Sodium bisulfite, reaction with carbonyl compounds

Several representative compounds from which abnormal products had been previously isolated in ozonizations carried out by other investigators were selected to test the above theory. Ozonizations were carried out in pure methanolic solutions at about —20° C. and in each case the yield of peroxide, based on the ozone consumed, was determined quantitatively. Overozonization was avoided, inasmuch as excess ozone is known to cause side reactions or decomposition of the peroxides (5). The peroxides thus formed were reduced with aqueous sodium bisulfite and the carbonyl compounds isolated as their 2,4-dinitrophenylhydrazones, which were separated quantitatively by chromatography through a mixture (2 to 1) of silica gel and Celite. In no case were any of the abnormal products found. The results are summarized in Table I. 

Acetaldehyde can be isolated and identified by the characteristic melting points of the crystalline compounds formed with hydrazines, semicarbazides, etc these derivatives of aldehydes can be separated by paper and column chromatography (104,113). Acetaldehyde has been separated quantitatively from other carbonyl compounds on an ion-exchange resin in the bisulfite form the aldehyde is then eluted from the column with a solution of sodium chloride (114). In larger quantities, acetaldehyde may be isolated by passing the vapor into ether, then saturating with dry ammonia acetaldehyde—ammonia crystallizes from the solution. Reactions with bisulfite, hydrazines, oximes, semicarb azides, and 5,5-dimethyl-1,3-cyclohexanedione [126-81 -8] (dimedone) have also been used to isolate acetaldehyde from various solutions. 

The reaction is reversible, but the state of equilibrium highly favors the desired products. Preparations of large quantities for synthetic work are illustrated for methyl ethyl ketoxime, cyclohexanone oxime, hept-aldoxime, and benzophenone oxime, the procedures varying somewhat with the nature of the carbonyl compound. In some instances, a readily available and cheap reagent like sodium hydroxylamine disulfonate, HON(SO,Na)j, is first prepared from sodium nitrite and sodium bisulfite and, without isolation, treated with the carbonyl compound, Hydioxylamine-O sulfonic add, Ii,NOSO,H, is still another reagent and, like sodium hydroxylamine disulfonate, is used in the absence of a base. The preparation of hydroxylamine hydrochloride is described. ... 

---