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H. Prinz et al. / Bioorg. Med. Chem. 19 (2011) 4183–4191
manner as described for the preparation of 15e. Purification by
chromatography (EE/PE 8:2) afforded 15g as red powder
(0.08 g, 6% yield): mp 210–212 °C; FTIR 1667 cmÀ1 1H NMR
for the preparation of 17d. Purification by silica gel chromatogra-
phy (EE/PE 1:1) afforded 17a as a red powder (1.20 g, 20% yield):
a
;
mp 173 °C; FTIR 1629 cmÀ1 1H NMR (CDCl3, 400 MHz) d 9.17 (s,
;
(CDCl3, 400 MHz) d 8.31–7.26 (m, 8H), 6.08 (s, 2H), 3.88 (s, 3H),
3.77 (s, 6H); MS m/z 373 (49), 360 (4), 359 (25), 358 (100), 316
(2), 315 (20), 314 (81), 286 (47) ; Anal. (C23H19NO4) C, H, N.
1H), 8.47–8.45 (m, 1H), 8.39 (d, 1H, J = 8.22 Hz), 8.30 (d, 1H,
J = 7.83 Hz), 8.23 (dd, 1H, J = 7.8 Hz, J = 0.8 Hz), 7.80–7.76 (m, 1H),
7.70–7.61 (m, 2H), 7.50–7.46 (m, 1H), 7.38–7.32 (m, 4H), 7.04–
6.80 (m, 1H); MS m/z 298 (100), 297 (88), 270 (13), 269 (14); Anal.
(C20H14N2O) C, H, N, Calcd: C, 80.52; H, 4.73; N, 9.39. Found: C,
80.14; H, 4.60; N, 9.15.
4.2.10. 10-(3-Hydroxy-4-methoxy-phenylimino)-10H-
anthracen-9-one (15h)
The title compound was prepared from 14a (2.14 g, 3.66 mmol)
and 5-amino-2-methoxyphenol (1.02 g, 7.32 mmol) as described
for the preparation of 15e. Purification by chromatography (MC/
MeOH 9.8:0.2) afforded 15h as orange-red crystals (0.21 g, 18%
4.2.15. 9-[2-(4-Methoxyphenyl)hydrazone]-9,10-
anthracenedione (17b)50
The title compound was prepared from 13a (3.88 g, 20 mmol)
and 4-methoxyaniline (2.46 g, 20.0 mmol) in a similar manner as
described for the preparation of 17d. Purification by silica gel chro-
matography (EE/PE 1:1) afforded 17b as a dark-red powder (4.46 g,
yield): mp 171–172 °C; FTIR 3381, 1673 cmÀ1 1H NMR (CDCl3,
;
400 MHz) d 8.45 (d, 1H, J = 7.82 Hz), 8.31–8.25 (m, 2H), 7.74–7.70
(m, 1H), 7.66–7.63 (m, 1H), 7.54–7.50 (m, 1H), 7.41–7.39 (m,
1H), 7.32–7.29 (m, 1H), 6.83 (d, 1H, J = 8.4 Hz), 6.55 (d, 1H,
J = 2.4 Hz), 6.27 (dd, 1H, J = 8.5 Hz, J = 2.5 Hz), 5.69 (s, 1H), 3.92
(s, 3H); MS m/z 331 (3), 330 (22), 329 (100), 316 (2), 315 (20),
314 (81), 286 (47); Anal. (C21H15NO3), Calcd: C, 76.58; H, 4.59; N,
4.25. Found: C, 76.19; H, 4.19; N, 4.08.
68% yield): mp 184–185 °C; FTIR 1651 cmÀ1 1H NMR (CDCl3,
;
400 MHz) d 9.12 (s, 1H), 8.47 (dd, 1H, Jo = 7.82 Hz, J = 0.8 Hz),
8.38 (d, 1H, J = 7.8 Hz), 8.32–8.9 (m, 1H), 8.24–8.22 (m, 1H),
7.81–7.77 (m, 1H), 7.68–7.65 (m, 1H), 7.61–7.57 (m, 1H), 7.49–
7.45 (m, 1H), 7.28 (d, 2H, J = 9.0 Hz), 6.93 (d, 2H, J = 9.0 Hz), 3.81
(s, 3H); MS (APCI) calcd for C21H16N2O2 [M+H]+ 329.13; found
329.1310; Anal. (C21H16N2O2) Calcd: C, 76.81; H, 4.91; N, 8.53.
