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Abstract
ENGLISH SUMMARY
SYNTHESIS OF SOME NITROGENOUS
HETEROAROMATIC COMPOUNDS: STUDIES
ON 2(1H)-QUINOLONE DERIVATIVES:
SYNTHETIC ACCESS TO PYRANO[3,2-c]
QUINOLINE AND 3-SUBSTITUTED QUINOLINE
DERIVATIVES
Pyranoquinoline derivatives constitute the parent structure of
pyranoquinoline alkaloids which occur in the plant family. They are good
synthons for substituted quinolinones which have been of increasing interest
since many of these compounds have found useful applications as
chemotherapeutic agents.
On the basis of the above importance, the present work aim to synthesize
a series of pyranoquinoline and 3- substituted quinoline derivatives which are
important in the field of organic chemistry.
Thus, 2-amino-4-aryl-5-oxo-5,6-dihydro-4H-pyrano[3,2-c]quinolines 6a-f
were prepared via reacting arylmethylenemalononitriles 2-c,g with 4-
hydroxyquinolines 1a-c or 1e,f in refluxing ethanol containing catalytic amounts
of piperidine (cf.Scheme 1).
Refluxing 2-amino-4-(2-chlorophenyl)-6-methyl -5-oxo-5,6-dihydro -4Hpyrano[
3,2-c] quinoline-3-carbonitrile 6d with formic acid or acetic anhydride
give 7-(2-chlorophenyl)-5-methyl-5H-pyrimido [5’4’:5,6 ]pyrano[3,2-c]
quinoloine-6,8-(7H,11H)-dione 7 and 7-(2-chlorophenyl) -5,10-dimethyl-5Hpyrimido
[5’4’:5,6] pyrano[3,2-c] quinoloine-6,8-(7H,9H) -dione 9
respectively(cf.Scheme 2).
II
ENGLISH SUMMARY
Reacting 3-acetyl-1-benzyl-4-hydroxyquinolin-2(1H)-one1d with aryl
methylenemalononitiriles 2a,d give 5-amino-4-aryl-2-(1-benzyl-4-hydroxy-2-
oxo-1,2-dihydroquinoline-3-yl)-7-imino-7H-pyrano[2,3-b]pyridine-6-
carbonitriles 12a,b(cf.Scheme 3) .
Compounds 2-acetyl-1-hydroxy-6,7-dihydropyrido [3,2,1-ij] quinolin-
3(5H)-one 1c or1-hydroxy-6,7-dihydropyrido [3,2,1-ij] quinolin-3(5H)-one 1g
reacted with arylmethylenemalononitiriles 2e,f to give 11-amino-8-oxo-9-
substituted-5,6,8,9-tetrahydro-4H-pyrano[3,2-c] pyrido[3,2,1-ij] quinoline-10-
carbonitriles 15a,b(cf.Scheme 4).
Reacting 2-acetyl-1-hydroxy-6,7-dihydropyrido [3,2,1-ij]quinolin-3(5H)-
one 1c or 1g with ethoxymethylenemalononitrile 16 afford 11-imino -4H, 5H,
6H, 9H-benzo [ij][2,3-b]quinolizin-8-one 18(cf.Scheme 5) .
Also, reacting 2-acetyl-1-hydroxy-6,7-dihydropyrido [3,2,1-ij] quinolin-
3(5H)-one 1c or1-hydroxy-6,7-dihydropyrido [3,2,1-ij] quinolin-3(5H)-one 1g
with methyl 2-benzolyamino-3-dimethylaminopropionate 19 yield N-(6-(1-
hydroxy-3-oxo-3,5,6,7-tetrahydropyrido[3,2,1-ij]quinolin-2-yl)-2-oxo-2Hpyran-
3-yl)benzamide 21 and N-(8,11-dioxo-5,6,8,11-tetrahydro-4H-pyrano[3,2-
c]pyrido[3,2,1-ij]quinolin-10-yl)benzamide 22 respectively(cf.Scheme 6) .
Condensation of 2-acetyl-1-hydroxy-6,7-dihydropyrido [3,2,1-
ij]quinolin-3(5H)-one 1c with aromatic aldehydes afford 2,2’-
(arylmethylene)bis(1-hydroxy-6,7-dihydropyrido[3,2,1-ij]quinolin-3(5H)-ones)
28a-d (cf.Scheme 7).
