Oxidation of 4,7-phenanthroline derivatives

Article abstract of DOI:10.1007/s11178-005-0014-4

Oxidation of 1,3-diphenyl-4,7-phenanthroline with potassium permanganate in alkaline medium results in transformation of the 4,7-phenanthroline ring system into 1,8-diaazafluorenone. Oxidation of 12-aryl-and 12-aryl-9,9-dimethyl-8,9, 10,12-tetrahydro-7H-benzo[b][4,7]phenanthrolin-11-ones (condensation products of 6-arylmethylene-aminoquinolines with 1,3-cyclohexanedione and dimedone) with sodium nitrite in acetic acid leads to 12-aryl-9,10-dihydro-8H-benzo[b][4,7] phenanthrolin-11-ones. 13-Aryl-7,13-dihydro-12H-indeno-[2,1-b][4,7] phenanthrolin-12-ones obtained by reaction of 6-arylmethyleneaminoquinolines with 1,3-indandione are oxidized to 13-aryl-12H-indeno[2,1-b][4,7]phenanthrolin- 12-ones on heating in nitrobenzene.

Full text of DOI:10.1007/s11178-005-0014-4

Russian Journal of Organic Chemistry, Vol. 40, No. 9, 2004, pp. 1322–1328. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004,
pp. 1369–1375.
Original Russian Text Copyright © 2004 by Gusak, Kozlov, Tereshko.
Oxidation of 4,7-Phenanthroline Derivatives
K. N. Gusak, N. G. Kozlov, and A. B. Tereshko
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 220072 Belarus
e-mail: loc@ifoch.bas-net.by
Received March 23, 2004
Abstract—Oxidation of 1,3-diphenyl-4,7-phenanthroline with potassium permanganate in alkaline medium
results in transformation of the 4,7-phenanthroline ring system into 1,8-diaazafluorenone. Oxidation of 12-aryl-
and 12-aryl-9,9-dimethyl-8,9,10,12-tetrahydro-7H-benzo[b][4,7]phenanthrolin-11-ones (condensation products
of 6-arylmethylene-aminoquinolines with 1,3-cyclohexanedione and dimedone) with sodium nitrite in acetic
acid leads to 12-aryl-9,10-dihydro-8H-benzo[b][4,7]phenanthrolin-11-ones. 13-Aryl-7,13-dihydro-12H-indeno-
[2,1-b][4,7]phenanthrolin-12-ones obtained by reaction of 6-arylmethyleneaminoquinolines with 1,3-indan-
dione are oxidized to 13-aryl-12H-indeno[2,1-b][4,7]phenanthrolin-12-ones on heating in nitrobenzene.
Among chemical transformations of 4,7-phenan-
throline derivatives, oxidation of these compounds
attracts specific attention. Formerly, 4,7-phenanthro-
line was oxidized with the goal of proving the angular
structure of the compound obtained from p-phenylene-
diamine or 6-aminoquinoline according to Skraup
[1, 2]. The subsequent interest in oxidation of
4,7-phenanthrolines arose from search for efficient
methods of synthesis of 4,7-phenanthroline-5,6-dione
and its analogs which exhibit a high antibacterial
activity and are used for treatment of gastrointestinal
diseases [3–8]. It was shown that 5- or 6-hydroxy-,
methoxy-, or amino-substituted 4,7-phenanthrolines
are oxidized to 4,7-phenanthroline-5,6-dione more
readily than unsubstituted 4,7-phenanthroline [6–8].
The formation of an analogous compound, 4,5-di-
azafluoren-9-one, as an impurity to 3,3'-bipyridinedi-
carboxylic acid was observed previously in the oxida-
tion of 1,10-phenanthroline with an alkaline solution of
KMnO4 [10]. This fact has attracted interest from the
viewpoint of possible synthesis of difficultly accessible
compounds of the diazafluorenone series. A procedure
was developed for the preparation of isomeric diaza-
fluoren-9-ones by oxidation of 1,7-, 1,8-, 1,9-, 1,10-,
and 2,8-phenanthrolines with potassium permanganate;
however, the yield of 1,8-diazafluoren-9-one from
4,7-phenanthroline did not exceed 2% [11]. Therefore,
1,8-diazafluoren-9-one was obtained by oxidation of
5-methoxy-4,7-phenanthroline to 4,7-phenanthroline-
5,6-dione and subsequent thermal treatment of the
latter with alkali [11].
