Formyl Derivatives of Amino-Substituted Polyfluorotriphenyl-4,5-dihydro-1H-pyrazoles: Synthesis and Use as Donor Blocks of Nonlinear Optical Chromophores

Article abstract of DOI:10.1134/S1070428019100087

A series of new formyl derivatives of polyfluorinated triphenyl-4,5-dihydro-1H-pyrazoles containing various amine residues in the fluorinated benzene ring have been synthesized and used as donor building blocks in the synthesis of donor–acceptor dyes as potential chromophores for nonlinear electro-optics. Effects of substituents in the donor and acceptor moieties of the obtained chromophores on their spectral characteristics have been studied.

Full text of DOI:10.1134/S1070428019100087

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 10, pp. 1504–1517. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 10, pp. 1551–1566.
Formyl Derivatives of Amino-Substituted Polyfluorotriphenyl-
4,5-dihydro-1H-pyrazoles: Synthesis and Use as Donor Blocks
of Nonlinear Optical Chromophores
V. V. Shelkovnikova, b, N. A. Orlovaa,* I. Yu. Kargapolovaa, K. D. Erinc,
A. M. Maksimova, and A. A. Chernonosovd
a Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch,
Russian Academy of Sciences, Novosibirsk, Russia
*e-mail: ona@nioch.nsc.ru
b Novosibirsk State Technical University, Novosibirsk, Russia
c Tomsk Polytechnic University, Tomsk, Russia
d Institute of Chemical Biology and Fundamental Medicine, Siberian Branch, Russian Academy of Sciences,
Novosibirsk, Russia
Received April 10, 2019; revised August 14, 2019; accepted August 15, 2019
Abstract—A series of new formyl derivatives of polyfluorinated triphenyl-4,5-dihydro-1H-pyrazoles con-
taining various amine residues in the fluorinated benzene ring have been synthesized and used as donor
building blocks in the synthesis of donor–acceptor dyes as potential chromophores for nonlinear electro-optics.
Effects of substituents in the donor and acceptor moieties of the obtained chromophores on their spectral
characteristics have been studied.
Keywords: formylation, polyfluorotriarylpyrazolines, donor–acceptor structures, nonlinear optical chromo-
phores, electronic absorption spectra.
DOI: 10.1134/S1070428019100087
Dipolar chromophores with a high molecular
polarizability are promising for the design of nonlinear
optical (NLO) materials used in electro-optical mod-
ulators [1–3]. Such properties are intrinsic to unsym-
metrical polymethine dyes containing strong electron-
withdrawing and electron-donating groups as terminal
fragments [4–6]. Donor fragments of these dyes are
commonly obtained from dialkylamino-substituted
aromatic aldehydes as starting materials. We propose
to build up donor fragments from aldehydes of the
polyfluorinated triaryldihydropyrazole series, which
can be regarded as heterocyclic analogs of dialkyl-
aminobenzaldehydes. Pyrazole derivatives have
already been reported as donor moieties of NLO
chromophores [7]; in these cases, the aldehyde group
was directly linked to the pyrazole ring.
substituents provides the possibility of further func-
tionalization via replacement of fluorine atoms by
various nucleophilic groups [9, 10]. Formyl derivatives
of perfluorophenyl-substituted dihydropyrazoles were
used by us to obtain styryl type chromophores con-
taining thioflavylium groups as acceptor moieties [11].
In this work we synthesized new aldehydes on the
basis of polyfluorinated triaryldihydropyrazoles con-
taining various amino groups in the fluorinated phenyl
ring and used them in the synthesis of NLO chromo-
phores. The amine residues were derived from piperi-
dine, dibutylamine, and piperazine. Replacement of the
para-fluorine atom in pentafluorophenyl ring by
an electron-donating group reduces its acceptor power,
and the donor substituent nature affects such important
properties of the resulting chromophore as solubility,
thermal stability, film-forming ability, and spectral
characteristic. A spirocyclic fragment usually improves
film-forming properties, whereas dibutylamino group
increases the solubility and makes it possible to com-
We previously synthesized polyfluorinated triaryl-
dihydropyrazoles [8] which showed strong fluores-
cence and enhanced photostability in comparison to
fluorine-free analogs. The presence of perfluorophenyl
1504

FORMYL DERIVATIVES OF AMINO-SUBSTITUTED
1505
pare nonlinear optical and electro-optical properties of
the chromophore with those of analogous dye derived
from 4-(dibutylamino)benzaldehyde [12]. The pres-
ence of functional groups in the substituent gives rise
to additional ways of further modification. For in-
stance, 4-hydroxypiperidine and piperazine fragments
can be subjected to acylation, in particular with
a branched reagent to obtain a dendritic structure.
of the para-fluroine atom in the fluorinated benzene
ring of 3a by secondary amine. We thus obtained
aldehydes 3b–3e (Scheme 1). When the formylation
was preceded by substitution of fluorine in 2a by
4-hydroxypiperidine residue, the subsequent reaction
of 2c with POCl3/DMF was accompanied by replace-
ment of the hydroxy group by chlorine to give alde-
hyde 3f. The fluorine atom in both 2a and 3a was
readily replaced by piperidine residue; however, we
succeeded in introducing dibutylamino group only into
the initial chalcone 1a molecule (Scheme 1).
In the general case, the synthesis of aldehydes
based on polyfluorinated triaryldihydropyrazoles in-
cluded three stages: (1) condensation of pentafluoro-
benzylideneacetophenone 1a with phenylhydrazine
to give dihydropyrazole 2a, (2) Vilsmeier formylation
of 2a to aldehyde 3a, and (3) nucleophilic substitution
It is known that electro-optical properties of
chromophores are largely determined by the presence
of bulky spacers, including those with a branched
Scheme 1.
O
F
PhNHNH2
EtOH, ∆, 6 h
Ph
F
N
Ph
Ph
N
1a
2a
X
N
NH
F
F
X
POCl3/DMF
90–100°C
DMF, 60°C
N
N
Ph
Ph
N
N
CHO
CHO
3a
3b–3e
2a
X
N
NH
X
POCl3/DMF
90–100°C
F
DMF, 60°C
3b, 3f
N
Ph
Ph
2b, 2c
N
NBu2
NBu2
O
F
F
Bu2NH
DMF, 60°C
POCl3/DMF
90–100°C
PhNHNH2
Ph
1a
F
N
N
Ph
Ph
Ph
NBu2
N
N
CHO
1b
2e
3g
2, 3, X = CH2 (b), CHOH (c), 1,3-dioxolane-2,2-diyl (d), NH (e), CHCl (f).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

SHELKOVNIKOV et al.
1506
Scheme 2.
O
Ph
N
F
O
Ph
PhCOCl, Et3N
PhH/PhMe, ∆
3c
N
N
6–15%
CHO
3h
O
CF3
N
F
N
S
F
TAFSCl, Et3N
PhH, ∆
Ph
Me
3e
N
N
S
F
CHO
F3C
3i
(dendritic) structure, in both donor and acceptor
moieties [12]. We modified the donor moiety by
acylation of the hydroxypiperidine fragment of 3c with
benzoyl chloride in boiling benzene or toluene in the
presence of triethylamine. However, the yield of 3h
was poor (6% in benzene and 15% in toluene), and the
most part of initial aldehyde 3c remained unchanged.
The acylation of piperazine derivative 3e with a den-
dritic agent, 4-methyl-3,5-bis{[2,3,5,6-tetrafluoro-4-
(trifluoromethyl)phenylsulfanyl]methyl}benzoyl
chloride (TAFSCl, Toluic Acid, Fluorinated Sulfide,
Chloride) in benzene in the presence of Et3N afforded
amide 3i (Scheme 2).
In order to compare the reactivities of regioisomeric
aldehydes containing a polyfluorinated phenyl ring in
position 3 or 5 of the dihydropyrazole heterocycle and
spectral characteristics of chromophores obtained
therefrom, we synthesized aldehydes 4a–4c according
to a similar scheme starting from dihydropyrazole 5
(Scheme 3).
Aldehydes 3b–3i, 4b, and 4d were then used as
donor blocks in the synthesis of chromophores. The
acceptor moieties of NLO chromophores are generally
obtained from furan or pyrrole derivatives with elec-
tron-withdrawing substituents such as cyano and/or
trifluoromethyl groups. As shown previously [12],
Scheme 3.
Ph
Ph
N
POCl3/DMF
100°C
N
Ph
N
N
F
F
CHO
5
4a
Ph
Ph
NH
, DMF
X
TAFSCl
N
N
N
N
F
F
N
CHO
N
CHO
X
N
TAFS
4b, 4c
4d
4, X = CH2 (b), NH (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

