Spiro heterocyclization of 4,5-diaroyl-2,3-dihydro-1H-pyrrole-2,3-diones with ethyl 3-amino-3-phenylprop-2-enoate

Full text of DOI:10.1134/S1070428011100290

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 10, pp. 1602–1603. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © P.S. Silaichev, N.V. Kudrevatykh, A.N. Maslivets, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 10,
pp. 1572–1573.
SHORT
COMMUNICATIONS
Spiro Heterocyclization of 4,5-Diaroyl-2,3-dihydro-1H-pyrrole-
2,3-diones with Ethyl 3-Amino-3-phenylprop-2-enoate
P. S. Silaicheva, b, N. V. Kudrevatykhb, and A. N. Maslivetsa, b
a Institute of Natural Sciences, Perm State University, ul. Genkelya 4, Perm, 614990 Russia
b Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received December 24, 2010
DOI: 10.1134/S1070428011100290
We previously described recyclizations of 4,5-di-
aroyl-1H-pyrrole-2,3-diones in reactions with aromatic
amines [1] and substituted hydrazines [2, 3], which led
to the formation of 1,5-diaryl-5-hydroxy-4-(2-aryl-1-
arylamino-2-oxoethylidene)pyrrolidine-2,3-diones and
substituted N-aryl-2-(5-aryl-3-aroyl-1H-pyrazol-4-yl)-
2-oxoacetamides, respectively. However, there no pub-
lished data on reactions of 4,5-diaroyl-1H-pyrrole-2,3-
diones with 1,3-binucleophiles.
bonyl group attached to C5 in the pyrrole ring. The
described reaction is the first example of direct spiro
heterocyclization of substituted 4,5-diaroyl-1H-pyr-
role-2,3-diones by the action of enamines with forma-
tion of difficultly accessible 1,7-diazaspiro[4.4]nona-
3,6,8-triene derivatives.
Ethyl 4-benzoyl-3-hydroxy-2-oxo-1-(4-methyl-
phenyl)-6,8-diphenyl-1,7-diazaspiro[4.4]nona-3,6,8-
triene-9-carboxylate (IIIa). A solution of 1.0 mmol of
compound Ia and 1.0 mmol of enamine II in 20 ml of
anhydrous benzene was heated for 2 h under reflux.
The mixture was concentrated by half, the residue was
diluted with an equal volume of petroleum ether
(bp 40–70°C), the mixture was cooled, and the precip-
itate was filtered off and recrystallized from benzene–
ethyl acetate (1:1). Yield 71%, mp 196–197°C. IR spec-
trum, ν, cm–1: 3280 (OH), 1719 (C=O, ester), 1669
By heating a solution of equimolar amounts of
4,5-diaroyl-1-(4-methylphenyl)2,3-dihydro-1H-pyr-
role-2,3-dione Ia or Ib and ethyl 3-amino-3-phenyl-
prop-2-enoate II in anhydrous benzene under reflux
over a period of 2–3 h (the progress of the reaction was
monitored by TLC) we obtained ethyl 6-aryl-4-aroyl-
3-hydroxy-2-oxo-1-(4-methylphenyl)-8-phenyl-1,7-
diazaspiro[4.4]nona-3,6,8-triene-9-carboxylates IIIa
and IIIb whose structure was confirmed by the X-ray
diffraction data for compound IIIa.
1
(C2=O), 1659 (4-C=O), 1640 (C=N). H NMR spec-
trum, δ, ppm: 1.14 t (3H, CH2CH3), 2.21 s (3H, Me),
4.14 m (2H, OCH2), 6.89–8.00 m (19H, Harom), 12.73 br.s
(1H, OH). Found, %: C 75.99; H 4.91; N 4.89.
C36H28N2O5. Calculated, %: C 76.04; H 4.96; N 4.93.
Compounds IIIa and IIIb are likely to be formed
via initial addition of the β-CH group in enamine II at
the C5 atom of pyrrole-2,3-dione Ia or Ib to give inter-
mediate A which undergoes intramolecular cyclization
with participation of the amino group and ketone car-
Ethyl 3-hydroxy-2-oxo-4-(4-methylbenzoyl)-1,6-
bis(4-methylphenyl)-8-phenyl-1,7-diazaspiro[4.4]-
COAr
HO
Ar
COAr
N
O
O
COAr
OH
N
NH2
O
Ar
NH2
Ph
O
N
+
Ph
EtO
O
COAr
–H2O
Ph
OEt
N
O
4-MeC6H4
C6H4Me-4
O
C6H4Me-4
O
OEt
Ia, Ib
II
A
IIIa, IIIb
Ar = Ph (a), 4-MeC6H4 (b).
1602

SPIRO HETEROCYCLIZATION OF 4,5-DIAROYL-2,3-DIHYDRO-1H-PYRROLE-2,3-DIONES
1603
nona-3,6,8-triene-9-carboxylate (IIIb) was synthe-
sized in a similar way. Yield 76%, mp 215–216°C
(from benzene–ethyl acetate, 1:1). IR spectrum, ν,
cm–1: 3275 (OH), 1725 (C=O, ester), 1667 (C2=O),
the products was checked by TLC on Silufol plates
using benzene–ethyl acetate (5:1) as eluent; spots were
detected by treatment with iodine vapor.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 2.19.10).
1
1642 (4-C=O, C=N). H NMR spectrum, δ, ppm:
1.14 t (3H, CH2CH3), 2.21 s (3H, CH3), 2.35 s (3H,
CH3), 2.37 s (3H, CH3), 4.11 m (2H, OCH2), 6.89–
7.90 m (17H, Harom), 12.61 br.s (1H, OH). Found, %:
C 76.42; H 5.39; N 4.67. C38H32N2O5. Calculated, %:
C 76.49; H 5.41; N 4.69.
REFERENCES
1. Silaichev, P.S., Kudrevatykh, N.V., Aliev, Z.G., and Mas-
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, using DMSO-d6 as solvent and
tetramethylsilane as internal reference. The purity of
livets, A.N., Russ. J. Org. Chem., 2010, vol. 46, p. 1103.
2. Silaichev, P.S., Aliev, Z.G., and Maslivets, A.N., Russ. J.
Org. Chem., 2009, vol. 45, p. 1269.
3. Silaichev, P.S., Kudrevatykh, N.V., Aliev, Z.G., and Mas-
livets, A.N., Russ. J. Org. Chem., 2010, vol. 46, p. 1546.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011