Regioselective synthesis of benzo[g]- and benzo[f]quinolines by reaction of chalcones with naphthalen-2-amine

Article abstract of DOI:10.1134/S1070428017040108

Reactions of 4- and 4′-substituted chalcones with naphthalen-2-amine afforded isomeric benzo[g]- and benzo[f]quinoline derivatives. Depending on the substituent in the initial chalcone, the cyclization follows two pathways through different intermediates.

Full text of DOI:10.1134/S1070428017040108

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 4, pp. 562–568. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © V.D. Pak, Ya.V. Bykov, N.N. Yaganova, A.A. Gorbunov, V.A. Glushkov, M.V. Dmitriev, P.A. Slepukhin, 2017, published in Zhurnal
Organicheskoi Khimii, 2017, Vol. 53, No. 4, pp. 557–562.
Regioselective Synthesis of Benzo[g]- and Benzo[f]quinolines
by Reaction of Chalcones with Naphthalen-2-amine
V. D. Paka, Ya. V. Bykova,* N. N. Yaganovaa, A. A. Gorbunovb, V. A. Glushkovb, c,
M. V. Dmitrievc, and P. A. Slepukhind, e
a Pryanishnikov Perm State Agricultural Academy, ul. Petropavlovskaya 23, Perm, 614990 Russia
*e-mail: bykovjav@mail.ru
b Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences,
ul. Akademika Koroleva 3, Perm, 614013 Russia
c Perm National State Research University, ul. Bukireva 15, Perm, 614990 Russia
d Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences,
ul. S. Kovalevskoi/Akademicheskaya 22/20, Yekaterinburg, 620990 Russia
e Ural Federal University, ul. Mira 19, Yekaterinburg, 620002 Russia
Received July 29, 2016
Abstract—Reactions of 4- and 4′-substituted chalcones with naphthalen-2-amine afforded isomeric benzo[g]-
and benzo[f]quinoline derivatives. Depending on the substituent in the initial chalcone, the cyclization follows
1
two pathways through different intermediates. The product structure was confirmed by IR, H and 13C NMR,
and mass spectra and X-ray analysis.
DOI: 10.1134/S1070428017040108
Benzoquinolines can be synthesized by the classical
Skraup, Doebner–Miller, Doebner, Knorr, and Fried-
länder reactions which were originally proposed for
the synthesis of quinolines. Some alternative ways of
constructing benzo[f]- [1–15] and benzo[g]quinoline
heterocyclic systems [16–19] have also been reported,
and these methods in any case utilize the aromatic ring
of naphthalen-2-amine.
quinolines, the angularly fused isomer being the major
product [21]. Benzo[f]quinoline was formed as the
only product in the condensation catalyzed by zinc
chloride. The reaction of naphthalen-2-amine with
dibenzoylmethane gave a mixture of benzo[f]- and
benzo[g]quinoline derivatives [22].
We previously showed [23] that the condensation of
substituted chalcones with primary aromatic amines of
the aniline series in anhydrous ethanol in the presence
of the corresponding amine hydrochloride as catalysts
gives unsaturated Schiff bases or β-arylamino ketones,
depending on the electronic properties of substituents
in the initial chalcone. The present work was aimed at
elucidating whether the regularities observed in [23]
are valid for the reaction of chalcones with naphthalen-
2-amine. The reaction was regioselective at both initial
addition and cyclization steps.
Heterocyclization could lead to the formation of
linearly or angularly fused isomers. For example,
β-aminotetralin reacted with glycerol in the presence
of concentrated sulfuric acid and nitrobenzene or
β-nitrotetralin as oxidant (analog of Skraup reaction) to
produce 65% of a mixture of 5,6- and 6,7-tetra-
methylenequinolines which were then converted to the
corresponding benzo[f]- and benzo[g]quinolines [20].