FORMYL DERIVATIVES OF AMINO-SUBSTITUTED
1507
chromophores with pyrrole-based acceptor moieties
are characterized by a considerable red shift (up to
100 nm) of the long-wavelength absorption maximum
in comparison to furan derivatives. Therefore, we used
2-(3-cyano-4-methyl-5-oxo-1,5-dihydro-2H-pyrrol-2-
ylidene)propanedinitrile (6, TCP) [12] to build up the
acceptor moiety. By condensation of 3b–3i with TCP
we obtained dyes 7a–7d which were further modified
at the pyrrole NH group by treatment with diethyl sul-
fate, benzyl chloride, benzoyl chloride, and TAFSCl.
As a result, chromophores 8a–8j were synthesized
(Scheme 4). We failed to introduce two TAFS frag-
ments into molecule 3c by simultaneous acylation of
the hydroxy group in the piperidine residue and nitro-
gen atom of the dihydropyrrole ring, and the product
contained only one TAFS residue on the nitrogen atom.
However, the acylation of piperazine derivative 7c
with TAFSCl gave dye 8g containing two dendritic
fragments in the donor and acceptor moieties. Like-
wise, from aldehydes 4b and 4d we obtained dyes 9a,
9b, 10a, and 10b (Scheme 5).
phenyl-4,5-dihydro-1H-pyrazol-1-yl}phenyl)buta-1,3-
diene-1,1,3-tricarbonitrile (11). Obviously, compound
11 is the condensation product of aldehyde 3b and
malononitrile dimer (2-aminoprop-1-ene-1,1,3-tricar-
bonitrile) which is likely to remain in the reaction
mixture in the synthesis of TCP despite twofold excess
of ethyl pyruvate or exist in equilibrium with TCP
(Scheme 6).
The optimal conditions for the reaction of most
aldehydes 3 with TCP were stirring of the reaction
mixture at 50–55°C for 4–5 h; the highest yield of 7
was thus attained. For instance, the yield of 7a was
only 22% when the reaction mixture was refluxed for
1 h [12], and it increased to 42% at 55°C. Regardless
of the conditions, only traces of the target dye were
detected in the reaction with aldehyde 3d containing
a 1,4-dioxa-8-azaspiro[4.5]decane residue, whereas the
initial aldehyde remained mostly unchanged. Com-
pounds 4b and 4d in which the fluorinated benzene
ring is attached to C3 of the pyrazole ring and is
conjugated to the aldehyde group also exhibited low
reactivity toward TCP.
The yields of 7 and 9 did not exceed 50%, and in all
cases the reaction mixtures contained a bright orange
impurity. The latter was isolated in the synthesis of 7a
from 3b and TCP and was identified as 2-amino-4-(4-
{5-[4-(piperidin-1-yl)-2,3,5,6-tetrafluorophenyl]-3-
The structure of the synthesized dyes and their
precursors was determined on the basis of their 1H and
19F NMR and mass spectra. The 1H NMR spectra of all
compounds displayed signals of three protons of the
Scheme 4.
R1
R1
R2
R2
N
N
F
F
O
Me
NC
N
N
3b–3i, EtOH
NH
Ph
Ph
N
N
O
O
R3
CN
NH
N
NC
CN
CN
NC
NC
NC
NC
6, TCP
7a–7d
8a–8j
O
TAFS =
S
Me
S
F
F
F3C
CF3
7, R1R2N = piperidin-1-yl (a), 4-hydroxypiperidin-1-yl (b), 4-TAFS-piperazin-1-yl (c); R1 = R2 = n-Bu (d); 8, R1R2N = piperidin-
1-yl, R3 = Et (a), PhCH2 (b), PhCO (c), TAFS (d); R1R2N = 4-hydroxypiperidin-1-yl, R3 = TAFS (e); R1R2N = 4-TAFS-piperazin-
1-yl, R3 = Et (f), TAFS (g); R1 = R2 = n-Bu, R3 = Et (h), PhCO (i), TAFS (j).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

SHELKOVNIKOV et al.
1508
Scheme 5.
X
X
N
N
F
F
Ph
Ph
N
N
N
N
(EtO)2SO2
K2CO3, MeCN, ∆
6, EtOH
4b, 4d
O
O
NH
N
Et
NC
NC
NC
CN
NC
CN
9a, 9b
10a, 10b
X = CH2 (a), N-TAFS (b).
Scheme 6.
N
O
F
Me
O
NH2
∆
3b
NC
+
NH
OEt
Me
EtOH
NC
NC
NC
CN
N
O
NH2
Ph
CN
N
NC
TCP
CN
NC
11
dihydropyrazole ring as an ABX spin system charac-
terized by one geminal and two vicinal 1H–1H coupling
constants, as well as signals of aromatic protons and
protons of aliphatic and alicyclic fragments present in
their molecules. Protons at the exocyclic double C=C
bond gave rise to an AB system with a coupling
constant 3J of ~16 Hz corresponding to E configuration
1
of the double bond. In the H NMR spectra of 7 in
DMSO-d6, the NH proton resonated as a broadened
downfield signal at about 12.7 ppm. The 19F NMR
spectra contained two signals from four pairwise
equivalent fluorine atoms in the para-substituted tetra-
fluorophenyl ring. The ortho-fluorine signals of com-
pounds with the fluorinated benzene ring on C5 were
strongly broadened, presumably due to steric hin-
drances created by the phenyl substituent on N1; no
such broadening was observed in the spectra of
3-(tetrafluorophenyl) isomers. The 19F NMR spectra of
compounds with TAFS substituents showed additional
triplets of CF3 groups (δF > 100 ppm) and signals of
aromatic fluorines.
λ, nm
Figure 1 shows the electronic absorption spectra of
8h in chloroform at a concentration of about 10–4
M
Fig. 1. Normalized electronic absorption spectra of com-
pounds (1) 8h and (2) 12 in chloroform.
and of its analog 12 [12] with a dibutylaminophenyl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

