L. M. Yudovich

Saturated nitrogen-containing heterocycles. 16. Catalytic synthesis of N-arylperhydroacridines

Catalytic hydroamination of methylene-2,2′-dicyclohexanone in the presence of substituted anilines or nitrobenzenes involves the formation of N-arylperhydroacridines. The stereoisomeric composition and yields of the latter are determined by the nature and position of the substituent in the aromatic ring of the aminating agent. The structure of isomeric N-arylperhydroacridines was established from data of 13C NMR spectroscopy and x-ray diffraction analysis.

Peculiarities of the reaction of cycloalka[b]thiopyrylium salts and their hetero analogs with bases

The reaction of aryl-substituted cycloalka[b]thiopyrylium salts, as well as their O and N analogs, with bases (pyridine, NaOH, NaHCO3) was studied. The formation of 6,6′,7,7′-tetrahydro-2,2′,4,4′-tetraarylbis(5H-1-benzothiopyrans) through the intermediate anhydro bases was established for the cyclohexa[b]thiopyrylium salts, while the formation of 2,4-diphenyl-7-(2,4-diphenyl-8-cyclopenta[b]thiopyranyl)-Δ7,8-cyclopenta[b]thiopyran was established for 2,4-diphenylcydopenta[b]thiopyrylium perchlorate. The peculiarities of the behavior of the O and N analogs of the cycloalka[b]thiopyrylium salts in reactions with bases were ascertained. The investigation was carried out using electronic, IR, and PMR spectroscopy.

Saturated nitrogen-containing heterocycles. 15. Catalytic synthesis and isomerization of 9-substituted10-methylperhydroacridines

In the catalytic hydromethylamination of 8-substituted 2-hydroxytricyclo[7.3.1.02,7]tridecane-13-ones they are converted into 9-substituted 10-methyl-Δ9,9a-dodecahydroacridines and 10-methylperhydroacridines with trans,anti,cis- and cis,syn,cis-conformation. The ability of the latter to isomerize into the trans,cis,tans-form has been established.

Characteristics of heterocyclization of triketones of the 2-(3-oxopropyl)cyclohexane-1,3-dione series with hydroxylamine hydrochloride

A rearrangement that leads to the formation of mixtures of 2,4- and 2,3-diaryl-substituted 5-oxotetrahydroquinoline oximes was observed in the heterocyclization of oxo 1,5-diketones of the 2-(3-oxopropyl)cyclohexane-1,3-dione series, as well as in the recyclization of 5-oxotetrahydro-4H-chromenes, in the presence of excess hydroxylamine hydrochloride. It was established that the rearrangement proceeds only when electron-donor groups are present in the starting compounds.

Saturated nitrogen-containing heterocycles. 14. Synthesis and three-dimensional structures of n-r-dicyclopenta[b,e]piperidines

The catalytic hydroamination of threo-methylenedicyclopentanone using ammonia, methylamine, and monoethanolamine as the aminating agents proceeds stereospecifically with the formation of N-R-cis-syn-cis-dicyclopenta[b,e]piperidines (R=H, CH3, CH2CH2OH). The structures of the latter were proved by 13C NMR spectroscopy. The molecular structure of N-(Β-hydroxyethyl)cis-syn-cis-dicyclopenta[b,e]piperidinium acid tartrate was investigated by x-ray diffraction analysis, and the absolute configuration of its chiral centers was determined.

Stereochemical peculiarities of the catalytic reduction of sym-octahydrothioxanthylium salts

The three-dimensional structures of the products of catalytic hydrogenation of sym-octahydrothioxanthylium salts in the presence of palladium on carbon were studied by 13C NMR spectroscopy. It was shown that the reaction proceeds stereoselectively with the formation of cis-syn-cis isomers. The stereochemistry of the reduction products is in agreement with the previously proposed reaction mechanism.

Saturated nitrogen-containing heterocycles. 13. Perhydroacridines. Synthesis and stereochemistry

The configurations of the perhydroacridines formed in the catalytic hydroamination of threo-methylenedicyclohexanone and the product of its cyclization — 2-hydroxy-2,3-tetramethylenebicyclo[3.3.1]nonan-9-one — were established by means of the 13C NMR spectra and alternative synthesis. It is shown that isomers with cis-anti-cis and cis-syn-cis configurations are formed as a result of the reactions. The results of x-ray diffraction analysis are presented for cis-syn-cis-N-(2-hydroxyethy1)perhydroacridine.

Heterogyclization of triketones of the 2-(3-oxopropyl)-cyclohexane-1,3-dione series

Triketones of the 2-(3-oxopropyl) cyclohexane-1,3-dione series have been shown for the first time to react with boron trifluoride etherate to give the novel 5-oxo-5,6,7,8-tetrahydrochromylium fluoroborates, which in turn react with ammonia to give 5-oxo-5,6,7,8-tetrahydroquinolines. These were also obtained directly from ammonium acetate and 2-(3-oxopropyl)cyclohexane-1,3-diones.