Study of geometric isomerism of ethyl β-aryl(hetaryl)-α-nitroacrylates by 1H NMR spectroscopy method

Article abstract of DOI:10.1134/S1070363216010102

Features of Z→E isomerization of ethyl α-nitrocinnamates as well as their furyl and thienyl heteroanalogs depending on the nature of the substituent in the β-position of α-nitroacrylates, deuterated solvent and duration of exposure of the sample were stud

Full text of DOI:10.1134/S1070363216010102

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 1, pp. 51–57. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © R.I. Baichurin, D.B. Berestovitskaya, L.V. Baichurina, N.I. Aboskalova, V.M. Berestovitskaya, 2016, published in Zhurnal Obshchei
Khimii, 2016, Vol. 86, No. 1, pp. 56–62.
Study of Geometric Isomerism
of Ethyl β-Aryl(hetaryl)-α-nitroacrylates
by 1H NMR Spectroscopy Method
R. I. Baichurina, D. B. Berestovitskayaa, L. V. Baichurinab,
N. I. Aboskalovaa, and V. M. Berestovitskayaa
a Herzen State Pedagogical University of Russia, nab. reki Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
b Kirov Military Medical Academy, St. Petersburg, Russia
Received June 11, 2015
Abstract—Features of Z→E isomerization of ethyl α-nitrocinnamates as well as their furyl and thienyl
heteroanalogs depending on the nature of the substituent in the β-position of α-nitroacrylates, deuterated
solvent and duration of exposure of the sample were studied by means of 1H NMR spectroscopy.
Keywords: nitroalkenes, α-nitroacrylates, geometric isomerism, 1H NMR spectroscopy
DOI: 10.1134/S1070363216010102
This work consisted in the study the geometric
isomerism of ethyl β-aryl(furyl, thienyl)-α-nitro-
acrylates 1–7 synthesized by the condensation of ethyl
nitroacetate with the corresponding aldehydes (1–4, 6,
7) [1, 2] or azomethine (5) [3]. The configuration of
compounds 1–7 was unambiguously determined based
on the analysis of their spectral characteristics in com-
parison with those of the model E-nitroethenes [1, 2].
This fact suggests that immediately after dissolution in
CDCl3 compounds 1–7 are individual Z-isomer [cis-
orientation of aryl(hetaryl) and nitro moieties].
Previously [2] compound 6 (mp 46–48°C) has been
obtained as a mixture of Z- and E-isomers in a ratio of
2 : 1. After repeated treatment of the mixture with
different solvents, we isolated and characterized an
individual Z-isomer of 6 (mp 50–51°C).
R
NO2
It was interesting to find out the main factors
affecting the stability of Z-isomers of α-nitroacrylates
1
1–7 and their transformation into E-form using H
NMR spectroscopy method.
HA
COOEt
Z
1_7
The first experiments on studying Z →← E transforma-
tions among β-aryl(hetaryl)-α-nitroacrylates under
conditions of photo and thermal isomerization were
performed earlier by the example of α-nitrocinnamate
[6]. Thus, upon irradiation of a benzene solution of
ethyl Z-α-nitrocinnamte with the use of high pressure
R = Ph (1), 4-MeOC6H4 (2), 4-Me2NC6H4 (3), 4-ClC6H4 (4),
4-O2NC6H4 (5), 2-furyl (6), 2-thienyl (7).
The main criterion in determining the configuration
of α-nitroacrylates 1–7 was the chemical shift value of
olefin proton НА: when the proton НА is cis-oriented
towards the nitro group, its value of chemical shift is
higher than that in the trans-isomer (because of the
anisotropy of NO2 moiety [4, 5]).
→
mercury lamp a Z ← E equilibrium (Z : E = 1 : 1) was
established after 8 h. Moreover, the individual E-
isomer (nD20 = 1.5780) was isolated by column chro-
matography [6]. A reverse isomerization E→Z took
place under similar conditions.
1
In the H NMR spectra (CDCl3) of the considered
compounds 1–7 the proton signals are upfield (7.33–
7.70 ppm) with respect to the position thereof in the
spectra of the model E-nitroethenes (7.69–8.08 ppm).
