Synthesis and structure of styryl-substituted azines

Article abstract of DOI:10.1134/S107042801102014X

New photochromic derivatives of 2-styrylquinoline and 2-styrylquinoxaline were obtained by the condensation of the methyl derivatives of the mentioned heterocycles with substituted benzaldehydes in the presence of basic and acidic catalysts, and also unde

Full text of DOI:10.1134/S107042801102014X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 2, pp. 245252. Pleiades Publishing, Ltd., 2011.
Original Russian Text  E.N. Gulakova, A.G. Sitin, L.G. Kuz’mina, O.A. Fedorova, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 2,
pp. 253260.
Synthesis and Structure of Styryl-Substituted Azines
E. N. Gulakovaa, A. G. Sitinb, L. G. Kuz’minac, and O. A. Fedorovaa,b
aNesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences,
Moscow, 119991 Russia
e-mail: gulakova@ineos.ac.ru
bMendeleev Russian University of Chemical Engineering, Moscow, Russia
cKurnakov Institute of General and Inorganic Chemistry,
Russian Academy of Sciences, Moscow, Russia
Received January 4, 2010
Abstract—New photochromic derivatives of 2-styrylquinoline and 2-styrylquinoxaline were obtained by the
condensation of the methyl derivatives of the mentioned heterocycles with substituted benzaldehydes in the
presence of basic and acidic catalysts, and also under the conditions of Wittig reaction. The structure of compounds
obtained was proved by physicochemical analysis methods including XRD
.
DOI: 10.1134/S107042801102014X
Styryl-substituted derivatives of quinoline and qui-
noxaline are interesting as compounds with a potential
biological activity. The derivatives of quinoline and qui-
noxaline possess bactericidal and fungicidal properties [1,
2]. It was shown recently that quinoline derivatives are
promising substrates for the photoinduced electrocyclic
reaction [3]. The synthetic potential of these phototrans-
formations is sufficiently wide and makes it possible to
use them for the synthesis of new polyfused heteroaro-
matic compounds (Scheme 1).
compounds, e.g., potential antitumor agents [4].
It is known [5–12] that the main procedure for the
synthesis of styrylheterocycles is the aldol-type conden-
sation of methyl derivatives of heterocyclic bases with
benzaldehyde derivatives. The primary conditions of the
condensation contained the use of relatively strong protic
acids and bases, and the range of the possible reaction
products was limited. Yet the importance of this conden-
sation as one of the main procedures for the preparation
of the polyfunctional products is so high that the devel-
opment of various versions of its performance becomes
nowadays a special field of research.
π-Conjugated organic compounds based on aromatic
systems attract significant attention with respect to the
application as semiconductors in organic field transis-
tors (OFETs), organic light-emitting diodes (OLEDs),
and photogalvanic batteries, and also as biological active
We tested this method for the synthesis of methoxy-
substituted 2-styrylquinoline (II). The acidity character-
istic of the alkyl groups in the α-position of the pyridine
Scheme 1.
R2
X
N
X
R1
X
N
hv
R1
and/or
N
R2
R2
R1
X = CH, N.
245

GULAKOVA et al.
246
ring is also observed in the methyl group in the position
2 of quinoline. The condensation of 2-methylquinoline
(I) with 3-methoxybenzaldehyde was performed using an
additional activation both of the base and the acid; in the
second case the reaction proceeded involving enamines,
and in the first event the corresponding resonance-stabi-
lized anion took part (Scheme 2).
styryl-substituted quinolines and quinoxalines both with
electron-donor and electron-acceptor substituents in the
benzene ring. The results of the condensation of quinal-
dine (I) with a series of substituted benzaldehydes are pre-
sented in Table 1. The introduction of electron-acceptor
substituents (OH, NO2) into the benzaldehyde activates
the carbonyl group in the reactions of the nucleophilic
addition and results in higher yields of substituted 2-sty-
rylquinolines compared with 2-styrylquinoline VII. The
electron-donor substituents (OMe, Me) on the contrary
deactivate the carbonyl group of the substituted benzal-
dehyde in the reaction with quinaldine (I).
The widely known method of preparation of olefin
derivatives is Wittig reaction [13, 14] consisting in
the reaction of phosphorus ylides with carbonyl com-
pounds. The 3-methoxybenzyltriphenylphosphonium
salt obtained in the first stage was further subjected to
α-deprotonation under the treatment with a strong base
(NaOH), and thus formed phosphonium ylide reacted
with quinoline-2-carbaldehyde giving 2-styrylquinoline
(II) in 74% yield (Scheme 3).
