Synthesis, Structure, and Biological Activity of (2Z)-2-[(2,4-Dinitrophenyl)hydrazinylidene]butanedioic Acid Esters

Article abstract of DOI:10.1134/S1070363219010018

Dialkyl (2Z)-2-[(2,4-dinitrophenyl)hydrazinylidene]butanedioates have been synthesized by reaction of dialkyl (2Z)-2-hydroxybut-2-enedioates with 2,4-dinitrophenylhydrazine, and their structure has been studied by IR and ¹H NMR spectroscopy, ma

Full text of DOI:10.1134/S1070363219010018

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 1, pp. 1–7. © Pleiades Publishing, Ltd., 2019.
Russian Text © P.P. Mukovoz, E.S. Dankovtseva, V.P. Mukovoz, P.A. Slepukhin, I.N. Ganebnykh, A.N. Sizentsov, E.A. Danilova, 2019, published in Zhurnal
Obshchei Khimii, 2019, Vol. 89, No. 1, pp. 3–10.
Synthesis, Structure, and Biological Activity
of (2Z)-2-[(2,4-Dinitrophenyl)hydrazinylidene]butanedioic
Acid Esters
P. P. Mukovoza*, E. S. Dankovtsevaa, V. P. Mukovoza, P. A. Slepukhinb,c, I. N. Ganebnykhb,c,
A. N. Sizentsovd, and E. A. Danilovae
a All-Russian Research Institute of Phytopathology, ul. Institut 5, Bol’shie Vyazemy, Moscow oblast, 143050 Russia
*e-mail: mpp27@mail.ru
b Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences,
ul. S. Kovalevskoi/Akademicheskaya 22/20, Yekaterinburg, 620990 Russia
c Yeltsin Ural Federal University, ul. Mira 19, Yekaterinburg, 620002 Russia
d Orenburg State University, pr. Pobedy 13, Orenburg, 460018 Russia
e Ivanovo State University of Chemistry and Technology, Sheremetevskii pr. 7, Ivanovo, 153000 Russia
Received May 17, 2018; revised May 17, 2018; accepted May 24, 2018
Abstract—Dialkyl (2Z)-2-[(2,4-dinitrophenyl)hydrazinylidene]butanedioates have been synthesized by reaction
of dialkyl (2Z)-2-hydroxybut-2-enedioates with 2,4-dinitrophenylhydrazine, and their structure has been
studied by IR and 1H NMR spectroscopy, mass spectrometry, and X-ray analysis.
Keywords: (2Z)-2-hydroxybut-2-enedioic acid esters, (2Z)-2-[(2,4-dinitrophenyl)hydrazinylidene]butanedioic
acid esters, 1,2,4-tricarbonyl compounds
DOI: 10.1134/S1070363219010018
It is known that 1,2,4-tricarbonyl compounds, such
as acylpyruvic acids and their esters and amides, react
with hydrazines or arylhydrazines to give biologically
active compounds [1]. Depending on the conditions
and substrate reactivity, the reaction can take different
paths to produce either pyrazole-3-carboxylic acid
esters or pyrazole-3-carboxylic acids or the
corresponding hydrazides. However, in all cases the
primary nucleophilic attack of hydrazine on the most
reactive C2=O carbonyl group is followed by
heterocyclization involving the C4=O carbonyl group
with the formation of pyrazole derivatives [1, 2]. There
are no published data on reactions of arylhydrazines
with such 1,2,4-tricarbonyl compounds as 2-oxo-
butanedioic acid esters [3–5].
dinitrophenyl)hydrazinylidene]butanedioates
2a–2f
(Scheme 1). Compounds 2a–2f are yellow crystalline
solids readily soluble in most organic solvents and
insoluble in water. Their structure was determined on
1
the basis of their IR, H NMR, and mass spectra and
X-ray diffraction data.
