Synthesis and structure of nitroethylpyrrolidone carboxylates

Article abstract of DOI:10.1134/S1070363211080172

3-Methoxycarbonyl-4-phenyl- and 4-(3-pyridyl)-2-pyrrolidones react with 2-aryl(heteryl)-1-nitroethenes to form C₃-adducts as one or two diastereomers. Their structure was characterized by the IR, ¹H, and ¹³C NMR spectrosco

Full text of DOI:10.1134/S1070363211080172

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 8, pp. 1681–1690. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.A. Nikonorov, E.S. Ostroglyadov, O.S. Vasil’ev, V.M. Berestovitskaya, 2011, published in Zhurnal Obshchei Khimii, 2011,
Vol. 81, No. 8, pp. 1336–1345.
Synthesis and Structure of Nitroethylpyrrolidone Carboxylates
A. A. Nikonorov, E. S. Ostroglyadov, O. S. Vasil’ev, and V. M. Berestovitskaya
Herzen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received March 10, 2011
Abstract—3-Methoxycarbonyl-4-phenyl- and 4-(3-pyridyl)-2-pyrrolidones react with 2-aryl(heteryl)-1-nitro-
1
ethenes to form C3-adducts as one or two diastereomers. Their structure was characterized by the IR, H, and
13C NMR spectroscopy, using the two-dimensional correlation spectroscopy.
DOI: 10.1134/S1070363211080172
The esters of pyrrolidone carboxylic acids are
known to be valuable starting materials for the targeted
synthesis of various derivatives of γ-aminobutyric acid
and α-pyrrolidone, the compounds of great practical
and theoretical importance [1, 2]. Suffice it to say that
phenibut and phenotropil, widely used in medical
practice, were synthesized on their basis [1–4]. In this
respect the reactions of pyrrolidone carboxylates with
aryl(heteryl)nitroethenes are of an undoubted interest
as they open the way to the synthesis of fundamentally
new derivatives of the γ-aminobutyric acid and
pyracetam containing either aryl or aryl and heteryl
fragments simultaneously.
of compounds XXIIa, XXIIb, XXIII, XXIV, XXVII,
and XXIX has been described in [5–7], but the
synthesis conditions are somewhat different from those
developed by us. According to [6], compounds XXIII,
XXIV, XXVII, and XXIX were obtained as single
diastereomers, but not pairs of diasteremers as in our
study. All the previously synthesized substances
XXIIa, XXIIb, XXIII, XXIV, XXVII, XXIX have
been described in [5–7] only by the IR spectroscopy
and elemental analysis; and their melting points not
always coincide with those of the samples obtained in
our work.
The reactions of 4-phenyl(3-pyridyl)-pyrrolidone
carboxylates I and II with the gem-substituted
nitroethenes XX and XXI, as well as the reactions of
4,5-aryl(heteryl)derivatives III and VI with both gem-
substituted (XX, XXI) and gem-unsubstituted
nitroalkenes (V, X) were unsuccessful: Michael ad-
ducts were not obtained. In the reactions of compounds
III and IV with 2-aryl(heteryl)-1-nitro-1-phenyl-
ethenes XX and XXI metoxynitroethenes XLII,
XLIIIa, and XLIIIb were isolated. Apparently, in
these cases the nitroalkenes alkoxylation was a faster
process. The substances XLII and XLIII are identical
in physical characteristics to the samples obtained in
the reactions of nitroethenes XX and XXI with sodium
methoxide in the absence of pyrrolidone carbo-
xylate. This result seems to be associated with a
greater steric loading of the reactants molecules,
pyrrolidone carboxylates (III, IV) and nitroalkenes
(XX, XXI).
We studied the reactions of 4-phenyl-, 4-(3-
pyridyl)-, 4,5-diphenyl- and 4-(1-methylbenzimidazol-
2-yl)-5-phenyl-3-methoxycarbonyl-2-pyrrolidones I–IV
with a series of 2-aryl(heteryl)-1-nitroethenes V–XIX
and their gem-substituted analogs: 2-phenyl- and 2-(1-
methylbenzimidazol-2-yl)-1-nitro-1-phenylethenes XX
and XXI.
