ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 2, p. 312. © Pleiades Publishing, Ltd., 2013.
Original English Text © E.S. Denislamova, N.V. Bubnov, A.N. Maslivets, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 2, p. 318.
SHORT
COMMUNICATIONS
Regioselective Reduction of 1Н-Pyrrole-2,3-diones
with Thioacetamide
E. S. Denislamova, N. V. Bubnov, and A. N. Maslivets
Perm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received November 30, 2011
DOI: 10.1134/S107042801302022X
The addition of primary amines to carbon atoms in the
positions 2and 5of 1-aryl-4-aroyl-5-methoxycarbonyl-1Н-
pyrrole-2,3-diones is described [1, 2]; the reactions of these
pyrrolediones with amides and thioamides are not studied.
ОМе), 5.84 s (1H, H5), 7.26–7.80 group of signals (10H,
2Ph), 12.43 br.s (1Н, OН). Found, %: С 67.69; Н 4.46; N
4.12. С19H15NO5. Calculated, %: С 67.65; Н 4.48; N 4.15.
4-Benzoyl-3-hydroxy-5-methoxycarbonyl-1-(4-
chlorophenyl)-2,5-dihydro-1Н-pyrrol-2-one (IIIb).
Yield 63%, mp 245–247°С (from methanol). IR spectrum,
cm–1: 3410 br, 3160 br (OH), 1723 (COOMe, C2=O),
On melting 1-aryl-4-benzoyl-5-methoxycarbonyl-1Н-
pyrrole-2,3-diones Ia, Ib with thioacetamide (II) we ob-
tained 1-aryl-4-benzoyl-3-hydroxy-5-methoxycarbonyl-
2,5-dihydro-1Н-pyrrol-2-ones IIIа, IIIb.
1
1622 (СОPh). Н NMR spectrum, δ, ppm: 3.58 s (3H,
ОМе), 5.87 s (1H, H5), 7.50–7.79 group of signals (9H,
Ph + C6H4), 12.10 br.s (1Н, OН). Found, %: С 61.42;
Н 3.76; Cl 9.52; N 3.80. С19H14ClNO5. Calculated, %:
С 61.38; Н 3.80; Cl 9.54; N 3.77.
The spectral characteristics of compounds IIIа,
IIIb are very similar to those of the known substituted
3-hydroxy-2,5-dihydro-1Н-pyrrol-2-ones [2].
S
O
PhCO
PhCO
OH
IR spectra of compounds obtained were recorded on
a spectrophotometer FMS-1201 from mulls in mineral
oil. 1Н NMR spectra were registered on a spectrometer
Bruker WP-400 in DMSO-d6, internal reference TMS.
The homogeneity of compounds obtained was proved by
TLC on Silufol plates, eluent ethyl acetate, development
in iodine vapor.
Me
NH2
II
120_130°С
H
O
O
MeOOC
MeOOC
N
N
Ar
Ar
IIIа, IIIb
Iа, Ib
Ar = Ph (а), 4-ClC6H4 (b).
ACKNOWLEDGMENTS
Apparently at the attack of thioacetamide on
1Н-pyrrole-2,3-diones Ia, Ib a regioselective reduction
occurs of the double bond of the dihydropyrrole ring
resulting in the formation of the tetrahydropyrrole-2,3-
diones IIIа, IIIb existing in the enol form.
The study was carried out under the financial support
of the Ministry of Education and Science of the Russian
Federation, the Ministry of Education of Perm Territory,
and of the Russian Foundation for Basic Research (grant
no. 12-03-00696).
The described reaction is a new way of the regioselec-
tive reduction of the substituted 1Н-pyrrole-2,3-diones.
REFERENCES
4-Benzoyl-3-hydroxy-5-methoxycarbonyl-1-
phenyl-2,5-dihydro-1Н-pyrrol-2-one (IIIа).Amixture
of 1 mmol of compound Ia and 1 mmol of thioacetamide
(II) was melted at 120–130°С for 30 min, and cooled.
Yield 56%, mp 226–227°С (from methanol). IR spectrum,
cm–1: 3400 br, 3150 br (OH), 1723 (COOMe, C2=O),
1. Maslivets, A.N., Smirnova, L.I., and Andreichikov, Yu.S.,
Zh. Org. Khim., 1989, vol. 25, p. 1748.
2. Andreichikov, Yu.S., Gein, V.L., Zalesov, V.V., Kozlov,
A.P., Kollents, G., Maslivets, A.N., Pimenova, E.V., and
Shurov, S.N., Khimiya pyatichlennykh 2,3-dioksogeterotsik-
lov (Chemistry of Five-Membered 2,3-Dioxoheterocycles),
Perm’: Izd. Perm. Gos., 1994.
1
1624 (СОPh). Н NMR spectrum, δ, ppm: 3.57 s (3H,
312
Denislamova
