Barbituric acid in the synthesis of fused 1,7-phenanthroline derivatives

Article abstract of DOI:10.1134/S1070428014070124

New 7-aryl(hetaryl)-7,8,9,10,11,12-hexahydropyrimido[5,4-b][1,7] phenanthroline-9,11-diones have been synthesized by three-component condensation of barbituric acid with quinolin-5-amine and aromatic or heteroaromatic aldehydes.

Full text of DOI:10.1134/S1070428014070124

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 7, pp. 1006–1011. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © N.G. Kozlov, A.B. Tereshko, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 7, pp. 1024–1028.
Barbituric Acid in the Synthesis of Fused
1,7-Phenanthroline Derivatives
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 January 17, 2014
Abstract—New 7-aryl(hetaryl)-7,8,9,10,11,12-hexahydropyrimido[5,4-b][1,7]phenanthroline-9,11-diones have
been synthesized by three-component condensation of barbituric acid with quinolin-5-amine and aromatic or
heteroaromatic aldehydes.
DOI: 10.1134/S1070428014070124
Barbituric acid [pyrimidine-2,4,6(1H,3H,5H)-tri-
one] is a structural base of numerous anticonvulsant,
soporific, and anesthetic agents [1–3]. Due to their
structural diversity and broad spectrum of biological
activity, fused heterocyclic systems with partially or
completely hydrogenated pyrimidine ring are attractive
as target compounds of organic synthesis. Efficient
drugs for the treatment of oncological diseases have
been designed on the basis of pyrrolo[2,3-d]- and pyr-
ido[2,3-d]pyrimidine derivatives [4–8]. Therefore, syn-
thesis of new pyrimidinetrione derivatives is important
not only from the theoretical viewpoint but also for
practical purposes.
We previously described [9] the three-component
condensation of naphthalen-2-amine with substituted
benzaldehydes and barbituric acid, which involved
intermediate formation of the corresponding 5-aryl-
methylidenepyrimidine-2,4,6(1H,3H,5H)-triones and
afforded new 12-aryl-7,8,9,10,11,12-hexahydrobenzo-
[f]pyrimido[4,5-b]quinoline-9,11-diones. The present
study was aimed at synthesizing pyrimidine-fused
1,7-phenanthroline derivatives. For this purpose, we
examined three-component condensation of barbituric
aicd with quinolin-5-amine and aromatic or hetero-
aromatic aldehyde. High reactivity of barbituric acid is
determined by the presence in its molecule of four
acidic hydrogen atoms, the most active of which are
those attached to C5. Barbituric acid readily undergoes
alkylation and condensations with carbonyl com-
pounds [10, 11]. Like carbocyclic analogs of the cyclo-
hexane-1,3-dione series, the molecule of barbituric
acid possesses a β-dicarbonyl fragment which ensures
high efficiency in the synthesis of fused azahetero-
cycles via cascade heterocyclization of 1,3-diketones
with amines and aromatic or heteroaromatic aldehydes
[12, 13].
The reactions of quinolin-5-amine (I) with substi-
tuted benzaldehyde IIa–IIo or thiophenecarbaldehyde
IIp or IIq and barbituric acid (III) were carried out by
heating the reactants in boiling butanol for 20–30 min.
As a result, we isolated 60–87% of the corresponding
7-aryl(hetaryl)-7,8,9,10,11,12-hexahydropyrimido-
[5,4-b][1,7]phenanthroline-9,11-diones IVa–IVq
(Scheme 1).
In the three-component condensations of hetero-
aromatic amines with aromatic aldehydes and cyclic
β-diketone, partly hydrogenated pyrimidine ring in the
resulting polynuclear heterocyclic system originates
from the amidine fragment in the heteroaromatic
amine, carbonyl group of the aldehyde, and enol frag-
ment of the diketone [14]. In the condensation of
compounds I–III, pyrimidine ring is introduced as
a finished building block fused to 1,4-dihydropyridine
ring, while the latter is formed from the enol fragment
of barbituric acid, amino group of quinolin-5-amine,
and aldehyde carbonyl group.
The final step in the formation of 7,8,9,10,11,12-
hexahydropyrimido[5,4-b][1,7]phenanthroline-9,11-di-
ones IVa–IVq is intramolecular cyclization of inter-
mediate arylamino trione A which may be generated in
two ways. The first of these is the condensation of
barbituric acid (III) with aldehyde II to produce
5-arylmethylidenehexahydropyrimidine-2,4,6-trione V
1006

BARBITURIC ACID IN THE SYNTHESIS OF FUSED 1,7-PHENANTHROLINE
1007
Scheme 1.
