Five-Membered 2,3-Dioxo Heterocycles: XLV. Thermolysis of 5-Aryl-4-phenyl-2,3-dihydrofuran-2,3-diones in the Absence of Other Partners and in the Presence of Carbonyl Compounds

Aroyl(phenyl)ketenes generated by thermolysis of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones undergo [4+2]-cyclodimerization to 3-aroyl-6-aryl-3,5-diphenyl-3,4-dihydro-2H-pyran-2,4-diones. Heating of the latter leads to rearrangement with formation of 4-aroyloxy-6-aryl-3,5-diphenyl-2H-pyran-2-ones. Thermolysis of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones in the presence of carbonyl compounds yields 6-aryl-5-phenyl-4H-1,3-dioxin-4-ones.     

Five-Membered 2,3-Dioxo Heterocycles: XLVII. Reaction of 5-Aryl-4-phenyl-2,3-dihydrofuran-2,3-diones with Compounds Containing C = N and C≡N Bonds

Thermal decarbonylation of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones gives rise to intermediate aroyl(phenyl)ketenes which react with nonactivated Schiff bases, N,N'-dicyclohexylcarbodiimide, and p-di-methylaminobenzonitrile according to the [4 + 2]-cycloaddition pattern with formation of 6-aryl-5-phenyl-4H-1,3-oxazin-4-ones. Reactions of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones with activated Schiff bases at a temperature below the thermolysis temperature lead to 4-aroyl-4-phenyltetrahydropyrrole-2,3-diones.     

7-Aryl-6,7-dihydro-8h-indeno[1′,2′∶2,3]pyrano-[5,6-c]benzo[c]pyran-6,8-diones and their thio analogs

The ability of 3-[-(1,3-dioxo-2-indanyl)benzyl]-4-hydroxy-substituted 2H-benzo [b]pyran-2-ones and benzo[b]thiopyran-2-ones to undergo dehydration under the influence of dehydrating agents to give 7-aryl-6,7-dihydro-8H-indeno[1,2-2,3]pyrano[5,6-c]benzo[c]pyran-6,8-diones and their thio analogs was demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1475–1476, November, 1985.     

Spirocyclic betaines or 2-amino-Δ2-1,3,4-thiadiazoline-5-acetic acid and their rearrangement in acetic anhydride

Reaction of N-(1-pyrrolidinyl)-, N-(1-piperidinyl)-, N-(4-morpholinyl)-, and N-(1-hexahydroazepinyl)-thioureas with propiolic acid gives hetero-N-spiro-4-(2-amino-²-1,3,4-thiadizolin-4-io-5-acetates), which rearrange in acetic anhydride to 2-(N-heteryl)imino-2,3-dihydro-4H-1,3-thiazin-4-ones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 263–265, February, 1993.     

Kinetics of opening of the ring of 5-aryl-2,3-dihydrofuran-2,3-diones under the influence of methanol

The kinetics of the opening of the ring of 5-aryl-2,3-dihydrofuran-2,3-diones under the influence of methanol, which leads to the formation of methyl esters of aroylpyruvic acids, were studied by PMR spectroscopy. A mechanism is proposed for the reaction.Communication 26 from the series Chemistry of oxalyl derivatives of methyl ketones. See [1] for Communication 25.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 744–746, June, 1982.     

Reactions of Acylpyruvic Acids and 2,3-Dihydrofuran-2,3-diones with 2,3-Diaminopyridine

Acylpyruvic acids readily react with 2,3-diaminopyridine to form (Z)-3-acylmethylene-1H-3,4-di- hydropyrido[2,3-b]pyrazin-2-ones. 5-Aryl-2,3-dihydrofuran-2,3-diones which can be regarded as lactones derived from -enolized aroylpyruvic acids react with 2,3-diaminopyridine under mild conditions, yielding regioisomeric (Z)-2-aroylmethylene-4H-1,2-dihydropyrido[2,3-b]pyrazin-3-ones. The structure of the products and reaction chemoselectivity are discussed.     

