Nucleophilic [3+3]-addition of heterocyclic enamine to monocyclic 1H-pyrrole-2,3-diones

Full text of DOI:10.1134/S1070428009080302

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 8, pp. 1264−1265. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © E.S. Denislamova, Yu.N. Bannikova, A.N. Maslivets, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45,
No. 8, pp. 1272−1273.
SHORT
COMMUNICATIONS
Nucleophilic [3+3]-Addition of Heterocyclic Enamine
to Monocyclic 1H-Pyrrole-2,3-diones
E. S. Denislamova, Yu. N. Bannikova, and A. N. Maslivets
Perm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received July 14, 2008
DOI: 10.1134/S1070428009080302
2
4
Reactions of monocyclic 1H-pyrrole-2,3-diones with
heterylamines were not described before.
II to atoms C and C respectively in monocyclic
pyrrolediones Ia and Ib.
In reactions of substituted 1H-pyrrole-2,3-diones
methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-
-carboxylates) Ia and Ib with 6-amino-1,3-dimethyl-
The described reaction is the first example of the
nucleophilic [3+3]-addition of an enamino fragment of
a heterylamine to monocyclic 1H-pyrrole-2,3-diones, and
also a new preparation method for difficultly available
functionalized bridged heterocyclic system of 4,6,8,11-
(
2
pyrimidine-2,4(1H,3H)-dione (II) in 1:1 ratio at boiling in
anhydrous 1,2-dichloroethane for 4–6 h (till the intense
red color of initial compounds Ia and Ib disappeared) we
unexpectedly obtained methyl 11-aryl-12-aroyl-9-hy-
droxy-4,6-dimethyl-3,5,10-trioxo-4,6,8,11-tetraazatri-
2
,7
tetraazatricyclo[7.2.1.0 ]dodecene.
Methyl 12-benzoyl-9-hydroxy-4,6-dimethyl-
3
,5,10-trioxo-11-phenyl-4,6,8,11-tetraazatricyclo-
2
,7
cyclo[7.2.1.0 ]dodec-2(7)-ene-1-carboxylate IIIa and
IIIb. The spectral characteristics of compounds IIIa
and IIIb are close to those of a model substituted -
2,7
[
7.2.1.0 ]dodec-2(7)-ene-1-carboxylate (IIIa).
A solution of 1 mmol of compound Ia and 1 mmol of
enamine II in 10 ml of anhydrous 1,2-dichloroethane was
boiled for 4 h, and on cooling the separated precipitate
was filtered off. Yield 74%, mp 210–211°C (decomp.,
1
,10 4,9 14,19
3
4
,10,13-triazapentacyclo[10.7.1.0 .0 .0
]eicosa-
,6,8,14(19)-tetraene whose structure was proved by
XRD [1].
–1
dichloroethane). IR spectrum, ν, cm : 3330 (NH),
5
3
Evidently the formation of bridged compounds IIIa
3160 br (OH), 1759 (C =O), 1738 (C =O), 1721
10
1
and IIIb occurred due to the addition of groups β-CH
(COOMe), 1704 (C =O), 1643 (COPh). H NMR spec-
and NH of the enamino fragment from the heterylamine
trum, δ, ppm: 3.09 s (3H, Me), 3.16 s (3H, Me), 3.37 s
2
O
Me
N
COOMe
Ar2
O
N
NH2
O
1
Ar CO
O
O
Me
II
Me
O
N
H
N
O
1
COAr
MeOCO
N
Ar2
Iа, Ib
N
N
H
Me
OH
IIIа, IIIb
1
2
1
2
Ar =Ar = Ph (a);Ar = C H Br-4,Ar = C H Me-4 (b).
6
4
6
4
1264

NUCLEOPHILIC [3+3]-ADDITION OF HETEROCYCLIC ENAMINE
1265
1
2
(
3H, COOΜε), 4.83 s (1H, C H), 7.19–7.99 group of
%: C 53.66; H 4.09; Br 13.52; N 9.55. C H BrN O .
Calculated, %: C 53.53; H 3.97; Br 13.70; N 9.60.
26
23
4
7
signals (10H, 2Ph), 7.84 s (1H, OH), 8.52 s (1H, NH).
C NMR spectrum, δ, ppm: 27.73, 30.14 (2Me), 51.37
CH), 54.70 (C ), 65.50 (MeOCO), 85.64 (C ), 125.43,
1
3
IR spectra of compounds obtained were recorded on
a spectrophotometer FMS-1201 from mulls in mineral
1
9
(
1
1
%
%
5
2
27.97, 128.87, 133.86, 137.33, 150.80 (C ), 157.85 (C ),
1
oil. H NMR spectra were registered on a spectrometer
1
0
66.08 (ΜεOCO), 167.05 (C ), 196.15 (PhCO). Found,
Bruker WP-400 in DMSO-d , internal reference TMS.
6
: C 61.42; H 4.64; N 11.38. C H N O . Calculated,
25 22 4 7
The homogeneity of compounds obtained was confirmed
by TLC on Silufol plates, eluent ethyl acetate, develop-
ment in iodine vapor.
: C 61.22; H 4.52; N 11.42.
Methyl 12-p-bromobenzoyl-9-hydroxy-4,6-di-
methyl-3,5,10-trioxo-11-p-tolyl-4,6,8,11-tetra-
azatricyclo[7.2.1.0 ]dodec-2(7)-ene-1-carboxylate
IIIb). Yield 73%, mp 220–221°C (decomp., ethyl
acetate). IR spectrum, ν, cm : 3306 (NH), 3180 br (OH),
780 (C =O), 1761 (C =O), 1727 (COOMe), 1708
C =O), 1628 (COPh). H NMR spectrum, δ, ppm:
.28 s (3H, C H Me-4), 3.14 s (6H, 2Me), 3.37 s (3H,
COOMe), 4.83 s (1H, C H), 7.08–7.93 group of signals
8H, 2C H ), 7.77 s (1H, OH), 8.52 s (1H, NH). Found,
2
,7
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant no.
07-03-96036).
(
–1
5
3
1
(
2
1
0
1
REFERENCES
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4
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1. Bozdyreva Ks.S., Maslivets A.N., and Aliev Z.G.,
Mendeleev Commun. 2005, p. 163.
(
6
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 8 2009