Synthesis of hydrobenzo[b]phenanthrolinone derivatives proceeding from 8-aminoquinoline, and their spectral and luminescent properties

Article abstract of DOI:10.1134/S1070428012110061

By a three-component condensation of 8-aminoquinoline, aromatic aldehydes, and 1,3-diketones accompanied by the Hofmann-Martius rearrangement hydrobenzophenanthroline derivatives were synthesized. Their spectral and luminescence properties in ethanol solution were investigated at 293 and 77 K.

Full text of DOI:10.1134/S1070428012110061

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 11, pp. 1439−1446. © Pleiades Publishing, Ltd., 2012.
Original English Text © N.G. Kozlov, S.L. Bondarev, Yu.D. Zhikharko, V.N. Knyukshto, L.I. Basalaeva, 2012, published in Zhurnal Organicheskoi Khimii,
2012, Vol. 48, No. 11, pp. 1455−1462.
Synthesis of Hydrobenzo[b]phenanthrolinone Derivatives
Proceeding from 8-Aminoquinoline, and Their Spectral
and Luminescent Properties
N. G. Kozlova, S. L. Bondarevb, Yu. D. Zhikharkoa, V. N. Knyukshtoc, and L. I. Basalaevaa
aInstitute of Physical Organic Chemistry of the National Academy of Sciences of Belarus, Minsk, 220072 Belarus
e-mail: loc@ifoch.bas-net.by
bMinsk State Higher Radioengineering College, Minsk, Belarus
c Stepanov Physical Institute of the National Academy of Sciences of Belarus, Minsk, Belarus
Received April 30, 2012
Abstract—By a three-component condensation of 8-aminoquinoline, aromatic aldehydes, and 1,3-diketones
accompanied by the Hofmann–Martius rearrangement hydrobenzophenanthroline derivatives were synthesized.
Their spectral and luminescence properties in ethanol solution were investigated at 293 and 77 K.
DOI: 10.1134/S1070428012110061
The 8-aminoquinoline is the least studied among all
the known aminoquinolines. It is known from published
data that 8-aminoquinoline in reaction with para-substi-
tuted benzaldehyde does not provide Schiff bases and
forms only aminals [1]. The influence of the unshared
electron pair of the endocyclic nitrogen on the nega-
tive charge of the adjacent amino group likely prevents
the formation of the azomethine bond in the reaction
of 8-aminoquinoline with benzaldehyde. As a result of
this effect the nucleophilic substitution with the second
molecule of 8-aminoquinoline occurs at the carbon atom
of benzaldehyde with the formation of aminals. It was
formerly noted that in case the isolation of azomethines
is difficult or impossible the preparation of heterocyclic
products by three-component condensation of initial
reagent would be efficient [2, 3].
ing equimolar amounts of reagents in ethanol. Formerly
unknown 5-[(2-hydroxy-4,4-dimethyl-6-oxocyclohex-
1-en-1-yl)(4-R-phenyl)methyl]-10,10-dimethyl-7-(4-
R-phenyl)-10,11-dihydrobenzo[b][1,10]phenanthrolin-
8(5H,7H,9H)-ones Va–Ve and methyl 5-[(2-hydroxy-
5-(methoxycarbonyl)-4,4-dimethyl-6-oxocyclohex-1-
en-1-yl)(4-R-phenyl)methyl]-10,10-dimethyl-8-oxo-7-
(4-R-phenyl)-7,8,9,10,11,12-hexahydrobenzo[b]-[1,10]
phenanthrolin-9-carboxylates VIa–Ve were obtained in
51–75% yields.
In the reaction we have investigated it is reasonable
to suggest that first aldehydes Ia–Ie with diketones II,
III formed 2-arylidene-5,5-dimethylcyclohexane-1,3-
dione A that interacts along Mannich reaction with
8-aminoquinoline (IV) resulting in an intermediate
aminoarylidenediketone B which suffers the Hofmann–
Martius rearrangement giving compound C. Compound
C adds to the primary amino group the second molecule
of arylidenedione A providing compound D. Further the
heterocyclization of the initially added fragment occurs
to afford compound E which undergoes the Hofmann–
Martius rearrangement resulting in the hydrobenzophen-
anthrolinone derivatives Va–Ve, VIa–VIe. The driving
force of Hofmann–Martius rearrangement is likely to be
the electrostatic repulsion of the electronic cloud of the
nitrogen heteroatom from the carbonyl group oxygen
In this work we performed by the first time the
three-component condensation of aldehydes Ia–Ie and
two 1,3-diketones [5,5-dimethyl-1,3-cyclohexanedione
(dimedone) (II) and methyl 2,2-dimethyl-4,6-dioxocy-
clohexanecarboxylate (III)] with 8-aminoquinoline (IV).
The goal of our study was the synthesis of new hy-
drobenzophenanthroline derivatives with substituents
providing intense fluorescence [4].
The condensation of aldehydes Ia–Ie, 1,3-diketones
II, III, and 8-aminoquinoline (IV) was carried out by boil-
1439

KOZLOV et al.
1440
in the arylidenediketone resulting in the decrease of the
energy of the molecule and consequently in its more
stable state as hydrobenzophenanthrolinone derivatives.
through the reaction at the more accessible (unshielded
by the ester substituent) carbonyl group of diketone III.