Conversion of Z-isomer of ethyl α-nitrocinnamate
into the E-form (50%) when heated for 8 h at 175°C
under reduced pressure (3 mmHg) was also observed
51

52
BAICHURIN et al.
EtO
C
[6]. A reverse process E→Z took place at room tem-
perature in the dark.
C
O_
H
C
Somewhat later [7], the thermal isomerization of
methyl Z-α-nitrocinnamate was performed at 180°C in
10 h; the composition of the equilibrium mixture was
E : Z = 41 : 59.
NO2
Me+2N
The isomerization of methyl Z-α-nitrocinnamate in
some aprotic solvents to form an equilibrium mixture
of Z- and E-isomers has been observed in [7, 8]. An
analogous transformation Z→E has also been observed
by Blaha et al. [9] when the process was performed in
nitrobenzene at room temperature (several h) or on
heating (several minutes); and E-isomer was not
isolated preparatively.
The maximum content of E-isomer of compound 3
in a CDCl3 solution was observed after exposure for 28 h
(51%), in (CD3)2CO, after 19.5 h (53%), in CD3CN,
after 2.5 h (58%), and in (CD3)2SO, after 0.5 h (64%).
The influence the electronic nature of the sub-
stituent in the benzene ring on the tendency of α-nitro-
acrylates 1–5 to E→Z isomerization was estimated by
the content of E-isomers measured for the same time
interval of exposure in a particular solvent. For
example, after 30 min in a (CD3)2SO solution the
proportion of E-isomer reached 45 (1), 50 (2) 64 (3),
40 (4), 13% (5). It should be noted that for the above
compounds 1–3 the E-isomer content is maximal, and
for compounds 4 and 5 the maximum proportion of E-
isomer (45% for E-4 and 46% for E-5) was attained
after 1.2 and 28 h, respectively.
Recently [1], we found a tendency to Z→E iso-
merization of individual Z-isomer of α-nitrocinnamate
3 containing strong electron-donor dimethylamino
group in benzene ring when solved in CDCl3. An
exposure of a solution of compound Z-3 in CDCl3 at
18–20°C for 2 days resulted in a formation of isomer
mixture with a ratio of Z : E = 1 : 1.1.
A detailed study of the isomerization process of Z-3
showed that in CDCl3 solution the content of E-isomer
increases gradually to about 51%, and then changed
very little with increasing the exposure time from 4
minutes to 28 h. In contrast, other Z-α-nitroacrylates 1,
2, 4 and 5 are quite stable in solution and almost no
isomerization occurs. In the case of furyl and thienyl
analogs 6 and 7 (exposure in CDCl3 for 4–7 days) the
maximum content of E-isomer was only 2%.
For furyl and thienyl analogs 6 and 7 the maximum
content of E-isomer in a (CD3)2SO solution was 41
(after ~7 days) and 48% (after 19.5 h), respectively.
1
Analysis of H NMR spectra of the solutions of α-
nitrocinnamates 1–4 in CD3OD showed that in this
case E→Z isomerization [after 1.5 h, the content of E-
isomer was 8% for compound 1, 0% for 2, 53% for 3
(no change since 16 minute), and 14% for 4] was accom-
panied by addition of CD3OD as nucleophile to the
C=C bond of α-nitroacrylates. This is evidenced by the
appearance of the signals of the methine proton of
The 1Н NMR data for α-nitroacrylates 1–7 in
(CD3)2SO, (CD3)2CO, CD3CN, and CD3OD solutions
are listed in table; the spectral characteristics of
compounds 1–7 in CDCl3 have been shown in our
previous reports [1, 2].
1
adducts at ~5 ppm in their H NMR spectra and by
shifting the signals of ethoxy groups (after 8.7 h for
compound 1, after 44 h for compound 2, after 96 h for
compound 3, after 19.6 h for compound 4).