A study of 1,2,3,4-tetrahydro-4-azafluorene-3,9-diones

Intramolecular cyclization of the diamides and N,N-dimethylamides of -[indan-1,3-dion-2-yl]benzylmalonic acids (I) has given 1-aryl-2-carbamoyl-1,2,3,4-tetrahydro-4-azafluorene-3, 9-diones and 1-aryl-4-methyl-2-methylcarbamoyl-1,2,3,4-tetrahydro-4-azafluorene-3,9-diones (II). The structure of compounds II was shown by chemical methods: bromination, xanthylation, and hydrolysis in alkaline and acid media, and also by a study of IR and UV spectra.     

Chemistry of oxalyl derivatives of methyl ketones. 28. Reaction of carbonyl compounds of adamantane with 5-phenyl-2,3--dihydrofuran-2,3-dione

The reaction of substituted methyl 1-adamantyl ketones with an equimolar amount of 5-phenyl-2,3-dihydrofuran-2,3-dione under the conditions of the thermal decarbonylation of the latter leads to the corresponding 2-methyl-2-adamantyl-6-pheny1-1,3-dioxen-4-ones, 6-phenyl-3-benzoyl-2,4-dione, and the starting ketones. The steric and electronic factors that affect the yields of the dioxen-4-ones were examined. -Hydroxymethyl 1-adamantyl ketones open up the furan ring to give 1-adamantoylmethyl benzoylpyruvate. Data from the IR, PMR, and UV spectra are presented.See [1] for communication 27.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1312–1315, October, 1982.     

Synthesis of 2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine and its 1-α-L-arabinopyranoside

A new type of isatin analog-2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine — was obtained by oxidation of 4-methyl-6-chloro-1H-pyrrolo(2,3-b]pyridine. Condensation of L-arabinose with 4-methyl-6-chloro-2,3-dihydropyrrolo[2,3-b]pyridine and subsequent acetylation and dehydrogenation gave 1-(2,3,4-tri-O-acetyl--L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine, which served as the starting compound for the synthesis of 1--L-arabinopyranosyl-4-methyl-6-chloropyrrolo[2,3-b]pyridine. Oxidation of 1-(2,3,4-tri-O-acetyl-L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine gave 1-(2,3.4-tri-O-acetyl--L-arabinopyranosyl)-2,3-dioxo-2,3-dihydro-4-methyl-6-chloropyrrolo [2,3-b]pyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1083–1086, August, 1977.     

Five-membered 2,3-dioxo heterocycles: LII. Reactions of 5-aryl-4-(quinoxalin-2-yl)-2,3-dihydrofuran-2,3-diones with Schiff bases and dicyclohexylcarbodiimide. Crystalline and molecular structure of substituted 2-(4-oxo-3,4-dihydro-2<Emphasis Type="Italic">H</Emphasis>1,3-oxazin-5-yl)quinoxalines

Aroyl(quinoxalinyl)ketenes generated by thermolysis of 5-aryl-4-(quinoxalin-2-yl)-2,3-dihydrofuran-2,3-diones react with N-benzylideneanilines and N,N’-dicyclohexylcarbodiimide according to the [4+2]-cycloaddition pattern where the aroylketene acts as diene, and C=N component, as dienophile, to give 3-aryl-2-(2,3,6-triaryl- and 6-aryl-3-cyclohexyl-2-cyclohexylimino-4-oxo-3,4-dihydro-2H-1,3-oxazin-5-yl)quinoxalines. The structure of two cycloaddition products was proved by X-ray analysis.     