O
O
I
HN
HN
R
+
RCHO
O
N
H
O
O
N
H
O
III
IIa–IIq
Va–Vq
H
N
O
O
NH2
R
NH
O
O
R
N
HN
A
NH2
N
R
O
IIa–IIq
III
NH
N
H
O
N
N
N
I
VIa–VIq
B
2
3
1
O
H
N
N
11
12
NH
9
5
N
H
O
7
6
R
IVa–IVq
R = 2-MeC6H4 (a), 4-MeC6H4 (b), 4-і-PrC6H4 (c), 2-BrC6H4 (d), 2-IC6H4 (e), 2-CF3C6H4 (f), 3-HOC6H4 (g), 3,4,5-(MeO)3C6H2 (h),
3,4-(OCH2O)C6H3 (i), 4-EtOC6H4 (j), 4-PrOC6H4 (k), 3-EtO-4-HOC6H3 (l), 4-MeSC6H4 (m), 4-PhC6H4 (n), 4-PhCH2OC6H4 (o),
thiophen-2-yl (p), 3-methylthiophen-2-yl (q).
products were 7-aryl(hetaryl)-7,8,9,10,11,12-hexahy-
dropyrimido[5,4-b][1,7]phenanthroline-9,11-diones
IVa–IVq.
and subsequent addition of quinolin-5-amine (I) by the
electron-rich C6 atom to the exocyclic double bond of
V. According to the second pathway, initial reaction of
amine I with aldehyde II yields Schiff base VI,
Michael type addition of barbituric acid (III) to the
C=N bond of VI gives amino triketone B, the latter
undergoes hydramine fission into initial quinolin-5-
amine (I) and 5-arylmethylidenehexahydropyrimidine-
2,4,6-trione V, and addition of V to I leads to the same
intermediate A as in the first pathway. It should be
noted that migration of the arylmethylidenepyrimidine-
trione fragment may be regarded as Hoffman–Martius
rearrangement [15].
Both reactions path were confirmed by us by car-
rying out two-component condensations of aldehydes
IIa–IIq with barbituric acid (III) and amine I and
isolation of 5-arylmethylidenehexahydropyrimidinetri-
ones Va–Vq and N-arylmethylidenequinolin-5-amines
VIa–VIq, which were then brought into reaction with
the third component, quinolin-5-amine (I) and barbi-
turic acid (III), respectively. In all cases, the final
The substituent R in the aldehyde II molecule
exerts some effect on the yield of the target product.
Benzaldehydes IIg and IIj–IIl containing hydroxy
or/and alkoxy groups (–I or –I/–M effect) give rise to
pyrimidophenanthrolines IVg and IVj–IVl in fairly
high yields (83–87%). Donor methyl, 3,4,5-trimethoxy,
and methylenedioxy groups reduced the yield of
phenanthrolines IVb, IVh, and IVi to 68–82% because
of weakened polarization and lower reactivity of the
carbonyl group in aldehydes IIb, IIh, and IIi. Steric
hindrances created by the halogen atom in the ortho
position of aldehydes IId and IIe affect the reaction to
a greater extent despite lower –I effect of halogen
compared to methoxy group, and phenanthrolines IVd
and IVe are formed in lower yield (73–78%). Appre-
ciable steric effect is also observed (in combination
with the deactivating +I effect of the methyl group) in
the reactions with 2-methylbenzaldehyde (IIa) and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

KOZLOV, TERESHKO
1008
EXPERIMENTAL
3-methylthiophene-2-carbaldehyde (IIIq), where the
yields of IVa and IVq were 60–72%.
The IR spectra were recorded in KBr on a Nicolet
Protégé-460 spectrometer with Fourier transform. The
1H NMR spectra were measured on Bruker AC-500
(500 MHz) and Tesla BS-567 (100 MHz) spectrom-
eters from 5% solutions in DMSO-d6 using tetra-
methylsilane as internal reference. The mass spectra
(electron impact, 70 eV) were obtained on a Hewlett
Packard 5890/5972 GC/MS system (HP-5MS capillary
column, 30 m×0.25 mm, film thickness 0.25 μm;
injector temperature 250°C). The melting points were
determined on a Kofler hot stage.