The structure and composition of compounds Va–Ve,
VIa–VIe were established from the data of 1H, 13C NMR,
IR spectroscopy, mass spectrometry, and elemental analy-
sis. The structure of compounds synthesized was confirmed
and the assignment of the signal in the NMR spectra was
refined by the correlation 2D experiments COSY-45, NO-
The three-component condensation of aromatic alde-
hydes Ia–Ie, methyl 2,2-dimethyl-4,6-dioxocyclohexan-
ecarboxylate (III), and 8-aminoquinoline (IV) proceeded
strictly regioselectively. The formation of regioisomers
VIa–VIe corresponds to the intermediate formation
NH2
H3C
CH3
R2
N
O
H3C
CH3
R2
R1
Iа_Ie
+
IV
O
O
O
O
CH
H3C
CH3
R2
HN
N
R1
R1
O
O
II, III
A
B
R1
H3C
R2
O
O
CH3
H3C
CH3
R2
R2
H3C
H3C
CH
A
O
O
O
O
NH
NH2
CH
CH
N
N
R1
R1
D
C
H3C CH3
R2
O
R1
10
9
8
11
7a
11a
R2
O
O
HN12
12a
7
H3C CH3
N
6a
H3C
H3C
R2
1
2'''
1'''
12b
4a
3'''
6''' 4'''
2
3
CH
N
6
4
5
5'''
R1
O
N
O
CH
6'
6"
3"
5"
4"
1'
2'
5'
4'
1"
2"
CH3
CH3
3'
R1
HO
R1
R2
Vа_Ve, VIа_VIe
E
R1 = OH (a), OCH3 (b), N(CH3)2 (c), N(C2H5)2 (d), NO2 (e); R2 = H (V), COOCH3 (VI).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

SYNTHESIS OF HYDROBENZO[b]PHENANTHROLINONE DERIVATIVES
1441
ESY, HSQC, and HMCC performed on compound IVb
which possessed the best solubility in DMSO-d6 among the
synthesized samples.All experimental data were obtained
and processed using software XWIN-NMR 3.5.
The 1H NMR spectra of compounds Va–Ve, VIa–VIe
contain the signals from four methyl groups at 0.87–0.95
(2Me), 0.93–1.03, and 1.00–1.09 ppm; the methyl groups
attached to C10 appear as one singlet, and at C4′, as two
singlets. Two doublets of the protons at the atom C9 are ob-
served at 2.03–2.08 and 2.17–2.21 ppm with the geminal
coupling constant 2J 17 Hz in the spectra of compounds
Va–Ve. In the spectra of compounds VIa–VIe the proton
at the atom C9 gives rise to a singlet at 1.99–2.03 ppm
for the cis-isomers and a singlet at 2.04–2.09 ppm for
trans-isomers. Two doublets of protons at 2.56–2.67 and
2.74–2.82 ppm with the geminal constant 2J 17 Hz belong
to the protons at the atom C11 in compounds Va–Ve, and
at signals 2.55–3.04 and 2.62–2.95 ppm correspond to
the protons of the cis- and trans-isomers of compounds
VIa–VIe respectively. The singlet of the proton linked
to the atom C7 that is characteristic of phenanthrolines
spectra apears in the spectra of compounds Va–Ve at
4.87–5.30 ppm, and in the spectra of the cis- and trans-
isomers of compounds VIa–VIe two singlets at 4.82–5.26
and 4.92–5.33 ppm are observed, respectively. In the
spectra of all compounds synthesized also the signals of
four protons characteristic of the quinoline ring appear
6.94–8.50, 7.44–7.52, 8.11–8.30 and 8.33–8.90 ppm.
Fig. 1. Electron absorption spectra of compounds Va , 1; Vc,
2; Ve, 3 in ethanol, 293 K.
vibration bands in the UV range (Fig. 1, Table 1), which
may be divided in three groups. The first group consists
of the bands in the range 200–240 nm possessing a high
molar extinction factor (ε ~35000 l mol–1 cm–1), the bands
in the region 240–330 nm (ε 18000–32000 l·mol–1·cm–1)
belong to the second group, and weak bands in the region
330–450 nm (ε 5000–8000 l mol–1 cm–1) belong to the
third group.
The electronic spectra of compounds Vb, Vd, VIa–
VIe are similar to the EAS of Va, Vc, Ve, therefore they
are not shown in the figure.
In the mass spectra of obtained hydrobenzophenanth-
rolinones Va–Ve, VIa–VIe the peak of the molecular ion
is the most abundant showing the stability of the com-
pound against the electron impact. Also single-charged
ions [M + 1]+, [M – 1]+ were detected, characteristic of
the fused heteroaromatic compounds.
Each of these groups is corresponding to the electron
transition Sn ← S0 (n = 1–3) possessing the respective
oscillator strength f calculated by formula (1) [5].
(1)
IR spectra of compounds Va–Ve, VIa–VIe contain
absorption bands in the region 1612–1589 cm–1 charac-
teristic of the stretching vibrations of the carbonyl group.
Methylene groups of the cyclohexene rings give rise to
two absorption bands at 2930–2910 and 2880–2856 cm–1,
the stretching vibrations of CH in aromatic rings appear
at 3100–3000 cm–1. The strong band belonging to vibra-
tions of the OCH3 group is observed in the spectra of
compounds Vb, VIb in the region 2831 and 2834 cm–1.
Characteristic bands of compounds Ve, VIe at 1519 and
1430 cm–1 correspond respectively to symmetric and
antisymmetric vibrations of N–O bond.