For example, compound Z-3 demonstrates clearly
the dependence of the rate of Z→E isomerization on
the solvent polarity. Thus, in a series of deuterated
solvents CDCl3–(CD3)2CO–CD3CN–(CD3)2SO, arranged
in order of increasing dielectric constant, which is a
measure of polarity [10], a growing E-isomer content
was observed. For example, the percentage of E-3 after
30 minutes was 6% in CDCl3, 6.5% in (CD3)2CO, 56%
in CD3CN, 64% in (CD3)2SO. This fact is quite logical,
as the more polar solvents better solvated the bipolar
structure that facilitates the rotation around the quasi-
single bond and promotes the isomerization process.
R
H
NO2
COOEt
R
H
NO2
D
Z
CD3OD
* *
D3CO
COOEt
R
COOEt
NO2
H
E
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

STUDY OF GEOMETRIC ISOMERISM OF ETHYL β-ARYL(HETARYL)-α-NITROACRYLATES
53
1Н NMR spectral data of the solutions of α-nitroacrylates 1–7 in (CD3)2SO, (CD3)2CO, CD3CN, and CD3OD (δ, ppm)
R
NO2
R
COOEt
HA
COOEt
HA
NO2
Z
E
1_7
Comp.
no.
CH3O
[(CH3)2N]
R
Solvent
HA
CH3
OCH2
4.32 q
Ar [Het]
Configuration
1
Ph
(CD3)2SO
7.84 s
1.25 t
–
7.42–7.63 m (5Н)
Z
3J = 7.1
8.36 s
7.64 s
1.22 t
3J = 7.1
1.33 t 4.35 q
3J = 7.2
1.30 t 4.40 q
3J = 7.2
1.25 t 4.30 q 3.79 s
3J = 7.1
1.26 t 4.40 q
3J = 7.1
1.32 t 4.33 q
3J = 7.1
1.33 t 4.42 q
3J = 7.2
1.23 t 4.25 q
3J = 7.1
1.27 t 4.38 q
3J = 7.1
1.29 t 4.29 q
3J = 7.2
1.34 t 4.43 q
3J = 7.2
1.27 t 4.27 q
3J = 7.1
1.32 t 4.41 q
3J = 7.2
1.31 t 4.29 q
3J = 7.2
1.35 t 4.42 q
4.38 q
–
–
–
7.42–7.63 m (5Н)
Eа
Z
CD3OD
7.39–7.47 m (4Н),
7.47–7.53 m (1Н)
8.18 s
7.73 s
8.30 s
7.54 s
8.12 s
7.52 s
8.13 s
7.45 s
8.04 s
7.42 s
8.02 s
7.39 s
8.02 s
7.35–7.58 m (5Н)
Eb
Z
2
3
4-MeOC6H4 (CD3)2SO
CD3OD
7.05 d, 7.46 d
3J = 8.9
3.82 s
3.83 s
7.05 d, 7.46 d
Eа
Z
3J = 8.9
6.98 d, 7.41 d
3J = 9.0
3.85 s
7.02 d, 7.53 d
Eb
Z
3J = 9.0
4-Me2NC6H4 (CD3)2SO
(CD3)2CO
[2.98 s]
[3.02 s]
[3.05 s]
[3.08 s]
[2.99 s]
[3.03 s]
[3.03 s]
[3.07 s]
6.71 d, 7.29 d
3J = 9.1
6.76 d, 7.42 d
Eа
Z
3J = 9.1
6.73 d, 7.33 d
3J = 9.0
6.78 d, 7.48 d
Eb
Z
3J = 9.0
CD3CN
6.68 d, 7.27 d
3J = 9.2
6.72 d, 7.38 d
Eа
Z
3J = 9.2
CD3OD
6.69 d, 7.29 d
3J = 9.2
6.75 d, 7.40 d
Eа
3J = 9.2
3J = 7.2
1.25 t 4.31 q
(CD3)2SO
4-ClC6H4
7.85 s
–
7.47 d, 7.55 d
3J = 8.6
Z
Z
4
3J = 7.1
7.47 d, 7.55 d
3J = 8.6
8.36 s
7.63 s
1.22 t
3J = 7.1
1.33 t 4.35 q
4.38 q
–
–
7.56–7.61 m
7.56–7.61 m
7.42 d, 7.45 d
3J = 9.0
Eа
Eа
Z
CD3OD
3J = 7.2
1.30 t 4.41 q
8.16 s
–
7.48 d, 7.53 d
3J = 8.9
7.48 d, 7.53 d
3J = 8.9
Eb
Eb
3J = 7.2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

54
BAICHURIN et al.