FORMYL DERIVATIVES OF AMINO-SUBSTITUTED
1509
O
of the 4-hydroxypiperidino group is most appreciable.
On the other hand, the effect of the substituent on the
pyrrole nitrogen atom in the acceptor TCP moiety was
more significant. The absorption maximum of 7a
(NH group) is located at λ 728 nm, while replacement
of the NH hydrogen by ethyl, benzyl, benzoyl, and
TAFS groups leads to red shift of the absorption
maximum to λ 738, 743, 756, and 768 nm, respec-
tively, in keeping with the acceptor power of the
N-substituent. The effect of substituents in the donor
moiety of chromophores on their spectral character-
istics depended on the position of the polyfluorophenyl
group in the dihydropyrazole ring (C3 or C5), as well as
on the substituent in the fluorinated ring. The positions
of the absorption maxima of regioisomeric piperidine
derivatives are similar (cf. 7a and 9a, 8a and 10a),
whereas the 3-isomers containing a TAFS-piperazine
residue showed a small blue shift of the absorption
maximum relative to that of the corresponding
5-isomers (cf. 7c and 9b, 8f and 10b). Obviously,
introduction of an acceptor dendritic TAFS fragment
into the donor moiety through an alicyclic spacer
insignificantly influences the absorption spectrum. In
particular, compound 8g containing TAFS substituents
in both donor and acceptor moieties absorbs at
λmax 760 nm, i.e., almost in the same region as dye 8j
Et
N
CN
Bu2N
NC
NC
12
substituent as donor fragment. It is seen that the
absorption spectra of 8h and 12 are almost identical to
each other. The most intense long-wavelength band
originates from intramolecular charge transfer involv-
ing orbitals of the donor and acceptor fragments.
Taking into account that the acceptor moieties of 8h
and 12 are similar, the donor power of the dihydro-
pyrazole fragment in the D–A chromophore is similar
to that of the 4-(dibutylamino)phenyl fragment of 12;
therefore, polyfluorinated triaryldihydropyrazole deriv-
atives can be used as efficient donors in the design of
NLO chromophores.
The long-wavelength absorption maxima and molar
absorption coefficients of compounds 7–10 are col-
lected in Table 1. It is seen that the nature of amino
group in the fluorinated ring of 7a–7d (piperidine,
piperazine, 4-hydroxypiperidine, dibutylamine) almost
does not affect the position of the absorption maximum
which is located in the region λ 725–735 nm; the effect
Table 1. Electronic absorption spectra of compounds 7a–7d, 8a–8j, 9a, 9b, 10a, and 10b in chloroform
Compound no.
R1R2N
R3
λmax, nm
logε
07a
07b
07c
07d
08a
08b
08c
08d
08e
08f
Piperidin-1-yl
H
728
735
726
725
731
743
754
769
765
724
760
730
757
763
728
714
733
716
4.84
a
4-Hydroxypiperidin-1-yl
4-TAFS-piperazin-1-yl
Bu2N
H
–
H
4.86
4.81
4.85
4.87
4.87
4.91
4.89
4.80
4.82
4.81
4.91
4.88
4.80
4.83
4.82
H
Piperidin-1-yl
Et
Piperidin-1-yl
PhCH2
PhCO
TAFS
TAFS
Et
Piperidin-1-yl
Piperidin-1-yl
4-Hydroxypiperidin-1-yl
4-TAFS-piperazin-1-yl
4-TAFS-piperazin-1-yl
Bu2N
08g
08h
08i
TAFS
Et
Bu2N
PhCO
TAFS
H
08j
Bu2N
09a
09b
10a
10b
Piperidin-1-yl
4-TAFS-piperazin-1-yl
Piperidin-1-yl
H
Et
a
4-TAFS-piperazin-1-yl
Et
–
a
Not determined.
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SHELKOVNIKOV et al.
1510
(λmax 763 nm) with only one TAFS fragment in the
acceptor moiety.
(98%, Aldrich), diethyl sulfate (>99%, Fluka), pipera-
zine (99%, Aldrich), piperidine (reagent-grade,
Reakhim), triethylamine (99.5%, AppliChem), phenyl-
hydrazine (97%, Acros Organics), and ethyl pyruvate
(98%, Alfa Aesar) were used.
The NLO parameters of materials for electro-
optical modulators are commonly measured at
λ 1310 nm, i.e., in the transparency region of optical
fiber. Shift of absorption spectrum toward that wave-
length can be achieved as a result of extension of con-
jugation chain or/and increase of electron-withdrawing
power of the acceptor moiety. Enhancement of the
acceptor properties of the TCP fragment by introduc-
tion of additional electron-withdrawing substituents
increases charge separation upon excitation of donor–
acceptor chromophore and increases its hyperpolariz-
ability at the molecular level. A relation between large
nonlinear susceptibility values and intramolecular
charge transfer was found in a large number of
examples [13].
5-(Pentafluorophenyl)-1,3-diphenyl-4,5-dihydro-
1H-pyrazole (2a) [9] and 3-(pentafluorophenyl)-1,5-di-
phenyl-4,5-dihydro-1H-pyrazole (5) [11] were syn-
thesized according to reported procedures.
4-Methyl-3,5-bis{[2,3,5,6-tetrafluoro-4-(trifluoro-
methyl)phenylsulfanyl]methyl}benzoyl chloride
(TAFSCl). A suspension of 0.23 g (0.35 mmol) of
4-methyl-3,5-bis{[2,3,5,6-tetrafluoro-4-(trifluoro-
methyl)phenylsulfanyl]methyl}benzoic acid [14] in
10.1 g (84.7 mmol) of thionyl chloride was refluxed
for 5 h and left overnight; the mixture became trans-
parent. Excess thionyl chloride and volatile products
were removed on a rotary evaporator, and the residue
was evacuated with an oil pump at 30–40°C; the prod-
uct crystallized. Yield 0.22 g (93%), colorless crystals
decomposing at 74°C. 1H NMR spectrum (CD3CN), δ,
ppm: 2.58 s (3H, CH3), 4.30 s (4H, CH2), 7.55 s (2H,
In summary, we have synthesized a series of new
aldehydes on the basis of polyfluorinated triaryldihy-
dropyrazoles and shown that these compounds are
promising as donor blocks of donor–acceptor NLO
chromophores with a wide possibility of further
modification.
H
arom). 19F NMR spectrum (CD3CN), δF, ppm: 22.1,
32.0, 107.1 (2:2:3). Mass spectrum: m/z 677.9543
[M]+. C24H9ClF14OS2. Calculated: M 677.9554.
EXPERIMENTAL
3-[4-(Dibutylamino)-2,3,5,6-tetrafluorophenyl]-
1-phenylprop-2-en-1-one (1b). Dibutylamine,
5.93 mL (4.52 g, 35.0 mmol), was added to a solution
of 5.22 g (17.5 mmol) of 3-(pentafluorophenyl)-1-
phenylprop-2-en-1-one (1a) in 30 mL of DMF, and the
mixture was stirred for 5 h at 50–55°C. The mixture
was cooled and extracted with diethyl ether, and the
extract was washed with aqueous ammonium chloride
and water, dried over Na2SO4, and evaporated under
reduced pressure (water-jet pump). Yield 6.35 g (89%),
The spectral and analytical data were obtained at
the Joint Chemical Research Center, Siberian Branch,
1
Russian Academy of Sciences. The H and 19F NMR
spectra were recorded on a Bruker AV-300 instrument
(Germany) at 300.13 and 282.37 MHz, respectively,
using CDCl3 as solvent and reference (CHCl3,
δ 7.24 ppm); the 19F chemical shifts were determined
relative to C6F6. The electronic absorption spectra were
measured on a Hewlett Packard 8453 spectrophotom-
eter (USA) from solutions in chloroform. The high-
resolution mass spectra (electron impact, 70 eV) of
compounds with a molecular weight lower than 800
were recorded on a Thermo Electron DFS GC/MS
instrument (USA) with direct sample admission into
the ion source. The mass spectra of compounds with
a molecular weight higher than 1000 were obtained
with a Bruker Daltonic Autoflex Speed MALDI-TOF
spectrometer (Germany) (positive reflectron mode,
laser frequency 1000 Hz, accelerating voltage 19 kV)
at the Mass Spectrometric Analysis Center of the
Institute of Chemical Biology and Fundamental Medi-
cine, Siberian Branch, Russian Academy of Sciences.
1
cream-colored oil. H NMR spectrum (CDCl3), δ,
ppm: 0.87 t (6H, CH3, J = 7.3 Hz), 1.20–1.35 m (4H,
CH2), 1.42–1.55 m (4H, CH2), 3.24 t (4H, NCH2, J =
7.3 Hz), 7.44–7.59 m (3H, Harom), 7.74 d and 7.81 d
(1H each, CH=CH, J = 16.1 Hz), 7.96–8.03 m (2H,
H
arom). 19F NMR spectrum (CDCl3), δ, ppm: 10.75,
20.08 (1:1). Mass spectrum: m/z 407.1873 [M]+.
C23H25F5NO. Calculated: M 407.1867.
Reaction of 5-(pentafluorophenyl)-1,3-diphenyl-
4,5-dihydro-1H-pyrazole (2a) with piperidine deriv-
atives (general procedure). The corresponding piperi-
dine derivative, 10.30 mmol, was added to a suspen-
sion of 2.0 g (5.15 mmol) of compound 2a in 5 mL of
DMF, and the mixture was stirred for 4 h at a bath
temperature of 60°C. The mixture was cooled in
Commercial acryloyl chloride (97%, Aldrich),
4-hydroxypiperidine (97%, Alfa Aesar), dibutylamine
(99.5%, Aldrich), 1,4-dioxa-8-azaspiro[4.5]decane
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

