Synthesis and Structural Study of Dichlorodiazadienes Derived from 4-Methoxybenzaldehyde

Article abstract of DOI:10.1134/S1070428020020013

Abstract: The transformation of N-substituted N-methoxybenzaldehyde hydrazones into the corresponding 1,2-diazabuta-1.3-dienes under the action of carbon tetrachloride in the presence of copper(I) chloride was studied. It was shown that hydrazones of diff

Full text of DOI:10.1134/S1070428020020013

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 2, pp. 185–192. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Organicheskoi Khimii, 2020, Vol. 56, No. 2, pp. 173–181.
Synthesis and Structural Study of Dichlorodiazadienes Derived
from 4-Methoxybenzaldehyde
N. G. Shikhaliyeva,*, U. F. Askerovaa, S. H. Mukhtarovaa, A. A. Niyazovaa,
A. M. Magerramova, P. V. Dorovatovskiib, V. N. Khrustalevc,d, and V. G. Nenajdenkoe
a Baku State University, Baku, 1148 Azerbaijan
b Kurchatov Institute National Research Center, Moscow, 123182 Russia
c Russian University of Peoples’Friendship, Moscow, 117198 Russia
d Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
e Lomonosov Moscow State University, Moscow, 119991 Russia
*e-mail: namiqst@gmail.com
Received September 2, 2019; revised October 14, 2019; accepted December 20, 2019
Abstract—The transformation of N-substituted N-methoxybenzaldehyde hydrazones into the corresponding
1,2-diazabuta-1.3-dienes under the action of carbon tetrachloride in the presence of copper(I) chloride was stud-
ied. It was shown that hydrazones of different nature, containing both donor and acceptor groups in the hydrazine
fragment, can be involved in the reaction. Further evidence in favor of a radical mechanism of this transformation
was obtained using a 3,5-bis(trifluoromethyl)phenylhydrazine derivative. The structural features of the synthesized
products were studied by X-ray diffraction analysis.
Keywords: catalytic olefination, 1,2-diazabuta-1.3-dienes, hydrazone
DOI: 10.1134/S1070428020020013
We recently showed that the copper-catalyzed reac-
tion of polyhalogenated compounds with hydrazones is
of a general nature, and not only N-unsubstituted hydra-
zones can be involved in it [1–10], but also derivatives
containing a substituent on the nitrogen atom.As a result,
we developed a new reaction of C–C bond formation
between N-monosubstituted hydrazones and polyhalo-
alkanes, leading to 1,2-diazabuta-1,3-dienes [11]. This
highly efficient copper-catalyzed transformation opens up
wide synthetic opportunities. It should be noted that the
diazadienes obtained by this method are a very interesting
class of compounds with broad potential applications in
organic synthesis (Scheme 1) [12–17].
of 4-methoxybenzaldehyde hydrazones with different
substituents in the hydrazine part (Scheme 2). These sub-
strates were then reacted with carbon tetrachloride in the
presence of copper(I) chloride as a catalyst and obtained
a series of previously unknown dichlorodiazadienes in
yields of up to 80%.
As already mention, this reaction is very general, and
its scope is only limited by the nature of the substituents
in the hydrazine part. For example, we earlier failed to
react hydrazines containing strongly electron-acceptor
groups (derivatives of 2,4-dinitrophenylhydrazine, as
well as acyl- and sulfonylhydrazines). In the present work
we studied the reaction with hydrazones containing such
electron-acceptor substituents as C≡N, NO2, and CF3.
The goal of the present work was to gain a deeper
insight into the mechanism of this transformation. We
focused on the synthesis of 4-methoxybenzaldehyde
derivatives as an aldehyde component of the reaction.
Our assumption was that the presence of a strongly
donor substituent can increase the electron density on
the hydrazone carbonyl atom of hydrazone and thus
affect the reaction route. Initially, we prepared a series
It was found that the presence of the donor MeO group
in the para position of the aldehyde part of the hydrazone
results allows successful reaction with practically any
combinations of substituents. Thus we could obtain the
corresponding products with hydrazones derived from
para-cyano- and para-nitrophenylhydrazine, which ex-
tends considerably the synthetic potential of the studied
185

186
SHIKHALIEV et al.
