Oxidation, with hypobromite

In the synthesis of 1,6-anhydro-D-glucitol, at least, a 2,6-anhydride is a byproduct.53 Its structure was assigned on the basis of its i.r. spectrum, in comparison with those of the 1,6- and 1,5-anhydro-D-glucitols, and the fact that no diglycolic acid was obtained after periodate oxidation followed by oxidation with hypobromite. 

Gravimetric Methods.—The main difficulty is to obtain the cobalt in the form of one of its compounds entirely free from nickel or other metal. This may be accomplished by the cyanide method described under Wet Tests above. The solution, after separation of the nickel, is evaporated with dilute sulphuric acid until white fumes are evolved. On addition of water a solution of cobalt sulphate results, and the cobalt may be precipitated in a variety of ways, for example as oxide with hypobromites or persulphates,2 as sulphide, as cobalti-nitroso p-naphthol, or as basic carbonate.3 In each case the precipitate is ignited and reduced to metallic cobalt in a current of pure hydrogen. 

The pinacolone may be employed for the preparation of trimethylacetlc acid (plvallc acid) by oxidation with sodium hypobromite solution ... 

Ha.logen Compounds. Fluorine is unreactive toward ozone at ordinary temperatures. Chlorine is oxidized to Cl20 and Cl20y, bromine to Br Og, and iodine to I2O2 and I4O2. Oxidation of haUde ions by ozone increases with the atomic number of haUde. Fluoride is unreactive chloride reacts slowly, ultimately forming chlorate and bromide is readily oxidized to hypobromite (38). Oxidation of iodide is extremely rapid, initially yielding hypoiodite the estimated rate constant is 2 x 10 (39). HypohaUte ions are oxidized to haUtes hypobromite reacts faster than hypochlorite (40). 

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Alicyclic hydroxamic acids undergo several specific oxidative cleavage reactions which may be of diagnostic or preparative value. In the pyrrolidine series compounds of type 66 have been oxidized with sodium hypobromite or with periodates to give y-nitroso acids (113). Ozonolysis gives the corresponding y-nitro acids. The related cyclic aldonitrone.s are also oxidized by periodate to nitroso acids, presumably via the hydroxamic acids.This periodate fission was used in the complex degradation of J -nitrones derived from aconitine. 

The action of chlorine in alkaline media is much slower than that of bromine. Lewin29 reported that the rate of oxidation of D-glucose at pH 9.8 by hypobromite is 1360 times higher than that by hypochlorite at the same pH. For cellulose, the ratio is much smaller (33 to 1). The complexity of the latter system is, however, revealed by the variability of this ratio over the pH range of 8-13 at pH 6-7, the action of hypochlorite is actually slightly faster than that of hypobromite. Maltodextrins and starch have been oxidized with alkaline sodium hypochlorite. The resulting oxidized polysaccharide formed stable complexes with calcium cations.30... 

Dicarboxyl starch can also be made by oxidation with sodium hypochlorite or hypobromite (see reference 116). Reaction with hypochlorite is accelerated by use of catalytic amounts of sodium bromide.123,124... 

These compounds are very stable, but as derivatives of aldonic acids they undergo epimerization with hot sodium hydroxide. They are oxidized by hypobromite to salts of the labile 2-phenyl-1,3,4-thia-diazole-5-carboxylic acid (15). The corresponding products from fucose and hexuronic acids were described in later papers. 

Aminopyrazine 1-oxide has been prepared from 3-carbamoylpyrazine 1-oxide with sodium hypobromite (108, 547a), and the interaction of iminodiacetonitrile ... 

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