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426 (10.2), 336 (10.6), 337 (4.2), 275 (3.8), 276 (52), 218
(5.8), 215 (4.3), 163 [(M+) – C13H23O2S, 11.8], 149 (36.7),
150 (10.2), 165 (9.4), 166 (10.0), 167 (4.8), 147 (11.0), 148
[(M+) – C13H25NO3S, 10.0], 149 (36.7), 150 (10.2), 136
(16.6), 137 (5.3), 133 (9.8), 134 [(M + 1) – C15H20N3O3,
58.8], 121 (9.5), 118 [M+ – C16H23N3O3, 13.0], 119 (6.3).
(4.1), 149 (26.9), 150 (5.3), 151 (4.1), 137 (4.5), 130 (16.5),
131 (3.7), 121 (6.2), 116 (4.5), 117 (3.3), 118 (7.8), 110 (5.3),
105 (3.3), 107 (4.5), 95 (4.9), 94 (3.3), 93 (6.2), 91 (3.3), 89
(7.4), 87 (7.4), 85 (24.0), 83 (6.2), 82 (3.3), 81 (14.9), 80
(3.7), 76 (31.1), 74 (21.1), 72 (10.3), 71 (4.1); and (6) as pale
yellow oily liquid, 528 mg, (34.5%), Rf = 0.32 (benzene–
diethylether, 6:4 v/v). mmax 3200 (N–H), 3000 (OH), 2900,
2850 (C–H), 1700 (COOH), 1680 (CON), 1650 (CONH),
1600 (phenyl), 1520 (NO2 asym. str.), 1350 (NO2, sym. str.),
1420 (S–CH2), 1360, 1210, 1125 cm–1. The dH and dC values
are given in Tables 4,5. DCI-MS (NH3); m/z (%): 525 [(M +
1)+, C24H35N3O6S2, 22.0], 526 (98.6), 527 (31.0), 524 (58.6),
543 [(M + 18)+, 31.7], 544 (8.9), 541 (8.9), 480 [(M+) –
COOH, 15.0], 471 (9.8), 454 (9.6), 436 (8.2), 419 [(M + 1)+
– SCH(CH3)COOH, 17.2], 405 (7.2), 308 [(M+) –
(C12H23O2S, 17.2], 290 [(M + 1)+ – C10H8N2O3S, 33.1], 289
(9.2), 288 (10.4), 280 [(M+) – C13H25O2S, 10.0], 273 [(M+) –
C10H10N3O3S, 9.6], 271 (9.4), 237 [(M+) – C14H26NO3S,
100.0], 238 (15.8), 239 (10.3), 229 (14.6), 218 (15.8), 207
(37.2), 199 (20.0), 184 (17.9), 180 (18.6), 164 (15.2), 165
(15.0), 166 (15.5), 151 (14.9), 147 (22.7), 138 (28.9), 130
(20.6), 121 (17.9), 108 (15.2), 87 (17.2), 75 (16.5).
Further elution of the column yielded (4) as a yellow oily
liquid, 810 mg (54.0%), Rf = 0.38 (benzene–diethylether,
6:4 v/v). mmax 3250 (N–H), 3050 (OH), 2900, 2850 (C–H),
1725 (COOH), 1685 (CON), 1660 (CONH), 1610 (phenyl),
1525 (NO2 asym. str.), 1355 (NO2, sym. str.), 1430 (S–CH2),
1405, 1260, 1165 cm–1; The dH and dC values are given in
Table 3. DCI-MS (NH3) m/z (%): 498 [(M + 1)+, 14.5], 499
(10.1), 452 [(M+) – CO2H, 10.2], 424 [(M + 1)+ – SCH2CO,
10.4], 425 (4.8), 332 (9.5), 273 (10.4), 274 (7.6), 275 (13.6),
276 [(M + 1)+ – C9H7N2O3S, 72.2], 277 (31.3), 278 (14.0),
258 [(M + 1)+ – C9H9N3O3S, 10.0], 239 (7.2), 240 [(M + 1)+
– C13H22O3S, 91.8], 241 (35.9), 242 (11.8), 230 (10.9), 231
[(M+) – C8H9N3O2S, 25.4], 232 (16.3), 223 [(M+) –
C13H24NO9S, 27.2], 224 (12.2), 210 [(M + 1)+
–
C13H24N2O3S, 39.5], 212 (24.0), 213 (13.1) 214 (6.4), 215
[(M+) – C13H24NO3S, 47.7], 216 (22.2), 217 (8.1), 218
(14.5), 193 (25.0), 194 (12.2), 195 (29.5), 196 (11.3), 176
(11.8), 178 (12.7), 162 (8.1), 163 (8.2), 164 (8.1), 165 (7.9),
166 (40.4), 148 (15.0), 149 (10.0), 150 (9.0), 151 (15.4), 152
(16.3), 153 (7.5), 134 (42.2), 135 (20.0), 136 (32.2), 137
(19.0), 138 (30.0), 139 (18.1), 118 (32.2), 119 (9.5), 110
(8.2), 81 (13.1), 82 (9.0), 83 (14.5), 87 (11.8), 89 (10.4), 91
(12.7), 93 (13.6), 94 (29.0), 95 (17.7), 96 (8.4), 97 (8.6), 99
(20.0), 100 (9.5).