The isomers were successfully separated by treatment
with picric acid and subsequent extraction of the
picrates with ethanol. The extract contained 60% of
benzo[g]quinolinium picrate and 27% of benzo[f]-
quinolinium picrate. Analogous reaction of glycerol
with naphthalen-2-amine in the presence of sulfuric
acid also afforded isomeric benzo[f]- and benzo[g]-
Benzylideneacetophenones 1a–1h reacted with
naphthalen-2-amine (2) in anhydrous methanol in the
presence of naphthalen-2-amine hydrochloride as cata-
lyst to give 3-(naphthalen-2-ylamino)prop-2-en-1-ones
3 or unsaturated Schiff bases 4 (Scheme 1). Presum-
ably, as with substituted anilines, the reaction direction
562

REGIOSELECTIVE SYNTHESIS OF BENZO[g]- AND BENZO[f]QUINOLINES
563
Scheme 1.
O2N
o
o'
N
5
H+
H+
HN
O
NO2
–H2O, –2H
NO2
O
3
R2 = NO2
N
R2
R1
1a–1h
6
+
m
m'
NH2
R1
p' R2
p
o
i
o'
i'
2
3
1
2
10
7
N4
10b
10a
6a
9
8
4a
5
6 7b–7h
H+
N
H+
–2H
R1
–H2O
p
m
o
R2
R1
4b–4h
i
6
5
4
3
2
7
8
o'
1
N
i'
m'
9
10
p'
R2
8b–8g
R1 = H, R2 = O2N (a), Cl (b), Br (c); R1 = Me2N, R2 = H (d); R1 = H, R2 = MeO (e); R1 = Br, R2 = H (f);
R1 = Cl, R2 = H (g); R1 = R2 = H (h).
is determined by electronic properties of substituents
in chalcone 1. The presence of an electron-withdraw-
ing nitro group in the aromatic ring of the ketone
fragment favors formation of intermediate 3, whereas
chalcones with weakly acceptor or donor substituents
in both benzene rings give rise to Schiff base interme-
diate 4. The nitro group in 1a reduces the polarity of
the carbonyl group and increases polarization of the
Cα=Cβ bond.
atom afforded angularly fused tricyclic structures 5
and 7, whereas alternative cyclization through the
γ-carbon atom led to the formation of linearly fused
isomers 6 and 8 (Scheme 1). The structure of com-
pounds 5–8 was determined on the basis of their IR,
1H and 13C NMR, and mass spectra and elemental
analyses, and the structures of 5 and 7d were proved
by X-ray analysis.
Regioselective formation of benzo[f]quinolines was
observed previously in the three-component condensa-
tion of acetophenones with benzaldehydes and naph-
thalen-2-amines catalyzed by HCl [24]. In the first
Intermediates 3 and 4 possess two nucleophilic
centers in the α- and γ-positions of the naphthalene
fragment. Heterocyclization involving the α-carbon
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 4 2017

PAK et al.
ammonium salt as catalyst allows formation of both
564
O1
N2
O2
unsaturated Schiff base and β-arylamino ketone and
their subsequent heterocyclization. The isomer ratio
was determined by GC/MS. It was found that in all
cases the corresponding benzo[f]quinoline (angular
isomer) was the major product; it was characterized by
a shorter retention time than the linearly fused isomer
(benzo[g]quinoline). Linear isomers 6, 8b, 8c, 8f, and
8g were detected by GC/MS, but only compound 8d
was isolated as individual compound in the reaction
with chalcone 1d derived from 4-(dimethylamino)-
benzaldehyde and acetophenone.
C22
C21
C23
C24
C25
C10
C20
C3
C11
C15
C16
C2
C1
C9
C4
C12
C14
C17
C8
C13
N1
C5
C6
C18
The formation of compounds 7 and 8 from interme-
diate 4, as well as the formation of 5 and 6 from inter-
mediate 3, is accompanied by loss of two hydrogen
atoms, most probably, as a result of oxidation with
atmospheric oxygen. Simple calculations showed that
the available air is sufficient to oxidize intermediate 4
or 3. However, chromatographic study of the reaction
1d → 7d + 8d revealed that the process is more com-
plicated. In the reaction mixture we detected the
product of reduction of the C=C bond in the initial
chalcone, and its amount increased as the reaction
progressed. These findings suggest that the initial chal-
cone acts as hydrogen acceptor.
