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K. Chanawanno et al. / European Journal of Medicinal Chemistry 45 (2010) 4199e4208
H-500), 4.11 (q, J ¼ 6.9, OeCH2), 1.41 (t, J ¼ 6.9, CH3), 7.66 (d, J ¼ 8.7, H-
2000, H-6000), 6.82 (d, J ¼ 8.7, H-3000, H-5000), 3.78 (s, 4000-OCH3). Anal.
calcd. for C23H25NO5S: C, 64.62; H, 5.89; N, 3.28; S, 7.50; O, 18.71.
Found: C, 64.55; H, 6.10; N, 3.20; S, 7.49; O, 18.66.
evaporated to give a yellow solid. The resultant yellow solid was
filtered off, washed with diethyl ether, dried in vacuo and purified
by recrystallization. M.p. 218e219 ꢂC, 0.20 g (89%) yield. UV
(CH3OH) lmax (nm): 328.6, 521.1; IR (KBr, cmꢀ1):
nC]C; 1600 s,
n
CeN; 1280 s,
n
S ¼ O s; 1167; 1H NMR (d6-DMSO mixed with
2.2.2.3. (E)-2-(4-ethoxystyryl)-1-methylpyridinium 4-bromobenzen-
esulfonate (8). M.p. 190e193 ꢂC, 0.20 g (73%) yield. UV (CH3OH)
CDCl3):
d
4.50 (s,1-CH3), 3.15 (s, N-(CH3)2), 8.42 (d, J ¼ 9.0, H-3), 8.71
(d, J ¼ 9.0, H-4), 8.35 (d, J ¼ 7.8, H-5), 7.80 (t, J ¼ 7.8, H-6), 8.12 (t,
J ¼ 7.8, H-7), 8.35 (d, J ¼ 7.8, H-8), 7.60 (d, J ¼ 15.6, H-10), 8.00 (d,
J ¼ 15.6, H-20), 7.73 (d, J ¼ 8.7, H-200, H-600), 6.80 (d, J ¼ 8.7, H-300, H-
500), 7.10 (d, J ¼ 8.1, H-2000, H-6000), 7.55 (d, J ¼ 8.1, H-3000, H-5000), 2.28 (s,
4000-CH3). Anal. calcd. for C27H28N2O3S: C, 70.71; H, 6.13; N, 6.08; S,
6.96; O, 10.42. Found: C, 70.49; H, 6.26; N, 6.19; S, 6.94; O, 10.12.
Compounds 12e15 were synthesized with identical procedure
of 11 by replacing silver (I) 4-methylbenzenesulfonate with silver
(I) 4-methoxybenzenesulfonate (for 12), silver (I) 4-bromobenze-
nesulfonate (for 13), silver (I) 4-chlorobenzenesulfonate (for 14),
and silver (I) 4-aminobenzenesulfonate (for 15). All of the resulting
solids were further purified by recrystallization.
lmax (nm): 210.0, 266.0, 366.0; IR (KBr, cmꢀ1):
nC]C; 1595 s,
n
C ¼ O; 1224 s,
n
S ¼ O; 1179 s; 1H NMR (d6-DMSO mixed with
CDCl3):
d
4.40 (s, 1-CH3), 8.42 (d, J ¼ 8.7, H-3), 8.51 (t, J ¼ 8.7, H-4),
7.64 (t, J ¼ 8.7, H-5), 8.91 (d, J ¼ 8.7, H-6), 7.41 (d, J ¼ 15.9, H-10), 7.85
(d, J ¼ 15.9, H-20), 7.80 (d, J ¼ 8.7, H-200, H-600), 6.91 (d, J ¼ 8.7, H-300,
H-500), 4.12 (q, J ¼ 6.9, OeCH2),1.43 (t, J ¼ 6.9, CH3), 7.86 (d, J ¼ 8.7, H-
2000, H-6000), 6.98 (d,
J
¼
8.7, H-3000, H-5000). Anal. calcd. for
C22H22BrNO4S: C, 55.47; H, 4.65; N, 2.94; S, 6.73; O, 13.43. Found: C,
55.44; H, 4.60; N, 2.87; S, 6.61; O, 13.69.
