Synthesis of methyl-substituted 1,7-phenanthroline derivatives by condensation of 2-methylquinolin-5-amine with aromatic aldehydes and cyclic 1,3-diketones

Article abstract of DOI:10.1134/S1070428010070195

Previously unknown 7-aryl(hetaryl)-3-methyl-7,10,11,12-tetrahydro-9H- benzo[b][1,7]phenanthrolin-8-ones and their 10,10-dimethyl-substituted analogs were synthesized by three-component condensation of 2-methylquinolin-5-amine with aromatic aldehydes and c

Full text of DOI:10.1134/S1070428010070195

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 7, pp. 1074–1078. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © N.G. Kozlov, K.N. Gusak, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 7, pp. 1075–1079.
Synthesis of Methyl-Substituted 1,7-Phenanthroline Derivatives
by Condensation of 2-Methylquinolin-5-amine with Aromatic
Aldehydes and Cyclic 1,3-Diketones
N. G. Kozlov and K. N. Gusak
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 220072 Belarus
e-mail: loc@ifoch.bas-netby
Received June 26, 2009
Abstract—Previously unknown 7-aryl(hetaryl)-3-methyl-7,10,11,12-tetrahydro-9H-benzo[b][1,7]phenanthro-
lin-8-ones and their 10,10-dimethyl-substituted analogs were synthesized by three-component condensation of
2-methylquinolin-5-amine with aromatic aldehydes and cyclic β-diketones (cyclohexane-1,3-dione and
dimedone) in butyl alcohol.
DOI: 10.1134/S1070428010070195
Some methyl-substituted aza- and diazaphenan-
threne derivatives were found to exhibit analgesic and
antiallergic properties, as well as bactericidal, breath
stimulating, and antienzyme activity; they can also be
used as diagnostic agents for detection of leukocytes
and erythrocytes [1–4]. The presence of a methyl
group therein is important; it is responsible for a broad
spectrum of biological activity and a variety of chem-
ical reactions that could lead to new strongly conjugat-
ed systems and polymeric materials having pharmaco-
phoric fragments [5–10].
Methyl-substituted 1,7-phenanthroline derivatives
have been studied poorly because of difficulties in
their synthesis. Methyl-substituted nitrogen-containing
heterocycles are generally obtained by condensation of
aromatic amines with α,β-unsaturated carbonyl com-
pounds, such as methyl vinyl ketone and crotonalde-
hyde or their precursors (acetone, formaldehyde, or
paraldehyde) known as Doebner–Miller reaction. How-
ever, this reaction turned out to be weakly effective for
the synthesis of 1,7-phenanthrolines from m-phenyl-
enediamine or quinolin-5-amine: the yields of the
target products were poor because of low reactivity of
the initial amines, and the main processes were con-
densation and polymerization of carbonyl compounds.
For this purpose, we examined for the first time three-
component condensation of 2-methylquinolin-5-amine
(I) with cyclic β-diketones, cyclohexane-1,3-dione (II)
and 5,5-dimethylcyclohexane-1,3-dione (III, dime-
done), and aromatic (heteroaromatic) aldehydes IVa–
IVm. The reactions were carried out by heating equim-
olar amounts of the reactants in boiling butan-1-ol. As
a result, the corresponding 7-aryl(hetaryl)-3-methyl-
7,10,11,12-tetrahydro-9H-benzo[b][1,7]phenanthrolin-
8-ones Va–Vm and their 10,10-dimethyl-substituted
analogs VIc, VId, and VIl were formed with high
selectivity (yield 46–76%;).
Presumably, the formation of benzo[b][1,7]phenan-
throlinone system involves initial condensation of
amine I with aldehyde IV to give Schiff base A,
addition of diketone II or III at the C=N bond in A,
rearrangement of adduct B thus formed via elimination
of α,β-unsaturated diketone C and its subsequent
migration to the aromatic ring (to the carbon atom in
the α-position with respect to the amino group, which
possesses the highest electron density), and intramo-
lecular condensation of rearrangement product D
(Scheme 1). An alternative reaction path includes
initial reaction of diketone II or III with aromatic
aldehyde IV with formation of 2-arylmethylidene-
cyclohexan-1,3-dione B which then reacts with amino-
quinoline according to the above scheme.
