3076 Abood et al.
Asian J. Chem.
1H NMR (400 MHz, DMSO-d6): δ = 2.505-2.513 (DMSO
oxazepine ring), 8.384 (s, 1H, 1 × O-H phenolic proton).7.117
(d, 1H, 1 × Ha), 7.198 (d, 2H, 2 × Hb), 7.369 (s, 1H, 1 × Hc,
oxazepine ring), 7.772 (s, 1H, 1 × Hd), 7.873 (d, 1H, 1 × He),
8.026-8.032 and 8.048-8.054 (dd, 2H, 2 × Hf). Elemental
analysis (%) calc. for C20H15N5O5S2, C 51.16, H 3.22, N 14.92,
S 13.66; Found: C 51.44, H 3.34, N 14.79, S 13.04.
2-[5-{(2,4-Dimethylphenyl)diazenyl}-2-hydroxyphenyl]-
3-(5-mercapto-1,3,4-thiadiazol-2-yl)-2,3-dihydro-1,3-
oxazepine-4,7-dione (3f): IR (cm–1): 3410(νO-H), 3060(νC-H,
benzene rings), 2980 and 2929 (νas.C-H, CH3), 2868 (νs. C-H, CH3),
2551 (νS-H), 1720 (νC=O, O=C-O and O=C-N,vib. Coupling,oxazepine), 1626 (νC=C,
solvent),6.281 (s, 1H, 1 × olefinic =C-H proton bonded with
O–C=O inside oxazepine ring), 6.65 (s, 1H, 1 × olefinic =C-H
proton bonded with O=C–N inside oxazepine ring), 7.196-
8.191 (Ar-H and C-H proton of oxazepine ring), 11.590 (s,
1H, 1 × O-H phenolic proton).7.196-7.218 (d, 1H, 1 × Ha),
7.635-7.657 (d, 2H, 2 × Hb), 7.870- 7.892 (d, 1H, 1 × Hc),
8.088 (s, 1H, 1 × Hd), 8.184-8.191 (d, 2H, 2 × He). Elemental
analysis (%) calc. for C19H12N5O4S2Cl, C 48.15, H 2.55, N
14.78, S 13.53; Found: C 48.70, H 2.72, N 14.21, S 13.97.
2-[5-{(2,4-Dichlorophenyl)diazenyl}-2-hydroxyphenyl]-
3-(5-mercapto-1,3,4-thiadiazol-2-yl)-2,3-dihydro-1,3-
oxazepine-4,7-dione (3c): IR (cm–1): 3259 (νO-H), 3091 (νC-H,
benzene rings), 2928 (νC-H, CH=CH, oxazepine), 2863 (νC-H, oxazepine), 1664
(νC=O, O=C-O and O=C-N,vib. Coupling, oxazepine), 1620 (νC=C, oxazepine), 1586 and
oxazepine), 1539 and 1506 (νC=N and νC=C, aromatic rings), 1454 (δas.C-H,
CH3), 1381 (δs.C-H, CH3), 1257 and 1236 (νC-N), 860, 819,
773, 742 and 694 (δ o.o.p. C-H, benzene rings).
1H NMR (400 MHz, DMSO-d6): δ =2.387 (s, 6H, 2 × CH3),
2.509 (DMSO solvent),2.509 (DMSO solvent), 6.250-6.367
(s,1H, 1 × olefinic =C-H proton bonded with O–C=O inside
oxazepine ring), 6.638 (s,1H, 1 × olefinic =C-H proton bonded
with O=C–N inside oxazepine ring), 7.249-7.643 (Ar-H and
C-H proton of oxazepine ring), 8.154 (s, 1H, 1 × O-H phenolic
proton).7.249-7.251 (d, 1H, 1 × Ha), 7.275-7.290 (d, 1H, 1 ×
Hb), 7.320 (s, 1H, 1 × Hc), 7.344 (s, 1H, 1 × Hd, oxazepine
ring), 7.430 (s, 2H, 2 × He), 7.631-7.643 (d, 1H, 1 × Hf).
Elemental analysis (%) calc. for C21H17N5O4S2, C 53.95, H
3.66, N 14.98, S 13.72; Found: C 53.79, H 3.81, N 14.70, S
13.61.
1492 (νC=N and νC=C, aromatic rings), 1375, 1323 and 1286 (νC-N), 1101
(νC-Cl), 900, 875, 829, 769, 753 and 700 (δo.o.p. C-H, benzene rings).
1H NMR (400 MHz, DMSO-d6): δ =2.505-2.513 (DMSO
solvent), 6.280 (s, 1H, 1 × olefinic =C-H proton bonded with
O–C=O inside oxazepine ring), 6.635 (s, 1H, 1 × olefinic =C-H
proton bonded with O=C–N inside oxazepine ring), 7.221-
8.124 (Ar-H and C-H proton of oxazepine ring), 8.214 (s, 1H,
1 × O-H phenolic proton). 7.221-7.243 (d, 1H, 1 × Ha), 7.551-
7.556 (d, 1H, 1 × Hb), 7.573- 7.578 (d, 1H, 1 × Hc, oxazepine),
7.681-7.702 (d, 1H, 1 × Hd), 7.894-7.899 (d, 1H, 1 × He), 8.095-
8.102 (d, 1H, 1 × Hf), 8.117-8.124 (d, 1H, 1 × Hg). Elemental
analysis (%) calc. for C19H11N5O4S2Cl2, C 44.89, H 2.18, N
13.78, S 12.61; Found: C 44.76, H 2.41, N 13.70, S 13.10.
