Hexose basic conditions

By analogy with the synthesis of /V-acetylneuraminic acid,63 di-A-acetyl derivatives of 5,7-diamino-3,5,7,9-tetradeoxynon-2-ulosonic acids could be obtained by condensation of 2,4-diacetamido-2,4,6-trideoxyhexoses with oxaloacetic acid under basic conditions. Four chiral centers in the C precursors, C-2 C-5, correspond to the centers C-5-C-8 in the target C9 products, and the fifth asymmetric center, C-4, is formed upon condensation. At present, derivatives of twelve 2,4-diamino-2,4,6-trideoxy-hexoses with the d-gluco, o-manno, L-allo, r>-galacto, D- and L-altro, D- and L-talo, D- and l-gulo, D- and L-ido configurations have been prepared by multistep chemical syntheses.11,17,18,64,65... 

At American University, Harriet Frush and Horace Isbell worked on the mechanism of oxidation of carbohydrates by peroxides. They discovered that, in aqueous alkaline hydrogen peroxide, aldoses are quantitatively degraded to formic acid, so that hexoses produce six moles of this acid and pentoses produce five moles. A detailed study of the mechanism of the reaction revealed that degradation takes place by several pathways, the most rapid one involving the formation of peroxy radicals and hydroxy radicals. Thus, when a hydroperoxide-aldose adduct reacts with hydrogen peroxide, a peroxy radical is formed, which decomposes to a hydroxy radical, formic acid, and the next lower aldose. It was also found that, under basic conditions, hydroxy radicals oxidize alditols and aldonic acids to carbonyl compounds in much the same way they do with Fe2+ in the Fenton reaction. During the years she spent at American University, Dr. Frush was able to publish 10 papers without help from any research assistant or laboratory technician. This brought her total to more than 70 papers. 

According to the conditions, hexose monophosphate and trehalose phosphate also accumulate in varying amounts. Separation of the fructose diphosphate from the monophosphate can be effected by precipitating the diphosphate with neutral lead acetate or barium ions, followed by precipitation of the monophosphate from the supernatant liquid with basic lead acetate or barium ions in 50% or stronger ethanol (199). The separation of the different monophosphates was carried out by fractional crystallization (200). Chromatographic methods have also been used (Chapter XI). 

The carbohydrates failed to undergo certain reactions that were typical of aldehydes. Although the hexoses and pentoses were readily oxidized at C-1 under mild alkaline conditions, they did not give a positive result with the Schiff test (reaction with basic fuchsin), and they did not form bisulfite addition products, reactions that are typical of aldehydes. The cyanohydrin and phenylhydrazine reactions also went much more slowly than they did for other a-hydroxy aldehydes. 

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