8524
M. Batra et al. / Bioorg. Med. Chem. 14 (2006) 8519–8526
M++2ꢀCl), 307 (10%, M+ꢀ2C2H2), 266 (9%, M+ꢀH–
C6H5N), 208 (72%, unsym. rDA frag.), 165 (15%, sym.
rDA frag.), 136 (70%, rDA frag.-CO), 91 (30%,
C6H5N+), 77 (40%, C6H5+).
4.3.5. 2,5-Bis(40-chloroanilino)-3,6-dichloro-1,4-benzoqui-
none (3e). Yield: 385 mg, 90%; as dark green needles mp
350 ꢁC (from dimethylformamide/benzene); Anal. Calcd
for C18H10Cl4N2O2: C, 50.46; H, 2.33; N, 6.54. Found:
C, 50.42; H, 2.31; N, 6.49%. UV/vis kmax (cmꢀ1) 385;
mmax in cmꢀ1 (KBr) 3230 (N–H), 1650 (C@O), 1590,
1322, 1250, 1190, 1045; dH (300 MHz; DMSO) 8.26
(1H, s, NH, D2O exchangeable), 7.505–7.534 (2H, d,
J = 8.7 Hz, ArH (30 and 300)), 7.375–7.404 (2H, d,
J = 8.7 Hz, ArH (50 and 500)), 7.082–7.111 (2H, d,
J = 8.7 Hz, ArH (20 and 200)), 7.033–7.062 (2H, d,
J = 8.7 Hz, ArH (60 and 600)); dc (300 MHz; DMSO)
124.6, 125.2, 127.2, 128.9, 134.8, 136.7, 140.6, 145.4,
160.1, 170.2 (C@O); FAB MS (298 ꢁC) m/z (%, frag-
ment), 428 (77, M+), 430 (100, M++2), 432 (44,
M++4), 434 (10, M++4), 427 (25, M+ꢀ1), 357 (40,
M+ꢀ2Cl), 392 (46, M+ꢀHCl), 336 (11), 321 (17), 289
(88), 265 (37), 235 (26), 205 (15), 189 (76), 157 (50)
136 (35) 105 (65), 77 (40).
4.3.2. 2,5-Bis (20-methylanilino)-3,6-dichloro-1,4-benzo-
quinone (3b). Yield: 333 mg, 86%; as brown needles mp
198 ꢁC (from dimethylformamide/benzene); Anal. Calcd
for C20H16Cl2N2O2: C, 61.97; H, 4.16; N, 7.23; C, 60.13;
H, 3.31; N, 7.72. Found: C, 61.92; H, 4.12; N, 7.19%.
UV/vis kmax (cmꢀ1) 367.2; mmax in cmꢀ1 (KBr) 3242
(N–H), 1652 (C@O), 1564, 1328, 1236, 1195, 1112,
1022; dH (300 MHz; DMSO) 8.192 (1H, s, NH, D2O
exchangeable), 7.235–7.260 (2H, d, J = 7.5 Hz, ArH (60
and 600)), 7.181–7.212 (4H, dd, J = 4.5 Hz, J = 4.8 Hz,
ArH (40, 50, 400 and 500)) 7.086–7.107 (2H, d,
J = 6.3 Hz, ArH (30 and 300)), 2.280 (6H, s, 2CH3); dc
(300 MHz; DMSO) 17.6 (CH3), 125.2, 126.9, 127.8,
129.5, 134.6, 137.6, 139.5, 144.7, 172.5 (C@O) FAB
MS (298 ꢁC) m/z (%, fragment), 387 (100, M+), 389
(33, M++2), 386 (15, M+ꢀ1), 351 (35, M+ꢀHCl), 315
(15, M+ꢀ2HCl), 307 (48), 289 (25), 279 (10), 277 (11),
242 (8), 233 (17, M+ꢀHCN), 215 (10), 203 (15), 191
(8), 177 (25), 107 (20).
4.3.6. 2,5-Bis(40-bromoanilino)-3,6-dichloro-1,4-benzoqui-
none (3f). Yield: 439 mg, 85%; as yellowish-green needles
mp 325 ꢁC (D) (from dimethylformamide/benzene);
Anal. Calcd for C18H10Cl2Br2N2O2: C, 41.77; H, 1.93;
N, 5.41. Found: C, 41.70;H, 1.90;N, 5.36%. UV/vis kmax
(cmꢀ1) 390; mmax in cmꢀ1 (KBr) 3230 (N–H), 1650
(C@O), 1595, 1318, 1245, 1175, 1100, 1035; dH
(300 MHz; DMSO) 8.24 (s, 1H, NH, D2O exchange-
able), 7.583–7.612 (2H, d, J = 8.7 Hz, ArH (30 and
300)), 7.439–7.468 (2H, d, J = 8.7 Hz, ArH (50 and 500)),
7.380–7.409 (2H, d, J = 8.7 Hz, ArH (20 and 200)),
7.089–7.118 (d, 2H, J = 8.7 Hz, ArH (60 and 600)); dc
(300 MHz; DMSO) 124.3, 125.2, 127.2, 128.2, 130.2,
134.6, 137.2, 142.6, 159.8, 171.2 (C@O); FAB MS
(298 ꢁC) m/z (%, fragment), 517 (38, M+), 519 (100,
M++2), 521 (89, M++4), 523 (32, M++4), 482 (45,
M+ꢀCl), 446 (85, M+ꢀ2Cl), 437 (25, M+ꢀBr), 357
(40, M+ꢀ2Br), 337 (15), 313 (26), 291 (28), 256 (84),
218 (23), 200 (17), 188 (65), 165 (45), 136 (70), 108
(43), 77 (35).
