Hypochlorite, oxidation with

Hetero-substituted 4,7-diarj lbenzofuroxans (Section V,C) are known. The only representative 5-arylbenzofuroxan in Table I is 5,5 -bisbenzofuroxanyl (23), prepared from 4,4 -diamino-3,3 -dinitro-biphenyl by oxidation with hypochlorite. 

For producing bromates, oxidation with hypochlorite as shown here is a useful reaction ... 

Tetranitrodispiro[3.1.3.1 ]decane (24) was obtained as a mixture of isomers by treating the oxime (22) with chlorine in methylene chloride, followed by oxidation with hypochlorite and rednctive dehalogenation of the resnlting gm-chloronitro intermediate (23) with zinc... 

Baum and Archibald reported the synthesis of 2,2,6,6-tetranitrobicyclo[3.3.1]nonane (142). This synthesis starts from the dioxime (140), which on halogenation with chlorine, followed by oxidation with hypochlorite and reductive dehalogenation with hydrogen in the presence of palladium on carbon, yields 2,6-dinitrobicyclo[3.3.1]nonane (141). Oxidative nitration of (141) with sodium nitrite and silver nitrate under alkaline conditions yields 2,2,6,6-tetranitrobi-cyclo[3.3.1]nonane (142). The greater molecular freedom in 2,2,6,6-tetranitrobicyclo[3.3.1] nonane (crystal density-1.45 g/cm ) compared to the isomeric 2,2,6,6-tetranitroadamantane (crystal density-1.75 g/cm ) is reflected is their considerably different crystal densities. 

By this method, azopropane is said to have been prepared in 100% yield, azo-K-butane in 54% yield, and azocyclohexane in 80% yield (m.p. 33°C). The identity of the product was determined by vapor-phase chromatography and by comparison with products obtained from the corresponding hydrazine derivatives on oxidation with hypochlorite ions. 

FIGURE 6.S /DP versus D for cotton oxidized with hypochlorite at pH 7. 

The haloform oxidation with hypochlorite convert acetyl groups at positions 1 and 2 into carboxylic acids and also oxidizes to the 5,5-dioxide. Working in heterogeneous phase, acids unoxidized at sulfur may be obtained. The same results are obtained on oxidation under alkaline conditions. Oxidation of acetyl to carboxyl groups with KMn04 is also mentioned in the literature. ... 

After its separation on an anion exchanger it is oxidized with hypochlorite and subsequently reacted with OPA/2-mercaptoethanol. As seen in the corresponding chromatogram in Fig. 6-20, even the main glyphosate metabolite — aminomethanesulfonic acid (AMPA) - may be detected in the same run. 

Acid catalysis is preferable to base for the condensation of 5a-cholestan-3-one (341) with pentyl nitrite to form the hydroxyimino-ketone (342). The dioxime (343) afforded the [2,3-c]furazan 2-oxide (344) on oxidation with hypochlorite. Nitration of the 3-ketone (341) with ethyl nitrate and base gave the 2-nitro-enol (345) the derived 3-oxime (346) gave the furazan oxide (344) on reaction with acid. Nitration of 5a-cholestan-7-one gave the 6a- and 6)5-nitro-ketones (347), apparently the first epimeric pair of steroidal nitro-ketones to be... 

In the laboratory, small quantities may be evaporated in a hood in the absence of a hot plate, open flame, or nearby ignition source. Carbon disulfide can be destroyed by oxidizing with hypochlorite ... 

His laboratory produced a number of papers on the oxidation of polysaccharides, with a particular focus on the products of the oxidation of starch with alkaline solutions of chlorine (hypochlorite) (1951-1968). Starches oxidized with hypochlorite were commercial products, but until his work, the actual products of oxidation were unknown. 

Matsumura [185-188] has oxidized a wide range of polysaccharides, starch, xyloses, amyloses, pectins, and the like with hypochlorite/periodate. The products are either biodegradable at low oxidation levels or functional at high oxidation levels the balance has not yet been established for commercial success. Other than Matsumura, van Bekkum and co-workers, at Delft University, has been the major player in the search to control the hypochlorite/periodate liquid-phase oxidations of starches [189-191]. He has been searching for catalytic processes to speed up the oxidation with hypochlorite. Hypobromite is a more active oxidant than hypochlorite but more expensive, however, it may be generated in situ from the cheap hypochlorite and bromide ion in one solution [191, 192]. This is shown in Scheme 16. 

A special purified grade of the diaphragm cell sodium hydroxide is made by extracting the 50% solution with liquid ammonia to remove chloride, chlorate, and carbonate. Metal ions, such as iron, nickel, cobalt, and copper, can be removed by electroplating them onto porous cathodes. Electrolysis also removes some anions such as sulfide. Iron and nickel are also removed by filtration using magnesium oxide filter aid after oxidation with hypochlorite. ... 

Oxidation with hypochlorite has been studied but does not appear to be as effective (Soilleaux, 1998). 

Sodium hypochlorite tetrabutylammonium hydrogen sulfate NaOCUBu N HSOf Phase transfer catalyzed oxidations with hypochlorite... 

---