Chemistry of heterocyclic N-oxides and related compounds. 11. Reaction of pyridine N-oxide with metal ketyls and benzophenone dianions

The reaction of pyridine N-oxide with metal ketyls of benzophenone was studied. It is shown that diphenyl(2-pyridyl)carbinol N-oxide is formed with the lithium and sodium derivatives of benzophenone, whereas diphenyl(2-pyridyl)carbinol is formed with the potassium derivative of benzophenone. Diphenyl(2-pyridyl)carbinol N-oxide is obtained in lower yields in the reaction of pyridine N-oxide with benzophenone dianions. Pyridine and 4,4- and 2,2-dipyridyls are simultaneously formed in all of the reactions.See [1] for Communication 10.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 655–658, May, 1979.     

The Reaction of Indole Magnesium Bromide with Ketones I. The Reaction of Indole Magnesium Bromide with Cyclohexanone

Indole magnesium bromide, produced by reacting indole with n-butyl magnesium bromide in ether, was reacted with cyclohexanone at ice or room temperature to yield 1-(indol-I-yl)-cyclohexanol (I), which is unstable and may be decomposed easily into indole and cyclohexanone in acidic condition. Indole magnesium bromide reacted with cyclohexanone in refluxing benzene or in anisole at 80°C, to form two products, 1-(indol-3-yl)-cyclohexanol (II) and 1-(indol-3-yl)-cyclohexene (III). (II) could be converted to (III) by heating (II) in phosphoric acid. Reaction of III with maleic anhydride gave a Diels-Alder adduct (IV). Reaction of indole magnesium bromide with cyclohexanone in anisole at 130°C yielded (III) and a trimolecular condensation product of cyclohexanone (V).     

Chemistry of heterocyclic N-oxides and related compounds. 10. Reaction of pyridine N-oxide with 4-methyl- and 4-phenyl-substituted hantzsch esters

The corresponding dehydrogenation products were obtained in the reaction of diethyl 1,4-dihydro-2,4,6-collidine-3,5-dicarboxylates and diethyl 1,4-dihydro-4-phenyl-2, 6-lutidine-3,5-dicarboxylate with pyridine N-oxide. The reaction with dihydrocollidine is accompanied by simultaneous demethylation in the 4 position and methylation of the pyridine ring.See [1] for Communication 9.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 652–654, May, 1979.     

Polycyclic N-hetero compounds. XXII Reaction of pyridine N-oxides and Pyrazine di-N-oxides with formamide

Reactions of pyridine N-oxides, pyrazine di-N-oxides, and their benzologues with formamide are described. Carbamoylation mainly occurred at aromatic ring with loss of the N-oxide oxygen atom, however, 2,4,6-trimethylpyridine 1-oxide gave 2- and 4-pyrimidinyl derivatives.     

Reaction of triethylsilanethiol and related compounds with triethylaluminum

Conclusions The reaction of triethylaluminum with compounds of the (C₂H₅)₃SiXH series (X=S, Se, Te) proceeds with a stepwise replacement of the ethyl groups by (C₂H₅)₃SiX moieties. Depending on the ratio of the reactants, it is possible to obtain either the monosubstitution products (C₂H₅)₃SiXAl(C₂H₅)₂, or the disubstitution products [(C₂H₅)₃SiX]₂AlC₂H₅. The disproportionation reactions of these products were investigated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1995–1999, September, 1971.     

Synthesis of polycylic compounds related to steroids XIII. Reaction of carbocyclic ketones with 1-acetyl-1-cyclohexene

Summary The condensation has been carried out of 1-decalone (III), 8a-methyl-1-octalone (V), and 3a,4,7,7a-tetrahydro-3,7a-dimethyl-1-indanone (VI) with 1-acetyl-1-cyclohexene. The products were the polycyclic kiketones VII, IX, and XI, which under the conditions of the experiment did not undergo a further intramolecular crotonic condensation.     

