CH3), 4.32 (1H, s, 3-H), 5.99 (1H, d, J 8.2, 9-H), 6.54 (1H, d,
J 8.2, 7-H), 6.79 (1H, t, J 8.2, 8-H), 9.12 (1H, s, NH), 9.62 (1H,
s, NH) and 10.75 (1H, s, OH); δC (50 MHz; DMSO-d6; Me4Si)
24.1 (CH3), 24.2 (CH3), 95.8 (CH), 113.7, 116.3, 120.3, 129.8,
136.2, 149.9, 175.2 and 176.6; m/z (EI) 188 (Mϩ – 1, 80%), 173
(28), 148 (49) and 64 (100).
94.7 (CH), 110.7, 111.1, 125.4, 125.9, 135.9, 159.9, 173.0 and
174.1; m/z (EI) 202 (Mϩ – 1, 100%), 187 (77), 147 (24), 119 (10)
and 80 (11).
7-Methoxy-2,4-dimethyl-5H-benzo[b][1,4]diazepin-1-ium
trifluoroacetate 19b
4-Methoxy-o-phenylenediamine dihydrochloride 6 (1.05 g,
5 mmol) was used; yield 1.16 g, 73%; mp 208–210 ЊC; m/z
(HRESI) Found: 203.1182. C12H15N2O requires 203.1184; λmax
6-Hydroxy-2,4-dimethyl-5H-benzo[b][1,4]diazepin-1-ium
trifluoroacetate 17b
2,3-Diaminophenol 4 (0.41 g, 3.3 mmol) was used; yield 0.82 g,
82%; mp 190–193 ЊC (Found: C, 51.6; H, 4.3; N, 9.2. C13H13-
F3N2O3 requires C, 51.7; H, 4.3; N, 9.3%); m/z (HRESI) Found:
189.1029. C11H13N2O requires 189.1028; λmax (H2O)/nm 492;
λmax (MeOH)/nm 370 and 496; λmax (EtOH)/nm 256, 372 and
484; νmax (KBr)/cm Ϫ1 3241, 3073, 3005, 1663, 1633, 1607, 1590,
1460 and 1391; δH (200 MHz; DMSO-d6; Me4Si) 1.80 (3H, s,
CH3), 1.89 (3H, s, CH3), 4.31 (1H, s, 3-H), 6.00 (1H, dd, J 8.1
and 1.1, 9-H), 6.56 (1H, dd, J 8.1 and 1.1, 7-H), 6.79 (1H, t,
J 8.1, 8-H), 9.10 (1H, br s, NH), 9.74 (1H, br s, NH) and 11.06
(1H, s, OH); δC (50 MHz; DMSO-d6; Me4Si)33 24.0 (CH3), 24.2
(CH3), 95.7 (CH), 113.7, 116.3, 120.3, 129.8, 136.2, 150.1, 175.1
and 176.4; m/z (EI) 188 (Mϩ – 1, 100%), 173 (44), 148 (46), 107
(15) and 79 (11).
(H2O)/nm 520; λmax (MeOH)/nm 334 and 522; λmax (EtOH)/nm
Ϫ1
334 and 522; νmax (KBr)/cm
3045, 2903, 1637, 1602, 1572,
1473 and 1385; δH (200 MHz; DMSO-d6; Me4Si) 1.76 (3H, s,
CH3), 1.80 (3H, s, CH3), 3.63 (3H, s, OCH3), 4.02 (1H, s, 3-H),
6.37 (2H, m, 6,9-H), 6.68 (1H, m, 8-H), 9.82 (1H, s, NH) and
10.53 (1H, s, NH); δC (50 MHz; DMSO-d6; Me4Si)33 23.4
(CH3), 23.5 (CH3), 55.4 (OCH3), 94.3 (CH), 110.3, 110.7, 125.0,
125.5, 135.5, 159.5, 172.6 and 173.7; m/z (EI) 202 (Mϩ – 1,
100%), 187 (77), 147 (16) and 118 (7).
7-Mercapto-2,4-dimethyl-5H-benzo[b][1,4]diazepin-1-ium
hydrogensulfate 20a
3,4-Diaminobenzenethiol 7 (0.14 g, 1 mmol) was used; yield
0.256 g, 85% (oily product); m/z (HRESI) Found: 205.0735.
