Five-membered 2,3-dioxo heterocycles: LXXI. * Recyclization of 4,5-diaroyl-1H-pyrrole-2,3-diones by the action of substituted hydrazines. Crystalline and molecular structure of 2-(3-benzoyl- 1-benzyl-5-phenyl-1H- pyrazol-4-yl)-N-(4-methoxyphenyl)- 2-oxoacetamide

Article abstract of DOI:10.1134/S1070428010100180

1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-diones reacted with benzyl- and phenylhydrazines to give N-aryl-2-(5-aryl-3-aroyl-1-benzyl(phenyl)-1H-pyrazol-4- yl)-2-oxoacetamides whose structure was proved by X-ray analysis.

Full text of DOI:10.1134/S1070428010100180

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 10, pp. 1546–1549. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © P.S. Silaichev, N.V. Kudrevatykh, Z.G. Aliev, A.N. Maslivets, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46,
No. 10, pp. 1540–1543.
Five-Membered 2,3-Dioxo Heterocycles: LXXI.* Recyclization
of 4,5-Diaroyl-1H-pyrrole-2,3-diones by the Action of Substituted
Hydrazines. Crystalline and Molecular Structure of 2-(3-Benzoyl-
1-benzyl-5-phenyl-1H-pyrazol-4-yl)-N-(4-methoxyphenyl)-
2-oxoacetamide
P. S. Silaicheva, N. V. Kudrevatykhb, Z. G. Alievc, and A. N. Maslivetsa, b
a Institute of Natural Sciences, Perm State University, ul. Genkelya 4, Perm, 614990 Russia
e-mail: koh2@psu.ru
b Perm State University, ul. Bukireva 15, Perm, 614990 Russia
c Institute of Chemical Physics Problems, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, Russia
Received January 4, 2010
Abstract—1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-diones reacted with benzyl- and phenylhydrazines to give
N-aryl-2-(5-aryl-3-aroyl-1-benzyl(phenyl)-1H-pyrazol-4-yl)-2-oxoacetamides whose structure was proved by
X-ray analysis.
DOI: 10.1134/S1070428010100180
Methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-
pyrrole-2-carboxylates reacted with arylhydrazines to
give substituted methyl 1,5-diaryl-4-(N-aryloxamoyl)-
1H-pyrazole-3-carboxylates as a result of successive
nucleophilic attacks by the primary and secondary
amino groups in the hydrazine on the ester carbonyl
carbon atom and ketone carbonyl carbon atom in the
aroyl substituent on C3, respectively, followed by
cleavage of the pyrrole ring [2, 3]. Reactions of 4,5-di-
aroyl-substituted 1H-pyrrole-2,3-diones with hydrazine
derivatives were not reported previously.
common organic solvents and insoluble in saturated
hydrocarbons and water.
The IR spectra of IIIa–IIIm contained absorption
bands due to stretching vibrations of NH bond
(a broadened band in the region 3248–3380 cm–1),
ketone and amide carbonyl groups in the oxamoyl
fragment (1660–1690 cm–1), and aroyl carbonyl group
(1640–1664 cm–1). Compounds IIIa–IIIm displayed in
the 1H MNMR spectra signals from protons in aromat-
ic rings and substituents therein, a singlet from the NH
proton at δ 10.52–10.76 ppm, and a singlet from the
benzyl methylene protons at δ 5.38–5.41 ppm (in the
spectra of IIIa–IIIf). In the 13C NMR spectra of IIIa
and IIIg we observed signals from aromatic carbon
atoms, benzyl methylene carbon atom (IIIa), carbonyl
carbon atom in the aroyl substituent (δC 187.39–
187.40 ppm), ketone carbonyl carbon atom in the
oxamoyl fragment (δC 184.86–185.10 ppm), and amide
carbonyl carbon atom (δC 160.18–160.40 ppm).
