ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 5, pp. 636–643. © Pleiades Publishing, Ltd., 2016. Original Russian Text © P.P. Mukovoz, V.O. Koz’minykh, P.A. Slepukhin, I.N. Ganebnykh, O.S. El’tsov, A.V. Gorbunova, E.N. Koz’minykh, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 5, pp. 652–658.

Reaction of 3,4-Dioxohexane-1,6-dioic Acid Esters with 2,4-Dinitrophenylhydrazine P. P. Mukovoza, V. O. Koz’minykhb, P. A. Slepukhinc,d, I. N. Ganebnykhc,d, O. S. El’tsovd, A. V. Gorbunovae, and E. N. Koz’minykhb a

Moscow Technologic Institute, Orenburg Branch, pr. Pobedy 75, Orenburg, 460018 Russia e-mail: [email protected] b

c

Perm State Humanitarian and Pedagogical University, Perm, Russia

Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Yekaterinburg, Russia d

El’tsin Ural Federal University, Yekaterinburg, Russia e

Orenburg State University, Orenburg, Russia Received December 11, 2015

Abstract—Reaction was studied of 3,4-dihydroxyhexa-2,4-diene-1,6-dioic acid esters with 2,4dinitrophenylhydrazine that led to the formation of esters of (3E)-3-[2-(2,4-dinitrophenyl)-hydrazinylidene]-4oxohexane-1,6-dioic and (3E,4E)-3,4-bis[2-(2,4-dinitrophenyl)hydrazinylidene]-hexane-1,6-dioic acids. The structural features of compounds synthesized were established from the data of IR and NMR spectra and X-ray diffraction (XRD) analysis.

DOI: 10.1134/S1070428016050043 No published information exists beside our preliminary communication [5] on the reaction of 1,3,4,6-tetracarbonyl compounds having terminal ester groups with 2,4-dinitrophenylhydrazine.

Reactions of 1,3,4,6-tetracarbonyl compounds, in particular, of 1,6-disubstituted 1,3,4,6-tetraketones with arylhydrazines resulted in heterocyclization giving biologically active pyrazole derivatives [1–4].

Scheme 1. OH AlkO

O

O AlkO

OAlk O

OH

O

O

O

N

O NO2

B AlkO

O OAlk

H

NO2 OAlk

1a_1d

A AlkO

O

_

H2O H2N

O2N

N

O

H N NO2

H

N

N

N

N

O

O2N

O 2N

NO2

NO2

3a_3c

2a, 2b

Alk = Me (1a, 2a), Et (1b, 2b, 3a), Pr (1c, 3b), Bu (1d, 3c).

636

H

OAlk

REACTION OF 3,4-DIOXOHEXANE-1,6-DIOIC ACID ESTERS

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Hydrogen bonds in crystals of compound 2а and 3b D‒H

A

D‒H, A

H···A, A

Angle DHA, deg

D···A, A

2.01(3) 2.35(3)

129(2) 141(2)

2.632(3) 3.062(3)

2.04(3) 2.64(3)

126(2) 122(2)

2.608(3) 3.157(3)

2а N2–H2 N2–H2

O1 O5

0.85(3) 0.85(3)

N1–H1 N1–H1

O3 O2

0.82(3) 0.82(3)

