Fructopyranose esters

In the reaction of ammonia with l,3,4,5-tetra-0-benzoyl-/3-n-fructopyranose, a significant proportion of benzoic acid was formed, indicating that the ammonolysis of the sugar ester occurred to a certain extent through acyloxy-group rupture. As neither the formation of imidazole nor of pyrazine derivatives (see Section VI,3, p. 124) re-... 

This ease of synthesis of cyclic acetals makes them appropriate for the preparation of certain well-defined, mono-substituted esters of different origin. 2,3 4,5-Di-0-isopropylidene-/8-D-fructopyranose has been used for the synthesis of certain phosphoramidate compounds. The acetal is dissolved in 20 ml of toluene and refluxed for 6 to 8 hours in the presence of phosphoramidic chloride. The sirupy l-[iV,W-bis-(2-chloroethyl)phos-phoramidic chloride] (5) is then used for the preparation of other derivatives, such as the phosphoramidate itself. Hydrolysis with ethanolic hydrogen chloride removes the isopropylidene groups and results in the formation of ethyl /3-D-fructopyranoside l-[iV,JV-bis-(2-chloroethyl)phosphoramidate]. 

Micovic and StojiljkoviC synthesized a di-O-cyclohexylidene-D-fructose, m.p. 142°, which, on the basis of its lack of reaction with alkaline potassium permanganate, was assumed to be l,2 4,5-di-0-cyclohexylidene-D-fructopyranose (94). They also prepared a syrupy di-O-cyclopentylidene-D-fructose, which was characterized as a crystalline p-toluenesulfonic ester it, too, did not react with alkaline potassium permanganate. 

By Nucleophilic Displacement - Reaction of 2,3 4,5-di-0-isopropylidene-P-D-fructopyranose 1-triflate with tyrosine benzyl ester gave an Amadori-type... 

The glucose-lysine Amadori compounds monofructosy1-lysine and dlfructosy1-lysine have been Isolated, and the kinetics of their formation studied. 1-Deoxy-l-tolylamino-D-fructopyranose has been obtained by amlnatlon of fructose with g -toluldine, and shown to form an acyclic oxime and, on reaction with glycine ethyl ester, the glycosylamlne derivative (3). ... 

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