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The Chemistry of the Thiosulfinyl Group: Preparation, Structure, and Spectroscopic and Chemical Properties of Cyclic Thionosulfites
Author(s) -
Nakayama Juzo,
Yoshida nee Tanaka Sanae,
Sugihara Yoshiaki,
Sakamoto Akira
Publication year - 2005
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200590117
Subject(s) - chemistry , diastereomer , yield (engineering) , raman spectroscopy , group (periodic table) , reactivity (psychology) , tetrahydrothiophene , crystallography , stereochemistry , thioether , ring (chemistry) , carbon group , nmr spectra database , sulfide , medicinal chemistry , organic chemistry , spectral line , medicine , materials science , physics , alternative medicine , pathology , astronomy , optics , metallurgy
Treatment of the tetrahydrothiophene‐3,4‐diol 5 with 1,1′‐thiobis‐(1 H ‐benzimidazole) ( 6 ) furnished two diastereoisomers of the novel cyclic thionosulfite 4 with different configurations at the pseudo‐tetrahedral center of the thiosulfinyl (SS) group. The configuration of the SS 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. 1 H‐NMR Spectroscopic analysis clarified that the shielding and deshielding zones of the SS group are similar to those of the well‐documented SO group. Characteristic absorptions of the SS group in the IR, Raman , and UV/VIS spectra were assigned on the basis of calculations at the B3LYP/6‐31G* level. The reactivity of the SS group toward thermolysis, hydrolysis, and oxidation was examined. The SS group is more resistant toward oxidation than the divalent sulfide S‐atom, but is oxidatively converted to the SO group.