FORMYL DERIVATIVES OF AMINO-SUBSTITUTED
1511
a refrigerator or poured onto ice, and the precipitate
was filtered off, washed with water and a small amount
of hexane, and dried in air.
described in [11]; the products were purified by silica
gel column chromatography.
4-{3-Phenyl-5-[2,3,5,6-tetrafluoro-4-(piperidin-1-
yl)phenyl]-4,5-dihydro-1H-pyrazol-1-yl}benzalde-
hyde (3b). Yield 74%, cream-colored powder,
1-[4-(1,3-Diphenyl-4,5-dihydro-1H-pyrazol-5-yl)-
2,3,5,6-tetrafluorophenyl]piperidine (2b). Yield
69%, mp 182–183°C; published data [8]: mp 182–
1
mp 203–205°C. H NMR spectrum (CDCl3), δ, ppm:
1
184°C. The H and 19F NMR spectra were identical to
1.51–1.72 m (6H, CH2, pip), 3.11–3.20 m (4H, CH2, pip);
3.33 d.d, 3.87 d.d, and 5.74 d.d (1H each, ABX, Hpyr,
J = 17.4, 12.9, 5.8 Hz); 7.12 d (2H, Harom, J = 8.7 Hz),
7.36–7.45 m (3H, Harom), 7.68–7.78 m (4H, Harom),
9.76 s (1H, CHO). 19F NMR spectrum (CDCl3), δF,
ppm: 11.30, 16.21 (1:1). Mass spectrum: m/z 481.1770
[M]+. C27H23F4N3O. Calculated: M 481.1772.
those reported in [8].
1-[4-(1,3-Diphenyl-4,5-dihydro-1H-pyrazol-5-yl)-
2,3,5,6-tetrafluorophenyl]piperidin-4-ol (2c). Yield
41%, mp 140–143°C; published data [10]: mp 142–
1
145°C. The H and 19F NMR spectra were identical to
those reported in [10].
4-{5-[4-(4-Chloropiperidin-1-yl)-2,3,5,6-tetra-
fluorophenyl]-3-phenyl-4,5-dihydro-1H-pyrazol-
1-yl}benzaldehyde (3f). Yield 62%, light yellow
8-[4-(1,3-Diphenyl-4,5-dihydro-1H-pyrazol-5-yl)-
2,3,5,6-tetrafluorophenyl]-1,4-dioxa-8-azaspiro[4.5]-
decane (2d). Yield 60%, yellow powder, mp 204–
1
needles, mp 190–192°C. H NMR spectrum (CDCl3),
1
206°C (from benzene–hexane, 1:1). H NMR spec-
δ, ppm: 1.88–2.01 m (2H, Hpip), 2.09–2.20 m (2H,
Hpip), 3.06–3.18 (2H, Hpip); 3.35 d.d, 3.90 d.d, and
5.76 d.d (1H each, ABX, Hpyr, J = 17.9, 13.0, 5.6 Hz);
3.40–3.51 m (2H, Hpip), 4.14–4.24 m (1H, CHCl),
7.10–7.15 m (2H, Harom), 7.37–7.46 m (3H, Harom),
7.69–7.78 m (4H, Harom), 9.76 s (1H, CHO). 19F NMR
spectrum (CDCl3), δF, ppm: 11.76, 16.89 (1:1). Mass
spectrum: m/z 515.1377 [M]+. C27H22ClF4N3O. Calcu-
lated: M 515.1382.
trum (CDCl3), δ, ppm: 1.81–1.88 m (4H, CH2, pip),1
3.29–3.40 m (5H, CH2, pip, Hpyr), 3.86 d.d (1H, Hpyr, J =
17.0, 13.2 Hz), 4.02 s (4H, OCH2), 5.72 d.d (1H, Hpyr,
J = 13.2, 6.6 Hz), 6.85 t (1H, Harom, J = 7.3 Hz), 7.11–
7.16 m (2H, Harom), 7.23–7.31 m (2H, Harom), 7.34–
7.49 m (3H, Harom), 7.74–7.82 m (2H, Harom). 19F NMR
spectrum (CDCl3), δF, ppm: 11.19, 16.79 (1:1). Mass
spectrum: m/z 511.1879 [M]+. C28H25F4N3O2. Calcu-
lat-ed: M 511.1877.
4-{5-[4-(Dibutylamino)-2,3,5,6-tetrafluoro-
phenyl]-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl}-
benzaldehyde (3g). Yield 66%, colorless powder,
N,N-Dibutyl-4-(1,3-diphenyl-4,5-dihydro-1H-
pyrazol-5-yl)-2,3,5,6-tetrafluoroaniline (2e). Phenyl-
hydrazine, 2.95 mL (3.24 g, 30 mmol), was added to
2.04 g (5.0 mmol) of chalcone 1b in 70 mL of acetic
acid, and the mixture was refluxed for 6 h. The mixture
was cooled in a refrigerator, and the precipitate was
filtered off, washed with water, and dried in air. Yield
1.74 g. An additional portion of the product containing
80% of 2e (according to the NMR data), 0.54 g, was
isolated from the filtrate. Overall yield 2.17 g (87%),
1
mp 175–178°C. H NMR spectrum (CDCl3), δ, ppm:
0.84 t (6H, CH3, J = 7.2 Hz), 1.17–1.31 m (4H, CH2),
1.34–1.46 m (4H, CH2), 3.11 t (4H, NCH2, J = 7.3 Hz);
3.37 d.d, 3.88 d.d, and 5.75 d.d (1H each, ABX, Hpyr,
J = 17.4, 12.8, 5.7 Hz); 7.11–7.16 m (2H, Harom), 7.35–
7.46 m (3H, Harom), 7.70–7.78 m (4H, Harom), 9.75 s
(1H, CHO). 19F NMR spectrum (CDCl3), δF, ppm:
13.07, 16.29 (1:1). Mass spectrum: m/z 525.2402
[M]+. C30H31F4N3O. Calculated: M 525.2398.
1
colorless powder, mp 127–129°C. H NMR spectrum
(CDCl3) δ, ppm: 0.85 t (6H, CH3, J = 7.3 Hz), 1.18–
1.32 m (4H, CH2), 1.33–1.46 m (4H, CH2), 3.11 t (4H,
NCH2, J = 7.2 Hz); 3.33 d.d, 3.82 d.d, and 5.67d.d (1H
each, ABX, Hpyr, J = 17.3, 13.1, 6.6 Hz); 6.77–6.84 m
(1H, Harom), 7.06–7.42 m (7H, Harom), 7.70–7.76 m
(2H, Harom). 19F NMR spectrum (CDCl3), δF, ppm:
12.67, 16.43 (1:1). Mass spectrum: m/z 497.2444
[M]+. C29H31F4N3. Calculated: M 497.2449.
4-[3-(Pentafluorophenyl)-5-phenyl-4,5-dihydro-
1H-pyrazol-1-yl]benzaldehyde (4a). Yield 56%,
1
yellow powder, mp 124–127°C. H NMR spectrum
(CDCl3), δ, ppm: 3.28 d.d, 3.99 d.d, and 5.43 d.d (1H
each, ABX, Hpyr, J = 18.0, 12.4, 5.8 Hz); 7.10 d (2H,
H
arom, J = 8.6 Hz), 7.22–7.34 m (5H, Harom), 7.68 d
(2H, Harom, J = 8.6 Hz), 9.74 s (1H, CHO). 19F NMR
spectrum (CHCl3), δF, ppm: 0.21, 8.86, 23.24 (2:1:2).
Mass spectrum: m/z 416.0954 [M]+. C22H13F5N2O. Cal-
culated: M 416.0943.
The Vilsmeier formylation of dihydropyrazoles 2a–
2e and 5 was carried out according to the procedure
1
Reaction of aldehydes 3a and 4a with alicyclic
Hereinafter, the subscripts “pip,” “pyr,” and “pz” refer to the pi-
peridine, dihydropyrazole, and piperazine protons, respectively.
amines (general procedure). Aldehyde 3a or 4a,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

SHELKOVNIKOV et al.
J = 8.6 Hz), 7.41–7.52 m (3H, Harom), 7.75 d (2H,
1512
0.42 g (1 mmol), was dispersed in 5 mL of DMF,
2 mmol of the corresponding amine was added, and the
mixture was stirred for 6 h at 60°C. The mixture was
poured onto ice, and the precipitate was filtered off and
washed with water and a small amount of hexane. The
product was purified by column chromatography on
silica gel using methylene chloride as eluent.
H
arom, J = 8.6 Hz), 7.78–7.83 m (2H, Harom), 9.71 s
(1H, CHO). 19F NMR spectrum (DMSO-d6), δF, ppm:
11.51, 17.28 (1:1). Mass spectrum: m/z 482.1730 [M]+.
C26H22F4N4O. Calculated: M 482.1724.
4-{5-Phenyl-3-[2,3,5,6-tetrafluoro-4-(piperidin-1-
yl)phenyl]-4,5-dihydro-1H-pyrazol-1-yl}benzalde-
hyde (4b) was synthesized from aldehyde 4a and
piperidine. Yield 83%, yellow crystals, mp 135–137°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.57–1.71 m (6H,
CH2, pip), 3.20–3.31 m (5H, CH2, pip, Hpyr), 3.96 d.d (1H,
Hpyr, J = 18.2, 12.3 Hz), 5.35 d.d (1H, Hpyr, J = 12.3,
5.7 Hz), 7.08 d (2H, Harom, J = 8.8 Hz), 7.20–7.37 m
(5H, Harom), 7.66 d (2H, Harom, J = 8.8 Hz), 9.73 s (1H,
CHO). 19F NMR spectrum (CDCl3), δF, ppm: 9.92,
20.73 (1:1). Mass spectrum: m/z 481.1766 [M]+.
C27H23F4N3O. Calculated: M 481.1772.
4-{3-Phenyl-5-[2,3,5,6-tetrafluoro-4-(piperidin-
1-yl)phenyl]-4,5-dihydro-1H-pyrazol-1-yl}benzal-
dehyde (3b) was synthesized from aldehyde 3a and
piperidine. Yield 67%. The product was identical in the
melting point and NMR spectra to a sample obtained
as described above by formylation of 2b.
4-{3-Phenyl-5-[2,3,5,6-tetrafluoro-4-(4-hydroxy-
piperidin-1-yl)phenyl]-4,5-dihydro-1H-pyrazol-
1-yl}benzaldehyde (3c) was synthesized from alde-
hyde 3a and 4-hydroxypiperidine. Yield 65%, yellow
1
powder, mp 217–220°C. H NMR spectrum
4-{5-Phenyl-3-[2,3,5,6-tetrafluoro-4-(piperazin-
1-yl)phenyl]-4,5-dihydro-1H-pyrazol-1-yl}benzalde-
hyde (4c) was synthesized from aldehyde 4a and
piperazine. Yield 57%, yellow powder, mp 70–72°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.90–3.10 m (4H,
Hpz), 3.17–3.43 m (6H, Hpz, Hpyr, NH), 3.94 d.d (1H,
Hpyr, J = 18.4, 12.4 Hz), 5.35 d.d (1H, Hpyr, J = 12.4,
5.4 Hz), 6.97–7.12 m (2H, Harom), 7.17–7.38 m (5H,
(DMSO-d6), δ, ppm: 1.37–1.52 m (2H, Hpip), 1.73–
1.84 m (2H, Hpip), 2.97–3.09 m (2H, Hpip), 3.25–
3.32 m (2H, Hpip); 3.53 d.d, 4.00 d.d, and 5.97 d.d (1H
each, ABX, Hpyr, J = 17.8, 12.8, 5.2 Hz); 3.57–3.67 m
(1H, Hpip), 4.71 d (1H, OH, J = 4.2 Hz), 7.09 d (2H,
H
arom, J = 8.7 Hz), 7.41–7.53 m (3H, Harom), 7.75 d
(2H, Harom, J = 8.7 Hz), 7.78–7.84 m (2H, Harom),
9.71 s (1H, CHO). 19F NMR spectrum (CDCl3), δF,
ppm: 11.8, 17.24 (1:1). Mass spectrum: m/z 497.1719.
C27H23F4N3O2. Calculated: M 497.1721.
H
arom), 7.61–7.70 m (2H, Harom), 9.72 s (1H, CHO).
19F NMR spectrum (CDCl3), δF, ppm: 10.12, 21.19
(1 : 1). Mass spectrum: m/z 482.1716 [M]+.
C26H22F4N4O. M 482.1724.
4-{5-[4-(1,4-Dioxa-8-azaspiro[4.5]dec-8-yl)-
2,3,5,6-tetrafluorophenyl]-3-phenyl-4,5-dihydro-
1H-pyrazol-1-yl}benzaldehyde (3d) was synthesized
from aldehyde 3a and 1,4-dioxa-8-azaspiro[4.5]-
decane. Yield 0.32 g (39%), colorless powder,
Acylation of aldehydes 3c, 3e, and 4c (general
procedure). Triethylamine, 0.8 mmol (0.11 mL), was
added to a suspension of 0.4 mmol of aldehyde 3c, 3e,
or 4c in 10 mL of anhydrous benzene. The mixture was
heated until it became homogeneous (~40°C), and
a solution of 0.5 mmol of benzoyl chloride or TAFSCl
in 5 mL of benzene was added. The mixture was
refluxed for 5 h, cooled, and treated with benzene, the
benzene solution was washed with water and dried
over MgSO4, and the solvent was removed under
reduced pressure. The residue was dissolved in chloro-
form and subjected to column chromatography on SiO2
or Al2O3; a bright yellow fraction was collected.
1
mp 222–225°C. H NMR spectrum (CDCl3) δ, ppm:
1.70–1.85 m (4H, Hpip), 3.23–3.41 m (5H, Hpip, Hpyr),
3.87 d.d (1H, Hpyr, J = 17.6, 13.0 Hz), 3.97 s (4H,
OCH2), 5.75 d.d (1H, Hpyr, J = 13.0, 5.6 Hz), 7.13 d
(2H, Harom, J = 8.0 Hz), 7.37–7.45 m (3H, Harom), 7.68–
7.78 m (4H, Harom), 9.74 s (1H, CHO). 19F NMR spec-
trum (CDCl3), δF, ppm: 11.55, 16.54 (1:1). Mass spec-
trum: m/z 539.1825 [M]+. C29H25F4N3O3. Calculated:
M 539.1827.
4-{3-Phenyl-5-[2,3,5,6-tetrafluoro-4-(piperazin-
1-yl)phenyl]-4,5-dihydro-1H-pyrazol-1-yl}benzalde-
hyde (3e) was synthesized from aldehyde 3a and
piperazine. Yield 0.35 g (72%), cream-colored powder,
mp 215–218°C. H NMR spectrum (DMSO-d6), δ,
ppm: 2.68–2.81 m (4H, CH2, pz), 3.04–3.14 m (4H,
CH2, pz); 3.52 d.d, 4.02 d.d, and 5.98 d.d (1H each,
1-{2,3,5,6-Tetrafluoro-4-[1-(4-formylphenyl)-
3-phenyl-4,5-dihydro-1H-pyrazol-5-yl]phenyl}-
piperidine-4-yl benzoate (3h) was synthesized from
aldehyde 3c and benzoyl chloride in benzene or
toluene under reflux. Yield 6% (in benzene), 15% (in
toluene); light yellow powder, mp 179–181°C. 1H NMR
spectrum (CDCl3), δ, ppm: 1.85–1.99 m (2H, Hpip),
2.02–2.14 m (2H, Hpip), 3.17–3.29 m (2H, Hpip);
1
ABX, Hpyr, J = 18.0, 12.8, 5.2 Hz), 7.11 d (2H, Harom
,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