2.2.2.4. (E)-2-(4-ethoxystyryl)-1-methylpyridinium 4-chlorobenzene-
sulfonate (9). M.p. 185e186 ꢂC, 0.24 g (85%) yield. UV (CH3OH) lmax
(nm): 202.0, 222.0, 366.0; IR (KBr, cmꢀ1):
nC]C; 1627 s,
n
C ¼ O;
2.2.3.2. (E)-2-(4-(dimethylamino)styryl)-1-methylquinolinium 4-me-
1230 s,
n
S ¼ O; 1179 s; 1H NMR (d6-DMSO mixed with CDCl3):
d
4.40
thoxybenzenesulfonate (12). M.p. 279e281 ꢂC, 0.26 g (81%) yield. UV
(s,1-CH3), 8.42 (d, J ¼ 7.5, H-3), 8.30 (t, J ¼ 7.5, H-4), 7.77 (d, J ¼ 7.5, H-
5), 8.90 (d, J ¼ 7.5, H-6), 7.41 (d, J ¼ 15.9, H-10), 7.84 (d, J ¼ 15.9, H-20),
7.71 (d, J ¼ 8.4, H-200, H-600), 6.98 (d, J ¼ 8.4, H-300, H-500), 4.12 (q,
J ¼ 6.9, OeCH2), 1.42 (t, J ¼ 6.9, CH3), 7.72 (d, J ¼ 8.4, H-2000, H-6000),
7.30 (d, J ¼ 8.4, H-3000, H-5000). Anal. calcd. for C22H22ClNO4S: C, 61.18;
H, 5.13; N, 3.24; S, 7.42; O, 14.82. Found: C, 60.95; H, 5.09; N, 3.22; S,
7.43; O, 15.11.
(CH3OH) lmax (nm): 311.6, 524.5; IR (KBr, cmꢀ1):
nC]C; 1568 s,
n
CeN; 1339 s,
n
S ¼ O; 1162 s; 1H NMR (d6-DMSO mixed with
CDCl3):
d
4.50 (s, 1-CH3), 3.13 (s, N-(CH3)2), 8.41 (d, J ¼ 9.0, H-3), 8.70
(d, J ¼ 9.0, H-4), 8.16 (d, J ¼ 7.9, H-5), 7.81 (t, J ¼ 7.9, H-6), 7.99 (t,
J ¼ 7.9, H-7), 8.31 (d, J ¼ 7.9, H-8), 7.50 (d, J ¼ 15.3, H-10), 8.09 (d,
J 0¼0 15.3, H-20), 7.76 (d, J ¼ 8.7, H-200, H-600), 6.80 (d, J ¼ 8.7, H-300, H-
5 ), 6.81 (d, J ¼ 8.1, H-2000, H-6000), 7.69 (d, J ¼ 8.1, H-3000, H-5000), 3.82 (s,
4000-OCH3). Anal. calcd. for C27H28N2O4S: C, 68.04; H, 5.92; N, 5.88; S,
6.73; O, 13.43. Found: C, 68.11; H, 5.89; N, 5.79; S, 6.76; O, 13.45.
