Chemistry of oxalyl derivatives of methyl ketones. 40. Reaction of 5-aryl-2,3-dihydro-2,3-furandiones with aryl and aroyl cyanamides

Starting from 5-aryl-2,3-dihydro-2,3-furandiones and benzoyl cyanamide, 2-benzoylamino-6-aryl-1,3-oxazin-4-ones were obtained. It was shown that on reaction of o-chlorophenyl cyanamide with furandiones, 2-imino-3-(o-chlorophenyl)-5-phenacyliden-4-oxazolidones are formed which in acid medium rearrange to 3-(o-chlorophenyl)-5-phenacylideneimidazolidin-2,4-diones and on thermolysis in acid medium they form 2-(o-chloroanilino)-6-aryl-1,3-oxazin-4-ones.For Communication 39, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 166–169, February, 1985.     

Chemistry of oxalyl derivatives of methyl ketones

It was established by IR, UV, and PMR spectroscopy that 2-phenacylidenebenzo-1,4-thiazin-3-ones are formed in the reaction of o-aminothiophenol with aroylpyruvic acids or 5-arylfuran-2,3-diones. 2-Carbomethoxy-2-phenacyl-1,3-benzothiazolines were isolated in the reaction of o-aminothiophenol with aroylpyruvic acid esters.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 755–757, June, 1977.     

Reactions of cyclic oxalyl compounds XXXIX. Reactions of 4-Ethoxycarbonyl-5-phenyl-2,3-dihydrofuran-2,3-dione with heterocumulenes andSchiff bases

Summary Furan-2,3-dione1 reacts with arylisocyanates to the corresponding pyrrol-2,3-diones2, whereas conversion with diisopropylcarbodiimide affords the oxazepin-6,7-dione derivative3 in 68% yield. 1,3-Oxazines5,6, and7 were obtained by thermolysis of1 in boiling xylene in presence of arylisocyanates, diphenylketen-p-tolylimine, andSchiff bases, most likely by trapping the -oxoketene intermediate4. Preparative flash vakuum pyrolysis (FVP) of1 and2b gave8 and9, respectively.

---

Reaktionen cyclischer Oxalylverbindungen, 39. Mitt. Umsetzungen von 4-Ethoxycarbonyl-5-phenylfuran-2,3-dion mit Heterocumulenen undSchiffschen Basen

Zusammenfassung Das Furan-2,3-dion1 reagiert mit Arylisocyanaten zu den entsprechenden Pyrrol-2,3-dionen, wohingegen mit Diisopropylcarbodiimid das 1,3-Oxazepinderivat3 in 68%iger Ausbeute gebildet wird. Die 1,3-Oxanzine5,6 und7 werden durch Thermolyse von1 in siedendem Xylol in Gegenwart von Arylisocyanaten, Diphenylketen-p-tolylimin undSchiffschen Basen erhalten, offensichtlich durch Abfangen des intermediär gebildeten -Oxoketens4. Präparative Flash-Vakuum-Pyrolyse (FVP) von1 bzw.2b ergaben8 bzw.9.

     

Condensed imidazo-1,2,4-azines. 15. Reaction of 1,2-diaminobenzimidazole with 5-phenyl-2,3-dihydrofuran-2,3-dione

The reaction of 1,2-diaminobenzimidazole with 5-phenyl-2,3-dihydrofuran-2,3-dione in acetic acid gave a mixture of 2-benzoylmethyl-1,2,4-triazino [2,3-a]-benzimidazol-4H-3-one and 3-benzoylmethyl-1,2,4-triazino[2,3-a]benzimidazol-1H-2-one, the intramolecular cyclization of which gave isomeric 2-phenylfuro-[5,4-e]- and 2-phenylfuro[4,5-e]-1,2,4-triazino[2,3-a]benzimidazoles. Only the corresponding furo[4,5-e]-1,2,4-triazino[2,3-a]benzimidazole was isolated when the reaction was carried out in sulfuric acid.See [1] for Communication 14.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 533–535, April, 1987.     

Reaction of 5-phenyl-2,3-dihydrofuran-2,3-dione with 6,7-dimethoxy-3,4-dihydroisoquinoline. Crystal structure of 1-benzoyl-8,9-dimethoxy-2,3,5,6-tetrahydropyrrolo[2,1-a]isoquinoline-2,3-dione

The reaction of 5-phenyl-2,3-dihydrofuran-2,3-dione with 6,7-dimethoxy-3,4-dihydroisoquinoline gave 1-benzoyl-2-hydroxy-8,9-dimethoxy-3,5,6,10b-tetrahydropyrrolo[2,1-a]isoquinolin-3-one and its oxidation product,viz., 1-benzoyl-8,9-dimethoxy-2,3,5,6-tetrahydropyrrolo[2,1-a]isoquinoline-2,3-dione. The last-mentioned compound was studied by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1845–1848, October, 1997.     

Five-membered 2,3-dioxoheterocycles. 28. Reaction of 5-aryl-2,3-dihydrofuran-2,3-diones with thioamides and thiosemicarbazides

The reaction of 5-aryl-2,3-dihydrofuran-2,3-diones (I) with thiocarbonyl compounds has been described only for thiourea. The products of this reaction are 3-aryl-5-phenacylidene-4-oxoimidazolidine-2-thiones [2]. It seemed of interest to study the conversion of the furandiones (I) with a wider range of thiocarbonyl compounds such as thioamides and thiosemicarbazides.For Communication 27 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1461–1464, November, 1992.     

