Oxidative chlorination, mercaptan, chlorine

Smaller uses of 1-butene are in 1,2-butylene oxide, butyl mercaptan, and butyl phenols. Butylene oxide, produced by the chlorohydrin process, is used as a corrosion inhibitor in chlorinated solvents. Butyl mercaptan is a precursor for organophosphate herbicides, pharmaceutical intermediates, and is used as a gas odorant. 

The oxidation of mercaptans with chlorine in water gives sulfonyl chlorides. Ethyl mercaptan and pentyl mercaptan afford ethanesulfonyl chloride and pentanesulfonyl chloride in yields of 73 and 78% at 5 and 1-5 C, respectively [6S3]. 

In the alternative Route B, the easily available 2-chloronicotinic acid is utilized as starting material. As above, this acid is converted by successive treatment with thionyl chloride and dimethylamine to the nicotinamide. The chlorine at the 2-position is then replaced by a benzylthio group, by treating with benzyl mercaptan and potassium carbonate in dimethyl sulfoxide. Oxidative chlorination followed by reaction of the interme ate sul-fonyl chloride with ammonia then provides the target intermediate. 

Manufacture. Methanesulfonic acid is made commercially by oxidation of methyl mercaptan by chlorine in aqueous hydrochloric acid to give methanesulfonyl chloride which is then hydrolyzed to MSA. 

Sodium chlorite has also been used for treatment and removal of toxic and odorous gases such as hydrogen sulfide and mercaptans. Chlorine dioxide from chlorite is also useful for microbial and slime control in paper mills and alkaline paper machine systems (164,165). The use of sodium chlorite in textile bleaching and stripping is well known. Cotton is not degraded by sodium chlorite because the oxidation reactions are specific for the hemiceUulose and lignin components of the fibers. 

Mercaptans Mercury Powerful oxidizers Acetylenic compounds, chlorine, fulminic acid, ammonia, ethylene oxide, metals, methyl azide, oxidants, tetracarbonylnickel... 

More than 80% of all sodium chlorite produced is used for the generation of chlorine dioxide. Sodium chlorite is also used in disinfectant formulations and sterilization. Like chlorine dioxide, it must be registered with EPA under FIFRA for each specific application use as a disinfection. Sodium chlorite is used in other industrial settings in NO and SO combustion flue gas scrubber systems in the treatment and removal of toxic and odorous gases such as hydrogen sulfide and mercaptans and as a solution formulation to oxidize copper surfaces in multilayer circuit boards (Kaczur and Cawlfield 1993). 

Oxidation of a sulfim c acid, a mercaptan, or a disulfide. For example, the chlorine in o-nitrochlorobenzene is not reactive enough to be replaced directly by the sulfo group according to (1) above the compound can be converted, however, to o,o -dinitrodiphenyldisulfide by the action of Na2S2, and this, in turn, can be oxidized to o-nitrobenzenesulfonic acid.23 The reactions involved are ... 

Oxidations by chlorine are limited to only few types of compounds. In organic solvents and pyridine [681] or hexamethylphosphoramide (HMPA) [682] as cosolvents, primary alcohols are oxidized to aldehydes and secondary alcohols to ketones [681, 682]. Secondary alcohols are oxidized in preference to primary alcohols [681]. Many oxidations with chlorine are carried out in aqueous media and involve sulfur-containing compounds. Mercaptans [683], alkyl thiolcarboxylates [683], thiocyanates [684], isothioureas [684], disulfides [655], and sulfinic acids [656] are transformed into sulfonyl chlorides. The chlorination of dimethyl disulfide in acetic anhydride yields methanesulfinyl chloride [657]. 

In chemical oxidation, chemicals with high positive oxidation potential, such as ozone (2.1 V) and hydrogen peroxide (1.8 V), are used to destroy a wide variety of organic and inorganic compounds such as chlorinated VOCs, mercaptans, phenols, and cyanide (NaCN). 

Methanesulfonic acid is primarily manufactured by the batch or continuous oxidation of the methyl mercaptan or dimethyl disulfide with chlorine in saturated aqueous hydrochloric acidJ This chemistry is also the basis for much of the worldwide production of MSC, with photochlorination of methane (vide infra) being the most significant commercial alternative. Other alkanesulfonyl chlorides and sulfonic acids have also been produced in lesser quantities by the CI2/H2O oxidation. Reaction yields are typically 92-100%. The HCl by-product separates as vapor from the saturated reaction mixture. It is absorbed into water to afford a... 

A good example of the competitiveness between chlorine and peroxygen oxidants is the preparation of rubber accelerators such as sulphenamides. Sulphenamides are prepared by the oxidative coupling of a mercaptan with an amine (Fig. 1). 

POE Mercaptans, RS(C2H/))XH Unstable to oxidizing agents, such as chlorine, hypochlorites, per-oxides, and strong acids. (This may be an advantage when inactivation of surfactant after use is desired.) Stable in hot, strong alkali. Good lime soap dispersants. 

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