Catalytic rearrangement of O,S-dialkyl dithiocarbonates to S,S-dialkyl dithiocarbonates by pyridine N-oxides. The reaction mechanism was written by Harano, Kazunobu;Shinohara, Ikuo;Sugimoto, Shinichiro;Matsuoka, Toshikazu;Hisano, Takuzo. And the article was included in Chemical & Pharmaceutical Bulletin in 1989.Electric Literature of C7H9NO This article mentions the following:
The reaction of O-alkyl S-Me dithiocarbonates (xanthates) (I) with pyridine N-oxides (II) gave the corresponding S-alkyl S-Me dithiocarbonates (III) together with the sym. S,S-dialkyl and S,S-di-Me dithiocarbonates in good yields. Pyridine N-oxides bearing electron-donating substituents are efficient catalysts for rearrangement of I to III. The reaction is pseudo-first-order and the apparent first-order rate constant is proportional to the concentration of II. The role of pyridine N-oxides and the reaction behavior of O,S-dialkyl dithiocarbonates are discussed on the basis of kinetic and MO calculation data. The rearrangement may proceed by nucleophilic attack of –SCOSR derived from a complex of I and II on the O-alkyl group of xanthates. The reaction provides a useful preparation method for alkanethiols by aminolysis of the products with ethanolamine. In the experiment, the researchers used many compounds, for example, 3,5-Dimethylpyridine 1-oxide (cas: 3718-65-8Electric Literature of C7H9NO).
3,5-Dimethylpyridine 1-oxide (cas: 3718-65-8) belongs to pyridine derivatives. In contrast to benzene, Pyridine’s electron density is not evenly distributed over the ring, reflecting the negative inductive effect of the nitrogen atom. Pyridine derivatives are also useful as small-molecule α-helix mimetics that inhibit protein-protein interactions, as well as functionally selective GABA ligands.Electric Literature of C7H9NO