52196-65-3Relevant academic research and scientific papers
The thiosulfinyl group serves as a stereogenic center and shows diamagnetic anisotropy similar to that of the sulfinyl group
Tanaka, Sanae,Sugihara, Yoshiaki,Sakamoto, Akira,Ishii, Akihiko,Nakayama, Juzo
, p. 9024 - 9025 (2003)
The pseudotetrahedral geometry of the thiosulfinyl group (>SS) in the thionosulfite which was prepared by treatment of cis-3,4-di-tert-butylthiolane-3,4-diol with 1,1'-thiobisbenzimidazole is stable enough to allow the isolation of two diastereomers. X-ray crystallographic analysis revealed that the configuration of the >S S group of the major diastereomer (45% isolated yield) is syn to the thiolane ring, while that of the minor diastereomer (10% isolated yield) is anti to the thiolane ring. 1H NMR spectrum analysis clarified that the shielding and deshielding zones of the >SS group are similar to those >SS group; Chemical properties of the > 5 S group toward thermolysis, hydrolysis, and oxidation were clarified. The absorptions or bands in the UV/ vis IR and Raman spectra, which originate from the > SSgroup, were assigned on the basis of the B3LYP/ 6-31G* level calculations. Copyright
The chemistry of the thiosulfinyl group: Preparation, structure, and spectroscopic and chemical properties of cyclic thionosulfites
Nakayama, Juzo,Yoshida, Sanae,Sugihara, Yoshiaki,Sakamoto, Akira
, p. 1451 - 1471 (2007/10/03)
Treatment of the tetrahydrothiophene-3,4-diol 5 with 1,1′-thiobis- (1H-benzimidazole) (6) furnished two diastereoisomers of the novel cyclic thionosulfite 4 with different configurations at the pseudo-tetrahedral center of the thiosulfinyl (S=S) group. The configuration of the S=S group of the major diastereoisomer (isolated in 45% yield) was established to be syn to the thiolane ring, as determined by X-ray crystallographic analysis, while that of the minor diastereoisomer (isolated in 10% yield) was anti. 1H-NMR Spectroscopic analysis clarified that the shielding and deshielding zones of the S=S group are similar to those of the well-documented S=O group. Characteristic absorptions of the S=S group in the IR, Roman, and UV/VIS spectra were assigned on the basis of calculations at the B3LYP/6-31G* level. The reactivity of the S=S group toward thermolysis, hydrolysis, and oxidation was examined. The S=S group is more resistant toward oxidation than the divalent sulfide S-atom, but is oxidatively converted to the S=O group.