The reactions occur in the presence of sodium
methoxide in methanol at room temperature. The reac-
tion was found to proceed only with the pyrrolidone
carboxylates I and II containing no substituents at the
C5-atom, and nitroalkenes V–XIX, having no
substituents in the gem-position relative to NO2-group.
As a result, the products of nucleophilic addition to the
C3-atom of pyrrolidone ring XXII–XLI were formed
either as single diastereomers (XXV, XXXI–XXXVI,
XXXVIII, XLI) or mixtures of two diastereomers
[XXIIa, XXIIb, XXIIIa, XXIIIb, XXVIa–XXXb,
XXXVIIa, XXXVIIb, XXXIXa, XXXIXb, XLa and
XLb (2:1), XXIVa and XXIVb (5:1)]. The synthesis
In the reactions of 3-methoxycarbonyl-4-phenyl-2-
pyrrolidone I with the studied nitroethenes V–XIX the
1681

1682
NIKONOROV et al.
NO2
R3
NO2
R1
*
6
*
7
*
4
*
R3
*
*
3
9
8
V_XIX
I, II (R2 = H),
H'
COOCH3
5
CH3ONa
Ph
O
N
R1
H''
COOCH3
O
H
XXIIа, XXIIb_XXIVа, XXIV, XXV, XXVIа, XXVI_XXXа,
XXXb, XXXI_XXXVI, XXXVIIа, XXXVIIb, XXXVIII,
XXXIXа, XXXIXb, XLа, XLb, XLI
R2
N
H
I_IV
R3
XX, XXI
NO2
H3CO
HB
Ph
CH3ONa
2
1
XX, XXI
HA
NO2
CH3ONa
R3
XLII, XLIIIа, XLIIIb
R1 = C6H5: R2 = H (I), C6H5 (III); R1 = 3-pyridyl, R2 = H (II); R1 = 1-methylbenzimidazol-2-yl, R2 = C6H5 (IV); R3 = C6H5
(V, XX, XLII), 4-CH3C6H4 (VI), 4-CH3OC6H4 (VII), 4-(CH3)2NC6H4 (VIII), 4-ClC6H4 (IX), 4-O2NC6H4 (X), 3-pyridyl
(XI), 2-furyl (XII), 1-methylbenzimidazol-2-yl (XIII, XXI, XLIIIа, XLIIIb), indol-3-yl (XIV), 1-methylindol-3-yl (XV),
1-benzindol-3-yl (XVI), 2-methylindol-3-yl (XVII), 1,2-dimethylindol-3-yl (XVIII), 1-benzyl-2-methylindol-3-yl (XIX);
R1 = C6H5: R3 = C6H5 (XXIIа, XXIIa), 4-CH3C6H4 (XXIIIа, XXIIIb), 4-CH3OC6H4 (XXIVа, XXIVb), 4-(CH3)2NC6H4
(XXV), 4-ClC6H4 (XXVIа, XXVIb), 4-O2NC6H4 (XXVIIа, XXVIIb), 3-pyridyl (XXVIIIа, XXVIIIb), 2-furyl (XXIXа,
XXIXb), 1-methylbenzimidazol-2-yl (XXXа, XXXb), indol-3-yl (XXXI), 1-methylindol-3-yl (XXXII), 1-benzylindol-3-yl
(XXXIII), 2-methylindol-3-yl (XXXIV), 1,2-dimethylindol-3-yl (XXXV), 1-benzyl-2-methylindol-3-yl (XXXVI); R1 = 3-
pyridyl: R3 = C6H5 (XXXVIIа, XXXVIIb), 4-CH3OC6H4 (XXXVIII), 4-ClC6H4 (XXXIXа, XXXIXb), 4-O2NC6H4 (XLа,
XLb), 3-pyridyl (XLI).
efficiency of the process depended on the nature of
substituent in the nitroalkene molecule. Pyrrolidone
carboxylate I forms with aryl-, pyridyl-, furyl- and
benzimidazolylnitroethenes V–XIII the desired
products XXII, XXIV, XXV, XXVI–XXX at the
equimolar ratio of the reagents in the yields up to 96%.
In the case of indolylnitroalkenes XIV–XIX the yields
of the target adduct XXXI–XXXVI were 55–60%,
even with a 1.5-fold excess of compound I (Table 1).
