Ethane thiol, oxidation

Methane and ethane thiols are more readily oxidized than their parent alkanes [106(a), 107]. 

Experiments with simple thiols have been extended by Cullis et al. [113], care being taken to exclude metal contamination from the systems. The oxidation of ethane thiol in sodium hydroxide solutions has been found to be stoichiometric to disulphide, the kinetics of reaction changing at ca. 10—30% of reaction, viz. 

Detailed investigation of the oxidation of ethane thiol in the presence of copper-, cobalt-, and nickel-containing catalysts was also carried out [138]. The reaction was stoichiometric to disulphide, and the dependence of the rates of oxidation on the concentration of individual reactants is summarised in Table 4. It can be seen that the concentrations of added metal bear little resemblance to the concentrations of catalytically active metal. The change from initial to final rates usually occurred at about 10— 30% of total conversion and was attributed to the formation of disulphides which can compete for coordination sites on the metal ion. 

The kinetics of the oxidation of ethane thiol catalysed by copper, cobalt, and nickel [138]... 

Co-oxidation of thiols with 1,3-butadiene, the simplest conjugated diolefin, has been studied in the presence of r-butylamine . Products derived from 1,2- and 1,4-addition were observed in the reaction with methane- and ethane-thiols, predominant 1,2-co-oxidation products were formed when benzene or p-toluenethiol were used (equation 104). 

The compound in which the 3-keto group is reduced to a hydrocarbon interestingly still acts as an orally active progestin. The preparation of this compound starts with the hydrolysis of dihydrobenzene (13-2) to afford 19-nortestosterone (15-1). Reaction with ethane-1,2-thiol in the presence of catalytic acid leads to the cyclic thioacetal (15-2). Treatment of this intermediate with Raney nickel in the presence of alcohol leads to the reduced desulfurized derivative (15-3). The alcohol at 17 is then oxidized by any of several methods, such as chromic acid in acetone (Jones reagent), and the resulting ketone (15-4) treated with hthium acetylide. There is thus obtained the progestin lynestrol (15-5) [18]. 

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