FORMYL DERIVATIVES OF AMINO-SUBSTITUTED
1513
3.34 d.d, 3.89 d.d, and 5.75 d.d (1H each, ABX, Hpyr,
J = 17.8, 13.1, 5.7 Hz), 3.40–3.52 m (2H, Hpip), 5.15–
5.24 m (1H, CHOCO), 7.0–7.17 m (2H, Harom), 7.38–
7.47 m (5H, Harom), 7.52–7.59 m (1H, Harom), 7.69–
7.79 m (4H, Harom), 8.00–8.07 m (2H, Harom), 9.75 s
(1H, CHO). 19F NMR spectrum (CDCl3), δF, ppm:
11.73, 16.80 (1:1). Mass spectrum: m/z 601.1984 [M]+.
C34H27F4N3O3. Calculated: M 601.1983.
2-{3-Cyano-5-oxo-4-[(E)-2-(4-{3-phenyl-5-
[2,3,5,6-tetrafluoro-4-(piperidin-1-yl)phenyl]-4,5-di-
hydro-1H-pyrazol-1-yl}phenyl)ethenyl]-1H-pyrrol-
2(5H)-ylidene}propanedinitrile (7a) was synthesized
by reaction of aldehyde 3b with TCP. Yield 42%, blue–
1
green powder, decomposition point ~300°C. H NMR
spectrum (DMSO-d6), δ, ppm: 1.51–1.62 m (6H, Hpip),
3.11–3.18 m (4H, Hpip); 3.57 d.d, 4.03 d.d, and 6.03 d.d
(1H each, ABX, Hpyr, J = 17.4, 12.7, 4.4 Hz); 9.96–
7.14 m (3H, Harom, CH=), 7.42–7.55 m (3H, Harom),
7.70–7.87 m (4H, Harom), 8.35 d (1H, CH=, J =
16.0 Hz), 12.65 br.s (1H, NH). 19F NMR spectrum
(DMSO-d6), δF, ppm: 11.72, 17.28 (1:1). Mass spec-
trum: m/z 647.2048 [M]+. C36H25F4N7O. Calculated:
M 647.2051.
4-(3-Phenyl-5-{2,3,5,6-tetrafluoro-4-[4-(4-meth-
yl-3,5-bis{[2,3,5,6-tetrafluoro-4-(trifluoromethyl)-
phenylsulfanyl]methyl}benzoyl)piperazin-1-yl]-
phenyl}-4,5-dihydro-1H-pyrazol-1-yl)benzaldehyde
(3i) was synthesized from aldehyde 3e and TAFSCl.
Yield 51%, light yellow powder, mp 120–123°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.54 s (3H, CH3),
3.05–4.03 m (10H, Hpz, Hpyr), 4.23 s (4H, SCH2),
5.78 d.d (1H, Hpyr, J = 12.8, 5.5 Hz), 7.09–7.17 m (4H,
Harom), 7.38–7.46 m (3H, Harom), 7.69–7.79 m (4H,
Harom), 9.76 s (1H, CHO). 19F NMR spectrum (CDCl3),
δF, ppm: 11.75, 17.54, 21.98, 30.35, 105.39
(1 : 1 : 2 : 2 : 3). Mass spectrum (MALDI-TOF):
m/z 1123.03 [M – H]+. C50H30F18N4O2S2. M 1124.15.
The ether washings were evaporated under reduced
pressure, and the residue was subjected to chromatog-
raphy on silica gel using chloroform as eluent. From
the bright orange fraction we isolated 0.09 g (30%) of
2-amino-4-(4-{3-phenyl-5-[2,3,5,6-tetrafluoro-4-(pi-
peridin-1-yl)phenyl]-4,5-dihydro-1H-pyrazol-1-yl}-
phenyl)buta-1,3-diene-1,1,3-tricarbonitrile (11) as
orange powder with mp 179–182°C. Electronic ab-
1
sorption spectrum: λmax 486 nm (logε 4.64). H NMR
4-(5-Phenyl-3-{2,3,5,6-tetrafluoro-4-[4-(4-meth-
yl-3,5-bis{[2,3,5,6-tetrafluoro-4-(trifluoromethyl)-
phenylsulfanyl]methyl}benzoyl)piperazin-1-yl]-
phenyl}-4,5-dihydro-1H-pyrazol-1-yl)benzaldehyde
(4d) was synthesized from aldehyde 4c and TAFSCl.
spectrum (acetone-d6), δ, ppm: 1.51–1.72 m (6H, CH2,
pip), 3.14–3.24 m (4H, CH2, pip); 3.60 d.d, 4.15 d.d, and
6.03 d.d (1H each, ABX, Hpyr, J = 18.2, 12.7, 5.3 Hz);
7.22 d (2H, Harom, J = 8.9 Hz), 7.40–7.53 m (3H,
H
arom), 7.80–7.92 m (3H, Harom, CH=), 7.92–8.05 m
1
Yield 77%, yellow powder, mp 190–193°C. H NMR
(2H, Harom). 19F NMR spectrum (acetone-d6), δF, ppm:
12.55, 17.89 (1:1). Mass spectrum: m/z 595.2111 [M]+.
C33H25F4N7. Calculated: M 595.2102.
spectrum (CDCl3), δ, ppm: 2.54 s (3H, CH3), 3.15–
3.60 m (7H, Hpz, Hpyr), 3.68–3.92 m (2H, Hpz), 3.99 d.d
(1H, Hpyr, J = 17.6, 12.4 Hz), 5.38 d.d (1H, Hpyr, J =
12.4, 5.6 Hz), 7.08–7.36 m (9H, Harom), 7.62–7.70 m
(2H, Harom), 9.74 s (1H, CHO). 19F NMR spectrum
(CDCl3), δF, ppm: 10.69, 21.70, 21.95, 30.57, 105.37
(1 : 1 : 2 : 2 : 3). Mass spectrum (MALDI-TOF):
m/z 1124.21 [M]+. C50H30F18N4O2S2. M 1124.15.
When a mixture of 3b and TCP in ethanol was
refluxed for 1 h, the yield of 7a was 22%, and the yield
of 11, 26%.
2-{3-Cyano-5-oxo-4-[(E)-2-(4-{3-phenyl-5-
[2,3,5,6-tetrafluoro-4-(4-hydroxypiperidin-1-yl)-
phenyl]-4,5-dihydro-1H-pyrazol-1-yl}phenyl)-
ethenyl]-1H-pyrrol-2(5H)-ylidene}propanedinitrile
(7b) was synthesized by reaction of 3c with TCP. Yield
Compounds 7a–7e, 9a, and 9b (general proce-
dure). A solution of TCP was prepared as described in
[12] by heating a mixture of 0.15 mL (1.38 mmol) of
ethyl pyruvate and 0.09 g (0.68 mmol) of 2-amino-
prop-1-ene-1,1,3-tricarbonitrile in 5 mL of anhydrous
ethanol under reflux. It was cooled to 50–55°C,
0.48 mmol of aldehyde 3b–3h or 4c was added, and
the mixture was stirred for 3–5 h at that temperature
under argon, the progress of the reaction being
monitored by TLC on Sorbfil plates. The mixture was
cooled, and the product was precipitated with diethyl
ether, filtered off (green solid), washed with diethyl
ether, and dried in air.
1
42%, blue–green powder, mp > 300°C. H NMR spec-
trum (DMSO-d6), δ, ppm: 1.37–1.53 m (2H, Hpip),
1.72–1.85 m (2H, Hpip), 2.97–3.10 m (2H, Hpip), 3.50–
3.67 m (2H, Hpip, Hpyr), 4.03 d.d (1H, Hpyr, J = 17.6,
12.4 Hz), 6.01 d.d (1H, Hpyr, J = 12.4, 5.0 Hz), 6.98–
7.14 m (3H, Harom, CH=), 7.43–7.56 m (3H, Harom),
7.72–7.88 m (4H, Harom), 8.33 d (1H, CH=, J =
15.2 Hz), 12.65 br.s (1H, NH). 19F NMR spectrum
(DMSO-d6), δF, ppm: 11.88, 17.29 (1:1). Mass spec-
trum: m/z 663.2004 [M]+. C36H25F4N7O2. Calculated:
M 663.2000.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

