E. S. Denislamova

Five-membered 2,3-dioxo heterocycles: LXXV. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with 1,3-diphenylguanidine. Crystalline and molecular structure of 9-Benzoyl-8-hydroxy-2-imino-6-(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro-[4.4]non-8-ene-4,7-dione

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 1,3-diphenylguanidine to give the corresponding 6-aryl-9-aroyl-8-hydroxy-2-imino-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-diones. The molecular and crystalline structures of 9-benzoyl-8-hydroxy-2-imino-6-(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-dione were determined by X-ray analysis.

Five-membered 2,3-dioxo heterocycles: CV. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with methyl 2-arylamino-4-(2-naphthyl)-4-oxobut-2-enoates. Crystal and molecular structure of substituted 1,7-diazaspiro[4.4]nonane

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with methyl 2-arylamino-4-(2-naphthyl)-4-oxobut-2-enoates to give methyl 1,7-diaryl-4-aroyl-3-hydroxy-9-(2-naphthalen-2-ylcarbonyl)-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-8-carboxylates.

Five-membered 2,3-dioxo heterocycles: LXXVI. Reaction of methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with 6-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione

Methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 6-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione to give methyl 11-aryl-12-benzoyl-9-hydroxy-4,6-dimethyl-3,5,10-trioxo-4,6,8,11-tetraazatricyclo[7.2.1.02,7]dodec-2(7)-ene-1-carboxylates which underwent thermal recyclization to 1-aryl-3-benzoyl-4-hydroxy-1′,3′-dimethylspiro[pyrrole-2,5′-pyrrolo[2,3-d]pyrimidine]-2′,4′,5,6′(1H,1′H,3′H,7′H)-tetraones.

Nucleophilic [3+3]-addition of N-Unsubstituted enamine to monocyclic 1H-Pyrrole-2,3-diones

A reaction is described of substituted 1H-pyrrole-2,3diones (methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1Hpyrrole-2-carboxylates) with N-alkyland N-arylsubstituted 3-amino-5,5-dimethyl-2-cyclohexen-1-ones providing 1-alkyland 1-aryl-susbtituted 6,6-dimethyl2,4-dioxo-2,3,4,5,6,7-hexahydro-1H-indole-3-spiro2-(1-aryl-3-aroyl-4-hydroxy-5-oxo-2,5-dihydro1H-pyrroles) [1, 2]. The reaction proceeds as successive attacks of β-CH and NH groups of the enamino fragment of the carbocyclic enamines first on the carbon atom in the position 2 and then on the carbonyl group of the methoxycarbonyl moiety (substituent in the position 2) of pyrrolediones followed by methanol elimination. In reaction of methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5dihydro-1H-pyrrole-2-carboxylates Ia and Ib with N-unsubstituted 3-amino-5,5-dimethyl-2-cyclohexen-1-one (II) taken in a ratio 1:1 performed by boiling in anhydrous benzene for 1–2 min (to the disappearance of the bright red color of initial compounds Ia and Ib) we unexpectedly obtained methyl 11-aryl-12-benzoyl-9-hydroxy-5,5dimethyl-3,10-dioxo-8,11-diazatricyclo[7.2.1.02,7]dodec2(7)-ene-1-carboxylates IIIa and IIIb. Spectral characteristics of compounds IIIa and IIIb are close to those of a model substituted 3,10,13-triazapentacyclo[10.7.1.01,10.04,9.014,19]eicosa-4,6,8,14(19)-tetraene, whose structure was confirmed by XRD analysis [3]. Evidently the bridged compounds IIIa and IIIb formed by the addition of β-CH and NH2 groups of the enamino fragment of carbocyclic enamine II to atoms C2 and C4 respectively of monocyclic pyrrolediones Ia and Ib.

Five-membered 2,3-dioxo heterocycles: LXXX. Recyclization of 1H-pyrrole-2,3-diones into pyrazolo[1,5-a]pyrimidines by the action of pyrazolamine. Crystalline and molecular structure of substituted pyrazolo[1,5-a]pyrimidine

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 3-methyl-4-phenyl-1H-pyrazol-5-amine to give methyl 7-arylcarbamoyl-6-aroyl-2-methyl-3-phenylpyrazolo[1,5-a]-pyrimidine-5-carboxylates. The molecular and crystalline structures of methyl 6-benzoyl-7-(4-chlorophenylcarbamoyl)-2-methyl-3-phenylpyrazolo[1,5-a]pyrimidine-5-carboxylate were studied by X-ray analysis.