Atomic spectroscopy for detection in thermal analysis

An atomic absorption spectrophotometer is coupled to a conventional thermoanalytical quartz furnace as used for TG and DTG to detect the thermally evolved products. In this combined system, the dry aerosol (smoke) obtained by cooling the vapour evolved is transported from the furnace to the flame for metal-specific atomic absorption detection. The particular design of the furnace outlet promotes the formation of stable aerosols. Optimum experimental conditions were determined, using zinc chloride solution, by varying the specimen mass, the heating rate and the flow rate of the furnace gas at a linear temperature program. The absorbancevs. temperature curves obtained with this method for various zinc compounds are compared with the corresponding DTG curves. The applicability of the technique for studying heterogeneous reactions with carbon tetrachloride and hexane vapours is presented. The utilization of an atomic absorption spectrophotometer equipped with a quartz cuvette for detecting the thermal evolution of mercury vapours is described, as well as detection potentials by molecular absorption (for NO and NH₃) and light scattering (for smoke evolved from organic matter). The results obtained with the suggested methods may, in some respects, valuably complement the results achieved with DTG and with flame ionization detection.

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Zusammenfassung Ein Atomabsorptionsspektrometer wurde mit einem konventionellen thermoanalytischen Quarzofen gekoppelt um thermische Abspaltprodukte nachzuweisen. In diesem kombinierten System wird das durch Kühlung des entwickelten Dampfes erhaltene Aerosol (Rauch) vom Ofen in die Flamme für den metallspezifischen Atomabsorptionsnachweis übergeleitet. Die spezielle Ausbildung der Austrittsöffnung gewährleistet die Bildung eines stabilen Aerosols. Die optimalen Versuchsbedingungen wurden durch Zinkchloridlösungen bei Anderung der Probenmasse, der Aufheizgeschwindigkeit und der Strömungsgeschwindigkeit des Ofengases im linearen Temperaturprogramm ermittelt. Die mit dieser Methode für verschiedene Zinkverbindungen erhaltenen Absorptions—Temperatur-Kurven wurden mit den entsprechenden DTG-Kurven verglichen. Die Anwendbarkeit dieser Technik bei dem Studium heterogener Reaktionen mit Kohlenstofftetrachlorid und Hexandämpfen wird gezeigt. Der Einsatz eines mit einer Quarzküvette zum Nachweis der thermischen Entwicklung von Quecksilberdampf versehenen Atomabsorptionsspektrometers wird beschrieben, sowie die Nachweisgrenze durch molekulare Absorption (für NO und NH₃) und Lichtstreuung (für aus organischem Material entwickelten Rauch). Die bei den beschriebenen Methoden erhaltenen Ergebnisse können, in mancher Hinsicht, die durch DTG und Flammenionisationsnachweis erhaltenen Ergebnisse wertvoll ergänzen.

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- , , . (), , . . , . — , , -. . - , , , ( NO NH₃) ( , ). , , , - .

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Presented in part at the 24th Hungarian Conference on Analytical Sptecroscopy, Miskolc, June 15–18, 1981. Abstracts pp. 159–162.

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The authors wish to express their thanks to S. Gál for his assistance in the present application of the temperature programmer developed by him and his group, and for the valuable discussions on the subject. Thanks are also due to K. Tomor and J. Kmives who participated in the comparative thermoanalytical measurements and their analysis.     

Reaction of 2-methylene-2,3-dihydroindoles with acrylamide

1,3-Dihydrospiro[2H-indolo-2,2-piperidine] derivatives were obtained by the reaction of 2-methylene-2,3-dihydro-1H-indole derivatives with acrylamide in proton-containing solvents. 2-(3-Carbamoylpropyl)-3H-indolium perchlorates were formed when the 1,3-dihydrospiro[2H-indolo-2,2-piperidine] derivatives were treated with perchloric acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 902–904, July, 1988.     

Five-membered 2,3-dioxoheterocycles

The reaction of 5-aryl-2,3-dihydrofuran-2,3-diones with benzamide oxime, diaminoglyoxime, and hydroxyurea gave 3-phenyl-5-aroylacetyl-1,2,4-oxadiazoles, 5,6-dihydroxyimino-3-phenacylidenepiperazin-2-ones, and 3-hydroxy-5-phenacylideneimidazolidine-2,4-diones, respectively. 6-Phenacylidene-5-oxo-4,5,6,7-tetrahydrofurazano [3,4-b]pyrazines are formed in the reaction of 5-aryl-2,3-dihydrofuran-2,3-diones with diaminofurazan.For Communication 7, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1457–1460, November, 1988.     

