Five-membered 2,3-dioxoheterocycles: LXVII. Pyrroledione-pyrroledion recyclization of isopropyl 2-(1-aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol-3- yl)-2-oxoacetates under the action of arylamines. Crystal and molecular structure of (z)-isopropyl 2-hydroxy-4,5-dioxo-1-phenyl-3-[phenyl(phenylamino)- methylene]pyrrolidine-2-carboxylate

Article abstract of DOI:10.1134/S1070428010020193

Reactions of isopropyl 2-(1-aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol- 3-yl)-2-oxoacetates with aromatic amines involve a pyrroledione-pyrroledione recyclization to form isopropyl 1-aryl-2-hydroxy-4,5-dioxo-3-[phenyl(arylamino) methylene]pyrrolidine-2-carboxylates. The crystal and molecular structure of (Z)-isopropyl 2-hydroxy-4,5-dioxo-1-phenyl-3-[phenyl(phenylamino)methylene] pyrrolidine-2-carboxylate was proved by XRD analysis.

Full text of DOI:10.1134/S1070428010020193

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 2, pp. 255−259. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © P.S. Silaichev, M.V. Dmitriev, Z.G. Aliev, A.N. Maslivets, 2009, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46,
No. 2, pp. 261−264.
Five-membered 2,3-Dioxoheterocycles: LXVII.*
Pyrroledione−Pyrroledion Recyclization of Isopropyl
2-(1-Aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol-3-yl)-2-
oxoacetates under the Action of Arylamines.
Crystal and Molecular Structure of (Z)-Isopropyl 2-Hydroxy-4,5-
dioxo-1-phenyl-3-[phenyl(phenylamino)-
methylene]pyrrolidine-2-carboxylate
P. S. Silaicheva, M. V. Dmitrieva, Z. G. Alievb, and A. N. Maslivetsa
aPerm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
Received April 6, 20
Abstract—Reactions of isopropyl 2-(1-aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol-3-yl)-2-oxoacetates with
aromatic amines involve a pyrroledione- pyrroledione recyclization to form isopropyl 1-aryl-2-hydroxy-4,5-dioxo-
3-[phenyl(arylamino)methylene]pyrrolidine-2-carboxylates. The crystal and molecular structure of (Z)-isopropyl
2-hydroxy-4,5-dioxo-1-phenyl-3-[phenyl(phenylamino)methylene]pyrrolidine-2-carboxylate was proved by XRD
analysis.
DOI: 10.1134/S1070428010020193
hydroxy-4,5-dioxo-3-[phenyl(arylamino)methylene]-
pyrrolidine-2-carboxylates IIIa–IIIj. The structure of
compound IIIa was proved by XRD analysis.
The reaction of 1-aryl-4-aroyl-5-methoxycarbonyl-
1H-pyrrole-2,3-diones with arylamines was shown to
result in the formation of the products of primary amino
group addition to the carbon atom in the position 5 of
pyrrolediones, substituted 5-arylamino-3-hydroxy-1H-
pyrrol-2(5H)-ones [2, 3].
Compounds IIIa–IIIj are bright yellow or orange high-
melting crystalline substances, readily soluble in DMSO,
DMF, and common organic solvents, insoluble in alkanes
and water.
In extension of the research on the nucleophilic
recyclization of 1H-pyrrole-2,3-diones we studied the
reactions of the representatives of another class of
monocyclic pyrrolediones, isopropyl 2-(1-aryl-4,5-dioxo-
2-phenyl-4,5-dihydro-1H-pyrrol-3-yl)-2-oxoacetates Ia–
Ic [4] with primary amines IIa–IId.
The IR spectra of compounds IIIa–IIIj contain the
absorption bands of the stretching vibrations of OH and
NH group as a broad band in the region 3237–3441 cm–1,
of a lactam carbonyl group C5=O at 1722–1755 cm–1, of
an ester carbonyl group in the region 1719–1728 cm–1,
and of a ketone carbonyl group involved into the formation
of an intramolecular hydrogen bond as a broad band at
1609–1619 cm–1.