Chemistry of heterocyclic N-oxides and related compounds VI. Reaction of pyridine,dipyridyl, and quinoline N-oxides with ammonia and ammonium salts

The amination of pyridine, quinoline, and 2,3- and 4,4-dipyridyl N-oxides with ammonia and ammonium salts in the presence of p-toluenesulfonyl chloride was studied. 2-Aminopyridine, N-(p-tosyl)-2-aminopyridine, and N-(p-tosyl)-2,2-dipyridyls were obtained in reactions with pyridine N-oxide. 2-Aminoquinoline was obtained in the amination of quinoline N-oxide. Dipyridyl N-oxides do not undergo amination.See [1] for communication V.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 229–232, February, 1976.     

π-electron approximation in pyridine and related compounds

A semi-empirical LCAO calculation including a- and -electrons has been performed for pyridine and related heterocyclics. The diagonal matrix elements of Hamiltonian are evaluated from atomic spectroscopic data through the use of a formula derived from the SCF equations. The non-diagonal matrix elements are estimated through the Wolfsberg-Helmholz formula. All overlap integrals have been included. The results disagree with what one can expect from a-electron treatment, mainly with respect to population analysis, but they seem strongly supported by the conclusions of ab initio calculations for other compounds and the trend of dipole moment in the sequence pyridine, quinoline, acridine.

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Resume Für Pyridin und verwandte Heterozyklen wurde eine LCAO-Rechnung mit und-Elektronen durchgeführt. Die Diagonalelemente des Hamiltonoperators wurden mittels atomspektroskopischer Daten berechnet unter Benutzung einer aus SCF Rechnungen abgeleiteten Formel, die Nicht-Diagonalelemente mit der Wolfsberg-Helmholz-Formel. Alle Überlappungsintegrale wurden berücksichtigt. Die Ergebnisse stimmen mit solchen aus-Elektronen-Behandlungen nicht überein (besonders die Dichteverteilung), scheinen aber stark durch ab initio-Rechnungen für andere Verbindungen und das Verhalten des Dipolmoments in der Folge Pyridin, Chinolin, Acridin gestützt zu werden.

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Zusammenfassung L'ensemble des systèmes électroniques et de la pyridine et de ses homoogues supérieurs a été étudiée par une méthode LCAO semi-empirique. Les élements de matrice diagonaux de l'hamiltonien sont évalués à partir de données de spectroscopie atomique, en faisant appel à une formule dérivée des équations du champ self-consistant. Les éléments de matrice non diagonaux sont calculés par la formule de Wolfsberg-Helmholz. Toutes les intégrales de recouvrement ont été introduites. Surtout en ce qui concerne l'analyse de population, les résultats sont en désaccord avec ce que l'on peut attendre d'un calcul limité au système d'électrons; par ailleurs, ils paraissent confirmés par les conclusions de calculs ab initio relatifs à d'autres composés et par l'évolution du moment dipolaire dans la série pyridine, quinoléine, acridine.

     

Electron transfer reactions. Reaction of tetracyclone,tetraphenylfuran and related substrates with potassium

The reaction of tetracyclone (1) with potassium in THF gave a mixture of benzoic acid (4), tetraphenylfuran (5) and cis-1,2-dibenzoylstilbene (6). The reaction of 1 with potassium in oxygen-saturated THF gave a mixture of 2-hydroxy-2,4,5-triphenyl-3(2H)furanone (3), 4, 5 and 6, whereas the reaction of 1 with potassium superoxide gave a moderate yield of 3,4,5,6-tetraphenyl-2-pyrartone (7), besides 3, 4, 5, and 6. The reaction of tetraphenylfuran (5) itself with potassium in THF gave a mixture of 6, 1,2,3,4-tetraphenylbutan-1-one (9), 2,3-diphenyl-1-indenone (10) and 2,3-epoxy-4-hydroxy-2,3,4-tnphenyltetralone-l (11), whereas practically no reaction occurred on treatment of 5 with potassium superoxide. Treatment of 10 with potassium in THF, however, gave a mixture of 4, dibenzo[a,c]-13-fluorenone (13), 2,3-diphenyl-2-hydroxyl-1-indanone (14) and 2,3-diphenylbenzofuran (15). A similar mixture of products consisting of 4, 13, 14 and 15 was obtained when the reaction of 10 with potassium was carried out in oxygen-saturated THF or when 10 was treated with potassium superoxide. Treatment of 2,3-diphenyl-2,3-epoxy-1-indanone (16) with potassium on the other hand, gave 10 in excellent yield. Cyclic voltammetric studies have been carried out to measure the reduction potentials of 1, 5, 10 and 16 in the generation of their radical anions. The radical anions of 1, 5, 10 and 16 were also generated pulse radiolytically in methanol and their spectra showed absorption maxima in the region 320–380 nm.     

