Acetaldehyde periodate oxidation

A 2,3,6-trideoxyhexose, namely, rhodinose (63), was shown to be the neutral sugar component in the antibiotic rhodomycin. 24 The structure was established by periodate oxidation, with isolation of acetaldehyde and... 

Oxidation of compounds of the types thus far discussed proceeds readily at room temperature. Certain compounds which show no substantial reaction with periodic acid at room temperature can be oxidized at elevated temperature.22- 23 26 Thus, at 100° in aqueous solution the acetone mole exile is split to produce acetic acid and formaldehyde diethyl ketone yields propionic acid and probably ethanol lactic acid gives acetaldehyde and carbon dioxide acetaldehyde is oxidized to formic acid and methanol, which is converted into formaldehyde and pyruvic acid yields acetic acid and carbon dioxide. 

The incorporation of [2-14C]pyruvate and [l-14C]acetate into sugars 17 and 18 was investigated.27 Oxidation of the methyl glycosides of sugar 17 with periodate yielded acetaldehyde from the 1-hydroxyethyl branch. The acetaldehyde (2,4-dinitrophenyl)hydrazone was further oxidized by Kuhn-Roth oxidation to acetic acid, which was degraded by the Schmidt reaction to methylamine and carbon dioxide. Periodate oxidation of the methyl glycosides of sugar 18 produced acetic acid from the C-acetyl branch. The acetic acid was isolated, and purified as 1-acetamidonaphthalene. 

Lead tetraacetate (abbreviated LTA) reacts with diols to give the same kind of oxidative cleavage. When 69 is treated with LTA, the initial cyclic product is cyclic intermediate 73, which fragments to butanal and acetaldehyde. Periodic acid gives the same cleavage reaction. Both periodic acid and lead tetraacetate are mild and effective reagents for the oxidative cleavage of diols. 

Unique methods based on new principles have been developed within the past 10 years. Threonine (27,28,249) is oxidized by lead tetraacetate or periodic acid to acetaldehyde, which is determined by photometric analysis of its p-hydroxydiphenyl complex or iodometric titration of its combined bisulfite. Serine is oxidized similarly to formaldehyde, which is determined gravimetrically (207) as its dimedon (5,5-dimethyldihydro-resorcinol) derivative or photometric analysis (31) of the complex formed with Eegriwe s reagent (l,8-dihydroxynaphthalene-3,5-disulfonic acid). It appears that the data obtained for threonine and serine in various proteins by these oxidation procedures are reasonably accurate. [Block and Bolling (26) have given data on the threonine and serine content of various proteins. ]... 

Divalent Metal Molybdates. Except for the first point, the conversion of ethane did not change in the conditioning period at 823 K and it lay in the same range as for the N2O as oxidant. The main product was ethylene the selectivity of its foimation mai kedly exceeded that obtained with N2O as oxidant. Acetaldehyde was formed with 4.8% and 6.8% selectivity on the Mg and Zn salts. As a result, the yields for ethylene and acetaldehyde were much higher than in the case of N2O oxidation (Figure 5). Other hydrocarbons and alcohols were also detected in very small concentrations, with less than 1% selectivity. 

It is not possible to propose a general mechanism from these studies, for results do not correspond to a definite pattern. Although, in all the systems, secondary amines are the most effective inhibitors, the role played by tertiary amines is confusing. In several systems (Table I, No. 1, 2, and 3) tertiary amines are much more effective than primary amines, but in others they appear to have little or no effect. Again, in acetaldehyde oxidation (Table I, No. 1 and 2) there is generally a linear relationship between the amount of inhibitor added and the induction period before either slow oxidation or ignition of the fuel occurs. In other systems (Table I, No. 3, 4, and 5), however, a much more complex relationship is obtained. Thus, amines may be acting by different mechanisms in different systems. 

When amines are added to the acetaldehyde-oxygen and ethyl ether-oxygen systems, a period of time elapses before oxidation of the fuel begins. The length of this induction period is dependent on the amount of amine added and the structure of the amine. Detailed analysis has shown that the length of the induction period can be used as a parameter for the efficiency of the inhibitor, for it is only when the amine has been consumed that oxidation of the fuel can take place (28). 

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