We previously showed that three-component con-
densation of quinolin-5-amine with aromatic aldehydes
and cyclohexane-1,3-dione gives fused 1,7-phenan-
throline derivatives [11]. The present work was aimed
at synthesizing methyl-substituted 1,7-phenanthrolines.
The substituent R′ in the aldehyde molecule some-
what affects the yield of target products V and VI.
Benzaldehydes IVa–IVd and IVl having halogen
1074

SYNTHESIS OF METHYL-SUBSTITUTED 1,7-PHENANTHROLINE DERIVATIVES
1075
Scheme 1.
R'
NH2
O
N
+
+
R'CHO
R
N
Me
O
O
Me
N
R
R
I
II, III
IVa–IVm
A
Me
Me
O
R'
O
O
NH2
HN
I
R'
R
–I
R
O
R'
O
R
Me
N
Me
N
B
C
D
R
10
11
R
12
HN
2
1
9
3
Me
8
N
O
7
R'
5
6
Va–Vm, VIc, VIh, VIl
II, V, R = H; III, VI, R = Me; IV–VI, R′ = 4-FC6H4 (a), 4-BrC6H4 (b), 4-HOC6H4 (c), 3,4-(HO)2C6H3 (d), 2-MeOC6H4 (e),
4-MeOC6H4 (f), 2,4-(MeO)2C6H3 (g), 3,4-(MeO)2C6H3 (h), 3-MeO-4-HOC6H3 (i), 4-Me2NC6H4 (j), 4-(ClCH2CH2)2NC6H4 (k),
4-MeOCOC6H4 (l), pyridin-3-yl (m).
stretching vibration bands of aromatic C–H bonds
appeared at 3060–3030 cm–1. Compounds Ve–Vi, Vl,
and VIl also displayed in the IR spectra absorption
bands in the region 1240–1230 cm–1 due to vibrations
of the C–O–C fragment, and ester carbonyl group in
phenanthrolines Vl and VIl was characterized by
absorption at 1725–1720 cm–1.
atoms or alkoxycarbonyl or hydroxy groups in the
aromatic ring, which activate the carbonyl group due
to negative inductive effect, ensure fairly high yields
(68–76%) of the products. Likewise, phenanthroline
Vm was obtained in 61% yield from pyridine-3-carb-
aldehyde (IVm) where the reactivity of the aldehyde
group is enhanced due to –I effect of the pyridine ni-
trogen atom. Dialkylamino-substituted phenanthrolines
Vj and Vk were formed in lower yields (46–48%). The
presence of methyl groups in the molecule of diketone
III almost did not affect the yield of methylphenan-
throlines.
In the mass spectra of benzophenanthrolinones Va–
Vm, VIc, VId, and VIl the molecular ion peaks [M]+
had a relative intensity of 15–43%, while the base peak
(100%) was that of the [M – R]+ ion: m/z 263 (Va–
Vm), 291 (VIc, VId, VIl). The spectra of all phenan-
throlines contained a fragment ion peak with m/z 207
(Irel 10–23%), which corresponds to elimination of
CH2CH2CO (Va–Vm) or Me2CCH2CO moiety (VIc,
VId, VIl) from the molecular ion.
The structure of compounds Va–Vm, VIc, VId, and
VIl was determined on the basis of their IR, NMR, and
mass spectra. Their IR spectra contained strong ab-
sorption bands at 1590 and 1525 cm–1 due to vibrations
of the vinylogous amide fragment (1580, 1520 cm–1
[11]). Strong bands at 3440 and 1620 cm–1 were as-
signed, respectively, to stretching and bending vibra-
tions of the secondary amino group. Stretching vibra-
tions of aliphatic and cycloaliphatic C–H bonds gave
rise to absorption in the region 2960–2870 cm–1, and
The 1H NMR spectra of compounds V and VI were
similar to those reported previously for structurally
related 1,7-phenanthrolines having no methyl group on
C3 [11]; signals of the latter were assigned by analysis
of two-dimensional COSY, NOESY, HSQC, and
1
HMBC spectra [11]. The H NMR spectra of Va–Vm,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 7 2010

KOZLOV, GUSAK
1076
VIc, VId, and VIl lacked signal assignable to proton
on C3, but a singlet at δ 2.58–2.67 ppm appeared due
to 3-Me group. The 7-H proton in the dihydropyridine
fragment resonated as a singlet at δ 5.11–5.68 ppm. It
is displaced downfield [12] due to magnetically aniso-
tropic effect of the neighboring aromatic ring. Aromat-
ic protons in the R' substituent suffer from deshielding
effect of substituents in the phenyl ring, and the posi-
tion and multiplicity of their signals are consistent with
their arrangement with respect to the substituent.