In the present work we were the first to study
oxidation of 1,3-diphenyl-4,7-phenanthroline (I) with
potassium permanganate in alkaline medium. Phenan-
throline I was prepared by condensation of 6-ben-
zylideneaminoquinoline with acetophenone in butyl
alcohol in the presence of concentrated hydrochloric
acid [9]. The oxidation was carried out by heating
a suspension of phenanthroline I in an aqueous solu-
tion of KMnO4 and KOH. By analogy with the data of
[1, 2], we anticipated that the oxidation product will be
4,6-diphenyl-3,3'-bipyridine-2,2'-dicarboxylic acid A.
Its decarboxylation should give rise to the corre-
sponding 3,3'-bipyridine B. However, instead of acid
A, the only oxidation product was 2,4-diphenyl-1,8-
diazafluoren-9-one (II) (yeld 36%).
Taking into account the above data, as well as the
data on transformations of phenanthrene- and diaza-
phenanthrenequinones in alkaline medium [12, 13], we
presumed that the primary oxidation product of
phenanthroline I is 1,3-diphenyl-4,7-phenanthroline-
5,6-dione C which undergoes rearrangement (by
analogy with benzilic acid rearrangenent [14]) into
unstable α-hydroxy acid D. Decarboxylation of the
latter yields 2,4-diphenyl-1,8-diazafluoren-9-one (II)
(Scheme 1).
The IR spectrum of diazafluorenone II contained
a strong absorption band at 1740 cm–1 due to stretching
vibrations of the carbonyl group. The molecular ion
[M]+, m/z 334, was the most abundant (Irel = 100%) in
1070-4280/04/4009-1322 © 2004 MAIK “Nauka/Interperiodica”

OXIDATION OF 4,7-PHENANTHROLINE DERIVATIVES
1323
Scheme 1.
O
Ph
Ph
Ph
Ph
Ph
N
NH
NH
PhCOMe
N
N
N
E
F
Ph
Ph
N
Ph
Ph
Ph
Ph
N
N
COOH
COOH
N
N
N
I
A
B
Ph
Ph
Ph
Ph
N
Ph
Ph
N
N
N
N
O
N
COOH
O
HO
O
C
D
II
synthesis of initial 1,3-diaryl-4,7-phenanthrolines by
reaction of CH acids with Schiff bases derived from
6-aminoquinoline, in particular in the synthesis of
1,3-diphenyl-4,7-phenanthroline (I). In the first stage,
CH acid (acetophenone) adds at the C=N bond of
6-benzylideneaminoquinoline to give 1,3-diphenyl-3-
(6-quinolylamino)propanone E which undergoes intra-
molecular ring closure to 1,3-diphenyl-3,4-dihydro-
4,7-phenanthroline F with elimination of water. The
subsequent oxidation (or dehydrogenation) of F yields
1,3-diphenyl-4,7-phenanthroline (I) (Scheme 1).
the mass spectrum of II; in addition, the following
fragment ion peaks were present in the mass spectrum,
m/z (Irel, %): 305 (31) [M – 1 – CO]+, 281 (19) [M –
2 – CO – HCN]+, 254 (20) [M – 2 – CO – 2HCN]+.
The UV spectrum of II, as well as of isomeric 4,5-di-
azafluoren-9-one [10], consists of three absorption
bands with their maxima at 207 (logε = 4.48), 255
(logε = 4.26), and 320 nm (logε = 4.18). Unlike the
4,5-diaza analog, the long-wave absorption band in
the spectrum of 1,8-diazafluoren-9-one (II), which
originates from the presence of a carbonyl group, lacks
vibrational structure; presumably, the reason is that
both nitrogen atoms are located close to the carbonyl
By analogy with Skraup’s procedure, where
an oxidant is added to the reaction medium in order
to effect dehydrogenation of intermediate dihydro
derivative [1, 2], we performed condensation of
6-benzylideneaminoquinoline with acetophenone in
the presence of nitrobenzene. We also tried to isolate
intermediate dihydrophenanthroline by carrying out
the reaction in the absence of nitrobenzene. However,
in the absence of an oxidant at room temperature,
the product was aminoketone E, while at elevated
temperature 1,3-diphenyl-4,7-phenanthroline (I) was
obtained. These data indicate ready oxidation of the
1
group. In the H NMR spectrum of diazafluorenone
II we observed no one-proton doublets at δ 8.22 and
8.33 ppm, which are typical of initial 1,3-diphenyl-4,7-
phenanthroline (5-H and 6-H, respectively).