2.2.2.5. (E)-2-(4-ethoxystyryl)-1-methylpyridinium 4-aminobenzen-
esulfonate (10). M.p. 216e218 ꢂC, 0.20 g (68%) yield. UV (CH3OH)
lmax (nm): 204.0, 252.0, 366.0; IR (KBr, cmꢀ1):
n
C]C; 1603 s,
2.2.3.3. (E)-2-(4-(dimethylamino)styryl)-1-methylquinolinium 4-bro-
n
C ¼ O; 1230 s,
n
S ¼ O; 1179 s; 1H NMR (d6-DMSO mixed with
mobenzenesulfonate (13). M.p. 282e283 ꢂC, 0.18 g (59%) yield. UV
CDCl3):
d
4.40 (s, 1-CH3), 8.43 (d, J ¼ 8.4, H-3), 8.39 (t, J ¼ 8.4, H-4),
(CH3OH) lmax (nm): 289.5, 328.0, 522.2; IR (KBr, cmꢀ1):
nC]C;
7.94 (d, J ¼ 8.4, H-5), 8.89 (d, J ¼ 8.4, H-6), 7.39 (d, J ¼ 15.9, H-10), 7.82
(d, J ¼ 15.9, H-20), 7.76 (d, J ¼ 8.4, H-200, H-600), 6.98 (d, J ¼ 8.4, H-300,
H-500), 4.12 (q, J ¼ 6.9, OeCH2), 1.43 (t, J ¼ 6.9, CH3), 7.46 (d, J ¼ 8.4,
H-2000, H-6000), 6.52 (d, J ¼ 8.4, H-3000, H-5000), 4.72 (br s, 4000-NH2). Anal.
calcd. for C22H24N2O4S: C, 64.06; H, 5.86; N, 6.79; S, 7.77; O, 15.52.
Found: C, 64.00; H, 6.11; N, 6.70; S, 7.69; O, 15.50.
1569 s,
CDCl3):
n
d
CeN; 1377 s,
n
S ¼ O; 1189 s; 1H NMR (d6-DMSO mixed with
4.52 (s, 1-CH3), 2.50 (s, N-(CH3)2), 8.41 (d, J ¼ 9.0, H-3), 8.84
(d, J ¼ 9.0, H-4), 8.14 (d, J ¼ 7.8, H-5), 7.88 (t, J ¼ 7.8, H-6), 8.01 (t,
J ¼ 7.8, H-7), 8.37 (d, J ¼ 7.8, H-8), 7.72 (d, J ¼ 15.3, H-10), 8.05 (d,
J ¼ 15.3, H-20), 7.82 (d, J ¼ 7.5, H-200, H-600), 6.74 (d, J ¼ 7.5, H-300, H-
500), 6.95 (d, J ¼ 8.7, H-2000, H-6000), 7.63 (d, J ¼ 8.7, H-3000, H-5000). Anal.
calcd. for C26H25BrN2O3S: C, 59.43; H, 4.80; N, 5.33; S, 6.10; O, 9.13.
Found: C, 59.24; H, 4.77; N, 5.51; S, 6.01; O, 9.17.
2.2.3. (E)-2-(4-(dimethylamino)styryl)-1-methylquinolinium
iodide (QAM)
(E)-2-(4-(dimethylamino)styryl)-1-methylquinoliniumiodidewas
synthesized by mixing a solution (1:1:1 mole ratio) of 1,2-dime-
thylquinolinium iodide (2.00 g, 7.01 mmol) 4-dimethylamino-
benzaldehyde (1.05 g, 7.01 mmol) and piperidine (0.69 ml, 7.01 mmol)
in hot methanol (50 ml). The resulting solution was refluxed for 6 h
under a nitrogen atmosphere. The resulting solid was filtered off,
washed with methanol, dried in vacuo and recrystallized from
methanol to give green crystals. M.p. 218e219 ꢂC, 2.52 g (89%) yield.