Methyl groups on C10 in dimedone derivatives VIc,
VId, and VIl give rise to two singlets in the region
δ 0.90–1.11 ppm.
The precipitate was filtered off, washed with diethyl
ether, and recrystallized from ethanol (Va, Vi), 1:3
ethanol–benzene mixture (Vb, Vc, Vf–Vh, Vj–Vm,
VIc, VId, VIl), or dimethylformamide (Vd, Ve).
12-(4-Fluorophenyl)-3-methyl-7,10,11,12-tetra-
hydro-9H-benzo[b][1,7]phenanthrolin-8-one (Va).
1
Yield 75%, mp 187–188°C. H NMR spectrum, δ,
ppm: 1.93 m (1H, 10-Hax), 2.08 m (1H, 10-Heq), 2.24 m
(2H, 9-H), 2.59 s (Me), 2.61 m (1H, 11-Hax), 2.78 d.t
(1H, 11-Heq, J11-eq,10-ax = J11-eq,10-eq = 4.6 Hz), 5.19 s
(7-H), 7.11 d (2H, 2′-H, 6′-H, J = 8.5 Hz), 7.32 m (2H,
3′-H, 5′-H) 7.36 d (1H, 6-H, J6,5 = 8.8 Hz), 7.40 d (1H,
2-H, J2,1 = 8.4 Hz), 7.45 d (1H, 5-H, J5,6 = 8.8 Hz),
8.80 d (1H, 1-H, J1,2 = 8.4 Hz), 9.29 s (NH). Found, %:
N 7.59. C23H19FN2O. Calculated, %: N 7.82.
Thus three-component condensation of 2-methyl-
quinolin-5-amine with aromatic aldehydes and cyclic
β-diketones provides a convenient one-pot procedure
for the synthesis of a number of difficultly accessible
methyl-substituted 1,7-phenanthroline derivatives. The
condensation products obtained from dimedone pos-
sess a CMe2 fragment which is typical of many bio-
logically active compounds. However, the most prom-
ising in the structure of the obtained 1,7-phenanthro-
lines is the presence of a methyl group in the quinoline
fragment; broad synthetic potential of that group
attracts interest from the viewpoint of the design of
new compounds with practically useful properties.
7-(4-Bromophenyl)-3-methyl-7,10,11,12-tetra-
hydro-9H-benzo[b][1,7]phenanthrolin-8-one (Vb).
1
Yield 71%, mp 279–280°C. H NMR spectrum, δ,
ppm: 1.98 m (1H, 10-Hax), 2.05 m (1H, 10-Heq), 2.28 m
(2H, 9-H), 2.60 s (3H, Me), 2.65 m (1H, 11-Hax),
2.80 d.t (1H, 11-Heq, J11-eq,10-ax = J11-eq,10-eq = 4.5 Hz),
5.26 s (1H, 7-H), 7.18 d (2H, 2′-H, 6′-H, J = 8.4 Hz),
7.38 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.47 d (3H, 2-H,
5-H, 6-H, J2,1 = J5,6 = 8.9 Hz), 8.82 d (1H, 1-H, J1,2
=
8.9 Hz), 9.42 s (NH). Found, %: C 65.76; H 4.39;
Br 18.90; N 6.53. C23H19BrN2O. Calculated, %:
C 65.87; H 4.53; Br 19.09; N 6.68.
EXPERIMENTAL
7-(4-Hydroxyphenyl)-3-methyl-7,10,11,12-tetra-
hydro-9H-benzo[b][1,7]phenanthrolin-8-one (Vc).
Yield 76%, mp 237–238°C. 1H NMR spectrum, δ, ppm:
1.95 m (1H, 10-Hax), 2.03 m (1H, 10-Heq), 2.25 m (2H,
The IR spectra were recorded in KBr on a Nicolet
Protégé-460 spectrometer with Fourier transform. The
NMR spectra were measured on Bruker AC-500
(500 MHz) and Tesla BS-567 (100 MHz) spectrom-
eters from solutions in DMSO-d6 using tetramethyl-
silane as internal reference. The mass spectra (electron
impact, 70 eV) were obtained on a Finnigan MAT
INCOS-50 instrument, as well as on a Hewlett–
Packard 5890/5972 GC–MS system (electron impact,
70 eV; HP-5MS column, 30 m×0.25 mm, film thick-
ness 0.25 μm; injector temperature 250°C). The melt-
ing points were determined on a Kofler hot stage.