Insofar as 2,4-diphenyl-1,8-diazafluoren-9-one (II)
was the only product, the oxidation of 1,3-diaryl-4,7-
phenanthrolines with potassium permanganate can be
regarded as a method for preparation of new deriva-
tives of the 1,8-diazafluoren-9-one series. It should
be noted that redox processes also occur during the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 9 2004

GUSAK et al.
1324
1,2-dihydropyridine ring in the 4,7-phenanthroline
molecule. Furthermore, no appreciable affect of
an oxidant on the yield of phenanthroline I was
observed; therefore, further condensations of 6-aryl-
methyleneaminoquinolines with acetophenone were
performed in the absence of nitrobenzene. The reac-
tions of halo- and hydroxy-substituted Schiff bases
with acetophenone (in the absence of nitrobenzene),
apart from the target 1,3-diaryl-4,7-phenanthrolines,
afforded the corresponding 6-benzylaminoquinolines
which were likely to be formed by reduction of the
initial Schiff bases with hydrogen liberated during
aromatization (dehydrogenation or oxidation) of the
3,4-dihydro-4,7-phenanthroline ring [9].
Scheme 2.
O
R'
R'
R
R
O
O
G
N
+
R'
R'
R'
O
O
R'
N
NH
N
H
R
R
10
R'
R'
O
O
9
R'
11
R'
8
12
1
NH
N
2
3
6
N
N
5
III–V
VI–VIII
R
R
O
O
N
+
O
O
N
XIII, XIV
11
O
12
10
R
R
O
9
13
8
1
NH
N
2
3
6
N
N
5
IX, X
XI, XII
III, VI, R = 3-OH; IV, VII, R = 2,4-Cl2; V, VIII, R = 3,4-OCH2O; IX, XI, XIII, R = 4-Br; X, XII, XIV, R = 3-NO2;
III, IV, VI, VII, R' = H; V, VIII, R' = Me.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 9 2004

OXIDATION OF 4,7-PHENANTHROLINE DERIVATIVES
1325
The condensation of 6-arylmethyleneaminoquino-
lines with cyclic β-dicarbonyl compounds, 1,3-cyclo-
hexanedione, dimedone, and 1,3-indandione takes
a different pathway. Due to high reactivity of the
methylene group in position 2 of cyclic 1,3-diketone
(CH acid) and the carbonyl groups, 1,3-cyclohexane-
dione and dimedone are capable of reacting with each
precursor of the Schiff base which undergoes hydrol-
ysis in alcoholic medium, i.e., with aromatic aldehyde
and 6-aminoquinoline to give, respectively, enedione
G and enamine H. Cyclocondensation of intermediate
G with 6-aminoquinoline and of enamine H with
aromatic aldehyde leads to formation of the same
product, 4,7-phenanthroline incorporating a 1,4-di-
hydropyridine ring fused to a cyclohexane ring,
12-aryl-8,9,10,12-tetrahydro-7H-benzo[b][4,7]phen-
anthrolin-11-one III or IV or 9,9-dimethyl derivative
V (Scheme 2).
system leads to appearance of a highly intense absorp-
tion band at λ 295–296 nm (logε 4.78–4.85) and less
intense bands at λ 253–255 (logε 4.49–4.52) and 337–
345 nm (logε 3.98–4.00); the presence of these bands
makes the UV spectra of VI–VIII similar to those of
1,3-diaryl-4,7-phenanthrolines [9], and they can be
identified as p-, β-, and α-bands according to Clar. As
compared to 1,3-diarylphenanthrolines, the vibrational
structure of the α-band in the spectra of VI–VIII is
smoothed, presumably due to the presence of a fused
cyclohexane ring [15].
The 1H NMR spectra of VI–VIII contain no signals
at δ 9.57–9.60 and 5.78–5.80 ppm, which are observed
in the spectra of initial phenanthrolines III–V (NH and
12-H in the 1,4-dihydropyridine ring, respectively).
Aromatization of the 4,7-phenanthroline ring system in
VI–VIII makes the substituted benzene ring on C12
acoplanar to the tricyclic system, and the 1-H proton
appears in the cone affected by the ring current of the
aryl substituent; as a result, the 1-H signal shifts con-
siderably upfield relative to the corresponding signal
of initial phenanthrolines III–V and is located at
δ 7.59–7.80 ppm. The 5-H and 6-H signals in the
spectra of VI–VIII are displaced to a weaker field
due to effect of the electronegative pyridine-like
nitrogen atom.
