272 Los et al.
filtrate was concentrated. The formed solid was
recrystallized from MeOH (5 mL).
reaction mixture was filtered by a Bu¨chner funnel,
and the filtrate was concentrated. The formed solid
was recrystallized from MeOH (10 mL).
Yield, 68%; mp: 135–138◦C; IR (KBr, cm−1): 3438
(OH in CO2H), 2921 (CH), 2849 (CH), 1694 (C O),
1612 (C N), 1499 (C C), 1469, 1387, 1323, 1288,
1229 (C OH), 1155, 999, 942, 910, 845, 796, 760, 725;
1H NMR (DMSO-d6) δ (ppm): 12.30 (s, 1H, CO2H),
11.34 (s, 1H, C2 OH), 9.90 (s, 1H, C4 OH), 8.15
(dd, 1H, CAR H), 7.87 (m, 3H, CAR H), 7.73 (dd, 1H,
CAR H), 7.44 (s, 1H, CAR H), 7.31 (dd, 1H, CAR H),
6.97 (d, 1H, CAR H), 6.17 (d, 1H, CAR H), 2.02 (s, 3H,
CH3); 13C NMR δ (ppm): 169.7, 165.2, 162.5, 160.2,
146.2, 134.3, 132.2, 130.7, 130.0, 129.2, 128.2, 126.0,
125.5, 124.0, 117.9, 116.1, 111.5, 107.6, 106.6, 102.7,
8.5; EI-MS (m/z, %): 394 (M+, 100), 376 (7), 365 (7),
349 (79), 333 (20), 321 (10), 295 (13), 165 (6), 258
(9), 244 (17), 229 (7), 166 (8), 151 (34), 124 (47), 107
(6), 95 (7), 77 (13), 65 (9), 77 (13), 65 (9), 51 (9), 44
(42), 39 (30). Anal. Calcd for C21H15ClN2O4 (394.81):
C, 63.89; H, 3.83; N, 7.10. Found: C, 63.96; H, 3.81;
N, 7.07.
Yield, 67%; mp: 314◦C (dec.); IR (KBr, cm−1):
3224 (OH), 1628 (C N), 1582 (C N), 1513 (C C),
1460, 1255 (C OH), 1181, 1084, 993, 976, 845, 792,
761, 724; 1H NMR (DMSO-d6) δ (ppm): 14.22 (s, 2H,
NH), 11.73 (s, 2H, C3 OH), 8.13 (d, J = 8.8 Hz, 2H,
C5 H), 8.04 (s, 2H, CAR H), 7.91 (d, J = 8.4 Hz, 2H,
CAR H), 7.82 (d, J = 8.4 Hz, 2H, CAR H), 6.76 (s, 2H,
CAR H), 6.58 (dd, J = 8.7 and 1.8 Hz, 2H, C6 H); 13
C
NMR δ (ppm): 163.8 (2C), 159.5 (2C), 148.0 (2C),
137.0 (2C), 132.0 (2C), 131.0 (2C), 130.7 (2C), 124.6
(2C), 114.2 (2C), 111.6 (2C), 109.1 (2C), 103.0 (2C),
100.4 (2C); ESI+-MS (m/z): 451.3 [M + H]+. Anal.
Calcd for C26H18N4O4 (450.45): C, 69.33; H, 4.03; N,
12.44. Found: C, 69.21; H, 4.01; N, 12.48.
4-(3,4-Dihydroquinazolin-2-yl)benzene-1,3-diol (9).
A mixture of 2-(aminomethyl)aniline (0.004 mol)
and STB (0.0045 mol) in MeOH (20.5 mL) was re-
fluxed for 3 h. The hot reaction mixture was filtered
by a Bu¨chner funnel. The water was added to the
filtrate. The formed solid was filtered off and recrys-
tallized from MeOH (7 mL).
4-[5-Chloro-2-(5-chloro-2,4-dihydroxyphenyl)-1H-
benzimidazol-1-yl]benzoic Acid (7). A mixture of
4-[(2-amino-4-chlorophenyl)amino]benzoic
acid
(0.0021 mol) and SClTB (0.0013 mol) in MeOH
(9.5 mL) was refluxed for 3 h. The hot reaction
mixture was filtered by a Bu¨chner funnel, and the
filtrate was concentrated. The formed solid was
recrystallized from MeOH/H2O (3:1, 6 mL).
