Five-membered 2,3-dioxoheterocycles: XC. Reaction of 4,5-bis(methoxycarbonyl)-1H-pyrrole-2,3-diones with enaminoesters. crystal and molecular structure of 4-methyl 9-ethyl 7-benzyl-3-hydroxy-8-methyl-1-(4-methoxyphenyl)-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-4,9-dicarboxylate

1-Aryl-4,5-bis(methoxycarbonyl)-1H-pyrrole-2,3-diones react with ethyl 3-(benzylamino)but-2-enoate and ethyl 3-(benzylamino)-3-phenylacrylate giving 4-methyl 9-ethyl 1-aryl-7-benzyl-3-hydroxy-8-methyl- and 4-methyl 9-ethyl 1-aryl-7-benzyl-3-hydroxy-8-phenyl-2,6-dioxo-1,7-diazaspiro[4.4]nona-3,8-diene-4,9-dicarboxylates.     

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: 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.     

Five-membered 2,3-dioxo heterocycles: C. Reaction of methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carbocylates with acyclic enamines

Methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carbocylates react with N-substituted ethyl 3-amino-3-phenylprop-2-enoates, ethyl 3-aminobut-2-enoates, 3-amino-1,3-diphenylprop-2-en-1-ones, and dimethyl 2-arylaminofumarates to give 9-ethoxycarbonyl-, 9-benzoyl-, and 8,9-bis(methoxycarbonyl)-4-cinnamoyl-1,7-diazaspiro[4.4]nona-3,8-dienes.     

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.     

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: CIII. Spiro heterocyclization of 4,5-diaroyl-1H-pyrrole-2,3-diones with 3-aminobut-2-enenitrile

1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-diones reacted with 3-aminobut-2-enenitrile to produce 1,6-diaryl-4-aroyl-3-hydroxy-8-methyl-2-oxo-1,7-diazaspiro[4.4]nona-3,6,8-triene-9-carbonitriles.     

Five-membered 2,3-dioxo heterocycles: LVI. Reaction of 3-aroyl-1<Emphasis Type="Italic">H</Emphasis>-pyrrolo[2,1-<Emphasis Type="Italic">c</Emphasis>][1,4]benzoxazine-1,2,4-triones with acyclic enamino ketones

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with 4-arylaminopent-3-en-2-ones and 3-amino-1,3-diphenylprop-2-en-1-ones to give substituted 4-aroyl-3-hydroxy-1-(o-hydroxyphenyl)-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-diones.     

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: 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.     

Experimental and Theoretical DFT Investigations in the [2,3]-Wittig-Type Rearrangement of Propargyl/Allyl-Oxy-Pyrazolones

Here we report the synthesis of interesting 3-alkyl-4-hydroxy-1-aryl-4-(propa-1,2-dienyl)1H-pyrazol-5(4H)-ones and 9-alkyl-7-aryl-1-oxa-7,8-diazaspiro[4.4]nona-3,8-dien-6-ones, starting from 1,2-diaza-1,3-dienes (DDs) and propargyl alcohol. The reaction proceeds through a sequence Michael-type nucleophilic attack/cyclization/[2,3]-Wittig rearrangement. In the same way, the reaction between the aforementioned DDs and allyl alcohol furnished 4-allyl-4-hydroxy-3-alkyl-1-aryl-1H-pyrazol-5(4H)-ones. A DFT study was also carried out, in order to have decisive clarifications about the mechanism.     

Tetraacetylethylene and nitrile oxides: Synthesis of spirofuranisoxazoles

trans and cis-3-Hexen-2,5-dione, 2 , reacted with nitrile oxides to give 4,5-dihydroisoxazoles 3a-c with the trans configuration. On the contrary the reaction between 3,4-diacetyl-3-hexen-2,5-dione, 1 , with nitrile oxides yielded 3-aryl-8,9-diacetyl-7-hydroxy-7-methyl-1,6-dioxa-2-azaspiro[4.4]nona-3,8-dienes 9a-e. The reaction is completely regiospecific. The cycloadducts show ring-open chain tautomerism.     

Spiro heterocyclization of 4-aryl-4-oxobutane-1,1,2,2-tetracarbonitriles to 3H-pyrrole derivatives, 2-oxa-7-azaspiro[4.4]nona-3,6,8-trienes

4-Aryl-3-methyl-4-oxobutane-1,1,2,2-tetracarbonitriles reacted with morpholine to give 8-amino-3-aryl-1-imino-4-methyl-6-(morpholin-4-yl)-2-oxa-7-azaspiro[4.4]nona-3,6,8-triene-9-carbonitriles.     