C19
C7
Fig. 1. Structure of the molecule of 1-(4-nitrophenyl)-3-
phenylbenzo[f]quinoline (5) according to the X-ray diffrac-
tion data. Non-hydrogen atoms are shown as thermal vibra-
tion ellipsoids with a probability of 50%.
stage, two intermediates were formed, the correspond-
ing chalcone and N-(benzylidene)naphthalen-2-amine.
The latter reacted with acetophenone to give β-aryl-
amino ketone which underwent hydramine fission in
acid medium to produce chalcone 1h and naphthalen-
2-amine (2). The latter reacted wth each other to form
intermediate 4h where the vinylic β-carbon atom is
likely to coordinate to Cα of the naphthalene fragment,
and the cyclization furnished benzo[f]quinoline 7h.
Figure 1 shows the molecular structure of com-
pound 5 in crystal. All bond lengths and bond angles in
molecule 5 approach the corresponding reference
values. The benzoquinoline fragment is not planar, and
it can be represented as a part of a helix, in contrast to
1-unsubstituted benzo[f]quinolines with almost planar
tricyclic system [25, 26]. The dihedral angles between
the mean-square planes of the pyridine ring and
C4C5C6C7C8C9 and C8C9C10C11C12C13 fragments are
4.6 and 10.0°, respectively. The phenyl substituent is
almost coplanar to the pyridine ring, whereas the
p-nitrophenyl substituent is turned through a dihedral
angle of 66.5° with respect to the pyridine ring.
Molecules 5 in crystal are packed in parallel layers,
where the neighboring aromatic fragments of mole-
cules in the adjacent layers approach each other to
a distance of ~3.4–3.7 Å due to weak π–π-stacking
interactions stabilizing the layered structure.
In this work, the reaction was carried out under
milder conditions. The use of anhydrous solvent and
C17
C27
C16
C18
C19
N2
C23
C24
C22
C21
C15
C2
N1
C3
C1
C20
C25
C4
C5
C26
C7
C14
C13
C6
C11
C8
C9
C12
The X-ray diffraction data for compound 5 were
obtained from a 0.67×0.41×0.22-mm yellow single
crystal on an Xcalibur R diffractometer with a CCD
detector according to standard procedure [Mo Kα radia-
tion, 295(2) K, ω-scanning through a step of 1 deg]
[27]. A correction for absorption was applied empiri-
cally by the SCALE3 ABSPACK algorithm [27].
C10
Fig. 2. Structure of the molecule of 1-(4-dimethylamino-
phenyl)-3-phenylbenzo[f]quinoline (7d) according to the
X-ray diffraction data. Non-hydrogen atoms are shown as
thermal vibration ellipsoids with a probability of 50%.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 4 2017

REGIOSELECTIVE SYNTHESIS OF BENZO[g]- AND BENZO[f]QUINOLINES
565
Monoclinic crystal system, space group P-1; unit cell
parameters: a = 8.7263(14), b = 9.7151(13), c =
12.4512(18) Å; α = 69.683(13), β = 70.802(14), γ =
88.946(12)°; V = 929.4(2) Å3; C25H16N2O2; Z = 2.
The structure was solved by the direct method
(SHELXS-97) and was refined against F2 by the full-
matrix least-squares method in anisotropic approxima-
tion for all non-hydrogen atoms (SHELXL-97) [28].
The positions of hydrogen atoms were refined accord-
ing to the riding model in isotropic approximation with
dependent thermal parameters. Final divergence fac-
tors: R1 = 0.0512, wR2 = 0.1403 [for 3286 reflections
with I > 2σ(I)]; R1 = 0.0655, wR2 = 0.1502 (for 4256
independent reflections); goodness of fit S = 1.105.
