Microwave-assisted solvent-free synthesis of 2-styrylquinolines in the presence of zinc chloride

Article abstract of DOI:10.1134/S1070428012060139

An efficient solvent-free procedure has been developed for the synthesis of (E)-2-styrylquinoline derivatives under microwave irradiation in the presence of zinc chloride. The developed procedure is advantageous due to shorter reaction time and simpler wo

Full text of DOI:10.1134/S1070428012060139

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 6, pp. 823–828. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.M. Li, T.N. Gavrishova, M.F. Budyka, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 6, pp. 826–831.
Microwave-Assisted Solvent-Free Synthesis of 2-Styrylquinolines
in the Presence of Zinc Chloride
V. M. Li, T. N. Gavrishova, and M. F. Budyka
Institute of Chemical Physics Problems, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, 142432 Russia
e-mail: leevit@icp.ac.ru
Received February 4, 2011
Abstract—An efficient solvent-free procedure has been developed for the synthesis of (E)-2-styrylquinoline
derivatives under microwave irradiation in the presence of zinc chloride. The developed procedure is advan-
tageous due to shorter reaction time and simpler workup.
DOI: 10.1134/S1070428012060139
Derivatives of 2-styrylquinoline (I) are used in the
synthesis of compounds exhibiting various kinds of
biological activity, including antifungal [1], antitumor
[2], anti-inflammatory, and antiallergic [3], as well as
of compounds acting as HIV-1 integrase [4] and
lipoxygenase inhibitors [3] and leukotriene d4 anta-
gonists [3]. In addition, they can be used as models for
the design of molecular logic devices [5] and supra-
molecular systems [6].
energy, reduce expenses for chemicals and amount of
wastes, and avoid laborious workup for isolation of the
products [9].
The synthesis of 2-styrylquinolines under micro-
wave irradiation has been reported in some publica-
tions. Li et al. [10] described the microwave-activated
condensation of quinaldine with substituted benzalde-
hydes in acetic anhydride. However, acetic anhydride
is a quite potent acylating agent capable of reacting
with hydroxy and amino groups, so that subsequent
hydrolysis of the corresponding acetates and acet-
amides was necessary. Musiol et al. [11, 12] reported
on the synthesis of 2-styrylquinoline derivatives under
microwave (MW) irradiation in the absence of solvent
and catalyst, but this procedure was effective only in
the case of 2-styrylquinolines containing carboxy or
hydroxy groups in the quinoline fragment; therefore, it
cannot be regarded as general method.
The most general procedure for the synthesis of
2-styrylquinolines is based on condensation of quinal-
dine with aromatic aldehydes, which is usually carried
out in acetic anhydride [7, 8]. However, this traditional
procedure involves prolonged heating of the reaction
mixture, while the yields of targeted compounds are
reduced as a result of tarring and formation of by-
products.
In recent time, much interest is attracted by the
synthesis of heterocyclic derivatives in a microwave
oven under solvent-free conditions. This methodology
makes it possible to shorten the reaction time, save
We previously synthesized a number of 4-styryl-
quinoline derivatives by condensation of 4-methyl-
quinoline with substituted benzaldehydes under MW
Scheme 1.
X
N
X
Y
Y
ArCHO, ZnCl2, MW
46–78%
Me
N
Ar
I–XVIII
I–XV, X = Y = H; I, Ar = Ph; II, Ar = 4-O2NC6H4; III, Ar = 4-MeOCOC6H4; IV, Ar = 4-IC6H4; V, Ar = 4-FC6H4; VI, Ar =
4-EtOC6H4; VII, Ar = 4-Me2NC6H4; VIII, Ar = 4-HOC6H4; IX, Ar = 2-HOC6H4; X, Ar = 1-naphthyl; XI, Ar = 2-naphthyl;
XII, Ar = 9-anthryl; XIII, Ar = pyridin-2-yl; XIV, Ar = pyridin-3-yl; XV, Ar = pyridin-4-yl; XVI, XVII, X = H, Y = 5,6-benzo;
XVI, Ar = Ph; XVII, Ar = pyridin-2-yl; XVIII, X = Cl, Y = 6,7-benzo, Ar = Ph.
823

LI et al.