Here n is the refraction index of the solvent, ν is the
wave number. It is clear from the data of f in Table 1
corresponding to the long-wave absorption band (330–
450 nm) that the oscillator strengths vary in the range
0.05–0.10. The oscillator strength of the longwave
transition S1 ← S0 is approximately tenfold less than that
of the S3
← S0 transition, and it is proportional to the
rate constant (kfcalc) of the radiation transition S1 → S0
calculated from the absorption and fluorescence spectra
[6] by formula (2).
Electron absorption spectra in ethanol of compounds
synthesized contain a characteristic set of the electronic-
(2)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

KOZLOV et al.
Table 1 Spectral and luminescence properties of compounds Va–Ve, VIa–VIe in ethanol solution at room temperature
1442
Compound no
Absorption maximum, λ
f
kfcalc × 10–8, s–1
Fluorescence maximum, λ
Φf
Va
Vb
Vc
Vd
Ve
VIa
VIb
VIc
VId
VIe
380 (3.9)
387 (3.7)
380 (3.4)
386 (3.8)
389 (3.8)
381 (3.7)
380 (3.6)
381 (3.6)
379 (3.9)
368 (3.65)
0.09
0.06
0.07
0.09
0.09
0.06
0.05
0.05
0.10
0.06
0.70
0.45
0.52
0.65
0.65
0.45
0.40
0.39
0.78
0.45
440
450
447
448
453
442
443
441
435
448
0.0020
0.0021
0.0010
0.0011
0.0001
0.0037
0.0044
0.0011
0.0007
0.0001
430–480 nm (Table 1, Fig. 2). The absorption (1) and
fluorescence excitation (2) spectra coincide (Fig. 2),
indicating that the luminescence originates from just the
compound possessing the absorption spectrum 1. Quan-
tum yields of the fluorescence Φf listed in the table are
very small (10–4–10–3). Consequently, the fluorescence
duration is also small τf (≤0.1 ns).
Here ν is the wave number of the 0-0-transition de-
termined from the crossing of absorption and fluorescence
spectra. The kfcalc values given in the table indicate that
their variations agree well with the changes in f of the
long wave S1 ← S0 transition. The relatively large values
of f and kfcalc show that S1 S0 is an allowed transition.
It is necessary to note the difference in the EAS of
compounds (Fig. 1): At going from Va to Vc,Ve the ab-
sorption spectra broaden. This effect is due to the charge
transfer from the dimethylamino group of compound Vc
to the conjugation system of the molecule in the ground
state S0 and to the electron-withdrawing nitro group from
the conjugation system of compound Ve.
Φf of compounds under study in toluene is larger by
an order of magnitude and more as compared with Φf
in ethanol (Table 2). Still the spectral properties of the
compounds in ethanol and toluene have close values. The
measured values of τf made it possible to calculate kf =
Φf /τf (Table 2). The comparison of two last columns of
Table 2 shows that the kf values obtained experimentally
and those resulting from the calculation using the absorp-
tion and fluorescence spectra are in good agreement. This
fact indicates that the fluorescence occurs from the lower
singlet-excited state S1.
Fluorescence spectra in ethanol originating from the
radiation transition S1 → S0 are characterized by a wide
electronic-vibration band with the maxima in the region
The large difference in quantum yield of compounds
fluorescence in ethanol and toluene may originate from
the existence of an additional electronic excitation state
near the singlet excited state S1 and the quenching of
the fluorescence occurs through this additional state. In
the polar ethanol this additional state is located nearer
to S1 than in nonpolar toluene. This reasoning is well
consistent with Marcus theory [7] that regarded this ad-
ditional state as the state with the charge transfer. This is
supported by the additional quenching of the fluorescence
in compounds Ve, VIe containing electron-withdrawing
group NO2. This assumption is also consistent with the
strong growth of Φf at cooling the solution to 77 K. The
quantum yield in ethanol increased, e.g., for compounds
Va, VIa 200-fold and it is estimated at 0.40 and 0.74,
respectively. The fluorescence spectrum at 77 K is nar-
rower and displaced to the shortwave region (maximum
Fig. 2. Absorption (1), fluorescence (3, 4, λexcit 380 nm), and
fluorescence excitation (2, λreg 450 nm) spectra of compound
Va in ethanol at 293 K (1–3) and 77 K (4)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

SYNTHESIS OF HYDROBENZO[b]PHENANTHROLINONE DERIVATIVES
1443
Table 2. Spectral and luminescence properties of compounds Va–Ve, VIa–VIe in toluene solution at room temperature
Absorption
maximum, λ, nm
Fluorescence
maximum, λ
Compound no
Φf
τf, ns
kfexp × 10–8, s–1
kfcalc × 10–8, s–1
Va
Vb
Vc
Vd
Ve
VIa
VIb
VIc
VId
VIe
380
388
380
383
389
381
376
378
379
369
452
458
459
459
455
442
442
455
457
453
0.0230
0.0210
0.0180
0.0270
0.0092
0.0240
0.0250
0.0200
0.0260
0.0049
0.42
0.49
0.38
0.57
0.20
0.50
0.53
0.50
0.55
0.12
0.54
0.43
0.47
0.47
0.46
0.48
0.47
0.40
0.47
0.41
0.70
0.45
0.52
0.65
0.65
0.45
0.40
0.39
0.78
0.45
of fluorescence at 420 nm).