3b

We thoroughly studied the reaction of dialkyl ketipinates 1a–1d as mixtures of the prevailing dienol tautomer А (3,4-dihydroxyhexa-2,4-diene-1,6-dioic acid esters) and the minor dioxoform B (Scheme 1) with 2,4-dinitrophenylhydrazine affording esters of (3E)-3-[2-(2,4-dinitrophenyl)hydrazinylidene]-4-oxohexane-1,6-dioic acid 2a and 2b or esters of (3E,4E)3,4-bis[2-(2,4-dinitrophenyl)hydrazinylidene]hexane1,6-dioic acid 3а–3с. Compounds 2a, 2b, and 3a–3c are orange crystalline substances insoluble in water and well soluble in the majority of organic solvents. The structural features of compounds 2a, 2b, and 3a–3c were established from the data of IR and NMR spectra and X-ray diffraction (XRD) analysis. IR spectra of esters 2a and 2b contain absorption bands of the secondary amino group (3198–3223 cm–1), ester carbonyl groups C1,6=O (1722–1729 cm–1), oxo group C4=O (1685–1687 cm–1), and also of the multiple bonds of the aromatic ring (1613, 1576, 1524 and 1438–1445 cm–1). The absorption bands at 1501 cm–1 (asymmetric vibrations) and 1333 cm–1 (sym-metric vibrations) confirm the presence of nitro groups in the molecule. The reduced frequency of the asymmetric vibrations of the nitro groups at 1501 cm–1 (standard values for aromatic nitro compounds are 1515–1550 cm–1 [6]) indicate their involvement in the formation of strong intra- or intermolecular contacts. The absorption at 1302–1299 cm–1 (ester band) proves the presence of ester units in the molecules of compounds 2a and 2b. The high absorption frequency of the ester carbonyl groups, oxo group C4=O, and also the absorption band of the NH group show that the structures 2a and 2b lack enhydrazine and enol fragments. Spectral methods are insufficient for unambiguously establishing the structure of compounds 2 in the solid phase; to confirm their structure we have grown single crystals of compound 2a and studied them by XRD method.

According to XRD data (Fig. 1) the molecule of compound 2a exists in the form of (3E)-isomer, the azomethine group C3=N and oxo group C4=O are in the mutual trans-position. No notable equalizing was observed of ordinary and double bonds in the mentioned fragments indicating a negligible conjugation and no enolization in the ester fragment of the 3-ketoacid. The lengths of the double bonds N1=C9 1.284(3), O7=C10 1.211(3) Å, of ordinary bonds N1–N2 1.362(3), N2–C1 1.368(3), and C9–C10 1.493(3) Å are close to the standard values (N=C 1.28, C=O 1.21, N–N 1.37, N–C 1.36, C–C 1.54 Å [7]). NH Group of the hydrazine forms a bifurcate intramolecular hydrogen bond with the 2-NO2 group and the carbonyl of the ester fragment. The oxygen atom of the 2-NO2 group of the aromatic ring and the proton of the NH group of the hydrazine unit form a planar (within 0.08 Å) six-membered chelate fragment NH···О=N, fixing the nitro group and the hydrazine residue in the plane of the aromatic ring. Due to steric interactions the ester fragment in the molecule of compound 2а deviates from the plane of

O8 O7

C10 C8

O

11

C

C13 O9

C9

6

N1 C7

C14

C12

O5

N2

O1

C6

C1 C2

N3

C5 C4

O4

C3 N4 O2

O3

Fig. 1. Molecule of compound 2а shown with atoms represented by ellipsoids of thermal oscillations of 50% probability.

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hydrazinylidene, and the oxygen atom of carbonyl C1=O is brought spatially near to the proton of the NH group with the interatomic distance 2.35 Å (see the table). In the crystal the molecules of compound 2а form centrosymmetric dimers where the oxygen atoms of the 2-NO2 group of the aromatic ring have a shortened π-contact with the nitrogen atom of the 4-NO2 group of the contiguous molecule with the distance 3.019 Å (by 0.05 Å less than the sum of van der Waals radii). The involvement of the nitro groups in the intermolecular contacts as well as the spatially close position of the carbonyl acceptor and the proton of the NH group of the chelate fragment is evidently the reason of the decrease in the absorption frequency of the asymmetric vibrations νas(NO2) in the IR spectra of compounds 2a and 2b. In nonpolar solvents compounds 2a and 2b same as in the solid state exist in hydrazone form as confirmed by IR (chloroform) and 1H NMR spectra (CDCl3). The absorption band of the secondary amino group of compounds 2a and 2b at 3020 cm–1 in chloroform significantly shifts to low frequency region, and its intensity is considerably greater than in the IR spectra in the solid state indicating the formation of intermolecular hydrogen bonds involving the proton of the NH group. The positions of the absorption bands of the oxo groups C1,6=O (1735–1740 cm–1) and C4=O (1695–1698 cm–1) of compounds 2a and 2b in chloroform shift to higher frequencies (by 11–13 and 10–11 cm–1 respectively) compared to the IR spectra in the solid phase that excludes the involvement of the carbonyl acceptors in the intermolecular hydrogen bonds. At the same time the frequency of the ester band at 1215 cm–1 significantly shifts to the low frequency (by 84–87 cm–1) compared to the IR spectra in the solid state; consequently the oxygen atom of the ester unit takes part in the formation of an intermolecular hydrogen bond with the proton of the secondary amino group. In the 1H NMR spectra of compounds 2a and 2b marker singlets are present of the methylene groups C2H2 (δ 3.84–3.87) and C5H2 (3.96–3.98 ppm), and also a signal of the NH group (δ 11.86–11.90 ppm). The difference in the chemical shift of the protons in C2H2 and C5H2 groups is apparently caused by the closeness of C2H2 group to the aromatic substituent. In the 1H NMR spectra of similar esters of 3-[(2,4-dinitrophenyl)hydrazinylidene]-4,6-dioxoalkanoic acids the proton signals of the methylene group C2H2 and of