Scheme 1.
conjugation chain [C6H4–C(=CCl2)–N=N–C6H4–C=N (9)
and (C6H4–C=N–NH–C6H4)2 (16)], on the one hand, and
the steric repulsion between the chlorine atoms and aryl
substituents (in 9) or between the trifluoromethyl and two
aryl groups (in 16), on the other. As a result, equilibrium
twist molecular conformations are realized (Fig. 1).
Molecule 9 comprises three planar fragments, spe-
cifically, a central 2,2-chloro-1-vinyldiazenyl fragment
(A) (the rms deviation of atoms from the mean plane is
0.036 Å) and two terminal fragments: 4-methoxyphenyl
(B) (except for methyl hydrogens; the rms deviation of
atoms from the mean plane is 0.021 Å) and benzonitrile
(C) (the rms deviation of atoms from the mean plane is
0.016 Å). The A/B and A/C dihedral angles are 52.23(4)
and 27.76(5)°, respectively.
reaction. These data are consistent with the previously
proposed mechanism of the reaction, involving addition
of the trichloromethyl radical to the carbon atom of the
hydrazone fragment (Scheme 3).
The reaction with the hydrazone derived from 3,5-bis-
(trifluoromethyl)phenylhydrazine gave a new type of
product. In this case we isolated the product of linking of
two hydrazone molecules, the formation of which can be
explained in terms of a radical mechanism of the reaction
(Scheme 4).
Molecule 16 has intrinsic C2(2) symmetry and occupies
special position on the second-order rotation axis. Con-
sequently, it comprises four pairwise equivalent planar
fragments: two 3,5-bis[(trifluoromethyl)phenyl]hydra-
zylidene (A, A') (except for trifluoromethyl fluorines; the
rms deviation of atoms from the mean plane is 0.018 Å)
and two 4-methoxyl (B, B') (except for methyl hydrogens;
the rms deviation of atoms from the mean plane is 0.048
Å). The A/B (A'/B'), A/A', and B/B' dihedral angles are
12.69(11), 86.24(3), and 84.82(6)°, respectively.
For unambiguous structural assessment of the newly
synthesized compounds we performed an X-ray diffrac-
tion analysis of compounds 9 and 16. Their molecular
structures of these compounds with atom numbering are
shown in Fig. 1. All geometrical parameters are given in
Supporting Materials.
It is important to note that molecule 9 is an E-isomer
with respect to the N=N bond, whereas molecule 16 is a
Z,Z-isomer with respect to two C=N bonds.
The molecules have quite rigid conformations, which
are apparently defined by two oppositely acting factors:
the tendency for flattening due to the presence of a long
Scheme 2.
Cl
R
Cl
N
O
NHNH2
CCl4, CuCl (1%)
O
O
R
TMEDA (2.5 eq)
DMSO, rt
CH3COOH,
EtOH, reflux
N
N
N
H
O
R
9–15
1–7
R = 4-CN, 4-OCH3, 4-CH3, 4-NO2, 3,5-(CH3)2, 4-F, 2,4-(Cl)2.
Scheme 3.
CCl4
CuCl2 L
TMEDA
CuCl L
L =
Cl
Cl3C
N Ar
CCl3
Cl
N
TMEDA
HN Ar
_HCl TMEDA
N
Cl3C
R H
R H
HN Ar
E
R
N Ar
N
N
_HCl TMEDA
R
CuCl2 L
D
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

SYNTHESIS AND STRUCTURAL STUDY OF DICHLORODIAZADIENES
187
Scheme 4.
CF3
CF3
O
H2NHN
CF3
O
CH3COOH, EtOH,
N
O
reflux
N
CF3
H
8
O
C
O
C
CCl4, CuCl (1%)
TMEDA (2.5 equiv)
DMSO, rt
N
N
HN
CF3
F3C
NH
CF3
CF3
16
Molecules 9 in a crystal form stacks along the a axis
(Fig. 2). The molecules in stacks are held together by
weak π–π stacking interactions (the interplanar spacings
between the corresponding benzene rings are 3.405(4)
and 3.468(4) Å, respectively; the shortest distances
between carbon atoms are as follows: C4∙∙∙C8 [x+1, y, z]
3.436(3), C5∙∙∙C7 [x+1, y, z] 3.447(3), and C10∙∙∙C12 [x+1,
y, z] 3.512(3) Å), as well as by weak hydrogen bonds
C8–H8∙∙∙Cl1 (x–1, y, z) [C∙∙∙Cl 3.704(2) Å, H∙∙∙Cl 2.88 Å,
angle C–H∙∙∙Cl 146°]. The stacks the stacks are con-
nected into corrugated layers parallel to the (010) plane
by weak hydrogen bonds С12–H12∙∙∙O1 (x–1, –y+1½, z+½)
[C∙∙∙O 3.391(3) Å, H∙∙∙O 2.47 Å, angle C–H∙∙∙Cl 165°].