0.25 μm) was attached directly to the ion source of the
spectrometer, the samples were introduced dissolved in
dichloromethane.
Thus the spectral and luminescence investigation of
compounds Va–Ve, VIa–VIe showed that they possess
strong oscillators f of the allowed electron transitions
Sn ← S0 (n = 1–3). The low quantum yields of the fluo-
rescence of the compounds under study (Φf ~10–4–10–3) in
ethanol, their growth in toluene (~10–2) at room tempera-
ture and at cooling to 77 K (~10–1) are fairly rationalized
proceeding from Marcus theory [7], which suggests that
the fluorescence quenching occurs through an addi-
tional state with the charge transfer. The position of the
state with the charge transfer depends on the electronic
donor-acceptor properties of the molecule and from the
characteristics of the medium (polarity and viscosity).
Therefore it seems advisable to explore the luminescence
properties of the compounds in rigid polymer matrices at
room temperature aiming at making therefrom large flex-
ible fine-film panels suitable for photovoltaic elements,
optical filters, and electroluminescence displays.
IR spectra were recorded on an IR Fourier spectrom-
eter Protege-460 Nicolet.
Electron absorption spectra were registered at room
temperature on a spectrophotometer Cary-500 (Varian,
USA). Fluorescence spectra were measured on an instal-
lation described in [8], the concentration of the substance
in the solution (in ethanol or toluene) did not exceed 2 ×
10–5 mol l−1. Quantum yields of the fluorescence were
measured by a relative method using as a standard quinine
sulfate dissolved in 1N H2SO4 (Φf 0.55 [9]).The measure-
ments of the fluorescence duration was performed in the
Division of the automation of spectral research of the
Physical Institute of the Belarusian National Academy
of Sciences on a pulse fluorimeter PRA-3000 operating
in the mode of time-correlated photon counting. The er-
ror in the measurement of molar extinction factors was ε
20%, fluorescence quantum yields Φf, 15%, fluorescence
duration τf , 10%.
EXPERIMENTAL
Compounds Va–Ve were prepared by boiling in al-
coholic solution a mixture of 0.01 mol of an appropriate
aromatic aldehyde Ia–Ie, 2.1 g (0.015 mol) of dimedone
(II), and 1.44 g (0.01 mol) of 8-aminoquinoline (IV) till
crystals started to separate (30–60 min). On cooling the
separated precipitate was filtered off, washed with ether
from tar, and recrystallized from the mixture alcohol–
benzene, 1:1.
1H and 13C NMR spectra were registered on a spec-
trometerAvance-500 Bruker–Biospin (operating frequen-
cies 500.13 and 125.77 MHz respectively) from 2–5%
solutions in deuterodimethyl sulfoxide, chemical shifts
were measured according to the internal TMS standard.
Mass spectra of compounds synthesized were obtained
on an instrument Agilent 6890N equipped with a mass-
selective detectorAgilent 5975 Inert operating in electron
impact ionization mode, ionizing electrons energy 70 eV,
adjusted to the highest sensitivity to the substances under
study. Capillary column HP-5MS (30 m × 0.25 mm ×
5-[(2-Hydroxy-4,4-dimethyl-6-oxocyclohex-1-
enyl)(4-hydroxyphenyl)methyl]-10,10-dimethyl-
7-(4-hydroxyphenyl)-10,11-dihydrobenzo[b][1,10]
phenanthrolin-8(5H,7H,9H)-one (Va). Yield 72%,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

KOZLOV et al.
1444
58%, brown crystals, mp 180–182°C. IR spectrum, cm–1:
3381, 3254, 2953, 2924, 2869, 2800, 1612, 1563, 1517,
1478, 1400, 1385, 1365, 1328, 1247, 1223, 1146, 1124,
1062, 820, 789. 1H NMR spectrum, δ, ppm: 0.93 s (6H,
C4′Me2), 0.99 s (3H, 10-CH3), 1.04 s (3H, 10-CH3), 2.08
d, 2.19 d (2H, C9H2), 1.90–2.50 m (4H, C3′H2, C5′H2),
2.61 d (1H, C11H2), 2.73 s (12H, 2NMe2), 2.78 d (1H,
C11H2), 4.85 s (1H, C7H), 5.90 s (1H, CH), 6.39 d (2H,
C3′′′H, C5′′′H), 6.54 d (2H, C3′′ H, C5′′H), 6.75 d (2H, C2′′′H,
C6′′′H), 6.89 d (2H, C2′′H, C6′′H), 7.02 s (1H, C6H), 7.46 s
(1H, C3H), 8.18 s (1H, C4H), 8.82 s (1H, C2H), 9.40 s
(1H, NH). Mass spectrum, m/z (Irel,%): [M + 1]+ 669 (33),
[M]+ 668 (100), [M – 1]+ 667 (62), [M – N(CH3)2]+ 624
(18), [M – C6H4N(CH3)2]+ 548 (11). Found, %: C 77.19;
H 7.28; N 8.42. C43H48N4O3. Calculated, %: C 77.21; H
7.23; N 8.38. m 668.37.
