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The latest advances in the chemistry of condensed bicyclic thiacyclohexanes of the type of thiadecalins and their analogues are examined. The results of studies on the methods of synthesis, chemical reactions, and the conformational and configurational analysis of thiadecalins, their analogues, and derivatives are surveyed. The bibliography includes 99 references.

The Pummerer rearrangement was investigated in the case of 3,5-diphenyl-2-thiabicyclo [4.4.0]decane S-oxide. It is shown that, of the two possible isomers, this compound forms only 3,5-diphenyl-2-thiabicyclo[4.4.0]dec-Δ1,6-ene under the conditions of the Pummerer reaction; a secondary transformation, viz., disproportionation of the latter to 3,5-diphenyl-2-thiabicyclo[4.4.0]decane and 2,4-diphenyl-5, 6-tetramethylenethiopyrylium acetate, is observed. 3,5-Diphenyl-2-thiabicyclo[4.-4.0] dec-Δ1,6-ene was subjected to an x-ray diffraction study; it was proved unambiguously that the C1=C6 double bond has a length of 1.335 A and that the dihydrothiopyran and cyclohexene rings have a distorted half-chair conformation: the dihedral angles between the phenyl rings and the planar fragment of the heteroring are 76.8 and 93.2 °C.

The structure of aryl-substituted cis-1-thiadecalins formed together with 5,6-tetramethylenethiopyrylium salts in disproportionation reactions of condensed 4H-, 6H-thiopyrans and dihydrothiopyrans with CF3COOH, as well as in the ionic reduction of the latter by the ion pair trifluoroacetic acid-triethylsilane, was studied. It was shown that the reduction proceeds stereospecifically with the formation of configurationally and conformationally homogeneous aryl-cis-1-thiadecalins possessing 2α-R1- and 2α-R1-4α-R2-configurations. The configurational and conformational assignments were made by the 13C NMR method.

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.

Methods for the synthesis of thiochromenes and hydrothiochromenes and their chemical properties and spectral characteristics are examined.

The disproportionation of isomeric 2,4-diphenyl-5,6-tetramethylene-4H-thiopyran,-6H-thiopyran, and 2,4-diphenyl-5,6,7,9-tetrahydrothiochromene with trifluoroacetic and deuterotrifluoroacetic acids was investigated for the first time. The direction of protonation of the sulfides was established, and this made it possible to form a judgment regarding the structure of the intermediate carbonium ions, which are hydride-ion acceptors. The correctness of the mechanism of disproportionation of condensed two-ring sulfides with a 4H-thiopyran ring was proved. A mechanism for the disproportionation of isomeric 2,4-diphenyl-5,6-tetramethyl-6H-thiopyran and 2,4-dipheny1-5,6,7,9-tetrahydrothiochromene was proposed.

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.

Bicyc!ic polydithioacetals such as (I-III) are readily accessible, by the reaction of !,3-diaryl-3-(2-oxocyclohexyl)propan-l-ones with hydrogen sulfide in acidic media, and can be used for the preparation of biologically active compounds [i, 2]. The attention of workers has hitherto been largely directed towards the alkylation of the mercapto group in alkaline solution [3]. We here report attempts to alkylate the sulfide sulfur with the object of obtaining S-R-sulfonium salts. S-Methylsulfonium salts are known to play an important part in reactions occurring in the living organism involving "active methionine." However, synthetic S-R-sulfonium salts are still largely unknown in a biological respect, There have been literature reports of the pharmacological effects of S-methyl-4-hydroxy-4phenylthiacyclohexane iodide [4], and of tests for anticholinergic properties in S-R-sulfonium salts of dihydroisonaphthene and dihydrobenzo[c,e]thiepin [5].

A. F. Oleinik, T. I. Vozyakova, G. A. Modnikova, et al., Khim. Geterotsikl. Soedin., No. Ii, 1448-1452 (1972). A. F. Oleinik, G. A. Modnikova, and K. Yu. Novitskii, Khim. Geterotsikl. Soedin., No. 4, 437-439 (1972). L. F. Fieser and M. Fieser, Reagents for Organic Synthesis, Vol. I, Wiley-Interscience, New York (1968). H. Sakashi and J. Matsuo, Synthesis of Furan Derivatives [Russian translation], J. Pharmacol. S,c. Japan, 88, 1306 (1968); Ref. Zh. Khimiya, No. 12, 410 (1969). A. F. Oleinik, G. A. Modnikova, K. Yu. Novitskii, et al., Khim.-Farmats. Zh., No. 5, 7-13 (1974). A. F. Oleinik, G. A. Modnikova, T. I. Vozyakova, et al., Khim. Geterotsikl. Soedin., No. 4, 452-456 (1975).

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.

2,4-Diphenyl-5,6,7,9-tetrahydrothiochromene was isomerized to 2,4-diphenyl-5,6-tetramethylene-4H-thiopyran in the presence of HCl and DCl. The relative thermodynamic stabilities of 2,4-diphenyl-5,6-tetramethylene-6H-thiopyran and the compound thus obtained were studied. The reactivities of the isomers of all three compounds in oxidation, disproportionation, and alkylation reactions are discussed. The structures of 2,4-diphenyl-5,6,7,9-tetrahydrothiochromene and 2,4-diphenyl-5,6-tetramethylene-4H-thiopyran were established by x-ray diffraction analysis.

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.

Methods for the synthesis of thiochromenes and hydrothiochromenes and their chemical properties and spectral characteristics are examined.

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.

The latest advances in the chemistry of condensed bicyclic thiacyclohexanes of the type of thiadecalins and their analogues are examined. The results of studies on the methods of synthesis, chemical reactions, and the conformational and configurational analysis of thiadecalins, their analogues, and derivatives are surveyed. The bibliography includes 99 references.