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Paper | Regular issue | Vol 45, No. 3, 1997, pp.507-525
Published online, 1st January, 1970
DOI: 10.3987/COM-96-7706
The Conversion of Thioketones to 1,2,4,5-Tetrathianes and Its Mechanism

Rolf Huisgen* and Jochen Rapp

*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany


TThiobenzophenone and adamantanethione react with sulfur (1:1) under catalysis by sodium thiophenoxide in acetone at rt furnishing 1,2,4,5-tetrathianes (9 and 43) in high yields. An attack of the oligothiolate (R-Sx-) on the C-atom of C=S is proposed as initiating step. Thione S-sulfides (R2C=S+—S-, thiosulfines) cannot be intermediates, since they combine fast with thiones affording 1,2,4-trithiolanes with more sulfur pentathiepane-bis(spiroadamantane) (44) which interconverts with the tetrathiane, but not with the 1,2,4-trithiolane, in an equilibrium catalyzed by R-Sx-. According to 13C NMR evidence, the tetrathiane-bis(spiroadamantane) occurs in a twist conformation which inverts with δG= 16.0 kcal mol-1.