JOURNAL OF CHEMICAL RESEARCH 2009 735
CHCl3) to give 1a (425 mg, 37%) as yellow needles, m.p. 187°C;
(Found: M+, 275.9748. C14H6O235Cl2 requires M+, 275.9745).
dH (270 MHz, CDCl3) 7.68 (2H, s), 7.77–7.81 (2H, m), 8.17–8.21
(2H, m); dC (67.8 MHz, CDCl3) 126.9 (2C, CH), 132.1 (2C, Cquat),
133.6 (2C, Cquat), 134.0 (2C, Cquat), 134.2 (2C, CH), 137.2 (2C, CH),
181.6 (2C, Cquat, CO). MS (EI, 70 eV) m/z (%) = 276 (M+) (100).
1,4-Dichloro-6,7-dimethylanthraquinone (1b); general procedure
A: Pale yellow needles, m.p. 194°C; (Found: M+, 304.0060.
C16H10O235Cl2 requires M+, 304.0058). dH (270 MHz, CDCl3) 2.42
(6H, s, 2 CH3), 7.64 (2H, s), 7.92 (2H, s); dC (67.8 MHz, CDCl3) 20.3
(2C, CH3), 127.7 (2C, CH), 129.6 (2C, Cquat), 131.6 (2C, Cquat), 133.8
(2C, Cquat), 140.0 (2C, CH), 144.3 (2C, Cquat), 181.7 (2C, Cquat, CO);
MS (EI, 70 eV) m/z (%) = 304 (M+) (100).
1,4-Bis(4-pentoxyphenyl)-6,7-dimethylanthraquinone (9e); general
procedure B: Pale orange needles, m.p. 215°C; (Found: MH+,
561.3006. C38H41O4 requires MH+, 561.3005 [FAB]). nmax (KBr/
cm-1) 2950, 2867, 1673, 1604, 1515, 1458, 1389, 1373, 1320, 1279,
1242, 1204, 1023, 971, 857, 828; dH (270 MHz, CDCl3) 0.96 (6H, t,
3J = 7.0 Hz, 2 CH3), 1.81–1.86 (4H, m), 1.41–1.54 (8H, m), 2.35 (6H,
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s, 2 CH3), 4.03 (4H, t, J = 6.5 Hz), 6.98 (4H, d, J = 8.6 Hz), 7.24
(4H, d, 3J = 8.6 Hz), 7.51 (2H, s), 7.83 (2H, s); dC (67.8 MHz, CDCl3)
14.1 (2C), 20.2 (2C), 22.5 (2C), 28.3 (2C), 29.1 (2C), 67.9 (2C), 114.1
(4C), 127.6 (2C), 129.2 (4C), 132.1 (2C), 133.0 (2C), 134.4 (2C),
136.4 (2C), 143.4 (2C), 143.6 (2C), 158.4 (2C), 184.5 (2C); MS (FAB,
3-nitrobenzyl alcohol) m/z (%) = 561 (MH+) (28), 419 (7.4), 326 (10).
Calcd for C38H40O4: C, 81.40; H, 7.19. Found: C, 80.87; H, 7.14%.
1,4-Bis(4-formylphenyl)anthraquinone (9f); general procedure B:
Yellow solid; m.p. 243°C; (Found: M+, 417.1130. C28H17O4 requires
M+, 417.1127). nmax (KBr/cm-1) 3068, 1687, 1677, 1602, 1380, 1319,
1259, 1211, 1168, 1091, 958, 827, 730; dH (270 MHz, CDCl3) 7.51 (4H,
d, 3J = 8.1 Hz), 7.60 (2H, s), 7.73–7.76 (2H, m), 8.02 (4H, d, 3J = 8.1 Hz),
8.06–8.09 (2H, m), 10.1 (2H, s, 2 CHO); dC (67.8 MHz, CDCl3) 127.0
(2C, CH), 128.5 (4C, CH), 129.7 (4C, CH), 132.6 (2C, Cquat), 133.5
(2C, Cquat), 134.2 (2C, CH), 135.2 (2C, Cquat), 135.9 (2C, CH), 143.3
(2C, Cquat), 148.6 (2C, Cquat), 183.5 (2C, CO), 191.92 (2C, CHO); MS
(FAB, 3-nitrobenzyl alcohol) m/z (%) 417 (MH+) (3.4).
1,4-Dibromo-5,8-dichloroanthraquinone(1c);generalprocedureA:
Colourless solid, m.p. 210°C; (Found: M+, 433.7930. C14H4O2
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Cl37Cl79Br2 requires M+, 433.7933). dH (270 MHz, CDCl3) 7.60 (2H,
s), 7.72 (2H, s); MS (EI, 70 eV) m/z (%) = 438 (3.3), 436 (9.2), 434
(9.6), 432 (3.9), 149 (34), 58 (100).
