Vol. 66, No. 3 (2018)
Chem. Pharm. Bull.
317
N′-(4-Methoxyphenyl)-2-oxo-2-(2-(2-oxo-2H-chromen-3- 3.56 (s, 2H, CH ), 7.12–7.18 (s, 1H, pyran C4), 7.20–7.95 (m,
2
13
yl)-1H-benzo[d]imidazol-1-yl)acetohydrazonoyl Chloride (9c)
8H, 2C H ). C-NMR (DMSO-d ) δ: 113.5, 114.2, 115.1, 116.7,
6 4 6
−1
Brown crystals; mp: 213–215°C; IR (KBr, cm ): 3335, 120.7, 123.8, 123.8, 125.0, 126.2, 127.5, 130.5, 133.5, 138.5,
1
+
3
056, 2928, 1707, 1601, 1570, 1499, 1452. H-NMR (DMSO- 142.1, 150.2, 161.2, 165.8, 172.3. MS (EI): m/z (%) 331 [M+2]
+
+
+
d ) δ: 3.87 (s, 3H, CH ), 7.13–8.01 (m, 12H, 3C H ), 8.10 (0.19), 330 [M+1] (0.25), 329 [M] (0.37), 327 [M−2] (0.25),
6
3
6
4
13
(
s, 1H, pyran C4), 9.14 (s, 1H, NH). C-NMR (DMSO-d6) 57 (100.00). Anal. Calcd for C H N O (329.31): C, 69.30; H,
19 11 3 3
δ: 55.6, 114.4, 115.2, 115.5, 115.5, 116.0, 117.2, 117.2, 119.4, 3.37; N, 12.76. Found: C, 69.68; H, 3.71; N, 12.95.
23.9, 123.9, 124.9, 127.8, 128.3, 130.2, 129.5, 132.9, 138.5, Preparation of 2-((1-(2-Chloroacetyl)-1H-benzo[d]imida-
45.5, 153.2, 154.2, 158.7, 161.7, 167.5, 175.3. MS (EI): m/z (%) zol-2-yl)methyl)thiazol-4(5H)-one (11)
1
1
75 [M+2] (0.28), 474 [M+1] (0.70), 473 [M]+ (0.70), 472
+
+
To a solution of compound 2 (2.33g, 0.01mol) in acetic acid
M−1] (0.14), 471 [M−2]+ (0.08), 396 (100.00). Anal. Calcd (15mL), thioglycollic acid (0.92g, 0.01mol) was added. The
for C H N O Cl (472.88): C, 63.50; H, 3.62; N, 11.85. Found: reaction mixture was heated under reflux system for about
4
+
[
2
5
17
4
4
C, 63.81; H, 3.91; N, 12.10.
5h and then poured onto ice/water mixture. The solid product
2
-Oxo-2-(2-(2-oxo-2H-chromen-3-yl)-1H-benzo[d]- formed was collected by filtration, dried and crystallized from
imidazol-1-yl)-N′-(p-tolyl)acetohydrazonoyl Chloride (9d)
1,4-dioxane.
Pale yellow crystals; mp: 295–297°C; IR (KBr, cm ): 3082,
−1
−1
Orange crystals; mp: 223–225°C; IR (KBr, cm ): 3394,
1
1
3
053, 2922, 1709, 1603, 1570, 1508, 1453. H-NMR (DMSO- 3010, 2955, 2885, 1713, 1624, 1590, 1469. H-NMR (DMSO-
d ) δ: 2.40 (s, 3H, CH ), 7.21–8.01 (m, 12H, 3C H ), 8.14 (s, d ) δ: 3.38 (s, 2H, CH ), 3.70 (s, 2H, CH ), 4.38 (s, 2H, CH ),
6
3
6
4
6
2
2
2
13
13
1
H, pyran C4), 9.16 (s, 1H, NH). C-NMR (DMSO-d ) δ: 7.26–7.55 (m, 4H, C H ). C-NMR (DMSO-d ) δ: 38.7, 39.8,
6 6 4 6
5
5.5, 114.5, 115.3, 115.9, 115.9, 116.5, 117.3, 117.3, 119.4, 122.5, 45.8, 112.1, 113.0, 123.1, 123.5, 130.4, 139.0, 164.1, 168.0,
+
+
1
22.5, 125.0, 127.8, 128.5, 129.4, 130.3, 132.8, 138.2, 145.6, 172.3, 178.1. MS (EI): m/z (%) 310 [M+2] (5.61), 309 [M+1]
53.1, 154.4, 158.7, 161.5, 167.3, 176.2. MS (EI): m/z (%) 456 (4.43), 57 (100.00). Anal. Calcd for C H N O SCl (307.76): C,
1
13
10
3
2
M−1] (0.29), 455 [M−2]+ (0.78), 91 (100.00), 77 [C H ]
+
+
50.73; H, 3.28; N, 13.65; S, 10.42. Found: C, 50.99; H, 3.51; N,
12.31). Anal. Calcd for C H N O Cl (456.88): C, 65.72; H, 13.90; S, 10.66.