Found: C, 76.53; H, 4.79; N, 8.38.
4.2.11. 10-(3,4-Methylenedioxyphenylimino)-10H-anthracen-9-
one (15i)
The title compound was prepared from 14a (2.14 g, 3.66 mmol)
and 3,4-(methylenedioxy)aniline (1.00 g, 7.32 mmol) in a similar
manner as described for the preparation of 15e. Purification by
4.2.16. 9-[2-(3-Methoxyphenyl)hydrazone]-9,10-
anthracenedione (17c)
chromatography (MC) afforded 15i as
a
orange-red crystals
The title compound was prepared from 13a (3.88 g,
20.00 mmol) and 3-methoxyaniline (2.46 g, 20 mmol) in a similar
manner as described for the preparation of 17d. Purification by
chromatography (MC) afforded 17c as a fine orange powder
(0.32 g, 27 % yield): mp 148–150 °C; FTIR 1668 cmÀ1
;
1H NMR
(CDCl3, 400 MHz) d 8.44–8.42 (m, 1H), 8.32–8.25 (m, 2H), 7.72–
7.70 (m, 1H), 7.66–7.63 (m, 1H), 7.56–7.52 (m, 1H), 7.43–7.41
(m, 1H), 7.36–7.34 (m, 1H), 6.80 (d, 1H, J = 8.2 Hz), 6.43 (d, 1H,
J = 1.96 Hz), 6.27 (dd, 1H, J = 8.02 Hz, J = 1.96 Hz), 6.07 (s, 2H); MS
(m/z), 342 (23), 328 (44); Anal. (C21H13NO3) Calcd: C, 77.05; H,
4.00; N, 4.28. Found: C, 76.80; H, 3.71; N, 4.06.
(1.83 g, 28% yield): mp 128–131 °C; FTIR 1654 cmÀ1 1H NMR
;
(CDCl3, 300 MHz) d 9.18 (s, 1H), 8.42–8.39 (m, 2H), 8.37–8.35 (m,
1H), 8.28–8.25 (m, 1H), 8.22–8.19 (m, 1H), 7.74–7.71 (m, 1H),
7.69–7.63 (m, 1), 7.58–7.47 (m, 1H), 7.28–7.23 (m, 1H), 7.00–
6.99 (m, 1H), 6.87–6.84 (m, 1H), 6.59–6.55 (m, 1H), 3.87 (s, 3H);
MS (APCI) calcd for C21H16N2O2 [M+H]+ 329.13; found 329.1313;
Anal. (C21H16N2O2) Calcd: C, 76.81; H, 4.91; N, 8.53. Found: C,
76.78; H, 5.00; N, 8.25.