The IR spectra of 2a–2f showed a relatively low-
frequency NH stretching band at 3281–3228 cm–1 due
to the secondary amino group, two ester carbonyl
bands at 1732–1702 (C4=O) and 1703–1681 cm–1
(C1=O), absorption bands at 1620–1594, 1593–1576,
1523–1509, and 1457–1436 cm–1 belonging to
stretching vibrations of aromatic C=C bonds and bands
at 1508–1495 and 1345–1326 cm–1 due to asymmetric
and symmetric vibrations, respectively, of the nitro
groups. The asymmetric stretching vibration frequency
of the nitro groups is lower than the standard
frequency for aromatic nitro compounds (1550–
1515 cm–1 [6]), which indicates formation of strong
intra- or/and intermolecular contacts with participation
of the nitro groups. The absorption at 1277–1187 cm–1
Herein, we report the reaction of 2,4-dinitro-
phenylhydrazine with dialkyl (2Z)-2-hydroxybut-2-
enedioates 1a–1f which exist as mixtures of major enol
tautomer 1A and minor oxo form (2-oxobutanedioate
1B) [5]. Instead of expected pyrazole derivatives, we
isolated the corresponding dialkyl (2Z)-2-[(2,4-
1

2
MUKOVOZ et al.
Scheme 1.
H2N
NH
O
O
NO2
OAlk
OAlk
AlkO
AlkO
+
1a_1е
O
O
O
O
H
NO2
A
B
AlkO
O
N
O
O−
O
H
N
N+
_H2O
AlkO
NO2
Alk = Me (а), Et (b), Pr (c), i-Pr (d), Bu (e), t-Bu (f).
2a_2f
was assigned to vibrations of the ester C–O bonds. The
lower C1=O stretching frequency and relatively low
NH stretching frequency suggest participation of these
groups in intramolecular hydrogen bonding typical of
structure 2A (Scheme 2).
has Z configuration of the C=N bond (structure 2A), so
that the C2=N and C1=O groups are oriented cis with
respect to each other.
There is no appreciable equalization of single and
double bonds in the above fragments. This indicates
both insignificant bond conjugation and the lack of
enolization of the MeOC1(O) fragment. The N2=C9 and
O5=C10 double bond lengths are 1.288(2) and 1.200(3) Å,
respectively, and the N1–N2, N1–C1, and C9–C10 single
bond lengths are 1.348(2), 1.373(2), and 1.499(3) Å,
respectively; these values are close to the correspond-
ing reference values (N=C 1.28 Å, C=O 1.21 Å, N–N
1.37 Å, N–C 1.36 Å, C–C 1.54 Å) [7]. The NH group
of the hydrazone fragment is involved in bifurcated
intramolecular hydrogen bond with the o-NO2 group
and C1=O carbonyl group (Table 1). This hydrogen
bond gives rise to two six-membered H-chelate rings
The IR spectra of 2a–2f contained no broadened
low-frequency enol OH bands in the region 3500–
2500 cm–1; this means that enol fragments
characteristic of tautomer 2B are absent in the
crystalline state. Furthermore, the presence of only one
NH band in the spectra of 2a–2f makes it possible to
rule out enhydrazine tautomer 2C in crystal.
However, spectral methods do not allow us to
unambiguously determine the structure of hydrazones
2a–2f in the crystalline state. Therefore, we performed
X-ray analysis of a single crystal of 2a (Fig. 1).
According to the X-ray diffraction data, molecule 2a
Scheme 2.
AlkO
O
N
OAlk
OAlk
O
OAlk
O
AlkO
AlkO
O
H
N
O
N
O
N
H
N
H
N
H
O
N+
H
O
O
N+
N+
O−
O−
O−
NO2
NO2
NO2
2B
2A
2C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019

SYNTHESIS, STRUCTURE, AND BIOLOGICAL ACTIVITY
3
Fig. 1. Structure of the molecule of dimethyl (2Z)-2-[(2,4-
dinitrophenyl)hydrazinylidene]butanedioate (2a) in crystal
according to the X-ray diffraction data.