Five-membered 2,3-dioxo heterocycles. 21. Reaction of 1,5-diaryl-4-ethoxycarbonyl-tetrahydropyrrole-2,3-diones with 2-aminopyridine

The reaction of 2-aminopyridine with 1,5-diaryl-4-ethoxycarbonyltetrahydropyrrole-2,3-diones gave 11 complexes, which are converted to N-(2-pyridyl)-1,5-diaryl-3-hydroxy-2-oxo-2,5-dihydropyrrole-4-carboxamides when they are heated above their melting points without a solvent. The character of the hydrogen bonds in the complexes obtained is discussed.See [1] for Communication 20.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 32–36, January, 1992.     

Synthesis and study of spiro [(indane-1,3-dione)-2,3′-azir-1′-ines] and their cleavage products

Spiro[(indane-1,3-dione)-2,3 (2-substituted 1-azirines)] were obtained by intramolecular cyclization of 2-acylindane-1,3-dione oximes. Their structures and properties were investigated, and it was established that the C-N and C-C single bonds are cleaved during opening of the three-membered ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 65–69, January, 1976.     

Five-membered 2,3-dioxoheterocycles. 10. Reaction of 5-aryl-2,3-dihydrofuran-2,3-diones with N-substituted ureas and their thio and seleno analogs

3-Aryl-5-phenacylideneimidazolidine-2,4-diones, 3-aryl-5-phenacylidene-4-oxoimidazolidine-2-thiones, and 5-phenacylidene-4-oxoimidazolidine-2-selenones were obtained from 5-aryl-2,3-dihydrofuran-2,3-diones and arylureas, arylthioureas, and selenoureas respectively in glacial acetic acid. In the reaction of 5-aryl-2,3-dihydrofuran-2,3-diones with cyanoguanidine in 98% acetic acid 5-phenacylideneimidazolidine-2,4-diones were isolated, and in anhydrous acetic acid 2-imino-3-amidino-5-phenacylidene-4-oxazolidones were isolated. When heated in a water-dioxane solution of hydrochloric acid, the latter are converted into 5-phenacylideneimidazolidine-2, 4-diones.For Communication 9, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1411–1413, October, 1988.     

Studies in the area of 2,3′-biquinolyl. 1. Arylation and hetarylation of 2,3′-biquinolyl dianion

The 2,3-biquinolyl dianion, when reacting with aryl- and hetaryl halides, forms arylation products at the 4 position, and treatment of these products with alkyl halides or water yields 1-alkyl-4-aryl-1,4-dihydro-2,3-biquinolyls or 4-aryl-1,4-dihydro-2,3-biquinolyls, respectively. Oxidation of the latter yields 4-aryl-2,3-biquinolyls. The cation dependence of the arylation reaction is demonstrated.Stavropol' State University, Stavropol' 355009. Russian Chemical Engineering University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1094–1099, August, 1997.     

New nitrogen-containingα-oxides

N-(2,3-Epoxypropyl)--pyrrolidone and N-(2,3-epoxypropyl)--suecinimide have been obtained for the first time. It has been shown that N-(2,3-epoxypropyl)--pyrrolidone readily reacts with ammonia and diethylamine to form the corresponding amino alcohols.     

Pyrido[2,3-d]pyrimidines 3. Synthesis and properties of 7-chloro- and 6-nitro-7-chloropyrido[2,3-d]pyrimidine-2,4,5-triones

7-Chloropyridopyrimidine was obtained by diazotization of 1,3-dimethyl-7-amino-8H-pyrido[2,3-d]pyrimidine-2,4,5-trione in HCl, and its nitration and reactions with nucleophilic reagents were studied. An imidazo[1,2:1, 6]pyrido[2,3-d]pyrimidine derivative was synthesized.See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 497–501, April, 1991.