O
R2
+
H
N
CH3
R1
Although the yield of styrylquinoline (II) in Wittig
reaction is high, the necessity of the preliminary synthesis
of the phosphonium salts, and in the most cases of the
substituted halobenzyl derivatives considerably reduces
the synthetic value of this reaction compared to the con-
densation of commercially availably reagents affording
the target styrylheterocycles in one stage with sufficiently
high yields.
I
4
5
8
3
6
7
b
2'
R1
R2
N
a
6'
5'
II_VII
R1 = OMe (II, IV), H (III, VII), NO2 (V), OAc (VI);
R2 = H (II, V–VII), Me (III), OMe (IV).
To extend the study of physicochemical properties of
styryl-substituted azines it was necessary to synthesized
Scheme 2.
O
H
a_c
OMe
N
N
CH3
OMe
I
II, 42 (a), 55 (b), 53% (c)
a: t-BuOK–DMF; b: piperidine, AcOH–toluene; c: Ac2O.
Scheme 3.
3'''
4'''
5''
O
2'''
,
N
C
H
6''
4''
3''
CH2Cl
5'''
PPh3, MeCN
NaOH, CH2Cl2
6'''
P
OMe
2''
2'
6
N
_
Cl
6'
5
2
3'
OMe
II, 74%
5'
4'
4
OMe
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

SYNTHESIS AND STRUCTURE OF STYRYL-SUBSTITUTED AZINES
247
Table 1. Condensation conditions and yields of 2-styrylquino-
line derivatives II–VII
Styrylquinolines III–VII were previously described
in the literature. The styrylquinolines with the electron-
donor substituents in the benzene ring were obtained by
the condensation of reagents in the presence of ZnCl2
(IV, yield 30% [15]) or AC2O (III, yield 22% [16]). The
condensation conditions that we elaborated increased the
yield of the target product more than twice.
As a result of the condensation of 3-hydroxybenzal-
dehyde with quinaldine (I) oxyacetyl-substituted 2-sty-
rylquinoline VI was isolated, the product of the hydroxy
group acetylation.
Compound no.
Condensation conditions
PPy, ACOH–toluene, 120°C
PPy, ACOH–toluene, 120°C
Yield, %
55
II
III
60
IV
V
PPy, ACOH–toluene, 120°C
AC2O, 140°C
64
75
74
70
VI
VII
AC2O, 140°C
AC2O, 140°C
By the reduction of nitro-substituted styrylquinoline
V we prepared the corresponding amino derivative VIII
(Scheme 4).
Table 2. Condensation conditions and yields of
2-styrylquinoxaline derivatives X–XIV
2-Methylquinoxaline (IX) also is capable to enter into
the condensation via the intermediate deprotonation of
the methyl group like 2-methylquinoline I. The arising
intermediate anion is stabilized by the secondary negative
induction effect of the second nitrogen atom, therefore
the 2-styrylquinoxaline derivatives X–XIV form in higher
yields than analogous 2-styrylquinolines II–VII (Table
2, Scheme 5).
All synthesized derivatives of 2-styrylquinoline and
2-styrylquinoxaline were isolated as trans-isomers as
showed the coupling constants (~16 Hz) in the 1H NMR
spectra.
Compound no. Condensation conditions
Yield, %
60
X
PPy, ACOH–toluene,
120°C
XI
PPy, ACOH–toluene,
120°C
77
XII
AC2O, 140°C
67
77
XIII
AC2O, 140°C
AC2O, 140°C
XIV
75
caused by pedal motion resulting from the temperature
dependent dynamic process in the solid phase [17, 18].
This dynamic process consists in the rotation of the eth-
ylene fragment around its ordinary bonds, whereas the
aromatis fragments connected thereto are subjected only
to small displacements in their proper planes.
Below are reported the XRD results for 2-styrylquino-
lines III–VIII.
The crystal unit cells of the methoxy derivative IV and
nitro compound V contain each two crystallographically
independent molecules, and the unit cell of unsubstituted
compound VII contains three independent molecules. In
crystals of methyl derivative III a disordering was found
The crystal unit cell of acetoxy-substituted styryl-
quinoxaline XIV contains two crystallographically
Scheme 4.