the proton of NH group are observed in similar regions (δ 3.90–4.12 and 11.83–11.88 ppm respectively [8]). No signals have been found in the 1H NMR spectra of methine protons, protons of enol hydroxy groups, and protons of NH group of the enhydrazine units thus proving the absence in the nonpolar solvents of probable enhydrazine and enol forms of compounds 2a and 2b. The structure of compounds 2a and 2b is proved with the data of high resolution mass spectra registered in electrospray mode from solution in acetonitrile. The mass spectra contain characteristic signals of protonated and cationated molecules: [M + H]+, [M + Na]+, [M + K]+, [M + NH4]+, and of cluster ions [2M + Na]+. IR spectra of bishydrazones 3а–3с contain absorption bands of secondary amino groups (3278– 3317 cm–1), ester groups C1,6=O (1717–1739 cm–1), and also of aromatic rings (1610–1614, 1580–1588, 1516–1522, and 1437–1449 cm–1). The bands at 1490– 1496 and 1325–1335 cm–1 prove the presence of nitro groups in the molecules. The high frequency of the absorption of the ester carbonyl groups as well as the absorption band of the NH groups show the absence of enhydrazine fragments in the structures 3а–3с. Relatively low absorption frequency of 1489–1499 cm–1 corresponding to the asymmetric vibrations of the NO2 groups indicates their involvement in the formation of intra- or intermolecular contacts. To prove the structure of compounds 3 in the solid phase single crystals of compound 3b were grown and investigated by XRD method. In keeping with XRD data (Fig. 2), compound 3b exists in the solid state as a (3E,4E)-bishydrazonoester. In the crystal the molecule of compound 3b is located in a particular position in the inversion center. The hydrazinylidene units in the molecule of compound 3b are present in the trans-position with respect to each other in the same plane as the aromatic substituents (within 0.09 Å). The length of the central tentatively ordinary bond C7–C7 (the numeration of atoms, see Fig. 2) 1.472(3) Å is typical for ordinary bonds of conjugated polyene systems and indicates the conjugation of two hydrazinylidene fragments in the molecule through a bisazomethine unit N1=C7–C7=N1. The conjugation of the hydrazinylidene units is seen from the equalization of lengths of N1–N2 [1.362(3) Å] and N1–C1 bonds [1.359(3) Å]. Similarly to compound 2а in the molecule of compound 3b the 2-NO2 groups

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of the aromatic ring form a chelate fragment NH···О=N with the proton of the secondary amino group which is fixed with an intramolecular hydrogen bond. Unlike 2а structure in the molecule of compound 3b no intermolecular contacts exist between the proton of the NH group and the carbonyl groups, only a weak bond is present with the atom О2 of the alkoxy group (see the table). The ester groups deviate from the plane of the conjugated π-system of the molecule, their propyl residues are disordered by two positions with population coefficients 0.7 and 0.3.