CH3O
Table. (Contd.)
Comp.
R
Solvent
HA
CH3 OCH2
Ar [Het]
Configuration
no.
[(CH3)2N]
5
4-O2NC6H4 (CD3)2SO 8.04 s 1.27 t 4.35 q
–
7.70 d, 8.29 d
3J = 8.8
Z
3J = 7.1
8.49 s 1.21 t 4.38 q
3J = 7.1
7.81 d, 8.31 d
3J = 8.8
Eа
Zc
Z
CD3OD
7.83 s 1.35 t 4.39 q
–
–
–
–
–
–
7.68 d, 8.29 d
3J = 8.9
3J = 7.2
6
2-Furyl
(CD3)2SO 7.70 s 1.23 t 4.28 q
3J = 7.1
[6.74 d.d (3J 1.8, 3J 3.6), 7.29 d
(3J = 3.6), 8.02 d (3J = 1.8)]
8.22 s 1.28 t 4.38 q
3J = 7.1
[6.80 d.d (3J 1.8, 3J 3.6), 7.41 d
(3J = 3.6), 8.09 d (3J = 1.8)]
Eа
Z
CD3OD
7.48 s 1.31 t 4.32 q
3J = 7.1
[6.64 d.d (3J 1.8, 3J 3.6), 7.06 d
(3J = 3.6), 7.75 d (3J = 1.8)]
[6.69 d.d (3J = 1.8, 3J = 3.6), 7.21 d
(3J = 3.6), 7.82 d (3J = 1.8)]
[7.26 d.d (J = 3.8, 5.1), 7.79 d.d.d
(J = 3.8, 1.2, 0.5), 8.06 d.d.d (J = 5.1,
1.1, 0.9)]
7.83 s 1.39 t 4.46 q
3J = 7.1
Eb
Z
7
2-Thienyl
(CD3)2SO 8.12 s 1.25 t 4.30 q
3J = 7.1
8.64 s 1.30 t 4.41 q
3J = 7.1
–
–
[7.29 d.d (J = 3.8, 5.0), 7.79 d.d.d
(J = 3.8, 1.2, 0.5), 8.06 d.d.d (J = 5.0,
1.2, 1.0)]
[7.27 d.d (J = 3.8, 5.1), 7.71 d.d.d
(J = 3.8, 1.1, 0.6), 7.98 d.d.d (J = 5.1,
1.2, 0.8)]
Eа
Z
(CD3)2CO 7.96 s 1.30 t 4.34 q
3J = 7.1
8.47 s 1.36 t 4.46 q
–
–
–
[7.30 d.d (J = 3.8, 5.1), 7.86 d.d.d
(J = 3.8, 1.2, 0.6), 8.03–8.06 m]
Eb
Z
3J = 7.2
7.86 s 1.32 t 4.33 q
3J = 7.2
CD3OD
[7.18 d.d (J = 3.8, 5.1), 7.57 m, 7.85 m]
8.39 s 1.37 t 4.45 q
3J = 7.2
[7.21 m, 7.68 m, 7.91 m]
Eb
a
Formation of E-isomer was detected almost immediately after the sample dissolution. b E-Isomer appeared after exposure in time. c The
signals of the alkoxylation product were registered within 7 min.
For example, ethyl-3-(4-chlorophenyl)-2-nitropropeno-
It should be noted that addition of alcohols to the
esters of α-nitrocinnamic acid was first observed before
[6, 7].
ate 4 in a solution of CD3OD after a week (Fig. 1) is
almost completely converted to the alkoxylation product
8a, 8b, which is a mixture of diastereomers a : b = 1.2 : 1
[δH, ppm: diastereomer a, 0.96 t (CH3), 3.97 d.q and
Undoubtedly, the rate of the reaction of alcohols
with α-nitroacrylates depends on the electrophilicity of
the double bond. Thus, according to [11], methyl
α-nitrocinnamate attached readily ethanol at 20°C,
and its dimethylamino-substituted analog did not react
with an alcohol, even while boiling. Some O-adducts,
for example, the adducts of methanol and ethanol with
ethyl β-(4-acetoxy-3-methoxyphenyl)-α-nitroacrylate
were obtained in yields of 90–100% [12].