(1) SnCl2, HCl
(2) NaOH
NO2
NH2
N
N
VIII, 72%
V
Scheme 5.
N
N
N
O
H
R1
R2
R2
+
N
CH3
R1
IX
X_XIV
R1 = H (X), OMe (XI, XII), NO2 (XIII), OAc (XIV); R2 = Me (X), OMe (XI), H (XII–XIV).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

GULAKOVA et al.
248
VIII
III
X
IV
XI
V
XII
VI
XIV
VII
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SYNTHESIS AND STRUCTURE OF STYRYL-SUBSTITUTED AZINES
249
3-methoxybenzaldehyde, and 0.118 g (1.05 mmol)
t-BuOK in 3.5 ml of anhydrous DMF was stirred in
an argon flow at room temperature for 24 h, then to the
reaction mixture 20 ml of distilled water was added.
The separated precipitate was filtered off, dried, and
subjected to chromatography on a column packed with
SiO2 (eluent CH2Cl2). Yield 0.07 g (42%), mp 44–46°C
(hexane). Electron absorption spectrum, λmax, nm (log ε)
281.7 (4.37), 337.2 (4.28). 1H NMR spectrum (CDCl3),
δ, ppm: 3.74 s (3H, OCH3), 6.79 d (1H, C4’H, J 7.9 Hz),
7.09 s (1H, C2’H), 7.11–7.24 m (2H, C6’H, C5’H), 7.30 d
(1H, CbH, J 16.2 Hz), 7.38 m, 7.60 m (2H, C6H, C7H),
7.52 d (1H, C3H, J 6.8 Hz), 7.54 d (1H, CaH, J 16.1 Hz),
7.66 d (1H, C5H, J 8.2 Hz), 7.99 m (2H, C4H, C8H).
Mass spectrum, m/z (Irel, %): 261.2 (42) [M]+, 260.2
(100) [M – 1]+, 246.2 (8), 245.2 (19), 230.4 (6), 218.3
(12), 217.3 (38), 216.3 (9), 143.3 (9), 115.2 (5). Found,
%: C 82.79; H 5.91; N 5.21. C18H15NO. Calculated, %:
C 82.73; H 5.79; N 5.36.
independent molecules, and one of them suffers the pedal
disordering, whereas the other one does not.
The more comprehensive XRD investigation of
compounds synthesized in this study will be published
elsewhere.
Hence in this research the methods of synthesis were
developed for the 2-styrylquinoline derivatives and for
the previously unknown 2-styrylquinoxaline derivatives.
The dependence of the yield of the target products on
the substituents in benzaldehyde and the reaction condi-
tions were investigated that made it possible to optimize
the preparation conditions of the styrylheterocycle with
electron-donor substituents in the styryl fragment, and
to increase their yield more than twice compared to the
published methods. With the use of NMR spectroscopy
and XRD analysis the structure of compounds obtained
in solution and in the crystalline state was established.
EXPERIMENTAL
b. To a solution of 0.419 g (1 mmol) of 3-methoxyben-
zyltriphenylphosphonium chloride and 0.157 g (1 mmol)
of quinoline-2-carbaldehyde in 3 ml of CH2Cl2 was added
3 ml of 50% solution of NaOH, the mixture obtained was
stirred for 2 h, then 20 ml of water was added, and the
reaction product was extracted into dichloromethane. The
combined extracts were dried with Mg2SO4, and evapo-
rated in a vacuum. The residue was subjected to column
chromatography (SiO2, gradient elution with cyclohex-
ane–CH2Cl2, from 1 : 1 to 100% CH2Cl2). Yield 74%.
Melting points were measured in open capillaries
on a Mel-Temp II instrument. H NMR spectra were
1
registered on spectrometers Varian XR-250 (operating
frequency 250 MHz) and Bruker DRX-300, internal
reference TMS. The chemical shifts were measured with
the accuracy up to 0.01 ppm, the coupling constants,
to 0.1 Hz. Mass spectra were obtained on a Kratos
MS-30 instrument, ionizing electrons energy 70 eV,
with the direct admission of the sample into the ion
source. Electron absorption spectra were recorded at
25°C on a spectrophotometer Specord-M40 coupled
with a computer. The spectrophotometer control, data
acquisition, and the simplest processing of the spectra
was carried out using standard program SPECORD
(version 2.0, Etalon). TLC monitoring was performed
on DC-Alufolien Kieselgel 60 F254 (Merck) plates. The
column chromatography was carried out on Kieselgel,
0.062–0.200mm, d 6 nm (Acros Organics).