yellow crystals, mp 263–264°C. IR spectrum, cm–1: 2950,
1589, 1566, 1509, 1476, 1387, 1315, 1244, 1169, 1148,
1122, 830, 676. 1H NMR spectrum, δ, ppm: 0.91 s [6H,
C4′(Me)2], 0.96 s (3H, 10-CH3), 1.02 s (3H, 10-CH3),
2.03 d, 2.17 d (2H, C9H2), 1.80–2.50 m (4H, C3′H2,
C5′H2), 2.57 d, 2.77 d (1H, C11H2), 4.87 s (1H, C7H),
5.91 s (1H, CH), 6.49 d (2H, C3′′′H, C5′′′H), 6.60 d (2H,
C3′′H, C5′′H), 6.75 d (2H, C2′′′H, C6′′′H), 6.85 d (2H, C2′′H,
C6′′H), 6.92 s (1H, C6H), 7.45 s (1H, C3H), 8.11 s (1H,
C4H), 8.82 s (1H, C2H), 9.08 s (1H, OH), 9.16 s (1H,
OH), 9.49 s (1H, NH), 10.41 s (1H, OH). Mass spectrum,
m/z (Irel, %): [M + 1]+ 615 (44), [M]+ 614(100), [M – 1]+
613 (27), [M – OH]+ 597 (16), [M – C6H4OH]+ 521 (11).
Found, %: C 76.25; H 6.19; N 4.62. C39H38N2O5. Calcu-
lated, %: C 76.20; H 6.23; N 4.56. m 614.28.
5-[(2-Hydroxy-4,4-dimethyl-6-oxocyclohex-1-
enyl)(4-methoxyphenyl)methyl]-10,10-dimethyl-
7-(4-methoxyphenyl)-10,11-dihydrobenzo[b][1,10]
phenanthrolin-8(5H,7H,9H)-one (Vb). Yield 64%,
yellow crystals, mp 250–251°C. IR spectrum, cm–1: 3302,
2947, 2831, 1608, 1582, 1563, 1508, 1483, 1406, 1386,
1365, 1328, 1300, 1251, 1174, 1147, 1123, 1037, 831,
786. 1H NMR spectrum, δ, ppm: 0.91 s [6H, C4′(Me)2],
0.96 s (3H, 10-CH3), 1.02 s (3H, 10-CH3), 2.03 d, 2.17 d
(2H, C9H2), 1.90–2.60 m (4H, C3′H2, C5’H2), 2.56 d,
2.74 d (2H, C11H2), 3.62 s (3H, OCH3), 3.71 s (3H,
OCH3), 4.93 s (1H, C7H), 5.97 s (1H, CH), 6.67 d (2H,
C3′′′H, C5′′′H), 6.76 d (2H, C3′′H, C5′′H), 6.89 d (2H, C2′′′H,
C6′′′H), 6.92 s (1H, C6H), 6.94 d (2H, C2′′H, C6′′H), 7.47 s
(1H, C3H), 8.13 s (1H, C4H), 8.82 s (1H, C2H), 9.54 s
(1H, NH), 10.52 s (1H, OH). 13C NMR spectrum, δ,
ppm: 196.19 (C6′), 193.59 (C8), 171.82 (C2′), 157.38 (C4′′),
157.32 (C4′′′), 151.94 (C11a), 148.09 (C2), 140.02 (C1′′′),
137.13 (C12b), 134.86 (C5), 134.58 (C1′′), 132.49 (C4),
129.99 (C2′′,6′′), 129.62 (C6a), 129.23 (C6), 127.66 (C2′′′,6′′′),
125.26 (C4a), 122.35 (C12a), 120.99 (C3), 115.97 (C1′),
113.51 (C3′′′,5′′′), 113.23 (C3′′,5′′), 106.88 (C7a), 54.96, 55.02
(OCH3), 50.44 (C9), 43.38, 50.19 (C3′,5′), 40.30 (C11),
39.66 (CH), 39.34 (C7), 32.11 (C10), 31.59 (C4′), 26.96,
29.26 (10-CH3), 27.60, 28.18 (4′-CH3). Mass spectrum,
m/z (Irel, %): [M + 1]+ 643 (45), [M]+ 642 (100), [M – 1]+
641 (75), [M – CH3O]+ 611 (14), [M – C6H4OCH3]+ 535
(21). Found, %: C 76.65; H 6.54; N 4.39. C41H42N2O5.
Calculated, %: C 76.61; H 6.59; N 4.36. m 642.31.
5-[(2-Hydroxy-4,4-dimethyl-6-oxocyclohex-1-
enyl)-(4-diethylaminophenyl)methyl]-10,10-dimeth-
yl-7-(4-diethylaminophenyl)-10,11-dihydrobenzo-
[b]-[1,10]phenanthrolin-8(5H,7H,9H)-one (Vd). Yield
53%, brown crystals, mp 227°C. IR spectrum, cm–1:
3385, 3256, 2963, 2927, 2889, 2869, 1610, 1584, 1564,
1516, 1481, 1366, 1327, 1262, 1196, 1170, 1148, 1122,
1
1068, 1024, 1012, 783. H NMR spectrum, δ, ppm:
0.93 s (6H, C4′Me2), 0.99 s (3H, 10-Me), 1.04 s (3H,
10-Me), 1.07 t [6H, N(CH2Me)2], 2.08 d, 2.19 d (2H,
C9H2), 2.05–2.60 m (4H, C3′H2, C5′H2), 2.61 d, 2.78 d
(2H, C11H2), 3.32 q [4H, N(CH2Me)2], 4.85 s (1H, C7H),
5.90 s (1H, CH), 6.39 d (2H, C3′′′H, C5′′′H), 6.54 d (2H,
C3′′H, C5′′H), 6.75 d (2H, C2′′′H, C6′′′H), 6.89 d (2H, C2′′H,
C6′′H), 7.02 (1H, C6H), 7.46 s (1H, C3H), 8.18 s (1H,
C4H), 8.82 s (1H, C2H), 9.40 s (1H, NH), 10.39 s (1H,
OH). Mass spectrum, m/z (Irel, %): [M + 1]+ 723 (55),
[M]+ 724 (100), [M – 1]+ 723 (59), [M – N(C2H5 )2]+ 652
(11), [M – C6H4N(C2H5 )2]+ 576 (48). Found, %: C 77.90;
H 7.75; N 7.78. C47H56N4O3. Calculated, %: C 77.87; H
7.79; N 7.73. m 724.44.
