May-Jun 2003
Useful Synthons for the Construction of New Heterocyclic Systems
485
2
(s, 2H, CH ), 2.86 (s, 2H, CH ), 6.62-7.84 (m, 9H, arom-H),
([ H ]DMSO) δ: 6.46-7.6(m, 9H, arom-H), 8.43(s, 1H, H-4),
2
2
6
13
2
+
8.40 (s, 1H, H-5). C-NMR ([ H ]DMSO) δ: 197.6, 187.0
11.1(s, 1H, NH), 12.4(s, 1H, NH). MS: m/z 360(M ).
6
(CO-carbons), 155.6 (imine-carbon), 152.1, 144.7, 133.7, 112.4
(ethylene-carbons), 146.7, 137.2, 134.4, 134.4, 132.4, 129.8,
129.5, 129.3, 129.3, 118.5, 115.1, 115.1 (aromatic-carbons),
Anal. Calcd. for C
23.32 %. Found: C, 73.20; H, 3.66; N, 23.63.
H N (360.37): C, 73.32; H, 3.36; N,
22 12 6
Reactions of 2 with Benzimidazol-2-acetonitrile (10) and ω−Cyano
Compounds 12a,b: Formation of Compounds 11 and 14a,b.
53.7, 43.3 (CH -aliphatic), 17.0 (CH-aliphatic), 26.8, 26.8
2
(methyl-carbons).
Anal. Calcd. for C
7.60 %. Found: C, 78.20; H, 5.66; N, 7.63.
H N O (368.43): C, 78.24; H, 5.47; N,
24 20 2 2
To a solution of 2 (2.91 g, 0.01 mol) in ethanol (30 mL)
containing piperidine (0.5 mL) as a catalyst, was added
(0.01 mol) of compound 10 or compound 12. The reaction
mixture was heated under reflux for several hours. And the
progress was monitored by tlc. The solid deposited after cooling
was collected by filtration and recrystallized from the proper
solvent to give 11, 14a,b respectively.
8-Furan-3-yl-6-phenyl-6H-5,6-diazabenzo[a]azulene-10-one
(20a).
Compound 20a was obtained as deep brown crystals from
ethanol/DMF, m.p.203-205 °C, yield 80%. ν
: 1700(CO),
max
1
2
1590(C=N). H-NMR ([ H ]DMSO) δ: 4.82 (d, 1H J = 5.1, H-4),
6
8-(Phenylhydrazono)-8H-5,12c-diazaindeno[2,1-c]flourene-6-
carbonitrile (11).
13
6.06-7.8 (m, 12H, arom-H), 8.1 (d, 1H, J = 8.3, H-5). C-NMR
2
([ H ]DMSO) δ: 187.0 (CO-carbon), 155.6 (imine-carbon),
6
144.7, 133.7, 127.7, 119.4 (ethylene-carbons), 146.7, 143.2,
139.3, 137.2, 134.4, 132.4, 131.3, 129.8, 129.5, 129.3, 129.3,
124.5, 118.5, 115.1, 115.1, 107.7 (aromatic-carbons).
Compound 11 was obtained as brown crystals from
ethanol/dioxane, m.p. 238-240 °C, yield 80 %ν : 3330(NH),
max
1
2
2220(CN), 1590 (C=N). H-NMR ([ H ]DMSO) δ: 6.46-7.9 (m,
6
Anal. Calcd. for C
H N O (338.36): C, 78.09; H, 4.17; N,
22 14 2 2
13H, arom-H), 8.23 (s, 1H, H-4), 11.1 (s, 1H, NH). MS: m/z
8.28 %. Found: C, 78.29; H, 4.32; N, 8.38.
+
385(M ).
Anal. Calcd. for C
18.17 %. Found: C, 77.90; H, 3.66; N, 18.63.
H N (385.42): C, 77.91; H, 3.92; N,
25 15 5
6-Phenyl-8-thiophene-3-yl-6H-5,6-diazabenzo[a]azulene-10-one
(20b).
[2-Imino-5-(phenylhydrazono)-2,5-dihydroindeno[1,2-b]pyran-
3-yl]-phenylmethanon (14a).
Compound 20b was obtained as deep brown crystals from
ethanol/DMF, m.p.210-212 °C, yield 70%. ν
: 1700(CO),
max
1
2
1585(C=N). H-NMR [ H ]DMSO) δ: 4.50 (d, 1H, J = 5.1, H-4),
6
Compound 14a was obtained as orange crystals from ethanol,
6.20-7.65 (m, 12H, arom-H), 8.22 (d, 1H, J = 8.3, H-5).
m.p.261 °C, yield 68%. ν
: 3360, 3335(NH), 1710(CO),
max
Anal. Calcd. for C
H N OS (354.43): C, 74.66; H, 4.12; N,
1
2
22 14 2
1595(C=N). H-NMR ([ H ]DMSO) δ: 3.1 (s, 1H, NH), 6.62-
6
8.00 %. Found: C, 74.55; H, 3.98; N, 7.90.