2
9-H), 2.63 s (3H, Me), 2.73 d.d.d (1H, 11-Hax, J =
17.0, J11-ax,10-eq = 4.3 Hz), 2.85 d.t (1H, 11-Heq,
J11-eq,10-ax = J11-eq,10-eq = 4.3 Hz), 5.19 s (1H, 7-H),
6.38 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 6.49 d (2H, 3′-H,
5′-H, J = 8.4 Hz), 7.39 d (1H, 6-H, J6,5 = 9.0 Hz),
7.42 d (1H, 2-H, J2,1 = 8.9 Hz), 7.44 d (1H, 5-H, J5,6
9.0 Hz), 8.64 s (1H, OH), 8.83 d (1H, 1-H, J1,2
=
=
8.9 Hz), 9.25 s (NH). Found, %: C 77.42; H 5.50;
N 7.74. C23H20N2O2. Calculated, %: C 77.53; H 5.62;
N 7.86.
7-Aryl(hetaryl)-3-methyl-7,10,11,12-tetrahydro-
9H-benzo[b][1,7]phenanthrolin-8-ones Va–Vm and
7-aryl-3,10,10-trimethyl-7,10,11,12-tetrahydro-9H-
benzo[b][1,7]phenanthrolin-8-ones VIc, VId, and
VIl (general procedure). A solution of 2-methylquino-
lin-5-amine (I), 5 mmol of cyclohexane-1,3-dione (II,
in the synthesis of compounds Va–Vm) or 5,5-dimeth-
ylcyclohexane-1,3-dione (III, in the synthesis of VIc,
VId, and VIl), and 5 mmol of aldehyde IVa–IVm in
20 ml of butan-1-ol was heated for 3–4 h under reflux.
7-(3,4-Dihydroxyphenyl)-3-methyl-7,10,11,12-
tetrahydro-9H-benzo[b][1,7]phenanthrolin-8-one
1
(Vd). Yield 69%, mp 173–174°C. H NMR spectrum,
δ, ppm: 1.90 m (1H, 10-Hax), 2.01 m (1H, 10-Heq),
2.24 m (2H, 9-H), 2.61 s (3H, Me), 2.70 m (1H,
11-Hax), 2.79 d.t (1H, 11-Heq, J11-eq,10-ax = J11-eq,10-eq
4.8 Hz), 5.17 s (1H, 7-H), 6.58 d (1H, 6′-H, J6′,5′
=
=
8.6 Hz), 6.63 d (1H, 5′-H, J5′,6′ = 8.6 Hz), 6.70 s (1H,
2′-H), 7.47 d (1H, 2-H, J2,1 = 8.8 Hz), 7.53 d (1H, 6-H,
J6,5 = 8.9 Hz), 7.58 d (1H, 5-H, J5,6 = 8.9 Hz), 8.58 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 7 2010

SYNTHESIS OF METHYL-SUBSTITUTED 1,7-PHENANTHROLINE DERIVATIVES
1077
2
(1H, OH), 8.62 s (1H, OH), 8.86 d (1H, 1-H, J1,2
=
11-Hax, J = 17.2, J11-ax,10-eq = 4.5 Hz), 2.80 d.t (1H,
11-Heq, J11-eq,10-ax = J11-eq,10-eq = 4.5 Hz), 3.70 s (3H,
MeO), 3.77 s (3H, MeO), 5.40 s (1H, 7-H), 6.65 d (1H,
6′-H, J6′,5′ = 8.6 Hz), 6.72 d (1H, 5′-H, J5′,6′ = 8.6 Hz),
6.80 s (1H, 2′-H), 7.46 d (1H, 2-H, J2,1 = 8.8 Hz),
8.8 Hz), 9.30 s (NH). Found, %: C 73.98; H 5.19;
N 7.33. C23H20N2O3. Calculated, %: C 74.19; H 5.39;
N 7.53.
7-(2-Methoxyphenyl)-3-methyl-7,10,11,12-tetra-
7.53 d (1H, 6-H, J6,5 = 9.0 Hz), 7.57 d (1H, 5-H, J5,6
=
hydro-9H-benzo[b][1,7]phenanthrolin-8-one (Ve).