5-[(2-Hydroxy-4,4-dimethyl-6-oxocyclohex-1-
enyl)(4-nitrophenyl)methyl]-10,10-dimethyl-7-(4-
nitrophenyl)-10,11-dihydrobenzo[b][1,10]phenanthro-
lin-8(5H,7H,9H)-one (Ve). Yield 75%, yellow crystals,
mp 258–259°C. IR spectrum, cm–1: 3381, 3249, 3067,
2957, 2928, 2888, 2869, 1624, 1582, 1564, 1519, 1482,
1405, 1386, 1346, 1253, 1225, 1150, 1109, 1016, 855,
1
790. H NMR spectrum, δ, ppm: 0.98 s [6H, 4′-Me2],
1.03 s (3H, 10-Me), 1.04 s (3H, 10-Me), 2.08 d, 2.21 d
(2H, C9H2), 2.05–2.60 m (2H, C3′H2, C5′H2), 2.67 d,
2.82 d (1H, C11H2), 5.30 s (1H, C7H), 6.19 s (1H, CH),
6.97 s (1H, C6H), 7.99 d (2H, C3′′′H, C5′′′H), 8.05 d (2H,
5-[(2-Hydroxy-4,4-dimethyl-6-oxocyclohex-1-
enyl)-(4-dimethylaminophenyl)methyl]-10,10-dimeth-
yl-7-(4-dimethylaminophenyl)-10,11-dihydrobenzo[b]
[1,10]-phenanthrolin-8(5H,7H,9H)-one (Vc). Yield
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

SYNTHESIS OF HYDROBENZO[b]PHENANTHROLINONE DERIVATIVES
1445
C3′′H, C5′′H), 7.12 d (2H, C2′′′H, C6′′′H), 7.35 d (2H, C2′′H,
C6′′H), 7.52 s (1H, C3H), 8.12 s (1H, C4H), 8.90 s (1H,
C2H), 9.74 s (1H, NH), 10.76 s (1H, OH). Mass spectrum,
m/z (Irel, %): [M + 1]+ 673 (65), [M]+ 672 (100), [M – 1]+
671 (58), [M – NO2]+ 626 (23), [M – C6H4NO2]+ 550
(53). Found, %: C 69.60; H 5.44; N 8.38. C39H36N4O7.
Calculated, %: C 69.63; H 5.39; N 8.33. m 672.26.
2.69 d (1H, C11H2, cis-isomer), 2.74 d (1H, C11H2,
trans-isomer), 2.78 d (1H, C11H2, trans-isomer), 2.95 d
(1H, C11H2, cis-isomer), 3.61 s (3H, OCH3), 3.69 s (3H,
OCH3), 4.92 s (1H, C7H, cis-isomer), 4.98 s (1H, C7H,
trans-isomer), 5.99 s (1H, CH), 6.63 d (2H, C3′′′H, C5′′′H),
6.68 d (2H, C3′′H, C5′′H), 6.84 d (2H, C2′′′H, C6′′′H), 6.97 d
(2H, C2′′H, C6′′H), 7.48 s (1H, C3H), 8.13 s (1H, C4H),
8.33 s (1H, C2H), 8.50 s (1H, C6H), 10.46 s (1H, OH),
11.71 s (1H, NH, cis-isomer), 11.73 s (1H, NH, trans-
isomer). Mass spectrum, m/z (Irel, %): [M + 1]+ 759 (42),
[M]+ 758 (100), [M – 1]+ 757 (75), [M – CH3O]+ 727(23),
[M – C6H4OCH3]+ 651 (10). Found, %: C 71.28; H 6.07;
N 3.66. C45H46N2O9. Calculated, %: C 71.22; H 6.11;
N 3.69. m 758.32.
Compounds VIa–VIe were obtained analogously
using methyl 2,2-dimethyl-4,6-dioxocyclohexanecar-
boxylate (III).