Fig. 2. A fragment of crystal packing of compound 2a.
and thus fixes planar configuration of the polyene
fragment. It should be noted that the other ester
fragment (C4OOMe) deviates from the plane of the
hydrazone fragment for steric reasons, and the C4-ester
group plane is almost orthogonal to the plane of the
hydrazone fragment (the corresponding dihedral angle
is 85°).
proximity of the carbonyl acceptor to the chelated NH
proton are responsible for the reduced frequency of
asymmetric stretching vibrations of the nitro groups in
the IR spectra of 2a–2f.
As in the crystalline state, compounds 2a–2f in
nonpolar solutions exist in the hydrazone form (2A),
1
which is confirmed by NMR data. The H NMR
Molecules 2a in crystal are packed in layers (Fig. 2)
where the oxygen and nitrogen atoms of the ortho-
nitro groups of the neighboring molecules form a short
π-contact with a O1···N3 distance of 3.009 Å [1 – x,
1 – y, 1 – z], which is shorter by 0.06 Å than the sum
of the corresponding van der Waals radii. Among other
intermolecular contacts, a short T-shaped polar contact
between the oxygen atom of the nitro group and sp2-
carbon atom of the ester group not included in the
conjugation system {C7···O4 3.043 Å, [–x, –y, 1 – z],
0.177 Å shorter than the sum of the van der Waals
radii; Fig. 3} and intermolecular hydrogen bond
C5–H5···O2 [x, y – 1, z] between the aromatic proton
and oxygen atom of the nitro group should be noted
(Table 1). Thus, both nitro groups in molecule 2a are
involved in significant intermolecular contacts which
determine the configuration of the nearest molecular
environment. Presumably, participation of the nitro
groups in intermolecular interactions and spatial
spectra of 2a–2f in CDCl3 contain signals typical of
ester alkyl protons, and the signals of the AlkOC1(O)
fragment are located in a weaker field (by 0.03–
0.23 ppm) than those of the AlkOC4(O) protons. This
is consistent with the IR and X-ray diffraction data,
according to which the C1=O group is involved in
hydrogen bonding. In addition, compounds 2a–2f
displayed an indicator two-proton singlet of the C3H2
group at δ 3.58–3.89 ppm and NH signal at δ 11.73–
14.28 ppm, corresponding to tautomer 2A. It should be
1
noted that the H NMR spectra of structurally related
3-[(2,4-dinitrophenyl)hydrazinylidene]-4,6-dioxo-
alkanoic and 3-[2-(2,4-dinitrophenyl)hydrazinylidene]-
4-oxohexane-1,6-dioic acid esters showed C2H2 and
NH proton signals in close regions, at 3.90–4.12 and
11.83–11.88 ppm [8] or 3.84–3.87 and 11.86–
11.90 ppm, respectively [9, 10]. No signals assignable
to CH=C, enolic OH, or enehydrazine NH protons
1
were detected in the H NMR spectra, which con-
Table 1. Hydrogen bonds in the crystal structure of compound 2a
D–H
d(D–H), Å
0.91(3)
d(H···A), Å
2.01(2)
d(D···A), Å
2.624(2)
A
∠DHA, deg
124(2)
N1–H1
N1–H1
С5–Н5
O1
O5
0.91(3)
1.95(2)
133(2)
2.660(2)
0.93(3)
2.38(2)
171(2)
3.305(2)
О2 [x, y–1, z]
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4
MUKOVOZ et al.
P-209, Bacillus licheniformis VKPM V 7038) and
gram-negative bacteria (Escherichia coli M17,
Salmonella typhimurium 14028S WT), as well as
antifungal activity against phytopathogenic fungi
Fusarium sp., Alternarium sp., and Bipolaris
soraciniana (Table 2). It was found that the activity of
compounds 2a, 2d, and 2f against Staphylococcus
aureus exceeds or is comparable to the activity of
nitrofurazone and that compounds 2c and 2e exhibit
antimicrobial activity exceeding or comparable to the
activity of ethacridine lactate. The antimicrobial
activity of 2a, 2e, and 2f against Bacillus licheniformis
was higher than or comparable to the activity of
nitrofurazone, and the antimicrobial activity of 2b, 2c,
and 2d was comparable to the activity of ethacridine
lactate. The activity of 2a, 2d, and 2e against
Salmonella typhimurium was comparable to that of
nitrofurazone but higher than the activity of
ethacridine lactate. The antimicrobial activity of 2b
and 2c was comparable to that of ethacridine lactate.