Yield, 73%; mp: 207–209◦C; IR (KBr, cm−1): 3277
(OH, NH), 2926 (CH), 2851 (CH), 1623 (C N), 1582
(C C), 1540 (C C), 1458, 1423, 1364, 1302, 1248,
1210 (C OH), 1161, 1132, 1083, 980, 944, 841, 797,
759, 722; 1H NMR (DMSO-d6) δ (ppm): 11.65 (s, 1H,
C3 OH), 10.38 (s, 1H, C1 OH), 7.10 (d, 1H, C5 H),
6.44 (d, 1H, C2 H), 6.29 (m, 1H, C6 H), 4.78 (s, 2H,
CH2); EI-MS (m/z, %): 240 (M+, 4), 239 (M+-1, 100),
212 (36), 197 (18), 181 (56), 169 (57), 154 (12), (9),
277 (20), 263 (10), 242 (13), 229 (8), 209 (11), 188
(7), 171 (28), 144 (9), 125 (8), 110 (10), 81 (29), 69
(26), 51 (29), 44 (66). Anal. Calcd for C14H12Cl2N2O4
(240.26): C, 69.99; H, 5.03; N, 11.66. Found: C, 70.03;
H, 5.04; N, 11.64.
Yield, 81%; mp: 183–185◦C; IR (KBr, cm−1): 3420
(OH in CO2H), 3301 (OH), 2920 (CH), 1676 (C O),
1614 (C N), 1583 (C N), 1501 (C C), 1458, 1400,
1340, 1294, 1247, 1208 (C OH), 1163, 1080, 1052,
1
992, 984, 940, 907, 865, 800, 751; H NMR (DMSO-
d6) δ (ppm): 13.03 (s, 1H, C2 OH· · ·N), 11.60 (s, 1H,
CO2H), 10.96 (s, 1H, C4 OH), 8.13 (dd, J = 7.9 and
1.5 Hz, 1H, CAR H), 7.78 (d, J = 2.2 Hz, 1H, CAR H),
7.86–7.80 (m, 2H, CAR H), 7.51 (d, J = 8.7 Hz, 1H,
CAR H), 7.40–7.36 (m, 2H, CAR H), 6.97 (d, J =
8.7 Hz, 1H, CAR H), 6.79 (m, 1H, CAR H); 13C NMR δ
(ppm): 169.6, 163.3, 158.3, 157.0, 146.5, 134.1, 133.9,
132.8, 131.6, 130.1, 129.3, 128.4, 126.5, 124.0, 117.8,
113.9, 113.1, 111.4, 104.1, 103.8; EI-MS (m/z, %): 414
(M+, 87), 369 (100), 361 (61), 353 (18), 334 (15), 305
(12), 293 (9), 277 (20), 263 (10), 242 (13), 229 (8),
209 (11), 188 (7), 171 (28), 144 (9), 125 (8), 110 (10),
81 (29), 69 (26), 51 (29), 44 (66). Anal. Calcd for
C20H12Cl2N2O4 (415.23): C, 57.85; H, 2.91; N, 6.75.
Found: C, 58.03; H, 2.92; N, 6.72.
4-(3,4-Dihydroquinazolin-2-yl)-6-ethylbenzene-1,
3-diol(10). A mixture of 2-(aminomethyl)aniline
(0.004 mol) and SETB (0.0046 mol) in MeOH
(20.5 mL) was refluxed for 3 h. The hot reaction
mixture was filtered by a Bu¨chner funnel, and the
filtrate was concentrated. The formed solid was
recrystallized from MeOH/H2O (3:1, 8 mL).
Yield, 70%; mp: 191–194◦C; IR (KBr, cm−1): 3434
(OH), 2925 (CH), 2842 (CH), 1635 (C N), 1585
(C N), 1520 (C C), 1488 (C C), 1459, 1396, 1236
1
(C OH), 1173, 1094, 845, 782; H NMR (DMSO-d6)
4,4ꢁ-(1H,3ꢁH-5,5ꢁ-Bibenzo[d]imidazole-2,2ꢁ-diyl)di-
benzene-1,3-diol (8). A mixture of biphenyl-3,3ꢁ,4,4ꢁ-
tetramine (0.0027 mol) and STB (0.0033 mol) in
MeOH (15 mL) was refluxed for 3 h. The hot
δ (ppm): 11.53 (s, 1H, C3 OH), 10.29 (s, 1H, C1 OH),
8.06 (d, 1H, C5 H), 7.81 (s, 1H, CAR H), 7.47 (m, 2H,
CAR H), 7.30 (m, 1H, CAR H), 6.44 (d, 1H, C2 H),
4.76 (s, 2H, CH2), 2.61 (s, 2H, CH2CH3), 1.17 (s, 3H,
Heteroatom Chemistry DOI 10.1002/hc