SHELKOVNIKOV et al.
1514
2-(3-Cyano-5-oxo-4-{(E)-2-[4-(3-phenyl-5-
methyl}benzoyl)piperazin-1-yl]phenyl}-4,5-dihy-
dro-1H-pyrazol-1-yl)phenyl]ethenyl}-1H-pyrrol-
2(5H)-ylidene)propanedinitrile (9b) was synthesized
by reaction of aldehyde 4c with TCP (45–50°C, 22 h).
Yield 11%, blue–green powder, mp 238–241°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.55 s (3H, CH3),
3.20–3.94 m (9H, Hpz, Hpyr), 4.04 d.d (1H, Hpyr, J =
15.4, 11.8 Hz), 4.24 s (4H, CH2), 5.46 d.d (1H, Hpyr,
J = 11.8, 4.8 Hz), 7.00 d (1H, CH=, J = 15.5 Hz),
7.06–7.42 m (7H, Harom), 7.48–7.60 m (2H, Harom),
8.40–8.52 m (2H, CH=, NH). 19F NMR spectrum
(CDCl3), δF, ppm: 10.77, 22.09, 22.63, 30.54, 105.53
(1 : 2 : 1 : 2 : 3). Mass spectrum (MALDI-TOF):
m/z 1290.14 [M]+. C59H32F18N8O2S2. Calculated:
M 1290.18.
{2,3,5,6-tetrafluoro-4-[4-(4-methyl-3,5-bis{[2,3,5,6-
tetrafluoro-4-(trifluoromethyl)phenylsulfanyl]-
methyl}benzoyl)piperazin-1-yl]phenyl}-4,5-dihy-
dro-1H-pyrazol-1-yl)phenyl]ethenyl}-1H-pyrrol-
2(5H)-ylidene)propanedinitrile (7c) was synthesized
by reaction of aldehyde 3i with TCP. Yield 31%, blue–
1
green powder, mp 262–265°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.51 s (3H, CH3), 3.12–3.53 m
(6H, Hpz, Hpyr), 3.72–3.99 m (2H, Hpz, Hpyr), 4.34 s
(4H, CH2), 6.06 d.d (1H, Hpyr, J = 12.6, 5.2 Hz), 6.98–
7.11 m (5H, Harom, CH=), 7.46–7.54 m (3H, Harom),
7.72–7.86 m (4H, Harom), 8.32 d (1H, CH=, J =
15.4 Hz). 19F NMR spectrum (DMSO-d6), δF, ppm:
11.98, 17.65, 20.93, 31.34, 106.93 (1:1:2:2:3).
Mass spectrum (MALDI-TOF): m/z 1290.15 [M]+.
C59H32F18N8O2S2. Calculated: M 1290.18.
Modification of chromophores 7 and 9 (general
procedure). A suspension of 0.11 mmol of 7a–7d or 9a
and 0.31 mmol of freshly calcined potassium carbonate
in 3 mL of anhydrous acetonitrile was refluxed for
10 min with stirring in a stream of argon; the mixture
turned dark violet. The corresponding alkylating or
acylating agent, 0.21 mmol, was added (the mixture
changed its color to dark green), and the mixture was
refluxed for 1 h. When the green color disappeared,
an additional 0.21 mmol of the reagent was added, and
the mixture was refluxed for 30 min. It was then
cooled, and the product was precipitated with diethyl
ether, filtered off, washed with water to remove
potassium carbonate, dried in air, and purified by silica
gel column chromatography using methylene chloride
as eluent; the first bright green fraction was collected.
2-{3-Cyano-4-[(E)-2-(4-{5-[4-(dibutylamino)-
2,3,5,6-tetrafluorophenyl]-3-phenyl-4,5-dihydro-
1H-pyrazol-1-yl}phenyl)ethenyl]-5-oxo-1H-pyrrol-
2(5H)-ylidene}propanedinitrile (7d) was synthesized
by reaction of aldehyde 3g with TCP under reflux for
1.5 h. Yield 18%, blue–green powder, decomposition
point ~290°C. 1H NMR spectrum (DMSO-d6), δ, ppm:
0.81 t (6H, CH3, J = 7.3 Hz ), 1.16–1.26 m (4H, CH2),
1.32–1.41 m (4H, CH2), 3.07–3.15 m (4H, CH2);
3.65 d.d, 4.03 d.d, and 6.04 d.d (1H each, ABX, Hpyr,
J = 17.6, 12.5, 2.8 Hz); 7.00–7.11 m (2H, Harom, CH=),
7.45–7.54 m (3H, Harom), 7.74–7.86 m (4H, Harom),
8.3 d (1H, CH=, J = 15.4 Hz), 12.67 br.s (1H, NH).
19F NMR spectrum (DMSO-d6), δF, ppm: 13.20, 17.35
(1 : 1). Mass spectrum: m/z 691.2668 [M]+.
C39H33F4N7O. Calculated: M 691.2627.
2-{3-Cyano-1-ethyl-5-oxo-4-[(E)-2-(4-{3-phenyl-
5-[2,3,5,6-tetrafluoro-4-(piperidin-1-yl)phenyl]-
4,5-dihydro-1H-pyrazol-1-yl}phenyl)ethenyl]-1H-
pyrrol-2(5H)-ylidene}propanedinitrile (8a) was
synthesized from 7a and diethyl sulfate. Yield 62%,
2-{3-Cyano-5-oxo-4-[(E)-2-(4-{5-phenyl-3-
[2,3,5,6-tetrafluoro-4-(piperidin-1-yl)phenyl]-4,5-di-
hydro-1H-pyrazol-1-yl}phenyl)ethenyl]-1H-pyrrol-
2(5H)-ylidene}propanedinitrile (9a) was synthesized
by reaction of aldehyde 4b with TCP (50–52°C, 12 h).
Yield 23%, green powder, decomposition point
~260°C. 1H NMR spectrum (DMSO-d6), δ, ppm: 1.52–
1.69 m (6H, CH2, pip), 3.14–3.32 m (5H, CH2, pip, Hpyr),
4.10 d.d (1H, Hpyr, J = 18.2, 12.0 Hz), 5.78 d.d (1H,
Hpyr, J = 12.0, 5.0 Hz), 6.98–7.45 m (8H, Harom), 7.70–
7.88 m (3H, Harom), 12.72 br.s (NH). 19F NMR spec-
trum (DMSO-d6), δF, ppm: 10.80, 21.90 (1:1). Mass
spectrum: m/z 647.2049 [M]+. C36H25F4N7O. Calculat-
ed: M 647.2051.
1
green powder, mp 297–299°C. H NMR spectrum
(DMSO-d6), δ, ppm: 1.31 t (3H, CH2CH3, J = 7.0 Hz),
1.54–1.68 m (6H, CH2, pip), 3.12–3.21 m (4H, CH2, pip);
3.37 d.d, 3.92 d.d, and 5.79 d.d (1H each, ABX, Hpyr,
J = 17.3, 12.6, 5.3 Hz); 4.10 q (2H, CH2CH3, J =
7 Hz), 7.02 d and 8.45 d (1H each, AB, CH=CH, J =
15.4 Hz), 7.11 d and 7.57 d (2H each, AB, Harom, J =
8.3 Hz), 7.37–7.48 m (3H, Harom), 7.71–7.83 m (2H,
Harom). 19F NMR spectrum (DMSO-d6), δF, ppm: 11.6,
16.4 (1:1). Mass spectrum: m/z 675.2358 [M]+.
C38H29F4N7O. Calculated: M 675.2364.
2-(3-Cyano-5-oxo-4-{(E)-2-[4-(5-phenyl-3-
{2,3,5,6-tetrafluoro-4-[4-(4-methyl-3,5-bis{[2,3,5,6-
tetrafluoro-4-(trifluoromethyl)phenylsulfanyl]-
2-{1-Benzyl-3-cyano-5-oxo-4-[(E)-2-(4-{3-phenyl-
5-[2,3,5,6-tetrafluoro-4-(piperidin-1-yl)phenyl]-4,5-
dihydro-1H-pyrazol-1-yl}phenyl)ethenyl]-1H-pyr-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