4.2.12. 1,8-Dichloro-[10-(4-methoxy-phenylimino)]-10H-
anthracen-9-one (16a)
The title compound was prepared from 14b (1.02 g, 3.00 mmol)
and 4-methoxyaniline (0.74 g, 6 mmol) in a similar manner as de-
scribed for the preparation of 15e. Purification by chromatography
(EE/PE 1:1) afforded 16a as orange-red crystals (0.35 g, 30% yield):
4.2.17. Preparation of 9-[(2,5-Dimethoxyphenyl)hydrazone)]-
9,10-anthracenedione (17d)
mp 229 °C; FTIR 1685 cmÀ1
;
1H NMR (CDCl3, 400 MHz) d 8.22 dd,
A solution of sodium nitrite (1.4 g, 20 mmol, in 6 mL H2O) was
added to a solution of 2,5-dimethoxyaniline (3.06 g, 20 mmol) in
HCl 37% (6.7 mL)/H2O (21 mL)/THF (5 mL) at 0 °C. Then, this solu-
tion was added dropwise to an ethanolic (60 mL) suspension of
13a (3.88 g, 20 mmol) and NaOH (150 mmol, 6.0 g, in 16 mL
H2O). The mixture was stirred until the reaction was complete
and then poured into ice water (500 mL). The product precipitated
and was collected by filtration and subsequently dried (Dean
stark). Removal of toluene and purification of the residue by col-
umn chromatography gave the product. Purification by silica gel
chromatography (EE/PE 1:1) afforded 17d as dark-red needles
1H, J = 8.2 Hz, J = 1.2 Hz), 7.61–7.59 (m, 1H), 7.56–7.52 (m, 1H),
7.49–7.46 (m, 1H), 7.16–7.12 (m, 1H), 7.09–7.06 (m, 1H), 6.86 (d,
2H, J = 9.0 Hz), 6.81 (d, 2H, J = 9.0 Hz), 3.82 (s, 3H); MS m/z 385
(11), 381 (100), 366 (82); Anal. (C21H13Cl2NO2) Calcd: C, 65.99;
H, 3.43; N, 3.66. Found: C, 65.83; H, 3.10; N, 3.52.
4.2.13. 1,8-Dichloro-[10-(3-hydroxy-4-methoxy-phenylimino)]-
10H-anthracen-9-one (16b)
The title compound was prepared from 14b (1.03 g, 3 mmol)
and 5-amino-2-methoxyphenol (1.60 g, 6 mmol) in a similar man-
ner as described for the preparation of 15e. Purification by chroma-
tography (MC) afforded 16b as fine-red crystals (0.22 g, 18% yield):
(4.37 g, 61% yield): mp 183–184 °C; FTIR 1644, 1521 cmÀ1 1H
;
NMR (CDCl3, 300 MHz) d 9.66 (s, 1H), 8.50–8.48 (m, 1H), 8.41–
8.33 (m, 2H), 8.25–8.22 (m, 1H), 7.82–7.77 (m, 1H), 7.67–7.60
(m, 2H), 7.51–7.45 (m, 1H), 7.36 (d, 1H, J = 3.0 Hz), 6.79 (d, 1H,
J = 8.8 Hz), 6.46 (dd, 1H, J = 8.8 Hz, J = 3 Hz), 3.85 (s, 6H); MS m/z
357.98 (100); Anal. (C22H18N2O3) Calcd: C, 73.73; H, 5.06; N,
7.82. Found: C, 73.92; H, 5.00; N, 7.77.
mp 247 °C; FTIR 3446, 1678 cmÀ1 1H NMR (CDCl3, 400 MHz) d
;
8.20 (dd, 1H, Jo = 7.62 Hz, Jm = 1.17 Hz), 7.61–7.59 (m, 1H), 7.56–
7.54 (m, 1H), 7.49–7.46 (m, 1H), 7.15–7.14 (m, 2H), 6.76 (d, 1H,
J = 8.40 Hz), 6.57 (d, 1H, J = 2.5 Hz), 6.25 (dd, 1H, J = 8.5 Hz,
J = 2.5 Hz), 5.66 (s, 1H), 3.89 (s, 3H); MS m/z 399 (65), 398 (22),
397 (100); Anal. (C21H13Cl2NO3), Calcd: C, 63.34; H, 3.29; N, 3.52.
Found: C, 63.23; H, 3.33; N, 3.32.
4.2.18. 9-[2-(3,4,5-Trimethoxyphenyl)hydrazone]-9,10-
anthracenedione (17e)
4.2.14. 9-[(2-Phenyl)hydrazone]-9,10-anthracenedione (17a)
The title compound was prepared from 13a (3.88 g, 20 mmol)
and aniline (1.86 g, 20 mmol) in a similar manner as described
The title compound was prepared from 13a (3.88 g, 20 mmol)
and 3,4,5-trimethoxyaniline (3.66 g, 20 mmol) in a similar manner
as described for the preparation of 17d. Purification by silica gel