9.0 Hz), 8.81 d (1H, 1-H, J1,2 = 8.8 Hz), 9.32 s (NH).
Found, %: C 74.90; H 5.83; N 6.94. C25H24N2O3. Cal-
culated, %: C 75.00; H 6.00; N 7.00.
1
Yield 68%, mp 293–294°C. H NMR spectrum, δ,
ppm: 1.96 m (1H, 10-Hax), 2.02 m (1H, 10-Heq), 2.25 m
(2H, 9-H), 2.60 s (3H, Me), 2.73 m (1H, 11-Hax),
2.90 d.t (1H, 11-Heq, J11-eq,10-ax = J11-eq,10-eq = 4.4 Hz),
3.90 s (3H, MeO), 5.68 s (1H, 7-H); 6.78 t, 6.90 d,
7.04 t, 7.09 t (4H, 3′-H, 4′-H, 5′-H, 6′-H, J3′,4′ = 8.0,
J4′,5′ = J5′,6′ = 8.5 Hz); 7.40 (1H, 2-H, J2,1 = 8.7 Hz),
7-(4-Hydroxy-3-methoxyphenyl)-3-methyl-
7,10,11,12-tetrahydro-9H-benzo[b][1,7]phenan-
throlin-8-one (Vi). Yield 75%, mp 220–221°C.
1H NMR spectrum, δ, ppm: 1.94 m (1H, 10-Hax),
2.03 m (1H, 10-Heq), 2.29 m (2H, 9-H), 2.62 s (3H,
7.44 d (1H, 6-H, J6,5 = 8.8 Hz), 7.58 d (1H, 5-H, J5,6
=
2
Me), 2.71 d.d.d (1H, 11-Hax, J = 17.6, J11-ax,10-eq
4.6 Hz), 2.80 d.t (1H, 11-Heq, J11-eq,10-ax = J11-eq,10-eq
=
=
8.8 Hz), 8.79 d (1H, 1-H, J1,2 = 8.7 Hz), 9.31 s (NH).
Found, %: C 77.67; H 5.83; N 7.35. C24H22N2O2. Cal-
culated, %: C 77.84; H 5.94; N 7.57.
4.6 Hz), 3.72 s (3H, MeO), 5.32 s (1H, 7-H), 6.69 d
(2H, 5′-H, 6′-H, J5′,6′ = 8.6 Hz), 6.80 s (1H, 2′-H),
7-(4-Methoxyphenyl)-3-methyl-7,10,11,12-tetra-
7.47 d (1H, 2-H, J2,1 = 8.7 Hz), 7.53 d (1H, 6-H, J6,5
=
hydro-9H-benzo[b][1,7]phenanthrolin-8-one (Vf).
8.9 Hz), 7.57 d (1H, 5-H, J5,6 = 8.9 Hz), 8.61 s (1H,
OH), 8.89 d (1H, 1-H, J1,2 = 8.7 Hz), 9.35 s (NH).
Found, %: C 74.43; H 5.67; N 7.11. C24H22N2O3. Cal-
culated, %: C 74.61; H 5.70; N 7.25.
1
Yield 70%, mp 271–272°C. H NMR spectrum, δ,
ppm: 1.91 m (1H, 10-Hax), 2.03 m (1H, 10-Heq), 2.24 m
(2H, 9-H), 2.60 s (3H, Me), 2.69 d.d.d (1H, 11-Hax,
J11-ax,11-eq = 17.1, J11-ax,10-eq = 4.3 Hz), 2.85 d.t (1H,
11-Heq, J11-eq,10-ax = J11-eq,10-eq = 4.3 Hz), 3.69 s (3H,
MeO), 5.22 s (1H, 7-H), 6.73 d (2H, 2′-H, 6′-H, J =
8.4 Hz), 7.13 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.48 d
7-(4-Dimethylaminophenyl)-3-methyl-7,10,11,12-
tetrahydro-9H-benzo[b][1,7]phenanthrolin-8-one
(Vj). Yield 46%, mp 187–188°C. 1H NMR spectrum,
δ, ppm: 1.95 m (1H, 10-Hax), 2.03 m (1H, 10-Heq),
2.25 m (2H, 9-H), 2.60 s (3H, Me), 2.75 m (1H,
11-Hax), 2.82 m (1H, 11-Heq), 3.32 s (6H, NMe2),
5.11 s (1H, 7-H), 6.50 d (2H, 2′-H, 6′-H, J = 8.8 Hz),
6.97 d (2H, 3′-H, 5′-H, J = 8.8 Hz), 7.40 m (3H, 2-H,
5-H, 6-H), 8.73 d (1H, 1-H, J1,2 = 8.9 Hz), 9.28 s
(NH). Found, %: C 78.19; H 6.50; N 10.71.