We found that 1-aryl-4,5-diaroyl-1H-pyrrole-2,3-di-
ones Ia–Ig react with an equimolar amount of benzyl-
or phenylhydrazine (IIa or IIb) in anhydrous chloro-
form at room temperature (15–20 min), followed by
heating in boiling ethanol (20–30 min) to produce
N-aryl-2-(5-aryl-3-aroyl-1-benzyl(phenyl)-1H-pyrazol-
4-yl)-2-oxoacetamides IIIa–IIIm in good yields
(Scheme 1). The product structure was proved by
X-ray diffraction data for compound IIIe. Compounds
IIIa–IIIm were isolated as light yellow or colorless
crystalline substances. They are readily soluble in
According to the X-ray diffraction data (see figure),
all interatomic distances C2=C3, C1=N1, and C=O in
molecule IIIe do not differ appreciably from the corre-
sponding standard values. Steric overcrowding of the
pyrazole ring by bulky substituents is responsible for
* For communication LXX, see [1].
1546

FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LXXI.
1547
Scheme 1.
O
O
Ar2
N
O
Ar2
Ar2
Ar2
OH
O
R
NH
+
RNHNH2
R
O
–H2O
HN
N
N
O
O
Ar2
N
N
H
Ar1
O
Ar1
Ar1
Ar2
O
O
Ia–Ig
IIa, IIb
O
Ar2
Ar1
NH
O
O
N
Ar2
N
R
IIIa–IIIm
I, Ar1 = Ph, Ar2 = Ph (a), 4-MeC6H4 (b); Ar1 = 4-MeC6H4, Ar2 = Ph (c), 4-MeC6H4 (d); Ar1 = 4-MeOC6H4, Ar2 = Ph (e),
4-MeC6H4 (f); Ar1 = 4-MeOC6H4, Ar2 = 4-ClC6H4 (g); II, R = PhCH2 (a), Ph (b); III, R = PhCH2, Ar1 = Ph, Ar2 = Ph (a), 4-MeC6H4 (b);
Ar1 = 4-MeC6H4, Ar2 = Ph (c), 4-MeC6H4 (d); Ar1 = 4-MeOC6H4, Ar2 = Ph (e), 4-MeC6H4 (f); R = Ph, Ar1 = Ph, Ar2 = Ph (g),
4-MeC6H4 (h); Ar1 = 4-MeC6H4, Ar2 = Ph (i), 4-MeC6H4 (j); Ar1 = 4-MeOC6H4, Ar2 = Ph (k), 4-MeC6H4 (l), 4-ClC6H4 (m).
the lack of π-conjugation between the carbonyl groups.
The benzoyl group on C3 is not planar, and the torsion
angle O1C6C14C19 is 21.8°. The O1 atom deviates from
the pyrazole ring plane by 0.66 Å (torsion angle
N1C1C6O1 155.2°), and the O2 atom deviates from the
pyrazole ring plane by 0.74 Å (torsion angle C3C2C4O2
49.0°); the torsion angles O2C4C5N3 and C4C5N3C26 are
17.9 and 18.7°, respectively. The benzene ring in the
benzoyl substituent on C3 and the pyrazole ring form
a dihedral angle of 128.4°. Orientation of the benzyl
fragment on N1 is described by the torsion angle
N2C7C8C9 equal to 58.1°.
EXPERIMENTAL
The IR spectra were recorded on an FSM-1201
spectrometer. The 1H and 13C NMR spectra were meas-
ured on a Bruker AM-400 spectrometer at 400 and
100 MHz, respectively, from solutions in DMSO-d6
using tetramethylsilane as internal reference. The
purity of the products was checked by TLC on Silufol
plates using benzene–ethyl acetate (5 :1) or ethyl
acetate as eluent.
C23
C22
C21
Molecules IIIe in crystal are linked through
medium-strength intermolecular hydrogen bonds
N3–H3···O2 (N3···O2 2.974, H3···O2 2.13 Å, ∠N3H3O2
166°) to give centrosymmetric dimers. No other short-
ened intermolecular contacts were found in the crystal-
line structure of compound IIIe.