C10

O6 O

N4 C5 O

C6

C

N

1

C

C3

2

C

O2 C

C8 C9

C8

O3

C7

N1 C2

N2

1

O

C10

12

In the crystal the molecules of compound 3b form a stacking-parquet arrangement (Fig. 3) without any notable shortened contacts save the intermolecular πinteraction of carbonyl groups О1···С9 [1‒x, ‒y, ‒z] (contact distance 3.130 Å, by 0.09 Å less than the sum of van der Waals radii). The probable reason of the decreased frequency of the asymmetric vibrations νas (NO2) in the IR spectra of compounds 3а–3с, as well as in structures 2a and 2b, is the involvement of these groups in the formation of the intramolecular hydrogen bond and the conjugation with the benzene ring.

C7

N1

O3

N3

2

C12

C11 O2

1

C9

4

5

O4

639

1

N3

C C6

O4

C3 5 C4 O

C5

N4 O6

C11

Fig. 2. Molecular structure of compound 3b with atoms represented by ellipsoids of thermal oscillations of 50% probability. The disordered components of propyl groups are not shown.

IR spectra taken in the solid state. This confirms the involvement of the proton of the NH group in the intermolecular hydrogen bond. Structurally related compounds 2a and 2b have close values of absorption frequencies of NH group in the IR spectra in chloroform. The absorption bands of the ester carbonyl groups (1734–1730 cm–1) of compounds 3a–3c materially conserve their values in chloroform as compared with the IR spectra in the solid state. At the same time the ester band at 1215–1217 cm–1 of compounds 3а–3с in chloroform shifted to lower

In nonpolar solvents compounds 3а–3с same as in the solid phase exist in the hydrazone form as confirmed by IR spectra (chloroform) and 1H NMR spectra (CDCl3). The absorption band of the secondary amino group (3020–3065 cm–1) of compounds 3а–3с in chloroform appears at lower frequencies than in the

c

0

b

a

Fig. 3. Fragment of packing of dipropyl (3Z,4Z)-3,4-bis[2-(2,4-dinitrophenyl)hydrazinylidene]hexane-1,6-dioate 3b. RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

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Scheme 2.

O

O

O

O

H N

H

H

AlkO

O

O

OH OAlk

O

NO2

δ+

AlkO

H2N ..

NO2

OAlk

HN

NH

O 2N

δ_

NO2 4

B δ_ O δ+

AlkO

O OAlk

O

HN

H 2N ..

NO2

H N

N

NO2

_

H 2O

O2N

NO2 2a, 2b

NO2

NO2

O2N

O 2N

HN

NH

O

AlkO OH O

HN

N

N OAlk

H

H

O 2N

_

NH

AlkO

O OAlk

H 2O O

HN

N

O2N

NO2

NO2 5

frequencies by 45–51 cm–1 compared to the IR spectra in the solid phase thus confirming the involvement of the ester unit and the secondary amino group in the formation of the intermolecular hydrogen bond similar to the behavior in solutions of compounds 2a and 2b. In the 1H NMR spectra of compounds 3а–3с the signals of four protons of two methylene groups C2,5H2 (δ 4.03–4.05 ppm), as well as the signals of two protons of NH groups of (3E,4E)-isomers (δ 11.89–

3a_3c

11.93 ppm) appear as singlets confirming the axial symmetry of the bishydrazones 3 with respect to the central C3–C4 bond. The 1H NMR spectra contained no signals of methine protons and protons of NH groups of enhydrazine units confirming the absence in the nonpolar solvents of probable enhydrazine forms of compounds 3а–3с. The structure of compounds 3а–3с is proved with the data of high resolution mass spectra that contain

