W. Wang et al. / European Journal of Medicinal Chemistry 56 (2012) 320e331
329
(CH2)10eCH3), 0.90 (t, J ¼ 6.0 Hz, 6.0H, 2ꢃ (CH2)11eCH3); Anal.
Calcd for C31H44BrNO5$1.5H2O: C 60.29, H 7.67, N 2.27; found: C
60.12, H 7.19, N 2.05; ESI-MS m/z 512.1 (M ꢂ Br)þ.
3.37 (s, 6.0H, Ne(CH3)2), 1.27 (m, 64.0H, 2ꢃ (CH2)16-CH3), 0.90 (t,
J
¼
5.6 Hz, 6.0H, 2ꢃ (CH2)17eCH3); Anal. Calcd for
C37H56BrNO5$1.0H2O: C 64.15, H 8.44, N 2.02; found: C 64.56, H
7.96, N 1.87; ESI-MS m/z 595.0 (M ꢂ Br)þ.
4.2.5.4. N-((8-Hydroxy-1,3-dimethoxy-9,10-anthraquinone-6-yl)met-
hyl)-N,N-dimethyltetradecan-1-aminium bromide (11d) and N-((1-
hydroxy-3,8-dimethoxy-9,10-anthraquinone-6-yl)methyl)-N,N-dime-
thyltetradecan-1-aminium bromide (12d). According to the general
procedure, 9 and 10 were treated with N,N-dimethyltetradecan-1-
amine, and then purified on silica gel column using dichloro-
methane, chloroform/ethanol (v/v 50:1), chloroform/ethanol (v/v
20:1) as eluent to give compounds 11d and 12d.
4.2.5.7. N-((8-Hydroxy-1,3-dimethoxy-9,10-anthraquinone-6-yl)met-
hyl)-N-methyl-N-octyloctan-1-aminium bromide (11g) and N-((1-
hydroxy-3,8-dimethoxy-9,10-anthraquinone-6-yl)methyl)-N-methyl-
N-octyloctan-1-aminium bromide (12g). According to the general
procedure, 9 and 10 were treated with N-methyl-N-octyloctan-1-
amine, and then purified on silica gel column using dichloro-
methane, chloroform/ethanol (v/v 50:1), chloroform/ethanol (v/v
25:1) as eluent to give compounds 11g and 12g.
Yield: 66.8%; orange solid; mp: 191e193 ꢁC; IR (KBr)
3017, 2921, 2851, 1670, 1632, 1596, 1335, 1267, 924, 609 cmꢂ1
NMR (400 MHz, CDCl3) : 13.08 (s, 1.0H, OH), 13.05 (s, 1.0H, OH),
n
: 3386,
;
1H
Yield: 66.4%; orange powder; mp: 91e93 ꢁC; IR (KBr)
3009, 2925, 2855, 1674, 1633, 1596, 1335, 1265, 923, 607 cmꢂ1
NMR (400 MHz, CDCl3) : 13.04 (s, 2.0H, OH), 8.65 (s, 1.0H, AreH),
n
: 3401,
d
;
1H
8.60 (s,1.0H, AreH), 7.82 (s,1.0H, AreH), 7.77 (s,1.0H, AreH), 7.69 (s,
1.0H, AreH), 7.40 (d, J ¼ 2.0 Hz, 1.0H, AreH), 7.27 (d, J ¼ 2.4 Hz, 1.0H,
AreH, overlapped with CHCl3), 6.79 (d, J ¼ 2.0 Hz, 1.0H, AreH), 6.71
(d, J ¼ 2.0 Hz, 1.0H, AreH), 5.38 (s, 2.0H, AreCH2eN), 5.22 (s, 2.0H,
AreCH2eN), 4.23 (s, 3.0H, OCH3), 4.05 (s, 3.0H, OCH3), 4.03 (s, 3.0H,
OCH3), 3.95 (s, 3.0H, OCH3), 3.60 (m, 4.0H, 2ꢃ NeCH2eC13H27), 3.41
(s, 6.0H, Ne(CH3)2), 3.37 (s, 6.0H, Ne(CH3)2), 1.27 (m, 48.0H, 2ꢃ
(CH2)12eCH3), 0.90 (t, J ¼ 5.6 Hz, 6.0H, 2ꢃ (CH2)13eCH3); Anal.
