Three-component spiro-heterocyclization of 4,5-diphenyl-1H-pyrrole-2,3- dione under the action of malononitrile and 3-hydroxycyclohex-2-en-1-ones

Full text of DOI:10.1134/S1070428012020236

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 2, pp. 299−300. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © P.S. Silaichev, P.V. Melyukhin, Yu.G. Stepanyan, A.N. Maslivets, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48,
No. 2, pp. 305−306.
SHORT
COMMUNICATIONS
Three-Component Spiro-Heterocyclization
of 4,5-Diphenyl-1Н-pyrrole-2,3-dione
under the Action of Malononitrile
and 3-Hydroxycyclohex-2-en-1-ones
P. S. Silaicheva, P. V. Melyukhinb, Yu. G. Stepanyanb, and A. N. Maslivetsa,b
aInstitute of Natural Sciences at Perm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
bPerm State University, Perm, Russia
Received February 10, 2011
DOI: 10.1134/S1070428012020236
Acondensation is described of 5-(4-tolyl)-1H-pyrrole-
2,3-dione with malononitrile providing a dicyanometh-
ylene derivative at the carbonyl group in the position 3
[1]. This process is a convenient model reaction for in-
vestigating three-component syntheses involving analogs
of this pyrroledione.
4,5-diphenyl-1H-pyrrole-2,3-dione (I), malononitrile,
and substituted 3-hydroxycyclohex-2-en-1-ones IIа,
IIb in the ratio 1 : 1 : 1 we obtained in good yields sub-
stituted 2-amino-2',5-dioxo-4',5'-diphenyl-1',2',5,6,7,8-
hexahydrospiro[chromene-4,3'-pyrrole]-3-carbonitriles
IIIа, IIIb.
By boiling for 5–15 min in anhydrous toluene in
the presence of triethylamine (TLC monitoring) of
Spectral characteristics of compounds IIIа, IIIb
are similar to those of the model 2-amino-2',5-dioxo-
NC
O
Ph
Ph
C
CN
O
CH2(CN)2
_H2O
Ph
O
N
H
Ph
N
H
I
IV
R2
R2
O
R1
R1
R1
O
OH
CN
HC
O
Ph
OH
O
Ph
R2
IIа, IIb
NH2
CN
O
Ph
O CN
Ph
N
N
H
H
IIIа, IIIb
R1 = R2 = Me (a), R1 = H, R2 = Ph (b).
299

SILAICHEV et al.
300
1',2',5,6,7,8-hexahydrospiro[chromene-4,3'-indole]-3-
carbonitriles [2].
26.03 (Me), 27.90 (Me), 31.52 (C7), 39.89 (С8), 49.95
(C4), 52.28 (C6), 56.27 (C3), 109.82 (C4a), 117.38 (CN),
126.84–136.49 group of signals (Сarom, С4', C5'), 159.20
(C8a), 164.23 (C2), 179.39 (C2'), 194.86 (C5). Found, %:
C 74.06; H 5.25; N 9.54. C27H23N3O3. Calculated, %:
C 74.13; H 5.30; N 9.60.
The formation of compounds IIIа, IIIb occurs due to
the primary condensation of the keto carbonyl group of
pyrroledione I with malononitrile giving pyrrolone IV
followed by the nucleophilic addition of β-CH group and
the hydroxy group of the enol fragment of compounds IIа,
IIb to the carbon atom in the position 3 and the carbon
atom of the nitrile group of pyrrolone IV respectively.
2-Amino-2',5-dioxo-4',5',7-triphenyl-1',2',5,6,7,8-
hexahydrospiro[chromene-4,3'-pyrrole]-3-carbo-
nitrile (IIIb) was similarly obtained. Yield 84%, mp
268–269°С (acetone–ethyl acetate, 1:1). IR spectrum, ν,
cm–1: 3466, 3226, 3164 (NН2, NH), 2195 (C≡N), 1698
(C2'=O), 1673 (C5=O). 1Н NMR spectrum, δ, ppm:
2.51–3.46 group of signals (5H, C8H2, C7H, C6H2),
6.90–7.38 group of signals (17H, NH2, 3Ph), 10.12 s (1H,
NH). Found, %: C 76.62; H 4.73; N 8.60. C31H23N3O3.
Calculated, %: C 76.69; H 4.77; N 8.65.
The described reaction is an example of a spirobis-
heterocyclization of monocyclic 1Н-pyrrole-2,3-diones
possessing no additional functional groups in the three-
component condensation with binucleophilic reagents,
and it also exemplifies the synthesis of difficultly ac-
cessible heterocyclic system of spiro[chromene-4,3'-
pyrrole].
IR spectra of compounds obtained were recorded on
a spectrophotometer FSM-1201 from mulls in mineral
2-Amino-7,7-dimethyl-2',5-dioxo-4',5'-diphenyl-
1',2',5,6,7,8-hexahydrospiro[chromene-4,3'-pyrrole]-
3-carbonitrile (IIIа). To a solution of 1.0 mmol of
pyrroledione I in 15 ml of toluene was added 1.0 mmol
of malononitrile and 0.2 ml of triethylamine, the mixture
was boiled for 5 min (TLC monitoring), 1.0 mmol of
3-hydroxy-5,5-dimethylcyclohex-2-en-1-one (IIа) was
added, and the mixture was boiled for 10 min (TLC
monitoring). On cooling the separated precipitate was
filtered off and recrystallized from acetone. Yield 87%,
mp 265–266°С. IR spectrum, ν, cm–1: 3358, 3315, 3178
(NН2, NH), 2195 (C≡N), 1698 (C2'=O), 1661 (C5=O).
1Н NMR spectrum, δ, ppm: 0.63 s (3H, Me), 0.98 s (3H,
Me), 2.08 d (1H, С8Н2, J 15.7 Hz), 2.21 d (1H, С8Н2,
J 15.7 Hz), 2.23 d (1H, С6Н2, J 17.4 Hz), 2.48 d (1H,
С6Н2, J 17.4 Hz), 6.95–7.30 group of signals (12H, NH2,
2Ph), 10.13 s (1H, NH). 13C NMR spectrum, δ, ppm:
1
oil, Н and 13C NMR spectra, on spectrometer Bruker
AM-400 [operating frequency 400 (1Н) and 100 (13С)
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).
REFERENCES
1. Mumm, O. and Hornhardt, H., Ber., 1937, vol. 70, p. 1930.
2. Shemchuk, L.A., Chernykh, V.P., and Red'kin, R.G., Zh.
Org. Khim., 2008, vol. 44, p. 1816.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012