5-Arylmethylidenehexahydropyrimidine-2,4,6-tri-
ones Va–Vq were synthesized by heating equimolar
mixtures of barbituric acid (III) and the corresponding
aldehydes IIa–IIq in boiling alcohol for 20–30 min.
The physical constants of Va–Vq were consistent with
published data [17–19]. N-[Aryl(hetaryl)methylidene]-
quinolin-5-amines VIa–VIq were synthesized accord-
ing to the procedure described in [20].
Pyrimido[5,4-b][1,7]phenanthrolinediones IVa–
IVq were isolated as light yellow or yellow high-
melting (mp >300°C) crystalline substances which are
soluble in DMF, DMSO, and nitrobenzene, poorly
soluble in alcohols on heating, and insoluble in diethyl
ether, acetone, and water. The product structure was
determined on the basis of their IR and NMR spectra.
1
According to the H NMR data, compounds IVa–
IVq belong to the same structural type as the products
of three-component condensation of quinolin-5-amine
with aromatic aldehydes and cyclohexane-1,3-dione
derivatives and are nitrogen analogs of hexahydro-
1
benzo[b][1,7]phenanthrolines. The H NMR spectra of
IVa–IVq in the aromatic region (δ 6.40–7.00 ppm)
were identical to the spectra of benzo[b][1,7]phenan-
throlinones [11, 12]. The singlet at δ 5.72–5.92 ppm
belongs to 7-H, and the singlet at δ 9.90–10.43 ppm, to
N12H. A large difference in the chemical shifts of 7-H
and 12-H and the lack of spin–spin coupling between
these protons indicate formation of 1,4-dihydropyri-
dine ring. The NHCONH fragment of the pyrimidine
ring in IVa–IVq is represented in the 1H NMR spectra
by broadened singlets in the regions δ 10.51–11.14 and
10.71–11.29 ppm.
7-Aryl(hetaryl)-7,8,9,10,11,12-hexahydropyrimi-
do[5,4-b][1,7]phenanthroline-9,11-diones IVa–IVq
(general procedures). a. A solution of 6 mmol of
quinolin-5-amine (I), 5 mmol of aldehyde IIa–IIj, and
5 mmol of barbituric acid (III) in 15 mL of butan-1-ol
was heated for 20–30 min under reflux. After cooling,
the crystalline solid was filtered off, washed with hot
water and diethyl ether to remove unreacted initial
compounds, and dried. Compounds IVa–IVo were
recrystallized from ethanol–benzene (1:3), and thio-
phene derivatives IVp and IVq, from toluene.
b. A solution of 5 mmol of 5-arylmethylidenebar-
bituric acid Va–Vq and 6 mmol of quinolin-5-amine
(I) in 15 mL of butan-1-ol was heated under reflux
until crystals began to separate (20–30 min). The pre-
cipitate was filtered off and recrystallized from etha-
nol–benzene (1:3) or toluene.
The IR spectra of IVa–IVq contained absorption
bands belonging to stretching vibrations of secondary
amino (3470–3160 cm–1) and carbonyl groups (1715–
1700 cm–1). Strong absorption bands at 1600–1580 and
1520–1515 cm–1 were assigned to the vinylogous
amide fragment (1580, 1520 cm–1 [16]). Stretching
vibrations of C–H bonds in methyl (methoxy) groups
appeared at 2920–2890 cm–1, and aromatic C–H bonds
gave rise to absorption at 3060–3040 cm–1.
The molecular ion peaks in the mass spectra of
IVa–IVq had intensities of 20–35%, while the base
peaks (Irel 100%) were those corresponding to the
[M – R]+ ions (m/z 265). Also, ion peaks with m/z 266
(Irel 65–70%) [M – R + 1]+, and fragment ion peaks
with m/z 128 (Irel 29–34%), 140 (Irel 39–42%), and 167
(Irel 31–37%) were present.
c. A solution of 5 mmol of barbituric acid (III) and
5 mmol of Schiff base VIa–VIq in 15 mL of butan-1-
ol was heated for 30 min under reflux. The products
were isolated as desribed above.
7-(2-Methylphenyl)-7,8,9,10,11,12-hexahydropy-
Thus, barbituric acid is an efficient building block
in the synthesis of new fused heterocyclic systems con-
taining pyrimidine, pyridine, and quinoline fragments
and pharmacophoric aryl and hetaryl substituents
which could endow the synthesized compounds with
a broad spectrum of biological activity.
rimido[5,4-b][1,7]phenanthroline-9,11-dione (IVa).
