Oxidative Cleavage of Nitrogen-containing Carbohydrates

C02Et HC-NHC02Et HOCH 1 HCO 1 1 1 HCOH CHPh 1 h2co—1 C02Et HC=NC02Et CO2M6 HCNHCPh 1 11 HC=0° r 

Glycol cleavage of diacetamides proceeds smoothly and without apparent attack on the fV-substituted carbon atom,44 1, l-bis(acetamido)-l-deoxy-D-erythritol and -D-threitol giving rate curves similar to that of glyceritol. Rate curves for pentitol diacetamides resembled those of eryth-ritol. 

Some related iV-aryl compounds were examined in model experiments in connection with lead tetraacetate cleavage of samandarin derivatives.194 Oxidation in aqueous acetic acid at 60-70° of 1 -deoxy-1-(p-toluidino)-l-arabinitol (LXXXV) and -D-mannitol yielded two moles of formaldehyde per mole, one mole being derived from the terminal carbinol group and the second from subsequent hydrolysis of the Schiff base (LXXXVI) pro- 

An a-hydroxy tertiary amine is oxidized with difficulty. At 60°, however, 2-(7V, Ar-diethylamino)ethanol took up lead tetraacetate, but scission occurred between the carbon-nitrogen bond (instead of between the carbon-carbon bond), possibly by a free-radical mechanism.196 

The action of lead tetraacetate on osazones of Cw-labeled sugars in warm aqueous acetic acid has been employed46 for determining specific activity of the oxidizable carbon atoms present, that is, C4, C5, and C6 of D-glucose phenylosotriazole. In the potassium acetate-catalyzed oxidation, D-glucos-azone (o-arabino-hexose phenylosazone) yielded two moles of formic acid 

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