C24
C25
C20
O2
C5
C12
C13
C8
C3
C4
C7
C11
C2
N3
N2
Presumably, compounds IIIa–IIIm are formed via
initial nucleophilic attack by the primary amino group
of hydrazine IIa or IIb on the carbon atom in position
5 of pyrroledione I, followed by pyrazole ring closure
as a result of intramolecular nucleophilic attack by the
secondary amino group in the hydrazine fragment on
the carbonyl carbon atom in the aroyl substituent on
C4. Cleavage of the pyrrole ring in the bicyclic inter-
mediate thus formed yields final products III. The
described reaction is an example of recyclization of
pyrrolediones to pyrazoles by the action of hydrazine
derivatives.
C27
C29
C26
C9
C10
O3
C28
N1
O1
C1
C6
C14
C31
O4
C30
C32
C15
C16
C19
C18
C17
Structure of the molecule of 2-(3-benzoyl-1-benzyl-5-phen-
yl-1H-pyrazol-4-yl)-N-(4-methoxyphenyl)-2-oxoacetamide
(IIIe) according to the X-ray diffraction data.
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SILAICHEV et al.
1548
(19H, Harom), 10.52 s (1H, NH). Found, %: C 74.48;
2-(3-Benzoyl-1-benzyl-5-phenyl-1H-pyrazol-4-
H 4.86; N 8.07. C32H25N3O4. Calculated, %: C 74.55;
H 4.89; N 8.15.
yl)-2-oxo-N-phenylacetamide (IIIa). A solution of
1.0 mmol of benzylhydrazine in 5 ml of anhydrous
chloroform was added to a solution of 1.0 mmol of
compound Ia in 10 ml of anhydrous chloroform, and
the mixture was stirred for 20 min at room tempera-
ture. The precipitate was filtered off and dissolved in
ethanol, the mixture was heated for 20 min under
reflux and cooled, and the precipitate was filtered off.
Yield 82%, mp 199–200°C (from EtOH). IR spectrum,
ν, cm–1: 3298, 1682, 1660, 1640. 1H NMR spectrum, δ,
ppm: 5.41 s (2H, CH2Ph), 7.02–8.13 m (17H, Harom),
10.65 s (1H, NH). 13C NMR spectrum, δC, ppm: 53.22
(CH2Ph), 118.18 (C4), 120.15–137.54 (Carom), 146.93
(C3), 150.59 (C5), 160.40 (CONH), 184.86 (4-CO),
187.40 (3-CO). Found, %: C 76.62; H 4.75; N 8.61.
C31H23N3O3. Calculated, %: C 76.69; H 4.77; N 8.65.
X-Ray diffraction data for compound IIIe. Yel-
low well defined crystals, C32H25N3O4, triclinic crystal
system; unit cell parameters: a = 11.093(2), b =
11.765(2), c = 13.194(3) Å; α = 115.75(3), β =
90.66(3), γ = 116.00(3)°; V = 1349.9(5) Å3; M 515.55;
dcalc = 1.268 g/cm3; Z = 2; space group P-1. Experi-
mental reflection intensities were measured on a KM-4
(KUMA Diffraction) automatic four-circle diffractom-
eter with χ-geometry [monochromatized MoKα irradia-
tion, ω/2Θ scanning, 2Θmax ≤ 53.2° (84% of the re-
verse space)]. Total of 4834 reflections were measured,
4598 of which were independent (Rint = 0.0126). No
correction for absorption was introduced (μ =
0.085 mm–1). The structure was solved by the direct
method using SIR92 program [4], followed by a series
of calculation of electron density maps. All hydrogen
atoms were placed into positions set on the basis of
geometry considerations, and their positions were
refined according to the riding model. The positions of
non-hydrogen atoms were refined by the full-matrix
least-squares procedure in anisotropic approximation
using SHELXL-97 software package [5, 6]; the final
divergence factors were R1 = 0.0424, wR2 = 0.1060 for
2431 reflections with I ≥ 2σ(I) and R1 = 0.1247, wR2 =
0.1204 for all reflections (365 refined parameters);
goodness of fit 0.956.
Compounds IIIb–IIIm were synthesized in a sim-
ilar way.