Unlike 3,4-dihydrophenanthrolines F, the dihydro-
pyridine ring in III–V is stable to oxidation. Aroma-
tization of the 4,7-phenanthroline system occurs
neither during the synthesis of III–V nor on prolonged
heating with excess nitrobenzene. We were the first to
effect oxidation of phenanthrolines III–V by the action
of sodium nitrite in acetic acid.
In contrast to initial compounds III–V, the IR spe-
ctra of their oxidation products, 12-aryl- and 12-aryl-
9,9-dimethyl-9,10-dihydro-8H-benzo[b][4,7]phenan-
throlin-11-ones VI–VIII lacked absorption band at
3290–3280 cm–1, which is typical of amino group
stretching vibrations. Instead of strong bands at 1580
and 1525 cm–1 due to vinylogous amide fragment in
the spectra of III–V [14], oxidation products VI–VIII
give rise to one carbonyl stretching vibration band at
1680–1675 cm–1.
Condensation products of 6-arylmethyleneamino-
quinolines with 1,3-indandiones, 13-aryl-7,13-dihydro-
12H-indeno[2,1-b][4,7]phenanthrolin-12-ones IX and
X, are oxidized more readily than their cyclohexene
analogs III–V. On heating in boiling nitrobenzene for
3–4 h, intensely red dihydro derivatives IX and X are
converted into aromatic 13-arylindeno[2,1-b][4,7]-
phenanthrolin-12-ones XI and XII which precipitate
from the reaction solution (after cooling) as greenish–
yellow crystals. While preparing initial dihydrophen-
anthrolines IX and X, we have found that the reaction
mixtures contained 2-arylmethylene-1,3-indandiones
XIII and XIV before formation of the target products.
Therefore, we presumed that dihydroindenophenan-
throlinones IX and X are formed via reaction of
1,3-indandione with aromatic aldehydes (which are
products of hydrolysis of the initial Schiff bases),
followed by condensation of 2-arylmethylene-1,3-in-
dandiones XIII and XIV with 6-aminoquinoline. This
reaction scheme was confirmed by the synthesis of
dihydrophenanthrolinones IX and X by condensation
of 6-aminoquinoline with 2-arylmethylene-1,3-in-
dandiones XIII and XIV which were prepared in
turn by reaction of 1,3-indandione with substituted
benzaldehydes.
The mass spectra of VI–VIII contain the molecular
ion peak [M]+ which has the maximal intensity
(Irel 100%), [M – C6H4R]+ ion peak ([M – C6H3R]+ for
compound VII) with m/z 247 (phenanthrolines VI and
VII, Irel 15–18%) or 275 (dimethyl derivative VIII,
Irel 24%), and ion peak with m/z 191 (Irel 10–17%)
which corresponds to elimination of the CH2CH2CO
fragment (Me2CCH2CO for compound VIII) from
[M – C6H4R]+.
The UV spectra of compounds VI–VIII having an
extended conjugated bond system differ from the
spectra of initial tetrahydro derivatives III–V which
possess three independent chromophores (quinoline
ring, aryl substituent, and carbonyl group) (see
Experimental). Aromatization of the heterocyclic
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 9 2004

GUSAK et al.
1326
It should be noted that dihydroindenophenanthro-
spectrometer. The NMR spectra were measured on
Bruker AC-500 (500 MHz, Bruker) and Tesla BS-567
(100 MHz) spectrometers using DMSO-d6 as solvent
and TMS as internal reference. The UV spectra were
recorded from solutions in ethanol (c = 10–4 M) on
a Specord UV-Vis spectrometer. The melting points
were recorded on a Kofler device.
linones IX and X undergo partial oxidation on melting;
however, we failed to attain the complete conversion
of IX and X into aromatic compounds XI and XII in
this way. In order to isolate pure oxidation products,
mixtures IX/XI and X/XII should be heated in boiling
nitrobenzene for an additional 3 h.
