Three component condensation of 1H-pyrrol-2,3-dione with malononitrile and 4-hydroxycoumarin

Full text of DOI:10.1134/S1070428011080288

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 8, pp. 1263−1264. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © M.V. Dmitriev, P.S. Silaichev, A.N. Maslivets, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 8, pp. 1243−1244.
SHORT
COMMUNICATIONS
Three Component Condensation of 1Н-Pyrrol-2,3-dione
with Malononitrile and 4-Hydroxycoumarin
M. V. Dmitrieva, P. S. Silaicheva,b, and A. N. Maslivetsa,b
aInstitute of Natural Sciences at Perm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
b Perm State University, Perm, Russia
Received November 9, 2010
DOI: 10.1134/S1070428011080288
The spiroheterocyclixation of isatin under the action
of malononitrile and 4-hydroxycoumarin was described
resulting in the formation of substituted spiro{indole-3,4'-
pyrano[3,2-c]chromene}-2,5’(1H)-diones [1].
(TLC monitoring) to obtain ethyl 2-amino-2',5-dioxo-
5’-phenyl-3-cyano-1',2'-dihydro-5H-spiro{pyrano[3,2-с]
chromene-4,3'-pyrrole}-4'-carboxylates IIa and IIb.
In the first stage of the reaction proceeds apparently the
condensation of the keto carbonyl group of pyrrolediones
Iа, Ib with the methylene group of the malononitrile to
form pyrrolones IIIa, IIIb followed by the successive
nucleophilic addition of the β-CH group and the hydroxy
group of the enol fragment of the 4-hydroxycoumarin to
the carbon atom in the position 3 and to the cyano group
We carried out the reaction of 5-phenyl-4-ethoxy-
carbonyl-1Н-pyrrole-2,3-diones Iа and Ib with malono-
nitrile and 4-hydroxy-2H-chromen-2-one (4-hydroxy-
coumarin) in the ratio 1 : 1 : 1 by boiling the solution
of the reagents in anhydrous toluene in the presence of
the equimolar amount of triethylamine for 25–40 min
CN
O
EtOOC
Ph
EtOOC
Ph
C CN
CN
CH2
CN
O
N
O
N
R
R
Iа, Ib
IIIа, IIIb
OH
O
H2N
CN
O
HO
NC
EtOOC
NC
EtOOC
O
O
O
O
Ph
O
O
Ph
O
N
R
N
R
IIа, IIb
R = CH2Ph (а), Ph (b).
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of the pyrrolones respectively.
IR spectrum, ν, cm–1: 3341 (NН2), 2199 (CN), 1742,
1705, 1686 (C=O). Н NMR spectrum, δ, ppm: 0.77 t
1
The reaction described is a rare example of the
spirobisheterocyclization of monocyclic 1Н-pyrrole-
2,3-dione at the successive condensation with two dif-
ferent nucleophilic reagents, and also an example of the
synthesis of difficultly accessible heterocyclic system of
spiro{pyrano[3,2-с]chromene-4,3’-pyrrole}.
(3Н, СН3CH2O, J 6.9 Hz), 3.80 m (2Н, СН3CH2O),
7.08–7.97 group of signals (16Н, 2Ph + С6Н4 + NH2).
13С NMR spectrum, δ, ppm: 13.23 (CH3CH2), 48.53 (C4),
54.44 (C3), 59.18 (CH3CH2), 100.74 (C4'), 110.43 (C10a),
112.22 (C7), 116.81 (CN), 116.91 (C4a), 122.36–151.97
(Carom), 155.13 (C6a), 155.42 (C5'), 158.74 (C2), 159.40
(C5), 161.37 (СOO), 176.89 (C2'). Found, %: C 69.99;
H 3.95; N 7.88. C31H21N3O6. Calculated, %: C 70.05;
H 3.98; N 7.91.
Ethyl 2-amino-1'-benzyl-2',5-dioxo-5'-phenyl-
3-cyano-1',2'-dihydro-5H-spiro{pyrano[3,2-с]-
chromen-4,3'-pyrrole}-4'-carboxylate (IIа). To
a solution of 1.0 mmol of pyrroledione Ia in 20 ml of
anhydrous toluene was added 1.0 mmol of malononitrile
and 1.0 mmol of triethylamine, the mixture was boiled
for 10 min, cooled, and 1.0 mmol of 4-hydroxycoumarin
was added, the mixture was boiled for 25 min, cooled, the
separated precipitate was filtered off and recrystallized
from acetone. Yield 87%, mp 293–294°С. IR spectrum,
ν, cm–1: 3426, 3310 (NН2), 2193 (CN), 1725, 1709,
IR spectra of compounds obtained were recorded on
a spectrophotometer FSM -1201 from mulls in mineral
oil. 1Н and 13C NMR spectra were registered on a spec-
trometer Bruker AM-400 [operating frequencies 400
(1Н) and 100 (13С) MHz] in DMSO-d6, internal refer-
ence TMS.
ACKNOWLEDGMENTS
1
1686 (C=O). Н NMR spectrum, δ, ppm: 0.71 т (3H,
CH3CH2O, J 6.9 Hz), 3.74 m (2H, CH3CH2O), 4.53 d
(1H, CH2Ph, J 16.4 Hz), 4.59 d (1H, CH2Ph, J 16.4 Hz),
7.12–7.96 group of signals (16H, 2Ph + С6Н4 + NH2).
Found, %: C 70.39; H 4.21; N 7.66. C32H23N3O6. Cal-
culated, %: C 70.45; H 4.25; N 7.70.
The study was performed under the financial support
of the Ministry of Education and Science of the Russian
Federation (project no. 2.19.10) and the Russian Founda-
tion for Basic Research (grant no. 08-03-01032).
Ethyl 2-amino-2',5-dioxo-1',5'-diphenyl-3-cyano-
1',2'-dihydro-5H-spiro{pyrano[3,2-с]chromene-4,3'-
pyrrole}-4'-carboxylate (IIb) was similarly prepared.
Yield 64%, mp 294–296°С (ethyl acetate–acetone, 1 : 1).
REFERENCE
1. Joshi, K.C., Dandia, A., Baweja, S.,and Joshi, A.,
J. Heterocycl. Chem., 1989, vol. 26, p. 1097.
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