Reaction of hydridohydroxodecacarbo-nyltriangulotriosmium with pyridine

Conclusions The following occurs when HOs₃(OH)(CO)₁₀ is reacted with pyridine or deuteropyridine: replacement of both bridge ligands in the osmium cluster, cleavage of the C-H or C-D bond, and migration of the H or D atom into the metal ring.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2793–2794, December, 1981.     

The Reaction of Indole with Propiolic Acid

The reaction of indole with propiolic acid ia 1 : 1 mole ratio gave an adduct (I) of 2 : 1 addition with decarboxylation. The reaction of indole with propiolic acid methyl ester gave a 2 : 1 adduct (II). Hydrolysis of adduct II yield the corresponding carboxylic acid (IV). Decarboxylation of IV also gave I. The mechanism of title reaction were fully studied.     

Indole derivatives. 129. Reaction of 5-vinylindole with brominating agents

The bromination of 5-vinylindole at two reaction centers, viz., the carbon-carbon multiple bond of the vinyl group and the pyrrole ring, was realized. In the case of the reaction with pyridinium bromide perbromide it was shown that the pyrrole ring is the most reactive with respect to electrophilic agents. It was established that the introduction of an electron-acceptor acetyl group into the pyrrole ring leads to a decrease in the reactivity of the pyrrole ring, and bromination takes place at the double bond.See [1] for communication 128.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 325–328, March, 1987.     

Reaction of N-cyanoformimidates with some heterocyclic compounds. A new synthesis of 5-azaadenine and related compounds

3-Amino-1,2,4-triazoles and 2-aminobenzimidazole were reacted with N-cyanoimidates to give 5-amino-1,2,4-triazolo[2,3-a]-1,3,5-triazines (5-azaadenines) and 4-aminobenzimidazo[1,2-a]-1,3,5-triazines, respectively. The structures of the compounds obtained were confirmed through the comparison with some of the possible isomers prepared by independant methods.     

Reaction of acyl isocyanates with pyridine

Conclusions The trichloroacetyl and trifluoroacetyl isocyanates react with pyridine to give N-(1-pyridinocarbonyl)trichloro(trifluoro)acetyl amidates, while ditrichloro(trifluoro)acetylcarbodiimides are formed in the presence of 3-phenyl-1-ethyl-3-phospholene 1-oxide, which add to the C = N bond of pyridine on the type of 1,4-cycloaddition.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 927–928, April, 1977.     

Reaction of biguanides and related compounds. XVI. Synthesis of s-triazinones and fused s-triazinones by carbonylation of biguanides and related compounds with diethyl azodicarboxylate

Biguanides and the related compounds, in which a moiety of biguanide is involved in the structure as a part of the ring, were allowed to react with diethyl azodicarboxylate to afford triazinones and fused heterocycles including a triazinone ring, respectively. The mechanism of the reaction was elucidated to proceed through the initial formation of the amide intermediate, followed by cyclization to triazinone ring systems with elimination of nitrogen.     

Reaction of nitro compounds with iminium salts 1. Nitrovinylation of indoles

Conclusions Iminium salts prepared from indoles, thionyl chloride, and dimethylformamide readily form the corresponding nitrovinyl derivatives by nucleophilic attack on the anion of an aliphatic nitro compound.Translated from Izvestiya Akademiya Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2310–2313, October, 1977.     

Reactivity of 1H-pyrrolo[2,3-b]pyridine. I. Synthesis of 3-acetyl-7- azaindole and related compounds

The behaviour of 1H-pyrrolo[2,3-b)pyridine (7-azaindole) towards several acylating reagents are reported. The preparation of 3-acetyl-7-azaindole, 3-chloroacetyl-7-azaindole and 3-(2-hydroxiethyl)-7-azaindole are described.