FORMYL DERIVATIVES OF AMINO-SUBSTITUTED
1515
rol-2(5H)-ylidene}propanedinitrile (8b) was synthe-
sized from 7a and benzyl chloride. Yield 11%, green
powder, decomposition point ~270°C. H NMR spec-
trum (CDCl3), δ, ppm: 1.56–1.68 m (6H, CH2, pip),
3.17–3.21 m (4H, CH2, pip); 3.38 d.d, 3.93 d.d, and
5.80 d.d (1H each, ABX, Hpyr, J = 17.4, 12.6, 5.3 Hz);
fluoro-4-(4-hydroxypiperidin-1-yl)phenyl]-4,5-dihy-
dro-1H-pyrazol-1-yl}phenyl)ethenyl]-5-oxo-1H-pyr-
rol-2(5H)-ylidene}propanedinitrile (8e) was synthe-
sized from 7b and TAFSCl. Yield 33%, black powder,
1
1
mp 244–246°C. H NMR spectrum (CDCl3), δ, ppm:
1.57–1.70 m (2H, CH2 pip), 1.89–2.00 m (2H, CH2, pip),
2.67 s (3H, CH3), 3.04–3.16 m (2H, CH2, pip), 3.34–
3.46 m (3H, CH2, pip, Hpyr), 3.78–3.88 m (1H, CHpip),
3.94 d.d (1H, Hpyr, J = 18.0, 12.4 Hz), 4.26 s (4H,
SCH2), 5.82 d.d (1H, Hpyr, J = 12.4, 5.1 Hz), 7.04 d
and 8.39 d (1H each, AB, CH=CH, J = 15.4 Hz), 7.09–
7.17 m (2H, Harom), 7.41–7.47 m (3H, Harom), 7.54 s
(2H, Harom), 7.60 d (2H, Harom, J = 8.9 Hz), 7.74–
7.81 m (2H, Harom). 19F NMR spectrum (CDCl3), δF,
ppm: 12.01, 16.77, 22.30, 30.22, 105.42 (1:1:2:2:3).
Mass spectrum (MALDI-TOF): m/z 1305.19 [M]+.
C60H33F18N7O3S2. Calculated: M 1305.18.
5.31 s (2H, CH2Ph), 7.05–7.20 m (5H, 4H, Harom
CH=), 7.29–7.39 m (3H, Harom), 7.40–7.48 m (3H,
,
H
arom), 7.60 d (2H, Harom, J = 8.8 Hz), 7.72–7.80 m
(2H, Harom), 8.51 d (1H, CH=, J = 15.6 Hz). 19F NMR
spectrum (CDCl3), δF, ppm: 11.64, 16.37 (1:1). Mass
spectrum: m/z 737.2538 [M]+. C43H31F4N7O. Calculat-
ed: M 737.2521.
2-{1-Benzoyl-3-cyano-5-oxo-4-[(E)-2-(4-{3-
phenyl-5-[2,3,5,6-tetrafluoro-4-(piperidin-1-yl)-
phenyl]-4,5-dihydro-1H-pyrazol-1-yl}phenyl)-
ethenyl]-1H-pyrrol-2(5H)-ylidene}propanedinitrile
(8c) was synthesized from 7a and benzoyl chloride.
Yield 72%, green powder, decomposition point
2-(3-Cyano-1-ethyl-5-oxo-4-{(E)-2-[4-(3-phenyl-
5-{2,3,5,6-tetrafluoro-4-[4-(4-methyl-3,5-bis-
{[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenylsul-
fanyl]methyl}benzoyl)piperazin-1-yl]phenyl}-4,5-di-
hydro-1H-pyrazol-1-yl)phenyl]ethenyl}-1H-pyrrol-
2(5H)-ylidene)propanedinitrile (8f) was synthesized
from 7c and diethyl sulfate. Yield 15%, green powder,
1
~270°C. H NMR spectrum (CDCl3), δ, ppm: 1.52–
1.62 m (6H, CH2, pip), 3.12–3.20 m (4H, CH2, pip);
3.38 d.d, 3.93 d.d, and 5.79 d.d (1H each, ABX, Hpyr,
J = 17.5, 12.7, 5.1 Hz); 7.01–7.15 m (3H, Harom, CH=),
7.40–7.47 m (3H, Harom), 7.50–7.60 m (4H, Harom),
7.68–7.81 m (3H, Harom), 7.90–7.97 m (2H, Harom),
8.39 d (1H, CH=, J = 15.4 Hz). 19F NMR spectrum
(CDCl3), δF, ppm: 11.34, 16.37 (1:1). Mass spectrum:
m/z 751.2297 [M]+. C43H29F4N7O2. Calculated:
M 751.2313.
1
mp 240–242°C. H NMR spectrum (CDCl3), δ, ppm:
1.31 t (3H, CH2CH3, J = 7.2 Hz), 2.52 s (3H, CH3),
3.22 br.s (6H, CH2,pz); 3.39 d.d, 3.97 d.d, and 5.83 d.d
(1H each, ABX, Hpyr, J = 18.0, 12.8, 5.0 Hz); 3.51–
3.88 m (2H, CH2, pz), 4.10 q (2H, CH2CH3, J = 7.2 Hz),
4.23 s (4H, CH2), 6.95 d and 8.42 d (1H each, AB,
CH=CH, J = 15.4 Hz), 7.05–7.15 m (4H, Harom), 7.41–
7.48 m (3H, Harom), 7.57 d (2H, Harom, J = 8.7 Hz),
7.74–7.80 m (2H, Harom). 19F NMR spectrum (CDCl3),
δF, ppm: 12.30, 17.63, 33.07, 30.44, 105.54
(1 : 1 : 2 : 2 : 3). Mass spectrum (MALDI-TOF):
m/z 1318.13 [M]+. C61H36F18N8O2S2. Calculated:
M 1318.21.
2-{3-Cyano-1-(4-methyl-3,5-bis{[2,3,5,6-tetra-
fluoro-4-(trifluoromethyl)phenylsulfanyl]methyl}-
benzoyl)-4-[(E)-2-(4-{3-phenyl-5-[2,3,5,6-tetra-
fluoro-4-(piperidin-1-yl)phenyl]-4,5-dihydro-1H-
pyrazol-1-yl}phenyl)ethenyl]-5-oxo-1H-pyrrol-
2(5H)-ylidene}propanedinitrile (8d) was synthesized
from 7a and TAFSCl. Yield 33%, green powder,
1
mp 225–228°C. H NMR spectrum (CDCl3), δ, ppm:
1.55–1.67 m (6H, CH2, pip), 2.67 s (3H, CH3), 3.14–
3.21 m (4H, CH2, pip); 3.40 d.d, 3.94 d.d, and 5.82 d.d
(1H each, ABX, Hpyr, J = 17.5, 12.5, 5.3 Hz); 4.27 s
(4H, CH2), 7.02 d and 8.37 d (1H each, AB, CH=CH,
2-(3-Cyano-1-(4-methyl-3,5-bis{[2,3,5,6-tetra-
fluoro-4-(trifluoromethyl)phenylsulfanyl]methyl}-
benzoyl)-5-oxo-4-{(E)-2-[4-(3-phenyl-5-{2,3,5,6-
tetrafluoro-4-[4-(4-methyl-3,5-bis{[2,3,5,6-tetra-
fluoro-4-(trifluoromethyl)phenylsulfanyl]methyl}-
benzoyl)piperazin-1-yl]phenyl}-4,5-dihydro-1H-
pyrazol-1-yl)phenyl]ethenyl}-1H-pyrrol-2(5H)-
ylidene)propanedinitrile (8g) was synthesized from
7c and TAFSCl. Yield 10%, dark green powder,
J = 15.4 Hz), 7.13 d and 7.59 d (2H each, AB, Harom
J = 9.0 Hz), 7.41–7.47 m (3H, Harom), 7.55 s (2H,
arom), 7.76–7.81 m (2H, Harom). 19F NMR spectrum
,
H
(CDCl3), δF, ppm: 11.56, 16.23, 22.16, 30.10, 105.29
(1 : 1 : 2 : 2 : 3). Mass spectrum (MALDI-TOF):
m/z 1289.26 [M]+. C60H33F18N7O2S2. Calculated:
M 1289.18.
1
mp 140–142°C. H NMR spectrum (CDCl3), δ, ppm:
2.53 s (3H, CH3), 2.69 s (3H, CH3), 3.04–3.86 m (9H,
CH2, pz, Hpyr), 3.97 d.d (1H, Hpyr, J = 18.2, 13.3 Hz),
4.22 s and 4.26 s (4H each, SCH2), 5.85 d.d (1H, Hpyr,
J = 13.3, 5.2 Hz), 7.05 d and 8.38 d (1H, AB, CH=CH,
2-{3-Cyano-1-(4-methyl-3,5-bis{[2,3,5,6-tetra-
fluoro-4-(trifluoromethyl)phenylsulfanyl]methyl}-
benzoyl)-4-[(E)-2-(4-{3-phenyl-5-[2,3,5,6-tetra-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

