Substituted and fused spiro[benzo-2-azepine-3,1′-cyclohexanes]

5-Methyl-4,5-dihydro-3H-spiro[benzo-2-azepine-3,1-cyclohexane] N-oxide was rear- ranged into 5-methyl-1-oxo-1,2,4,5-tetrahydro-3H-spiro[benzo-2-azepine-3,1-cyclohexane]. The latter was used for the synthesis of spiro{triazolo[3,4-a]- and-tetrazolo[5,1-a]benzo-2- azepinecyclohexanes}.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1647–1651, August, 2004.     

Conversion of 3-benzoyl-1-methyl-4-phenyl-γ-piperidol by arylamines and arylhydrazines. Synthesis of 3-arylamino-1-oxo-1-phenylpropanes and 1,3-diarylpyrazoles and their fragmentation under electron impact

It has been established that on heating, 3-benzoyl-4-hydroxy-1-methyl-4-phenylpiperidine is ring-opened in the presence of arylamines by a type of retroaldol reaction, with subsequent transamination of the intermediate Mannich base and the formation of 3-arylamino-1-oxo-1-phenylpropanes. When using arylhydrazines this γ-piperidol is recyclized with the formation of 1,3-diarylpyrazoles and their 4,5-dihydro derivatives. The mass spectral behavior of a series of 3-arylamino-substituted 1-phenylpropanones has been studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1486–1495, October, 2007.     

Reactions of 4,5-Dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane] N-Oxide with Some Nucleophilic Reagents

4,5-Dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane] N-oxide reacted with cyanide ion and isopropyl magnesium bromide to give the corresponding 1-cyano- and 1-isopropyl-4,5-dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane], but reaction with phenyl magnesium bromide, benzyl magnesium chloride, and nitromethane gave cyclic hydroxylamines: 1-substituted N-hydroxy-1,2,4,5-tetrahydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexanes] which were oxidized to the corresponding nitrones.     

9-α-Nitro(hydroxy,amino)benzylidene- and 9-Hydroxy(amino)methylene-4-azafluorenes

Nitration of 9-benzylidene-4-azafluorene with acetyl nitrate leads to the formation of its 9--nitrobenzylidene derivative; reduction of the latter gives the corresponding enamine and oxime. Reaction of 4-azafluorene with ethyl benzoate and ethyl formate gives the hydroxybenzylidene and hydroxymethylene derivatives, which upon condensation with amines generate the corresponding enamines. Reduction of 9-formylazafluorene oxime gives 9-aminomethyleneazafluorene. All of the newly synthesized compounds were isolated in the form of mixtures of their Z- and E-isomers, and their structures were established using PMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 212–217, February, 1991.     

Condensation of 1-Amino-4-azafluorene with α-Diketones and α,β-Unsaturated Ketones

Condensation of 1-amino-4-azafluorene with -diketones and with unsaturated ketones in basic medium gives novel substituted 1,4-diazafluoranthenes and also dihydro-4-azafluoreno[9,9a,1-b,c]cyclohexano[2',3'-e]- and indano[1',2'-e]azepines.     

Synthesis and molecular structures of dibenzo(perhydrotriazino)aza-14-crown-4 ethers

By triple condensation of thiourea or guanidine with 1,ω-bis(2-formylphenoxy)-3-oxapentane and ammonium acetate first representatives of the new class of ethers bis(benzo)aza-14-crown-4 were obtained in 28–73% yield that included as a subunit a symm-perhydrotriazine ring. This reaction also proceeds readily with N-monomethyl- and N-monopropenyl-substituted thioureas affording the corresponding derivatives of triazinoazacrown ether. At the same time urea in the similar condensation does not form the expected perhydrotriazinoazacrown ether. The molecular structure of one perhydroazacrown ether as a complex with a chloroform molecule was established by XRD analysis.     

Synthesis and molecular structure of bis(areno)piperidinoaza-14(17)-crowns-4(5)

The condensation of dialkyl ketones with α,ω-bis(2-formylphenoxy)- or α,ω-bis(1-formylnaphthalen-2-yloxy)-3-oxapentane and-3,6-dioxaoctane in the presence of ammonium acetate according to Petrenko-Kritchenko gave 14–41% of new bis(areno) aza crowns, bis(areno)piperidinoaza-14-crown-4 and bis(benzo)-piperidinoaza-17-crown-5, having functional substituents in the piperidine fragment. The yield of the aza crown ether appreciably decreases upon extension of the polyether chain in the aldehyde component. The molecular structure of two of the obtained macrocyclic compounds and the relative configuration of asymmetric carbon atoms in the piperidine ring were determined by X-ray analysis, and the size of their internal cavities was estimated.