Calcd for C33H48BrNO5$1.5H2O: C 61.39, H 7.96, N 2.17; found: C
61.36, H 7.50, N 2.02; ESI-MS m/z 539.2 (M ꢂ Br)þ.
d
7.77 (s,1.0H, AreH), 7.75 (s,1.0H, AreH), 7.71 (s,1.0H, AreH), 7.40 (d,
J ¼ 1.6 Hz, 1.0H, AreH), 7.27 (d, J ¼ 2.0 Hz, 1.0H, AreH, overlapped
with CHCl3), 6.79 (d, J ¼ 1.6 Hz, 1.0H, AreH), 6.71 (d, J ¼ 2.0 Hz, 1.0H,
AreH), 5.33 (s, 2.0H, AreCH2eN), 5.20 (s, 2.0H, AreCH2eN), 4.29 (s,
3.0H, OCH3), 4.05 (s, 3.0H, OCH3), 4.02 (s, 3.0H, OCH3), 3.95 (s, 3.0H,
OCH3), 3.50 (m, 8.0H, 2ꢃ Ne(CH2eC7H15)2), 3.35 (s, 3.0H, NeCH3),
3.31 (s, 3.0H, NeCH3), 1.43e1.30 (m, 48.0H, 4ꢃ (CH2)6eCH3),
0.92e0.89 (m, 12.0H, 4ꢃ (CH2)7eCH3); Anal. Calcd for
C34H50BrNO5$1.0H2O: C 62.76, H 8.06, N 2.15; found: C 62.27, H 7.57,
N 1.92; ESI-MS m/z 553.2 (M ꢂ Br)þ.
4.2.5.5. N-((8-Hydroxy-1,3-dimethoxy-9,10-anthraquinone-6-yl)met-
hyl)-N,N-dimethylhexadecan-1-aminium bromide (11e) and N-((1-
hydroxy-3,8-dimethoxy-9,10-anthraquinone-6-yl)methyl)-N,N-dime-
thylhexadecan-1-aminium bromide (12e). According to the general
procedure, 9 and 10 were treated with N,N-dimethylhexadecan-1-
amine, and then purified on silica gel column using dichloro-
methane, chloroform/ethanol (v/v 50:1), chloroform/ethanol (v/v
20:1) as eluent to give compounds 11e and 12e.
4.2.5.8. N-Decyl-N-((8-hydroxy-1,3-dimethoxy-9,10-anthraquinone-
6-yl)methyl)-N-methyldecan-1-aminium bromide (11h) and N-decyl-
N-((1-hydroxy-3,8-dimethoxy-9,10-anthraquinone-6-yl)methyl)-N-
methyldecan-1-aminium bromide (12h). According to the general
procedure, 9 and 10 were treated with N-decyl-N-methyldecan-1-
amine, and then purified on silica gel column using dichloro-
methane, chloroform/ethanol (v/v 50:1), chloroform/ethanol (v/v
25:1) as eluent to give compounds 11h and 12h.
Yield: 97.8%; orange solid; mp: 195e196 ꢁC; IR (KBr)
3018, 2919, 2850, 1670, 1632, 1596, 1335, 1267, 924, 609 cmꢂ1
NMR (400 MHz, CDCl3) : 13.01 (s, 1.0H, OH), 13.00 (s, 1.0H, OH),
n
: 3430,
;
1H
Yield: 79.6%; orange powder; mp: 81e83 ꢁC; IR (KBr)
3006, 2925, 2854, 1675, 1633, 1596, 1329, 1265, 924, 608 cmꢂ1; 1H
NMR (400 MHz, CDCl3) : 13.02 (s, 2.0H, OH), 8.63 (s, 1.0H, AreH),
n: 3413,
d
8.52 (s,1.0H, AreH), 7.80 (s,1.0H, AreH), 7.75 (s,1.0H, AreH), 7.68 (s,
1.0H, AreH), 7.32 (d, J ¼ 2.0 Hz, 1.0H, AreH), 7.21 (d, J ¼ 2.0 Hz, 1.0H,
AreH), 6.75 (d, J ¼ 2.0 Hz, 1.0H, AreH), 6.68 (d, J ¼ 2.0 Hz, 1.0H,
AreH), 5.43 (s, 2.0H, AreCH2eN), 5.28 (s, 2.0H, AreCH2eN), 4.21 (s,
3.0H, OCH3), 4.03 (s, 3.0H, OCH3), 4.02 (s, 3.0H, OCH3), 3.94 (s, 3.0H,
OCH3), 3.60 (m, 4.0H, 2ꢃ NeCH2eC15H31), 3.412 (s, 6.0H,
Ne(CH3)2), 3.38 (s, 6.0H, Ne(CH3)2), 1.26 (m, 56.0H, 2ꢃ
(CH2)14eCH3), 0.90 (t, J ¼ 5.6 Hz, 6.0H, 2ꢃ (CH2)15eCH3); Anal.