1
Yield 68 (a), 72 (b), 71% (c). H NMR spectrum, δ,
ppm: 2.48 s (Me), 5.91 s (1H, 7-H), 6.68–6.76 m and
3
7.04–7.13 m (4H, Harom), 7.39 d.d (1H, 2-H, J = 8.0,
4J = 4.3 Hz), 7.72 d and 8.12 d (1H each, 5-H, 6-H,
3J = 8.8 Hz), 8.47 d (1H, 3-H, 3J = 4.3 Hz), 8.79 d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

BARBITURIC ACID IN THE SYNTHESIS OF FUSED 1,7-PHENANTHROLINE
1009
3
1-H, J = 8.0 Hz), 10.07 s (1H, 12-H), 10.73 s (1H,
7-(2-Trifluoromethylphenyl)-7,8,9,10,11,12-hexa-
hydropyrimido[5,4-b][1,7]phenanthroline-9,11-di-
NH), 10.93 s (1H, NH). Found, %: C 70.72; H 4.49;
N 15.69. C21H16N4O2. Calculated, %: C 70.77; H 4.53;
N 15.72.
1
one (IVf). Yield 67 (a), 68 (b), 69% (c). H NMR
spectrum, δ, ppm: 5.78 s (1H, 7-H), 6.73–6.84 m and
3
7.09–7.18 m (4H, Harom), 7.45 d.d (1H, 2-H, J = 8.0,
7-(4-Methylphenyl)-7,8,9,10,11,12-hexahydropy-
4J = 4.3 Hz), 7.68 d and 8.12 d (1H each, 5-H, 6-H,
rimido[5,4-b][1,7]phenanthroline-9,11-dione (IVb).
3J = 8.8 Hz), 8.52 d (1H, 3-H, 3J = 4.3 Hz), 8.86 d (1H,
1
Yield 78 (a), 80 (b), 81% (c). H NMR spectrum, δ,
3
1-H, J = 8.0 Hz), 9.90 s (1H, 12-H), 10.51 s (1H,
ppm: 2.20 s (3H, Me), 5.92 s (1H, 7-H), 6.90 d and
7.12 d (2H each, Harom, 3J = 8.4 Hz), 7.30 d.d (1H, 2-H,
3J = 8.0, 4J = 4.3 Hz), 7.52 d and 7.92 d (1H each, 5-H,
6-H, 3J = 8.8 Hz), 8.33 d (1H, 3-H, 3J = 4.3 Hz), 8.68 d
(1H, 1-H, 3J = 8.0 Hz), 9.96 s (1H, 12-H), 10.61 s (1H,
NH), 10.88 s (1H, NH). Found, %: C 70.74; H 4.50;
N 15.68. C21H16N4O2. Calculated, %: C 70.77; H 4.53;
N 15.72.
NH), 10.71 s (1H, NH). Found, %: N 13.53.
C21H13F3N4O2. Calculated, %: N 13.65.
7-(3-Hydroxyphenyl)-7,8,9,10,11,12-hexahydro-
pyrimido[5,4-b][1,7]phenanthroline-9,11-dione
1
(IVg). Yield 83 (a), 85 (b), 84% (c). H NMR spec-
trum, δ, ppm: 5.75 s (1H, 7-H), 6.65–6.80 m and 7.10–
3
4
7.19 m (4H, Harom), 7.37 d.d (1H, 2-H, J = 8.0, J =
3
4.3 Hz), 8.52 d and 8.80 d (1H each, 5-H, 6-H, J =
3
7-(4-Isopropylphenyl)-7,8,9,10,11,12-hexahydro-
8.8 Hz), 8.88 d (1H, 3-H, J = 4.3 Hz), 9.52 d (1H,
3
pyrimido[5,4-b][1,7]phenanthroline-9,11-dione
1-H, J = 8.0 Hz), 10.07 s (1H, 12-H), 10.43 s (1H,
1
(IVc). Yield 85 (a), 86 (b), 86% (c). H NMR spec-
OH), 11.03 s (1H, NH), 11.13 s (1H, NH). Found, %:
C 66.98; H 3.90; N 15.64. C20H14N4O3. Calculated, %:
C 67.03; H 3.94; N 15.63.