The synthesized nitroethylpyrrolidone carboxylates
XXII–XLI containing either aryl or aryl and heteryl
substituents simultaneously are stable crystalline
substances with precise melting points.
spectroscopy using heteronuclear correlation spec-
troscopy (Tables 1 and 2). Thus, in the IR spectra of all
synthesized compounds along with the characteristic
absorption bands of the stretching vibrations of the
ester (1727–1750 cm–1) and lactam (1670–1719 cm–1)
carbonyl groups there are the absorption bands of the
nonconjugated nitro group at 1545–1560, 1360–
1380 cm–1; an absorption band of NH-groups of pyr-
rolidone ring is observed at 3090–3420 cm–1.
The NMR spectra of nitroethylpyrrolidone
carboxylates XXII, XXIV, XXV, XXVI, XXX,
XXXI–XXXVI, XXXVII, XXXVIII, XXXIX, XL,
1
and XLII contain the H and 13C signals of all
Compounds XXII, XXIII, XXVI, XXX, XXXVII,
XXXIX and XL isolated as mixtures of two
diastereomers were separated by the fractional crystal-
lization in two individual diastereomers a and b. Only
the isomer a was isolated as individual compound from
a mixture of diastereomers of XXIV; the second
diastereomer b was only registered spectrally and
characterized.
structural fragments (Tables 1 and 2). In addition, by
the spectral analysis data, the identical patterns were
found in the character of appearing of the signals of
methine and methylene protons C4H, C5H', and C5H''
of pyrrolidone ring for all series of diastereomeric
pairs. Based on a comparison of chemical shifts of
these signals the diastereomers with a greater
difference between the values of chemical shifts of the
proton signals C5H' and C5H'' were attributed to
diastereomers a, and the diastereomers with the closer
The structure of the obtained compounds XXII–
1
XLI was confirmed by the IR, H and 13C NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

SYNTHESIS AND STRUCTURE OF NITROETHYLPYRROLIDONE CARBOXYLATES
1683
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

1684
NIKONOROV et al.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

SYNTHESIS AND STRUCTURE OF NITROETHYLPYRROLIDONE CARBOXYLATES
1685
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

1686
NIKONOROV et al.
(a)
(b)
δ, ppm
δ, ppm
Fig. 1. Fragments of the 1Н NMR spectra of compounds (a) XXXа and (b) XXXb in DMSO-d6.
values, to b. For example, in the spectrum of
compound XXXb the proton signals of C5H' and C5H''
are closer (3.42, 3.50 ppm) compared with XXXa
(3.15 and 3.43 ppm) (Fig. 1). Note that the methine
proton C4H of pyrrolidone ring in the spectrum of
isomer XXXb resonates downfield (5.22 ppm)
compared with XXXa (3.38 ppm). A similar pattern is
observed in the spectra of other compounds of this
series (Table 1).
one another (Figs. 2 and 3). For example, in the
spectrum of compound XXXb the difference between
the chemical shifts of protons C5H' and C5H'' (∆Н'Н''
0.08 ppm) is significantly lower than for the dia-
stereoisomer XXXa (∆Н'Н'' 0.28 ppm). Table 1 shows
that similar pattern is typical for the whole range of the
1
substances obtained. In the H NMR spectra of the
nitroethylpyrrolidone carboxylates XXV, XXXI–
XXXVI, XXXIX, XLI isolated in the individual form
the values of the chemical shifts of the protons C4H,
C5H' and C5H'' are in a good agreement with those for
1
The validity of the signal assigning in the H and
13C spectra of the obtained compounds was confirmed
1
the protons signals in the H NMR spectra of dia-
using
a
special technique of two-dimensional
stereomers a (XXIIa–XXIVa, XXVIa–XXXa, XXXVIIa,
XXXIXa, XLa). This indicates that the molecules of
nitroethylpyrrolidone carboxylates XXV, XXXI–
XXXVI, XXXIX, XLI exist as diastereomers a.