Data Centre (CCDC entry nos. 1490079 and 1490087,
respectively) and are available free of charge at
www.ccdc.cam.ac.uk/data_request/cif.
Signals in the NMR spectra were assigned with
account taken of published data for 1,3-diphenylbenzo-
1
[f]quinoline as model [32], whose H NMR spectrum
spectrum is fairly simple. In addition, the data of [24]
were used. Compounds 5, 7d, and 8d were analyzed
using DEPT135, DEPTq, HSQC (direct 13C–1H cou-
plings) and HMBC (long-range 13C–1H correlations)
1
NMR techniques. The H NMR spectra of angularly
fused benzoquinolines 5 and 7b–7g characteristically
showed a singlet of the 2-H proton at δ 7.65–7.97 ppm,
4
a doublet of 7-H at δ 7.88–8.17 ppm (3J ≈ 7.6, J ≈
1.5 Hz), and doublets of 5-H and 6-H at δ 7.76–8.06
Figure 2 shows the molecular structure of com-
pound 7d according to the X-ray diffraction data. The
geometric parameters (bond lengths and bond angles)
of molecule 7d are typical of structurally related com-
pounds. The phenyl substituent lies in the heterocycle
plane. The C4 atom is characterized by the largest
deviation (0.225 Å) from the mean-square plane
formed by the system consisting of 20 atoms. This may
be due to perturbation effect of the dimethylamino-
phenyl group which is turned through a dihedral angle
of ~66° with respect to the heterocycle plane.
and 7.80–8.01 ppm, respectively (3J ≈ 7.6 Hz). Signals
1
in the H NMR spectra of linearly fused benzo[g]-
quinolines were observed in a stronger field relative
to the corresponding signals of their angular isomers
(Δδ = 0.1–0.3 ppm).
EXPERIMENTAL
The IR spectra were recorded on a Bruker IFS 66ps
spectrometer with Fourier transform from samples
dispersed in mineral oil. The NMR spectra of 5, 7d,
and 8d were measured on a Bruker instrument at
The X-ray diffraction data for compound 7d were
acquired on an Xcalibur E four-circle diffractometer
with a CCD detector from a 0.25×0.2×0.15-mm frag-
ment of a colorless single crystal. The data were col-
lected at 295(2) K and processed according to standard
procedure [Mo Kα radiation, λ 0.71073 Å; ω/2θ-scan-
ning with a step of 1 deg]. A correction for absorption
was applied empirically [29] using Olex2 [30], and the
structure was solved using Superflip [31]. The struc-
ture was refined against F2 by the full-matrix least-
squares method in anisotropic approximation for all
non-hydrogen atoms (SHELXL [28]). Hydrogen atoms
were placed in geometrically calculated positions
which were refined in isotropic approximation with
dependent thermal parameters according to the riding
model. Triclinic crystal system, space group P-1; unit
cell parameters: a = 9.4559(8), b = 10.1272(6), c =
10.8339(6) Å; α = 91.089(5), β = 95.785(6), γ =
105.521(6)°; V = 993.40(11) Å3; C27H22N2; Z = 2. Final
divergence factors: R1 = 0.0597, wR2 = 0.1591 [for
3306 reflections with I > 2σ(I)]; R1 = 0.1023, wR2 =
0.1921 (for all 5394 independent reflections); good-
ness of fit S = 1.009.