The IR spectra of indenophenanthrolines XI and
XII contain no NH stretching vibration band at 3260–
3230 cm–1, which is present in the spectra of initial
compounds IX and X. The carbonyl absorption band in
the spectra of XI and XII is displaced toward higher
frequencies, as compared to IX and X (νCO 1710
against 1670–1660 cm–1, respectively). The mass spe-
ctra of XI and XII contain the molecular ion peaks
[M]+ (Irel 100%) and fragment ion peaks [M – C6H4R]+
with m/z 281 (Irel 47–50%). In addition, [M – Br]+ ion
peak with m/z 357 (Irel 66%) was observed in the mass
spectrum of XI, and [M – NO]+ (m/z 373, Irel 26%) and
[M – NO2]+ ion peaks (m/z 357, Irel 20%), in the
spectrum of XII. As a result of aromatization of the
1,3-Diphenyl-4,7-phenanthroline (I) was synthe-
sized by the procedure reported in [9]. 2-Aryl-
methylene-1,3-indandiones XIII and XIV were ob-
tained and identified as described in [17, 18].
Oxidation of 1,3-diphenyl-4,7-phenanthroline
(I). Potassium hydroxide, 1.0 g, and powdered potas-
sium permanganate, 2.0 g, were added with stirring to
a suspension of 1.1 g (3 mmol) of phenanthroline (I)
in 300 ml of water. The mixture was heated for 12 h
at 100°C under vigorous stirring, cooled, and filtered
from MnO2. The filtrate was evaporated by half and
extracted with chloroform. The extract was evaporated,
the solid residue was treated with boiling benzene to
remove traces of unreacted phenanthroline I, and the
undissolved material was recrystallized from DMF.
Yield of 2,4-diphenyl-1,8-diazafluoren-9-one (II) 0.4 g
1
dihydropyidine ring, the H NMR spectra of XI and
XII lack signals at δ 5.92–6.20 and 9.95–9.98 ppm
which belong to the 13-H and NH protons in the
spectra of dihydro derivatives IX and X. The 1-H
signal in the spectra of XI and XII is displaced upfield,
as was observed for cyclohexene analogs VI–VIII.
1
(36%), mp 312–313°C. H NMR spectrum, δ, ppm:
4
7.18 d.d (6-H) (3J = 8.2, J = 4.1 Hz), 7.68 s (3-H),
3
4
7.90 d (5-H, J = 8.0 Hz), 8.33 d.d (7-H, 3J = 4.1, J =
2.0 Hz), 7.43 m and 8.22 m (10H, Harom). Found, %:
C 82.53; H 4.02; N 8.14. C23H14N2O. Calculated, %:
C 82.63; H 4.19; N 8.38.
Aromatization of the 4,7-phenanthroline ring
system also leads to transformation of the UV spectra
where intense absorption bands appear at λ 225, 253–
258 (p-band), and 298–299 nm (β-band). The result is
that the UV spectra of indenophenanthrolines XI and
XII become typical of those observed for compounds
of the azaphenanthrene series, specifically for 1,3-di-
aryl-4,7-phenanthrolines [9]. An exception is the long-
wave α-band. This band is fairly intense in the spectra
of azaphenanthrenes and is generally characterized by
vibrational structure [9, 16]. The corresponding band
in the spectra of XI and XII appears as a weak
shoulder at λ 334–337 nm.
12-Aryl-8,9,10,12-tetrahydro-7H-benzo[b][4,7]-
phenanthrolin-11-ones III and IV. A solution of
5 mmol of 1,3-cyclohexanedione and 5 mmol of the
corresponding Schiff base in 20 ml of 1-butanol was
heated for 3 h under reflux. The precipitate was filtered
off and recrystallized from ethanol–benzene (2:1).
12-(3-Hydroxyphenyl)-8,9,10,12-tetrahydro-7H-
benzo[b][4,7]phenanthrolin-11-one (III). Yield 75%,
1
mp 323–324°C. H NMR spectrum, δ, ppm: 1.92 m
(2H, 9-H), 2.25 m (2H, 8-H), 2.66 m (2H, 10-H),
5.75 s (12-H), 6.32–7.00 m (4H, Harom), 7.36 d (2-H,
3J = 8.1 Hz), 7.52 d and 7.87 d (5-H, 6-H, 3J = 8.5 Hz),
Thus, oxidation of 4,7-phenanthrolines having a di-
hydropyridine ring leads to formation of new com-
pounds of the 4,7-phenanthroline series, which possess
an extended conjugation system and are promising as
luminescent and light-sensitive materials.