It is interesting to note that in this structure we found no
intermolecular noncovalent halogen–halogen interac-
tions.
Fig. 1. Molecular structures of compounds (а) 9 and (b) 16. The indices A stand for symmetrically equivalent atoms with respect to the
second-order rotation axis. The thermal ellipsoids of non-hydrogen atoms are drawn at a 50% probability level. The lower occupied
alternative positions of disordered CF3 groups in compound 16 are not shown.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

188
SHIKHALIEV et al.
Crystal data for compounds 9 and 16
Compound no.
9
16·CH2Cl2
C33H24N4O2F12Cl2
0.10×0.12×0.18
0.78790
Rhombic
Pbcn
Empirical formula
C16H11N3OCl2
0.03×0.05×0.25
0.80246
Monoclinic
P21/c
Crystal dimensions, mm
λ, nm
Crystal system
Space group
a, A
3.9117(8)
25.109(5)
14.968(3)
90
13.479(3)
11.213(2)
22.552(5)
90
b, Å
c, Å
α, deg
β, deg
97.07(3)
90
90
γ, deg
90
V, Å3
1459.0(5)
4
3408.5(12)
4
Z
Dcalc, g·cm–3
1.512
1.574
μ, mm–1
0.621
0.385
F(000)
680
1632
0.08×0.12×0.25
30.86
0.24×0.18×0.15
31.03
Size, mm
Θmax, deg
Measured reflections
Unique reflections (Rint)
Reflections with I > 2σ(I)
Refined parameter
GOF по F2
22735
34331
3141 (0.068)
2975
3971 (0.062)
2478
201
237
1.065
1.018
R1; wR2 [for reflections with I > 2σ(I)]
R1; wR2 (for all measured reflections )
Extinction coefficient
Tmin/Tmax
0.045; 0.118
0.047; 0.121
0.048(5)
0.850/0.975
0.298/–0.436
0.079; 0.190
0.115; 0.215
0.0077(7)
0.920/0.960
0.521/–0.561
Δρmax/Δρmin, e.Å–3
Molecules 16 in a crystal are held together by strong
hydrogen bonds N2–H2∙∙∙O1 (x–½, y+½, –z+1½) [N∙∙∙O
3.041(4) Å, H∙∙∙O 2.32(4) Å, angle N–H∙∙∙O 152(4)°] to
form layers parallel to the (001) plane. The layers form a
3D framework due to weak nonvalent F1∙∙∙F6 interactions
at a distance of 2.864(2) Å (Fig. 2).
EXPERIMENTAL
The unit cell parameters and reflection intensities
for 9 and 16 were measured on a synchrotron radiation
station, Kuchatov Institute National Research Center,
using a Rayonix SX165 CCD two-coordinate detector
(T 100 K, φ scanning, step 1.0°). The experimental data
were processed using iMOSFLM software in CCP4 [18].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

SYNTHESIS AND STRUCTURAL STUDY OF DICHLORODIAZADIENES
189
Fig. 2. Crystal structures of compounds (а) 9 and (b) 16. Dashed lines show ibtermolecular hydrogen bonds and nonvalent F∙∙∙F in-
teractions.
Absorption was included using the Scala program [19].
The principal crystal data and refinement parameters are
listed in Table 1. The structures were solved by direct
methods and refined by full-matrix least squares on F2
with anisotropic displacement parameters. One of the two
crystallographically independent CF3 groupsis disordered
over three positions with the occupancy ratio of 0.6 : 0.2 :
0.2. The crystal of compound 16 contained dichlorometh-
ane solvent molecules in a 1:1 ratio to the main molecule,
i.e. the composition of the crystal is 16·CH2Cl2. Since the
dichloromethane molecules are strongly disordered, their
contribution in X-ray radiation scattering was included
SQUEEZE software in PLATON 09 [20]. The NH hy-
drogen atom in compound 9 was located objectively on
a difference Fourier map and refined isotropically with
fixed displacement parameters [Uiso(H) = 1.2Ueq(N)]. The
other hydrogen atoms in both compounds were placed in
in geometrically calculated positions and refined riding
on their carrier atoms with isotropic displacement param-
eters [Uiso(H) = 1.5Ueq(C) for CH3 groups and Uiso(H) =
1.2Ueq(C) for the other groups].All calculations were per-
formed using SHELXTL program suite [21]. The atomic
coordinates, bond lengths, bond and torsion angles, and
anisotropic displacement parameters for 9 and 16·CH2Cl2
were deposited at the Cambridge Crystallographic Data
Center (CCDC 1944939 and 1944940, respectively).