C25H25N3O. Calculated, %: C 78.33; H 6.53; N 10.97.
(1H, 2-H, J2,1 = 8.6 Hz), 7.53 d (1H, 6-H, J6,5
=
9.0 Hz), 7.59 d (1H, 5-H, J5,6 = 9.0 Hz), 8.87 d (1H,
1-H, J1,2 = 8.6 Hz), 9.39 s (NH). Found, %: C 77.55;
H 5.88; N 7.27. C24H22N2O2. Calculated, %: C 77.84;
H 5.94; N 7.57.
7-(2,4-Dimethoxyphenyl)-3-methyl-7,10,11,12-
tetrahydro-9H-benzo[b][1,7]phenanthrolin-8-one
1
(Vg). Yield 69%, mp 284–285°C. H NMR spectrum,
7-[4-Bis(2-chloroethyl)]aminophenyl]-3-methyl-
δ, ppm: 1.93 m (1H, 10-Hax), 2.03 m (1H, 10-Heq),
7,10,11,12-tetrahydro-9H-benzo[b][1,7]phenanthro-
1
2.28 m (2H, 9-H), 2.64 s (3H, Me), 2.77 d.d.d (1H,
lin-8-one (Vk). Yield 48%, mp 204–205°C. H NMR
2
11-Hax, J = 17.5, J11-ax,10-eq = 4.4 Hz), 2.83 d.t (1H,
spectrum, δ, ppm: 1.92 m (1H, 10-Hax), 2.02 m (1H,
10-Heq), 2.29 m (2H, 9-H), 2.58 s (3H, Me), 2.77 m
(1H, 11-Hax), 2.85 m (1H, 11-Heq), 3.60 s [8H,
N(C2H4Cl)2], 5.16 s (1H, 7-H), 6.52 d (2H, 2′-H, 6′-H,
J = 8.9 Hz), 7.03 d (2H, 3′-H, 5′-H, J = 8.9 Hz), 7.45 d
11-Heq, J11-eq,10-ax = J11-eq,10-eq = 4.4 Hz), 3.69 s (3H,
MeO), 3.75 s (3H, MeO), 5.40 s (1H, 7-H), 6.68 d (2H,
5′-H, 6′-H, J5′,6′ = 8.8 Hz), 6.81 s (1H, 3′-H), 7.43 d
(1H, 2-H, J2,1 = 8.9 Hz), 7.50 d (1H, 6-H, J6,5
=
9.0 Hz), 7.55 d (1H, 5-H, J5,6 = 9.0 Hz), 8.88 d (1H,
1-H, J1,2 = 8.9 Hz), 9.36 s (NH). Found, %: C 74.73;
H 5.87; N 6.90. C25H24N2O3. Calculated, %: C 75.00;
H 6.00; N 7.00.
(1H, 2-H, J2,1 = 8.7 Hz), 7.52 d (1H, 6-H, J6,5
=
9.0 Hz), 7.57 d (1H, 5-H, J5,6 = 9.0 Hz), 8.79 d (1H,
1-H, J1,2 = 8.7 Hz), 9.32 s (NH). Found, %: C 67.49;
H 5.50; Cl 14.58; N 8.56. C27H27Cl2N3O. Calculated,
%: C 67.50; H 5.63; Cl 14.7; N 8.75.
7-(3,4-Dimethoxyphenyl)-3-methyl-7,10,11,12-
tetrahydro-9H-benzo[b][1,7]phenanthrolin-8-one
(Vh). Yield 72%, mp 228–229°C. H NMR spectrum,
δ, ppm: 1.90 m (1H, 10-Hax), 2.01 m (1H, 10-Heq),
Methyl 4-(3-methyl-8-oxo-7,10,11,12-tetrahydro-
1
9H-benzo[b][1,7]phenanthrolin-7-yl)benzoate (Vl).
