N. N. Sorokin

Saturated nitrogen heterocycles. 11. Catalytic synthesis of 2-pyrrolidylalkanols

Furylakylamines have been catalytically converted into novel isomers of 2-pyrrrol-idylalkanols bearing a secondary alcohol group in the aliphatic chain, or a tert-butyl group attached to the heterocycle.

Stereochemistry of the ionic hydrogenation of pentasubstituted 4H-thiopyrans and structures of the thiacyclohexanes obtained from them

The structure of 3,5-dimethyl-2,4,6-triphenylthiacyclohexane, obtained as a result of the ionic hydrogenation of the corresponding 4H-thiopyran with the CF3COOH/HSi(C2H5)3 couple, was established. It is shown that the stereochemistry of the ionic hydrogenation of 2,3,4,5,6-pentasubstituted 4H-thiopyrans, both those that disproportionate and those that do not disproportionate under the influence of trifluoroacetic acid, is the same.

Saturated nitrogen heterocycles. 13. Mechanism of formation of hydroxyalkylpyrrolidines by catalytic hydrogenation of furan amines

The formation of hydroxyalkylpyrrolidines from furan amines has been modeled using deuterium exchange. The stages of the reaction were established by comparing the 13C NMR spectra of the nondeuterated and deuterated pyrrolidinylalkanols, and the similarly formed tetrahydrofuran amines.

Saturated nitrogen-containing heterocycles. 12. Stereochemical properties of hydroxyalkylpyrrolidines using 13C NMR spectroscopy

The 13C NMR spectra of fifteen compounds in a series of alkyl- and arylsubstituted cis-isomers of hydroxyalkylpyrrolidines have been recorded, and they have been fully interpreted on the basis of configurational and conformational assignments.

Sulfinyl and sulfonyl derivatives of aryl substituted cis-1-thiadecalins

Individual 2α-aryl- and 2α,4α-diaryl-cis-thiadecalin-1Β-oxides and 1,1-dioxides have been synthesized. The effect of sulfinyl and sulfonyl groups has been observed on the chemical shifts of carbon atoms in these conformationally homogeneous, stereochemically similar systems.

STEREOCHEMICAL SPECIFICITY OF THE PALLADIUM-CATALYZED HYDROGENATION OF CYCLOHEXA(b)THIOPYRANS AND THEIR DERIVATIVES

Conformationally and configurationally homogeneous 2α-R1-4α-R2-cis-1-thiadecalins with an equatorial orientation of the substituents attached to the C(2) and C(4) atoms were isolated as the final reduction products in the catalytic hydrogenation on palladium of 2-R1-4-R2-4H(6H)-cyclohexa[b]thiopyrans, cis-3-R1-5-R2-2-thiabicyclo[4.4.0]-δ1,6-decenes, and 2-R1-4-R2-cyclohexa[b]thiopyrylium tetrafluoroborates and trifluoroacetates. cis-3-R1-5-R2-2-Thiabicyclo[4.4.0]-δ1,6-decenes were obtained as intermediates in the incomplete reduction of 2-phenyl- and 2,4-diphenyl-4H-cyclohexa[b]thiopyrans and 2-(4-methoxyphenyl)-4-R2-cyclohexa[b]thiopyrylium salts; 2-R1-4-R2-6H-cyclohexa[b]thiopyrans undergo complete reduction of the double bonds of the heteroring. The hydrogenation products were oxidized to sulfoxides and sulfones.

Investigation of 2,6-diarylthiacyclohexanes and their complexes with Pt(II) and Pd(II) by 1H and 13C NMR spectroscopy

A conclusion regarding a diequatorial orientation of the aryl substituents was drawn on the basis of a study of the 1H and 13C NMR spectra of 2,6-diarylthiacyclohexanes. A trans structure of the complexes with an equatorial S→metal bond was established by a comparative analysis of the 13C NMR spectra of 2,6-diarylthiacyclohexanes and their complexes with Pt(II) and Pd(II).

An unusual product of the reaction of 1-phenyl-3-(3,4-dimethoxyphenyl)-3-(2-oxocyclohexyl)-1-propanone with hydrogen sulfide and acids: 2α-phenyl-2,4-ortho-(14,15-dimethoxybenzo)-cis-1-thiadecalin

The reaction of 1-phenyl-3-(3,4-dimethoxyphenyl)-3-(2-oxocyclohexyl)-1-propanone with hydrogen sulfide and acids gives an intramolecular rearrangement product, 2α-phenyl-2,4-ortho-(14,15-dimethoxybenzo)-cis-1-thiadecalin in addition to the usual products of disproportionation of intermediate 2-phenyl-4-(3,4-dimethoxyphenyl)-5,6-tetramethylene-4H-thiopyran, namely, 5,6-tetramethylenethiopyrilium salts and 2α-phenyl-4α-(3,4-dimethoxyphenyl)-cis-1-thiadecalin. The configurational and conformational assignments for the sulfides, their sulfoxides, and sulfones were made by 13C NMR spectroscopy.

Conversion of trans, trans-1-methoxy-3,5-diaryl-2-oxabicyclo[4.4.0]dec-3-enes into hemidithioacetals and 4H-thiopyrans. Structure of trans, trans-1-mercapto-3-phenyl-5-(4-methoxyphenyl)-2-thiabicyclo[4.4.0] dec-3-ene

The conversion of trans,trans-1-methoxy-3,5-diaryl-2-oxabicyclo[4.4.0]dec-3-enes into trans,trans-1-mercapto-3,5-diaryl-thiabicyclo[4.4,0]dec-3-enes or 2,4-diaryl-5,6-tetramethylene-4H-thiopyrans, which takes place when hydrogen Sulfide is reacted with the acetals in acetic acid with the use of gaseous hydrogen chloride as a catalyst, has been described. A mechanism for the reaction has been proposed. The structure and confirmations of the molecules have been determined by x-ray diffraction analysis and 13C NMR.

New data on the reaction of 1,3-diaryl-3-(2-oxocyclohexyl)-1-propanones with hydrogen sulfide and methanol

The stereochemical aspects of the reaction of 1-aryl- and 1,3-diaryl-substituted 3-(2-oxo-cyclohexyl)-1-propanones with hydrogen sulfide and methanol have been discussed. A mechanism is proposed for the formation of trans, trans-1-methoxy-3,5-diaryl-2-thia(oxa)bicyclo-[4.4.0]dec-3-enes.