1,4-Bis(4-methoxyphenyl)anthraquinone (9a): general procedure B:
A solution of 1a (245 mg, 0.89 mmol), 4-methoxyphenylboronic acid
(430 mg, 2.83 mmol), Pd(PPh3)4 (46 mg, 4.0.10-5 mol) [or Pd(PPh3)2Cl2
(30 mg, 4.10-5 mol) and triphenylphosphine (30 mg, 0.11 mmol)]
in a solvent mixture of DME (10 mL) and aq. Na2CO3 (2.32 g
Na2CO3 in 15 mL H2O, 6 mL) was kept at 70°C for 18 h in an inert
atmosphere. The solution was then cooled and poured into water
(25 mL) and extracted with chloroform (3 × 15 mL). The combined
organic phase was dried over anhydrous MgSO4 and concentrated in
vacuo. Column chromatography of the residue on silica gel (hexane/
CHCl3/ether 3:1:1) gave 9a (310 mg, 83%) as orange needles;
m.p. 231°C; (Found: M+, 420.1367. C28H20O4 requires M+, 420.1362).
1-Chloro-4-(4-methylphenyl)anthraquinone (9g); general procedure
B: Yellow solid; m.p. 224°C; (Found: 333.0685. C21H14O235Cl
requires M+, 333.0682). nmax (KBr/cm-1) 3001, 1672; dH (270 MHz,
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CDCl3) 2.45 (3H, s, CH3), 7.15 (2H, d, J = 8.4 Hz), 7.27 (2H, d,
3J = 8.4 Hz), 7.46 (1H, d, 3J = 8.1 Hz), 7.69–7.80 (2H, m), 7.75 (1H,
d, 3J = 8.1 Hz), 8.03–8.06 (1H, m), 8.22–8.26 (1H, m); dC (67.8 MHz,
CDCl3) 21.3 (CH3), 126.7 (CH), 126.9 (CH), 127.7 (2C, CH), 127.9
(Cquat), 129.0 (2C, CH), 131.2 (Cquat), 133.7 (Cquat), 133.9 (CH), 134.0
(CH), 134.1 (Cquat), 134.3 (Cquat), 136.4 (CH), 137.1 (Cquat), 137.3
(CH), 138.5 (Cquat), 143.8 (Cquat), 182.6 (Cquat, CO), 183.3 (Cquat, CO);
MS (FAB, 3-nitrobenzyl alcohol) m/z (%) 333 (MH+) (4.4). Calcd for
C21H14O2Cl: C, 75.79; H, 3.94. Found: C, 75.86; H, 3.99%.
n
max (KBr/cm-1) 2950, 2867, 1671, 1604, 1279, 1242, 1204, 1023, 971,
857, 830; dH (270 MHz, CDCl3) 3.89 (6H, s, 2 OCH3), 7.00 (4H, d,
3J = 8.6 Hz), 7.26 (4H, d, J = 8.6 Hz), 7.53 (2H, s), 7.68–7.72 (2H,
3
m), 8.06–8.09 (2H, m); dC (67.8 MHz, CDCl3) 55.2 (2C, OCH3), 113.7
(4C, CH), 126.7 (2C, CH), 129.3 (4C, CH), 133.7 (2C, CH), 132.9
(2C, Cquat), 134.1 (2C, Cquat), 134.5 (2C, Cquat), 136.6 (2C, CH), 143.6
(2C, Cquat), 158.9 (2C, Cquat), 184.3 (2C, Cquat, CO); MS (EI, 70 eV)
m/z (%) 420 (M+) (100), 389 (32), 333 (18), 313 (13), 276 (17). UV-
Vis (CH3CN, nm) lmax 253 (59610), 271 (sh, 23890), 313 (13280).