824
Table 1. Reaction of 2-methylquinoline with benzaldehyde
in the presence of zinc chloride under microwave irradiation
irradiation in the presence of zinc chloride without
a solvent [13]. In the present work we extended the
same procedure to the synthesis of a large series of
2-styrylquinolines.
Ratio quinaldine–
PhCHO–ZnCl2
Irradiation time,
min
Yield of I, %
The reaction conditions were optimized by studying
the condensation of 2-methylquinoline with benzalde-
hyde as model reaction. The kinetics of accumulation
of the E isomer of 2-styrylquinoline (I) was examined
by spectrophotometry, taking into account that the
initial compounds (benzaldehyde and quinaldine) do
not absorb in the region λ 330–380 nm and that com-
pound I in ethanol is characterized by an absorption
maximum at λ 340 nm (ε = 28900 l mol–1 cm–1) [14].
Therefore, we were able to estimate the yield of I
without isolating it from the reaction mixture. The
effects of reaction (irradiation) time and initial reactant
ratio (at a constant irradiation time) were studied
(Table 1).
1:2:0.45
1:2:0.45
1:2:0.45
1:2:0.45
1:2:0.45
1:2:0.45
1:2:0.45
1:2:0.45
1:2:0.45
2:1:0.45
1:1:0.45
1:2:0.45
1:2:0.00
1:2:0.25
1:2:0.45
1:2:1.00
00
01
02
03
05
08
10
12
16
10
10
10
10
10
10
10
00
37
57
65
70
75
78
79
77
37
58
78
00
61
78
76
We found that the yield of I reaches 37% in 1 min
after irradiation started; after irradiation for 10–12 min,
the yield of I no longer changed. The yield of I in-
creased in parallel with the amount of benzaldehyde.
The optimal amount of the catalyst was 0.45 equiv. In
subsequent preparative experiments the ratio quinal-
dine–benzaldehyde–zinc chloride was 1:2:0.45. Under
these conditions we performed condensations of quin-
aldine with various aromatic and heterocyclic alde-
hydes. Apart from quinaldine, the condensations with
its benzo-fused derivatives, 3-methylbenzo[f]quinoline
and 4-chloro-2-methylbenzo[g]quinoline [15, 16],
were carried out. The results are collected in Table 2.
Table 2. Yields of 2-styrylquinoline derivatives I–XVIII in
the condensation of 2-methylquinolines with aromatic alde-
hydes in the presence of zinc chloride under microwave
irradiation
Compound no.
Time, min
Yield, %
I
12
05
10
12
12
12
15
10
10
10
10
14
10
11
12
12
12
10
63
78
67
61
64
62
60
71
66
62
65
46
65
66
60
57
59
64
II
It is seen that the synthesis of nitro derivative II
required the shortest irradiation time and was charac-
terized by the highest yield. This may be due to strong
activating effect of electron-withdrawing nitro group.
It should be noted that the proposed procedure was
also efficient for compounds containing an electron-
donating substituent in the aldehyde component (com-
pounds VI–IX). The low yield of XII is likely to be
related to difficulties in its separation from excess
anthracene-9-carbaldehyde.
III
IV
V
VI
VII
VIII
IX
X
XI
Comparison of the developed procedure utilizing
MW irradiation (method a) with traditional condensa-
tion by heating in acetic anhydride (method b; Table 3)
shows that the former ensures much higher yield of the
target products in much shorter time (10–12 min
against 14 h). Moreover, method a implies simpler
isolation and purification procedures.
XII
XIII
XIV
XV
XVI
XVII
XVIII
Regardless of the method of synthesis, all com-
pounds I–XVIII had E configuration of the exocyclic
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MICROWAVE-ASSISTED SOLVENT-FREE SYNTHESIS OF 2-STYRYLQUINOLINES
825
Table 3. Yields of compounds IV–VI, X, and XI under
microwave irradiation (ZnCl2, method a) and under tradi-
tional conditions (Ac2O, method b)
double bond, as followed from the presence in their
1H NMR spectra of doublet signals due to olefinic
protons at δ 7.21–8.63 ppm with a coupling constant of
about 16 Hz. It is interesting that in all cases the Hβ
proton resonated in a weaker field as compared to Hα.
Analogous pattern was observed previously for struc-
turally related compounds in which the nitrogen atom
occupied ortho position with respect to the ethenyl
substituent due to formation of intramolecular hydro-
gen bond N···Hβ [17, 18]. In the spectrum of pyridine
derivative XIII having two nitrogen atoms in the ortho
positions with respect to the ethenyl substituent,
signals from both olefinic protons are displaced down-
field, and their chemical shifts are very similar.