heteronuclear correlation spectroscopy HMQC,
performed for the isomers XXXa and XXXb. In the
1
2D-correlation experiment the spectra of H and 13C
NMR (as heteronucleus) were used with the protons
decoupling. In the 1H–13C correlation spectrum of
compound XXXa there is an interaction between the
atoms С4Н (3.38 ppm) and С4 (47.67 ppm); between
С5Н'' (3.43 ppm), С5Н' (3.15 ppm) and С5 (45.53 ppm);
between С6Н (4.54 ppm) and С6 (38.22 ppm); between
С7Н'' (5.50 ppm), С7Н' (5.11 ppm) and С7 (77.70 ppm)
(Fig. 2). A similar correlation is typical for the
spectrum of the second isomer XXXb (Fig. 3). The
correlation spectra most clearly demonstrate the
difference in the manifestation of methylene protons
C5H' and C5H'' of pyrrolidone ring: The positions of
the proton signals H' and H'' in the spectrum of
diastereomer b are close together, while for the dia-
stereomer a they characteristically appear farther from
Thus, 4-phenyl-, 4-(3-pyridyl)pyrrolidone carbo-
xylates I and II react readily with monosubstituted
nitroethenes to afford the adducts in high (96%) yields.
1
Analysis of the H NMR spectra with the HMQC
experiment showed that the comparative analysis of
the chemical shifts of the signals of methine (C4H) and
methylene (C5H' and C5H'') protons of pyrrolidone ring
can be used as an analytical characteristics in
describing the diastereomeric origin of the compounds
XXII, XXIV, XXV, XXVI, XXX, XXXI–XXXVI,
XXXVII, XXXVIII, XXXIX, XL, and XLI.
The obtained nitroethylpyrrolidone carboxylates
XXII, XXIV, XXV, XXVI, XXX, XXXI–XXXVI,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

SYNTHESIS AND STRUCTURE OF NITROETHYLPYRROLIDONE CARBOXYLATES
1687
δ, ppm
δ, ppm
Fig. 2. Fragment of the HMQC 1H–13C spectrum of compound XXXа in DMSO-d6.
δ, ppm
δ, ppm
Fig. 3. Fragment of the HMQC 1H–13C spectrum of compound XXXb in DMSO-d6.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

1688
NIKONOROV et al.
XXXVII, XXXVIII, XXXIX, XL, and XLI contain-
ing either aryl or aryl and heteryl substituents simul-
taneously are of independent interest as potential bio-
logically active compounds and are promising starting
reagents for the synthesis of new derivatives of γ-
aminobutyric acid and pyracetam analogs.
3-Methoxycarbonyl-3-[1-(4-methylphenyl)-2-
nitroethyl]-4-phenyl-2-pyrrolidone (XXIII). Yield
87% (a:b = 2:1). Compound XXIIIa. Yield 28%, mp
184–185°С (methanol). Found, %: C 65.92; H 5.54; N
7.49. C21H22N2O5. Calculated, %: C 65.96; H 5.80; N
7.33. Compound XXIIIb. Yield 18%, mp 204–205°С
(methanol). Found, %: C 65.94; H 5.72; N 7.33.
C21H22N2O5. Calculated, %: C 65.96; H 5.80; N 7.33.
EXPERIMENTAL
3-Methoxycarbonyl-3-[1-(4-methoxyphenyl)-2-
nitroethyl]-4-phenyl-2-pyrrolidone (XXIV). Yield
95% (a:b = 5:1). Compound XXIVa. Yield 45%, mp
210–212°С (methanol). Found, %: C 63.09, 62.86; H
5.36, 5.38; N 6.82, 6.84. C21H22N2O6. Calculated, %: C
63.31; H 5.57; N 7.03.
1
1
The H, 13C–{1H}, H–13C HMQC NMR spectra
were obtained on a Jeol ECX400A spectrometer
[400 MHz (1H), 100 MHz (13C)] in DMSO-d6 relative
to the residual signal of undeuterated solvent. The IR
spectra were recorded on a Shimadzu IR Prestige-21
Fourier spectrometer from KBr pellets.
3-[1-(4-N,N-Dimethylaminophenyl)-2-nitro-
ethyl]-3-methoxycarbonyl-4-phenyl-2-pyrrolidone
(XXV). Yield 78%, mp178–180°С (methanol). Found,
%: C 64.76, 64.35; H 6.24, 6.21; N 10.22, 10.28.
C22H25N3O5. Calculated, %: C 64.22; H 6.12; N 10.21.