3-Methoxybenzyltriphenylphosphonium chloride.
A solution of 1.86 ml (12.78 mmol) of 3-methoxybenzyl
chloride and 3.55 g (13.55 mmol) of triphenylphosphine
in 10 ml of acetonitrile was boiled at stirring for 12 h.
On cooling the separated precipitate was filtered off and
dried. Yield 374 mg (70%), mp 271–272°C (262–263°C
[19]). 1H NMR spectrum (DMSO-d6), δ, ppm: 3.48 s (3H,
OCH3), 5.20 d (2H, CH2, J 15.6 Hz), 6.50 s (1H, C2H),
6.60 d, 6.85 d (2H, C4H, C6H, J 7.6, J 8.2 Hz), 7.15 t (1H,
C5H, J 8 Hz), 7.63–7.79 m (12H, C2’H, C3’H, C5’H, C6’H,
C2’’H, C3’’H, C5’’H, C6’’H, C2’’’H, C3’’’H, C5’’’H, C6’’’H),
7.85–7.94 m (3H, C4’H, C4’’H, C4’’’H).
Quinaldine
(I),
2-methylquinoxaline
(IX),
benzaldehyde, 3-methoxybenzaldehyde, 4-methyl-
benzaldehyde, 3,4-dimethoxybenzaldehyde, 3-nitro-
benzaldehyde,3-hydroxybenzaldehyde,1-chloromethyl-
3-methoxybenzene, triphenylphosphine, quinoline-2-
carbaldehyde, acetic anhydride, piperidine, potassium
tert-butylate, SnCl2 were commercial products used
without additional purification.
2-Styrylazines III, IV, X, XI. General procedure.
A solution of 1 mol of 2-methylheterocycle (I or
IX), 1.35 mol of benzaldehyde derivative, 0.5 mol of
piperidine, and 0.7 mol of acetic acid in toluene was
maintained in an inert atmosphere at 115°C for 48 h,
then the reaction mixture was evaporated in a vacuum.
The residue was subjected to column chromatography
2-(3-Methoxystyryl)quinoline (II). a. A solution of
0.47 ml (3.5 mmol) of quinaldine (I), 0.09 ml (0.7 mmol)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

GULAKOVA et al.
250
(SiO2, eluent CH2Cl2), for compound IV dля eluent
CH2Cl2–ethyl acetate, 1 : 1.
or 2-methylquinoxaline (IX), 1 mol of benzaldehyde
derivative, and 1 mol of acetic acid (3 mol of Ac2O in
the synthesis of compounds VI, XIV) was heated under
inert atmosphere at 140°C over 6 h, then it was cooled
and diluted with cold water. In the synthesis of styryla-
zines V, XIII the separated precipitate was filtered off,
dried, and recrystallized. In the other cases the reaction
product was extracted into ethyl acetate, the extract
was dried with Mg2SO4 and evaporated in a vacuum.
The residue was subjected to column chromatography
(SiO2, eluent CH2Cl2), for 2-styrylquinoline VII eluent
benzene–MeCN, 20 : 1.
2-(4-Methylstyryl)quinoline (III), mp 141–143°C
(octane–toluene, 1 : 1) (140°C [16]). Electron absorp-
tion spectrum, λmax, nm (log ε): 285.8 (4.5), 339 (4.5).
1H NMR spectrum (CDCl3), δ, ppm: 2.38 s (3H, CH3),
7.21 d (2H, C3’H, C5’H, J 7.90 Hz), 7.38 d (1H, CbH,
J 16.3 Hz), 7.49 m, 7.70 m (2H, C6H, C7H), 7.54 d (2H,
C2’H, C6’H), 7.64 d (1H, C3H, J 7 Hz), 7.64 d (1H, CaH,
J 16.1 Hz), 7.78 d (1H, C5H, J 8 Hz), 8.08 d (1H, C8H,
J 8.4 Hz), 8.12 d (1H, C4H, J 8.5 Hz).