1
Yield 73%, mp 219–220°C. H NMR spectrum, δ,
2.25 m (2H, 9-H), 2.64 s (3H, Me), 2.73 d.d.d (1H,
ppm: 1.98 m (1H, 10-Hax), 2.07 m (1H, 10-Heq), 2.32 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 7 2010

KOZLOV, GUSAK
1078
(2H, 9-H), 2.61 s (3H, Me), 2.73 m (1H, 11-Hax),
2.84 m (1H, 11-Heq), 3.79 s (3H, CO2Me), 5.38 s (1H,
7-H), 7.32 d (2H, 2′-H, 6′-H, J = 8.7 Hz), 7.40 d (1H,
6-H, J6,5 = 8.9 Hz), 7.46 d (1H, 2-H, J2,1 = 8.8 Hz),
7.53 d (1H, 5-H, J5,6 = 8.9 Hz), 7.71 d (2H, 3′-H, 5′-H,
J = 8.7 Hz), 8.83 d (1H, 1-H, J1,2 = 8.8 Hz), 9.27 s
(NH). Found, %: C 75.20; H 5.45; N 6.89. C25H22N2O3.
Calculated, %: C 75.38; H 5.5; N 7.04.
Methyl 4-(3,10,10-trimethyl-8-oxo-7,10,11,12-
tetrahydro-9H-benzo[b][1,7]phenanthrolin-7-yl)-
benzoate (VIm). Yield 74%, mp 204–205°C. 1H NMR
spectrum, δ, ppm: 0.93 s (3H, Me), 1.09 s (3H, Me),
2
2.10 d (1H, 9-Hax, J = 16.0 Hz), 2.21 d (1H, 9-Heq,
2J = 16.0 Hz), 2.42 d (1H, 11-Hax, 2J = 16.2 Hz), 2.50 d
2
(1H, 11-Heq, J = 16.2 Hz), 2.61 s (3H, Me), 3.84 s
(3H, CO2Me), 5.43 s (1H, 7-H), 7.34 d (2H, 2′-H, 6′-H,
J = 8.9 Hz), 7.43 d (1H, 6-H, J6,5 = 9.1 Hz), 7.47 d
3-Methyl-7-(pyridin-3-yl)-7,10,11,12-tetrahydro-
(1H, 2-H, J2,1 = 8.8 Hz), 7.52 d (1H, 5-H, J5,6
=
9H-benzo[b][1,7]phenanthrolin-8-one (Vm). Yield
1
9.1 Hz), 7.79 d (2H, 3′-H, 5′-H, J = 8.9 Hz), 8.86 d
(1H, 1-H, J1, 2 = 8.8 Hz), 9.29 s (NH). Found, %:
C 75.93; H 5.98; N 6.53. C27H26N2O3. Calculated, %:
C 76.06; H 6.10; N 6.57.
61%, mp 168–169°C. H NMR spectrum, δ, ppm:
1.90 m (1H, 10-Hax), 2.02 m (1H, 10-Heq), 2.24 m (2H,
9-H), 2.65 s (3H, Me), 2.76 m (1H, 11-Hax), 2.87 m
(1H, 11-Heq), 5.29 s (1H, 7-H), 7.19 d (2H, 5′-H, 6′-H,
J5′,6′ = J5′,4′ = 8.6 Hz), 7.41 d (1H, 2-H, J2,1 = 8.7 Hz),
This study was performed under financial support
by the Byelorussian Republican Foundation for Basic
Research (project no. Kh07-007).
7.49 d (1H, 6-H, J6,5 = 9.0 Hz), 7.55 d (1H, 5-H, J5,6
=
9.0 Hz), 8.25 d (1H, 4′-H, J4′,5′ = 8.6 Hz), 8.50 s (1H,
2′-H), 8.83 d (1H, 1-H, J1,2 = 8.7 Hz), 9.40 s (NH).
Found, %: C 77.29; H 5.50; N 12.21. C22H19N3O. Cal-
culated, %: C 77.42; H 5.57; N 12.32.
REFERENCES
1. Swiss Patent no. 290515, 1953; Chem. Abstr., 1955,
7-(4-Hydroxyphenyl)-3,10,10-trimethyl-
vol. 49, p. 7606g.
7,10,11,12-tetrahydro-9H-benzo[b][1,7]phenanthro-
1
2. Swiss Patent no. 296573, 1954; Chem. Abstr., 1956,
lin-8-one (VIc). Yield 72%, mp 220–221°C. H NMR
vol. 50, p. 5040a.
spectrum, δ, ppm: 0.90 s (3H, Me), 1.10 s (3H, Me),
2
3. Rittersdorf, W., Rey, H., Guethlein, W., and Rieck-
mann, P., FRG Patent no. 2235152, 1974; Chem. Abstr.,
1974, vol. 80, no. 142769d.