UV light. Column chromatography was performed on
Merck silica gel (63–200 μm).
Synthesis of hydrazones (general procedure). Etha-
nol (20–50 mL) and 0.820 g of CH3COONa were added
to phenylhydrazine (5 mmol) in a three-necked flask
equpped with a reflux condenser, dropping funnel, and
thermometer. Aldehyde (5 mmol) was then added drop-
wise, the reaction mixture was refluxed with stirring
for 5–10 min, cooled to room temperature, diluted with
50 mL of water, heated under vigorous stirring to 60°С,
and heating was then was discontinued. After cooling,
the product was filtered off, washed with water (if nec-
essary), and dried for 15–20 h at room temperature. The
1H and 13C NMR spectra of the products are consistent
with published data.
(E)-4-[(4-Methoxybenzylidene)hydrazin-2-yl]-ben-
zonitrile (1). Yield 82%, pearl-colored powder, mp 185–
187°C. 1H NMR spectrum (300 MHz, DMSO-d6), δ, ppm:
3.86 s (3H, OCH3), 6.94 d (2Harom, J 8.7 Hz), 7.12 d
(2Harom, J 8.6 Hz), 7.53 d (2Harom, J 8.6 Hz), 7.63 d
(2Harom, J 8.7 Hz), 7.73 s (1H, CH), 7.88 s (1H, NH).
13C NMR spectrum (75 MHz, DMSO-d6), δ, ppm: 50.8,
96.7, 107.8, 109.6, 115.6, 122.5, 123.5, 129.1, 135.6,
143.4, 156.0.
(E)-1-(4-Methoxybenzylidene)-2-(4-methoxyphe-
nyl)hydrazine (2). Yield 85%, dark yellow powder, mp
119–120°C. 1H NMR spectrum (300 MHz, DMSO-d6),
δ, ppm: 3.68 s (3H, CH3), 3.77 s (3H, ОCH3), 6.82 d
(2Harom, J 8.9 Hz), 6.96 t (4Harom, J 9.5 Hz), 7.55 d (2H, J
8.7 Hz), 7.77 s (1H, CH), 9.92 s (1H, NH). 13C NMR spec-
1
The H and 13C NMR spectra were measured on a
Bruker Avance 300 spectrometer at 300 MHz in CDCl3
and DMSO-d6, internal reference TMS. Thin-layer chro-
matography was performed on Silufol UV-254 plates, the
spots were vizualized with acidic KMnO4 solution and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

190
SHIKHALIEV et al.
trum (75 MHz, DMSO-d6), δ, ppm: 55.6, 113.2, 114.5,
115.0, 127.2, 129.1, 135.9, 140.1, 152.7, 159.5, 162.3.
(2Harom, J 8.8 Hz), 7.93 s (1H, CH), 10.85 s (1H, NH).
13C NMR spectrum (75 MHz, DMSO-d6), δ, ppm: 55.6,
113.0, 113.1, 114.6, 115.8, 116.1, 127.4, 128.8, 137.1,
142.7, 159.7.
(E)-1-(4-Methoxybenzylidene)-2-(p-tolyl)hydra-
zine (3). Yield 83%, light pearl-colored powder, mp 105–
106°C. 1H NMR spectrum (300 MHz, DMSO-d6), δ, ppm:
3.68 s (3H, CH3), 3.77 s (3H, ОCH3), 6.82 d (2Harom, J
8.9 Hz), 6.96 t (4Harom, J 9.5 Hz), 7.55 d (2Harom, J 8.7 Hz),
7.77 s (1H, CH), 9.92 s (1H, NH). 13C NMR spectrum
(75 MHz, DMSO-d6) δ, ppm: 20.6, 55.6, 112.2, 114.6,
127.3, 129.0, 129.9, 136.3, 143.8, 157.7, 159.6.