Methyl 5-[(2-hydroxy-4,4-dimethyl-5-methoxy-
carbonyl-6-oxocyclohex-1-enyl)(4-hydroxyphenyl)
methyl]-7-(4-hydroxyphenyl)-10,10-dimethyl-8-oxo-
7,8,9,10,11,12-hexahydrobenzo[b][1,10]phenanthrolin-
9-carboxylate (VIa). Yield 62%, yellow crystals, mp
195–196°C. IR spectrum, cm–1: 3460, 3358, 3000, 2947,
2928, 2850, 2836, 1734, 1610, 1512, 1482, 1437, 1389,
1371, 1320, 1246, 1178, 1150, 1102, 1032, 934, 825,
Methyl 5-[(2-hydroxy-5-methoxycarbonyl-4,4-di-
methyl-6-oxocyclohex-1-enyl)(4-dimethylaminophenyl)
methyl]-7-(4-dimethylaminophenyl)-10,10-dimethyl-
8-oxo-7,8,9,10,11,12-hexahydro-benzo[b][1,10]phen-
anthrolin-9-carboxylate (VIc). Yield 51%, dark brown
crystals, mp 168–169°C. IR spectrum, cm–1: 3372, 2950,
2924, 2871, 2798, 1731, 1610, 1518, 1506, 1477, 1427,
1367, 1317, 1267, 1248, 1156, 1127, 1059, 1027, 947,
820, 789. 1H NMR spectrum, δ, ppm: 0.93 s (6H, C4′Me2),
0.98 s (3H, 10-Me), 1.09 s (3H, 10-Me), 1.99 s (1H, C9H,
cis-isomer), 2.04 s (1H, C9 H, trans-isomer), 2.15 d (2H,
C5′H2), 2.43 s (1H, C3′H, cis-isomer), 2.46 s (1H, C3′H,
trans-isomer), 2.55 d (1H, C11H2, cis-isomer), 2.62 d (1H,
C11H2, trans-isomer), 2.65 d (1H, C11H2, trans-isomer),
2.70 d (1H, C11H2, cis-isomer), 2.73 s [12H, N(CH3)2],
4.82 s (1H, C7H, cis-isomer), 4.88 s (1H, C7H, trans-
isomer), 5.81 s (1H, CH), 6.49 d (2H, C3′′′H, C5′′′H), 6.64 d
(2H, C3′′H, C5′′H), 6.81 d (2H, C2′′′H, C6′′′H), 7.02 d (2H,
C2′′H, C6′′H), 7.09 s (1H, C6H), 7.51 s (1H, C3H), 8.23 s
(1H, C4H), 8.35 s (1H, C2H), 10.12 s (1H, OH), 10.37 s
(1H, NH, cis-isomer), 10.43 s (1H, NH, trans-isomer).
Mass spectrum, m/z (Irel, %): [M + 1]+ 785 (22), [M]+ 784
(100), [M – 1]+ 783 (53), [M – N(CH3)2]+ 740 (18), [M –
C6H4N(CH3)2]+ 664 (23). Found, %: C 71.89; H 6.63;
N 7.09. C47H52N4O7. Calculated, %: C 71.92; H 6.68;
N 7.14. m 784.38.
1
793. H NMR spectrum, δ, ppm: 0.87 s (6H, C4′Me2),
0.93 s (3H, 10-Me), 1.00 s (3H, 10-Me), 2.03 s (1H, C9H,
cis-isomer), 2.08 s (1H, C9H, trans-isomer), 2.15 d (2H,
C5′H2), 2.42 s (1H, C3′H, cis-isomer), 2.46 s (1H, C3′H,
trans-isomer), 2.77 d (1H, C11H2, cis-isomer), 2.84 d (1H,
C11H2, trans-isomer), 2.95 d (1H, C11H2, trans-isomer),
3.04 d (1H, C11H2, cis-isomer), 4.86 s (1H, C7H, cis-
isomer), 4.93 s (1H, C7H, trans-isomer), 5.97 s (1H, CH),
6.60 d (2H, C3′′′H, C5′′′H), 6.75 d (2H, C3′′H, C5′′H), 6.79 d
(2H, C2′′′H, C6′′′H), 6.85 d (2H, C2′′H, C6′′H), 6.94 s (1H,
C6H), 7.45 s (1H, C3H), 8.25 s (1H, C4H), 8.45 s (1H,
C2H), 9.08 s (1H, OH), 9.16 s (1H, OH), 9.46 s (1H,NH,
cis-isomer), 9.48 s (1H, NH, trans-isomer), 10.41 s (1H,
OH). Mass spectrum, m/z (Irel, %): [M + 1]+ 730 (32),
[M]+ 730 (100), [M – 1]+ 729 (43), [M – OH]+ 713 (22),
[M – C6H4OH]+ 637 (18). Found, %: C 70.70; H 5.73;
N 3.78. C43H42N2O9. Calculated, %: C 70.67; H 5.79;
N 3.83. m 730.29.
Methyl 5-[(2-hydroxy-5-methoxycarbonyl-4,4-
dimethyl-6-oxocyclohex-1-enyl)(4-methoxyphenyl)
methyl]-7-(4-methoxyphenyl)-10,10-dimethyl-8-oxo-
7,8,9,10,11,12-hexahydrobenzo[b]-[1,10]phenanthro-
lin-9-carboxylate (VIb). Yield 60%, yellow crystals, mp
250–251°C. IR spectrum, cm–1: 3463, 3363, 2949, 2923,
2834, 1737, 1607, 1508, 1479, 1441, 1369, 1315, 1301,
1248, 1174, 1157, 1107, 1034, 929, 820, 791. 1H NMR
spectrum, δ, ppm: 0.94 s (6H, C4’Me2), 0.98 s (3H, 10-
Me), 1.02 s (3H, 10-Me), 2.03 s (1H, C9H, cis-isomer),
2.09 s (2H, C9H, trans-isomer), 2.18 d (2H, C5′H2), 2.48 s
(1H, C3′H, cis-isomer), 2.54 s (1H, C3′H, trans-isomer),
Methyl 5-[(2-hydroxy-5-methoxycarbonyl-4,4-di-
methyl-6-oxocyclohex-1-enyl)(4-diethylaminophenyl)
methyl]-7-(4-diethylaminophenyl)-10,10-dimethyl-8-
oxo-7,8,9,10,11,12-hexahydro-benzo[b][1,10]phenan-
throlin-9-carboxylate (VId). Yield 52%, dark brown
crystals, mp 238–239°C. IR spectrum, cm–1: 3380, 3248,
2957, 2931, 2889, 1613, 1586, 1561, 1522, 1493, 1488,
1366, 1329, 1265, 1196, 1177, 1156, 1123, 1064, 1011,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

KOZLOV et al.
