Gluconic acid nitrile

It was pointed out that N-methyl-L-glucosaminic acid nitrile was only the second nitrile in the sugar series to be isolated in the cyanohydrin reaction and that extension of the general procedure by which it was prepared should result in the isolation of other members. The nitrile of N-methyl-L-glucosaminic acid showed the same unusual mutarotation as does that of the lower-melting form of D-gluconic acid nitrile. Wolfrom and Thompson have noted that N-methyl-L-glucosaminic acid nitrile hydrochloride was a much more stable compound than the free base. 

Acyl groups have a protective role in some synthetic reactions. Gluconic acid nitrile acetates (aldonitrile acetates) are analytically suitable sugar derivatives for gas chromatographic separation and identification of sugars. An advantage... 

S (2)-hydroxy-3-butenenitrile from acrolein and HCN trans hydrocyanation using, for instance, acetone cyanohydrin Hydrolysis of nitriles to amides, e.g. acrylonitrile to acrylamide Isomerization of glucose to fructose Esterifications and transesterifications Interesterify positions 1 and 3 of natural glycerides Oxidation of glucose to gluconic acid, glycolic acid to glyoxalic acid... 

Initially, only the nitrile of L-mannonic acid was found on addition of hydrocyanic acid to L-arabinose this acid retained the original arabinose in the asymmetry centers 3, 4, and 5. The new center of asymmetry created in this way at C-2 was first considered by Fischer to be racemic. This would have meant that the L-mannonic acid should be a partial racemate however, attempts to separate it into two stereoisomers failed. The idea of a partial racemate led to the question as to whether L-mannonic acid and D-gluconic acid (which are enantiomorphous on carbon atoms 3, 4, and 5) could form such a partial racemate (which would still be optically active). Such a compound could not be isolated, but negative results have only limited values as proof. ... 

These acids are important precursors in the preparation of sugars with fewer carbon atoms. Oxidative degradation with H2O2 and iron salts (see p. 118) produces an aldose of one less carbon atom thus, D-gluconic acid is converted to D-arabinose, and D-galactonic acid to D-lyxose. Nitriles and amides can also be degraded (see p. 119). 

When [this nitrile, 4,6-benzylidene-2,3,5-triacetyl-D-gluconic nitrile, was treated with sodium methoxide in methanol solution in the presence of nitromethane, there was obtained readily from the reaction mixture crystalline 4,6-benzylidene-l-nitro-l-desoxy-D-mannitol. Hydrolysis of the benzylidene acetal with dilute sulfuric acid then gave the crystalline 1 -nitro-1 -desoxy-D-mannitol. 

D-Gluconic nitrile, which can be obtained in 55 % yield by the action of hydroxylamine acetate on n-glucose in acetic acid solution, is degraded quantitatively to n-arabinose simply by the action of hot water 196), However, the usual Wohl degradation via the acetylated nitriles 197), even in the most favorable instances, gives over-all (aldose aldose) yields of only 30 to 35%. 

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