Glucosyl chloride

By treating 2,3,4,6-tetra-O-acetyl-a-D-glucosyl chloride in ether solution with silver nitrate (Schlubach, Stadtler, Wolf [19]) 2,3,4,6-O-acetyl-a-D-glucosyl nitrate was obtained. 

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... 

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. 

Silyl derivatives of purines are commonly used in the same way as in a synthesis of 9-(a, -D-glucopyranosyl)adenine from AT -benzoyl-9-bis(trimethylsilyl)adenine and 2,3,4,6-tetra-O-acetyl-a-D-glucosyl chloride at 150-160 °C over 4 hours to produce, after deblocking, a mixture of anomeric nucleosides (B-68MI40901,p. 135). The hypoxanthine nucleosides may be obtained in a similar fashion or by deamination of the adenine derivatives. 

Glucosyl bromide, 3,4,6-tri-0-acetyl-2-0-(methylsulfonyl)-a-D-, 264 Glucosyl chloride, 3,4,6-tri-0-acetyl-2-0-p-tolylsulfonyl-jS-D-, 264 Glucosyl cobalt tricarbonyl triphenyl-phosphine, 2,3,4,6-tetra-0-acetyl-/3-D-, 109... 

When a- or 8-D-glucopyranose pentaacetate is treated with piperidine (three molecular proportions are best), deacetylation occurs on Cl and C2, and the product is iV -(3,4,6-tri-0-acetyl-D-glucosyl)piperidine, whose structure was proved by conventional methods, including its conversion into 2-0-methyl-D-glucose. The same triacetate is obtained when piperidine reacts with 3,4,6-tri-O-acetyl-D-glucosyl chloride or with D-glucose 2,3,4,6-tetraacetate. Loss of the acetyl group on C2 must accompany or... 

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