Reaction of carbonyl compounds with dimethyl 3-ketoglutarate. Synthesis of bicyclic furan derivatives

Acid catalyzed reaction of cyelododecane-1,2-dione VI with dimethyl,3-ketoglutarate II led to the formation of methyl (E)-6,7,8,9,10,11,12,13-octahydro-3-(methoxycarbonyl)cyclododeca-[b]furan-2-aeetate IX, presumably formed through the dihydrodihydroxy furan VIII. This dihydrofuran intermediate VIII was shown to be characteristic of the reaction of 2-substituted carbonyl-compounds with 11 for both α-chlorocyclohexanone and α-chlorocyclopentanone furnished furans XVIa and XX, respectively, when treated with 11. The effect of dihydrodihydroxy-furan intermediates on the course of such reactions is discussed.     

Recyclization of 5-phenyl-2,3-dihydrofuran-2,3-dione to give 1,5-diphenylpyrazole-3-carboxylic acid

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 846–847, June, 1990.     

Reaction of substituted 5-aminopyrimidines with oxalyl chloride

Depending on the reaction conditions and the substituents, N-(2,4,6-substituted 5-pyrimidinyl)oxamyl chlorides and N,N-di(2,4,6-substituted 5-pyrimidinyl)oxamides are formed in the reaction of 5-aminopyrimidines with oxalyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 536–538, April, 1976.     

Reaction of azidobenzene with carbonyl compounds

Summary In the decomposition of azidobenzene in benzaldehyde and in cyclohexanone the corresponding Schiff bases are formed.Two possible mechanisms for this reaction are discussed.This article is published in accordance with a resolution of the Conference of Chief Editors of Journals of the Academy of Sciences of the USSR of July 12, 1962, as a dissertation paper by L. A. Neiman. For preliminary communication see [1].Translated from Izvestiya Akademii Nauk SSSR, Seria Khimicheskaya, No. 10, pp. 1831–1834, October, 1964     

Chemistry of sym-tetracyanoethane. 2. Condensation with carbonyl compounds

The reaction of tetracyanoethane with carbonyl compounds proceeds via the scheme of aldol addition with subsequent cyclization of the resulting adducts to give 5-amino-2,3-dihydrofuran derivatives, the structures of which were confirmed by the ¹³C NMR and mass spectra.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1605–1610, December, 1982.     

Reaction of triallylboron with carbonyl compounds

Conclusions Triallylboron reacts with carbonyl compounds according to the scheme of organometallic synthesis.Translated from Izvestiya Akademii Nauk SSSR, Seria Khimicheskaya, No. 10, pp. 1874–1876, October, 1964     

Reaction of trimethylsilylphenylphosphine with carbonyl compounds

Conclusion The addition of carbonyl compounds to trimethylsilylphenylphosphine gives adducts with a P-H bond.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1417–1419, June, 1982.     

Acetylenic ketones. Part III . Reaction of acetylenic ketones with nucleophilic sulfur compounds

Aroylphenylacetylenes reacted with ammonium dithiocarbamate and ammonium hydrogen sulfide in 60% dioxane-waler mixture at 15° to give mainly a mixture of the corresponding β-hydroxy-α-thiobenzoylstyrene derivatives (III) and (E,Z)-β,β'-di(α-aroylstyryl) sulfides (IV), whereas with sodium xanthate and sodium sulfide they gave only (III). However, when benzoyl-(Ia) or p-ehlorobenzoyl-(Id)phenylacetylenes was refluxed with ammonium dithiocarbamate in ethyl alcohol, it gave a mixture of (IIIa or d) and the (E,E)-β,β'-di(α-aroylstyryl) sulfide (VIa or d). β-Hydroxy-α-thiobenzoylstyrene derivatives (III), (E,Z)-(IV) and (E,E)-(VI)-β,β'-di(α-aroylstyryl) sulfides reacted with hydrazine hydrate and phenylhydrazine to give 3(5)-aryl-5(3)-phenyl-(IX)- and 5-aryl-1,3-diphenyl-(X)pyrazoles, respectively. The former compounds (III) reacted with guanidine and ethyl hydrazinecarboxylate to give the corresponding aminopyrimidines (XIII) and acetophenone-N-ethoxycarbonyl hydrazones (XI), respectively.     

Acetylinic ketones. Part II.. Reaction of acetylenic ketones with nucleophilic nitrogen compounds

Aroylphenylacetylenes (I) reacted with ethyl and phenyl hydrazinecarboxylates (II) to give ω-aroylacetophenone-N-ethoxycarbonyl-(Vla-f) and N-phenoxycarbonyl-(VIg-l) hydrazones, respectively. When these were healed with acetic anhydride they were converted to 5-aryl-1-ethoxycarbonyl-and 1-phenoxycarbonyl-3-phenylpyrazoles (VII), respectively, which on hydrolysis with rnethanolic potassium hydroxide gave the corresponding 5(3)aryl-3(5)phenylpyrazoles (VIII). Reaction of the above acetylenic ketones with guanidine hydrochloride in the presence of sodium carbonate gave the corresponding 2-amino-6-aryl-4-phenylpyrimidines (XII). Similarly, reaction of benzoylphenylacetylene with thiourea and with urea in the presence of sodium ethoxide gave rise to 2,4-diphenylpyrimidine-2-thione (XVIII) and 2,4-diphenyl-2(1H)pyrimidin-one (XV), respectively.