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characteristic signals of protonated and cationated molecules [M + H]+, [M + Na]+, [M + K]+, [M + NH4]+, and also of cluster ions [2M + Na]+. The reaction of compounds 1 with dinitrophenylhydrazine apparently starts with the nucleophilic addition of H2N group of the reagent to the carbonyl group at C3 of the oxo form В via the formation of intermediate 4 and completes by the elimination of a water molecule to yield compounds 2 (Scheme 2). The reactivity of the most electrophilic site C4=O results in the possibility of the addition of H2N group of the reagent to the carbonyl group at C4 of compound 2. Further the water elimination from the hemiaminal 5 results in the formation of compounds 3 (Scheme 2). EXPERIMENTAL IR spectra of saturated solutions in chloroform and of crystals of compounds 2a, 2b, and 3a–3c were recorded on an IR spectrophotometer Bruker Alpha (with an attachment for ATR, ZnSe). 1H NMR spectra were registered from solutions in CDCl3 on a Fourier spectrometer Bruker Avance II (400 MHz), internal reference TMS. Mass spectra were measured on a quadrupole time-of-flight super high resolution mass spectrometer maXis impact HD, Bruker Daltonik GmbH. The samples for measuring mass spectra were dissolved in acetonitrile and were delivered in the ion source of the mass spectrometer at a rate 240 µL/h using a syringe pump of the model 100 (of KD Scientific Inc., Holliston, MA). Positive ions were registered in the electrospray ionization mode (ESI) with a standard ionization source in the mass range 50–1300 Da with the parameters of the preset method Direct Infusion 100–1000. Mass calibration is external, improved quadratic, using the signals of a calibration mixture G1969–85000 (Adilent Technologies). The processing of mass spectra was performed using the program package (Compass for oTOF series 1.7, oTOF Control 3.4; Bruker Compass Data Analysis 4.2). XRD experiment was carried out on an automatic four-circle diffractometer with a CCD-detector Xcalibur 3 using a standard procedure [ω-scanning with a step 1°, monochromatic MоKα-radiation, 295(2) K]. An empiric correction for extinction was introduced. The structures were solved by the direct statistic method and refined in a full-matrix least-squares method with respect to F2 in an anisotropic approximation for all nonhydrogen atoms. Hydrogen atoms of the С‒Н bonds were placed in the geometrically calculated

641

positions and were refined in an isotropic approximation, the positions of protons of NH groups were refined independently. All calculations were carried out using software Olex2 [9]. Main crystallographic parameters of compound 2а are as follows: crystal triclinic, space group P-1, a 8.1344(9), b 8.4620(9), c 13.6107(17) Å; α 96.115(10), β 98.464(10), γ 112.789(11) deg; µ 0.129 mm–1. Within angles 2.65 < θ < 26.37° 6469 reflections were collected, among them 3441 independent (Rint 0.0272), 2010 of them with I > 2σ(I). The final refining parameters are as follows: R1 0.1010, wR2 0.1434 for all reflections, R1 0.0498, wR2 0.1157 for reflections with I > 2σ(I). The peaks of residual electron density are 0.19/‒0.18 ēÅ–3. Main crystallographic parameters of compound 3b are as follows: crystal monoclinic, space group P 21/c, a 10.2500(6), b 15.8727(10), c 8.6584(6) Å; β 101.929(3) deg, µ 0.122 mm–1. Within angles 2.03 < θ < 30.69° 6373 reflections were collected, among them 3614 independent (Rint 0.0280), 1995 of them with I > 2σ(I). The final refining parameters are as follows: R1 0.1148, wR2 0.1467 for all reflections, R1 0.0583, wR2 0.1178 for reflections with I > 2σ(I) at GooF 1.021. The peaks of residual electron density are 0.15/‒0.20 ēÅ–3. The full set of XRD data of compounds 2a and 3b was deposited in Cambridge Crystallographic Data Center (CCDC 1435771 and CCDC 1404997 respectively). The homogeneity of compounds obtained was proved by TLC on Sorbfil UV-254 plates in systems chloroform–methanol, 20 : 1; chloroform–hexane, 10 : 1; chloroform. Initial compounds 1a–1d were obtained by procedures [10, 11]. Compounds 2a, 2b, and 3а–3c. General procedure. 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 was added the necessary quantity of compound 1a–1d, and the mixture was boiled for 40 min (2a and 3b), 10 min (2b and 3c), 2 h (3a). The solvent was evaporated, the residue was dried and recrystallized from ethanol or ethyl acetate. Dimethyl (3Z)-3-[2-(2,4-dinitrophenyl)hydrazinylidene]-4-oxohexane-1,6-dioate (2а) was obtained from 2.02 g (10 mmol) of compound 1. Yield 0.99 g (26%), mp 124–125°С. IR spectrum (ATR, ZnSe), cm–1: 3223 [ν(NH)], 3094, 3064, 3015 [ν(СH, arom)], 2954 [νas(CH3)], 1729 [ν(C1,6=O)], 1687 [ν(C4=O)], 1613,

