Thiols reactions with hypochlorite

Some of the reactions of coordinated donor atoms are quite unexpected. Thus, coordinated thiol will react with alkyl bromides to form sulfonium salts. Here, there are lone pairs on the donor atom in addition to the one involved in forming the coordinate bond. Their qualitative reactivity is hardly affected by coordination. Ammonia which has been coordinated to platinum (IV) will form iV-chloro derivatives when treated with hypochlorite. This reaction involves an N-H bond rather than the lone pair. Coordinated PCI3 will undergo hydrolysis to give coordinated P(0H)3, a reaction which involves the P-Cl bonds rather than the lone pair. 

Thiol spills are handled ia the same manner that all chemical spills are handled, with the added requirement that the odor be eliminated as rapidly as possible. In general, the leak should be stopped, the spill should be contained, and then the odor should be reduced. The odor can be reduced by sprayiag the spill area with sodium hypochlorite (3% solution), calcium hypochlorite solution (3%), or hydrogen peroxide (3—10% solution). The use of higher concentrations of oxidant gives strongly exothermic reactions, which iacrease the amount of thiol ia the vapor, as well as pose a safety ha2ard. The apphcation of an adsorbent prior to addition of the oxidant can be quite helpful and add to the ease of cleanup. 

There was an attempt to treat spreadings of organic sulphides or thiols with calcium hypochlorite in the solid state. These treatments usually ended with a violent reaction followed by the compounds igniting. Nevertheless, this does not represent any danger when using sodium hypochlorite solutions at 15%. 

Contact of the sohd oxidant with organic thiols or sulfides may cause a violent reaction and flash fire [1]. This procedure was recommended formerly for treating spills of sulfur compounds [2,3], but is now withdrawn as potentially hazardous. Use of an aqueous solution of up to 15% concentration, or of 5% sodium hypochlorite solution is recommended [1]. Addition of 10 g of oxidant to 5 ml portions of... 

Several medio are available for the intnxluction of sulfenyl groups a to carbonyl derivatives and these have been reviewed. - The most versatile procedure involves reaction of the enolate with an appropriate thiol derivative, but the preferred m od is largely dependent on the nature of the substrate employed (see below). In most instances, sulfur has been introduced in the divalent state and subsequently oxidized, although the oxidative step has been avoided by the direct introduction of sulfur at the S oxidation level. The oxidation of sulfides to sulfoxides is a trivial procedure that can be effected by a variety of reagents. Sodium metaperiodate, m-chloroperbenzoic acid and hydrogen peroxide are the most common oxidants, but r-butyl hydroperoxide, r-butyl hypochlorite, N-chlorobenzotriazole,... 

PROPANE-1-THIOL (107-03-9) Forms explosive mixture with air (flash point —4°F/—20°C). May react with water, steam, or acids to produce toxic and flammable vapors. Violent reaction, ignition, or explosion with strong oxidizers, calcium hypochlorite, strong acids, alkalis, alkali metals. Incompatible with aliphatic amines, ethylene oxide, isocyanates, nitric acid, sulfuric acid. Attacks some forms of plastics, coatings, and rubber. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

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