Synthesis of {[(2,2-dichloro-1-phenylvinyl)dia-
zenyl]phenyl}methanes. Dimethyl sulfoxide (10–
12 mL), TMEDA (290 mg, 1.25 mol), CuCl (6 mg,
3 mol %), and CCl4 (4–5 mol, 1.5 g) were added in succes-
sion to 1 mmol of the starting hydrazone, and the reaction
mixture was magnetically stirred. The reaction progress
was monitored by TLC. After completion of the reaction
(most commonly, in 1.5–3 h), the reaction mixture was
transferred into a separatory funnel, diluted with 50–
60 mL of water, and treated with methylene chloride
(3 × 15 mL). The organic phase was washed with water
(3 × 50 mL) and saturated NaCl (1 × 50 mL), dried over
Na2SO4 or MgSO4, filtered, and evaporated in a vacuum.
The residue was separated by column chromatography
(eluent dichloromethane–hexane, 1 : 5), and the fractions
containing the main products were separated by TLC.
(E)-1-(4-Methoxybenzylidene)-2-(4-nitrophenyl)-
hydrazine (4). Yield 87%, burgundy powder, mp
152–155°C. 1H NMR spectrum (300 MHz, DMSO-d6),
δ, ppm: 3.80 s (3H, OCH3), 7.00 d (2Harom, J 8.6 Hz),
7.14 d (2Harom, J 8.8 Hz), 7.68 d (2Harom, J 8.5 Hz), 8.02 s
(1H, CH), 8.11 d (2Harom, J 9.0 Hz), 11.25 s (1H, NH). 13C
NMR spectrum (75 MHz, DMSO-d6), δ, ppm: 55.7, 111.4,
114.7, 126.6, 127.7, 128.5, 138.3, 142.4, 151.3, 160.7.
(E)-1-(3,5-Dimethylphenyl)-2-(4-methoxybenzyl-
idene)hydrazine (5). Yield 91%, caramel-colored
powder, mp 112–115°C. 1H NMR spectrum (300 MHz,
DMSO-d6), δ, ppm: 2.32 s (6H, CH3), 3.86 s (3H, OCH3),
6.54 s (1Harom), 6.75 s (2H, CH, NH), 6.93 d (3Harom, J
8.5 Hz), 7.62 d (3Harom, J 7.4 Hz). 13C NMR spectrum
(75 MHz, DMSO-d6), δ, ppm: 21.1, 55.5, 114.1, 120.9,
124.3, 131.7, 133.9, 139.2, 152.4, 152.7, 159.9, 162.3.
(E)-4-{[2,2-Dichloro-1-(4-methoxyphenyl)vinyl]-
diazenyl}benzonitrile (9). Yield 73%, orange crystals,
mp 197–198°C. 1H NMR spectrum (300 MHz, CDCl3),
δ,ppm:3.93–3.83m(3H),7.07–6.89m(2Harom),7.17–7.08m
(2Harom), 7.44–7.30 m (2Harom), 7.54 d (1Harom, J 7.0 Hz),
7.70–7.59 m (1Harom). 13C NMR spectrum (75 MHz,
CDCl3), δ, ppm: 14.1, 29.7, 55.5, 113.8, 115.0, 115.4,
130.3, 130.3, 130.5, 133.1, 133.8, 153.8.
(E)-1-(4-Fluorophenyl)-2-(4-methoxybenzylidene)-
hydrazine (6). Yield 69%, pearl-colored powder, mp
142–145°C. 1H NMR spectrum (300 MHz, DMSO-d6),
δ, ppm: 3.78 s (3H, OCH3), 6.95 d (2Harom, J 8.7 Hz),
7.07–6.99 m (4Harom), 7.58 d (2Harom, J 8.7 Hz), 7.81 s
(1H, CH), 10.13 s (1H, NH). 13C NMR spectrum (75 MHz,
DMSO-d6), δ, ppm: 55.6, 113.0, 113.1, 114.6, 115.8,
116.1, 127.5, 128.8, 137.1, 142.7.