Reaction time, h
Yield, %
Compound
no.
method a method b method a method b
IV
V
0.20
0.20
0.20
0.17
0.17
14
14
14
14
14
61
64
62
62
65
54
57
46
50
53
VI
X
XI
tandem mass spectrometer. The melting points were
measured on a Kofler hot stage by heating at a rate of
4 deg/min. The elemental compositions were deter-
mined on an Elementar Vario Micro Cube analyzer.
Microwave-assisted reactions were carried out in
a DAEWOO-KOR-4115SA household microwave
oven (600 W, 2450 MHz).
Hα
N
Hβ
Another interesting feature, a considerable down-
field shift of the Hβ signal, was observed for 1-naph-
thyl and 9-anthryl derivatives X and XII but not for
2-naphthyl derivative XI (Table 4). 1,2-Diarylethenes
with different aryl substituents exist as a set of s-con-
formers due to restricted rotation of the aryl groups
about quasisingle carbon–carbon bonds in the ethene
bridge [19]. In those conformers of X where the ortho-
fused benzene ring is oriented toward the Hβ proton the
latter appears strongly deshielded, and its signal shifts
downfield. The Hβ proton in 9-anthryl derivative XII is
deshielded by either one or another ortho-fused ben-
zene ring, regardless of the orientation of the anthra-
cene fragment; therefore, the Hβ signal in the spectrum
of XII is located most downfield.
Typical procedure for the synthesis of 2-styryl-
quinoline derivatives. a. Under microwave irradia-
tion. A glass test tube was charged with 1.0 mmol of
quinaldine, 2.0 mmol of aromatic aldehyde, and
0.45 mmol of zinc chloride. The test tube was placed
into a 100-ml beaker containing 15–20 ml of water and
subjected to MW irradiation at a power of 600 W in
2 to 4 4–5-min periods with 30-s intervals (overall
irradiation time 5–14 min). The progress of the
reaction was monitored by TLC using acetone–hexane
(1:5) as eluent. The mixture was cooled and treated
with a 5% solution of potassium hydroxide. In the
synthesis of hydroxy derivatives VIII and IX, the
mixture was treated with aqueous ethanol, and in the
synthesis of XIV and XV, with a hot concentrated
alkali solution. The solid or oily material thus formed
was separated by decanting and washed with a small
amount of hexane or hexane–methylene chloride, and
To conclude, we have developed a convenient,
cost-effective, and ecologically safe procedure for the
synthesis of (E)-2-styrylquinoline derivatives under
microwave irradiation in the absence of a solvent.
EXPERIMENTAL
1
Table 4. Chemical shifts of the CH=CH protons in the H
NMR spectra of 2-styrylquinoline derivatives HtCHα=CHβAr
1
The H NMR spectra were recorded on Bruker
Avance III, Bruker DRX-500, and Bruker DRX-200
spectrometers at 500 and 200 MHz using CDCl3,
DMSO-d6, or CCl4 as solvent and tetramethylsilane as
internal reference. The IR spectra were measured in
KBr on a Perkin Elmer Spectrum BX-2 spectrometer
with Fourier transform. The mass spectra were
obtained on an ESI O-TOF MS custom-made high-
resolution time-of-flight mass spectrometer [20] and
on a Q-TOF QSTAR MDS Sciex high-resolution
Compound no.
Hα
Hβ
I
7.41
7.47
7.53
7.29
7.68
8.52
7.86
8.63
X
XI
XII
XIII
7.86, 7.90
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 6 2012

LI et al.
826
the solid product thus obtained was recrystallized from
appropriate solvent.