1
400 MHz for H (relative to tetramethylsilane as
internal standard) and 100 MHz for 13C (relative to the
solvent signal). The NMR spectra of the other com-
pounds were recorded on a Varian Mercury Plus 300
1
spectrometer at 300 MHz for H (relative to hexa-
methyldisiloxane as internal standard) and 75 MHz for
13C (relative to the CDCl3 signal). The products were
isolated by column chromatography on Silicagel 60
(0.063–0.2 mm, Alfa Aesar). Their purity was checked
by GC/MS on an Agilent Technologies 6890N/5975B
GC/MS system (HP-5ms capillary column, 30000×
0.25 mm; injector temperature 260°C, oven tempera-
ture programming at a rate of 20–40 deg/min; carrier
gas He, flow rate 1 mL/min; electron impact, 70 eV).
The elemental analyses were obtained on a Leco
CHNS 9321P analyzer (USA). The melting points
were determined with a PTP melting point apparatus.
α,β-Unsaturated ketones 1a–1h were synthesized
by aldol condensation of the corresponding aceto-
phenones with benzaldehydes according to standard
procedure [33]. Their physical constants were con-
sistent with reference data [34].
The X-ray diffraction data for compounds 5 and 7d
were deposited to the Cambridge Crystallographic
1,3-Diarylbenzo[f]quinolines 5a and 7b–7h and
2,4-diarylbenzo[g]quinolines 6 and 8b–8g (general
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 4 2017

PAK et al.
1H NMR spectrum (CDCl3), δ, ppm: 7.16 d.d (1H,
566
procedure). A mixture of 6 mmol of chalcone 1a–1h,
6 mmol of naphthalen-2-amine (2), and 0.6 mmol of
naphthalen-2-amine hydrochloride in 3 mL of anhy-
drous methanol was heated for 6 h (12 h in the syn-
thesis of 7d and 8d) at 100°C in a sealed ampule. The
mixture was cooled, and the crystalline product was
filtered off and purified by column chromatography on
silica gel using petroleum ether (40–70°C)–ethyl
acetate (0 to 10 vol % of the latter) as eluent.
3
3
p-H, J = 7.5, 7.5 Hz), 7.28 d (2H, m-H, J = 8.1 Hz),
7.38–7.49 m (4H, Harom), 7.62 m (3H, Harom), 7.68 s
3
(1H, 2-H), 7.80 d (1H, 7-H, J = 8.1 Hz), 7.91 d (1H,
5-H, 3J = 9.3 Hz), 8.06 d (1H, 6-H, 3J = 9.3 Hz), 8.16 d
3
(2H, o′-H, J = 8.1 Hz). 13C NMR spectrum (CDCl3),
δC, ppm: 121.49, 122.32, 122.34, 125.57, 126.52,
127.29, 127.78, 128.66, 128.79, 129.01, 129.34,
130.07, 131.52, 132.34, 132.84, 138.73, 141.81,
1247.60, 149.75, 155.36. Mass spectrum, m/z (Irel, %):
411/409 (100) [M]+·, 330 (76), 250 (40), 226 (14), 165
(79), 150 (19). Found, %: C 72.77; H 3.75; N 3.12.
C25H16BrN. Calculated, %: C 73.18; H 3.93; N 3.41.
1-(4-Nitrophenyl)-3-phenylbenzo[f]quinoline (5).