2-(3,4-Dimethoxystyryl)quinoline (IV), mp 107–
110°C (octane–toluene, 1 : 1) (112–113°C [15]). Elec-
tron absorption spectrum, λmax, nm (log ε): 281 (4.6),
2-(3-Nitrostyryl)quinoline (V), mp 157–158°C
(methanol) (157–158°C [16]). Electron absorption spec-
trum, λmax, nm (log ε): 280.6 (4.7), 323.7 (4.5). 1H NMR
spectrum (CDCl3), δ, ppm: 7.50 d (1H, CbH, J 16.1 Hz),
7.53 m, 7.72 m (2H, C6H, C7H), 7.56 t (C5’H, J 8.0 Hz),
7.65 d (1H, C3H, J 8.5 Hz), 7.76 d (1H, CaH, J 16.3 Hz),
7.81 d (1H, C3H, J 8.2 Hz), 7.92 d (1H, C8H, J 7.7 Hz),
8.09 d (1H, C6’H, J 8.5 Hz), 8.15 m (1H, C4’H), 8.17 d
(1H, C4H, J 8.5 Hz), 8.48 s (1H, C4’H).
1
338 (4.5). H NMR spectrum (CDCl3), δ, ppm: 3.71 s,
3.77 s (6H, 2 OCH3), 6.65 d (1H, C5’H, J 8.2 Hz), 6.95
d (1H, C6’H, J 8.3 Hz), 7.04 s (1H, C2’H), 7.12 d (1H,
CbH, J 16.3 Hz), 7.29 m, 7.53 m (2H, C6H, C7H), 7.39 d
(1H, C3H, J 8.2 Hz), 7.42 d (1H, CaH, J 16.4 Hz), 7.55 d
(1H, C5H, J 8.7 Hz), 7.84 d (1H, C8H, J 8.5 Hz), 7.93 d
(1H, C4H, J 8.2 Hz).
2-(3-Oxyacetylstyryl)quinoline (VI), mp 83–84°C
(octane–toluene, 1 : 1) (83–84°C [20]). Electron ab-
sorption spectrum, λmax, nm (log ε): 281.7 (4.6), 337.2
2-(4-Methylstyryl)quinoxaline (X), mp 116–118°C
(octane–toluene, 1 : 1). Electron absorption spec-
trum, λmax, nm (log ε): 294.1 (4.45), 369.6 (4.47).
1H NMR spectrum (CDCl3), δ, ppm: 2.39 s (3H, CH3),
7.30 d (2H, C3’H, C5’H, J 8.1 Hz), 7.35 d (1H, CbH,
J 16.3 Hz), 7.56 d (2H, C2’H, C6’H, J 8.1 Hz), 7.66–
7.79 m (2H, C6H, C7H), 7.85 d (1H, CaH, J 16.3 Hz),
8.06 d (2H, C5H, C8H, J 8.2 Hz), 9.04 s (1H, C3H).
Mass spectrum, m/z (Irel, %): 246.1 (42) [M]+, 245.2
(100) [M – 1]+, 244.2 (4), 243.3 (4), 232.3 (6), 231.3
(39), 230.3 (4.97), 229.3 (4), 217.4 (5). Found, %:
C 82.79; H 5.62; N 11.31. C17H14N2. Calculated, %:
C 82.90; H 5.73; N 11.37.
1
(4.5). H NMR spectrum (CDCl3), δ, ppm: 1.94 s (3H,
CH3COO), 6.73 d (1H, C4’H, J 7.9 Hz), 6.94–7.12 m
(6H, C2’H, C5’H, C6’H, CbH, C7H), 7.26 d (1H, CaH,
J 16.8 Hz), 7.31 d (1H, C3H, J 7.7 Hz), 7.33 m (1H, C6H),
7.58 d (1H, C8H, J 8.5 Hz), 7.80 d (1H, C4H, J 8.8 Hz).
2-Styrylquinoline (VII), mp 97–99°C (methanol)
(100°C [16]). Electron absorption spectrum, λmax
,
1
nm (log ε): 281.7 (4.2), 337 (4.1). H NMR spectrum
(CDCl3), δ, ppm: 7.35–7.43 m (4H, CbH, C5H, C5’H,
C3’H), 7.51 m (1H, C4’H), 7.64–7.75 m (4H, C3H, C6H,
C7H, CaH), 7.80 d (2H, C2’H, C6’H, J 8.0 Hz), 8.15 m
(2H, C4H, C8H).
2-(3,4-Dimethoxystyryl)quinoxaline (XI), Mp
154–156°C (methanol). Electron absorption spec-
trum, λmax, nm (log ε): 290 (4.36), 383.6 (4.2).