3
3
8.29 d (1-H, J = 8.4 Hz), 8.67 d (3-H, J = 4.8 Hz),
9.06 s (OH), 9.85 s (NH). UV spectrum, λmax, nm
(logε): 219 (4.63), 254 (4.26), 299 (4.12), 336 (3.99),
382 (3.90). Found, %: C 76.81; H 5.29; N 7.96.
C22H18N2O2. Calculated, %: C 77.19; H 5.26; N 8.19.
EXPERIMENTAL
12-(2,4-Dichlorophenyl)-8,9,10,12-tetrahydro-
The mass spectra (electron impact, 70 eV) were
obtained on a Finnigan MAT INCOS 50 instrument.
The IR spectra were recorded on a Nicolet Protégé-460
7H-benzo[b][4,7]phenanthrolin-11-one (IV). Yield
1
80%, mp 307–308°C. H NMR spectrum, δ, ppm:
1.90 m (2H, 9-H), 2.21 m (2H, 8-H), 2.63 m (2H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 9 2004

OXIDATION OF 4,7-PHENANTHROLINE DERIVATIVES
1327
3
4
10-H), 6.00 s (12-H), 7.18 m (3H, Harom), 7.33 d (2-H,
8.9 Hz), 8.76 d.d (3-H, J = 4.2, J = 2.1 Hz). Found,
%: C 67.03; H 3.58; Cl 17.84; N 6.96. C22H14Cl2N2O.
Calculated, %: C 67.18; H 3.56; Cl 18.07; N 7.12.
3J = 8.4 Hz), 7.50 d and 7.86 d (5-H, 6-H, 3J = 8.8 Hz),
3
3
8.29 d (1-H, J = 8.4 Hz), 8.67 d (3-H, J = 4.8 Hz),
9.90 s (NH). UV spectrum, λmax, nm (logε): 219 (4.60),
248 (4.29), 2.97 (4.10), 335 (4.12), 383 (3.91). Found,
%: C 66.78; H 3.81; Cl 17.52; N 7.29. C22H16Cl2N2O.
Calculated, %: C 67.00; H 4.06; Cl 17.77; N 7.11.
9,9-Dimethyl-12-(3,4-methylenedioxyphenyl)-
9,10-dihydro-8H-benzo[b][4,7]phenanthrolin-11-
one (VIII). Yield 71%, mp 233–234°C. 1H NMR spec-
trum, δ, ppm: 1.10 s (6H, Me); 2.40–2.60 m (4H, 8-H,
10-H); 6.08 m (OCH2O); 6.62 d, 6.83 s, and 7.00 d
(3H, Harom, J = 7.2 Hz); 7.28 d.d (2-H, J = 8.1, J =
2.8 Hz); 7.52 d (1-H, J = 8.1 Hz); 8.09 d and 8.19 d
(5-H, 6-H, J = 8.9 Hz); 8.80 d.d (3-H, J = 4.6,
4J = 2.2 Hz). Found, %: C 75.48; H 4.98; N 7.03.
C25H20N2O3. Calculated, %: C 75.76; H 5.05; N 7.07.
9,9-Dimethyl-12-(3,4-methylenedioxyphenyl)-
8,9,10,12-tetrahydro-7H-benzo[b][4,7]phenanthro-
lin-11-one (V) was synthesized from dimedone and
6-(3,4-methylenedioxyphenylmethyleneamino)quino-
line following the procedure described above for com-
pounds III and IV. Yield 61%, mp 321–322°C.
1H NMR spectrum, δ, ppm: 0.89 s (Me), 1.10 s (Me),
3
3
4
3
3
3
13-Aryl-7,13-dihydro-12H-indeno[2,1-b][4,7]-
phenanthrolin-12-ones IX and X. a. A solution of
5 mmol of 6-arylmethyleneaminoquinoline and
5 mmol of 1,3-indandione in 30 ml of 2-propanol was
heated for 16 h under reflux. During that period,
1 mmol of 6-aminoquinoline was added in 2, 4, and
6 h. The red precipitate was filtered off and recrystal-
lized from nitrobenzene–toluene (2:1).