Greenish prisms, mp 210–212°C (from EtOAc). IR
spectrum, ν, cm–1: 1595, 1580, 1544, 1512 (NO2,
asym.), 1342 (NO2, sym.), 1305, 1205, 1285, 1260,
1105, 833, 774, 688, 661. 1H NMR spectrum (CDCl3),
1-(4-Dimethylaminophenyl)-3-phenylbenzo[f]-
quinoline (7d). Yellow–brown prisms, mp 171–174°C
(from EtOH). IR spectrum (film), ν, cm–1: 1677, 1607,
1579 1545, 1514, 1480, 1451, 1361, 1115, 836, 755,
3
4
δ, ppm: 7.23 (1H, p′-H, J = 8.1, 8.1, J = 1.5 Hz),
7.50–7.59 m (5H, 8-H, 9-H, 10-H, m′-H), 7.67 d (2H,
3
o-H, J = 12.0 Hz), 7.76 s (1H, 2-H), 7.93 d (1H, 7-H,
1
3J = 8.0 Hz), 8.03 d (1H, 6-H, 3J = 8.0 Hz), 8.16 d (1H,
696. H NMR spectrum (CDCl3), δ, ppm: 2.99 s (6H,
3
3
NMe2), 6.88 d (2H, m-H, J = 8.4 Hz), 7.24 d.d (1H,
p′-H, J = 7.5, 7.5 Hz), 7.32 d (2H, Harom, J = 8.4 Hz),
7.51–7.59 m (4H, Harom), 7.90 d (1H, Harom, J =
5-H, J = 8.0 Hz), 8.26 d (2H, o′-H, J = 8.0 Hz),
8.42 d (2H, m-H, J = 8.0 Hz). 13C NMR spectrum
3
(CDCl3), δC, ppm: 120.57, 121.47, 123.97, 125.32,
126.34, 126.83, 127.19, 128.40, 128.45, 128.55,
129.07, 129.11, 131.33, 132.53, 138.02, 145.92,
147.19, 149.16, 149.38, 155.06. Mass spectrum, m/z
(Irel, %): 376 (100) [M]+·, 329 (44), 251 (14), 164 (23).
Found, %: C 78.11; H 4.18; N 7.31. C25H16N2O2. Cal-
culated, %: C 79.77; H 4.28; N 7.44.
3
7.8 Hz), 7.91 s (1H, 2-H), 8.00 d (1H, 7-H, J =
3
7.2 Hz), 8.02 d (1H, 5-H, J = 9.0 Hz), 8.12 d (1H,
3
3
6-H, J = 9.0 Hz), 8.32 d (2H, o′-H, J = 7.5 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 40.06, 111.73,
112.25, 121.55, 124.77, 125.68, 126.84, 127.59, 127.91,
128.21, 128.55, 128.74, 129.58, 130.14, 130.64,
132.25, 138.80, 149.12, 149.35, 149.82, 154.81. Mass
spectrum, m/z (Irel, %): 377 (29) [M + 1]+, 376 (100)
[M]+·, 377 (24) [M – 1]+, 346 (15), 329 (46), 251 (12),
164 (16). Found, %: C 85.96; H 5.97; N 7.17.
C27H22N2. Calculated, %: C 86.60; H 5.92; N 7.48.
4-(4-Nitrophenyl)-2-phenylbenzo[g]quinoline (6)
was not isolated in the pure state. Mass spectrum, m/z
(Irel, %): 377 (27) [M + 1]+, 376 (100) [M]+·, 377 (34)
[M – 1]+, 346 (13), 329 (41), 164 (16).
3-(4-Chlorophenyl)-1-phenylbenzo[f]quinoline
(7b). Colorless plates, mp 156–157°C (from EtOH). IR
spectrum, ν, cm–1: 1577, 1544, 1525, 1491, 1451,
1360, 1331, 1283, 1255, 1106, 1255, 1106, 1093,
1014, 883, 869, 754, 699. 1H NMR spectrum (CDCl3),
3-(4-Methoxyphenyl)-1-phenylbenzo[f]quinoline
(7e). Colorless plates, mp 173–174°C (from EtOH). IR
spectrum, ν, cm–1: 1605, 1579, 1546, 1509, 1363,
1285, 1244, 1177, 1022, 893, 872, 839, 774, 694.