1H NMR spectrum (500 MHz, CDCl3), δ, ppm: 7.14 t
(2H, o-H, J = 8.6 Hz), 7.36 d (1H, =CH–, J = 16.3 Hz),
7.55 t (1H, Ht, J = 7.4 Hz), 7.63–7.78 m (5H, m-H,
–CH=, Ht), 7.83 d (1H, Ht, J = 8.1 Hz), 8.12 d (1H, Ht,
J = 8.4 Hz), 8.18 d (1H, Ht, J = 8.5 Hz). Mass spec-
trum: m/z 250.084 [M + H]+. Found, %: C 81.78;
H 4.88; N 5.56. C17H12NF. Calculated, %: C 81.91;
H 4.85; N 5.62. M 249.095.
b. Condensation in acetic anhydride. A mixture of
1 mmol of quinaldine and 2 mmol of aromatic alde-
hyde in 5 ml of acetic anhydride was heated for 14 h
under reflux. The mixture was cooled, treated with
an aqueous solution of sodium carbonate, and the dark
solid or oily material was subjected to chromatography
on silica gel (Silpearl) or recrystallization from appro-
priate solvent.
b. Yield 57% after purification by column chroma-
tography (heptane–methylene chloride, 1:1).
2-[(E)-2-Phenylethenyl]quinoline (I). Light
yellow crystals, mp 99–100°C (from hexane) [21].
1H NMR spectrum (500 MHz, CDCl3), δ, ppm: 7.30–
7.35 m (1H, C6H5), 7.37–7.44 m (3H, C6H5, =CH–),
7.47–7.52 m (1H, Ht), 7.61–7.73 m (5H, C6H5, –CH=,
Ht), 7.77 d (1H, Ht, J = 8.1 Hz), 8.08 d (1H, Ht, J =
8.7 Hz), 8.11 d (1H, Ht, J = 8.6 Hz).
2-[(E)-2-(4-Ethoxyphenyl)ethenyl]quinoline (VI).
a. Light yellow crystals, mp 135–137°C (from hex-
ane); published data [7]: mp 137.5–138°C. H NMR
1
spectrum (500 MHz, DMSO-d6), δ, ppm: 1.35 t (3H,
CH3, J = 7.0 Hz), 4.08 q (2H, OCH2, J = 7.0 Hz),
6.98 d (2H, o-H, J = 8.4 Hz), 7.33 d (1H, =CH–, J =
16.5 Hz), 7.53 t (1H, Ht, J = 7.6 Hz), 7.67 d (2H, m-H,
J = 8.4 Hz), 7.74 t (1H, Ht, J = 7.6 Hz), 7.78 d (1H,
–CH=, J = 16.5 Hz), 7.83 d (1H, Ht, J = 8.6 Hz),
7.93 d (1H, Ht, J = 8.0 Hz), 7.97 d (1H, Ht, J =
8.4 Hz), 8.32 d (1H, Ht, J = 8.5 Hz).
2-[(E)-2-(4-Nitrophenyl)ethenyl]quinoline (II).
Yellow crystals, mp 165–167°C (from EtOH–CHCl3);
1
published data [21]: mp 169°C. H NMR spectrum
(500 MHz, CDCl3), δ, ppm: 7.50–7.58 m (2H, Ht,
=CH–), 7.67 d (1H, Ht, J = 8.5 Hz), 7.71–7.85 m (5H,
m-H, –CH=, Ht), 8.10 d (1H, Ht, J = 8.4 Hz), 8.19 d
(1H, Ht, J = 8.5 Hz), 8.26 d (2H, o-H, J = 8.7 Hz).
b. Yield 46% after purification by column chroma-
tography (methylene chloride), followed by recrystal-
lization from heptane.
Methyl 4-[(E)-2-(quinolin-2-yl)ethenyl]benzoate
(III). White crystals, mp 133–135°C (from hexane);
published data [22]: mp 135–136°C. H NMR spec-
N,N-Dimethyl-4-[(E)-2-(quinolin-2-yl)ethenyl]-
aniline (VII). Yellow crystals, mp 185–187°C (from
EtOH); published data [23]: mp 184–185°C. H NMR
1
1
trum (200 MHz, CCl4), δ, ppm: 2.25 s (3H, CH3),
7.04 d (2H, m-H, J = 8.5 Hz), 7.21 d (1H, =CH–, J =
16.1 Hz), 7.37 t (1H, Ht, = J 7.4 Hz), 7.48 d (1H, Ht,
J = 8.5 Hz), 7.52–7.72 m (5H, Ht, o-H, –CH=), 7.92–
8.04 m (2H, Ht).
spectrum (500 MHz, CDCl3), δ, ppm: 3.07 s (6H,
NMe2), 6.78 d (2H, o-H, J = 8.8 Hz), 7.26 d (1H,
=CH–, J = 16.2 Hz), 7.49 t (1H, Ht, J = 7.5 Hz), 7.59 d
(2H, m-H, J = 8.8 Hz), 7.65 d (1H, –CH=, J =
16.2 Hz), 7.68–7.74 m (2H, Ht), 7.79 d (1H, Ht, J =
8.0 Hz), 8.08 d (1H, Ht, J = 8.5 Hz), 8.11 d (1H, Ht,
J = 8.6 Hz).