Only compound 2d turned out to be moderately active
against Escherichia coli; its activity exceeded the
activity of ethacridine lactate. The other compounds
tested showed no activity against E. coli. Compounds
2a, 2b, and 2f displayed antifungal activity against
Fusarium sp. at the same level as phytolavin. The
antifungal activity of 2a, 2b, 2d, and 2f against
Bipolaris soraciniana was moderate, and it did not
exceed the activity of phytolavin and previcur.
Compounds 2a–2f were inactive toward Alternarium
sp. The highest antimicrobial activity against gram-
positive bacteria was found for compounds 2a and 2d–
2f with methyl or branched alkyl groups in the ester
fragments. Compounds 2a, 2b, and 2f were most
active against Fusarium sp. Fairly high biological
activity of the examined compounds is likely to be
determined by the presence of nitro groups in the
Fig. 3. Short T-shaped polar C···O contact in the crystal
structure of compound 2a.
firmed the absence of enol tautomer 2B or enehyd-
razine 2C in solutions of 2a–2f in nonpolar solvents.
The structure of 2a–2f was also confirmed by their
high-resolution mass spectra (electropsray ionization
from acetonitrile solution) which characteristically
contained [M + H]+ ion peaks.
The reaction of diesters 1 with 2,4-dinitro-
phenylhydrazine is likely to begin with nucleophilic
addition of the primary amino group of the latter to the
most electrophilic C2=O carbon atom of oxo tautomer
1B, and elimination of water molecule from adduct X
yields compounds 2 (Scheme 3). The effect of
unshared electron pairs of the alkoxy oxygen atoms on
the C1 and C4 electrophilic centers hampers nucleo-
philic attack on the ester carbonyl groups and prevents
compounds 2 from undergoing heterocyclization to
pyrazole derivatives, as it occurs in the reactions of
other 1,2,4-tricarbonyl compounds (acylpyruvic acids
and their esters and amides) with arylhydrazines.
Compounds 2a–2f were tested for antimicrobial
activity against gram-positive (Staphylococcus aureus
Scheme 3.
AlkO
O
N
AlkO
O
N
..
OAlk
O
OAlk
O
H2N
NH
O
..
NO2
OAlk
HO
AlkO
H
N
H
N
..
_H2O
H
+
O
N+
O
O
NO2
O-
NO2
NO2
NO2
1B
2
X
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SYNTHESIS, STRUCTURE, AND BIOLOGICAL ACTIVITY
5
Table 2. Antimicrobial and antifungal activities (MIC, μg/mL) of compounds 2a–2f
St. aureus
P-209
B. licheniformis В
S. typhimurium
14028S WT
E. coli
M17
Bipolaris
soraciniana
Compound
Fusarium sp.
7038
2a
2b
2c
2d
2e
2f
125
1000
250
63
250
1000
1000
1000
250
250
1000
1000
500
–
–
–
31
16
250
125
–
–
125
63
1000
–
500
–
500
63
125
31
500
250
1000
125
–
500
Ethacridine lactate
Nitrofurazone
Phytolavin
500
125
1000
500
2000
500
16
8
63
31
Previcur
arylhydrazone fragment; reduction of the nitro groups
in pathogen cells could give rise to aromatic amines
that are toxic to microorganisms. It should be noted
that structurally related 3-[2-(2,4-dinitrophenyl)hyd-
razinylidene]-4-oxohexane-1,6-dioic acid esters con-
taining a similar dinitrophenylhydrazone fragment also
dhowed a high antimicrobial activity against S. aureus
[11].