The reaction of compounds Ia–Ic with amines IIa–
IId in a ratio 1:1 performed by keeping the reagents
solution in an anhydrous chloroform at room temperature
over 8–10 h provided in good yield isopropyl 1-aryl-2-
1
In the H NMR spectra of compounds IIIa–IIIj
alongside the signals of the protons of aromatic rings and
groups attached thereto appear two doublets of methyl
*For Communication LXVI, see [1].
255

SILAICHEV et al.
256
Scheme 1.
O
O
i-C3H7OOC
O
Ar2NH2
IIа_IId
i-C3H7OOC
O
OH
Ph
Iа_Ic
O
N
Ar1
NHAr2
Ph
N
Ar1
Ar2
O
N
i-C3H7OOC
HO
H
O
COCON
NHAr1
O
Ar2
i-C3H7OOC
H
N
Ar1
Ph
Ph
IIIа_IIIj
Ar1 = Ph (Ia, IIIa, IIIe, IIIh), C6H4Me-4(Ib, IIIb, IIIf, IIIi), C6H4OMe-4 (Ic, IIIc, IIId, IIIg, IIIj);Ar2 = Ph (IIa, IIIa–IIIc), C6H4Me-
4 (IIb, IIId), C6H4OMe-4 (IIc, IIIe–IIIg), C6H4Br-4 (IId, IIIh–IIIj).
groups of the isopropoxycarbonyl substituent at 0.73– pyrroledione ring, and also the signal from the carbon
0.79 and 0.82–0.85 ppm, a multiplet of the methine proton
from the same moiety in the region 4.32–4.34 ppm, and
abroadened singlet of the NH group proton (12.62–
12.68 ppm). The proton signal of the OH group is located
in the region of the aromatic protons signals.
atom in the position 2 (87.62–87.78 ppm). The location
of the carbon atoms of the pyrroledione ring is well
consistent with the data published for 1H-pyrrole-2,3-
diones and 5-hydroxy-2,3,4,5-tetrahydro-1H-pyrrole-2,3-
diones [5].
The 13C NMR spectra of compounds IIIc, IIIe, and
IIIg contain characteristic signals in the region 167.17–
167.29 and 178.86–179.80 ppm from the carbon atoms
of the lactam and ketone carbonyl groups of the
The final conclusion on the structure of compounds
synthesized was done based on the XRD analysis on
a single crystal of compound IIIa (Fig.. 1).
Compound IIIa crystallized with a molecule of water
in an equimolar ratio. The molecule is stabilized in the
...
crystal by the intramolecular hydrogen bond N2–H2 O2
2.756(4) forming a flat “bicycle”. The longer bond of
the carbonyl group C2=O2 (1.238 ) compared to the
bond C1=O1 (1.224 ) indicates the involvement of the
group C2=O2 in the intramolecular hydrogen bond and
the existence of the IIIa molecule in the crystalline state
in the enaminoketone form.All bond distances in the five-
membered ring and in its substituents are virtually identical
to analogous bond lengths in the similar in structure
molecule of (Z)-3-(1-benzyl-2-hydroxy-4,5-dioxo-2-p-
tolyltetrahydropyrrol-3-idene)-3,4-dihydro-2H-1,4-
benzoxazin-2-one [6]. The planes of the phenyl rings at
the atoms N1 and C5 are orthogonal to each other and to
the plane of the “bicycle”. The orientation of the
phenylamine fragment is characterized by the torsion
angle C5N2C19C20 of 153.8 deg. In the crystal IIIa
Fig. 1. Molecular structure of (Z)-isopropyl 2-hydroxy-4,5-dioxo-1-
phenyl-3-[phenyl(phenylamino)methylene]pyrrolidine-
2-carboxylate (IIIa).
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FIVE-MEMBERED 2,3-DIOXOHETEROCYCLES: LXVII.
257
molecules are connected through the water molecule into
dimeric associates (Fig. 2).
Unlike [6] where the formation of the analogous
dimeric associate was shown to involve two oxygen
atoms of the carbonyl groups of the pyrroledione ring, in
this study the water molecule is connected by the
...
hydrogen bond with a carbonyl (O6–H O1) and a hydroxy
...
(O6 H3–O3) groups. Dimeric associates multiplied by
the glide reflection plane are connected by a weaker
...
hydrogen bond O6–H O1 into an infinite chain. The
parameters of the hydrogen bonds in the crystal are given
below.
