Reaction of methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2-carboxylates with arylhydrazines. synthesis of isomeric 5-arylcarbamoyl-4-aroyl- and 5-aryl-4-aryloxamoyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazoles

Methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with arylhydrazines to give methyl 3-aroyl-1-aryl-2-(2-arylhydrazinyl)-4-hydroxy-5-oxo-2,5-dihydro-1H-pyrrole-2-carboxylates which underwent thermal recyclization into isomeric methyl 1-aryl-5-(arylcarbamoyl)-4-aroyl-1H-pyrazole- 3-carboxylates and methyl 1,5-diaryl-4-[2-oxo-2-(arylamino)acetyl]-1H-pyrazole-3-carboxylates.     

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.     

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-membred 2,3-dioxoheterocycles: LXXXI. Reactions of 4,5-bis(methoxycarbonyl)-1H-pyrrole-2,3-diones with N-substituted 3-amino-5,5-dimethyl-2-cyclohex-2-en-1-ones. crystal and molecular structure of methyl 4′-hydroxy-6,6-dimethyl-1,1′-bis(4-methylphenyl)-2,4,5′-trioxo-1,1′,2,4,5,5′,6,7-octahydrospiro[indole-3,2′-pyrrole]-3′-carboxylate

1-Aryl-4,5-bis(methoxycarbonyl)-1H-pyrrole-2,3-diones react with N-substituted 3-amino-5,5-dimethylcyclohex-2-en-1-ones affording methyl 1,1′-diaryl-4′-hydroxy-6,6-dimethyl-2,4,5′-trioxo-1,1′,2,4,5,5′,6,7-octahydrospiro[indole-3,2′-pyrrole]-3′-carboxylates whose structure was proved by XRD analysis.     

Five-membered 2,3-dioxo heterocycles: LV. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2-carboxylates with ethyl 3-arylaminobut-2-enoates

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with ethyl 3-aryl-aminobut-2-enoates to give the corresponding ethyl 1,7-diaryl-4-aroyl-3-hydroxy-8-methyl-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-9-carboxylates.     

Spirobisheterocyclization of 5-(Methoxycarbonyl)-1<Emphasis Type="Italic">H</Emphasis>-pyrrol-2,3-diones by the action of enaminoesters. Crystal and molecular structure of 1,7-diazaspiro[4.4]nonane

1-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.     

Synthesis and Structure of 5-(2-Alkoxy-2-oxoethyl)-1,2-diaryl-4-hydroxy-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-3-carboxylic Acid Esters

Dialkyl 3,4-dihydroxyhexa-2,4-dienedioates reacted with substituted anilines and aromatic aldehydes or with the corresponding Schiff bases to give 5-(2-alkoxy-2-oxoethyl)-1,2-diaryl-4-hydroxy-1H-pyrrole- 3-carboxylates.     

A solvent-free synthesis of ethyl 3,5-diaryl-1H-pyrrole-2-carboxylates via triethylphosphite mediated reductive cyclization of ethyl 2-nitro-5-oxo-3,5-diarylpentanoates under microwave irradiation

Ethyl 3,5-diaryl-1H-pyrrole-2-carboxylates have been synthesized in good yields from ethyl 2-nitro-5-oxo-3,5-diarylpentanoates by treatment with triethylphosphite under microwave irradiation. The integrity of the mechanism proposed has been augmented by ³¹P NMR and EIMS experiments.     

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

1-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.     

Five-membered 2,3-dioxo heterocycles: LXX. Spiro heterocyclization of 1H-pyrrole-2,3-diones by the action of 1,5-binucleophiles. Crystalline and molecular structure of ethyl 1′-benzyl-7-methoxy-3,3-dimethyl-1,2′-dioxo-5′-phenyl-1′,2,2′,3,4,10-hexahydro-1H-spiro[acridine-9,3′-pyrrole]-4′-carboxylate

Ethyl 1-alkyl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrole-3-carboxylates reacted with 3-arylamino-5,5-dimethylcyclohex-2-en-1-ones as carbon-centered 1,5-binucleophiles to give the corresponding substituted ethyl 1′-alkyl-3,3-dimethyl-1,2′-dioxo-5′-phenyl-1′,2,2′,3,4,10-hexahydro-1H-spiro[acridine-9,3′-pyrrole]-4′-carboxylates whose structure was proved by X-ray analysis.     

Synthesis of phenylpyrrolylpyrroles. Part II

A series of methyl or ethyl 3-(N-arylpyrrol-3-yl)-1H-pyrrole-2-carboxylates and 2,4-dicarboxylates have been synthesized using an alkyl isocyanides addition-cyclization with N-arylpyrrole derivatives such as the carboxaldehydes and nitropropenes.     

Reaction of methyl 2,4-dioxobutanoates with tetracyanoethylene

Reaction of methyl 2,4-dioxobutanoates with tetracyanoethylene yielded methyl 3-acyl-4-cyano-5-(dicyanomethylene)-2-hydroxy-2,5-dihydro-1H-pyrrole-2-carboxylates. X-Ray diffraction data showed that 3-acyl-4-cyano-5-(dicyanomethylene)-2-hydroxy-2,5-dihydro-1H-pyrrole-2-carboxylic acid methyl esters can form supramolecular structures with one-dimensional channels which make possible inclusion of large organic and bioorganic molecules.     