2
3
3.99 d.q (СН2, J = –10.8, J = 7.2 Hz), 5.00 s (СН);
diastereomer b, 1.24 t (CH3), 4.26 q (СН2, 3J = 7.2 Hz),
5.03 s (СН); 7.33–7.45 m (С6Н4, both diastereomers)].
In the case of α-nitrocinnamate 5 containing para-
nitro-substituted benzene ring almost immediately
(after 7 min) after dissolution in CD3OD the signals of
AdN product were registered in the 1H NMR spectrum.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

STUDY OF GEOMETRIC ISOMERISM OF ETHYL β-ARYL(HETARYL)-α-NITROACRYLATES
55
Z,E,a,b
Z-4
E-4
b
8a, 8b
b
b
δ, ppm
1
Fig. 1. Н NMR spectra of compound Z-4 in CD3OD registered after (a) 2 h (a mixture of Z- and E-isomers of 4) and (b) 1 week
(adduct 8a, 8b is highlighted with dotted line). R = 4-ClC6H4.
The reaction of ethyl α-nitrocinnamate 5 containing
para-nitro substituted benzene ring with methanol
(room temperature, 12 h) afforded the methoxylation
product 9 in 69% yield. According to the H NMR
spectrum recorded in CDCl3 (Fig. 2), compound 9 is a
The similar ethoxylation product 10a, 10b we
isolated as an oily substance by recrystallization of α-
nitroacrylate 5 from ethanol. According to the H
1
1
NMR data (CDCl3), unlike compound 9 this adduct is
a mixture of diastereomers a and b in a ratio of 1.5 : 1
[δ, ppm: diastereomer a, 5.28 (HA, 3JAB = 9.7 Hz), 5.23
diastereomerically pure compound.
3
3
O 2N
(HB, JAB = 9.7 Hz); diastereomer b, 5.25 (HA, JAB
8.3 Hz), 5.21 (HB, 3JAB = 8.3 Hz)].
=
c
d
b
a
H A
N O 2
Thus, studying β-aryl(hetaryl)-α-nitroacrylates 1–7
by means of H NMR spectroscopy showed that they
3
1
2
1
are Z-isomers, capable of isomerization when
maintained in solutions of (CD3)2CO, CD3CN,
(CD3)2SO, and CD3OD; maximal isomerization is
observed in (CD3)2SO solution. In the case of CD3OD
the isomerization is accompanied by adding the
alcohol to the double C=C bond, which must be
considered when carrying out the reactions of β-aryl-
(hetaryl)-α-nitroacrylates in an alcohol solution.
C O O E t
A lkO
H B
Alk = Me (9), Et (10а, 10b).
Its 1H NMR spectrum contained two doublet signals
of the methine protons HA and HB at 5.28 and 5.12 ppm
(3JAB = 9.7 Hz). The protons of methyl and methylene
groups of the ester moiety gave rise to triplet at 1.06
ppm and two doublets of quartets (due to magnetic
nonequivalence of the diastereotopic methylene
protons) at 4.01 and 4.08 ppm (3J = 7.2, –10.8 Hz).
The singlet at 3.26 ppm corresponded to the proton of
methoxy group; the protons of p-substituted benzene
ring resonated as doublets at 7.61 and 8.26 ppm (3J =
8.8 Hz). In the 13C NMR–{1H} spectrum there were
signals of all the carbon atoms. The signal assignments
were performed using HMQC and HMBC methods.
EXPERIMENTAL
Physicochemical studies were performed in the
Center for Collective Use of the faculty of chemistry,
Herzen State Pedagogical University of Russia.
1
1Н, 13С–{1Н}, Н–13С HMQC and HMBC NMR
spectra were recorded on a Jeol ECX400A spectro-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

56
BAICHURIN et al.