Fig. 2. Dimeric associate of molecules of compound IIIa in the
crystal.
Ia and 1.0 mmol of aniline (IIa) in 15 ml of anhydrous
chloroform was maintained at 20°C for 8 h, then the
solvent was removed, and the residue was ground with
ethanol. Yield 83%, mp 182–183°C (from toluene). IR
spectrum, ν, cm–1: 3252 br (OH, NH), 1754 (C5=O), 1723
(COO), 1614 (C4=O in internal H-bond). 1H NMR
spectrum, δ, ppm: 0.73 d (3H, Me, J 6.4 Hz), 0.82 d (3H,
Me, J 6.4 Hz), 4.32 m (1H, OCH, J 6.4 Hz), 6.88–7.43
group of signals (16H, 3Ph, OH), 12.67 br.s (1H, NH).
Found, %: C 74.04; H 5.27; N 6.24. C27H24N2O5.
Calculated, %: C 74.04; H 5.30; N 6.14.
The formation of compounds IIIa–IIIj occurs
apparently by initial addition of the primary amino group
of arylamines IIa–IId to the carbon atom in the position
2 of pyrrolediones Ia–Ic, the cleavage of the pyrroledione
ring at the N1–C2 bond and the subsequent closure of
a “new” pyrroledione ring by intramolecular nucleophilic
addition of the NH group of the oxamoyl fragment to the
keto carbonyl groyp of the isopropoxalyl substituent.
The reaction described is an example of pyrrolediones
recyclization under the action of anilines, namely, the
cleavage of a pyrroledione ring with the closure of a “new”
pyrroledione ring.
Compounds IIIb–IIIj were prepared similarly.
(Z)-Isopropyl 2-hydroxy-3-[4-methylphenyl-
amino(phenyl)methylene]-4,5-dioxo-1-phenyl-
pyrrolidine-2-carboxylate (IIIb). Yield 79%, mp 192–
193°C (from ethyl acetate). IR spectrum, ν, cm–1: 3246
br (OH, NH), 1755 (C5=O), 1724 (COO), 1616 (C4=O in
internal H-bond). 1H NMR spectrum, δ, ppm: 0.73 d (3H,
Me, J 6.4 Hz), 0.82 d (3H, Me, J 6.4 Hz), 2.18 s (3H,
Me), 4.32 m (1H, OCH, J 6.4 Hz), 6.77–7.42 group of
signals (15H, 2Ph + C6H4 + OH), 12.67 br.s (1H, NH).
Found, %: C 71.49; H 5.63; N 6.02. C28H26N2O5.
Calculated, %: C 71.47; H 5.57; N 5.95.
EXPERIMENTAL
IR spectra of compounds obtained were recorded on
a spectrophotometer FSM-1201from mulls in mineral oil.
1H and 13C NMR spectra were registered on a spec-
trometer BrukerAM-400 (operating frequency 400 MHz)
in DMSO-d6, internal reference TMS. The homogeneity
of compounds synthesized was proved by TLC on Silufol
plates, eluates benzene–ethyl acetate, 5:1, ethyl acetate.
Elemental analysis was performed using samples
preliminary dried at 100–105°C.
(Z)-Isopropyl 2-hydroxy-3-[4-methoxyphenyl-
amino(phenyl)methylene]-4,5-dioxo-1-phenyl-
pirrolidine-2-carboxylate (IIIc). Yield 85%, mp 189–
190°C (from toluene). IR spectrum, ν, cm–1: 3237 br (OH,
NH), 1755 (C5=O), 1726 (COO), 1609 (C4=O in internal
H-bond). 1H NMR spectrum, δ, ppm: 0.73 d (3H, Me,
(Z)-Isopropyl 2-hydroxy-4,5-dioxo-1-phenyl-3-
[phenyl(phenylamino)methylene]pyrrolidine-2-
carboxylate (IIIa).A solution of 1.0 mmol of compound
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SILAICHEV et al.