Pyrrolidone carboxylates I–IV were prepared
according to the procedures described in the following
publications: 4-phenyl- (I) [8], 4-(3-pyridyl)- (II) [9],
4,5-diphenyl- (III) and (IV) [10]. The synthesis of 2-
aryl(heteryl)- [11, 12], 1,2-diphenyl- [13] and 2-(1-
methylbenzimidazol-2-yl)-1-phenyl-1-nitroethenes [14]
was performed as described in the mentioned articles.
Synthesis of compounds XXXVII and XLI was
described previously [9].
3-Methoxycarbonyl-3-[2-nitro-1-(4-chlorophenyl)-
ethyl]-4-phenyl-2-pyrrolidone (XXVI). Yield 86%
(a:b = 2:1). Compound XXVIa. Yield 50%, mp 226–
227°С (methanol). Found, %: C 59.40; H 4.72; N 6.90.
C20H19N2O5Cl. Calculated, %: C 59.63; H 4.75; N
6.95. Compound XXVIb. Yield 5%, mp 190–191°С
(methanol). Found, %: C 59.41, 59.37; H 4.54.; N
6.83, 6.78. C20H19N2O5Cl . Calculated, %: C 59.63; H
4.75; N 6.95.
3-Methoxycarbonyl-3-(2-nitro-1-phenylethyl)-4-
phenyl-2-pyrrolidone (XXII). Equimolar pyrrolidone
carboxylate–nitroalkene ratio. To a methanol solution
of sodium methoxide prepared from 6 ml of methanol
and 0.23 g of sodium was added 2.18 g of 3-methoxy-
carbonyl-4-phenyl-2-pyrrolidone I. Then, at 0–5°C to
the stirred mixture was added a suspension of 1.49 g of
1-nitro-2-phenylethene V in 15 ml of methanol. The
reaction mixture was stirred for 1.5 h at 20°C and then
poured on the crushed ice containing 0.4 ml of
concentrated hydrochloric acid. The precipitate was
filtered off and dried in air. Yield 3.53 g (96%) (a:b =
2:1). The isomers XXIIa and XXIIb were separated
by a fractional crystallization from methanol. Com-
pound XXIIa. Yield 1.84 g (50%), mp 206–207°C
(methanol) {mp 197°C (methanol) [5]}. Found, %: C
3-Methoxycarbonyl-3-[1-(4-nitrophenyl)-2-nitro-
ethyl]-4-phenyl-2-pyrrolidone (XXVII). Yield 91%
(a:b = 2:1). Compound XXVIIa. Yield 35%, mp 234–
235°С (methanol). Found, %: C 58.23; H 4.64; N
10.17. C20H19N3O7. Calculated, %: C 58.11; H 4.63; N
10.16. Compound XXIIIa. Yield 10%, mp 190–192°С
(methanol). Found, %: C 57.92, 58.58; H 4.68, 4.68; N
10.30, 10.05. C20H19N3O7. Calculated, %: C 58.11; H
4.63; N 10.16.
3-Methoxycarbonyl-3-[2-nitro-1-(3-pyridyl)ethyl]-
4-phenyl-2-pyrrolidone (XXVIII). Yield 78% (а:b =
2:1). Compound XXVIIIa. Yield 25%, mp 184–186°С
(methanol). Found, %: С 61.45, 61.45; Н 5.28, 5.27; N
11.50, 11.49. C19H19N3O5. Calculated, %: С 61.78; Н
5.18; N 11.38. Compound XXVIIIa. Yield 25%, mp
158–160°С (methanol). Found, %: С 61.53, 61.56; Н
5.70, 5.63; N 11.21, 11.19. C19H19N3O5. Calculated,
%: С 61.78; Н 5.18; N 11.38.
65.25, 65.27;
H
5.38, 5.40;
N
7.72,
7.65. C20H20N2O5. Calculated, %: C 65.21; H 5.47; N
7.60. Compound XXIIb. Yield 0.55 g (15%),
mp 188–190°C (methanol) {mp 184°C (methanol)
[5]}. Found, %: C 65.18, 65.17; H 5.47, 5.49; N 7.62,
7.63. C20H20N2O5. Calculated, %: C 65.21; H 5.47; N
7.60.
Compounds XXIII–XXX, XXXVII–XLI were
3-Methoxycarbonyl-3-[2-nitro-1-(2-furyl)ethyl]-
prepared similarly.