C11H13N2S requires 205.0799; λmax (H2O)/nm 264 and 520; λmax
(MeOH)/nm 270 and 526; λmax (EtOH)/nm 268 and 524; νmax
(film)/cm Ϫ1 2977, 1636, 1590, 1508, 1474, 1374, 1283 and 1175;
δH (200 MHz; DMSO-d6; Me4Si) 1.78 (6H, s, 2 × CH3), 3.37
(s, SH), 4.23 (1H, s, 3-H), 6.50 (1H, d, J 8.3, 9-H), 6.63 (1H, d,
J 1.8, 6-H), 6.99 (1H, dd, J 8.3 and 1.8, 8-H), 9.69 (1H, s,
NH) and 9.89 (1H, s, NH); δC (50 MHz; DMSO-d6; Me4Si) 24.0
(2 × CH3), 95.9 (CH), 121.4, 124.3, 127.3, 133.2, 135.1, 135.9,
175.9 and 176.0; m/z (EI) 204 (Mϩ – 1, 18%), 164 (84), 131 (20),
96 (16) and 64 (100).
7-Hydroxy-2,4-dimethyl-5H-benzo[b][1,4]diazepin-1-ium
hydrogensulfate 18a
3,4-Diaminophenol 5 (0.248 g, 2.0 mmol) was used; yield
0.37 g, 64%; mp 225–227 ЊC; m/z (HRESI) Found: 189.1028.
C11H13N2O requires 189.1025; λmax (H2O)/nm 482; λmax
(MeOH)/nm 342 and 464; λmax (EtOH)/nm 262, 346 and 450;
νmax (KBr)/cm Ϫ1 3214, 3051, 2981, 1643, 1613, 1524, 1481 and
1383; δH (200 MHz; DMSO-d6; Me4Si) 1.71 (3H, s, CH3), 1.75
(3H, s, CH3), 4.08 (1H, s, 3-H), 5.94 (1H, d, J 2.5, 6-H), 6.20
(1H, dd, J 8.6 and 2.5, 8-H), 6.33 (1H, d, J 8.6, 9-H), 9.13 (1H,
s, NH), 9.82 (1H, br s, NH) and 9.99 (1H, s, OH); δC (50 MHz;
DMSO-d6; Me4Si) 23.7 (CH3), 23.8 (CH3), 94.3 (CH), 110.7,
113.0, 123.5, 125.2, 135.3, 158.3, 172.7 and 173.7; m/z (EI) 188
(Mϩ – 1, 100%), 173 (20), 148 (26), 118 (16), 106 (13) and 51
(35).
7-Mercapto-2,4-dimethyl-5H-benzo[b][1,4]diazepin-1-ium
trifluoroacetate 20b
3,4-Diaminobenzenethiol 7 (0.14 g, 1 mmol) was used; yield
0.30 g, 94%; mp 130–132 ЊC; m/z (HRESI) Found: 205.0791.
C11H13N2S requires 205.0799; λmax (H2O)/nm 270 and 516; λmax
(MeOH)/nm 272 and 526; λmax (EtOH)/nm 272 and 528; νmax
(KBr)/cm Ϫ1 3303, 3138, 3065, 1673, 1645, 1596, 1507, 1478 and
1373; δH (200 MHz; DMSO-d6; Me4Si) 1.77 (6H, s, 2 × CH3),
3.40 (s, SH), 4.21 (1H, s, 3-H), 6.50 (1H, d, J 8.3, 9-H), 6.63
(1H, d, J 2.0, 6-H), 6.98 (1H, dd, J 8.3 and 2.0, 8-H), 9.90 (1H,
s, NH) and 10.08 (1H, s, NH); δC (50 MHz; DMSO-d6; Me4Si)33
23.9 (CH3), 24.0 (CH3), 95.9 (CH), 121.4, 124.2, 127.2, 133.4,
135.3, 135.9, 175.7 and 175.8; m/z (EI) 204 (Mϩ – 1, 100%), 163
(25), 122 (16), 95 (11), 69 (54) and 51 (26).
7-Hydroxy-2,4-dimethyl-5H-benzo[b][1,4]diazepin-1-ium
trifluoroacetate 18b
3,4-Diaminophenol 5 (0.248 g, 2.0 mmol) was used; yield
0.526 g, 87%; mp 181–183 ЊC; m/z (HRESI) Found: 189.1028.