258
J 6.4 Hz), 0.82 d (3H, Me, J 6.4 Hz), 3.66 s (OMe),
4.32 m (1H, OCH, J 6.4 Hz), 6.72–7.40 group of signals
(15H, 2Ph + C6H4 + OH), 12.66 br.s (1H, NH). 13C NMR
spectrum (DMSO-d6), δ, ppm: 20.81 (Me), 55.12 (OMe),
69.27 (OCH), 87.78 (C2), 108.38 (C3), 113.79–161.60
(CAr + C3=C–NH), 161.89 (COO), 167.17 (C5), 178.86
(C4). Found, %: C 69.24; H 5.43; N 5.71. C28H26N2O6.
Calculated, %: C 69.12; H 5.39; N 5.76.
(OH, NH), 1752 (C5=O), 1719 (COO), 1612 (C4=O in
internal H-bond). 1H NMR spectrum, δ, ppm: 0.79 d
(3H, Me, J 6.4 Hz), 0.85 d (3H, Me, J 6.4 Hz), 3.66 s
(OMe), 3.74 s (OMe), 4.34 m (1H, OCH, J 6.4 Hz),
6.75–7.44 group of signals (14H, Ph + 2C6H4 + OH),
12.62 br.s (1H, NH). 13C NMR spectrum (DMSO-d6),
δ, ppm: 20.88 (Me), 20.91 (Me), 55.12 (OMe), 55.19
(OMe), 69.27 (OOCH), 87.67 (C2), 108.35 (C3), 113.77–
161.41 (CAr + C3=C–NH), 161.98 (COO), 167.29 (C5),
179.26 (C4). Found, %: C 67.31; H 5.37; N 5.35.
C29H28N2O7. Calculated, %: C 67.43; H 5.46; N 5.42.
(Z)-Isopropyl 2-hydroxy-1-(4-methylphenyl)-3-
[4-methoxyphenylamino(phenyl)-methylene]-4,5-di-
oxopyrrolidine-2-carboxylate (IIId). Yield 74%, mp
187–189°C (from toluene). IR spectrum, ν, cm–1: 3237 br
(OH, NH), 1753 (C5=O), 1721 (COO), 1619 (C4=O in
internal H-bond). 1H NMR spectrum, δ, ppm: 0.76 d (3H,
Me, J 6.4 Hz), 0.85 d (3H, Me, J 6.4 Hz), 2.28 C (3H,
Me), 3.66 C (OMe), 4.33 m (1H, OCH, J 6.4 Hz), 6.71–
7.40 group of signals (14H, Ph + 2C6H4 + OH), 12.64 br.s
(1H, NH). Found, %: C 69.54; H 5.52; N 5.56.
C29H28N2O6. Calculated, %: C 69.59; H 5.64; N 5.60.
(Z)-Isopropyl 1-(4-bromophenyl)-2-hydroxy-4,5-
dioxo-3-[phenyl(phenylamino)methylene]pyr-
rolidine-2-carboxylate (IIIh). Yield 88%, mp 183–
184°C (ethyl acetate). IR spectrum, ν, cm–1: 3264 br
(OH, NH), 1753 (C5=O), 1725 (COO), 1611 (C4=O in
internal H-bond). 1H NMR spectrum, δ, ppm: 0.73 d
(3H, Me, J 6.4 Hz), 0.85 d (3H, Me, J 6.4 Hz), 4.33 m
(1H, OCH, J 6.4 Hz), 6.83–7.62 group of signals (15H,
2Ph + C6H4 + OH), 12.68 br.s (1H, NH). Found, %:
C 60.65; H 4.35; N 5.23. C27H23BrN2O5. Calculated, %:
C 60.57; H 4.33; N 5.23.
(Z)-Isopropyl 2-hydroxy-1-(4-methoxyphenyl)-
4,5-dioxo-3-[phenyl(phenylamino)methylene]-
pyrrolidine-2-carboxylate (IIIe). Yield 79%, mp 192–
193°C (from toluene). IR spectrum, ν, cm–1: 3261 br (OH,
NH), 1753 (C5=O), 1722 (COO), 1613 (C4=O in internal
(Z)-Isopropyl 1-(4-bromophenyl)-2-hydroxy-3-
[4-methylphenylamino(phenyl)methylene]-4,5-di-
oxopyrrolidine-2-carboxylate (IIIi). Yield 85%, mp
193–194°C (from toluene). IR spectrum, ν, cm–1: 3255 br
(OH, NH), 1754 (C5=O), 1728 (COO), 1619 (C4=O in
internal H-bond). 1H NMR spectrum, δ, ppm: 0.73 d
(3H, Me, J 6.4 Hz), 0.85 d (3H, Me, J 6.4 Hz), 2.18 s
(3H, Me), 4.33 m (1H, OCH, J 6.4 Hz), 6.68–7.62 group
of signals (14H, Ph + 2C6H4 + OH), 12.67 br.s (1H, NH).