1H NMR spectrum (CDCl3), δ, ppm: 3.85 s (3H,
3
3
δ, ppm: 7.17 d.d (1H, p-H, J = 7.8, 7.8 Hz), 7.36 d
OMe), 7.00 d (2H, m-H, J = 8.1 Hz), 7.14 d.d (1H,
3
3
3
(2H, m′-H, J = 8.4 Hz), 7.41–7.51 m (6H, Harom),
p′-H, J = 8.1, 7.5 Hz), 7.32 d (2H, o-H, J = 8.4 Hz),
3
7.64 d (1H, Harom, J = 8.4 Hz), 7.70 s (1H, 2-H),
7.38–7.50 m (4H, Harom), 7.74 m (2H, 2-H, Ha3rom),
3
3
3
7.82 d (1H, Harom, J = 7.8 Hz), 7.93 d (1H, 5-H, J =
7.80 d (1H, 7-H, J = 8.1 Hz), 7.92 d (1H, 5-H, J =
3
3
9.0 Hz), 8.08 d (1H, 6-H, J = 8.7 Hz), 8.17 d (2H,
8.7 Hz), 8.08 d (1H, 6-H, J = 8.7 Hz), 8.18 d (2H,
o′-H, J = 7.2 Hz). 13C NMR spectrum (CDCl3), δC,
ppm: 121.57, 121.62, 122.46, 125.61, 126.53, 127.32,
127.80, 128.69, 128.81, 129.02, 129.42, 129.79, 131.54,
132.87, 132.88, 134.21, 138.76, 141.36, 147.68, 149.77,
155.39. Found, %: C 80.68; H 4.39; N 3.88.
C25H16ClN. Calculated, %: C 82.07; H 4.41; N 3.83.
3
o-H, J = 8.1 Hz). 13C NMR spectrum (CDCl3), δC,
ppm: 55.28, 114.57, 121.96, 122.95, 125.42, 126.33,
127.33, 127.93, 128.51, 128.75, 129.04, 129.19,
129.54, 129.81, 131.33, 132.82, 135.20, 139.02,
148.87, 149.76, 155.31, 159.53. Found, %: C 85.75;
H 5.27; N 3.84. C26H19NO. Calculated, %: C 86.40;
H 5.30; N 3.88.
3-(4-Bromophenyl)-1-phenylbenzo[f]quinoline
(7c). Colorless plates, mp 179–180°C (from EtOH). IR
spectrum, ν, cm–1: 1576, 1543, 1067, 1011, 751, 694.
1-(4-Bromophenyl)-3-phenylbenzo[f]quinoline
(7f). Colorless plates, mp 179–180°C (from EtOH). IR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 4 2017

REGIOSELECTIVE SYNTHESIS OF BENZO[g]- AND BENZO[f]QUINOLINES
567
3
spectrum, ν, cm–1: 1576, 1544, 1354, 951, 799, 675.
1H NMR spectrum (CDCl3), δ, ppm: 7.06 d.d (1H,
p′-H, J = 8.7, 7.2 Hz), 7.34–7.39 m (4H, 8-H, 9-H,
ppm: 3.02 s (6H, NMe2), 6.86 d (2H, m-H, J =
3
8.7 Hz), 7.16 d.d (1H, 8-H, J = 7.5, 7.5 Hz), 7.47–
7.55 m (4H, 7-H, m′-H, p′-H), 7.59–7.60 m (3H, 6-H,
3
3
m′-H), 7.40–7.46 m (4H, 10-H, o-H), 7.53 d (2H, o-H,
o-H), 8.00 d (2H, o′-H, J = 7.5 Hz), 8.09 d (1H, 9-H,
3J = 8.4 Hz), 7.57 d (1H, Harom, J = 8.4 Hz), 7.65 s
3J = 8.7 Hz). 13C NMR spectrum (CDCl3), δC, ppm:
39.77, 111.69, 120.40, 121.23, 124.89, 125.47, 127.22,
127.48, 127.78, 127.87, 127.94, 128.05, 128.62,
129.32, 130.84, 132.09, 142.71, 148.49, 148.78,
150.89, 154.77. Found, %: C 85.30; H 5.84; N 7.02.
C27H22N2. Calculated, %: C 86.60; H 5.92; N 7.48.