UV (CH3OH) lmax (nm): 205.3, 221.9, 280.9, 326.8, 521.1; IR (KBr,
2.2.3.4. (E)-2-(4-(dimethylamino)styryl)-1-methylquinolinium 4-chl-
orobenzenesulfonate (14). M.p. 284e285 ꢂC, 0.17 g (54%) yield. UV
(CH3OH) lmax (nm): 289.5, 326.9, 522.8; IR (KBr, cmꢀ1):
nC]C;
1570 s,
nCeN; 1335 s,
n
S ¼ O; 1164 s; 1H NMR (d6-DMSO mixed with
CDCl3):
d
4.50 (s, 1-CH3), 3.12 (s, N-(CH3)2), 8.46 (d, J ¼ 9.0, H-3), 8.90
(d, J ¼ 9.0, H-4), 8.35 (d, J ¼ 7.8, H-5), 7.91 (t, J ¼ 7.8, H-6), 8.12 (t,
J ¼ 7.8, H-7), 8.40 (d, J ¼ 7.8, H-8), 7.70 (d, J ¼ 15.3, H-10), 8.09 (d,
J ¼ 15.3, H-20), 7.88 (d, J ¼ 8.7, H-200, H-600), 7.05 (d, J ¼ 8.7, H-300, H-
500), 7.30 (d, J ¼ 8.1, H-2000, H-6000), 7.63 (d, J ¼ 8.1, H-3000, H-5000). Anal.
calcd. for C26H25ClN2O3S: C, 64.92; H, 5.24; N, 5.82; S, 6.67; O, 9.98.
Found: C, 64.81; H, 5.44; N, 5.86; S, 6.65; O, 9.99.
cmꢀ1):
CDCl3):
nC]C; 1600 s, n
CeN; 1280 s; 1H NMR (d6-DMSO mixed with
d
4.50(s,1-CH3), 3.15 (s, N-(CH3)2), 8.40 (d, J ¼ 9.0, H-3), 8.70 (d,
J ¼ 9.0, H-4), 8.14 (d, J ¼ 7.8, H-5), 7.80 (t, J ¼ 7.8, H-6), 8.01 (t, J ¼ 7.8, H-
7), 8.31 (d, J ¼ 7.5, H-8), 7.50 (d, J ¼ 15.3, H-10), 8.05 (d, J ¼ 15.3, H-20),
7.78 (d, J ¼ 8.7, H-200, H-600), 6.80 (d, J ¼ 8.7, H-300, H-500). Anal. calcd. for
C20H21IN2: C, 57.70; H, 5.08; N, 6.74. Found: C, 57.65; H, 5.10; N, 6.90.
2.2.3.5. (E)-2-(4-(dimethylamino)styryl)-1-methylquinolinium 4-am-
inobenzenesulfonate (15). M.p. 265e266 ꢂC, 0.29 g (89%) yield. UV
(CH3OH) lmax (nm): 203.0, 235.0, 252.0, 282.0, 327.0, 522.0; IR (KBr,
cmꢀ1):
DMSO mixed with CDCl3):
n
C]C; 1582 s,
n
CeN; 1334 s,
n
S ¼ O; 1182 s; 1H NMR (d6-
2.2.3.1. (E)-2-(4-(dimethylamino)styryl)-1-methylquinolinium 4-met
hylbenzenesulfonate (11). A 0.23 g (0.58 mmol) solution of QAM in
hot methanol (50 ml) was mixed with 0.20 g (0.58 mmol) of silver
(I) 4-methylbenzenesulfonate in hot methanol (50 ml). The mixture
turned to green and cloudy immediately. After stirring for 30 min,
the precipitate of silver iodide was filtered and the filtrate was
d 4.49 (s, 1-CH3), 3.12 (s, N-(CH3)2), 8.40
(d, J ¼ 8.2, H-3), 8.69 (d, J ¼ 8.2, H-4), 8.30 (d, J ¼ 8.2, H-5), 7.78 (t,
J ¼ 8.2, H-6), 8.08 (t, J ¼ 7.8, H-7), 8.18 (d, J ¼ 7.8, H-8), 7.47 (d,
J ¼ 15.9, H-10), 7.90 (d, J ¼ 15.9, H-20), 7.75 (d, J ¼ 8.4, H-200, H-600),
6.52 (d, J ¼ 8.4, H-300, H-500), 7.89 (d, J ¼ 8.1, H-2000, H-6000), 6.78 (d,
J
¼
8.1, H-3000, H-5000), 4.65 (br s, 4000-NH2). Anal. calcd. for