Found, %: C 61.12; H 4.49; N 5.07. C28H25BrN2O5.
Calculated, %: C 61.21; H 4.59; N 5.10.
1
H-bond). H NMR spectrum, δ, ppm: 0.79 d (3H, Me,
J 6.4 Hz), 0.85 d (3H, Me, J 6.4 Hz), 3.74 s (OMe),
4.34 m (1H, OCH, J 6.4 Hz), 6.88–7.43 group of signals
(15H, 2Ph + C6H4 + OH), 12.67 br.s (1H, NH). 13C NMR
spectrum (DMSO-d6), δ, ppm: 20.86 (Me), 20.92 (Me),
55.20 (OMe), 69.32 (OCH), 87.62 (C2), 108.80 (C3),
113.80–160.90 (CAr + C3=C–NH), 161.71 (COO), 167.17
(C5), 179.80 (C4). Found, %: C 69.17; H 5.43; N 5.72.
C28H26N2O5. Calculated, %: C 69.12; H 5.39; N 5.76.
(Z)-Isopropyl 1-(4-bromophenyl)-2-hydroxy-4,5-
dioxo-3-[4-methoxyphenylamino(phenyl)methyl-
ene]pyrrolidine-2-carboxylate (IIIj). Yield 73%, mp
190–191°C (from toluene). IR spectrum, ν, cm–1: 3269 br
(OH, NH), 1750 (C5=O), 1720 (COO), 1612 (C4=O in
internal H-bond). 1H NMR spectrum, δ, ppm: 0.73 d (3H,
Me, J 6.4 Hz), 0.85 d (3H, Me, J 6.4 Hz), 3.66 s (OMe),
4.34 m (1H, OCH, J 6.4 Hz), 6.72–7.62 group of signals
(14H, Ph + 2C6H4 + OH), 12.68 br.s (1H, NH). Found,
%: C 59.40; H 4.37; N 4.92. C28H25BrN2O6. Calculated,
%: C 59.48; H 4.46; N 4.95.
(Z)-Isopropyl 2-hydroxy-1-(4-methoxyphenyl)-3-
[4-methylphenylamino(phenyl)methylene]-4,5-
dioxopyrrolidine-2-carboxylate (IIIf). Yield 80%, mp
195–196°C (from toluene). IR spectrum, ν, cm–1: 3441
br (OH, NH), 1722 (C5=O, COO), 1618 (C4=O in internal
1
H-bond). H NMR spectrum, δ, ppm: 0.79 d (3H, Me,
J 6.4 Hz), 0.85 d (3H, Me, J 6.4 Hz), 2.18 s (3H, Me),
3.74 s (OMe), 4.34 m (1H, OCH, J 6.4 Hz), 6.75–7.42
group of signals (14H, Ph + 2C6H4 + OH), 12.64 br.s
(1H, NH). Found, %: C 69.55; H 5.52; N 5.73.
C29H28N2O6. Calculated, %: C 69.59; H 5.64; N 5.60.
X-ray diffraction analysis of compound IIIa. Yellow
clear edged crystals C27H24N2O5·H2O belong to
monoclinic crystal system: a 21.763(5), b 13.452(3), c
16.622(4) , β 96.46(2) deg, V 4835.3(19) 3, M 474.50,
dcalc 1.304 g/cm3, Z 8, space group C2/C. The set of
(Z)-Isopropyl 2-hydroxy-1-(4-methoxyphenyl)-3-
[4-methoxyphenylamino(phenyl)methylene]-4,5-
dioxopyrrolidine-2-carboxylate (IIIg). Yield 79%, mp
195–196°C (from toluene). IR spectrum, ν, cm–1: 3242 br
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FIVE-MEMBERED 2,3-DIOXOHETEROCYCLES: LXVII.
259
experimental reflections was obtained on an automatic
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