1H NMR spectrum (CDCl3), δ, ppm: 3.93 s, 3.97 s (6H,
2 OCH3), 6.91 d (1H, C5’H, J 8.8 Hz), 7.18–7.31 m (3H,
C6’H, C2’H, CbH), 7.72 m (2H, C6H, C7H), 7.81 d (1H,
CaH, J 16.3 Hz), 8.05 m (2H, C5H, C8H), 9.06 s (1H,
C3H). Mass spectrum, m/z (Irel, %): 292.0 (81) [M]+,
291.1 (100) [M – 1]+, 277.2 (45), 276.2 (13), 275.3 (14),
262.2 (14), 261.2 (23), 249.2 (16), 234.2 (19), 218.2
(14). Found, %: C 74.02; H 5.60; N 9.64. C18H16N2O2.
Calculated, %: C 73.96; H 5.52; N 9.58.
2-(3-Methoxystyryl)quinoxaline (XII), mp 120–
122°C (methanol). Electron absorption spectrum, λmax
,
nm (log ε): 289.4 (4.47), 367.8 (4.43). 1H NMR spectrum
(CDCl3), δ, ppm: 3.87 s (3H, OCH3), 6.93 d (1H, C4’H,
J 7.9 Hz), 7.20 s (1H, C2’H), 7.30 m (2H, C5’H, C6’H),
7.38 d (1H, CbH, J 16.4 Hz), 7.74 m (2H, C6H, C7H), 7.85
d (1H, CaH, J 16.4 Hz), 8.08 d (2H, C5H, C8H, J 7.90 Hz),
9.06 s (1H, C3H). Mass spectrum, m/z (Irel, %): 262.1 (40)
[M]+, 261.2 (100) [M – 1]+, 247.1 (11), 246.2 (10), 232.2
(5), 231.2 (19), 219.3 (17), 218.3 (27), 191.3 (5). Found,
%: C 77.94; H 5.19; N 10.59. C17H14N2O. Calculated, %:
C 77.84; H 5.38; N 10.68.
2-Styrylazines V–VII, XII–XIV. General pro-
cedure. A mixture of 1 mol of 2-methylquinoline (I)
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SYNTHESIS AND STRUCTURE OF STYRYL-SUBSTITUTED AZINES
251
2-(3-Nitrostyryl)quinoxaline (XIII), mp 196–
197.5°C (acetonitrile) (199.5°C [21]). Electron absorp-
tion spectrum, λmax, nm (log ε): 284.1 (4.5), 359.6 (4.36).
1H NMR spectrum (CDCl3), δ, ppm: 7.51 d (1H, CbH,
J 16.3 Hz), 7.60 t (1H, C5’H, J 8.0 Hz), 7.71–7.84 m (2H,
C6H, C7H), 7.94 d (1H, C6’H, J 7.8 Hz), 7.96 d (1H, CaH,
J 16.3 Hz), 8.10 d.d (2H, C5H, C8H, J1 7.3, J2 2.4 Hz),
8.20 d (1H, C4’H, J 8.2 Hz), 8.52 s (1H, C2’H), 9.05 s
(1H, C3H).
approximationforthenonhydrogenatoms.Thehydrogen
atoms were refined either in the isotropic approximation
or in the rider model.
All calculations were carried out using SHELXTL-
Plus software [24].
Compound III. C18H15N. M 245.31. Crystals rhombic,
space group P212121.At T 150 K a 5.9101(4), b 7.8477(6),
c 28.821(2) Å, V 1336.76(17) Å3, Z 4, μ(MoKα)
0.071 mm–1, validity by F2 0.950, 13816 reflections col-
lected, among them 3861 independent (Rint 0.0247). For
reflections with C I > 2σ(I) R1 0.0474, wR2 0.1251, for
all reflections R1 0.0474, wR2 0.1251, residual electron
density, min/max 0.175/0.419 e Å–3.
