Direct spiro heterocyclization of methyl 3-aroyl-1-aryl-4,5-dioxo-4,5- dihydro-1H-pyrrole-5-carboxylate by the action of 3-amino-1H-inden-1-one

Full text of DOI:10.1134/S1070428012030244

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 3, pp. 467–468. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © N.V. Bubnov, E.S. Denislamova, Z.G. Aliev, A.N. Maslivets, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 3,
pp. 465–466.
SHORT
COMMUNICATIONS
Direct Spiro Heterocyclization of Methyl 3-Aroyl-1-aryl-
4
,5-dioxo-4,5-dihydro-1H-pyrrole-5-carboxylate
by the Action of 3-Amino-1H-inden-1-one
a
b
c
a,b
N. V. Bubnov , E. S. Denislamova , Z. G. Aliev, and A. N. Maslivets
a
Institute of Natural Sciences, Perm State University, ul. Genkelya 4, Perm, 614990 Russia
e-mail: koh2@psu.ru
b
Perm State University, ul. Bukireva 15, Perm, 614990 Russia
c
Institute of Chemical Physics Problems, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, Russia
Received May 4, 2011
DOI: 10.1134/S1070428012030244
2
We previously described spiro heterocyclization of
C carbon atom of pyrrole I, followed by closure of
1
-substituted ethyl 4,5-dioxo-2-phenyl-1H-pyrrole-3-
new pyrrole ring as a result of intramolecular attack by
the amino group on the ester carbonyl carbon atom and
elimination of methanol.
The described reaction may be regarded as a new
method for building up difficultly accessible spiro-
carboxylates with 3-arylamino-1H-inden-1-ones at
ratios of 1:1 and 1:2, which led to the formation of
spiro[indeno[1,2-b]quinoline-10,3′-pyrrole] [1] and
spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-pyrrole]
derivatives [2], respectively. In both cases, the reac-
tions involved the 4-C=O group of the initial dioxopyr-
role. Reactions of other monocyclic 1H-pyrrole-2,3-di-
ones with 3-amino-1H-inden-1-ones were not reported
so far. By reaction of methyl 3-aroyl-1-aryl-4,5-dioxo-
[
indeno[1,2-b]pyrrole-3,2′-pyrrole] heterocyclic sys-
tem via direct spiro heterocyclization of monocyclic
H-pyrrole-2,3-diones with enamino ketones.
′-Benzoyl-1′-(4-chlorophenyl)-4′-hydroxy-1-
4-methylphenyl)-1H-spiro[indeno[1,2-b]pyrrole-
1
3
(
4
,5-dihydro-1H-pyrrole-2-carboxylates Ia and Ib with
3
1
,2′-pyrrole]-2,4,5′(1′H)-trione (IIIa). A solution of
mmol of compound Ia and 1 mmol of IIa in 10 ml of
an equimolar amount of 3-arylamino-1H-inden-1-ones
IIa and IIb in boiling anhydrous toluene (reaction time
anhydrous toluene was heated for 2 h under reflux. The
mixture was cooled, and the precipitate was filtered
off. Yield 82%, mp 223–224°C (from toluene). IR
1
.5–2 h; TLC monitoring) we obtained 3′-aroyl-1,1′-
diaryl-4′-hydroxy-1H-spiro[indeno[1,2-b]pyrrole-3,2′-
pyrrole]-2,4,5′(1′H)-triones IIIa and IIIb whose struc-
ture was confirmed by X-ray analysis of IIIb.
–1
2
spectrum, ν, cm : 3180 br (OH); 1763, 1715 (C =O,
5′
4
1
C =O); 1688, 1615 (C =O, 3′-C=O). H NMR spec-
trum, δ, ppm: 2.44 s (3H, Me), 6.43 d (1H, 8-H, J =
7.1 Hz), 7.12–7.76 m (16H, Harom), 12.20 br.s (1H,
Compounds III are likely to be formed via addition
of the =CH group in the enamino fragment of II at the
O COAr
O
O
4-YC H
6 4
OH
Ar
O
N
+
O
–
MeOH
N
O
O
N
C H X-4
6
4
MeO
NHC H Y-4
6 4
O
C H X-4
6
4
Ia, Ib
IIa, IIb
IIIa, IIIb
I, Ar = Ph, X = Cl (a); Ar = 2,4-Me
2
C
6
H
3
, X = H (b); II, Y = Me (a), H (b); III, Ar = Ph , X = Cl, Y = Me (a);
Ar = 2,4-Me , X = Y = H (b).
2
6 3
C H
4
67

4
68
BUBNOV et al.
1
OH). Found, %: C 71.47; H 3.65; Cl 6.13; N 4.69.
C H ClN O . Calculated, %: C 71.27; H 3.69;
The H NMR spectra were measured on a Bruker AM-
400 spectrometer from solutions in DMSO-d using
3
4
21
2
5
6
Cl 6.19; N 4.89.
tetramethylsilane as internal reference. The purity of
the products was checked by TLC on Silufol plates
using ethyl acetate as eluent; spots were visualized by
treatment with iodine vapor.
3
′-(2,4-Dimethylbenzoyl)-4′-hydroxy-1,1′-di-
phenyl-1H-spiro[indeno[1,2-b]pyrrole-3,2′-pyrrole]-
2
,4,5′(1′H)-trione (IIIb). Yield 84%, mp 255–256°C
–
1
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 2.19.10).
(
from toluene). IR spectrum, ν, cm : 3120 br (OH);
2
5′
4
1
3
773, 1703 (C =O, C =O); 1674, 1611 (C =O,
′-C=O). H NMR spectrum, δ, ppm: 2.26 s and 2.31 s
1
(
7
3H each, Me), 6.39 d (1H, 8-H, J = 7.1 Hz), 7.08–
.69 m (16H, Harom), 12.80 br.s (1H, OH). Found, %:
C 76.17; H 4.34 N 5.06. C H N O . Calculated, %:
REFERENCES
3
5
24
2
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C 76.10; H 4.39; N 5.09.
The IR spectra were recorded on an FSM-1201
spectrometer from samples dispersed in mineral oil.
2. Dmitriev, M.V., Silaichev, P.S., Aliev, Z.G., and Masli-
vets, A.N., Russ. J. Org. Chem., 2010, vol. 46, p. 931.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012