Di-D-glucosylamine

No further information is available as to the structure of the isomeric di-D-glucosylamines. 

The same reaction was found to occur with piperazine, an aromatic secondary amine. In this case, the di-D-glucosylamine was prepared by condensation in 95% ethanol, with ammonium chloride as the catalyst. If the reaction was performed at 80-100°, an 80% yield resulted within 30 minutes. Refluxing with diethyl malonate gave the corresponding Amadori product in 35% yield. 

With ammonium chloride as a catalyst, Frush and Isbell (3) obtained two D-galactosylamines, one as a complex with one mole of ammonia these apparently represent a- and iS-pyranoid isomers. Diglycosylamines may also form in this type of preparation, since two isomeric di-D-glucosylamines were prepared under very similar conditions (4). 

Reaction of D-fructose with potassium thiocyanate in the presence of hydrogen chloride affords a thiooxazoline derivative of unknown structure. From indirect evidence, formula (59) was suggested, as all attempts to isolate the amino sugar expected from structure (58) have been fruitless. In contrast, the D-glucosylamine and even the di-n-glucosylamine compound were found, by chromatography, as products from the corresponding... 

The Amadori rearrangement also occurs for the glycosylamine derivatives of some secondary alkylamines and of primary and secondary aralkyl-amines it occurs in alcoholic solution in the presence of compounds such as ethyl malonate and acetylacetone which contain active hydrogen atoms 66), The direct reaction product from D-glucose and dibenzylamine was actually 1-dibenzylamino-l-deoxy-D-fructose (XI) 66) and not VjV-di-benzyl-D-glucosylamine (XII) as indicated earlier by Kuhn and Birkofer 76), This rearrangement was effected without benefit of acid catalysis 70) or by the use of ethyl malonate 66), The true V,i T-dibenzylglu-cosylamine (XII) could not be isolated. 

The preparation of crystalline methyl ethers of iV-phenyl- or Af-p-tolyl-aldosylamine by condensation of aniline or p-toluidine with aldose methyl ethers proceeds, in many cases, readily and quantitatively in methanolic or ethanolic solution, either at room or reflux temperature. For this reason, such derivatives are frequently used to characterize aldose methyl ethers isolated during constitutional studies on polysaccharides. For D-glucose, for example, crystalline 2-0-methyl-, 6-0-methyl-,3,4-di-O-methyl-, 2,3,4-tri-O-methyl-, 2,4,6-tri-O-methyl-, " and 2,3,4,6-tetra-O-methyl-A-phenyl-n-glucosylamine have been prepared in this way. Although anomeric forms of A -arylaldosylamine methyl ethers are possible, such anomeric pairs have not been isolated. No similar derivatives have been obtained from ketose methyl ethers. 

Di-O-methyl-A -(4-nitrophenyl)glucosylamine, D-739 Dimethyl-2-phenyl-l,3-dioxolane-4,5-dicarboxylate, T-12 A -(3,4-Dimethylphenyl)-L-ribitylamine, A-326... 

Amino-2-deoxy-p-D-glucopyranosyl-(l ->4)-2-amino-2-deoxy-r>-glucosylamine p-D-Pyranose-ybrm l- -(4-L-AspartyI), 2,2 -di- -Ac, A-241... 

The fructofurano-oxazoline 16 was obtained by reaction of 1,6-di-O-trityl-D-fructosc with cyanamide, and used in the construction of nucleoside analogues (see Chapter 20). The imidazoline 17 formed through solvent incorporation when l,3,4,6-tetra-0-acetyl-2-allyloxycarbonylamino-2-deoxy- 3-D-glucose was used as a glycosylating agent in acetonitrile. Synthesis of the cross-conjugated betaines 18 from glucosylamine has been reported. ... 

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