2-(3-Oxyacetylstyryl)quinoxaline (XIV), mp 105–
107°C (methanol). Electron absorption spectrum, λmax
,
nm (log ε): 288.8 (4.78), 364.3 (4.7). 1H NMR spectrum
(CDCl3), δ, ppm: 2.23 s (3H, CH3COO), 6.98 d (1H, C4’H,
J 7.9 Hz), 7.12 d (1H, CbH, J 16.3 Hz), 7.21–7.33 m (3H,
C2’H, C5’H, C6’H), 7.55 m (2H, C6H, C7H), 7.61 d (1H,
CaH, J 16.3 Hz), 7.93 m (2H, C5H, C8H), 8.80 s (1H,
C3H). Mass spectrum, m/z (Irel, %): 290.1 (16) [M]+,
289.1 (13), 249.2 (6), 248.1 (39), 247.1 (100), 232.2 (38),
220.2 (6), 219.3 (16), 218.3 (10). Found, %: C 74.66;
H 5.16; N 10.57. C18H14N2O2. Calculated, %: C 74.47;
H 4.86; N 9.65.
Compound IV. C19H17NO2. M 291.34. Crystals
monoclinic, space group P21/n.At T 150 K a 10.6554(7),
b 21.1859(14), c 13.5206(9) Å, V 1023.7(3) Å3, Z 8,
μ(MoKα) 0.083 mm–1, validity by F2 1.011, 31101
reflections collected, among them 8753 independent
(Rint 0.0462). Fot reflections with I > 2σ(I) R1 0.0506,
wR2 0.1171, for all reflections R1 0.0871, wR2 0.1294,
residual electron density, min/max 0.194/0.272 e Å–3.
2-(3-Aminostyryl)quinoline (VIII). To a disper-
sion of 1 g (3.62 mmol) of 2-(3-nitrostyryl)quinoline
(V) in 5 ml of concn. HCl was added a solution of 13 g
of SnCl2·2H2O in 10 ml of concn. HCl. The mixture
obtained was boiled for 3 h, then cooled, diluted with
15 ml of water, and 20% solution of NaOH was added to
weak alkaline pH. The separated precipitate was filtered
off, dried, and recrystallized from nonane. Yield 577 mg
(72%), mp 164–165°C (nonane) (167–168°C [22]). Elec-
tron absorption spectrum, λmax, nm (log ε): 281 (4.5), 338
(4.4). 1H NMR spectrum (CD3CN), δ, ppm: 6.67 d (1H,
C4’H, J 7.7 Hz), 6.97 s (1H, C2’H), 7.04 d (1H, C6’H,
J 7.6 Hz), 7.18 t (1H, C5’H, J 7.7 Hz), 7.37 d (1H, CbH,
J 16.3 Hz), 7.49 m, 7.70 m (2H, C6H, C7H), 7.59 d (1H,
CaH, J 16.3 Hz), 7.67 d (1H, C3H, J 8.5 Hz), 7.78 d (1H,
C5H, J 8.2 Hz), 8.11 m (2H, C4H, C8H).
Compound V. C17H12N2O2. M 276.29. Crystals
triclinic, space group P ¯1. At T 150 K a 6.1153(7),
b 10.5326(12), c 20.548(2) Å, V 1295(7) Å3, Z 4, μ(MoKα)
0.095 mm–1, validity by F2 1.096, 15291 reflections
collected, among them 7516 independent (Rint 0.0198).
For reflections with I > 2σ(I) R1 0.0470, wR2 0.1364, for
all reflections R1 0.0618, wR2 0.1456, residual electron
density, min/max 0.288/0.338 e Å–3.
Compound VI. C19H15NO2. M 289.22. Crystals
monoclinic, space group P21/n. At T 150 K a 6.0406(6),
b 7.7835(7), c 31.213(3) Å, V 1463.4(2) Å3, Z 4, μ(MoKα)
0.085 mm–1, validity by F2 1.105, 14888 reflections
collected, among them 4345 independent (Rint 0.0404).
For reflections with I > 2σ(I) R1 0.0567, wR2 0.1513, for
all reflections R1 0.0984, wR2 0.1771, residual electron
density, min/max 0.280/0.409 e Å–3.
XRD of styrylazines III–VII, X–XII, XIV. Single
crystals of compounds III–VII, X–XII, XIV covered
with perfluorinated oil were placed in a diffractometer
Bruker SMART-CCD in a flow of cooled nitrogen.
The set of experimental reflections was obtained by
ω-scanning of the reflections from single crystals
under MoKα radiation. The primary processing of the
experimental reflections was performed using program
SAINT [23].