The newly synthesized compounds were elucidated by elemental analysis
and spectral data.
III
ENGLISH SUMMARY
N O
R1
R2
OH
R
1
1 R R1 R2
a H C2H5 COCH3
b H CH3 COCH3
c - (CH2)3 - COCH3
d H CH2Ph COCH3
e H C2H5 H
f H CH3 H
g - (CH2)3 - H
CN
X
2
R3
2 R3 X
a C6H4OPh(m) CN
b C6H4Cl(o) CN
c C6H4NO2(o) CN
d C6H4OH(p) CN
e H CN
f CH3 CN
g C6H4OPh(m) CO2C2H5
IV
ENGLISH SUMMARY
N O
R1
R2
OH
N
N
N
N
OH
O
R1
R1
O
O
R3
NC
X
COCH3
OH
R3
X
NC
O
R1
O
NH2
X
R3
O
R1
CN
X
CN
X
1 a,b
O
R3
X
NH2
R2 = COCH3
R3 = Ar
2
2
R2 = H
R3 = Ar
3
4
5
6
H2O - CH3CO2H
=
R3
R3
6 R1 R3 X
a C2H5 C6H4OPh(m) CN
b C2H5 C6H4Cl(o) CN
c C2H5 C6H4NO2(o) CN
d CH3 C6H4Cl(o) CN
e CH3 C6H4OPh(m) CN
f C2H5 C6H4OPh(m) CO2C2H5
Scheme 1
V
ENGLISH SUMMARY
N
O
N
O
HN N
N
O
CN
NHCOCH3
N
O
N NH
CH3
O
Ar
CN
NH2
O
Ar
O
CH3
O
CH3
Ar
CH3
O
Ar
O
CH3
6 d
9, Ar = C6H4Cl(o)
Scheme 2
=
8
7, Ar = C6H4Cl(o)
HCO2H
(CH3CO)2O
VI
ENGLISH SUMMARY
N
N
N
N
O N
OH
O
NH
CN
R3 NH2
Ph
Ph
O NH
CN
O
OH
R3
OH
Ph
CH3
O
O
OH
O
Ph
O R3
CN
CN
CN
CN
1 d 2 b,d
10
11
CH2(CN)2
12 a, R3 = C6H4Cl(o)
b, R3 = C6H4OH(p)
Scheme 3
-H2
+
R3
VII
ENGLISH SUMMARY
CN
CN
N
N
N
N
N
O
O
OH
COCH3
O
O
R3
CN
NC
OH
O
R3
CN
NC
NH2
CN
R3
O
COCH3 1 c
13
O
OH
1 g
14
15
2 e, f
H2O - CH3CO2H
a, R3 = H
b, R3 = CH3
Scheme 4
R3
CN
C2H5O CN
N
N
N
N
O
O
O
COCH3
NC
CN
O
OH
NH
CN
O
O
OH
COCH3
1 c
1g
16
17
18
H2O - CH3CO2H
Scheme 5
- C2H5OH
- C2H5OH
VIII
ENGLISH SUMMARY
NHCOPh
H3C N CO2CH3
CH3
N
N
N
N
N
OH
O
O
OH O
H3CO2C NHCOPh
O
OH
OH
O O
O
O
NHCOPh
O
NHCOPh
O
1c
COCH3
19
20
- NH(CH3)2
- CH3OH
21
1f
22
- NH(CH3)2
- C2H5OH
Scheme 6
IX
ENGLISH SUMMARY
N
OH
O
COCH3
ArCHO
N
N
N N
N
OH
O
COCH3
N N
Ar
O
O
O
O
O
Ar
O
OH
COCH3
Ar
HO
OH
O
OH
Ar
O
H3C
O
O
O Ar O
N O O N
OH Ar OH
H2O - CH3CO2H
- H2O
- CH3CO2H
H2O
1 c
23
24
26 25
1 c
27 28 a, Ar = C6H5
b, Ar = C6H4OH(p)
c, Ar = C6H4Cl(p)
d, Ar = C6H4Br(p)
Scheme 7