4-phenyl-2-pyrrolidone (XXIX). Yield 90% (a:b = 2:1).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

SYNTHESIS AND STRUCTURE OF NITROETHYLPYRROLIDONE CARBOXYLATES
1689
Compound XXIXa. Yield 36%, mp 195–196°С
(methanol). Found, %: C 60.21, 60.25; H 4.98, 5.03; N
7.71, 7.74. C18H18N2O6. Calculated, %: C 60.33; H
5.06; N 7.82. Compound XXIXa. Yield 34%, mp
155–156°С (methanol). Found, %: C 60.13, 60.19; H
4.88, 4.94; N 7.80, 7.76. C18H18N2O6. Calculated, %: C
60.33; H 5.06; N 7.82.
The reaction mixture was stirred for 2 h at 20°С and
poured on the crushed ice containing 0.9 ml of glacial
acetic acid. The precipitate was filtered off and dried in
air. Yield 3.68 g (59%), mp 210–212°С (methanol).
Found, %: C 65.06, 64.96; H 5.40, 5.45; N 10.50,
10.45. C22H23N3O5. Calculated, %: C 64.54; H 5.66; N
0.26.
3-Methoxycarbonyl-3-[1-(1-methylbenzimidazol-
2-yl)-2-nitroethyl]-4-phenyl-2-pyrrolidone (XXX).
Yield 75% (а:b = 2:1). Compound XXXa. Yield 40%,
mp 194–196°С (methanol). Found, %: C 62.02, 62.57;
H 5.29, 5.40; N 13.23, 13.44. C22H22N4O5. Calculated,
%: C 62.55; H 5.25; N 13.26. Compound XXXb.
Yield 15%, mp 119–121°С (methanol). Found, %: C
62.41, 62.54; H 5.59, 5.58; N 13.13, 13.08.
C22H22N4O5. Calculated, %: C 62.55; H 5.25; N 13.26.
Compounds XXXII–XXXVI were obtained
similarly.
3-Methoxycarbonyl-3-[1-(1-methylindol-3-yl)-2-
nitroethyl]-4-phenyl-2-pyrrolidone (XXXII). Yield
60%, mp 206–207°С (methanol). Found, %: C 64.97,
65.03; H 5.87, 6.04; N 9.54, 9.62. C23H25N3O5.
Calculated, %: C 65.24; H 5.95; N 9.92.
3-[1-(1-Benzylindol-3-yl)-2-nitroethyl]-3-methoxy-
carbonyl-4-phenyl-2-pyrrolidone (XXXIII). Yield
55%, mp 188–190°С (methanol). Found, %: C 69.88,
69.92; H 5.59, 5.56; N 8.39, 8.58. C29H29N3O5.
Calculated, %: C 69.72; H 5.85; N 8.41.
3-Methoxycarbonyl-3-[1-(4-methoxyphenyl)-2-
nitroethyl]-4-(3-pyridyl)-2-pyrrolidone (XXXVIII).
Yield 88%, mp 163–165°С (methanol). Found, %: C
59.89, 60.20; H 5.42, 5.46; N 10.13, 10.11.
C20H21N3O6. Calculated, %: C 60.14; H 5.30; N 10.52.
3-Methoxycarbonyl-3-[1-(2-methylindol-3-yl)-2-
nitroethyl]-4-phenyl-2-pyrrolidone (XXXIV). Yield
55%, mp 170–172°С (methanol). Found, %: C 65.15,
65.06; H 5.91, 5.98; N 9.69, 9.58. C23H25N3O5.
Calculated, %: C 65.24; H 5.95; N 9.92.
3-Methoxycarbonyl-3-[2-nitro-1-(4-chlorophenyl)-
ethyl]-4-(3-pyridyl)-2-pyrrolidone (XXXIX). Yield
90% (a:b = 2:1). Compound XXXIXa. Yield 33%,
mp 184–186°С (methanol). Found, %: C 56.85, 56.69;
H 4.61, 4.62; N 10.19, 10.25. C19H18N3O5Cl.
Calculated, %: C 56.51; H 4.49; N 10.41. Compound
XXXIXb. Yield 5%, mp 145–147°С (methanol).
Found, %: C 56.82, 56.19; H 4.44, 4.34.; N 9.98, 9.86.
C19H18N3O5Cl. Calculated, %: C 56.51; H 4.49; N
10.41.