Compound VII. C17H13N. M 289.22.Crys-
tals monoclinic, space group P21. At T 150 K
a 6.6258(15), b 19.419(4), c 14.796(3) Å, V 1895.8(7)
Å3, Z 12, μ(MoKα) 0.071 mm–1, validity by F2 0.946,
20967 reflections collected, among them 10020
independent (Rint 0.0479). For reflections with
I > 2σ(I) R1 0.0657, wR2 0.1783, for all reflections R1
0.1504, wR2 0.2184, residual electron density, min/max
0.242/0.435 e Å–3.
The structures were solved by the direct method
and refined by least-squares method in the anisotropic
Compound X. C17H14N2. M 246.12. Crystals mono-
clinic, space group P21/c. At T 150 K a 11.888(6),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

GULAKOVA et al.
252
b 4.710(2), c 23.005(11) Å, V 1285.5(11) Å3,
Z 4, μ(MoKα) 0.069 mm–1, validity by F2 1.033,
12731 reflections collected, among them 3880 in-
dependent (Rint 0.0517). For reflections with
I > 2σ(I) R1 0.0771, wR2 0.2016, for all reflections
R1 0.1332, wR2 0.2418, residual electron density, min/
max 0.326/0.714 e Å–3.
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Compound XI. C18H16N2O2. M 292.33. Crystals
rhombic, space group Pbca. At T 150 K a 13.323(2),
b 8.5813(15), c 25.240(4) Å, V 2885.6(7) Å3, Z 8,
μ(MoKα) 0.089 mm–1, validity by F2 0.798, 27724
reflections collected, among them 3483 independent
(Rint 0.1819). For reflections with I > 2σ(I) R1 0.0455,
wR2 0.0902, for all reflections R1 0.1094, wR2 0.1004,
residual electron density, min/max 0.196/0.249 e·Å–3.
7. Mekouar, K., Mouscadet, J.F., and Desmaele, D., J. Med.
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1992, p. 92.
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Chem., 1993, vol. 71, p. 1236.
Compound XII. C17H14N2O. M 262.3. Crystals
rhombic, space group P212121. At T 150 K a 6.5510(10),
b 11.5616(17), c 17.642(3) Å, V 1336.2(3) Å3, Z 4,
μ(MoKα) 0.083 mm–1, validity by F2 1.078, 13821
reflections collected, among them 3872 independent
(Rint 0.0240). For reflections with I > 2σ(I) R1 0.0557,
wR2 .1540, for all reflectionй R1 0.0596, wR2 0.1569,
residual electron density, min/max 0.283/0.662 e Å–3.
11. Fedorova, O.A., Andryukhina, E.N., Mashura, M.M., and
Gromov, S.P., ARKIVOC., 2005, vol. xv, p. 12.
12. Andryukhina, E.N., Mashura, M.M., Fedorova, O.A.,
Kuz’mina, L.G., Khovard, Dzh.A.K., and Gromov, S.P.,
Izv. Akad. Nauk, Ser. Khim., 2005, p. 1650.
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Compound XIV. C17H14N2O. M 262.3. Crystals
monoclinic, space group P21/c.At T 150 K a 28.091(5), b
6.2543(10), c 16.903(3) Å, V 2876.9(8) Å3, Z 8, μ(MoKα)
0.077 mm–1, validity by F2 0.895, 21910 reflections
collected, among them 8236 independent (Rint 0.0894),
R-factors for reflections with I > 2σ(I) R1 0.0885,
wR2 0.2287, for all reflectionй R1 0.1973, wR2 0.2737,
residual electron density, min/max 0.360/1.046 e Å–3.
1976, vol. 5, p. 409.
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ACKNOWLEDGMENTS
vol. 1, p. 63.
20. Zamboni, K., Belley, M., Chapnpion, E., Charette, L., Det-
taven, R., Fyenette, R., Gauthier, J.Y., Jones, T.R., Leger, S.,
Masson, P., McFarlane, C.S., Metters, K., Pong, S.S., Pi-
ethuta, H., Rokach, J., Thérien, M., Williams, H.W.R., and
Young, R.N., J. Med. Chem. Eng., 1992, vol. 35, p. 383.
The study was carried out under the financial support
of the Presidium of the Russian Academy of Sciences
(Program of the fundamental research “Development
of methods of preparation of chemical substances and
creation of new materials”) and the Russian Foundation
for Basic Research (grant no. 10-03-93106-NTsNIL_a).
21. Bennett, G.M. and Willis, G.H., J. Chem. Soc., 1928,
p. 1960.
22. Graff, E., Fredericksen, J.M., and Burger,A., J. Org. Chem.,
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