Halogen oxides dimethyl sulfide reaction

Dimethyl sulfoxide and chlorine form highly reactive intermediates which are of some limited use as oxidants for alcohols. These intermediates are related to those derived from the reaction of the halogens with dimethyl sulfide and probably have a structure such as (27). When formed at -4S C they allow the oxidation of primary and secondary alcdiols to aldehydes and ketones when used in a two-fold excess. For very simple alcdiols the reaction proceeds in yields of greater than 90%, but there are considerable drawbacks if some types of additional functionality are present in the molecule, e.g. alkenes react very rapidly to form vicinal dichlorides. 

Finally, there has been a great deal of interest in the halogen oxides IO, BrO, and CIO as potential oxidants for organic sulfur compounds such as dimethyl sulfide. We therefore also discuss the current status of these reactions. 

While a number of synthetic routes are available to various sulfoxides, the primary methods for commercial production of DMSO involve oxidation of dimethyl sulfide by oxides of nitrogen or by air in the presence of NO cat-alyst.f Dimethyl sulfoxide is both the product and the reaction solvent. To alleviate the potential for exothermic, and potentially explosive, runaway reactions in these oxidations, the feed rate for dimethyl sulfide is adjusted to ensure complete conversion and, thus, low instantaneous concentrations at any time. Alternate oxidants for the conversion of sulfides to sulfoxides include nitric acid, H202/acetic acid, peracids, and halogen/water. ... 

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