1446
793. H NMR spectrum, δ, ppm: 0.95 s (6H, C4′Me2),
1.00 s (3H, 10-Me), 1.04 s (3H, 10-Me), 1.11 t [6H,
N(CH2CH3)2], 2.01 s (2H, C9H, cis-isomer), 2.09 s (2H,
C9 H, trans-isomer), 2.21 d (2H, C5′H2), 2.42 s (1H, C3′H,
cis-isomer), 2.47 s (1H, C3′H, trans-isomer), 2.64 d (1H,
C11H2, cis-isomer), 2.70 d (1H, C11 H2, trans-isomer),
2.75 d (1H, C11 H2, trans-isomer), 2.90 d (1H, C11H2,
cis-isomer), 3.35 q [4H, N(CH2CH3)2], 4.83 s (1H, C7H,
cis-isomer), 4.92 s (1H, C7H, trans-isomer), 5.90 s (1H,
CH), 6.54 d (2H, C3′′′H, C5′′′H), 6.78 d (2H, C3′′H, C5′′H),
6.84 d (2H, C2′′′H, C6′′′H), 6.97 d (2H, C2′′H, C6′′H), 7.05 s
(1H, C6H), 7.44 s (1H, C3H), 8.30 s (1H, C4H), 8.38 s (1H,
C2H), 10.37 s (1H, OH), 10.42 s (1H, NH, cis-isomer),
10.45 s (1H, NH, trans-isomer). Mass spectrum, m/z (Irel,
%): [M + 1]+ 841 (30), [M]+ 40(100), [M – 1]+ 839 (47),
[M – N(C2H5)2]+ 768 (25), [M – C6H4N(C2H5)2]+ 706
(42). Found, %: C 72.86; H 7.15; N 6.64. C51H60N4O7.
Calculated, %: C 72.83; H 7.19; N 6.66. m 840.45.
C6′′H), 7.51 C (1H, C3H), 7.89 d (2H, C3′′′H, C5′′′H), 8.10 d
(2H, C3′′H, C5′′H), 8.30 s (1H, C4H), 8.52 s (1H, C2H),
9.76 s (1H, OH), 10.73 s (1H, NH, cis-isomer), 10.75 s
(1H, NH, trans-isomer). Mass spectrum, m/z (Irel, %):
[M + 1]+ 789 (72), [M]+ 788 (100), [M – 1]+ 787 (44),
[M – NO2]+ 742 (11), [M – C6H4NO2]+ 666 (49). Found,
%: C 65.43; H 5.15; N 7.06. C43H40N4O11. Calculated,
%: C 65.47; H 5.11; N 7.10. m 788.27.
1
ACKNOWLEDGMENTS
The authors express their gratitude to Senior Research-
er of the Stepanov Physical Institute of the Belarusian
National Academy of Sciences A.P.Stupak for the help
in the measurements of fluorescence duration.
REFERENCES
1. Kozlov, N.S. and Vorob’eva, G.V., Khim. Geterotsikl.
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vol. 46, p. 1639.
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vol. 97, p. 13457.
6. Forster, Th., Fluoreszenz Organisher Verbindungen, Göt-
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7. Marcus, R.A., Rev. Mod. Phys., 1993, vol. 92, p. 599.
8. Borisevich, E.A., Knyukshto, V.N., Kozyrev, A.N., and
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Methyl 5-[(2-hydroxy-5-methoxycarbonyl-4,4-
dimethyl-6-oxocyclohex-1-enyl)(4-nitrophenyl)
methyl]-7-(4-nitrophenyl)-10,10-dimethyl-8-oxo-
7,8,9,10,11,12-hexahydrobenzo[b][1,10]phenanthro-
lin-9-carboxylate (VIe). Yield 71%, brown crystals, mp
273–275°C. IR spectrum, cm–1: 3469, 3372, 3067, 2955,
2872, 1731, 1605, 1594, 1514, 1479, 1430, 1370, 1344,
1263, 1190, 1157, 1108, 1014, 854, 824, 788. 1H NMR
spectrum, δ, ppm: 0.92 s (6H, C4′Me2), 0.96 s (3H, 10-
Me), 1.07 s (3H, 10-Me), 2.01 s (1H, C9H, cis-isomer),
2.07 s (1H, C9H, trans-isomer), 2.22 d (2H, C5′H2), 2.35 s
(1H, C3′H, cis-andзO-mep), 2.41 s (1H, C3′H, trans-iso-
mer), 2.57 d (1H, C11H2, cis-isomer), 2.64 d (1H, C11H2,
trans-isomer), 2.70 d (1H, C11H2, trans-isomer), 2.76 d
(1H, C11H2, cis-isomer), 5.26 s (1H, C7H, cis-isomer),
5.33 s (1H, C7H, trans-isomer), 6.18 s (1H, CH), 7.03 s
(1H, C6H), 7.12 d (2H, C2′′′H, C6′′′H), 7.30 d (2H, C2′′H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012