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1576, 1524 [ν(С=C, arom)], 1501 [νas(NO2)], 1438 [ν(С=C, arom)], 1333 [νs(NO2)], 1302 [νas(OC–OСН3, ester)], 1224, 1133, 1114, 1063, 1029, 1001 [νskeletal(C–C)], 922, 835 [δout-of-plane bending(CH, arom)], 743 [δpendulum(C2,5Н2)], 707 [νskeletal(C–C)]. IR spectrum (CHCl3), cm–1: 3020 [ν(NH)], 1740 [ν(C1,6=O)], 1698 [ν(C4=O)], 1618, 1586, 1527 [ν(С=C, arom)], 1506 [νas(NO2)], 1438 [ν(С=C, arom)], 1336 [νs(NO2)], 1215 [νas(OC–OСН3, ester)], 1139 [νskeletal(C–C)], 920 [δout-of-plane bending(CH, arom)], 747 [δpendulum(C2,5Н2)], 668 [νskeletal(C–C)]. 1Н NMR spectrum, δ, ppm: 3.73 s (3H, C1OOCH3), 3.78 s (3H, C6OOCH3), 3.84 s (2H, C2H2), 3.96 s (2H, C5H2), 8.07–9.17 m (3HAr), 11.86 s (1H, NH). Found m/z 383.0834 [M + H]+. С14H15N4O9+. Calculated M 383.0834. Diethyl (3Z)-3-[2-(2,4-dinitrophenyl)hydrazinylidene]-4-oxohexane-1,6-dioate (2b) was obtained from 2.30 g (10 mmol) of compound 1b. Yield 2.50 g (48%), mp 100–105°С. IR spectrum (ATR, ZnSe), cm–1: 3198 [ν(NH)], 3096, 3064 [ν(СH, arom)], 2987 [νas(CH3)], 2943 [νas(CH2)], 1722 [ν(C1,6=O)], 1685 [ν(C4=O)], 1613, 1576, 1524 [ν(С=C, arom)], 1501 [νas(NO2)], 1445 [ν(С=C, arom)], 1333 [νs(NO2)], 1299 [νas(OC– OС2Н5, ester)], 1223, 1133, 1112, 1063, 1026, 1010 [νskeletal(C–C)], 921, 835 [δout-of-plane bending(CH, arom)], 743 [δpendulum(C2,5Н2)], 706 [νskeletal(C–C)]. IR spectrum (CHCl3), cm–1: 3020 [ν(NH)], 1735 [ν(C1,6=O)], 1695 [ν(C4=O)], 1618, 1586, 1527 [ν(С=C, arom)], 1506 [νas(NO2)], 1440 [ν(С=C, arom)], 1335 [νs(NO2)], 1215 [νas(OC–OСН3, ester)], 1139, 1047, 1028 [νskeletal(C–C)], 954 [δout-of-plane bending(CH, arom)], 747 [δpendulum(C2,5Н2)], 668 [νskeletal(C–C)]. 1Н NMR spectrum, δ, ppm: 1.28 t (3H, C1OOCH2CH3), 1.33 t (3H, C6OOCH2CH3), 3.87 s (2H, C2H2), 3.98 s (2H, C5H2), 4.22 q (2H, C1OOCH2CH3), 4.27 q (2H, C6OOCH2CH3), 8.10–9.25 m (3HAr), 11.90 s (1H, NH). Found m/z 411.1148 [M + H]+. С12H19N4O9+. Calculated M 411.1147. Diethyl (3Z,4Z)-3,4-bis[2-(2,4-dinitrophenyl)hydrazinylidene]hexane-1,6-dioate (3а) was obtained from 2.30 g (10 mmol) of compound 1b. Yield 1.12 g (30%), mp 225–227°С. IR spectrum (ATR, ZnSe), cm–1: 3278 [ν(NH)], 3107, 3064 [ν(СH, arom)], 2988 [νas(CH3)], 2940 [νas(СН2)], 1739 [ν(C1,6=О)], 1610, 1580, 1521 [ν(С=C, arom)], 1492 [νas(NO2)], 1449 [ν(С=C, arom)], 1335, 1311 [νs(NO2)], 1260 [νas(OC–OС2Н5, ester)], 1222, 1158, 1138, 1107, 1063, 1045, 1012 [νskeletal(C–C)], 916, 845 [δout-of-plane bending(CH, arom)], 740 [δpendulum(СН2)]. IR spectrum (CHCl3), cm–1: 3020 [ν(NH)], 1735 [ν(C1,6=O)], 1615, 1581, 1529 [ν(С=C, arom)], 1500 [νas(NO2)], 1441 [ν(С=C, arom)], 1337