[
(
6
5
2
5
17
4
3
3.75; N, 12.26. Found: C, 65.99; H, 4.01; N, 12.30.
GeneralProcedureforthePreparationof 5-Amino-2-((1-(2-
N′-(2,4-Dichlorophenyl)-2-oxo-2-(2-(2-oxo-2H-chromen-3- chloroacetyl)-1H-benzo[d]imidazol-2-yl)methyl)-7-phenyl-
yl)-1H-benzo[d]imidazol-1-yl)acetohydrazonoyl Chloride (9e)
7H-pyrano[2,3-d]thiazole-6-carbonitrileDerivatives(12a–d)
−1
Faint brown crystals; mp: 278–280°C; IR (KBr, cm ): 3385, To a solution of compound 11 (3.07g, 0.01mol) in 1,4-diox-
1
3
059, 1706, 1600, 1573, 1510, 1457. H-NMR (DMSO-d6) ane (20mL) containing a catalytic amount of triethylamine
δ: 7.14–8.07 (m, 11H, 2C H , C H ), 8.14 (s, 1H, pyran C4), (0.50mL) any of benzaldehyde (1.06g, 0.01mol), p-chloroben-
6
4
6
3
13
9
.20 (s, 1H, NH). C-NMR (DMSO-d ) δ: 113.3, 114.6, 118.0, zaldehyde (1.40g, 0.01mol), p-methoxybenzaldehyde (1.36g,
6
118.4, 120.4, 123.2, 123.2, 125.2, 125.8, 126.1, 126.7, 127.2, 0.01mol) or 2-nitrobenzaldehyde (1.51g, 0.01mol) and malo-
1
28.2, 130.1, 132.8, 135.6, 137.1, 145.5, 146.0, 155.3, 161.5, nonitrile (0.66g, 0.01mol) were added. The reaction mixture,
+
1
67.3, 170.3, 172.2. MS (EI): m/z (%) 511 [M] (0.14), 510 in each case, was heated under reflux system for 5h then
M−1] (0.29), 509 [M−2]+ (0.84), 261 (100.00). Anal. Calcd poured onto ice/water mixture containing a few drops of hy-
+
[
for C H N O Cl (511.74): C, 56.33; H, 2.56; N, 10.95. Found: drochloric acid. The solid products formed, in each case, was
2
4
13
4
3
3
C, 56.69; H, 2.82; N, 11.30.
collected by filtration, dried and crystallized from1,4-dioxane.