2-[1-Benzyl-3-(4-methylbenzoyl)-5-(4-methyl-
phenyl)-1H-pyrazol-4-yl]-2-oxo-N-phenylacetamide
(IIIb). Yield 75%, mp 160–161°C (from EtOH). IR
1
spectrum, ν, cm–1: 3314, 1680, 1665, 1653. H NMR
spectrum, δ, ppm: 2.35 s (3H, Me), 2.40 s (3H, Me),
5.39 s (2H, CH2Ph), 7.04–8.02 m (18H, Harom), 10.61 s
(1H, NH). Found, %: C 77.12; H 5.26; N 8.14.
C33H27N3O3. Calculated, %: C 77.17; H 5.30; N 8.18.
2-(3-Benzoyl-1-benzyl-5-phenyl-1H-pyrazol-4-
yl)-N-(4-methylphenyl)-2-oxoacetamide (IIIc). Yield
73%, mp 152–153°C (from EtOH). IR spectrum, ν,
2-[1-Benzyl-3-(4-methylbenzoyl)-5-(4-methyl-
phenyl)-1H-pyrazol-4-yl]-N-(4-methoxyphenyl)-2-
oxoacetamide (IIIf). Yield 82%, mp 168–169°C (from
EtOH). IR spectrum, ν, cm–1: 3346, 1683, 1643.
1H NMR spectrum, δ, ppm: 2.35 s (3H, Me), 2.40 s
(3H, Me), 3.70 s (3H, OMe), 5.38 s (2H, CH2Ph),
6.85–8.01 m (17H, Harom), 10.48 s (1H, NH). Found,
%: C 75.07; H 5.34; N 7.66. C34H29N3O4. Calculated,
%: C 75.12; H 5.38; N 7.73.
1
cm–1: 3281, 1686, 1661, 1651. H NMR spectrum, δ,
ppm: 2.23 s (3H, Me), 5.41 s (2H, CH2Ph), 7.03–
8.11 m (19H, Harom), 10.55 s (1H, NH). Found, %:
C 76.87; H 5.00; N 8.36. C32H25N3O3. Calculated, %:
C 76.94; H 5.04; N 8.41.
2-[1-Benzyl-3-(4-methylbenzoyl)-5-(4-methyl-
phenyl)-1H-pyrazol-4-yl]-N-(4-methylphenyl)-2-
oxoacetamide (IIId). Yield 80%, mp 161–162°C
(from EtOH). IR spectrum, ν, cm–1: 3283, 1680, 1661,
2-(3-Benzoyl-1,5-diphenyl-1H-pyrazol-4-yl)-2-
oxo-N-phenylacetamide (IIIg). Yield 75%, mp 191–
192°C (from EtOH). IR spectrum, ν, cm–1: 3294, 1673,
1
1647. H NMR spectrum, δ, ppm: 2.23 s (3H, Me),
1
2.35 s (3H, Me), 2.40 s (3H, Me), 5.39 s (2H, CH2Ph),
7.05–8.01 m (17H, Harom), 10.52 s (1H, NH). Found,
%: C 77.31; H 5.48; N 7.91. C34H29N3O3. Calculated,
%: C 77.40; H 5.54; N 7.96.
1658. H NMR spectrum, δ, ppm: 7.10–8.24 m (20H,
Ph), 10.76 s (1H, NH). 13C NMR spectrum, δC, ppm:
118.94 (C4), 120.24–138.11 (Carom), 146.28 (C3),
151.24 (C5), 160.18 (CONH), 185.10 (4-CO), 187.39
(3-CO). Found, %: C 76.38; H 4.46; N 8.85.
C30H21N3O3. Calculated, %: C 76.42; H 4.49; N 8.91.
2-(3-Benzoyl-1-benzyl-5-phenyl-1H-pyrazol-4-
yl)-N-(4-methoxyphenyl)-2-oxoacetamide (IIIe).
