Glucose oxime

The isolation of glucose oxime is unnecessary in this preparation. 

The viscous, syrupy glucose oxime dissolves with difficulty, and it may be necessary to warm the mixture slightly. If this is done, a pan of ice water should be at hand in order to cool the mixture should the temperature begin to rise rapidly. 

The above method for preparing glucose oxime is the modification of that of Jacobi1 developed by Wohl,2 who first converted the oxime into the pentaacetyl glucononitrile by means of acetic anhydride. The latter reaction was later employed for the same purpose by Zemplen and Kiss.3... 

In his first paper Wohl reported the conversion of D-glucose oxime (I) into pentaacetyl-D-glucononitrile (II). 

Afterward, Behrend found that the nitrile is also produced when o-glucose oxime is treated with pyridine and acetic anhydride, and this method has been extended to the preparation of other nitriles of aldonic acids. ... 

In the case of the oximes of the aldose sugars, the situation is more complicated because of the possibility of both open-chain and cyclic structures. That aldose oximes can react in the open-chain form follows from the formation of the nitriles and from the isolation of acylated open-chain aldose oximes as secondary products in preparation of nitriles. For example, Wolfrom and Thompson, by the action of sodium acetate-acetic anhydride on n-glucose oxime, not only obtained pentaacetyl-D-glucononitrile, in 40% yield, but also isolated a small amount of hexaacetyl-oWeAydo-D-glucose oxime (V) identical with that prepared by mild acetylation of pentaacetyl-aWe%do-D-glucose oxime (IV) whose structure was assured by its formation from pentaacetyl-aldehydo-D-glucoae (III). 

This hexaacetyl-aWe%do-D-glucose oxime was easily transformed into the nitrile by heating at 135-140 , or by treatment with sodium acetate-acetic anhydride, and Wolfrom and Thompson considered the open-chain oxime and its acetylated derivative to be an intermediate in the production of the nitrile. We have no proof of the original structure of the oxime. Under the conditions of temperature employed, even a syn oxime can be transformed into the nitrile. If we accept the assumption that the isolated open-chain oxime is the only intermediate, its... 

Wohl isolated a hexaacetyl-D-glucose oxime from the mother liquor obtained during the preparation of pentaacetyl-D-glucononitrile. The same acetylated oxime was prepared by Behrend. Wolfrom and Thompson studied it further, and showed conclusively that it possessed a ring structure XI, for it could not be transformed into a nitrile. Because of its low specific rotation, it was assigned to the jS-d series. 

D-Xylose oxime (XVIII) is also transformed into the nitrile even by mild acetylation. The configuration of carbon atoms 2, 3 and 4 is the same as in D-glucose oxime (XIX), but the latter reacts in a different form, giving almost exclusively the cyclic oxime upon mild acetylation. At higher temperatures the acetylated nitrile is produced. 

Preparation of propionylated nitriles from oximes. Pentapropionyl-n-glucono-nitrile. Twenty grams of n-glucose oxime was dissolved in 100 ml. of pyridine and 100 ml. of propionic anhydride was added the solution was heated for one hour at 100° and was then poured into ice water. The sirupy precipitate was extracted with ether, and the ether solution was washed with sodium bicarbonate solution (5%) and with water. The ether was evaporated and the remaining sirup was distilled at 0.001... 

Mason and Slover187 studied the separation of monosaccharides as the O-trimethylsilyl derivatives of the oximes, as an alternative method to analyzing for sugars in foods, and Clayton and H.G. Jones188 used trimethylsilylated D-glucose oxime. Both groups of workers referred to the instability of these derivatives, as noted in Section III (see p. 23). Laine and Sweeley189 proposed a similar method that used the methoxime derivatives. 

D- rafro-Tetrahydroxybutyl)pyrazine 1-oxide (7) has been prepared by Fujii and Kobatake (543, 544) by the condensation of 2-amino-2-deoxy-D-glucose oxime (6) or 2-amino-2-deoxy-D-mannose oxime with glyoxal in water at room temperature. 

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