2-[2-Hydroxy-5-{(4-nitrophenyl)diazenyl}phenyl]-3-
(5-mercapto-1,3,4-thiadiazol-2-yl)-2,3-dihydro-1,3-oxa-
zepine-4,7-dione (3d): IR (cm–1): 3163 and 3103 (νO-H), 3076
(νC-H, benzene rings), 2868 (νC-H, oxazepine), 1722 (νC=O, O=C-O, oxazepine), 1666
(νC=O, O=C-N,oxazepine), 1612 (νC=C, oxazepine), 1579 and 1479 (νC=N and
Synthesis of 1,3-oxazepine-4,7-dione derivatives (4b,
4d, 4e):A mixture of azoimine derivatives (2b, 2d, 2e) (0.002
mol) and phthalic anhydride (0.296 g, 0.002 mol) in dry
benzene (20 mL) was refluxed on a water bath at 70 ºC for 20-
24 h and monitored by TLC. The mixture wasthen allowed to
cool down to room temperature, dried upon filter paper then
in oven and recrystallized from ethanol.
2-[5-{(4-Chlorophenyl)diazenyl}-2-hydroxyphenyl]-3-
(5-mercapto-1,3,4-thiadiazol-2-yl)-2,3-dihydrobenzo-
[e][1,3]oxazepine-4,7-dione (4b): IR (cm–1): 3269 (νO-H), 3080
(νC-H, benzene rings), 1734 (νC=O, O=C-O, oxazepine), 1674 and 1639 (νC=O,
ν
C=C, aromatic rings), 1527 (νas.NO2), 1344 (νs.NO2), 1375, 1319
and 1284 (νC-N), 906, 854, 750, 719 and 688 (δ o.o.p. C-H, benzene
rings).
1H NMR (400 MHz, DMSO-d6): δ = 2.505-2.513 (DMSO
solvent),3.388 (H2O in DMSO), 7.198-7.220 (d, 2H, 2 ×
olefinic =C-H protons inside oxazepine ring), 8.002-8.399 (Ar-
H and C-H proton of oxazepine ring), 11.765 (s, 1H, 1 × O-H
phenolic proton).8.002-8.024 (d, 1H, 1 × Ha), 8.102-8.131 (t,
2H, 1 × Hb+1 × Hc, oxazepine ring), 8.209-8.215 (d, 3H, 3 ×
Hd), 8.376-8.399 (d, 2H, 2 × He). Elemental analysis (%) calc.
for C19H12N6O6S2, C 47.10, H 2.50, N 17.35, S 13.24; Found:
C 46.94, H 2.78, N 17.46, S 13.09.
O=C-N,oxazepine), 1573 and 1504 (νC=N and νC=C, aromatic rings), 1388 and
1292 (νC-N), 1134 (νC-Cl), 896, 839,808, 764, 720 and 683 (δ
o.o.p. C-H, benzene rings).
1H NMR (400 MHz, DMSO-d6): δ = 2.509-2.513 (DMSO
solvent), 3.355 (H2O in DMSO), 3.573 (s, 1H, 1 × S-H proton),
7.372 (s, 1H, 1 × O-H phenolic proton). 7.522-7.973 (Ar-H
and C-H proton of oxazepine ring). 7.522-7.530 (dd, 3H, 1 ×
Ha and 2 × Hb), 7.656-7.750 (dd, 2H, 1 × Hc and 1 × Hd), 7.772
(s, 3H, 3 × He), 7.814 (s, 2H, 2 × Hf), 7.954-7.973 (d, 1H, 1 ×
Hg). Elemental analysis (%) calc. for C23H14N5O4S2Cl, C 52.72,
H 2.69, N 13.36, S 12.24; Found: C 52.58, H 2.69, N 13.93, S
12.19.
2-[2-Hydroxy-5-{(4-methoxyphenyl)diazenyl}phenyl]-
3-(5-mercapto-1,3,4-thiadiazol-2-yl)-2,3-dihydro-1,3-
oxazepine-4,7-dione (3e): IR (cm–1): 3265 (νO-H), 3070 (νC-H,
benzene rings), 2968 (νas.C-H, CH3), 2870 (νs.C-H, CH3), 2584 (νS-H,
thioenol form), 1701 (νC=O, O=C-O and O=C-N,vib. Coupling,oxazepine), 1600 and
1502 (νC=N and νC=C, aromatic rings), 1352, 1273 (νC-N), 1247 (νas. C-O-C,
ether), 1030(νs. C-O-C, ether), 896, 837, 788, 750 and 690(δ o.o.p. C-H,
benzene rings).
2-[2-Hydroxy-5-{(4-nitrophenyl)diazenyl}phenyl]-3-
(5-mercapto-1,3,4-thiadiazol-2-yl)-2,3-dihydrobenzo-
[e][1,3]oxazepine-4,7-dione (4d): IR (cm–1): 3265 and 3200
(νO-H), 3074 (νC-H, benzene rings), 2881 (νC-H, oxazepine), 1734 (νC=O, O=C-O,
oxazepine), 1666 (νC=O, O=C-N,oxazepine), 1599 and 1574 (νC=N and νC=C,
aromatic rings), 1525 (νas.NO2), 1344 (νs.NO2), 1288 (νC-N), 898,
852, 808, 758 and 711 (δ o.o.p. C-H, benzene rings).
1H NMR (400 MHz, DMSO-d6): δ = 2.509 (DMSO
solvent), 3.867 (s, 3H, 1 × H3C-O), 6.204 (s, 1H, 1 × olefinic
=C-H proton bonded with O–C=O inside oxazepine ring),
6.637 (s, 1H, 1 × olefinic =C-H proton bonded with O=C–N
inside oxazepine ring), 7.117-8.054 (Ar-H and C-H proton of
1H NMR (400 MHz, DMSO-d6): δ = 2.50-2.51 (DMSO
solvent), 3.57 (H2O in DMSO), 7.18-8.43 (Ar-H and C-H