Oxirane reactions with thiols

The reaction of oxiranes with thiols permits the preparation of a-hydroxyalkyl thioethers. Reactions with thiophenols are presented in Eqs. 306 and 307.1 ... 

Oxiranes can be opened stereo- and regiospecifically under mild conditions with alcohols, thiols, amines, and acetic acid, with simultaneous activation of the nucleophilic and electrophilic centers on an alumina surface.Diols have been obtained on silica gel in the presence of water " and adsorbed FeCls. On an ion-exchange resin, the opening of oxirane isomers to diols and the separation of the latter, ethanolysis, the reaction with phenol,and catalytic ammonolysis have been described. Hydrolysis and methanolysis catalyzed by Nafion-H, a perfluorinated resinsulfonic acid have been reported. ... 

Autoclave reactions involving ethylene oxide with alkanethiols or an (unspecified) alcohol went out of control and exploded violently. Similar previous reactions had been uneventful [1], An arenethiol was being reacted with ethylene oxide under catalysis by a fraction of a percent of sodium hydroxide (solid) dissolved in the thiol to which the oxirane was slowly charged. After an initial exotherm a white solid precipitated, the exotherm died away and later resumed, with dissolution of the solid, the reaction then running out of control from the backlog of charged oxirane [2],... 

Oxiranes can also be cleaved by mercaptanes, this yielding -hydroxy sulfides. This reaction has been carried out386 with oxirane, 7-oxabicyclo[4.2.1]heptane, and epichlorohydrin [(chloromethyl)oxirane] and, as sulfur components, ethane-, 1-propane-, benzene-, and a>toluene-thiol in the presence of a little active charcoal as catalyst. 

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