3-[1-(1,2-Dimethylindol-3-yl)-2-nitroethyl]-3-me-
thoxycarbonyl-4-phenyl-2-pyrrolidone (XXXV).
Yield 63%, mp 230–232°С (methanol). Found, %: C
65.62, 65.68; H 6.12, 6.09; N 9.44, 9.51. C24H27N3O5.
Calculated, %: C 65.89; H 6.22; N 9.60.
3-[1-(1-Benzyl-2-methylindol-3-yl)-2-nitroethyl]-
3-methoxycarbonyl-4-phenyl-2-pyrrolidone (XXXVI).
Yield 53%, mp 195–196°С (methanol). Found, %: C
69.85, 69.91; H 5.96, 5.99; N 7.88, 7.95. C30H31N3O5.
Calculated, %: C 70.16; H 6.08; N 8.18.
3-Methoxycarbonyl-3-[1-(4-nitrophenyl)-2-nitro-
ethyl]-4-(pyrid-3-yl)-2-pyrrolidone (XL). Yield 93%
(a:b = 2:1). Compound XLa. Yield 40%, mp 181–
183°С (methanol). Found, %: C 54.72, 54.62; H 4.42,
4.47.; N 13.23, 13.38. C19H18N4O7. Calculated, %: C
55.07; H 4.38; N 13.52. Compound XLb. Yield 10%,
mp 158–160°С (methanol). Found, %: C 54.75, 55.04;
H 4.42, 4.43; N 13.56, 13.44. C19H18N4O7. Calculated,
%: C 55.07; H 4.38; N 13.52
1,2-Diphenyl-2-methoxy-1-nitroethane (XLII). a.
Reaction of compounds I and XX in methanol in the
presence of CH3ONa. To a methanol solution of
sodium methylate prepared from 2 ml of methanol and
0.105 g of sodium was added 1.00 g of 3-methoxy-
carbonyl-4-phenyl-2-pyrrolidone I. Then, at 0–5°С to
the stirred mixture was added a suspension of 1.03 g of
1,2-diphenyl-1-nitroethene XX in 10 ml of methanol.
The reaction mixture was stirred for 1.5 h at 20°С and
poured onto the crushed ice containing 0.16 ml of
concentrated hydrochloric acid. The precipitate was
filtered off and dried in air. Yield 0.34 g (30%), mp
113–115°С.
3-[1-(Indol-3-yl)-2-nitroethyl]-3-methoxycarbonyl-
4-phenyl-2-pyrrolidone (XXXI). Pyrrolidone carbo-
xylate–nitroalkene ratio 1.5:1. To a methanol solution
of sodium methoxide prepared from 9 ml of methanol
and 0.35 g of sodium was added 3.32 g of 3-methoxy-
carbonyl-4-phenyl-2-pyrrolidone I. Then, at 0–5°С to
the stirred mixture was added a suspension of 2.86 g of
2-(indol-3-yl)-1-nitroethene XVI in 35 ml of methanol.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

1690
NIKONOROV et al.
va, O.S., Izv. Ross. Gos. Pedagog. Univ. im. Gertsena,
b. Reaction of compound XX with sodium
Ser. Estestv. i Tochnye Nauki, 2002, no. 2(4), p. 133.
methoxide. To a methanol solution of sodium meth-
oxide prepared from 10 ml of methanol and 0.1 g of
sodium was added 1.03 g of 1,2-diphenyl-1-nitro-
ethene XX. Then the reaction mixture was stirred for
1.5 h at 20°С and poured onto the crushed ice
containing 0.16 ml of concentrated hydrochloric acid.
The precipitate was filtered off and dried in air. Yield
0.82 g (70%), mp 113–115°С (methanol).
2. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
Moscow: Novaya Volna, 2002, p.116.
3. Perekalin, V.V., Sopova, A.S., Zobacheva, M.M.,
Spunde, R.Ya., Kruzite, M.P., and Mikstais, U.Ya.,
USSR Inventor’s Certificate no. 238479, 1968.
4. Perekalin, V.V., Novikov, B.M., Zobacheva, M.M.,
Kiseleva, I.N., Grineva, V.S., Kovalev, G.V., Tyuren-
kov, I.N., and Polevoi, L.G., USSR Patent no. 797219,
1979; С. А., 1996, vol. 124, 278178 m.