Organic Compounds joint center of the Institute of
Organic Synthesis (Ural Branch, Russian Academy of
Sciences). The data were acquired at 295(2) K on an
Xcalibur 3 automated four-circle diffractometer with a
CCD detector according to standard procedure
(monochromatized MoKα radiation, ω-scanning with a
step of 1°). A correction for absorption was applied
empirically. The structure was solved by the direct
statistical method and was refined against F2 by the
full-matrix least-squares method in anisotropic
approximation for all non-hydrogen atoms. Hydrogen
atoms attached to carbons were placed in giometrically
calculated positions and were refined in isotropic
approximation, and the positions of OH hydrogens
were refined independently. All calculations were
performed using OLEX program [12] and SHELX
software package [13]. Principal crystallographic
parameters of compound 2a: triclinic crystal system,
space group P-1; unit cell parameters: a = 6.6752(5),
b = 8.0816(5), c = 15.2864(12) Å; α = 82.164(6), β =
81.802(6), γ = 67.286(7)°; μ = 0.129 mm–1. Total of
6588 reflection intensities were measured in the range
2.70° < θ < 30.50°, including 4034 independent
reflections (Rint = 0.0180), and 2684 reflections with
I > 2σ(I). Final divergence factors: R1 = 0.0798, wR2 =
0.1674 (all independent reflections); R1 = 0.0506,
wR2 = 0.1409 [reflections with I > 2σ(I)]. Residual
electron density (min/max) Δρe = 0.262/–0.213 ē/Å3.
The complete set of X-ray diffraction data for com-
pound 2a was deposited to the Cambridge Crystallo-
graphic Data Centre (CCDC entry no. 1441915).
In summary, the reaction of dialkyl (2Z)-2-hyd-
roxybut-2-enedioates with 2,4-dinitrophenylhydrazine
yields the corresponding hydrazones, dialkyl (2Z)-2-
[(2,4-dinitrophenyl)hydrazinylidene]butanedioates, which
do not undergo heterocyclization to pyrazole
derivatives. The synthesized compounds possess
antimicrobial and fungicidal activity at different levels,
which is likely to be determined by the presence of
nitro groups in their molecules.
EXPERIMENTAL
The IR spectra of crystalline samples were recorded
on a Bruker Alpha spectrometer with Fourier
transform, equipped with an ATR accessory (ZnSe,
1
incidence angle 45°). The H NMR spectra were
recorded on a Bruker Avance II spectrometer at 400
MHz using CDCl3 or DMSO-d6 as solvent and
tetramethylsilane as internal standard. The mass
spectra were obtained on a Bruker Daltonik MaXis
Impact HD quadrupole time-of-flight mass spectro-
meter (electrospray ionization from solutions in aceto-
nitrile, flow rate 240 μL/h; default parameters for
infusion analysis of small molecules). The X-ray
analysis of compound 2a was performed using the
equipment of the Spectroscopy and Analysis of
The antimicrobial and fungicidal activities of
compounds 2a–2e were evaluated by the serial dilution
method; each experiment was performed in triplicate.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019

6
MUKOVOZ et al.
The antimicrobial activity against Staphylococcus
aureus P-209, Bacillus licheniformis VKPM V 7038,
Escherichia coli M17, and Salmonella typhimurium
14028S WT were determined in meat infusion broth at
a bacterial load of 5×109 CFU/mL. The minimum
inhibitory concentration (MIC) was assumed to be
equal to that ensuring inhibition of bacterial growth on
the nutrient medium. The inhibitory effect was
confirmed by inoculation into solid nutrient media
from each test tube. Nitrofurazone and ethacridine
lactate were used as reference drugs. The fungicidal
activity of 2a–2f against Fusauium sp., Alternarium
sp., and Bipolaris soraciniana was evaluated on a
Saburo solid nutrient medium. Compounds 2a–2f were
dissolved in DMSO, and the stock solutions were
diluted with sterile saline to concentrations of 1000 to
8 μg/mL. Solutions of 2a–2f were added to test tubes
charged with nutrient medium (preliminarily melted
and cooled to 56°C) and were thoroughly mixed with
the medium. Fungal cultures were prepared by
inoculation of sterile Saburo medium with samples of
Fusauium sp., Alternarium sp., and Bipolaris soraciniana
from a fungal collection and were cultivated for two
weeks 18–22°C, and washouts therefrom were used to
inoculate the nutrient medium containing compounds
2a–2f. Nutrient medium without a compound to be
tested was used as control. The results were examined
after 48 h. The reference drugs were phytolavin and
previcur. The data were statistically processed by
Student t-test using XL 2012 program. The effect was
considered to be reliable at p < 0.001.