δ, ppm
Fig. 2. 1Н NMR spectrum of compound 9 in CDCl3.
2
meter [399.78 (1H), 100.52 (13C) MHz] using the
signal of the residual undeuterated solvent [CDCl3,
(CD3)2SO, (CD3)2CO, CD3CN, CD3OD] as an internal
reference. IR spectra (CHCl3) were obtained on a
Fourier spectrometer IRPrestige-21. Elemental analysis
was performed on an EuroVector EA 3000 analyzer
(CHN Dual mode).
OСН3), 4.01 d.q and 4.08 d.q (2Н, ОСН2, J = –10.8,
3J = 7.2), 5.12 d (1H, HB, JAB = 9.7), 5.28 d (1H, HA,
3
3JAB = 9.7), 7.61 d (2H, Hb, J = 8.8), 8.26 d (2H, Hc,
3
3J = 8.8). 13С–{1H} NMR spectrum (CDCl3), δС, ppm:
13.70 (СН3), 57.77 (OCH3), 63.45 (ОСН2), 80.56 (С3),
91.56 (С2), 124.10 (Сс), 129.20 (Cb), 141.85 (Ca),
148.74 (Cd), 161.42 (C1). Found, %: C 48.15, 48.08; H
4.63, 4.65; N 9.32, 9.35. C12H14N2O7. Calculated, %: С
48.32; Н 4.70; N 9.40.
α-Nitroacrylates 1–4 [1], 5 [6], 6 and 7 [2] were
obtained by the known procedures.
Ethyl 3-ethoxy-2-nitro-3-(4-nitrophenyl)propano-
ate (10a, 10b). Yield 96%, colorless oil (according to
1H NMR, the substance contains no impurities and is a
mixture of diastereomers а and b in a ratio of ~ 1.5 : 1),
Rf 0.45 (10a), 0.27 (10b) (Silufol UV-254, hexane–
acetone, 3 : 1). IR spectrum, ν, cm–1: 1528, 1570, 1351
The isomerization course was monitored by a
change in the ratio of the integrated intensities of the
signals of OCH2 groups (in most cases) or olefin
protons HA in the original Z- and formed E-isomers.
Ethyl 3-methoxy-2-nitro-3-(4-nitrophenyl)pro-
panoate (9). A slurry of 0.133 g (0.5 mmol) of ethyl 2-
nitro-3-(4-nitrophenyl)propenoate 5 in 10 mL of
methanol was stirred at room temperature. After 12 h,
the resulting solution was poured into a Petri dish.
After evaporation of the solvent, the residue was
treated with ethanol. Yield 0.103 g (69%), colorless
1
(2NO2), 1751 (C=O). Н NMR spectrum (CDCl33), δ,
ppm (J, Hz): diastereomer a, 1.04 t (3Н, СН3, J =
3
7.2), 4.00 d.q and 4.07 d.q (2Н, СOOCH2CH3, J =
2
3
7.2, J = –10.8), 1.13 t (3Н, СН3, J = 7.0), 3.40 d.q
and 3.43 d.q (2Н, OCH2CH3, 3J = 7.0, J = –9.2), 5.23
2
3
3
d (1H, HB, JAB = 9.7), 5.28 d (1H, HA, JAB = 9.7),
1
7.61 d (2H, Hb, J = 8.8), 8.24 d (2H, Hc, J = 8.8);
diastereomer b, 1.33 t (3Н, СН3, 3J = 7.2), 4.34 m (2Н,
СOOCH2CH3), 1.16 t (3Н, СН3, 3J = 7.0), 3.46 d.q and
3
3
crystals, mp 68–70°C (according to H NMR, the
substance contains no impurities and is a single
diastereomer). IR spectrum, ν, cm–1: 1529, 1571, 1351
1
3
2
(2NO2), 1751 (C=O). Н NMR spectrum (CDCl3), δ,
3.50 d.q (2Н, OCH2CH3, J = 7.0, J = –9.2), 5.21 d
3
(1H, HB, JAB = 8.3), 5.25 d (1H, HA, 3JAB = 8.3), 7.59
3
ppm (J, Hz): 1.06 t (3Н, СН3, J = 7.2), 3.26 s (3Н,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

STUDY OF GEOMETRIC ISOMERISM OF ETHYL β-ARYL(HETARYL)-α-NITROACRYLATES
57
d (2H, Hb, 3J = 8.8), 8.23 d (2H, Hc, 3J = 8.8). 13С–{1H}
NMR spectrum (CDCl3), δС, ppm: diastereomer a,
14.86 (СOOCH2CH3), 63.34 (СOOCH2CH3), 161.52
(С1), 13.60 (OCH2CH3), 65.85 (OCH2CH3), 78.76
(С3), 91.90 (С2), 123.97 (Сс), 129.05 (Cb), 142.62 (Ca),
148.54 (Cd); diastereomer b, 14.98 (СOOCH2CH3),
63.43 (СOOCH2CH3), 162.02 (С1), 13.93 (OCH2CH3),
66.25 (OCH2CH3), 78.34 (С3), 90.89 (С2), 123.97 (Сс),
128.70 (Cb), 143.31 (Ca), 148.54 (Cd).