The mixed test with the samples of XLII obtained
by the methods a and b did not give a depression of the
melting point. IR spectrum, ν, cm–1: 1557, 1366 (NO2).
5. Smirnova, A.A., Zobacheva, M.M., Perekalin, V.V., and
Piterskaya, I.V., Zh. Org. Khim., 1968, vol. 4, no. 9,
p. 1665.
1Н NMR spectrum, δ, ppm: 5.57 [1H, НА, J(HАНВ)
3
3
8.39 Hz], 5.08 [1H, НВ, J(HАНВ) 8.39 Hz], 3.16 (3H,
ОСН3), 7.55, 7.42, 7.35 (10H, С6Н5). Found, %: C
69.91, 69.79; H 5.96, 5.99; N 5.45, 5.33. C15H15NO3.
Calculated, %: C 70.02; H 5.88; N 5.44.
6. Kostrova, G.P., Zobacheva, M.M., and Smirnova, A.A.,
Abstract of Papers, ХХVI Gertsenovskie chteniya.
Khimiya (XXVI Herzen Readings. Chemistry), Lenin-
grad: Leningrad. Gos. Ped. Inst. im. Gertsena, 1973,
pt. 2, p. 10.
2-(1-Methylbenzimidazol-2-yl)-2-methoxy-1-
nitro-1-phenylethane (XLIII) was obtained similarly
by the method а. Yield (80%) (a:b = 1:1), mp 183–
185°С (methanol). IR spectrum, ν, cm–1: 1550, 1380
(NO23). 1Н NMR spectrum, δ, ppm (XLIIIа): 6.35 [1H,
7. Sokovishina, I.F., Mezhvuzovskii Sbornik Nauchnykh
Trudov, 1986, p. 85.
8. Perekalin, V.V. and Zobacheva, M.M., Zh. Obshch.
Khim., 1959, vol. 29, no. 9, p. 2905.
3
НА, J(HАНВ) 10.68 Hz], 5.85 [1H, НВ, J(HАНВ)
10.68 Hz], 3.22 (3H, ОСН3), 3.83 (3H, NCH3), 7.10–
9. Osroglyadov, E.S., Vasil’eva, O.S., Artemova, O.V.,
and Berestovitskaya, V.M., Zh. Org. Khim., 2007,
vol. 43, no. 8, p. 1263.
1
7.30, 7.81 (4Н, C7H4N2) 7.26 (5H, С6Н5). Н NMR
3
spectrum, δ, ppm (XLIIIb): 6.54 [1H, НА, J(HАНВ)
3
10.07 Hz], 5.93 [1H, НВ, J(HАНВ) 10.07 Hz], 2.97
10. Nikonorov, A.A., Osroglyadov, E.S., Vasil’eva, O.S.,
Artemova, O.V., and Berestovitskaya, V.M., Zh.
Obshch. Khim., 2010, vol. 80, no. 11, p. 1933.
(3H, ОСН3), 3.94 (3H, NCH3), 7.45–7.65 (4Н,
C7H4N2; 5H, С6Н5). Found, %: C 65.41, 65.49; H 5.46,
5.48; N 13.42, 13.35. C17H17N3O3. Calculated, %: C
65.58; H 5.50; N 13.50.
11. Gairaud, C.B. and Lappin, G.R., J. Org. Chem., 1952,
vol. 18, no. 1, p. 1.
12. Berestovitskaya, V.M., Ishmaeva, E.A., Litvinov, I.A.,
Vasil’eva, O.S., Vereshchagina, Ya.A., Ostroglya-
dov, E.S., and Fattakhova, G.R., Zh. Obshch. Khim.,
2004, vol. 74, no. 7, p. 1198.
ACKNOWLEDGMENTS
This work was financially supported by the Program
of the Government of St. Petersburg for students
and young scientists (grant no. 2.5/07-06/039).
13. Knoevenagel, E. and Walter, L., Chem. Ber., 1904,
vol. 37, p. 4502.
14. Osroglyadov, E.S., Nikonorov, A.A., Vasil’eva, O.S.,
Zobacheva, M.M., and Berestovitskaya, V.M., Zh. Org.
Khim., 2009, vol. 45, no. 4, p. 629.
REFERENCES
1. Berestovitskaya, V.M., Zobacheva, M.M., and Vasil’e-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011