2-[(E)-2-(4-Iodophenyl)ethenyl]quinoline (IV).
a. White crystals, mp 158–159°C (from hexane). IR
1
spectrum: δ 969 cm–1 (trans-CH=CH). H NMR spec-
4-[(E)-2-(Quinolin-2-yl)ethenyl]phenol (VIII).
Light yellow crystals, mp 270°C (from i-PrOH);
published data [3]: mp 268–270°C. 1H NMR spectrum
(500 MHz, DMSO-d6), δ, ppm: 6.77 d (2H, o-H, J =
8.4 Hz), 7.19 d (1H, =CH–, J = 16.2 Hz), 7.47–7.54 m
(3H, m-H, Ht), 7.66–7.73 m (2H, –CH=, Ht), 7.78 d
(1H, Ht, J = 8.6 Hz), 7.88 d (1H, Ht, J = 8.0 Hz),
7.92 d (1H, Ht, J = 8.4 Hz), 8.26 d (1H, Ht, J =
8.6 Hz), 10.25 br.s (1H, OH).
trum (500 MHz, CDCl3), δ, ppm: 7.36–7.44 m (3H,
o-H, =CH–), 7.52 t (1H, Ht, J = 7.5 Hz), 7.63 d (1H,
–CH=, J = 16.6 Hz), 7.66 d (1H, Ht, J = 8.7 Hz), 7.70–
7.77 m (3H, m-H, Ht), 7.80 d (1H, Ht, J = 8.0 Hz),
8.08 d (1H, Ht, = J 8.4 Hz), 8.15 d (1H, Ht, J =
8.6 Hz). Mass spectrum: m/z 358.011 [M + H]+. Found,
%: C 56.86; H 3.22; N 3.58. C17H12IN. Calculated, %:
C 57.16; H 3.39; N 3.92. M 357.001.
b. The precipitate obtained after decomposition of
the reaction mixture was washed with aqueous acetone
and recrystallized from hexane. Yield 54%.
2-[(E)-2-(Quinolin-2-yl)ethenyl]phenol (IX).
Light yellow crystals, mp 210–212°C (from i-PrOH);
published data [23]: mp 212°C. H NMR spectrum
1
2-[(E)-2-(4-Fluorophenyl)ethenyl]quinoline (V).
a. White crystals, mp 118–120°C (from hexane). IR
spectrum, ν, cm–1: 1219 (C–F), 967 (δtrans-CH=CH).
(500 MHz, DMSO-d6), δ, ppm: 6.85 t (1H, C6H4, J =
7.4 Hz), 6.91 d (1H, C6H4, J = 7.8 Hz), 7.16 t (1H,
C6H4, J = 7.5 Hz), 7.46 d (1H, =CH–, J = 16.4 Hz),
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MICROWAVE-ASSISTED SOLVENT-FREE SYNTHESIS OF 2-STYRYLQUINOLINES
827
7.53 t (1H, C6H4, J = 7.5 Hz), 7.68 d (1H, Ht, J =
7.6 Hz), 7.72 t (1H, Ht, J = 7.6 Hz), 7.78 d (1H, Ht, J =
8.6 Hz), 7.92 d (1H, Ht, J = 7.9 Hz), 7.97 d (1H, Ht,
J = 8.3 Hz), 8.03 d (1H, –CH=, J = 16.4 Hz), 8.31 d
(1H, Ht, J = 8.6 Hz), 9.99 s (1H, OH).
J = 8.1 Hz), 7.86 d (1H, =CH–, J = 16.0 Hz), 7.90 d
(1H, –CH=, J = 16.0 Hz), 8.15–8.21 m (2H, Ht),
8.65 d (1H, Py, J = 4.8 Hz).
2-[(E)-2-(Pyridin-3-yl)ethenyl]quinoline (XIV).