5. Ionin, B.I., Ershov, B.A., and Kol’tsov, A.I., YaMR
spektroskopiya v organicheskoi khimii (NMR Spectro-
scopy in Organic Chemistry), Leningrad: Khimiya,
1983.
6. Yamamura, K., Watarai, S., and Kinugasa, T., Bull.
Chem. Soc. Japan, 1971, vol. 44, no. 9, p. 2440. DOI:
10.1246/bcsj. 44.2440.
7. Babievskii, K.K., Belikov, V.M., Filatova, I.M., and
Garbalinskaya, N.S., Bull. Acad. Sci. USSR. Div. Chem.
Sci., 1973, vol. 22, no. 7, p. 1556. DOI: 10.1007/
BF00930060.
ACKNOWLEDGMENTS
8. Babievskii, K.K., Belikov, V.M., Vinogradova, A.I.,
and Latypov, V.K., Zh. Org. Khim., 1973, vol. 9, no. 8,
p. 1700.
This work was financially supported by the
Ministry of Education of Russia in the frame of the
basic part of the governmental task.
9. Blaha, I. and Leseticku, L., Coll. Czech. Chem.
Commun., 1986, vol. 51, no. 5, p. 1094. DOI: 10.1135/
cccc19861094.
REFERENCES
10. Traven’, V.F., Organicheskaya khimiya (Organic Che-
mistry), Moscow: BINOM. Laboratoriya Znanii, 2013,
vol. 1, p. 92.
1. Baichurin, R.I., Baichurina, L.V., Aboskalova, N.I., and
Berestovitskaya, V.M., Russ. J. Gen. Chem., 2013,
vol. 83, no. 9, p. 1764. DOI: 10.1134/S1070363213090223.
2. Baichurina, L.V., Baichurin, R.I., Aboskalova, N.I., and
Berestovitskaya, V.M., Russ. J. Gen. Chem., 2010,
vol. 80, no. 10, p. 2022. DOI: 10.1134/S1070363210100221.
11. Kochetkov, K.A., Babievskii, K.K., Belikov, V.M.,
Garbalinskaya, N.S., and Bakhmutov, V.I., Bull. Acad.
Sci. USSR. Div. Chem. Sci., 1980, vol. 29, no. 3, p. 458.
DOI: 10.1007/BF00949634.
3. Dornow, A. and Menzel, H., Lieb. Ann., 1954, vol. 588,
12. Babievskii, K.K., Filatova, I.M., Belikov, V.M.,
Makhnova, L.I., Pomilenko, R.I., Sapozhnikova, É.P.,
and Sveklova, V.I., Bull. Acad. Sci. USSR. Div. Chem.
Sci., 1976, vol. 25, no. 12, p. 2549. DOI: 10.1007/
BF00920896.
no. 1, p. 40. DOI: 10.1002/jlac.19545880105.
4. Perekalin, V.V., Sopova, A.S., and Lipina, E.S.,
Nepredel’nye nitrosoedineniya (Unsaturated Nitro Com-
pounds), Leningrad: Khimiya, 1982, p. 336.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016