1,4-Bis(4-pentoxyphenyl)anthraquinone (9b); general procedure B:
Rose-coloured solid; m.p. 202°C; (Found: MH+, 533.2697. C36H37O4
requires MH+, 533.2692 [FAB]). nmax (KBr/cm-1) 2953, 2869, 1604,
1515, 1385, 1375, 1320, 1281, 859, 828; dH (270 MHz, CDCl3) 0.96
(6H, t, 3J = 7.0 Hz), 1.46 (8H, m), 1.84 (4H, m), 4.04 (4H, t, 3J = 6.5 Hz),
1,4-Diphenylanthraquinone (9h);12,33 general procedure B: Yellow
solid; (Found: MH+, 361.1232. C26H17O2 requires MH+, 361.1229
[FAB]). nmax (KBr/cm-1) 3002, 1673, 758; dH (270 MHz, CDCl3)
7.29–7.35 (4H, m), 7.43–7.48 (6H, m), 7.56 (2H, s), 7.66–7.71 (2H,
m), 8.05–8.08 (2H, m); dC (67.8 MHz, CDCl3) 126.8 (2C, CH), 127.2
(2C, CH), 127.9 (4C, CH), 128.2 (4C, CH), 132.7 (2C, Cquat), 133.7
(2C, CH), 134.0 (2C, Cquat), 136.4 (2C, CH), 142.3 (2C, Cquat), 144.1
(2C, Cquat), 184.0 (2C, Cquat, CO); MS (FAB, 3-nitrobenzyl alcohol)
m/z (%) 361 (MH+) (5.6). UV-Vis (CH3CN, nm) lmax 253 (36370),
269 (sh, 19190), 288 (sh, 7320).
1,4,5,8-Tetrakis(4-methoxyphenyl)anthraquinone (9i); general
procedure B: Using 4-methoxyphenylboronic acid (860 mg, 5.66
mmol) and Pd(PPh3)4 (60 mg, 5.2 × 10-5 mol) [or Pd(PPh3)2Cl2
(40 mg, 5.2.10-5 mol) and triphenylphosphine (37 mg, 0.14 mmol)],
in DME (15 mL) and aq. Na2CO3 (9 mL): pale orange solid; m.p.
251°C; (Found: MH+, 633.2286. C42H33O6 requires MH+, 633.2277
[FAB]). nmax (KBr/cm-1) 1671, 1608, 1575, 1514, 1460, 1328, 1291,
1247, 1029, 831; dH (270 MHz, CDCl3) 3.84 (12H, s, 4 OCH3), 6.85
(8H, d, 3J = 8.4 Hz), 7.21 (8H, d, 3J = 8.4 Hz), 7.48 (4H, s); dC (67.8
MHz, CDCl3) 55.2 (4C, OCH3), 113.4 (8C, CH), 130.3 (8C, CH),
131.9 (4C, Cquat), 134.5 (4C, CH), 135.5 (4C, Cquat), 140.3 (4C, Cquat),
159.0 (4C, Cquat), 188.4 (2C, Cquat, CO); MS (FAB, 3-nitrobenzyl
alcohol) m/z (%) = 633 (MH+) (1.0).
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6.99 (4H, d, J = 8.6 Hz), 7.24 (4H, d, J = 8.6 Hz), 7.53 (2H, s),
7.67–7.71 (2H, m), 8.06–8.09 (2H, m); dC (67.8 MHz, CDCl3) 14.1
(2C, CH3), 22.5 (2C, CH2), 28.3 (2C, CH2), 29.1 (2C, CH2), 67.9
(2C, OCH2), 114.2 (4C, CH), 126.7 (2C, Cquat), 129.2 (4C, CH),
132.9 (2C, Cquat), 133.6 (2C, CH), 134.2 (2C, Cquat), 136.6 (2C, CH),
143.6 (2C, Cquat), 158.5 (2C, Cquat), 184.3 (2C, Cquat, CO); MS (FAB,
3-nitrobenzyl alcohol) m/z (%) 533 (MH+) (100), 391 (36). Calcd for
C36H36O4: C, 81.17; H, 6.81. Found: C, 80.79; H, 6.77%.