(E)-1-[2,2-Dichloro-1-(4-methoxyphenyl)vinyl]-
2-(4-methoxyphenyl)diazine (10). Yield 80%, orange
crystals, mp 136–138°C. 1H NMR spectrum (300 MHz,
CDCl3), δ, ppm: 3.87 s (3H, OCH3), 3.88 s (3H, OCH3),
7.01–6.91 m (4Harom), 7.14 d (2Harom, J 8.7 Hz), 7.79 d
(2Harom, J 9.0 Hz). 13C NMR spectrum (75 MHz, CDCl3),
δ, ppm: 50.9, 51.5, 109.5, 110.5, 119.9, 120.8, 128.1,
142.4, 147.6, 155.2, 157.7, 158.3.
(E)-1-(2,4-Dichlorophenyl)-2-(4-methoxybenzyl-
idene)hydrazine (7). Yield 71%, white material, mp
141–144°C. 1H NMR spectrum (300 MHz, DMSO-d6),
δ, ppm: 3.75 s (3H, OCH3), 6.95 d (2Harom, J 8.7 Hz),
7.07–7.00 m (4Harom), 7.58 d (2Harom, J 8.7 Hz), 7.81 s
(1H, CH), 10.13 s (1H, NH). 13C NMR spectrum (75 MHz,
DMSO-d6), δ, ppm: 55.6, 113.1, 114.6, 115.8, 116.1,
127.5, 128.8, 137.1, 142.7, 154.5, 157.6, 159.7.
(E)-1-[2,2-Dichloro-1-(4-methoxyphenyl)vinyl]-
2-(p-tolyl)diazine (11). Yield 78%, dark orange crystals,
mp 122–124°C. 1H NMR spectrum (300 MHz, CDCl3),
δ, ppm: 2.34 s (3H,CH3), 3.87 s (3H, OCH3), 6.98–6.90 m
(1Harom), 7.15 d.t (5Harom, J 18.8, 9.4 Hz), 7.63 d (2Harom
,
J 8.6 Hz). 13C NMR spectrum (75 MHz, CDCl3), δ, ppm:
14.2, 20.7, 29.7, 55.3, 60.9, 113.3, 113.9, 114.0, 129.7,
129.8, 129.9.
(E)-1-(3,5-Bis(trifluoromethyl)phenyl)-2-(4-me-
thoxybenzylidene)hydrazine (8). Yield 77%, pearl-
(E)-1-[2,2-Dichloro-1-(4-methoxyphenyl)vinyl]-
2-(4-nitrophenyl)diazine (12). Yield 75%, dark bur-
1
colored powder, mp 125–127°C. H NMR spectrum
1
(300 MHz, DMSO-d6), δ, ppm: 3.79 s (3H, OCH3), 6.99 d
(2Harom, J 8.8 Hz), 7.27 s (1Harom), 7.52 s (2Harom), 7.66 d
gundy crystals, mp 170–173°C. H NMR spectrum
(300 MHz, CDCl3), δ, ppm: 3.88 s (3H, OCH3), 6.99 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

SYNTHESIS AND STRUCTURAL STUDY OF DICHLORODIAZADIENES
191
(Harom, J 8.7 Hz), 7.13 d (2Harom, J 8.7 Hz), 7.91 d (2Harom
,
REFERENCES
J 8.9 Hz), 8.33 d (2Harom, J 8.9 Hz). 13C NMR spectrum
(75 MHz, CDCl3), δ, ppm: 14.1, 22.6, 29.7, 55.2, 113.8,
123.7, 124.6, 148.8, 155.9, 160.0, 162.3.
1. Shastin, A.V., Korotchenko, V.N., Nenaidenko, V.G.,
and Balenkova, E.S., Russ. Chem. Bull., 1999,
vol. 48, p. 2184.
https://doi.org/10.1007/s11172-006-0030-8
(E)-1-[2,2-Dichloro-1-(4-methoxyphenyl)vinyl]-
2-(3,5-dimethylphenyl)diazine (13). Yield 73%, orange
crystals, mp 124–126°C. 1H NMR spectrum (300 MHz,
CDCl3), δ, ppm: 2.32 s (6H, CH3), 3.80 s (3H, CH3),
6.99 d (2Harom, J 8.8 Hz), 7.20–7.10 m (3Harom), 7.31 s
(2Harom). 13C NMR spectrum (75 MHz, CDCl3), δ, ppm:
21.1, 55.5,114.1, 120.9, 124.3, 131.7, 133.9, 139.2, 152.4,
152.8, 159.9.
