(CH2); 33.77 (CH2Br); 68.72 (CH2O); 104.71, 111.72, 112.05, 115.68, 120.52, 122.38, 124.49, 124.67, 127.05,
150.88, 155.28, 156.90 (arom. C). Anal. calc. for C18H19BrO2: C 62.26, H 5.52; found: C 62.10, H 5.50.
2,2'-[Hexane-1,6-diylbis(oxy)]bis[dibenzofuran] (12b): Yield 38%. M.p. 126 1278. 1H-NMR (CDCl3):
1.61 1.92 (m, 4 CH2); 4.09 (t, J 6.4, 2 CH2O); 7.05 (dd, J 8.8, 2.8, 2 H, HÀC(3)); 7.42 (d, J 2.8, 2 H,
HÀC(1)); 7.45 (d, J 8.8, 2 H, HÀC(4)); 7.29 7.91 (m, 8 arom. H). Anal. calc. for C30H26O4: C 79.98, H 5.82;
found: C 79.69, H 5.90.
2-({6-[(9-Oxo-9H-xanthen-3-yl)oxy]hexyl}oxy)anthracene-9,10-dione (13). At r.t. 2-hydroxyanthracene-
9,10-dione (0.45 g, 2 mmol), K2CO3 (0.28 g, 2 mmol), and dry DMF (50 ml) were stirred for 30 min. To this
soln., 10a (0.75 g, 2 mmol) was added in dry DMF (10 ml) in one portion. The resulting mixture was stirred at r.t.
for 24 h (TLC monitoring) and then poured into ice-water (100 ml). The yellow solid thus obtained was
collected and purified by CC (silica gel, hexane/CH2Cl2 1:1) followed by crystallization from Et2O: 13 (0.99 g,
96%). M.p. 161 1628. 1H-NMR (CDCl3): 1.60 1.93 (m, 4 CH2); 4.10 (t, J 8.0, 1 CH2O); 4.17 (t, J 8.4,
1 CH2O); 6.86 (d, J 2.4, HÀC(4')); 6.94 (dd, J 9.2, 2.4, HÀC(2')); 8.23 (d, J 8.8, HÀC(1')); 7.25 (dd, J
8.8, 2.4, HÀC(3)); 7.70 (d, J 2.4, HÀC(1)); 8.24 (d, J 8.8, HÀC(4)); 7.34 8.32 (m, 8 arom. H). Anal. calc.
for C33H26BrO3: C 76.43, H 5.05; found: C 76.20, H 5.09.
Bis-Intercalators 14 and 15. As described for 13, 11a was converted to 14 and 3a to 15.