2
2.10 d.d (2H, 10-H, J = 16.0 Hz), 2.48 m (2H, 8-H),
5.67 s (12-H), 5.84 m (OCH2O), 6.59 s and 6.78 s (3H,
Harom), 7.27 d.d (2-H, 3J = 8.4, 4J = 2.8 Hz), 7.49 d and
3
3
7.80 d (5-H, 6-H, J = 8.6 Hz), 8.28 d (1-H, J =
3
8.4 Hz), 8.60 d (3-H, J = 4.6 Hz), 9.59 s (NH). UV
spectrum, λmax, nm (logε): 214 (4.58), 243 (4.23), 291
(4.08), 333 (4.10), 380 (3.98). Found, %: C 75.40;
H 5.31; N 7.11. C25H22N2O3. Calculated, %: C 75.38;
H 5.53; N 7.04.
b. A solution of 5 mmol of 2-arylmethylene-1,3-
indandione XIII or XIV and 7.5 mmol of 6-amino-
quinoline in 30 ml of 2-propanol was heated for 8–10 h
under reflux. The products were isolated as described
above in a.
Oxidation of 12-aryl-8,9,10,12-tetrahydro-7H-
benzo[b][4,7]phenanthrolin-11-ones III and IV and
9,9-dimethyl-12-(3,4-methylenedioxyphenyl)-8,9,-
10,12-tetrahydro-7H-benzo[b][4,7]phenanthrolin-
11-one (V). A solution of 10 mmol of NaNO2 in 5 ml
of water was added with stirring at 3–5°C to a solution
of 5 mmol of tetrahydrophenanthrolinone III–V in
15 ml of acetic acid, and the mixture was stirred for
30 min at that temperature. The mixture was
neutralized with aqueous ammonia, and the precipitate
of VI–VIII was filtered off and recrystallized from
ethanol–benzene (3:1) (VI, VII) or ethanol (VIII).
13-(4-Bromophenyl)-7,13-dihydro-12H-indeno-
[2,1-b][4,7]phenanthrolin-12-one (IX). Yield 54%
1
(a), 61% (b); mp 315–316°C. H NMR spectrum, δ,
ppm: 5.92 s (13-H), 7.29–7.48 m and 7.68 d (9H, 2-H,
3
8-H, 9-H, 10-H, 11-H, Harom, J = 7.1 Hz), 7.83 d and
8.04 d (5-H, 6-H, J = 9.0 Hz), 8.36 d (1-H, J =
7.4 Hz), 8.77 d (3-H, J = 4.9 Hz), 9.95 s (NH). UV
spectrum, λmax, nm (logε): 200 (4.81), 236 (4.80), 269
(4.76), 353 (4.09), 480 (3.80). Found, %: C 68.14;
H 3.29; Br 17.93; N 6.17. C25H15BrN2O. Calculated,
%: C 68.43; H 3.42; Br 18.22; N 6.38.
3
3
3
12-(3-Hydroxyphenyl)-9,10-dihydro-8H-benzo-
[b][4,7]phenanthrolin-11-one (VI). Yield 79%,
1
mp 307–308°C. H NMR spectrum, δ, ppm: 1.90 m
13-(3-Nitrophenyl)-7,13-dihydro-12H-indeno-
[2,1-b][4,7]phenanthrolin-12-one (X). Yield 69% (a),
(2H, 9-H), 2.21 m (2H, 8-H), 2.60 m (2H, 10-H), 6.41–
3
1
6.96 m (4H, Harom), 7.28 d (2-H, J = 8.0 Hz), 7.65 d
72% (b); mp 370–371°C. H NMR spectrum, δ, ppm:
3
(1-H, J = 8.0 Hz), 8.06 d and 8.18 d (5-H, 6-H,
6.20 s (13-H); 7.32–7.50 m, 7.56 t, 7.70 d, 7.80 d,
7.88 d, and 8.28 s (9H, 2-H, 8-H, 9-H, 10-H, 11-H,
3
4
3J = 8.8 Hz), 8.78 d.d (3-H, J = 4.9, J = 2.8 Hz),
9.00 s (OH). Found, %: C 77.34; H 4.69; N 7.93.
C22H16N2O2. Calculated, %: C 77.65; H 4.71; N 8.24.
3
3
H
arom, J = 7.4 Hz); 8.04 d and 8.10 d (5-H, 6-H, J =
3
3
8.9 Hz); 8.44 d (1-H, J = 7.6 Hz); 8.76 d (3-H, J =
4.7 Hz); 9.91 s (NH). UV spectrum, λmax, nm (logε):
202 (4.61), 238 (4.51), 268 (4.56), 350 (3.87), 475
(3.68). Found, %: C 73.78; H 3.61; N 10.11.
C25H15N3O3. Calculated, %: C 74.07; H 3.70; N 10.37.
