Spiro-heterocyclization of 1H-pyrrole-2,3-dione at the treatment with 3-arylamino-1H-inden-1-ones

Full text of DOI:10.1134/S1070428011020266

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 2, pp. 304305. Pleiades Publishing, Ltd., 2011.
Original Russian Text  M.V. Dmitriev, P.S. Silaichev, Z.G. Aliev, A.N. Maslivets, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 2,
pp. 309310.
SHORT
COMMUNICATIONS
Spiro-Heterocyclization of 1H-Pyrrole-2,3-dione
at the Treatment with 3-Arylamino-1Н-inden-1-ones
M. V. Dmitrieva, P. S. Silaicheva, Z. G. Alievb, and A. N. Maslivetsa,c
aInstitute of Natural Sciences at Perm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
cPerm State University, Perm Russia
Received March 12, 2010
DOI: 10.1134/S1070428011020266
The [3+3]-nucleophilic addition [1] and spiro-
heterocyclization [2] of substituted 1Н-pyrrole-2,3-diones
were described effected by cyclic enamines involved into
the reactions in both cases as СН,NН 1,3-binucleophiles.
and 3-arylamino-1H-inden-1-ones IIa, IIb by boiling the
reagents in anhydrous m-xylene solution at 139–140ºС
over 5–6 h we obtained ethyl 1'-benzyl-2',7-dioxo-5'-
phenyl-1,6-dihydro-1'H-spiro(indeno[1,2-b]quinoline-
6,3'-pyrrole)-4'-carboxylates IIIa, IIIb whose structure
was established by means of XRD analysis.
In the reaction of equimolar amounts of 1-benzyl-5-
phenyl-4-ethoxycarbonyl-1Н-pyrrole-2,3-dione (I) [3]
O
R
H
N
R
N
H
R
NH
O
EtOOC
Ph
O
IIa, IIb
EtOOC
Ph
EtOOC
OH
O
_H2O
O
O
N
Ph
N
N
O
CH2Ph
CH2Ph
CH2Ph
I
IVa, IVb
IIIa, IIIb
R = H (a), OMe (b).
The formation of compounds IIIa, IIIb evidently under the action of N-aryl-substituted enamines involved
proceeded through initial addition of the activated into the reaction as СН,СН 1,5-binucleophiles [4], and
СН group located in the ortho-position of the aryl also of the synthesis of difficultly accessible heterocyclic
substituent of cyclic enamines IIa, IIb to the carbon system of spiro(indeno[1,2-b]quinoline-6,3'-pyrrole).
atom in the position 3 of pyrroledione I, the formation
of intermediate compounds IVa, IVb followed by the
intramolecular cyclization involving the β-СН group of
the enamine fragment of reagents IIa, IIb.
Ethyl 1'-benzyl-2',7-dioxo-5'-phenyl-1,6-dihydro-
1'H-spiro(indeno[1,2-b]quinoline-6,3'-pyrrole)-
4'-carboxylate (IIа). A solution of 1.0 mmol of
pyrroledione I and 1.0 mmol of enamine IIa in 15 ml
This reaction is the second example of the direct spiro- of anhydrous m-xylene was boiled for 5 h, cooled, the
heterocyclization of the substituted 1Н-pyrrole-2,3-dione formed orange precipitate was filtered off. Yield 54%,
304

SPIRO-HETEROCYCLIZATION OF 1H-PYRROLE-2,3-DIONE
305
mp 239–241ºC (ethyl acetate). IR spectrum, ν, cm–1:
3252, 1694, 1688, 1626. 1H NMR spectrum, δ, ppm:
0.60 t (3Н, СН2СН3, J 7.1 Hz), 3.58 q (2Н, СН2СН3,
J 7.1 Hz), 4.51 d, 4.67 d (2Н, СН2Ph, J 16.3 Hz), 7.08–
7.67 group of signals (18Нarom), 11.02 s (1Н, NH). Found,
%: C 77.98; H 4.84; N 5.15. C35H26N2O4. Calculated, %:
C 78.05; H 4.87; N 5.20.
Bruker AM-400 (operating frequency 400 МHz) in
DMSO-d6, internal reference TMS.
ACKNOWLEDGMENTS
The study was carried out under the financial support
of the Ministry of Education and Science of the Russian
Federation (project 2.19.10) and the Russian Foundation
for Basic Research (grant no. 08-03-01032).
Ethyl 1'-benzyl-4-methoxy-2',7-dioxo-5'-phenyl-
1,6-dihydro-1'H-spiro(indeno[1,2-b]quinoline-6,3'-
pyrrole)-4'-carboxylate (IIb) was similarly obtained.
Yield 59%, mp 293–294ºC (ethyl acetate). IR spectrum,
REFERENCES
1
ν, cm–1: 3195, 1686, 1622. H NMR spectrum, δ, ppm:
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3.69 s (3Н, ОMе), 4.57 d, 4.61 d (2Н, СН2Ph, J 16.1 Hz),
6.50–7.64 group of signals (17Нarom), 11.02 s (1Н,
NH). Found, %: C 75.97; H 4.91; N 4.90. C36H28N2O5.
Calculated, %: C 76.04; H 4.96; N 4.93.
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IR spectra of compounds obtained were recorded on
a spectrophotometer FSM -1201 from mulls in mineral
oil. 1Н NMR spectra were registered on a spectrometer
4. Silaichev, P.S., Aliev, Z.G., and Maslivets, A.N., Zh. Org.
Khim., 2009, vol. 45, p. 1125.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011