N′-(4-Nitrophenyl)-2-oxo-2-(2-(2-oxo-2H-chromen-3-yl)-1H-
benzo[d]imidazol-1-yl)acetohydrazonoyl Chloride (9f)
5-Amino-2-((1-(2-chloroacetyl)-1H-benzo[d]imidazol-2-yl)
-
methyl)-7-phenyl-7H-pyrano[2,3-d]thiazole-6-carbonitrile (12a)
−1
−1
Brown crystals; mp: 243–245°C; IR (KBr, cm ): 3408,
Yellow crystals; mp: 290–292°C; IR (KBr, cm ): 3428,
1
1
3
060, 1716, 1601, 1570, 1519, 1456. H-NMR (DMSO-d ) δ: 3231, 3077, 2953, 2884, 2198, 1621, 1589, 1470. H-NMR
6
7
.21–7.98 (m, 12H, 3C H ), 8.17 (s, 1H, pyran C4), 9.17 (s, (DMSO-d ) δ: 3.56 (s, 2H, CH ), 4.38 (s, 2H, CH ), 4.60 (s,
6
4
6
2
2
13
1H, NH). C-NMR (DMSO-d ) δ: 113.5, 113.5, 114.2, 115.6, 1H, pyran C4), 7.23–7.93 (m, 9H, C H , C H ), 8.53 (s, 2H,
6
6
4
6
5
13
116.6, 120.1, 123.2, 123.2, 124.0, 124.0, 125.2, 127.0, 127.3, NH2). C-NMR (DMSO-d ) δ: 29.0, 30.0, 45.8, 59.0, 114.1,
6
1
30.0, 131.3, 137.3, 138.6, 145.7, 148.9, 153.7, 161.5, 167.1, 115.0, 119.5, 123.1, 123.5, 125.0, 128.0, 128.0, 129.4, 129.4,
+
+
1
70.3, 173.5. MS (EI): m/z (%) 490 [M +2] (0.03), 489 [M+1]
0.04), 488 [M]+ (0.04), 487 [M−1]+ (0.03), 486 [M−2]+ (EI): m/z (%) 462 [M] (0.30), 461 [M−1] (0.31), 233 (100.00).
0.08), 261 (100.00). Anal. Calcd for C H N O Cl (487.85): C, Anal. Calcd for C H N O SCl (461.92): C, 59.80; H, 3.49; N,
130.4, 134.3, 139.0, 141.0, 144.0, 150.6, 160.2, 164.0, 183.2. MS
+
+
(
(
2
4
14
5
5
23 16
5
2
5
9.09; H, 2.89; N, 14.36. Found: C, 59.29; H, 3.11; N, 14.60.
Preparation of 3-Oxo-3-(2-(2-oxo-2H-chromen-3-yl)-1H-
benzo[d]imidazol-1-yl)propanenitrile (10)
15.16; S, 6.94. Found: C, 59.91; H, 3.81; N, 15.30; S, 7.20.
5-Amino-2-((1-(2-chloroacetyl)-1H-benzo[d]imidazol-2-
yl)methyl)-7-(4-chlorophenyl)-7H-pyrano[2,3-d]thiazole-6-
A solution of compound 8 (3.38g, 0.01mol) in 1,4-dioxane carbonitrile (12b)
25mL) was heated on water bath at 60°C, then potassium Brown crystals; mp: 264–266°C; IR (KBr, cm ): 3429,
−
1
(
1
cyanide (0.65g, 0.01mol) in a least amount of water (2mL), 3226, 3097, 2952, 2884, 2196, 1621, 1587, 1470. H-NMR
was added with continuous stirring. The reaction mixture was (DMSO-d ) δ: 3.57 (s, 2H, CH ), 4.38 (s, 2H, CH ), 4.40 (s,
6
2
2
left in the water bath for 30min. at 60°C then poured onto ice/ 1H, pyran C4), 7.26–7.97 (m, 8H, 2C H ), 8.54 (s, 2H, NH ).
6
4
2
13
water mixture containing a few drops of hydrochloric acid.
The solid product, so formed, was collected by filtration and 119.4, 123.4, 123.4, 125.8, 125.8, 129.9, 129.9, 130.2, 131.9,
crystallized from ethanol.
133.3, 139.0, 141.3, 143.5, 150.4, 160.0, 164.5, 183.0. MS (EI):
C-NMR (DMSO-d ) δ: 29.8, 30.5, 45.8, 64.0, 114.2, 115.5,
6
−1
+
+
+
Brown crystals; mp: 210–212°C; IR (KBr, cm ): 3065, m/z (%) 498 [M+2] (0.13), 497 [M+1] (0.42), 496 [M ]
1
2
930, 2201, 1714, 1647, 1610, 1457. H-NMR (DMSO-d ) δ: (1.98), 495 [M−1]+ (5.83), 494 [M−2]+ (2.02), 57 (100.00).
6