7.84 (m, 14H, arom-H), 8.23 (s, 1H, H-4), 11.1 (s, 1H, NH).
Anal. Calcd. for C
10.74 %. Found: C, 76.20; H, 4.66; N, 10.63.
H N O (391.42): C, 76.71; H, 4.38; N,
3-Acetyl-1-phenyl-5-(phenylhydrazono)-1,5-dihydroindeno-
[1,2-b]pyridin-2-one (23a).
25 17 3 2
4-[2-Imino-5-(phenylhydrazono)-2,5-dihydroindeno[1,2-b]-
pyran-3-carbonyl]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-
one (14b).
Compound 23a was obtained as brown crystals from
ethanol/DMF, m.p.258-260 °C, yield 65 %. ν : 3360(NH),
max
1
2
1710(CO), 1700(CO), 1590 (C=N). H-NMR ([ H ]DMSO) δ:
6
2.3 (s, 3H, CH ), 6.62-7.60 (m, 14H, arom-H), 8.14 (s, 1H, CH),
3
Compound 14b was obtained as yellow crystals from
13
2
11.1 (s, 1H, NH). C-NMR ([ H ]DMSO) δ: 196.5, 158.4 (CO-
6
ethanol/dioxane, m.p.270-272 °C, yield 78%. ν
: 3350,
max
carbons), 155.6 (imine-carbon), 147.4, 146.0, 138.0, 102.3 (eth-
ylene-carbons), 146.7, 138.2, 134.5, 130.7, 129.3, 129.3, 128.9,
128.9, 128.7, 128.4, 127.8, 126.3, 124.4, 120.8, 120.4, 118.5,
115.1, 115.1 (aromatic-carbons), 22.2 (methyl-carbon).
1
3335(NH), 1710(CO), 1635 (CO), 1595(C=N). H-NMR
2
([ H ]DMSO) δ: 1.71 (s, 3H, CH ), 2.47 (s, 3H, CH ), 3.1 (s,
6
3
3
1H, NH), 6.62-7.84 (m, 14H, arom-H), 8.40 (s, IH, H-4), 11.1
(s, 1H, NH).
Anal. Calcd. for C
H N O (405.45): C, 77.02; H, 4.72; N,
26 19 3 2
Anal. Calcd. for C
H N O (501.54): C, 71.84; H, 4.62; N,
30 23 5 3
10.36 %. Found: C, 77.11; H, 4.66; N, 10.42.
13.96 %. Found: C, 71.70; H, 4.66; N, 13.63.
3-Acetyl-1-(4-chlorophenyl)-5-(phenylhydrazono)-1,5-dihy-
droindeno[1,2-b]pyridin-2-one (23b).
Reaction of 1 with Enaminones 15, 18 & 21: Formation of
Compounds 17, 20and 23.
Compound 23b was obtained as deep brown crystals from
A mixture of compound 1 (0.01 mol) and each of the enam-
inones 15, 18, 21 (0.01 mol) in acetic acid (30 mL) was heated
under reflux for several hours. The reaction was followed by tlc.
The volatile components were evaporated in vacuo and the
residue was recrystallized from an appropriate solvent to give 17,
20 and 23 respectively.
ethanol/DMF, m.p.241 °C, yield 70%. ν
1710(CO), 1700(CO), 1590 (C=N). H-NMR ([ H ]DMSO) δ:
: 3360(NH),
max
1
2
6
2.3 (s, 3H, CH ), 6.62-7.60 (m, 13H, arom-H), 8.14 (s, 1H, CH),
3
+
11.1 (s, 1H, NH). MS: m/z 439(M ).
Anal. Calcd. for C
H ClN O (439.89): C, 70.79; H, 4.36;
26 18 3 2
N, 9.38 %. Found: C, 70.99; H, 4.12; N, 9.55.
8,8-Dimethyl-6-phenyl-6,7,8,9-tetrahydro-diazabenzo[a,f]-
azulene-10,12-dione (17).
REFERENCES AND NOTES
Compound 17 was obtained as brown crystals from benzene/
ethanol, m.p. 148-150 °C, yield 60%. ν
: 1710(CO),
[1] F. Al-Omran, M. M. Abdel-Khalik, A. Abuel-Khair and
M. H. Elnagdi, Synthesis, ,91 (1997).
max
1
2
1700(CO). H-NMR ([ H ]DMSO) δ: 1.11 (s, 6H, diCH ), 2.45
6
3