(δC–Harom, out-of-plane), 740 (δC3H2, rocking), 701
1
(C–C, skeletal). H NMR spectrum (CDCl3), δ, ppm:
3.79 s (3H, C4OCH3), 3.86 s (2H, C3H2), 3.94 s (3H,
C1OCH3), 8.17–9.15 m (3H, C6H3), 11.73 s (1H, NH).
Mass spectrum: m/z: 341.0729 [M + H]+; calculated for
C12H13N4O8: 341.0728.
Diethyl (2Z)-2-[(2,4-dinitrophenyl)hydrazinyl-
idene]butanedioate (2b). Yield 3.46 g (47%), mp 147–
149°C. IR spectrum, ν, cm–1: 3228 (NH), 3091, 3054
(C–Harom), 2977 (νasCH3), 2953 (νasCH2), 1718 (C4=O),
1701 (C1=O), 1609, 1578, 1516 (C=Carom), 1503
(νasNO2), 1465 (δasCH3), 1449 (C=Carom), 1332 (νsNO2),
1263 (νasC–O–C), 1225, 1137, 1110, 1062, 1028, 1013
(C–C, skeletal), 920, 834 (δC–Harom, out-of-plane),
1
747 (δC3H2, rocking), 711 (C–C, skeletal). H NMR
spectrum (CDCl3), δ, ppm: 1.28 t (3H, C4OCH2CH3,
J = 7.2 Hz), 1.33 t (3H, C1OCH2CH3, J = 7.5 Hz), 3.65
s (2H, C3H2), 4.22 q (2H, C4OCH2, J = 7.2 Hz), 4.27 q
(2H, C1OCH2, J = 7.5 Hz), 8.11–9.15 m (3H, C6H3),
14.28 s (1H, NH). Mass spectrum: m/z 369.1043 [M +
H]+; calculated for C14H17N4O8: 369.1041.
Dipropyl (2Z)-2-[(2,4-dinitrophenyl)hydrazinyl-
idene]butanedioate (2c). Yield 4.28 g (54%), mp 141–
143°C. IR spectrum, ν, cm–1: 3260 (NH), 3096, 3067
(C–Harom), 2973 (νasCH3), 2968 (νasCH2), 2876
(νsCH3), 1709 (C4=O), 1689 (C1=O), 1601, 1582, 1523
(C=Carom), 1506 (νasNO2), 1469 (δasCH3), 1457
(C=Carom), 1345 (νsNO2), 1209 (νasC–O–C), 1144,
1169, 1032, 1008 (C–C, skeletal), 927, 901, 848 (δC–
H
arom, out-of-plane), 756 (δC3H2, rocking), 720 (C–C,
1
skeletal). H NMR spectrum (CDCl3), δ, ppm: 0.95 t
(3H, C4OCH2CH2CH3, J = 7.4 Hz), 1.02 t (3H,
C1OCH2CH2CH3, J = 7.7 Hz), 1.63–1.75 m (4H,
CH2CH2CH3), 3.69 s (2H, C3H2), 4.02 t (2H, C4OCH2,
J = 7.4 Hz), 4.17 t (2H, C1OCH2, J = 7.7 Hz), 8.05–
9.20 m (3H, C6H3), 13.82 s (1H, NH). Mass spectrum:
m/z: 397.1355 [M + H]+; calculated for C16H21N4O8:
397.1354.
Initial compounds 1a–1e were synthesized ac-
cording to the procedure described in [5].