Yield 76%, mp 177–178°C (from EtOH). IR spectrum,
ν, cm–1: 3344, 1683, 1643. 1H NMR spectrum, δ, ppm:
3.70 s (3H, OMe), 5.41 s (2H, CH2Ph), 6.84–8.11 m
2-[3-(4-Methylbenzoyl)-5-(4-methylphenyl)-1-
phenyl-1H-pyrazol-4-yl]-2-oxo-N-phenylacetamide
(IIIh). Yield 77%, mp 173–174°C (from EtOH). IR
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FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LXXI.
1549
1
spectrum, ν, cm–1: 3248, 1676, 1644. H NMR spec-
trum, δ, ppm: 2.28 s (3H, Me), 2.41 s (3H, Me), 7.09–
8.13 m (18H, Harom), 10.71 s (1H, NH). Found, %:
C 76.88; H 5.01; N 8.36. C32H25N3O3. Calculated, %:
C 76.94; H 5.04; N 8.41.
(3H, Me), 3.71 s (3H, OMe), 6.85–8.13 m (17H,
arom), 10.58 s (1H, NH). Found, %: C 74.78; H 5.10;
N 7.89. C33H27N3O4. Calculated, %: C 74.84; H 5.14;
N 7.93.
H
2-[3-(4-Chlorobenzoyl)-5-(4-chlorophenyl)-1-
phenyl-1H-pyrazol-4-yl]-N-(4-methoxyphenyl)-2-
oxoacetamide (IIIm). Yield 74%, mp 198–199°C
(from EtOH). IR spectrum, ν, cm–1: 3287, 1682, 1657.
1H NMR spectrum, δ, ppm: 3.71 s (3H, OMe), 6.87–
8.23 m (17H, Harom), 10.63 s (1H, NH). Found, %:
C 65.20; H 3.68; N 7.31. C31H21Cl2N3O4. Calculated,
%: C 65.27; H 3.71; N 7.37.
2-(3-Benzoyl-1,5-diphenyl-1H-pyrazol-4-yl)-N-
(4-methylphenyl)-2-oxoacetamide (IIIi). Yield 87%,
mp 222–223°C (from EtOH). IR spectrum, ν, cm–1:
3310, 1690, 1659. 1H NMR spectrum, δ, ppm: 2.24 s
(3H, Me), 7.09–8.22 m (19H, Harom), 10.64 s (1H,
NH). Found, %: C 76.59; H 4.70; N 8.61. C31H23N3O3.
Calculated, %: C 76.69; H 4.77; N 8.65.
2-[3-(4-Methylbenzoyl)-5-(4-methylphenyl)-1-
phenyl-1H-pyrazol-4-yl]-N-(4-methylphenyl)-2-oxo-
acetamide (IIIj). Yield 79%, mp 195–196°C (from
EtOH). IR spectrum, ν, cm–1: 3356, 1678, 1655.
1H NMR spectrum, δ, ppm: 2.24 s (3H, Me), 2.29 s
(3H, Me), 2.41 s (3H, Me), 7.09–8.13 m (17H, Harom),
10.62 s (1H, NH). Found, %: C 77.13; H 5.26; N 8.11.
C33H27N3O3. Calculated, %: C 77.17; H 5.30; N 8.18.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 2.19.10).
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(4-methoxyphenyl)-2-oxoacetamide (IIIk). Yield
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1
cm–1: 3375, 1674, 1656. H NMR spectrum, δ, ppm:
3.70 s (3H, OMe), 6.85–8.21 m (19H, Harom), 10.61 s
(1H, NH). Found, %: C 74.20; H 4.57; N 8.33.
C31H23N3O4. Calculated, %: C 74.24; H 4.62; N 8.38.
N-(4-Methoxyphenyl)-2-[3-(4-methylbenzoyl)-5-
(4-methylphenyl)-1-phenyl-1H-pyrazol-4-yl]-2-oxo-
acetamide (IIIl). Yield 86%, mp 172–173°C (from
EtOH). IR spectrum, ν, cm–1: 3380, 1682, 1664.
1H NMR spectrum, δ, ppm: 2.29 s (3H, Me), 2.41 s
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