1,4-Bis(4-heptoxyphenyl)anthraquinone (9c); general procedure B:
Rose-coloured solid, m.p. 205°C; (Found: MH+, 589.3313. C40H45O4
requires MH+, 589.3318 [FAB]). nmax (KBr/cm-1) 2950, 2867,
1673, 1604, 1515, 1318, 1280, 1244, 1206, 1023, 970, 858, 828; dH
(270MHz, CDCl3)0.92(6H, t,3J=6.8Hz, 2CH3), 1.34–1.56(16H, m),
1.83(4H,m),4.03(4H,t,3J=6.7Hz,2OCH2),6.98(4H,d,3J=8.6Hz),
7.24 (4H, d, 3J = 8.6 Hz), 7.53 (2H, s), 7.67–7.70 (2H, m), 8.06–8.09
(2H, m); dC (67.8 MHz, CDCl3) 14.1 (2C, CH3), 22.6 (2C, CH2),
26.1 (2C, CH2), 29.1 (2C, CH2), 29.4 (2C, CH2), 31.8 (2C, CH2),
67.9 (2C, OCH2), 114.1 (4C, CH), 126.7 (2C, Cquat), 129.2 (4C, CH),
132.9 (2C, Cquat), 133.6 (2C, CH), 134.2 (2C, CH), 134.3 (2C, Cquat),
1,4,5,8-Tetrakis(4-ethoxyphenyl)anthraquinone (9j); general
procedure: Analogous to the synthesis of 9i: yellow orange solid;
m.p. 307°C; (Found: MH+, 689.2910. C46H41O6 requires MH+,
689.2903 [FAB]). nmax (KBr/cm-1) 3002, 1673, 1245, 1205, 831;
d
H (270 MHz, CDCl3) 1.42 (12H, t, 3J = 7.0 Hz, 4 CH3), 4.06 (8H, q,
136.6 (2C, CH), 143.6 (2C, Cquat), 158.5 (2C, Cquat), 184.3 (2C, Cquat
,
3J=7.0Hz, 4OCH2), 6.82(8H, d, 3J=8.6Hz), 7.19(8H, d, 3J=8.6Hz),
7.47 (4H, s); dC (67.8 MHz, CDCl3) 14.9 (4C, CH3), 63.4 (4C,
OCH2), 113.9 (8C, CH), 130.3 (8C, CH), 131.7 (4C, Cquat), 134.4
(4C, CH), 135.6 (4C, Cquat), 140.3 (4C, Cquat), 158.4 (4C, Cquat), 188.5
(2C, Cquat, CO); MS (FAB, 3-nitrobenzyl alcohol) m/z (%) = 689
(MH+) (27).
CO); MS (FAB, 3-nitrobenzyl alcohol) m/z (%) 589 (MH+) (30).
1,4-Bis(4-decyloxyphenyl)anthraquinone (9d); general procedure
B: Orange-yellow solid, m.p. 197°C; (Found: MH+, 673.4277.
C46H57O4 requires MH+, 673.4275 [FAB]). nmax (KBr/cm-1) 2950,
2867, 1673, 1604, 1515, 1280, 1243, 1204, 1023, 971, 857, 828;
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dH (270 MHz, CDCl3) 0.89 (6H, t, J = 7.0 Hz, 2 CH3), 1.29–1.55
1-Hydroxy-4,5,8-tris(4-methoxyphenyl)anthraquinone (9k); general
procedure B: Analogous to the synthesis of 9i: reddish solid; m.p.
238°C; (Found: MH+, 543.1805. C35H27O6 requires MH+, 543.1808
[FAB]). nmax (KBr/cm-1) 3430 (bs, OH), 3054, 3002, 1673, 1515,
1461, 1295, 1243, 1205, 1179, 1031, 827, 754; dH (270 MHz,
CDCl3) 3.82 (3H, s, OCH3), 3.83 (3H, s, OCH3), 3.90 (3H, s, OCH3),
(28H, m), 1.78 – 1.86 (4H, m), 4.03 (4H, t, 3J 6.5 Hz, 2 OCH2), 6.98
(4H, d, 3J = 8.6 Hz), 7.24 (4H, d, 3J = 8.6 Hz), 7.53 (2H, s), 7.67–7.71
(2H, m), 8.06–8.09 (2H, m); dC (67.8 MHz, CDCl3) 14.1 (2C, CH3),
22.7 (2C, CH2), 26.1 (2C, CH2), 29.3 (2C, CH2), 29.4 (2C, CH2), 29.5
(2C, CH2), 29.6 (2C, CH2), 29.7 (2C, CH2), 31.9 (2C, CH2), 67.9 (2C,
OCH2), 114.2 (4C, CH), 126.7 (2C, Cquat), 129.2 (4C, CH), 132.9 (2C,
Cquat), 133.6 (2C,CH), 134.2 (2C, CH), 134.3 (2C, Cquat), 136.6 (2C,
CH), 143.6 (2C, Cquat), 158.5 (2C, Cquat), 184.3 (2C, Cquat, CO); MS
(FAB, 3-nitrobenzyl alcohol) m/z (%) = 673 (MH+) (8), 672 (M+) (10).
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6.84 (2H, d, J = 8.6 Hz), 6.87 (2H, d, J = 8.6 Hz), 7.00 (2H, d,
3J = 8.6 Hz), 7.14–7.29 (7H, m), 7.46 (1H, d, J = 7.8 Hz), 7.47
(1H, d, J = 8.4 Hz), 7.56 (1H, d, J = 7.8 Hz), 12.21 (s, 1H, OH);
dC (67.8 MHz, CDCl3) 55.2 (2C, OCH3), 55.3 (OCH3), 113.6 (6C,
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