4.1.5. 3-({11-[(2E)-2-(3-nitrobenzylidene)hydrazino]-11-
oxoundecyl}sulfanyl)propanoic acid (7) and
3-[(11-{[2-(3-nitrophenyl)-4-oxo-1,3-thiazinan-3-
yl]amino}-11-oxoundecenyl)sulfanyl]propanoic acid (8)
(reaction of (2) with 3-mercaptopropionic acid)
To a solution of (2) (1.02 g, 3.0 mmol) in anhydrous
benzene (20.0 ml) was added 3-mercaptopropionic acid
(961 mg, 9.0 mmol) and refluxed for 26 h as mentioned above
and then worked up as usual. The products on column chro-
matography (pet. ether (60–80 °C)–diethylether, 1:1 v/v)
yielded a yellow solid and an orange oily liquid. The former
on crystallization (benzene–acetone) afforded (7) as white
crystalline globules, 765 mg (58.0%), m.p. = 98 °C, Rf = 0.46
(benzene–diethylether, 6:4 v/v).
4.1.4. N-[5-methyl-2-(3-nitrophenyl)-4-oxo-1,3-thiazolidin-
3-yl]undec-10-enamide (5) and 2-[(11-{[5-methyl-2-
(3-nitrophenyl)-4-oxo-1,3-thiazolidin-3-yl]amino}-11-
oxoundecyl)sulfanyl]propanoic acid (6) (reaction of (2)
with 2-mercaptopropionic acid)
To a solution of (2) (1.01 g, 3.0 mmol) in anhydrous
benzene (20.0 ml) was added 2-mercaptopropionic acid
(961 mg, 9.0 mmol) and refluxed for 22 h as mentioned
above. The reaction mixture was worked up as usual and the
residue on purification by column chromatography (pet.
ether (60–80 °C)–diethylether, 4:6 v/v) yielded two liquid
compounds (5) as a colorless oily liquid, 536 mg (42.3%),
Rf = 0.46 (benzene–diethylether, 6:4 v/v).
mmax 3175 (N–H), 3040 (OH), 2900, 2800 (C–H), 1730
(COOH), 1645 (CONH), 1605 (phenyl), 1555 (C=N), 1520
(NO2), asym. str.), 1480 (S–CH2), 1340 (NO2, sym. str.),
1415, 1380, 1215, 1110, 800 cm–1; dH (acetone-d6): 8.18,
8.48 (~75%, 25%; 1H, s, H-7), 10.3, 10.66 (~75%, 25%; 1H,
s, NH), 2.31, 2.73 (~25%, 75%; 2H, t, J = 7.48, 7.31, H-2′),
1.56 (2H, br p, J ≈ 7.33, H-3′), 1.31 (12H, br s, H-4′–9′), 1.69
(2H, br p, J ≈ 7.33, H-10′), 2.55 (2H, t, J = 7.33, H-11′), 2.74
(2H, t, J = 7.17, H-1″), 2.57 (2H, t, J = 7.17, H-2″), 12.2 (1H,
br s, COOH), 8.51 (1H, dd, J = 1.99, 1.68, Ar-2), 8.24 (1H,
dd, J = 7.63, 1.83, Ar-4), 7.73 (1H, dd, J = 7.94, 7.63, Ar-5)
8.14 (1H, dd, J = 7.94, 1.98,Ar-6); dH (DMSO-d6): 8.11, 8.29
(~60%, 40%; 1H, s, H-7), 11.41, 11.55 (~60%, 40%; 1H, s,
NH), 2.23, 2.63 (~40%, 60%; 2H, t, J = 7.33, H-2′), 1.48 (2H,
br p, J ≈ 7.33, H-3′), 1.26 (12H, br s, H-4′–9′), 1.59 (2H, br p,
J ≈ 7.14, H-10′), 2.47 (2H, t, J = 7.14, H-11′), 2.65 (2H, t,
J = 6.77, H-1″), 2.49 (2H, t, J = 6.78, H-2″), 8.47 (1H, dd
, J = 1.99, 1.83,Ar-2), 8.23 (1H, dd, J = 8.05, 2.01,Ar-4) 7.72
(1H, dd, J = 7.88, 8.05, Ar-5), 8.08 (1H, dd, J = 7.88, 2.01,
mmax 3200 (N–H), 2900, 2850 (C–H), 1670 (CON), 1650
(CONH), 1580 (phenyl, C=C), 1510 (NO2 asym. str.), 1340
(NO2, sym. str.), 1410 (S–CH), 1380, 1250, 1180 cm–1. The
dH and dC values are given in Tables 4,5. DCI-MS (NH3); m/z
(%): 420 [(M + 1)+, C21H29N3O4S, 82.1], 421 (36.0), 422
(26.9), 437 [(M + 18)+, 6.6], 438 (3.7), 387 (9.1), 332 [(M +
18)+ – C3H4OS, 8.7], 313 (9.1), 266 (4.9), 254 [(M + 1)+ –
C11H19O, 82.1], 255 (13.6), 256 (4.9), 237 [(M + 1)+
–
C11H20NO, 100.0], 238 (20.7), 239 (7.8), 218 (4.1), 209
(3.3), 207 (4.5), 184 (11.6), 185 (6.6), 186 (3.3), 165 (7.0),
166 (8.7), 167 (60.5), 168 (9.1), 169 (3.3), 147 (21.9), 148