4.3.3. 2,5-Bis(20-methoxyanilino)-3,6-dichloro-1,4-benzo-
quinone (3c). Yield: 352 mg, 84%; as green needles mp
283 ꢁC (from dimethylformamide/benzene); Anal. Calcd
for C20H16Cl2N2O4: C, 57.29; H, 3.84; N, 6.68. Found:
C, 57.26; H, 3.81; N, 6.65%. UV/vis kmax (cmꢀ1) 390; mmax
in cmꢀ1 (KBr) 3240 (N–H), 1660 (C@O), 1580, 1340,
1200, 1140, 1040; dH (300 MHz; DMSO) 8.240 (1H, s,
NH, D2O exchangeable), 7.221–7.246 (2H, dd,
J = 1.5 Hz, J = 4.2 Hz, ArH (30 and 300)), 7.050–7.076
(2H, dd, J = 6.6 Hz, J = 1.2 Hz, ArH (60 and 600)),
6.902–6.984 (4H, m, ArH (40, 50, 400 and 500)), 3.87
(6H, s, 2OCH3); dc (300 MHz; DMSO) 55.9 (OCH3),
110.6, 119.6, 125.8, 126.9, 127.8, 139.7, 143.5, 152.2,
172.8 (C@O); FAB MS (298 ꢁC) m/z (%, fragment)
419 (100, M+), 421 (33, M++2), 418 (50, M+ꢀ1),
388 (25, M+ꢀOCH3), 387 (20, M+ꢀCH3OH), 357
(38, M+ꢀ2OCH3), 336 (25), 315 (5), 273 (12), 260 (18),
245 (8) 228 (11), 209 (12), 178 (10), 152 (20), 120 (35),
107 (60), 76 (20).
4.3.7. 2,5-Bis(40-methylanilino)-3,6-dichloro-1,4-benzo-
quinone (3g). Yield: 329 mg, 85%; as reddish brown nee-
dles mp 275 ꢁC (from dimethylformamide/benzene);
Anal. Calcd for C20H16Cl2N2O2: C, 62.03; H, 4.16; N,
7.23. Found: C, 62.01; H, 4.12; N, 7.19%. UV/vis kmax
(cmꢀ1) 420; mmax in cmꢀ1 (KBr) 3240 (N–H), 1650
(C@O), 1562, 1325, 1233, 1193, 1111, 1020; dH
(300 MHz; DMSO) 8.323 (1H, s, NH, D2O exchange-
able) 7.158–7.185 (4H, d, J = 8.1 Hz, ArH (20, 60, 200
and 600)), 7.013–7.040 (4H, d, J = 8.1 Hz, ArH (30, 50,
300 and 500)), 2.42 (6H, s, 2CH3); dc (300 MHz; DMSO)
17.9 (CH3), 125.6, 127.2, 127.5, 129.9, 134.8, 137.1,
144.6, 170.2 (C@O); FAB MS (298 ꢁC) m/z (%, frag-
ment), 387 (100, M+), 389 (63, M++2), 391 (10,
M++4), 386 (72, M+ꢀH), 351 (25, M+ꢀHCl), 349 (10),
333 (11) 315 (10, M+ꢀ2HCl), 307 (45), 279 (10) 277
(14), 242 (18), 233 (15), 215 (8), 203 (15), 191 (10), 177
(25), 154 (80), 152 (24), 136 (62), 135 (15), 107 (20).
4.3.4. 2,5-Bis(20-fluoroanilino)-3,6-dichloro-1,4-benzoqui-
none (3d). Yield: 328 mg, 83%; as brown needle mp
318 ꢁC (from dimethylformamide/benzene); Anal. Calcd
for C18H10F2Cl2N2O2: C, 54.71; H, 2.55; N, 7.08.
Found: C, 54.70; H, 2.52; N, 7.05%. UV/vis kmax
(cmꢀ1) 360; mmax in cmꢀ1 (KBr) 3240 (N–H), 1656
(C@O), 1576, 1331, 1221, 1105, 1035; dH (300 MHz;
DMSO) 8.280 (1H, s, NH, D2O exchangeable), 7.548–
7.646 (2H, dd, J = 1.5 Hz, J = 7.5 Hz, ArH (30 and
300)), 7.374–7.480 (2H, dd, J=1.2 Hz, J = 6.8 Hz, ArH
(60 and 600)), 7.210–7.327 (4H, m, ArH (40, 50, 400 and
50)); dc (300 MHz; DMSO) 126.6, 127.2, 128.2, 128.8,
133.8, 137.7, 139.6, 144.4, 162.1, 171.2 (C@O); FAB
MS (298 ꢁC) m/z (%, fragment), 395 (48, M+), 397 (16,
M++2), 394 (15, M+ꢀ1), 376 (10), 370 (9), 365 (38,
M+ꢀ2NH), 361 (17, M+ꢀ2F), 329 (50), 317 (10), 307
(20), 289 (20), 273 (7), 254 (70), 232 (40), 228 (9), 214
(10), 176 (90), 154 (89), 136 (85), 101 (80), 89 (35).
4.3.8. 2,5-Bis(40-methoxyanilino)-3,6-dichloro-1,4-benzo-
quinone (3h). Yield: 373 mg, 89%; as dark brown needles
mp 240 ꢁC (from dimethylformamide/benzene); Anal.