2. Shastin, A.V., Korotchenko, V.N., Nenaidenko, V.G.,
and Balenkova, E.S., Tetrahedron, 2000, vol. 56,
p. 6557.
https://doi.org/10.1016/S0040-4020(00)00606-2
3. Shastin, A.V., Korotchenko, V.N., Nenaidenko, V.G., and
Balenkova, E.S., Synthesis, 2001, p. 2081.
https://doi.org/10.1007/s11172-011-0359-5
4. Korotchenko, V.N., Shastin, A.V., Nenajdenko, V.G.,
and Balenkova, E.S., J. Chem. Soc. Perkin Trans. 1,
2002, p. 883.
(E)-1-[2,2-Dichloro-1-(4-methoxyphenyl)vinyl]-
2-(4-fluorophenyl)diazine (14). Yield 71%, orange
crystals, mp 155–156°C. 1H NMR spectrum (300 MHz,
CDCl3), δ, ppm: 3.84 s (3H, OCH3), 6.95 d (2Harom, J
8.6 Hz), 7.16–7.06 m (4Harom), 7.79 d.d (2Harom, J 8.7,
5.4 Hz). 13C NMR spectrum (75 MHz, CDCl3), δ, ppm:
50.6, 109.0, 111.3, 111.6, 119.6, 120.6, 120.7, 126.7,
155.1, 157.7.
https://doi.org/10.1039/B201131J
5. Korotchenko, V.N., Shastin, A.V., Nenajdenko, V.G.,
and Balenkova, E.S., Org. Biomol. Chem., 2003,
p. 1906.
https://doi.org/10.1039/B303221C
6. Nenajdenko, V.G., Shastin, A.V., Korotchenko, V.N.,
Varseev, G.N., and Balenkova, E.S., Eur. J. Org. Chem.,
2003, p. 302.
(E)-1-[2,2-Dichloro-1-(4-methoxyphenyl)ethyl]-
2-(2,4-dichlorophenyl)diazine (15). Yield 68%, orange
crystals, mp 151–152°C. 1H NMR spectrum (300 MHz,
CDCl3), δ, ppm: 3.87 s (3H, OCH3), 6.94 d.d (2Harom, J
https://doi.org/10.3103/S0027131411060071
7. Nenajdenko, V.G., Varseev, G.N., Korotchenko, V.N.,
Shastin, A.V., and Balenkova, E.S., J. Fluorine Chem.,
2003, vol. 124, p. 115.
17.0, 8.8 Hz), 7.18 d (2Harom, J 8.8 Hz), 7.31 d (1Harom
,
J 2.1 Hz), 7.54–7.48 m (1Harom), 7.64–7.56 m (1Harom).
13C NMR spectrum (75 MHz, CDCl3), δ, ppm: 14.1,
22.7, 29.7, 31.9, 55.2, 113.5, 113.8, 118.4, 127.7, 128.0,
130.0, 130.4, 131.5.
https://doi.org/10.1016/S0022-1139(03)00199-4
8. Muzalevskiy, V.N., Shastin, A.V., Demidovich, A.D.,
Shikhaliev, N.G., Magerramov, A.M., Khrustalev, V.N.,
Rakhimov, R.D., Vatsadze, S.Z., and Nenajdenko, V.G.,
Beilstein J. Org. Chem., 2015, vol. 11, p. 2072.
https://doi.org/10.3762/bjoc.11.223
(1Z,2Z)-1,2-Bis{2-[3,5-bis(trifluoromethyl)phenyl]-
hydrazinylidene}-1,2-bis(4-methoxyphenyl)ethane
(16). Yield 65%, coral-colored crystals, mp 118–120°C.
1H NMR spectrum (300 MHz, CDCl3), δ, ppm: 3.89 d
9. Muzalevskiy, V.M., Shikhaliev, N.G., Magerramov,A.M.,
Gurbanova, N.V., Geydarova, S.D., Balenkova, E.S.,
Shastin, A.V., and Nenajdenko, V.G., Russ. Chem. Bull.,
2013, vol. 62, p. 678.