12-(2,4-Dichlorophenyl)-9,10-dihydro-8H-benzo-
[b][4,7]phenanthrolin-11-one (VII). Yield 75%,
1
mp 304–305°C. H NMR spectrum, δ, ppm: 1.89 m
(2H, 9-H), 2.24 m (2H, 8-H), 2.61 m (2H, 10-H), 7.15–
3
7.24 m (3H, Harom), 7.30 d (2-H, J = 7.8 Hz), 7.68 d
Oxidation of 13-aryl-7,13-dihydro-12H-indeno-
[2,1-b][4,7]phenanthrolin-12-ones IX and X. A mix-
3
3
(1-H, J = 7.8 Hz), 8.02 d and 8.14 d (5-H, 6-H, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 9 2004

GUSAK et al.
1328
4. Bailenger, J., Therapie, 1961, vol. 16, p. 287; Chem.
Abstr., 1964, vol. 60, p. 2222z.
5. Mashkovskii, M.D., Lekarstvennye veshchestva (Drugs),
Khar’kov: Torsing, 1998, vol. 2, p. 313.
6. FRG Patent no. 1232156, 1967; Chem. Abstr., 1967,
vol. 66, p. 115700b.
7. Fr. Patent no. 1369625, 1964; Chem. Abstr., 1965,
vol. 62, p. 1664i.
8. Fr. Patent no. 1382542, 1964; Chem. Abstr., 1965,
vol. 63, p. 7912a.
9. Kozlov, N.S., Gusak, K.N., Serzhanina, V.A., and
Krot, N.A., Khim. Geterotsikl. Soedin., 1985, p. 1398.
10. Eckhard, J.F. and Summers, L.A., Aust. J. Chem.,
1973, vol. 26, p. 2727.
11. Klock, K., Mlochowski, J., and Szulc, Z., J. Prakt.
Chem., 1977, vol. 319, p. 959.
ture of 1 mmol of dihydro derivative IX or X and
10 ml of nitrobenzene was heated for 3–4 h under
reflux. The precipitate was filtered off and recrystal-
lized from nitrobenzene–toluene (2:1).
13-(4-Bromophenyl)-12H-indeno[2,1-b][4,7]-
phenanthrolin-12-one (XI). Yield 85%, mp 379–
1
380°C. H NMR spectrum, δ, ppm: 7.24–7.62 m (9H,
3
2-H, 8-H, 9-H, 10-H, 11-H, Harom), 7.74 d (1-H, J =
3
7.6 Hz), 7.92 d and 8.09 d (5-H, 6-H, J = 8.8 Hz),
8.73 d (3-H, 3J = 4.7 Hz). Found, %: C 68.55; H 3.02;
Br 18.15; N 6.27. C25H13BrN2O. Calculated, %:
C 68.65; H 2.97; Br 18.31; N 6.41.
13-(3-Nitrophenyl)-12H-indeno[2,1-b][4,7]-
phenanthrolin-12-one (XII). Yield 92%, mp 339–
1
340°C. H NMR spectrum, δ, ppm: 7.26–7.44 m and
3
12. Diesveld, J.W., Borkent, J.H., and Laarhoven, W.H.,
Tetrahedron, 1982, vol. 38, p. 1803.
13. Mlochowski, J. and Skrowarczewska, Z., Roczn. Chem.,
1973, vol. 47, p. 2255.
14. Martinez, R., Cortes, E., and Toscano, R.A.,
7.52 d (5H, 2-H, 8-H, 9-H, 10-H, 11-H, J = 7.3 Hz);
3
7.71 d, 7.84 d, and 8.28 s (4H, Harom, J = 7.6 Hz),
7.79 d (1-H, 3J = 7.7 Hz); 8.00 d and 8.08 d (5-H, 6-H,
3
3J = 8.5 Hz); 8.69 d (3-H, J = 4.4 Hz). Found, %:
C 74.19; H 3.34; N 10,23. C25H13N3O3. Calculated, %:
C 74.44; H 3.23; N 10.42.
J. Heterocycl. Chem., 1990, vol. 27, p. 363.
15. Kozlov, N.S., Gusak, K.N., and Serzhanina, V.A., Dokl.
Akad. Nauk SSSR, 1986, vol. 287, p. 1142.
16. Kozlov, N.S., 5,6-Benzokhinoliny (5,6-Benzoquino-
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