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Org. Synth. 1945, 25, 53
DOI: 10.15227/orgsyn.025.0053
β-d-GLUCOSE-2,3,4,6-TETRAACETATE
[D-Glucose, β-2,3,4,6-tetraacetyl-]
Submitted by Chester M. McCloskey and George H. Coleman.
Checked by C. S. Hamilton, Robert Angier, and Ivan Baumgart.
1. Procedure
A solution of 82.2 g. (0.2 mole) of acetobromoglucose (p. 11) (Note 1) in 125 ml. of dry acetone (Note 2) in a 250-ml. flask is cooled to 0° in an ice bath. To the cold solution is added 2.3 ml. of water and then 46.5 g. (0.17 mole) of silver carbonate (Note 3) in small portions in the course of 15 minutes. The mixture is shaken well during the addition and for 30 minutes longer (Note 4). The mixture is then warmed to 50–60° and filtered. The mass of silver salts is washed with 65 ml. of dry acetone (Note 5), removed from the funnel, warmed in a flask with 65 ml. more of acetone, filtered, and washed again on the funnel.
The combined filtrates are concentrated under reduced pressure in a 500-ml. filter flask (Note 6) until most of the solution is filled with crystals. The mixture is warmed to dissolve the crystals, the solution is poured into a 600-ml. beaker, and an equal volume of absolute ether and a similar volume of ligroin are added. The resulting solution is cooled in a freezing mixture with gentle stirring. The crystals of the tetraacetate form quickly and after about 10 minutes are filtered and air-dried. The crystals so obtained melt at 132–134° (Note 7). If a purer product is required, the product is dissolved in acetone, and ether and ligroin are added to the solution in the manner described. The yield of once-crystallized product melting at 132–134° is 52–56 g. (75–80%).
2. Notes
1. The acetobromoglucose that was used had a melting point of 87–88°.
2. The acetone was dried over calcium chloride.
3. The silver carbonate should be freshly prepared and finely ground. Silver carbonate can be prepared by the addition of a solution of sodium carbonate (53 g. in 600 ml. of water) to one of silver nitrate (172 g. in 2 l. of water). This is a very slight excess of the silver nitrate. The sodium carbonate solution is added slowly (10 minutes), and the reaction mixture is stirred vigorously with a mechanical stirrer. The silver carbonate is filtered, washed with a little acetone to facilitate drying, and then air-dried. All operations are carried out in dim light.
4. At the end of this time, evolution of carbon dioxide should no longer be appreciable. The time required for the reaction depends largely on the agitation of the silver carbonate. In large runs mechanical stirring is required.
5. Anhydrous chemicals are used throughout as the presence of any appreciable amount of water interferes with the crystallization of the tetraacetate.
6. The solution is not heated during the concentration, and thus the temperature is maintained below that of the room by the evaporation of the solvent. If a capillary is used it should be equipped with a drying tube.
7. β-d-Glucose-2,3,4,6-tetraacetate (2,3,4,6-tetraacetyl-β-d-glucose) decomposes slightly on prolonged standing and after 1–2 months has a melting range of 5–8 degrees. Such material can be purified by recrystallization.
3. Discussion
β-d-Glucose-2,3,4,6-tetraacetate has been prepared usually by the hydrolysis of acetobromoglucose.1

References and Notes
  1. Fischer and Delbruck, Ber., 42, 2776 (1909); Georg, Helv. Chim. Acta, 15, 924 (1932); Hendricks, Wulf, and Liddel, J. Am. Chem. Soc., 58, 1998 (1936); McCloskey, Pyle, and Coleman, J. Am. Chem. Soc., 66, 349 (1944).

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

ligroin

calcium chloride (10043-52-4)

ether (60-29-7)

silver nitrate (7761-88-8)

sodium carbonate (497-19-8)

carbon dioxide (124-38-9)

acetone (67-64-1)

d-Glucose (492-62-6)

Acetobromoglucose (572-09-8)

β-D-Glucose-2,3,4,6-tetraacetate

silver carbonate (534-16-7)

2,3,4,6-tetraacetyl-β-d-glucose