[νs(NO2)], 1215 [νas(OC–OС2Н5, ester)], 1134, 1097 [νskeletal(C–C)], 921 [δout-of-plane bending(CH, arom)], 746 [δpendulum(C2,5Н2)], 668 [νskeletal(C–C)]. 1Н NMR spectrum, δ, ppm: 1.31 t (6H, 2COOCH2CH3, J 7.5 Hz), 4.03 s (4H, 2C2,5H2), 4.26 q (4H, 2COOCH2CH3, J 7.5 Hz), 8.05–9.20 m (6HAr), 11.89 s (2H, 2NH). Found m/z 591.1422 [M + H]+. С22H23N8O+12. Calculated M 591.1430. Dipropyl (3Z,4Z)-3,4-bis[2-(2,4-dinitrophenyl)hydrazinylidene]hexane-1,6-dioate (3b) was obtained from 2.58 g (10 mmol) of compound 1c. Yield 1.12 g (21%), mp 167–169°С. IR spectrum (ATR, ZnSe), cm–1: 3297 [ν(NH)], 3103, 3062 [ν(СH, arom)], 2968 [νas(CH3)], 2941 [νas(СН2)], 2898 [νs(СН2)], 1736 [ν(C1,6=О)], 1611, 1581, 1522 [ν(С=C, arom)], 1490 [νas(NO2)], 1446 [ν(С=C, arom)], 1334, 1310 [νs(NO2)], 1263 [νas(OC–OС3Н7, ester)], 1223, 1166, 1139, 1104, 1060, 1029, 969 [νskeletal(C–C)], 911, 850 [δout-of-plane bending(CH, arom)], 740 [δpendulum(СН2)]. IR spectrum (CHCl3), cm–1: 3020 [ν(NH)], 1734 [ν(C1,6=O)], 1615, 1596, 1521 [ν(С=C, arom)], 1500 [νas(NO2)], 1440 [ν(С=C, arom)], 1338 [νs(NO2)], 1215 [νas(OC–OС3Н7, ester)], 1139, 1111, 1065, 1037 [νskeletal(C–C)], 920 [δout-of-plane bending(CH, arom)], 747 [δpendulum(C2,5Н2)], 668 [νskeletal(C–C)]. 1Н NMR spectrum, δ, ppm: 0.92 t (6H, 2COOCH2CH2CH3, J 7.2 Hz), 1.69 m (4H, 2COOCH2CH2CH3), 4.05 s (4H, 2C2,5H2), 4.16 t (4H, 2COOCH2CH2CH3, J 7.2 Hz), 8.05–9.20 m (6HAr), 11.93 s (2H, 2NH). Found m/z 619.1740 [M + H]+. С24H27N8O+12. Calculated M 619.1743. Dibutyl (3Z,4Z)-3,4-bis[2-(2,4-dinitrophenyl)hydrazinylidene]hexane-1,6-dioate (3с) was obtained from 2.86 g (10 mmol) of compound 1d. Yield 0.90 g (37%), mp 165–168°С. IR spectrum (ATR, ZnSe), cm–1: 3317 [ν(NH)], 3102, 3061 [ν(СH, arom)], 2961 [νas(CH3)], 2938 [νas(СН2)], 2872 [νs(СН2)], 1727 [ν(C1,6=О)], 1614, 1588, 1516 [ν(С=C, arom)], 1496 [νas(NO2)], 1437 [ν(С=C, arom)], 1325, 1309 [νs(NO2)], 1268 [νas(OC–OС4Н9, ester)], 1211, 1181, 1135, 1110, 1066, 1034, 1015 [νskeletal(C–C)], 920, 831 [δout-of-plane bending(CH, arom)], 735 [δpendulum(СН2)]. IR spectrum (CHCl3), cm–1: 3065 [ν(NH)], 1730 [ν(C1,6=O)], 1615, 1590, 1523 [ν(С=C, arom)], 1500 [νas(NO2)], 1433 [ν(С=C, arom)], 1338 [νs(NO2)], 1217 [νas(OC–OС4Н9, ester)], 1139, 1065, 1044 [νskeletal(C–C)], 923 [δout-of-plane bending(CH, arom)], 748 [δpendulum(C2,5Н2)], 669 [νskeletal(C–C)]. 1Н NMR spectrum, δ, ppm: 0.89 t (6H, 2COOCH2CH2· CH2CH3, J 7.2 Hz), 1.35 m (4H, 2COOCH2CH2CH2· CH3), 1.65 m (4H, 2COOCH2CH2CH2CH3), 4.04 s (4H, 2C2,5H2), 4.20 q (4H, 2COOCH2CH2CH2CH3, J