Five-membered 2,3-dioxo heterocycles: XCIII. Spiro heterocyclization of 4,5-diaroyl-1H-pyrrole-2,3-diones with acyclic enamine. Crystalline and molecular structure of substituted 1,7-diazaspiro[4.4]nonane

4,5-Diaroyl-1-aryl-1H-pyrrole-2,3-diones reacted with ethyl 3-amino-3-phenylprop-2-enoate to give ethyl 4-aroyl-1,6-diaryl-3-hydroxy-2-oxo-8-phenyl-1,7-diazaspiro[4.4]nona-3,6,8-triene-9-carboxylates. The crystalline and molecular structures of ethyl 4-benzoyl-3-hydroxy-1-(4-methylphenyl)-2-oxo-6,8-diphenyl-1,7-diazaspiro[4.4]nona-3,6,8-triene-9-carboxylate were determined by X-ray analysis.     

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[7.2.1.0^2,7]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.     

Light-induced Dehydrodimerization of 3-Hydroxypyrroles

Irradiation (λ > 280 nm) of 3-hydroxy-1H-pyrrole-2-carboxylates 1 in CH₃CN gives the [2.2′-bi(3-oxo-2,3-dihydro-1H-pyrrole)]-2-,2′-dicarboxylates 2 in reasonable to good yields. The corresponding N-methylpyrroles 3 only undergo slow photodecomposition under similar conditions. Several 2-methyl-3-oxo-2,3-dihydro-1H-pyrrole-2-carboxylates 4 and 5 were synthesized to compare their spectral data with those of the dehydrodimers 2 . A X-ray structure analysis was performed for diethyl [2,2′-bi(4,5-dimethyl-3-oxo-2,3-dihydro-1 H-pyrrole)]-2,2′-dicarboxylate ( 2b ). The originally proposed [3,3′-bi(3H-pyroole)] structure for compounds 2a - e proves incorrect.     

New synthesis of pyrrole-2-carboxylic and pyrrole-2,5-dicarboxylic acid esters in the presence of iron-containing catalysts

Alkyl 1H-pyrrole-2-carboxylates and dialkyl 1H-pyrrole-2,5-dicarboxylates were synthesized in quantitative yield by reactions of 1H-pyrrole, 2-acetyl-1H-pyrrole, and 1-methyl-1H-pyrrole with carbon tetrachloride and aliphatic alcohols in the presence of iron-containing catalysts. A probable reaction mechanism was proposed, and the rate constants and energies of activation of particular steps were determined on the basis of experimental data.     

Five-membered 2,3-dioxo heterocycles: LXI. Reaction of 3-aroyl-1 H -pyrrolo[2,1- c ][1,4]benzoxazine-1,2,4-triones with α -enamino esters. Crystalline and molecular structure of methyl 11-benzoyl-2- o -hydroxyphenyl-3,4,10-trioxo-6,9-diphenyl-7-oxa-2,9-diazatricyclo[6.2.1.01,5]undec-5-ene-8-carboxylate

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with methyl 4-aryl-2-arylamino-4-oxobut-2-enoate to give substituted methyl 7-aryl-4,9-bis(aroyl)-3-hydroxy-1-(2-hydroxyphenyl)-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-8-carboxylates which undergo thermal cyclization to methyl 9-aroyl-4,7-diaryl-1-(2-hydroxyphenyl)-2,3,8-trioxo-2,3,7,8-tetrahydro-1H,6H-6,8a-methanopyrrolo[2,3-e][1,3]oxazepine-6-carboxylates. The crystalline and molecular structures of methyl 9-benzoyl-1-(2-hydroxyphenyl)-2,3,8-trioxo-4,7-diphenyl-2,3,7,8-tetrahydro-1H,6H-6,8a-methanopyrrolo[2,3-e][1,3]oxazepine-6-carboxylate was studied by X-ray analysis. Original Russian Text ? N.L. Racheva, Z.G. Aliev, A.N. Maslivets, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 8, pp. 1197–1201. For communication LX, see [1].     

Five-membered 2,3-dioxo heterocycles: LXXXIX. Reaction of methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with (E)-4-arylaminopent-3-en-2-ones. Crystalline and molecular structure of 9-acetyl-4-cinnamoyl-3-hydroxy-1-(4-methoxyphenyl)-8-methyl-7-phenyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione

Methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 4-benzylamino- and 4-arylaminopent-3-en-2-ones to give 1-aryl-7-benzyl- and 1,7-diaryl-9-acetyl-4-cinnamoyl-3-hydroxy-8-methyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-diones. The crystalline and molecular structures of 9-acetyl-4-cinnamoyl-3-hydroxy-1-(4-methoxyphenyl)-8-methyl-7-phenyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione were studied by X-ray analysis.     

Five-membered 2,3-dioxo heterocycles: LIV. Double spiro heterocyclization of methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2-carboxylates with 3-arylamino-5,5-dimethylcyclohex-2-en-1-ones

Methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 3-arylamino-5,5-dimethylcyclohex-2-en-1-ones in boiling benzene to give the corresponding 1,1′-diaryl-3′-benzoyl-4′-hydroxy-6,6-dimethyl-1,1′,2,4,5,5′,6,7-octahydrospiro[indole-3,2′-pyrrole]-2,4,5′-triones and 1′-aryl-4-arylamino-3-benzoyl-6′,6′-dimethyl-1′,2′,4′,5′,6′,7′-hexahydro-5H-spiro[furan-2,3′-indole]-2′,4′,5-triones whose structure was proved by X-ray analysis.     

Synthesis of phenylpyrrolylpyrroles. Part III

Several ethyl 3-[(3-aryl-4-methyl)-2(1H)-pyrrolyl]-4-methyl-1H-pyrrole-2-carboxylates have been synthesized using two successive ethyl isocyanide addition-cyclizations to the appropriate nitropropene derivatives.