Spiro heterocyclization of methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates by the action of diphenylguanidine

Reactions of monocyclic 1H-pyrrole-2,3-diones with guanidines were not reported. We examined reactions of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates Ia and Ib with 1,3-diphenylguanidine (II) at a molar ratio of 1 : 1 in boiling anhydrous 1,2-dichloroethane (reaction time 1–2 h; TLC monitoring) and isolated 6-aryl-9-aroyl-8-hydroxy-2-imino-1,3-diphenyl-1,3,6-triazaspiro[4.4]non8-ene-4,7-diones IIIa and IIIb whose structure was confirmed by X-ray analysis. Presumably, compounds IIIa and IIIb are formed via addition of one secondary amino group in diphenylguanidine II at the C atom of pyrroledione Ia or Ib, followed by closure of imidazole ring as a result of intramolecular attack by the second secondary amino group in II on the ester carbonyl group and elimination of methanol molecule. and 1 mmol of diphenylguanidine II in 10 ml of anhydrous 1,2-di-chloroethane was heated for 1 h under reflux. The mixture was cooled, and the precipitate was filtered off. Yield 79%, mp 243–244°C (from 1,2-dichloroethane). IR spectrum, ν, cm: 3070 br (OH, NH), 1790 (C=O), 1730, 1700 (C=O), 1615 br (9-C=O). H NMR spectrum, δ, ppm: 2.41 s (3H, Me), 7.10–7.69 m (19H, Harom), 9.44 br.s (2H, NH, OH). Found, %: C 72.73; H 4.50; N 10.67. C32H24N4O4. Calculated, %: C 72.72; H 4.58; N 10.60. 9-(4-Ethoxybenzoyl)-8-hydroxy-2-imino-6(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-dione (IIIb) was synthesized in a similar way. Yield 75%, mp 251–252°C (from 1,2-dichloroethane). IR spectrum, ν, cm: 3050 br (OH, NH), 1790 (C=O), 1730, 1700 (C=O), 1610 br (9-C=O). H NMR spectrum, δ, ppm: 1.35 t (3H, CH3CH2, J = 7.0 Hz), 2.40 s (3H, Me), 4.08 q (2H, CH2O, J = 7.0 Hz), 6.85–7.81 m (18H, Harom), 9.28 br.s (2H, NH, OH). Found, %: C 71.38; H 4.88; N 9.70. C34H28N4O5. Calculated, %: C 71.32; H 4.93; N 9.78. The IR spectra were recorded on an FMS-1201 spectrometer from samples dispersed in mineral oil. The H NMR spectra were measured on a Bruker WP400 instrument from solutions in DMSO-d6 using 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. This study was performed under financial support by the Russian Foundation for Basic Research (project no. 07-03-96 036). Ar = Ph (a), 4-EtOC6H4 (b). ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 12, p. 1891.

Spirobisheterocyclization of 5-(Methoxycarbonyl)-1H-pyrrol-2,3-diones by the action of enaminoesters. Crystal and molecular structure of 1,7-diazaspiro[4.4]nonane

Abstract1-Aryl-4-aroyl-5-(methoxycarbonyl)-1Н-pyrrole-2,3-diones react with methyl 4-aryl-2-(arylamino)-4-oxobut-2-enoates with the formation of methyl 1,7-diaryl-4,9-diaroyl-3-hydroxy-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-8-carboxylates.

Five-membered dioxo heterocycles: CIV. Reaction of methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with cyclic enehydrazines. Crystal and molecular structure of N-[3′-benzoyl-1′-(4-chlorophenyl)-4′-hydroxy-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro-[indole-3,2′-pyrrol]-1(2H)-yl]benzamide

Methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with N′-(5,5-dimethyl-3-oxocyclohex-1-en-1-yl)benzohydrazides and N′-(5,5-dimethyl-3-oxocyclohex-1-en-1-yl)-2,2-diphenylacetohydrazide to give substituted N-[1′-aryl-3′-benzoyl-4′-hydroxy-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]benz- and -diphenylacetamides.

Five-membered 2,3-dioxoheterocycles: LXXXVI. Spiro-heterocyclization of 1-aryl-4-aroyl-5-methoxycarbonyl-1H-pyrrole-2,3-diones under the action of 3-arylamino-1H-inden-1-ones. Crystal and molecular structure of 4′-hydroxy-3′-(2,4-dimethylbenzoyl)-1,1′-diphenyl-1H-spiro[indeno[1,2-b]pyrrole-3,2′-pyrrole]-2,4,5′(1′H)-trione

Abstract1-Aryl-4-aroyl-5-methoxycarbonyl-1H-pyrrole-2,3-diones react with 3-arylamino-1H-inden-1-ones affording 1,1′-diaryl-3′-aroyl-4′-hydroxy-1H-spiro[indeno[1,2-b]pyrrole-3,2′-pyrrole]-2,4,5′(1′H)-triones. The crystal and molecular structure of 4′-hydroxy-3′-(2,4-dimethylbenzoyl)-1,1′-diphenyl-1H-spiro[indeno[1,2-b] pyrrole-3,2′-pyrrole]-2,4,5′(1′H)-trione.

Five-membered dioxoheterocycles: XCIX. Reaction of 1-aryl-4-aroyl-5-methoxycarbonyl-1H-pyrrole-2,3-diones with indoles. Crystal and molecular structure of substituted 2-(indol-3-yl)pyrrole

Abstract1-Aryl-4-aroyl-5-methoxycarbonyl-1H-pyrrole-2,3-diones react with indole and 2-methylindole with the formation of methyl 1-aryl-3-aroyl-4-hydroxy-2-(1H-indol-3-yl)-5-oxo-2,5-dihydro-1H-pyrrole-2-carboxylates. Crystal and molecular structure of methyl 3-benzoyl-4-hydroxy-2-(2-methyl-1H-indol-3-yl)-5-oxo-1-phenyl-2,5-dihydro-1H-pyrrole-2-carboxylate was examined.