Of glucosyl chloride

Direct C-glucosylation can also be effected by boiling methyl a-D-glucopyranoside in benzene in the presence of aluminum chloride and boron trichloride. In this way, 2,3,4,6-tetra-0-acetyl-/3-D-glucopyranosylbenzene was prepared in 32% yield.143 C-Glycosyla-... 

It is noteworthy that all attempts to convert 275 into the corresponding D-glucosyl bromide with hydrogen bromide in acetic acid were unsuccessful, because the reagent was also attached to the 2-(thiocyanato) group. Treatment of 275 with titanium tetrachloride in chloroform afforded crystalline 3,4,6-tri-0-acetyl-2-deoxy-2-(thiocyanato)-a-D-glucosyl chloride (277)... 

Lemieux32 has pointed out that the preparation by Brig]36 of 3,4,6-tri-0-acetyl-2-0-trichloroacetyl- -D-glucosyl chloride (XXI) through the interaction of penta-O-acetyl-0-D-glucopyranose (XVIII) with phosphorus pentachloride can be rationalized on the basis of modern chemical... 

Thus, Hickinbottom17 was able to prepare methyl a-D-glucopyranoside (in approximately 70% yield) by reaction of 3,4,6-tri-0-acetyl-2-0-tri-chloroacetyl-/3-D-glucosyl chloride in methanol, with silver oxide as catalyst and acceptor for hydrogen chloride. 

The further application of the mercuric acetate method made possible the synthesis of primeverose [6-0-/3-D-xylosyl-D-glucose] and also isoprime-verose [6-O-a-D-xylosyl-D-glucose] from 2,3,4-tri-O-acetyl-a-D-glucosyl chloride and tri-O-acetyl-D-xylosyl bromide. After the preparation of these sugars in larger quantities, the naturally occurring primeverosides could... 

The calcium salt of 2-amino-2-deoxy-D-glucosyl phosphate has been synthesized37 by the interaction of 2-acetamido-3,4,6-tri-0-acetyI-2-deoxy-a-D-glucosyl chloride with silver orthophosphate, with subsequent partial saponification. On the basis of optical rotation, the derivative has been assigned to the a-n series. 2-Amino-2-deoxy-D-glucosyl phosphate is much less stable than the 6-phosphate toward acidic hydrolysis, but it is markedly more... 

Since /8-D-gIucose pentaacetate had been shown to produce tetra-acetylglucosyl chloride in the presence of aluminum chloride,14 an attempt was made25 to employ the pentaacetate directly for the catalytic glucosylation of benzene. Such a scheme assumes that the acetylated aldose would undergo initial chlorination at the acylal function, and the intermediate chloride would then react with the aromatic hydrocarbon in the previously observed manner. Such a series of reactions was found to occur. 

When nine moles of phenyllithium in ether acted upon tetraacetyl-glucosyl chloride, the reaction mixture being subsequently decomposed with water, four products resulted. From the ether layer a quantitative yield of methyldiphenylcarbinol was recovered. Acetylation of the residue from the water layer, followed by fractional crystallization led to two crystalline substances and a residual sirup. The first crystalline product was (tetraacetyl-j3-D-glucopyranosyl)benzene (IV). The second m. p. 142-143°, [a]o24 — 2.3° (chloroform), appeared to be isomeric with IV. It oxidized to benzoic acid and deacetylated to give a sirup which consumed two moles of periodate with liberation of one mole of formic acid. While these properties are to be expected for a structure related to IV, this substance differed from both of the anomeric (tetraacetyl-n-glucopyranosyl)benzenes, nor did it appear to be a mixture of them. Its exact constitution is not yet known. 

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