trum, δ, ppm: 1.21 d [6H, CH(CH3)2, J = 7.0 Hz],
2.27 m [1H, CH(CH3)2], 5.80 s (1H, 7-H), 6.88 d and
7.13 d (2H each, Harom, 3J = 8.4 Hz), 7.29 d.d (1H, 2-H,
3J = 8.0, 4J = 4.3 Hz), 7.50 d and 7.91 d (1H each, 5-H,
6-H, 3J = 8.8 Hz), 8.31 d (1H, 3-H, 3J = 4.3 Hz), 8.67 d
(1H, 1-H, 3J = 8.0 Hz), 9.95 s (1H, 12-H), 10.57 s (1H,
NH), 10.78 s (1H, NH). Found, %: C 71.82; H 5.22;
N 14.52. C23H20N4O2. Calculated, %: C 71.86; H 5.24;
N 14.57.
7-(3,4,5-Trimethoxyphenyl)-7,8,9,10,11,12-hexa-
hydropyrimido[5,4-b][1,7]phenanthroline-9,11-di-
1
one (IVh). Yield 79 (a), 80 (b), 81% (c). H NMR
spectrum, δ, ppm: 3.16 s (3H, OMe), 3.63 s (3H,
OMe), 3.76 s (3H, OMe), 5.81 s (1H, 7-H), 6.61 m
3
4
(2H, Harom), 7.43 d.d (1H, 2-H, J = 8.2, J = 4.1 Hz),
3
7.65 d and 7.96 d (1H each, 5-H, 6-H, J = 8.8 Hz),
3
3
7-(2-Bromophenyl)-7,8,9,10,11,12-hexahydropy-
8.47 d (1H, 1-H, J = 8.2 Hz), 9.34 d (1H, 3-H, J =
4.4 Hz), 10.21 s (1H, 12-H), 11.14 s (1H, NH), 11.29 s
(1H, NH). Found, %: C 63.84; H 4.62; N 12.92.
C23H20N4O5. Calculated, %: C 63.88; H 4.66; N 12.96.
rimido[5,4-b][1,7]phenanthroline-9,11-dione (IVd).
1
Yield 73 (a), 75 (b), 74% (c). H NMR spectrum, δ,
ppm: 5.79 s (1H, 7-H), 6.74–6.86 m and 7.11–7.21 m
3
4
(4H, Harom), 7.46 d.d (1H, 2-H, J = 8.0, J = 4.3 Hz),
7-(1,3-Benzodioxol-5-yl)-7,8,9,10,11,12-hexahy-
3
7.70 d and 8.14 d (1H each, 5-H, 6-H, J = 8.8 Hz),
dropyrimido[5,4-b][1,7]phenanthroline-9,11-dione
3
3
1
8.53 d (1H, 3-H, J = 4.3 Hz), 8.86 d (1H, 1-H, J =
8.0 Hz), 9.91 s (1H, 12-H), 10.52 s (1H, NH), 10.73 s
(1H, NH). Found, %: C 56.98; H 3.07; Br 18.93;
N 13.24. C20H13BrN4O2. Calculated, %: C 57.02;
H 3.11; Br 18.97; N 13.30.
(IVi). Yield 80 (a), 82 (b), 81% (c). H NMR spectrum,
δ, ppm: 5.88 s (1H, 7-H), 5.93 m (2H, OCH2O), 6.66–
6.84 m and 7.05–7.09 m (3H, Harom), 7.39 d.d (1H,
2-H, 3J = 8.2, 4J = 4.4 Hz), 7.57 d and 7.83 d (1H each,
3
3
5-H, 6-H, J = 9.0 Hz), 8.28 d (1H, 1-H, J = 8.2 Hz),
3
8.78 d (1H, 3-H, J = 4.4 Hz), 10.28 s (1H, 12-H),
7-(2-Iodophenyl)-7,8,9,10,11,12-hexahydropy-
11.11 s (1H, NH), 11.23 s (1H, NH). Found, %:
C 65.24; H 3.61; N 14.46. C21H14N4O4. Calculated, %:
C 65.28; H 3.65; N 14.50.
rimido[5,4-b][1,7]phenanthroline-9,11-dione (IVe).
1
Yield 76 (a), 78 (b), 77% (c). H NMR spectrum, δ,
ppm: 5.77 s (1H, 7-H), 6.73–6.84 m and 7.10–7.19 m
3
4
(4H, Harom), 7.44 d.d (1H, 2-H, J = 8.0, J = 4.3 Hz),
7-(4-Ethoxyphenyl)-7,8,9,10,11,12-hexahydropy-
3
7.71 d and 8.13 d (1H each, 5-H, 6-H, J = 8.8 Hz),
rimido[5,4-b][1,7]phenanthroline-9,11-dione (IVj).