2.08 d (1H, 9-Hax, J = 16.1 Hz), 2.22 d (1H, 9-Heq,
2J = 16.1 Hz), 2.43 d (1H, 11-Hax, 2J = 16.4 Hz), 2.55 d
2
(1H, 11-Heq, J = 16.4 Hz), 2.67 s (3H, Me), 5.29 s
4. Berger, D., Fey, G., Kuhr, M., and Werner, W., EPV
Patent no. 14929, 1980; Chem. Abstr., 1981, vol. 94,
no. 43719z.
(1H, 7-H), 6.35 d (2H, 2′-H, 6′-H, J = 8.0 Hz), 6.47 d
(2H, 3′-H, 5′-H, J = 8.0 Hz), 7.40 d (1H, 6-H, J6,5
=
9.1 Hz), 7.44 d (1H, 2-H, J2,1 = 8.9 Hz), 7.50 d (1H,
5-H, J5,6 = 9.1 Hz), 8.60 s (1H, OH), 8.80 d (1H, 1-H,
J1, 2 = 8.9 Hz), 9.35 s (NH). Found, %: C 78.02;
H 6.14; N 7.25. C25H24N2O2. Calculated, %: C 78.1;
H 6.25; N 7.29.
5. Jastzebska-Glapa, M., Mlochowski, J., and Sliwa, W.,
J. Prakt. Chem., 1977, vol. 319, p. 883.
6. Konyukhov, V.N., P’yankova, L.N., and Pushkare-
va, Z.V., Zh. Obshch. Khim., 1962, vol. 32, p. 2745.
7. El’tsov, A.V., Nekrasov, S.V., and Smirnov, E.V.,
7-(3,4-Dihydroxyphenyl)-3,10,10-trimethyl-
7,10,11,12-tetrahydro-9H-benzo[b][1,7]phenanthro-
lin-8-one (VId). Yield 65%, mp 217–218°C. 1H NMR
spectrum, δ, ppm: 0.94 s (3H, Me), 1.11 s (3H, Me),
Zh. Org. Khim., 1972, vol. 8, p. 1309.
8. Mikhailenko, F.A. and Boguslavskaya, A.P., Ukr. Khim.
Zh., 1971, vol. 37, p. 1031.
9. Bachowska, B. and Matusiak, G., Khim. Geterotsikl.
Soedin., 2009, p. 95.
2
2.07 d (1H, 9-Hax, J = 16.4 Hz), 2.19 d (1H, 9-Heq,
2J = 16.4 Hz), 2.40 d (1H, 11-Hax, 2J = 16.3 Hz), 2.51 d
10. Carr, B. and Franklin, M., J. Biochem. Mol. Toxicol.,
2
(1H, 11-Heq, J = 16.3 Hz), 2.65 s (3H, Me), 5.33 s
1999, vol. 13, p. 77.
(1H, 7-H), 6.60 d (1H, 6′-H, J6′,5′ = 8.3 Hz), 6.71 d
(1H, 5′-H, J5′,6′ = 8.3 Hz), 6.77 s (1H, 2′-H), 7.41 d
11. Kozlov, N.G., Tereshko, A.B., and Gusak, K.N., Russ. J.
Org. Chem., 2007, vol. 43, p. 1371.
(1H, 2-H, J2,1 = 8.7 Hz), 7.52 d (1H, 6-H, J6,5
=
12. Dyer, J.R., Applications of Absorption Spectroscopy of
Organic Compounds, Englewood Cliffs: Prentice–Hall,
1965. Translated under the title Prilozheniya absorb-
tsionnoi spektroskopii organicheskikh soedinenii,
Moscow: Khimiya, 1970, p. 44.
9.0 Hz), 7.59 d (1H, 5-H, J5,6 = 9.0 Hz), 8.60 s (1H,
OH), 8.65 s (1H, OH), 8.84 d (1H, 1-H, J1,2 = 8.7 Hz),
9.38 s (NH). Found, %: C 74.83; H 5.90; N 6.77.
C25H24N2O3. Calculated, %: C 75.00; H 6.00; N 7.00.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 7 2010