General procedure for the synthesis of dialkyl
(2Z)-2-[(2,4-dinitrophenyl)hydrazinylidene]butane-
dioates 2a–2f. A solution of 20 mmol of compound
1a–1f in 10 mL of acetic acid was added to a solution
of 3.96 g (20 mmol) of 2,4-dinitrophenylhydrazine in a
mixture of 40 mL of acetic acid and 60 mL of ethanol.
The mixture was heated to the boiling point and
evaporated, and the residue was dried and recrystal-
lized from ethanol or ethyl acetate.
Diisopropyl (2Z)-2-[(2,4-dinitrophenyl)hydrazinyl-
idene]butanedioate (2d). Yield 3.01 g (38%), mp 152–
155°C. IR spectrum, ν, cm–1: 3232 (NH), 3103, 3088
(C–Harom), 2970 (νasCH3), 2932 (νasCH), 2869 (νsCH3),
1702 (C4=O), 1681 (C1=O), 1610, 1586, 1512
(C=Carom), 1501 (νasNO2), 1463 (δasCH3), 1441
(C=Carom), 1386, 1364 [δs(CH3)2CH], 1329 (νsNO2),
1187 (νasC–O–C), 1166, 1139, 1068 (C–C, skeletal),
909, 864 (δC–Harom), 766 (δC3H2, rocking), 707 (C–C,
Dimethyl (2Z)-2-[(2,4-dinitrophenyl)hydrazinyl-
idene]butanedioate (2a). Yield 2.18 g (32%), mp 177–
179°C. IR spectrum, ν, cm–1: 3247 (NH), 3119, 3087
(C–Harom), 2967 (νasCH3), 1732 (C4=O), 1696 (C1=O),
1603, 1584, 1521 (C=Carom), 1508 (νasNO2), 1443
(C=Carom), 1339 (νsNO2), 1277 (νas(C–O–C), 1213,
1112, 1096, 1052, 1003 (C–C, skeletal), 933, 841
1
skeletal). H NMR spectrum (CDCl3), δ, ppm: 1.29 t
[6H, C4OCH(CH3)2, J = 7.1 Hz], 1.32 t [6H, C1OCH
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SYNTHESIS, STRUCTURE, AND BIOLOGICAL ACTIVITY
7
(CH3)2, J = 7.2 Hz], 3.89 s (2H, C3H2), 4.30 m (1H,
REFERENCES
C4OCH), 4.53 m (1H, C1OCH), 8.10–9.25 m (3H, C6H3),
14.13 s (1H, NH). Mass spectrum: m/z 397.1354 [M +
H]+; calculated for C16H21N4O8: 397.1354.
1. Perevalov, S.G., Burgart, Ya.V., Saloutin, V.I., and
Chupakhin, O.N., Russ. Chem. Rev., 2001, vol. 70, no. 11,
p. 921. doi 10.1070/RC2001v070n11ABEH000685
2. Yanborisov, T.N., Zhikina, I.A., Andreichikov, Yu.S.,
Milyutin, A.V., and Plaksina, A.N., Pharm. Chem. J.,
1998, vol. 32, no. 9, p. 480. doi 10.1007/BF02539222
3. Yamashkin, S.A. and Zhukova, N.V., Chem. Heterocycl.
Compd., 2008, vol. 44, no. 2, p. 115. doi 10.1007/
s10593-008-0038-0
4. Houben, J., Die Methoden der organischen Chemie,
Leipzig: Georg Thieme, 1930, vol. 3, part 2. Translated
under the title Metody organicheskoi khimii, Moscow:
ONTI, 1935, vol. 3, part 2, p. 532.