3
3
(1H, 2-H), 7.76 d (1H, 5-H, J = 8.1 Hz), 7.88 d (1H,
3
3
6-H, J = 8.1 Hz), 8.00 d (2H, o′-H, J = 8.4 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 121.28, 122.90,
123.84, 125.57, 126.54, 128.01, 128.17, 128.30,
128.60, 128.86, 128.90, 129.22, 129.61, 131.65,
131.89, 132.90, 137.80, 142.81, 149.30, 149.71,
153.95. Mass spectrum, m/z (Irel, %): 411/409 (100)
[M]+·, 328 (68), 327 (17), 326 (123), 252 (25), 251
(20), 228 (17), 226 (15), 164 (57), 163 (36), 150 (21).
Found, %: C 72.87; H 3.93; N 3.11. C25H16BrN.
Calculated, %: C 73.18; H 3.93; N 3.41.
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Soedin., 1967, no. 3, p. 74.
1-(4-Chlorophenyl)-3-phenylbenzo[f]quinoline
(7g). Colorless plates, mp 173–174°C (from EtOH). IR
spectrum, ν, cm–1: 1576, 1545, 1491, 1355, 1280,
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1
1256, 1167, 1089, 1010, 834, 772, 753, 700. H NMR
3
spectrum (CDCl3), δ, ppm: 7.13 d.d.d (1H, p′-H, J =
5. Ardashev, B.I., Zarifyan, A.S., and Glukhovets, G.G.,
4
7.5, 7.5, J = 0.9 Hz), 7.41–7.52 m (8H, Harom), 7.63 d
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(1H, Harom, 3J = 9.0 Hz), 7.72 s (2-H), 7.84 d (1H, 7-H,
3J = 8.1 Hz), 7.95 d (1H, 5-H, 3J = 9.0 Hz), 8.07 d (1H,
6. Kozlov, N.S. and Nugumanov, Z.Z., Vesti Akad. Nauk
BSSR, Ser. Khim., 1968, no. 1, p. 67.
3
3
6-H, J = 9.3 Hz), 8.15 d (2H, o′-H, J = 8.4 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 121.40, 122.89,
125.60, 126.56, 127.02, 128.18, 128.32, 128.61,
128.94, 129.25, 129.64, 131.67, 132.93, 135.47,
137.37, 137.77, 142.85, 149.32, 153.99. Mass spec-
trum, m/z (Irel, %): 365 (100) [M]+·, 328 (17), 330 (76),
252 (31), 251 (24), 228 (12), 226 (13), 164 (36), 163
(28), 150 (15). Found, %: C 81.26; H 4.40; N 3.86.
C25H16ClN. Calculated, %: C 82.07; H 4.41; N 3.83.
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1,3-Diphenylbenzo[f]quinoline (7h). mp 142–
143°C; published data [32]: mp 144–145°C. H NMR
1
spectrum (DMSO-d6), δ, ppm: 7.18 d.d.d (1H, p′-H,
4
3J = 8.1, 8.1, J = 1.5 Hz), 7.51–7.61 m (10H, 8-H,
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9-H, 10-H, o-H, m-H, p-H, m′-H), 7.97 s (1H, 2-H),
3
4
8.01 d.d (1H, 7-H, J = 8.0, J = 1.6 Hz), 8.06 d (1H,
5-H, 3J = 8.0 Hz), 8.15 d (1H, 6-H, 3J = 8.0 Hz), 8.35 d
3
(2H, o′-H, J = 8.0 Hz). 13C NMR spectrum
(DMSO-d6), δC, ppm: 121.65, 122.51, 126.17, 127.22,
127.63, 127.74, 128.70, 128.83, 129.31, 129.53, 129.80,
130.08, 132.13, 133.03, 138.44, 142.68, 149.45,
149.50, 154.84. Found, %: C 89.64; H 5.05; N 3.91.
C25H17N. Calculated, %: C 90.60; H 5.17; N 4.23.
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spectrum (film), ν, cm–1: 1609, 1579, 1530, 1364,
1
1196, 836, 802, 754. H NMR spectrum (CDCl3), δ,
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