Recyclization of 4,5-bis(aroyl)-2,3-dihydro-1H-pyrrole-2,3-diones by the action of aromatic amines

Full text of DOI:10.1134/S1070428010070286

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 7, pp. 1103–1104. © 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. 7, pp. 1101–1102.
SHORT
COMMUNICATIONS
Recyclization of 4,5-Bis(aroyl)-2,3-dihydro-1H-pyrrole-2,3-diones
by the Action of Aromatic Amines
P. S. Silaicheva, N. V. Kudrevatykha, Z. G. Alievb, and A. N. Maslivetsa
a Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
b Institute of Chemical Physics Problems, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, Russia
Received October 27, 2009
DOI: 10.1134/S1070428010070286
We previously reported on reactions of monocyclic
2,3-dihydro-1H-pyrrole-2,3-diones with aromatic
amines, which resulted in the formation of addition
products at the C5 atom in the pyrrole ring, 5-aryl-
amino-3-hydroxy-1H-pyrrole-2(5H)-ones [1–3]. By re-
action of 4,5-bis(aroyl)-1-(4-methoxyphenyl)-2,3-dihy-
dro-1H-pyrrole-2,3-diones Ia and Ib with p-anisidine
at a molar ratio of 1:1 in anhydrous chloroform at
room temperature (reaction time 8–10 h) we obtained
(4Z)-5-aryl-[2-aryl-1-(4-methoxyphenylamino)-2-oxo-
ethylidene]-5-hydroxy-1-(4-methoxyphenyl)pyrroli-
dine-2,3-diones IIIa and IIIb in good yields. The
product structure was proved by X-ray analysis.
ring at the N1–C2 bond with formation of intermediate
compound IVa or IVb, and subsequent closure of new
pyrrole ring as a result of intramolecular nucleophilic
addition of the NH group at the ketone carbonyl group
in the aroyl substituent. An alternative mechanism is
also possible (path b); it involves initial addition of the
amino group at the C5 atom in the pyrrole ring,
followed by opening of the pyrrole ring via cleavage of
the N1–C5 bond, which also gives intermediate IV.
The described reaction is an example of recycliza-
tion of pyrrolediones by the action of aromatic amines,
i.e., opening of the pyrrole ring and subsequent closure
of new pyrrole ring.
Presumably, compounds IIIa and IIIb are formed
via initial addition of the primary amino group in
p-anisidine at the carbon atom in position 2 of the
pyrrole ring in Ia or Ib (path a), opening of the pyrrole
(4Z)-5-Hydroxy-1-(4-methoxyphenyl)-4-[1-(4-
methoxyphenylamino)-2-oxo-2-phenylethylidene]-
5-phenylpyrrolidine-2,3-dione (IIIa). A solution of
1.0 mmol of compound Ia and 1.0 mmol of p-anisidine
O
Ar2
Ar2
O
OH
NHAr1
a
N
Ar1
O
O
O
O
O
O
Ar1
N
Ar2
Ar2
O
NHAr1
HO
Ar2
Ar2
Ar2
Ar2
Ar1NH2
O
O
O
NHAr1
N
O
NHAr1
O
Ar1
Ar2
OH
O
O
Ar1NH
Ar2
Ia, Ib
IVa, IVb
IIIa, IIIb
b
N
Ar1
O
Ar1 = 4-MeOC6H4, Ar2 = Ph (a), 4-ClC6H4 (b).
1103

SILAICHEV et al.
1104
in 15 ml of anhydrous chloroform was kept for 8–10 h
at room temperature. The solvent was removed, and
the residue was ground with ethanol. Yield 79%,
mp 153–154°C (from ethyl acetate–methanol). IR
spectrum, ν, cm–1: 3266– 3359 br (OH, NH), 1701
The IR spectra were recorded on an FSM-1201
spectrometer from samples dispersed in mineral oil.
The H NMR spectra were obtained on a Bruker AM-
400 instrument (400 MHz) 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 ace-
tate as eluent.
1
1
(C2=O), 1677 (PhCO), 1647 (C3=O, assoc.). H NMR
spectrum, δ, ppm: 3.59 s (3H, CH3O), 3.69 s (3H,
CH3O), 6.88–7.43 m (19H, Harom, OH), 12.29 br.s (1H,
NH). Found, %: C 71.83; H 4.85; N 5.18. C32H26N2O6.
Calculated, %: C 71.90; H 4.90; N 5.24.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 07-03-96036, 08-03-01032).
(Z)-5-(4-Chlorophenyl)-4-[2-(4-chlorophenyl)-1-
(4-methoxyphenylamino)-2-oxoethylidene]-5-hy-
droxy-1-(4-methoxyphenyl)pyrrolidine-2,3-dione
(IIIb) was synthesized in a similar way. Yield 72%,
mp 200–201°C (from ethyl acetate). IR spectrum, ν,
cm–1: 3310 br (OH, NH), 1705 (C2=O), 1680
REFERENCES
1. Maslivets, A.N., Smirnova, L.I., and Andreichikov, Yu.S.,
Zh. Org. Khim., 1989, vol. 25, p. 1748.
1
(4-ClC6H4CO), 1650 (C3=O, assoc.). H NMR spec-
2. Maslivets, A.N., Smirnova, L.I., and Andreichikov, Yu.S.,
trum, δ, ppm: 3.69 s (3H, CH3O), 3.75 s (3H, CH3O),
6.60–7.95 m (17H, Harom, OH), 12.18 br.s (1H, NH).
Found, %: C 63.61; H 3.95; N 4.56. C32H24Cl2N2O6.
Calculated, %: C 63.69; H 4.01; N 4.64.
Zh. Org. Khim., 1992, vol. 28, p. 2141.
3. Maslivets, A.N. and Mashevskaya, I.V., 2,3-Digidro-2,3-
pirroldiony
(2,3-Dihydropyrrole-2,3-diones),
Perm:
Perm. Gos. Univ., 2005.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 7 2010