Dibutyl (2Z)-2-[(2,4-dinitrophenyl)hydrazinyl-
idene]butanedioate (2d). Yield 2.46 g (29%), mp 122–
124°C. IR spectrum, ν, cm–1: 3267 (NH), 3096, 3067
(C–Harom), 2962 (νasCH3), 2954 (νasCH2), 2868
(νsCH3), 1705 (C4=O), 1697 (C1=O), 1594, 1576, 1513
(C=Carom), 1495 (νasNO2), 1457 (δasCH3), 1438
(C=Carom), 1326 (νsNO2), 1194 (νasC–O–C), 1181,
1160, 1103, 1061, 1025, 1003 (C–C, skeletal), 914
(δC–Harom, out-of-plane), 777 (δC3H2, rocking), 695
1
(C–C, skeletal). H NMR spectrum (CDCl3), δ, ppm:
5. Mukovoz, P.P., Cand. Sci. (Chem.) Dissertation,
0.96 t [3H, C4O(CH2)3CH3, J = 7.5 Hz], 1.05 t [3H,
C1O(CH2)3CH3, J = 7.5 Hz], 1.35–1.45 m (4H,
CH2CH3), 1.60–1.70 m (4H, OCH2CH2), 3.64 s (2H,
C3H2), 4.00–4.25 m (4H, OCH2), 8.00–9.17 m (3H,
C6H3), 13.95 s (1H, NH). Mass spectrum: m/z:
425.1668 [M + H]+; calculated for C18H25N4O8: 425.1667).
Yaroslavl’, 2010.
6. Bellamy, L.J., The Infra-red Spectra of Complex
Molecules, London: Methuen, 1958.
7. Allen, F.H., Watson, D.G., Brammer, L., Orpen, A.G.,
and Taylor, R., International Tables for Crystallo-
graphy, Prince, E., Ed., 2006, vol. C, p. 790.
8. Mukovoz, P.P., Gorbunova, A.V., Slepukhin, P.A.,
El’tsov, O.S., and Ganebnykh, I.N., Russ. J. Org.
Chem., 2017, vol. 53, no. 7, p. 1017. doi 10.1134/
S1070428017070090
9. Mukovoz, P.P., Koz’minykh, V.O., Slepukhin, P.A.,
Ganebnykh, I.N., El’tsov, O.S., Gorbunova, A.V., and
Koz’minykh, E.N., Russ. J. Org. Chem., 2016, vol. 52,
no. 5, p. 636. doi10.1134/S1070428016050043
10. Mukovoz, P.P. and Koz’minykh, V.O., Vestn. Yuzhno-
Ural. Gos. Univ., 2009, no. 23 (156), p. 4.
11. Mukovoz, P.P., Koz’minykh, V.O., Korobova, I.V., and
Sizentsov, A.N., Privolzhsk. Khim.-Tekhnol. Vestn.,
2016, no. 1, p. 1.
Di-tert-butyl (2Z)-2-[(2,4-dinitrophenyl)hydrazinyl-
idene]butanedioate (2e). Yield 1.95 g (23%), mp 172–
177°C. IR spectrum, ν, cm–1: 3281 (NH), 3105, 3099
(C–Harom), 2975 (νasCH3), 2861 (νsCH3), 1724 (C4=O),
1703 (C1=O), 1620, 1593, 1509 (C=Carom), 1497
(νasNO2), 1436 (C=Carom), 1327 (νsNO2), 1228 (νasC–O–C),
1163, 1091, 1053 (C–C, skeletal), 855 (δC–Harom, out-
of-plane), 751 (δC3H2, rocking), 719 (C–C, skeletal).
1H NMR spectrum (CDCl3), δ, ppm: 2.10 s [9H, C4OC
(CH3)3], 2.22 s [9H, C1OC(CH3)3], 3.58 s (2H, C3H2),
8.00–9.05 m (3H, C6H3), 12.41 s (1H, NH). Mass
spectrum: m/z 425.1669 [M + H]+; calculated for
C18H25N4O8: 425.1667.
12. Dolomanov, O.V., Bourhis, L.J., Gildea, R.J., Ho-
ward, J.A.K., and Puschmann, H., J. Appl. Crystallogr.,
2009, vol. 42, no. 2, p. 339. doi 1107/
S0021889808042726
CONFLICT OF INTEREST
13. Sheldrick, G.M., Acta Crystallogr., Sect. A, 2008,
No conflict of interest was declared by the authors.
vol. 64, p. 112. doi 1107/S0108767307043930
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019