S. K. Klimenko

5,6-Trimethylenethiapyrylium and 5,6,7,8-tetrahydrothiochromylium salts

Abstract5,6-Trimethylenethiapyrylium salts have been obtained for the first time. 5,6-Trimethyleneγ-thiopyrans (or 5,6,7,8-tetrahydro-γ-thiochromenes), which belong to a previously unknown series of two-ring sulfides, are formed by reaction of the 5,6-trimethylenethiapyrylium salts (or 5,6,7,8-tetrahydrothiochromylium salts) with Grignard reagents and lithium aluminum hydride.

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.

Redox properties of 2,4-diaryl-substituted cyclohexa[b]thiopyrylium salts

Ascheme for formation of 6,6′,7,7′-tetrahydro-2,2′,4,4′-tetraaryl-8,8′-bis(5H-1-benzothiopyranyls) through intermediate radicals and cation radicals was substantiated as a result of a study of the electrochemical behavior of 2,4-diarylcylohexa[b]thiopyrylium tetrafluoroborates and 2,4-diaryl-4H-cyclohexa[b]thiopyrans and comparison with the results of their oxidative dimerization. The formation of 2,4-diarylcyclohexa[b]thiopyranyl radicals is also confirmed by EPR spectroscopy.

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.

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.

Electronic spectra of 5,6-polymethylenethiapyrylium salts and certain oxygen analogs

Electronic absorption and emission spectra of substituted 5,6-tri- and 5,6-tetramethylenethiapyrylium salts are examined to determine the influence of the degree and character of substitution of the heterocycle, the size of the condensed alicycle, the nature of the heteroatom and the counterion, and the polarity of the solvent.

Configuration and conformation of 3,5-diphenyl-2-thiabicyclo[4.4.0]decane

The PMR spectra of 3,5-diphenyl-2-thiabicyclo[4.4.0]decane and its 4,6-dideutero derivative and S-oxide in the presence of Eu(dpm)3 were studied. It was established that 3,5-diphenyl-2-thiabicyclo[4.4.0]decane has a cis,cis,cis configuration. The extremal spin-spin coupling constants (SSCC) constitute evidence for conformational rigidity of the investigated condensed system, which exists in the form of a puckered chair. The formation of the same cis,cis,cis isomer of 3,5-diphenyl-2-thiabicyclo[4.4.O]decane in the case of catalytic hydrogenation, disproportionation with trifluoroacetic acid, and ionic hydrogenation constitutes evidence for stereospecificity of the processes involving the reduction of the double bonds in 2,4-diphenyl-5,6-tetramethylene-6H-thiopyran.