Light yellow crystals, mp 95°C (from hexane);
1
published data [26]: mp 95–96°C. H NMR spectrum
2-[(E)-2-(1-Naphthyl)ethenyl]quinoline (X).
a. Light yellow crystals, mp 102–103°C (from hexane–
(500 MHz, CDCl3), δ, ppm: 7.32–7.36 m (1H, Py),
7.46 d (1H, =CH–, J = 16.3 Hz), 7.52 t (1H, Ht, J =
7.4 Hz), 7.65–7.75 m (3H, –CH=, Ht), 7.80 d (1H, Ht,
J = 8.1 Hz), 7.97 d (1H, Py, J = 7.8 Hz), 8.09 d (1H,
Ht, J = 8.7 Hz), 8.16 d (1H, Ht, J = 8.5 Hz), 8.55 d
(1H, Py, J = 4.7 Hz), 8.84 s (1H, Py).
1
CH2Cl2); published data [24]: mp 101°C. H NMR
spectrum (500 MHz, CDCl3), δ, ppm: 7.47 d (1H,
=CH–, J = 16.0 Hz), 7.49–7.55 m (3H, Harom), 7.56–
7.60 m (1H, Harom), 7.69–7.74 m (2H, Harom), 7.79 d
(1H, Harom, J = 8.1 Hz), 7.86 d (1H, Ht, J = 8.2 Hz),
7.90 t (2H, Ht, J = 7.3 Hz), 8.13 d (1H, Ht, J = 8.4 Hz),
8.15 d (1H, Ht, J = 8.6 Hz), 8.34 d (1H, Ht, J =
8.5 Hz), 8.52 d (1H, –CH=, J = 16.0 Hz).
2-[(E)-2-(Pyridin-4-yl)ethenyl]quinoline (XV).
Light yellow crystals, mp 123–125°C (from hexane);
1
published data [26]: mp 125–126°C. H NMR spec-
trum (500 MHz, CDCl3), δ, ppm: 7.48 d (2H, Py, J =
6.0 Hz), 7.51–7.59 m (2H, =CH–, Ht), 7.63 d (1H,
–CH=, J = 16.3 Hz), 7.67 d (1H, Ht, J = 8.5 Hz), 7.73 t
(1H, Ht, J = 7.7 Hz), 7.81 d (1H, Ht, J = 8.2 Hz),
8.09 d (1H, Ht, J = 8.2 Hz), 8.18 d (1H, Ht, J =
8.5 Hz), 8.63 d (2H, Py, J = 6.0 Hz).
b. Yield 50% after purification by column chroma-
tography (acetone–heptane, 1:5), followed by recrys-
tallization from heptane–diethyl ether.
2-[(E)-2-(2-Naphthyl)ethenyl]quinoline (XI).
a. Light yellow crystals, mp 163–164°C (from hexane–
acetone). IR spectrum: δ 963 cm–1 (trans-CH=CH).
1H NMR spectrum (500 MHz, CDCl3), δ, ppm: 7.45–
7.52 m (3H, Naphth, Ht),7.53 d (1H, =CH–, J =
16.3 Hz), 7.69–7.74 m (2H, Naphth), 7.80 d (1H, Ht,
J = 8.3 Hz), 7.82–7.89 m (5H, –CH=, Naphth, Ht),
8.00 s (1H, Naphth), 8.09 d (1H, Ht, J = 8.3 Hz),
8.15 d (1H, Ht, J = 8.5 Hz). Mass spectrum:
m/z 282.127 [M + H]+. Found, %: C 89.49; H 5.28;
N 4.90. C21H15N. Calculated, %: C 89.65; H 5.37;
N 4.98. M 281.120.
3-[(E)-2-Phenylethenyl]benzo[f]quinoline (XVI).
Light yellow crystals, mp 176–177°C (from EtOH);
1
published data [27]: mp 173–174°C. H NMR spec-
trum (500 MHz, CDCl3), δ, ppm: 7.33 t (1H, Ph, J =
7.3 Hz), 7.38–7.46 m (3H, =CH–, Ph), 7.61–7.71 m
(4H, Ph, Ht), 7.76 d (1H, –CH=, J = 16.3 Hz), 7.78 d
(1H, Ht, J = 8.6 Hz), 7.92 d (1H, Ht, J = 7.6 Hz), 7.97–
8.00 m (2H, Ht), 8.59 d (1H, Ht, J = 8.1 Hz), 8.90 d
(1H, Ht, J = 8.6 Hz).