C11H13N2O requires 189.1022; λmax (H2O)/nm 266, 330 and 480;
λmax (MeOH)/nm 266, 344 and 460; λmax (EtOH)/nm 268, 284,
Ϫ1
346 and 472; νmax (KBr)/cm
3443, 3311, 3086, 2998, 1659,
1604, 1538, 1484, 1438, 1397 and 1208; δH (200 MHz; DMSO-
d6; Me4Si) 1.71 (3H, s, CH3), 1.74 (3H, s, CH3), 4.06 (1H, s,
3-H), 5.96 (1H, d, J 2.5, 6-H), 6.20 (1H, dd, J 8.6 and 2.5, 8-H),
6.34 (1H, d, J 8.6, 9-H), 9.27 (1H, s, NH), 10.01 (1H, br s, NH)
and 10.17 (1H, s, OH); δC (50 MHz; DMSO-d6; Me4Si)33 23.6
(CH3), 23.7 (CH3), 94.2 (CH), 110.8, 113.0, 123.5, 125.1, 135.3,
158.4, 172.6 and 173.6; m/z (EI) 188 (Mϩ – 1, 100%), 172 (340),
146 (28), 118 (7), 6 (15) and 51 (10).
6-Carboxy-2,4-dimethyl-5H-benzo[b][1,4]diazepin-1-ium
hydrogensulfate 21a
2,3-Diaminophenol 8 (0.188 g, 1.24 mmol) and concentrated
HCl as a catalyst were used. Addition of H2SO4 in excess gave
the corresponding hydrogensulfate; yield 0.32 g, 80%; mp 182–
185 ЊC (Found: C, 44.9; H, 4.4; N, 8.7. C12H14N2O6Sؒ1/2 H2O
requires C, 44.6; H, 4.7; N, 8.7%); m/z (HRESI) Found:
217.0973. C12H13N2O2 requires 217.0970; λmax (H2O)/nm 498;
λmax (MeOH)/nm 344 and 498; λmax (EtOH)/nm 224, 274 and
338; νmax (KBr)/cm Ϫ1 2956, 2823, 1689, 1639, 1594, 1543, 1481
and 1378; δH (200 MHz; DMSO-d6; Me4Si) 1.89 (3H, s, CH3),
1.94 (3H, s, CH3), 4.68 (1H, s, 3-H), 6.82 (1H, dd, J 7.9 and
1.4, 9-H), 7.08 (1H, t, J 7.9, 8-H), 7.56 (1H, dd, J 7.9 and 1.4,
7-H) and 10.47 (2H, s, 2 × NH); δC (50 MHz; DMSO-d6; Me4Si)
24.4 (CH3), 25.1 (CH3), 98.7 (CH), 121.9, 127.9, 128.0,
130.8, 135.4, 138.3, 167.8, 177.5 and 180.7; m/z (EI) 216 (Mϩ,
10%), 172 (100), 130 (87), 103 (24), 89 (13), 77 (21), 63 (34) and
51 (24).
7-Methoxy-2,4-dimethyl-5H-benzo[b][1,4]diazepin-1-ium
hydrogensulfate 19a
4-Methoxy-o-phenylenediamine dihydrochloride 6 (0.422 g,
2 mmol) was used; yield 0.505 g, 91%; mp 210–212 ЊC; m/z
(HRESI) Found: 203.1180. C12H15N2O requires 203.1184; λmax
(H2O)/nm 330 and 500; λmax (MeOH)/nm 344 and 506; λmax
Ϫ1
(MeCN)/nm 332 and 520; νmax (KBr)/cm
3407, 3308, 3070,
3005, 1642, 1608, 1528 and 1482; δH (200 MHz; DMSO-d6;
Me4Si) 1.74 (3H, s, CH3), 1.78 (3H, s, CH3), 3.64 (3H, s, OCH3),
4.05 (1H, s, 3-H), 6.23 (1H, m, 9-H), 6.40 (1H, m, 6-H), 6.55
(1H, m, 8-H), 9.52 (1H, s, NH) and 10.19 (1H, s, NH); δC (50
MHz; DMSO-d6; Me4Si) 23.8 (CH3), 23.9 (CH3), 55.8 (OCH3),
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 4 3 4 2 – 4 3 5 0
4348