Recyclization of isopropyl 1-aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol- 3-yl(oxo)acetates in reactions with anilines

Full text of DOI:10.1134/S1070428008120233

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 12, pp. 1844–1845. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © P.S. Silaichev, Z.G. Aliev, A.N. Maslivets, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 12, pp. 1870–1871.
SHORT
COMMUNICATIONS
Recyclization of Isopropyl 1-Aryl-4,5-dioxo-2-phenyl-4,5-
dihydro-1H-pyrrol-3-yl(oxo)acetates in Reactions with Anilines
P. S. Silaicheva, 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 April 30, 2008
DOI: 10.1134/S1070428008120233
We previously reported on reactions of monocyclic
1H-pyrrole-2,3-diones with arylamines, which led to
the formation of amine addition products at the C5
atom of pyrrolediones, 5-arylamino-3-hydroxy-1H-
pyrrol-2(5H)-ones [1–3]. The reaction of isopropyl
1-aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol-3-yl-
(oxo)acetates Ia and Ib with anilines IIa and IIb at
a ratio of 1:1 in anhydrous chloroform at room tem-
perature (reaction time 8–10 h) gave the corresponding
isopropyl 1-aryl-2-hydroxy-4,5-dioxo-3-[(Z)-phenyl-
(arylamino)methylidene]pyrrolidine-2-carboxylates
IIIa and IIIb in good yields. The product structure was
proved by X-ray analysis.
the ketone carbonyl carbon atom in the alkoxalyl frag-
ment. An alternative mechanism (path b) implies initial
addition of aniline II at the C2 carbon atom of pyrrole-
dione I and opening of the pyrrole ring at the N1–C2
bonds, which yields the same intermediate IV.
The described reaction is an example of recycliza-
tion of pyrrolediones by the action of anilines with
cleavage of the pyrroledione ring and closure of new
pyrrolidine ring.
Isopropyl 2-hydroxy-4,5-dioxo-1-phenyl-3-
[(Z)-phenyl(phenylamino)methylidene]pyrrolidine-
2-carboxylate (IIIa). A solution of 1.0 mmol of com-
pound Ia and 1.0 mmol of aniline (IIa) in 15 ml of an-
hydrous chloroform was kept for 8 h at room tempera-
ture. The solvent was removed, and the residue was
ground with ethanol. Yield 83%, mp 182–183°C (from
toluene). IR spectrum, ν, cm–1: 3255 br (OH, NH),
1753 (C=O, ester), 1723 (C5=O), 1616 br (C4=O,
Presumably, compounds IIIa and IIIb are formed
via initial addition of the primary amino group of re-
agent IIa or IIb at the C5 carbonyl carbon atom of pyr-
roledione Ia or Ib (path a) and cleavage of the pyrrole
ring at the N1–C5 bond. The subsequent closure of new
pyrrolidine ring involves intramolecular nucleophilic
addition of the NH group in intermediate IVa or IVb at
1
H-bonded). H 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
O
O
O
a
i-PrO
OH
NHAr
O
Ph
O
Ar
O
O
N
i-PrO
O
ArNH2
IIa, IIb
O
O
N
Ar
HO
i-PrO
i-PrO
NHAr
O
O
O
Ph
O
O
N
O
OH
O
Ph
NHAr
NHAr
Ar
Ph
b
i-PrO
Ph
ArNH
Ia, Ib
IVa, IVb
IIIa, IIIb
N
Ar
Ar = Ph (a), 4-MeOC6H4 (b).
1844

RECYCLIZATION OF ISOPROPYL 1-ARYL-4,5-DIOXO-2-PHENYL-4,5-DIHYDRO-...
1845
1
(1H, OCH, J = 6.4 Hz), 6.88–7.43 m (16H, Harom, OH),
12.67 br.s (1H, NH). Found, %: C 74.12; H 5.18;
N 6.27. C27H24N2O5. Calculated, %: C 74.04; H 5.30;
N 6.14.
oil. The H NMR spectra were measured on a Bruker
AM-400 spectrometer at 400 MHz using DMSO-d6 as
solvent and 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.
Isopropyl 2-hydroxy-1-(4-methoxyphenyl)-3-
[(Z)-(4-methoxyphenylamino)phenylmethylidene]-
4,5-dioxopyrrolidine-2-carboxylate (IIIb) was syn-
thesized in a similar way. Yield 79%, mp 195–196°C
(from toluene). IR spectrum, ν cm–1: 3242 br (OH,
NH), 1752 (C=O, ester), 1719 (C5=O), 1612 br (C4=O,
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 07-03-96036, 08-03-01032).
1
REFERENCES
H-bonded). H 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 m (14H, Harom, OH), 12.62 br.s (1H, NH).
Found, %: C 67.31; H 5.37; N 5.35. C29H28N2O7. Cal-
culated, %: C 67.43; H 5.46; N 5.42.
1. Maslivets, A.N., Smirnova, L.I., and Andreichikov, Yu.S.,
Zh. Org. Khim., 1989, vol. 25, p. 1748.
2. Maslivets, A.N., Smirnova, L.I., and Andreichikov, Yu.S.,
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.
The IR spectra were recorded on an FSM-1201
spectrophotometer from samples dispersed in mineral
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 12 2008