Synthesis and chemical properties of 8-aryl-7-acyl-1-6-dimethyl-6-hydroxy-4-cyano-5,6,7,8-tetrahydro-3(2H)-isoquinolinones and isoquinolinethiones

8-Aryl-7-acetyl-1, 6-dimethyl-6-hydroxy-4-cyano-5, 6, 7, 8-tetrahydro-3(2H)-isoquinolinones and -isoquinolinethiones and their sodium salts were obtained by the reaction of cyanoacetamide and cyanothioacetamide with 3-aryl-2, 4-diacetyl-5-methyl-5-hydroxycyclohexanonesinbasicrnedium. 8-Aryl-7-acetyl-6-methoxycarbonyl-1, 6-dimethyl-4-cyano-5, 6, 7, 8-tetrahydro-3(2H)-isoquinolinones were obtained by the reaction of acetyl chloride and the above isoquinolinone sodium salts. The reaction of iodoacetamide and the above isoquinolinethione sodium salts yielded 8-aryl-7-acetyl-3-carbamoylmethylthio-1, 6-dimethyl-4-cyano-5, 6, 7, 8-tetra-hydroisoquinolines, which were cyclized into 1-amino-6-aryl-7-acetyl-2-carbamoyl-5, 8-dimethyl-8-hydroxy-6, 7, 8, 9-tetrahydrothiophene[2,3-c]isoquinolines in basic medium.     

Five-membered 2,3-dioxoheterocycles: LVIII. Reaction of methyl 1-Aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrol-2-carboxylates with substituted 1-methyl-3,4-dihydroisoquinolines. New approach to the synthesis of steroid 13-azaanalogs

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with substituted 1-methyl-3,4-dihydroisoquinolines with the formation of substituted 3-oxo-2,3,5,6-tetra-hydropyrrolo[2,1-a]-isoquinoline-2-spiro-2′-(1-aryl-3-aroyl-4-hydroxy-5-oxo-2,5-dihydro-1H-pyrroles). A new approach was developed to the synthesis of 13-azagonanes, substituted benzo[f]pyrrolo[2,1-a]isoquinoline-9-spiro-2′-pyrroles.     

Synthesis and properties of ethyl 1-aryl-5-methyl-4-[1-(phenylhydrazinylidene)ethyl]-1<Emphasis Type="Italic">H</Emphasis>-pyrazole-3-carboxylates

Ethyl 1-aryl-4-acetyl-5-methyl-1H-pyrazole-3-carboxylates reacted with phenylhydrazine to give the corresponding hydrazones, ethyl 1-aryl-5-methyl-4-[1-(phenylhydrazinylidene)ethyl]-1H-pyrazole-3-carboxylates, which were converted to ethyl 1′-aryl-4-formyl-5′-methyl-1-phenyl-1H,1′H-3,4′-bipyrazole-3′-carboxylates by treatment with the Vilsmeier–Haack reagent. No indole derivatives were formed from the same hydrazones under the Fischer reaction conditions, but cyclization to 2-aryl-3,4-dimethyl-6-phenyl-2,6-dihydro-7H-pyrazolo[3,4-d]pyridazin-7-ones was observed.     

Five-membered 2.3-dioxo heterocycles: LXVIII. Three pathways in the reaction of methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with 3-amino-5,5-dimethylcyclohex-2-en-1-one

Methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 3-amino-5,5-dimethylcyclohex-2-en-1-one having no substituent on the nitrogen atom to give 3-aroyl-4-arylamino-6′,6′-dimethyl-6′,7′-dihydro-5H-spiro[furan-2,3′-indole]-2′,4′,5′(1′H,5′H)-triones or methyl 12-aroyl-11-aryl-9-hydroxy-5,5-dimethyl-3,10-dioxo-8,11-diazatricyclo[7.2.1.0^2,7]dodec-2(7)-ene-1-carboxylates. The latter underwent thermal recyclization to 3′-aroyl-1′-aryl-4′-hydroxy-6,6-dimethyl-6,7-dihydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-triones.     

Five-membered 2,3-dioxo heterocycles: LXXII. Recyclization of isopropyl 2-(1-aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol-3-yl)-2-oxoacetates by the action of aliphatic amines

Reactions of isopropyl 2-(1-aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol-3-yl)-2-oxoacetates with alkylamines involve pyrroledione-pyrroledione recyclization with formation of isopropyl 1-aryl-2-hydroxy-4,5-dioxo-3-[phenyl(alkylamino)methylidene]pyrrolidine-2-carboxylates.     

Three-component reaction of 5-aryl-4-(quinoxalin-2-yl)-furan-2,3-diones,acetylenedicarboxylic acid dimethyl ester,and triphenylphosphine

Three-component synthesis from 5-aryl-4-(quinoxalin-2-yl)furan-2,3-diones, acetylenedicarboxylic acid dimethyl ester, and triphenylphosphine afforded methyl esters of 1,6-dioxaspiro[4.4]nona-3,7-diene-4-carboxylic and 4H-furo[3,2-c]pyran-3-carboxylic acids.     

Synthesis of new 3<Emphasis Type="Italic">H</Emphasis>-pyrrole derivatives from 3-aryl-2-oxa-7-azaspiro[4.4]nona-3,6,8-trienes

8-Amino-3-aryl-1-imino-4-methyl-6-(morpholin-4-yl)-2-oxa-7-azaspiro[4.4]nona-3,6,8-triene-9-carbonitriles reacted with acetic anhydride to give different products, depending on the solvent. The reaction in tetrahydrofuran gave the corresponding N-acyl derivatives at the imino group, whereas in pyridine 5-amino-2-morpholin-4-yl-3-(1-aryl-1-oxopropan-2-yl)-3H-pyrrole-3,4-dicarbonitriles were formed as a result of opening of the furan ring.