Calcd for C35H52BrNO5$0.5H2O: C 64.11, H 8.15, N 2.14; found: C
64.04, H 7.89, N 1.89; ESI-MS m/z 567.1 (M ꢂ Br)þ.
d
7.77 (s,1.0H, AreH), 7.74 (s, 1.0H, AreH), 7.71 (s,1.0H, AreH), 7.38 (d,
J ¼ 2.0 Hz, 1.0H, AreH), 7.26 (d, J ¼ 2.0 Hz, 1.0H, AreH, overlapped
with CHCl3), 6.77 (d, J ¼ 2.0 Hz, 1.0H, AreH), 6.69 (d, J ¼ 2.0 Hz,1.0H,
AreH), 5.35 (s, 2.0H, AreCH2eN), 5.22 (s, 2.0H, AreCH2eN), 4.21 (s,
3.0H, OCH3), 4.04 (s, 3.0H, OCH3), 4.02 (s, 3.0H, OCH3), 3.95 (s, 3.0H,
OCH3), 3.49 (m, 8.0H, 2ꢃ Ne(CH2eC9H19)2), 3.35 (s, 3.0H, NeCH3),
3.30 (s, 3.0H, NeCH3), 1.41e1.23 (m, 64.0H, 4ꢃ (CH2)8eCH3), 0.90 (t,
J
¼
5.6 Hz, 12.0H, 4ꢃ (CH2)9eCH3); Anal. Calcd for
C38H58BrNO5$0.7H2O: C 65.07, H 8.54, N 2.00; found: C 64.97, H
8.16, N 1.76; ESI-MS m/z 609.2 (M ꢂ Br)þ.
4.2.5.6. N-((8-Hydroxy-1,3-dimethoxy-9,10-anthraquinone-6-yl)met-
hyl)-N,N-dimethyloctadecan-1-aminium bromide (11f) and N-(1-
hydroxy-3,8-dimethoxy-9,10-anthraquinone-6-yl)-N,N-dimethylocta-
decan-1-aminium bromide (12f). According to the general proce-
dure, 9 and 10 were treated with N,N-dimethyloctadecan-1-amine,
and then purified on silica gel column using dichloromethane,
chloroform/ethanol (v/v 50:1), chloroform/ethanol (v/v 25:1) as
eluent to give compounds 11f and 12f.
4.2.5.9. N-Dodecyl-N-((8-hydroxy-1,3-dimethoxy-9,10-anthraquinone-
6-yl)methyl)-N-methyldodecan-1-aminium
bromide
(11i)
and
N-dodecyl-N-((1-hydroxy-3,8-dimethoxy-9,10-anthraquinone-6-yl)
methyl)-N-methyldodecan-1-aminium bromide (12i). According
to the general procedure, 9 and 10 were treated with N-dodecyl-
N-methyldodecan-1-amine, and then purified on silica gel column
using dichloromethane, chloroform/ethanol (v/v 50:1), chloro-
form/ethanol (v/v 30:1) as eluent to give compounds 11i and 12i.
Yield: 87.8%; orange solid; mp: 189e191 ꢁC; IR (KBr)
3013, 2919, 2850, 1670, 1632, 1596, 1334, 1267, 925, 609 cmꢂ1
NMR (400 MHz, CDCl3) : 13.09 (s, 1.0H, OH), 13.06 (s, 1.0H, OH),
n
: 3428,
;
1H
Yield: 72.3%; orange powder; mp: 81e83 ꢁC; IR (KBr)
3009, 2924, 2853, 1675, 1633, 1596, 1323, 1265, 922, 607 cmꢂ1; 1H
NMR (400 MHz, CDCl3) : 13.04 (s, 2.0H, OH), 8.64 (s, 1.0H, AreH),
n: 3434,
d
8.64 (s,1.0H, AreH), 7.82 (s,1.0H, AreH), 7.77 (s,1.0H, AreH), 7.69 (s,
1.0H, AreH), 7.42 (d, J ¼ 2.0 Hz, 1.0H, AreH), 7.29 (s, 1.0H, AreH),
6.81 (d, J ¼ 2.0 Hz, 1.0H, AreH), 6.72 (d, J ¼ 2.0 Hz, 1.0H, AreH),
5.37 (s, 2.0H, AreCH2eN), 5.19 (s, 2.0H, AreCH2eN), 4.24 (s, 3.0H,
OCH3), 4.06 (s, 3.0H, OCH3), 4.03 (s, 3.0H, OCH3), 3.95 (s, 3.0H,
OCH3), 3.60 (m, 4.0H, 2ꢃ NeCH2eC17H35), 3.41 (s, 6.0H, Ne(CH3)2),
d
7.77 (s, 1.0H, AreH), 7.75 (s, 1.0H, AreH), 7.72 (s, 1.0H, AreH), 7.39 (s,
1.0H, AreH), 7.29 (s, 1.0H, AreH, overlapped with CHCl3), 6.78 (s,
1.0H, AreH), 6.70 (s, 1.0H, AreH), 5.34 (s, 2.0H, AreCH2eN), 5.21 (s,
2.0H, AreCH2eN), 4.22 (s, 3.0H, OCH3), 4.04 (s, 3.0H, OCH3), 4.02 (s,
3.0H, OCH3), 3.95 (s, 3.0H, OCH3), 3.50 (m, 8.0H, 2ꢃ