3-[(E)-2-(Pyridin-2-yl)ethenyl]benzo[f]quinoline
(XVII). Light brown crystals, mp 149°C (from
aqueous acetone). IR spectrum: δ 974 cm–1 (trans-
b. Yield 53% after purification by column chroma-
tography (acetone–heptane, 1:5), followed by recrys-
tallization from petroleum ether–chloroform.
1
CH=CH). H NMR spectrum (500 MHz, CDCl3), δ,
2-[(E)-2-(9-Anthryl)ethenyl]quinoline (XII).
ppm: 7.22–7.26 m (1H, Py), 7.61 d (1H, Py, J =
7.8 Hz), 7.66 t (1H, Py, J = 7.7 Hz), 7.69–7.77 m (2H,
Ht), 7.84 d (1H, Ht, J = 8.6 Hz), 7.90–7.97 m (3H, Ht),
8.00–8.08 m (2H, CH=CH), 8.62 d (1H, Ht, J =
8.3 Hz), 8.69 d (1H, Py, J = 4.9 Hz), 8.97 d (1H, Ht,
J = 8.6 Hz). Found, %: C 84.83; H 5.02; N 9.85.
C20H14N2. Calculated, %: C 85.08; H 5.00; N 9.92.
Dark yellow crystals, mp 174–176°C (from petroleum
1
ether); published data [25]: mp 170–172°C. H NMR
spectrum (500 MHz, CDCl3), δ, ppm: 7.29 d (1H,
=CH–, J = 16.4 Hz), 7.47–7.52 m (4H, Harom), 7.53–
7.57 m (1H, Ht), 7.73–7.77 m (1H, Ht), 7.80 d (1H, Ht,
J = 8.5 Hz), 7.85 d (1H, Ht, J = 8.2 Hz), 8.01–8.06 m
(2H, Harom), 8.16 d (1H, Ht, J = 8.4 Hz), 8.23 d (1H,
Ht, J = 8.5 Hz), 8.41–8.47 m (3H, Harom), 8.63 d (1H,
–CH=, J = 16.4 Hz).
4-Chloro-2-[(E)-2-phenylethenyl]benzo[g]quino-
line (XVIII). Light yellow crystals, mp 143–144°C
(from acetone). IR spectrum: δ 972 cm–1 (trans-
1
2-[(E)-2-(Pyridin-2-yl)ethenyl]quinoline (XIII).
a. Yield 65%, light yellow crystals, mp 94–96°C (from
CH=CH). H NMR spectrum (500 MHz, CDCl3), δ,
ppm: 7.35–7.47 m (4H, Ph, =CH–), 7.55–7.59 m (2H,
Ht), 7.68 d (2H, Ph, J = 7.3 Hz), 7.70 d (1H, –CH=,
J = 16.3 Hz), 7.81 s (1H, Ht), 8.06–8.12 m (2H, Ht),
8.67 s (1H, Ht), 8.75 s (1H, Ht). Mass spectrum:
m/z 316.088/318.083 [M + H]+. Found, %: C 79.68;
1
hexane); published data [26]: mp 94–95°C. H NMR
spectrum (500 MHz, CDCl3), δ, ppm: 7.20–7.24 m
(1H, Py), 7.53 t (1H, Ht, J = 7.5 Hz), 7.61 d (1H, Ht,
J = 7.8 Hz), 7.68–7.75 m (3H, Py, Ht), 7.80 d (1H, Ht,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 6 2012

LI et al.
828
10. Li, F.-M., Wang, L.-Y., Wang, S.-K., and Zhang, Z.-X.,
H 4.51; N 4.38. C21H14ClN. Calculated, %: C 79.87;
H 4.47; N 4.44. M 315.081/317.079.
Chin. J. Org. Chem., 2004, vol. 24, p. 50.
11. Musiol, R., Podeszwa, B., Finster, J., Niedbala, H., and
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 07-03-00891, 10-03-00751) and by the Presidium
of the Russian Academy of Sciences (Basic Research
Program “Development of Methods for the Preparation
of Chemical Substances and Design of New Mate-
rials,” subprogram “Polyfunctional Materials for
Molecular Electronics,” subject “Development of
Scientific Grounds for the Design of Controllable
Photoswitches and Logic Devices on the Basis of Aza-
Diarylethylenes”).
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