(6Harom, J1.3 Hz), 7.00 d (4Harom, J8.7 Hz), 7.13 d (4Harom
,
J 8.7 Hz), 7.52 m (2Harom), 7.96 s (2Harom), 8.23 s
(4H). 13C NMR spectrum (75 MHz, CDCl3), δ, ppm: 25.1,
50.6, 109.2, 118.6, 118.9, 119.5, 125.4, 126.6, 127.8,
148.5, 155.4.
https://doi.org/10.1007/s11172-013-0091-4
10. Muzalevskiy, V.M., Magerramov, A.M., Shikhaliev, N.G.,
Balenkova, E.S., Shastin, A.V., Dorovatoskii, P.V.,
Zubavitchus, Y.V., Khrustalev, V.N., and Nenajdenko, V.G.,
Russ. Chem. Bull. Int. Ed., 2016, vol. 65, p. 1541.
https://doi.org/10.1007/s11172-016-1480-2
FUNDING
The work was financially supported by the Russian Foun-
dation for Basic Research (project no. 16-29-10669), Ministry
for Education and Science of the Russian Federation (project
no. 4.1154.2017/4.6), and Science Development Founda-
tion under the President of the Republic of Azerbaijan (grant
no. EİF-BGM-4-RFTF-1/2017-21/13/4).
11. Nenajdenko, V.G., Shastin, A.V., Gorbachev, V.M., Sho-
runov, S.V., Muzalevskiy, V.M., Lukianova, A.I., and
Dorovatovskii, P.V., ACS Catal., 2017, vol. 7, p. 205.
https://doi.org/10.1021/acscatal.6b03196
CONFLICT OF INTEREST
12. Shastin, A.V., Tsyrenova, B.D., Sergeev, P.G., Roznya-
tovsky, V.A., Smolyar, I.V., Khrustalev, V.N., and Ne-
The authors declare no conflict of interest.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

192
SHIKHALIEV et al.
Mahmudov, K.T., and Pombeiro, A.J.L., Cryst. Eng. Comm.,
najdenko, V.G., Org. Lett., 2018, vol. 20, p. 7803.
https://doi.org/10.1021/acs.orglett.8b03227
2019, vol. 21, p. 5032.
13. Shastin, A.V., Sergeev, P.G., Lukianova, A.I., Muzalev-
skiy, V.M., Khrustalev, V.N., Dorovatovskii, P.V., and Nena-
jdenko, V.G., Eur. J. Org. Chem., 2018, vol. 36, p. 4996.
https://doi.org/10.1002/ejoc.201800441
14. Shikhaliyev, N.G., Ahmadova, N.E., Gurbanov, A.V., Ma-
harramov, A.M., Mammadova, G.Z., Nenajdenko, V.G.,
Zubkov, F.I., Mahmudov, K.T., and Pombeiro, A.J.L.,
Dyes Pigm., 2018, vol. 150, p. 377.
https://doi.org/10.1039/C9CE00956F
17. Shikhaliyev, N.G., Suleymanova, G.T., İsrayilova, A.A.,
Ganbarov, Kh.G., Babayeva, G.V., Garazadeh, Kh.A.,
Mammadova, G.Z., and Nenajdenko, V.G., Arkivoc,
2019, vol. vi, p. 64.
https://doi.org/10.24820/ark.5550190.p010.979
18. Battye, T.G., Kontogiannis, L., Johnson, O., Powell, H.R.,
and Leslie, A.G.W., Acta Cryst. D, 2011, vol. 67, p. 271.
https://doi.org/10.1107/S0907444910048675
19. Spek, A.L., PLATON, A Multipurpose Crystallographic
Tool, Utrecht University, the Netherlands, 2009.
20. Evans, P., Acta Cryst. D, 2006, vol. 62, p. 72.
https://doi.org/10.1107/s0907444905036693
21. Sheldrick, G.M., Acta Cryst. C, 2015, vol. 71, p. 3.
https://doi.org/10.1107/S2053229614024218
https://doi.org/10.1016/j.dyepig.2017.12.033
15. Maharramov, A.M., Shikhaliyev, N.G., Suleymanova, G.T.,
Gurbanov, A.V., Babayeva, G.V., Mammadova, G.Z.,
Zubkov, F.I., Nenajdenko, V.G., Mahmudov, K.T., and
Pombeiro, A.J.L., Dyes Pigm., 2018, vol. 159, p. 135.
https://doi.org/10.1016/j.dyepig.2018.06.022
16. Shikhaliyev, N.G., Kuznetsov, M.L., Maharramov, A.M.,
Gurbanov, A.V., Ahmadova, N.E., Nenajdenko, V.G.,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020