NaOCl + NaBr

Amide degradation. In a liquid triphasic system made up of NaOCl, NaBr, a phase-tranfer agent, Na3P04, benzene, and water, primary amides are degraded to nitriles of one fewer carbon atom. After Hofmann rearrangement the amine products undergo bromination and eventually elimination. 

Sodium hypochlorite/sodium bromide NaOCl/NaBr... 

NaOCl + NaBr Liquid As other chlorine and Effective, easily Requires feeding... 

Current industrial methods of chemical modification of starch by oxidation are based mainly on oxidizing agents like NaOCl to introduce carboxyl groups or NaI04 to obtain aldehyde functions. 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO) was applied in combination with NaOCl/NaBr or with peroxide reagents (JO) to oxidise selectively primary hydroxyl groups in polysaccharides. While these oxidations are chemically efficient they lead to inorganic wastes. 

One of the most efficient methods for oxidation of primary alcohols to either aldehydes or carboxylic acids is the one, commonly known as the Anelli oxidation. This reaction is carried out in a two-phase (CH2Cl2/aq.buffer) system utilizing TEMPO/NaBr as a catalyst and NaOCl as the terminal oxidant The new system described here is an extension of the Anelli oxidation, but surprisingly, does not require the use of any organic solvents and replaces the KBr co-catalyst with the more benign, Na2B40y (Borax). The use of the new cocatalyst reduces the volume of the buffer solution and eliminates completely the need of a reaction solvent. The new system was successfully applied in the industrial synthesis of the 3,3-Dimethylbutanal, which is a key intermediate in the preparation of the new artificial sweetener Neotame. 

A starting point for the reaction to achieve equal molar ratios requires the mixing of these two chemicals in the ratio of NaBr solution NaOCl bleach solution = 1.0 2.3. 

NaBr, NaOCl, (n-Bu4N)HS04 KBr, H202, cat NILVO3, H20, HCCI3... 

Scheme 4 (a) 1. TEMPO, EtOAc, toluene, 0°C, BntCHstsNCl, NaBr, aqueous NaHC03, 2. 1.1 M NaOCl,... 

Examples are toluene/Bu4N+Br /NaBr, toluene/Bu4N Br /NaOH(aq), BU4N+HSO4/NaBr/NaOCl(aq), and toluene/PEG/KOH(aq), etc. 

Hypobromous acid is produced by reacting sodium bromide (21.2.3a.) with hypochlorous acid [HOCl, either from sodium hypochlorite (21.2.2a.) or chlorine (21.2.1.)]. For the generation of HOBr one can proceed as follows 0.55 g of NaBr are mixed with 5 ml of a 5.25% NaOCl solution and diluted to 100 ml with distilled water. At this ratio only HOBr will be produced. 

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