SHELKOVNIKOV et al.
1516
J = 15.6 Hz), 7.13 br.s (4H, Harom), 7.37–7.67 m (7H,
H
(CDCl3), δF, ppm: 12.42, 17.78, 21.96, 22.26, 30.18,
30.38, 105.50 (1:1:2:2:2:2:6). Mass spectrum
(MALDI-TOF): m/z 1932.30 [M]+. C83H40F32N8O3S4.
Calculated: M 1932.16.
(3H, CH3), 3.19 t (4H, NCH2, J = 7.5 Hz); 3.67 d.d,
4.20 d.d, and 6.12 d.d (1H each, ABX, 1Hpyr, J = 18.0,
12.8, 5.4 Hz); 4.52 s (4H, SCH2), 7.16 d and 8.38 d
(1H each, AB, CH=CH, J = 15.6 Hz), 7.23 d (2H,
arom), 7.73–7.82 m (2H, Harom). 19F NMR spectrum
H
arom, J = 8.6 Hz), 7.46–7.52 m (3H, Harom), 7.78–
7.83 m (4H, Harom), 7.88–7.92 m (2H, Harom). 19F NMR
spectrum (acetone-d6), δF, ppm: 14.64, 18.16, 22.42,
32.05, 107.64 (1:1:2:2:3). Mass spectrum (MALDI-
TOF): m/z 1040.14 [M – 1]+. C48H33F14N5O2S2. Cal-
culated :M 1041.19.
2-{3-Cyano-4-[(E)-2-(4-{5-[4-(dibutylamino)-
2,3,5,6-tetrafluorophenyl]-3-phenyl-4,5-dihydro-
1H-pyrazol-1-yl}phenyl)ethenyl]-1-ethyl-5-oxo-
1H-pyrrol-2(5H)-ylidene}propanedinitrile (8h) was
synthesized from 7d and diethyl sulfate. Yield 73%,
dark green powder with metallic lustre, mp 274–
2-{3-Cyano-1-ethyl-5-oxo-4-[(E)-2-(4-{5-phenyl-
3-[2,3,5,6-tetrafluoro-4-(piperidin-1-yl)phenyl]-4,5-
dihydro-1H-pyrazol-1-yl}phenyl)ethenyl]-1H-pyr-
rol-2(5H)-ylidene}propanedinitrile (10a) was synthe-
sized from 9a and diethyl sulfate. Yield 58%, bright
1
278°C. H NMR spectrum (CDCl3), δ, ppm: 0.84 t
[6H, (CH2)3CH3, J = 7.3 Hz], 1.17–1.46 m [11H,
NCH2(CH2)2, NCH2CH3], 3.13 t (4H, NCH2CH2, J =
7.4 Hz); 3.41 d.d, 3.95 d.d, and 5.82 d.d (1H each,
ABX, Hpyr, J = 18.0, 12.5, 5.3 Hz); 4.09 q (2H,
NCH2CH3, J = 7.1 Hz), 6.98 d and 8.42 d (1H each,
AB, CH=CH, J = 15.4 Hz), 7.07–7.13 m (2H, Harom),
7.41–7.46 m (3H, Harom), 7.56 d (2H, Harom, J =
9.0 Hz), 7.75–7.80 m (2H, Harom). 19F NMR spectrum
(CDCl3), δF, ppm: 13.28, 16.42 (1:1). Mass spectrum:
m/z 719.2883 [M]+. C41H37F4N7O. Calculated:
M 719.2990.
1
green powder, mp ~260°C (decomp.). H NMR spec-
trum (CDCl3), δ, ppm: 1.31 t (3H, CH3CH2, J =
7.0 Hz), 1.57–1.73 m (6H, CH2, pip), 3.23–3.31 m (5H,
CH2, pip, Hpyr), 4.01 d.d (1H, Hpyr, J = 18.0, 11.8 Hz),
4.11 q (2H, CH3CH2, J = 7.0 Hz), 5.41 d.d (1H, Hpyr,
J = 11.8, 5.2 Hz), 6.99 d (1H, CH=, J = 15.6 Hz),
7.07 d (2H, Harom, J = 8.6 Hz), 7.18–7.38 m (5H,
H
arom), 7.51 d (2H, Harom, J = 8.9 Hz), 8.42 d (1H,
CH=, J = 15.6 Hz). 19F NMR spectrum (CDCl3), δF,
ppm: 10.01, 21.31 (1:1). Mass spectrum: m/z 675.2360
[M]+. C38H29F4N7O. Calculated: M 675.2364.
2-{1-Benzoyl-3-cyano-4-[(E)-2-(4-{5-[4-(dibutyl-
amino)-2,3,5,6-tetrafluorophenyl]-3-phenyl-4,5-di-
hydro-1H-pyrazol-1-yl}phenyl)ethenyl]-5-oxo-1H-
pyrrol-2(5H)-ylidene}propanedinitrile (8i) was syn-
thesized from 7d and benzoyl chloride. Yield 65%,
dark green powder with metallic lustre, decomposition
point 255–257°C. 1H NMR spectrum (CDCl3), δ, ppm:
0.84 t (6H, CH3, J = 7.3 Hz), 1.17–1.31 m (4H, CH2),
1.34–1.46 m (4H, CH2), 3.13 t (4H, NCH2, J =
7.3 Hz); 3.42 d.d, 3.96 d.d, and 5.82 d.d (1H each,
ABX, Hpyr, J = 17.5, 12.5, 5.2 Hz); 7.02 d and 8.37 d
(1H each, AB, CH=CH, J = 15.4 Hz), 7.08–7.15 m
(2H, Harom), 7.40–7.47 m (3H, Harom), 7.51–7.59 m
(4H, Harom), 7.69–7.82 m (3H, Harom), 7.91–7.96 m
(2H, Harom). 19F NMR spectrum (CDCl3), δF, ppm:
13.35, 16.42 (1:1). Mass spectrum: m/z 795.2943 [M]+.
C46H37F4N7O2. Calculated: M 795.2939.
2-(3-Cyano-1-ethyl-5-oxo-4-{(E)-2-[4-(5-phenyl-
3-{2,3,5,6-tetrafluoro-4-[4-(4-methyl-3,5-bis-
{[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenylsul-
fanyl]methyl}benzoyl)piperazin-1-yl]phenyl}-4,5-di-
hydro-1H-pyrazol-1-yl)phenyl]ethenyl}-1H-pyrrol-
2(5H)-ylidene)propanedinitrile (10b) was isolated as
a minor product in the reaction of 9a with diethyl
1
sulfate. Green powder. H NMR spectrum (CDCl3), δ,
ppm: 1.32 t (NCH2CH3, J = 6.8 Hz), 2.55 s (3H, CH3),
3.17–3.95 m (9H, Hpz, Hpyr), 3.96–4.20 m (3H,
NCH2CH3, Hpyr), 4.24 s (4H, CH2), 5.46 d.d (1H, Hpyr,
J = 12.5, 5.0 Hz), 7.00 d and 8.42 d (1H each, AB,
CH=CH, J = 15.8 Hz), 7.03–7.40 m (11H, Harom).
19F NMR spectrum (CDCl3), δF, ppm: 10.74, 22.11,
30.46, 105.52 (1:3:2:3).
2-{3-Cyano-4-[(E)-2-(4-{5-[4-(dibutylamino)-
2,3,5,6-tetrafluorophenyl]-3-phenyl-4,5-dihydro-
1H-pyrazol-1-yl}phenyl)ethenyl]-1-(4-methyl-3,5-
bis{[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl-
sulfanyl]methyl}benzoyl)-5-oxo-1H-pyrrol-2(5H)-
ylidene}propanedinitrile (8j) was synthesized from
7d and TAFSCl. Yield 20%, dark green powder,
ACKNOWLEDGMENTS
The authors thank Joint Chemical Research Center,
Siberian Branch, Russian Academy of Sciences, for provid-
ing facilities for spectral and analytical measurements.
FUNDING
1
decomposition point 236–237°C. H NMR spectrum
(acetone-d6), δ, ppm: 0.83 t (6H, CH3, J = 7.0 Hz),
1.18–1.31 m (4H, CH2), 1.37–1.48 m (4H, CH2), 2.78 s
This study was performed under financial support by the
Russian Science Foundation (project no. 16-13-10156) and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019

FORMYL DERIVATIVES OF AMINO-SUBSTITUTED
1517
by the Federal budget program no. 0302-2019-0006. The
MALDI-TOF mass spectra were recorded under partial
financial support from the Federal budget program no. 0309-
2019-0007.
7. Lanke, S.K. and Sekar, N., Dyes Pigm., 2016, vol. 126,
p. 62.
https://doi.org/10.1016/j.dyepig.2015.11.014
8. Shmuilovich, K.S., Orlova, N.A., Karpova, E.V.,
Shakirov, M.M., and Shelkovnikov, V.V., Russ. Chem.
Bull., Int. Ed., 2010, vol. 59, p. 1408.
https://doi.org/10.1007/s11172-010-0255-4
9. Borodina, E.A., Orlova, N.A., and Shelkovnikov, V.V.,
Russ. Chem. Bull., Int. Ed., 2013, vol. 62, p. 2227.
https://doi.org/10.1007/s11172-013-0322-8
10. Soboleva, E.A., Orlova, N.A., and Shelkovnikov, V.V.,
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CONFLICT OF INTERESTS
The authors declare the absence of conflict of interests.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019