3
3
1
8.56 d (1H, 3-H, J = 4.3 Hz), 8.88 d (1H, 1-H, J =
8.0 Hz), 10.00 s (1H, 12-H), 10.61 s (1H, NH), 10.81 s
(1H, NH). Found, %: C 51.28; H 2.74; I 27.01;
N 11.92. C20H13IN4O2. Calculated, %: C 51.30; H 2.80;
I 27.10; N 11.97.
Yield 85 (a), 86 (b), 85% (c). H NMR spectrum, δ,
ppm: 1.28 t (3H) and 3.87 q (2H) (OEt), 5.80 s (1H,
7-H), 6.76 d (2H, 2′-H, 6′-H, J2′,3′ = J6′,5′ = 8.5 Hz),
7.14 d (2H, 3′-H, 5′-H, J3′,2′ = J5′,6 = 8.5 Hz), 7.50 d.d
(1H, 2-H, J2,1 = 8.8, J2,3 = 4.0 Hz), 7.53 d and 7.86 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

KOZLOV, TERESHKO
1010
3
(1H each, 5-H, 6-H, J = 9.0 Hz), 8.83 d (1H, 3-H,
J3,2 = 4.0 Hz), 8.91 d (1H, 1-H, J1,2 = 8.8 Hz), 10.27 s
(1H, 12-H), 11.12 s (1H, NH), 11.22 s (1H, NH).
Found, %: C 68.33; H 4.65; N 14.46. C22H18N4O3. Cal-
culated, %: C 68.38; H 4.70; N 14.50.
(1H, NH), 11.22 s (1H, NH). Found, %: C 74.60;
H 4.31; N 13.36. C26H18N4O2. Calculated, %: C 74.63;
H 4.34; N 13.39.
7-(4-Benzyloxyphenyl)-7,8,9,10,11,12-hexahydro-
pyrimido[5,4-b][1,7]phenanthroline-9,11-dione
1
7-(4-Propoxyphenyl)-7,8,9,10,11,12-hexahydro-
(IVo). Yield 72 (a), 77 (b), 75% (c). H NMR spec-
trum, δ, ppm: 4.96 m (2H, OCH2Ph), 5.74 s (1H, 7-H);
pyrimido[5,4-b][1,7]phenanthroline-9,11-dione
1
(IVk). Yield 84 (a), 88 (b), 86% (c). H NMR spec-
6.77 m, 7.07 m, 7.20 m, and 7.31 m (9H, Harom);
3
4
trum, δ, ppm: 0.96 t, 1.62 q, and 3.73 t (7H, OPr);
7.46 d.d (1H, 2-H, J = 8.0, J = 4.1 Hz), 7.54 d and
3
5.75 s (1H, 7-H), 6.75 d (2H, 2′-H, 6′-H, J2′,3′ = J6′,5′
=
7.89 d (1H each, 5-H, 6-H, J = 8.8 Hz), 8.85 d (1H,
8.5 Hz), 7.13 d (2H, 3′-H, 5′-H, J3′,2′ = J5′,6′ = 8.4 Hz),
7.52 d.d (1H, 2-H, J2,1 = 8.7, J2,3 = 4.0 Hz), 7.54 d and
3-H, J3,2 = 4.1 Hz), 8.92 d (1H, 1-H, J1,2 = 8.0 Hz),
10.21 s (1H, 12-H), 11.13 s (1H, NH), 11.25 s (1H,
NH). Found, %: C 72.27; H 4.44; N 12.44.
C27H20N4O3. Calculated, %: C 72.31; H 4.49; N 12.49.
3
7.88 d (1H each, 5-H, 6-H, J = 9.0 Hz), 8.81 d (1H,
3-H, J3,2 = 4.0 Hz), 8.90 d (1H, 1-H, J1,2 = 8.8 Hz),
10.26 s (1H, 12-H), 11.13 s (1H, NH), 11.21 s (1H,
NH). Found, %: C 68.92; H 4.97; N 13.93.
C23H20N4O3. Calculated, %: C 68.99; H 5.03; N 13.99.
7-(Thiophen-2-yl)-7,8,9,10,11,12-hexahydropy-
rimido[5,4-b][1,7]phenanthroline-9,11-dione (IVp).