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REACTION OF 3,4-DIOXOHEXANE-1,6-DIOIC ACID ESTERS

7.2 Hz), 8.05–9.20 m (6HAr), 11.90 s (2H, 2NH). Found m/z 647.2054 [M + H]+. С26H31N8O+12. Calculated M 647.2056. REFERENCES 1. Fusko, R. and Zumin, S., Gazz. Chim. Ital., 1946, vol. 76, p. 223. 2. Finar, I.L., J. Chem. Soc., 1955, p. 1205. 3. Shironina, T.M., Igidov, N.M., Koz’minykh, E.N., Kon’shina, L.O., Kasatkina, Yu.S., and Koz’minykh, V.O., Russ. J. Org. Chem., 2001, vol. 37, p. 1486. 4. Perevalov, S.G., Burgart, Ya.V., Saloutin, V.I., and Chupakhin, O.N., Russ. Chem. Rev., 2001, vol. 70, p. 921. 5. Mukovoz, P.P. and Koz’minukh, V.O., Vestn. YuzhnoUral. Gos. Univer., 2009, p. 4. 6. Bellami, L., Infrakrasnye spektry slozhnykh molekul (The Infrared Spectra of Complex), Moscow: Inostrannaya Literatura, 1963.

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7. International Tables for Crystallography, 2006, vol. C, p. 790. 8. Andreeva, V.A., Mukovoz, P.P., Slepukhin, P.A., El’tsov, O.S., Koz’minykh, E.N., and Koz’minykh, V.O., Innovatsionnye tekhnologii v nauke i obrazovanii. Materialy II mezhdynarodnoi nauchno-prakticheskoi konferentsii (Innovative Technologies in Science and Education. Proceedings of the II International Scientific and Practical Conference), Cheboksary: 2015, p. 20. 9. Dolomanov, O.V., Bourhis, L.J., Gildea, R.J., Howard, J.A.K., and Puschmann, H., J. Appl. Cryst., 2009, vol. 42, p. 339. 10. Koz’minykh, V.O., Mukovoz, P.P., and Kirillova, E.A., Vestn. Orenburg. Gos. Univer., 2009, p. 155. 11. Mukovoz, P.P., Dvorskaya, O.N., and Koz’minykh, V.O., Izv. Vuzov, Ser. Khim. Khim. Tekhnol., 2011, vol. 54, p. 96.

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