1
Yield 67 (a), 70 (b), 71% (c). H NMR spectrum, δ,
ppm: 5.73 s (1H, 7-H), 7.13–7.26 m (3H, 3′-H, 4′-H,
5′-H), 7.33 d.d (1H, 2-H, J2,1 = 8.0, J2,3 = 4.2 Hz),
7-(3-Ethoxy-4-hydroxyphenyl)-7,8,9,10,11,12-
hexahydropyrimido[5,4-b][1,7]phenanthroline-9,11-
3
1
7.58 d and 7.85 d (1H each, 5-H, 6-H, J = 9.0 Hz),
dione (IVl). Yield 83 (a), 86 (b), 87% (c). H NMR
8.23 d (1H, 1-H, J1,2 = 8.0 Hz), 8.64 d (1H, 3-H, J3,2
=
spectrum, δ, ppm: 1.27 t (3H, OCH2CH3), 3.82–3.91 m
4.2 Hz), 10.08 s (1H, 12-H), 11.02 s (1H, NH), 11.23 s
(1H, NH). Found, %: C 62.01; H 3.43; N 16.02;
S 9.16. C18H12N4O2S. Calculated, %: C 62.06; H 3.47;
N 16.08; S 9.20.
(2H, OCH2), 5.72 s (1H, 7-H), 6.69–6.85 m and 7.03–
3
4
7.08 m (3H, Harom), 7.39 d.d (1H, 2-H, J = 8.2, J =
3
4.4 Hz), 7.57 d and 7.83 d (1H each, 5-H, 6-H, J =
3
9.1 Hz), 8.28 d (1H, 1-H, J = 8.2 Hz), 8.78 d (1H,
3
3-H, J = 4.4 Hz), 10.43 s (1H, 12-H), 11.01 s (1H,
7-(3-Methylthiophen-2-yl)-7,8,9,10,11,12-hexa-
NH), 11.04 s (1H, OH), 11.15 s (1H, NH). Found, %:
C 65.59; H 4.47; N 13.86. C22H18N4O4. Calculated, %:
C 65.66; H 4.51; N 13.92.
hydropyrimido[5,4-b][1,7]phenanthroline-9,11-di-
1
one (IVq). Yield 60 (a), 63 (b), 64% (c). H NMR
spectrum, δ, ppm: 2.49 s (CH3), 5.76 s (1H, 7-H),
7.15–7.25 m (2H, 4′-H, 5′-H), 7.30 d.d (1H, 2-H, J2,1
=
7-(4-Methylsulfanylphenyl)-7,8,9,10,11,12-hexa-
8.0, J2,3 = 4.2 Hz), 7.57 d and 7.86 d (1H each, 5-H,
hydropyrimido[5,4-b][1,7]phenanthroline-9,11-di-
3
1
6-H, J = 9.0 Hz), 8.24 d (1H, 1-H, J1,2 = 8.0 Hz),
one (IVm). Yield 80 (a), 84 (b), 85% (c). H NMR
8.63 d (1H, 3-H, J3,2 = 4.2 Hz), 10.11 s (1H, 12-H),
11.04 s (1H, NH), 11.26 s (1H, NH). Found, %:
C 62.92; H 3.83; N 15.39; S 8.78. C19H14N4O2S. Cal-
culated, %: C 62.97; H 3.87; N 15.46; S 8.85.
spectrum, δ, ppm: 2.34 s (3H, SMe), 5.76 s (1H, 7-H),
6.73 d (2H, 2′-H, 6′-H, J2′,3′ = J6′,5′ = 8.4 Hz), 7.12 d
(2H, 3′-H, 5′-H, J3′,2′ = J5′,6′ = 8.4 Hz), 7.51 d.d (1H,
2-H, J2,1 = 8.8, J2,3 = 4.1 Hz), 7.54 d and 7.82 d (1H
3
each, 5-H, 6-H, J = 9.0 Hz), 8.84 d (1H, 3-H, J3,2
=
REFERENCES
4.0 Hz), 8.93 d (1H, 1-H, J1,2 = 8.8 Hz), 10.25 s (1H,
12-H), 11.12 s (1H, NH), 11.23 s (1H, NH). Found, %:
C 64.88; H 4.13; N 14.36; S 8.20. C21H16N4O2S. Cal-
culated, %: C 64.93; H 4.15; N 14.42; S 8.25.
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=
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014