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Org. Synth. 1942, 22, 56
DOI: 10.15227/orgsyn.022.0056
β-d-GLUCOSE-1,2,3,4-TETRAACETATE
[D-Glucose, β-1,2,3,4-tetraacetyl-]
Submitted by Delbert D. Reynolds and William Lloyd Evans.
Checked by Lee Irvin, Smith R. T. Arnold, Newman Bortnick, Aaron Lerner, and Everett Schultz.
1. Procedure
A. 6-Trityl-β-d-glucose-1,2,3,4-tetraacetate. A mixture containing 120 g. (0.67 mole) of anhydrous glucose, 193.2 g. (0.7 mole) of trityl chloride, and 500 ml. of anhydrous pyridine [Org. Syntheses Coll. Vol. 1, 100 (1941)], is heated on the steam cone until solution is complete (Note 1). Without cooling, 360 ml. of acetic anhydride is added in one portion (Note 2). After standing for 12 hours, the reaction mixture is poured slowly into 10 l. of ice water, to which 500 ml. of acetic acid has been added, and the resulting mixture is vigorously stirred mechanically for 2 hours (Note 3). The precipitate is filtered and is immediately stirred for a short time with 10 l. of ice water. The white, granular precipitate is filtered, washed well with cold water, and then air-dried (Note 4). The dried solid is digested with 500 ml. of ether (Note 5). The insoluble portion is dissolved in hot 95% ethanol (approximately 3 l.), and the solution is decolorized and filtered while hot. The filtrate, upon cooling, deposits fine needles of 6-trityl-β-d-glucose-1,2,3,4-tetraacetate of sufficient purity for further use. The yield at this point is about 169 g. (43%). Recrystallization from 95% ethanol gives the pure compound which melts at 166–166.5°. In pyridine, [α]19D is + 44.8°; [α]28D, +45.3°. The yield of purified material is 137 g. (35%) (Note 6).
B. β-d-Glucose-1,2,3,4-tetraacetate. A solution of 46 g. (0.078 mole) of 6-trityl-β-d-glucose-1,2,3,4-tetraacetate in 200 ml. of acetic acid is prepared by warming on the steam bath. The solution is then cooled to approximately 10°, 18 ml. of a saturated solution of dry hydrogen bromide in acetic acid is added, and the reaction mixture is shaken for about 45 seconds. The trityl bromide formed during the reaction is removed at once by filtration, and the filtrate is poured immediately into 1 l. of cold water. The tetraacetate is extracted with 250 ml. of chloroform; the chloroform extract is washed four times with ice water and dried over anhydrous sodium sulfate. The drying agent is removed, and the chloroform is evaporated, under reduced pressure at room temperature. The remaining syrup is covered with 100 ml. of anhydrous ether and is rubbed with a glass rod. Crystallization takes place immediately. The product is removed and is purified by dissolving it in the minimum amount of chloroform and adding anhydrous ether until crystallization begins. The purified product melts at 128–129°. In chloroform, [α]20D is +12.1°. The yield is 15 g. (55%).
2. Notes
1. The materials and apparatus used for this reaction must be strictly anhydrous in order to prevent hydrolysis of the trityl chloride.
2. Higher temperatures favor formation of the β-isomer.
3. The stirring must be unusually rapid, and the solution must be added to the water slowly and in a fine stream. If this is not done, the precipitate will not be granular and will be extremely difficult to filter.
4. If the material warms up to room temperature during the time required for drying, it becomes exceedingly sticky, and mechanical difficulties in manipulation result. This behavior appears to be due to the presence of traces of pyridine. The checkers found that the pure product, m.p., 166–166.5°, when recrystallized from pyridine, gave a sticky material.
5. The α-isomer is soluble in ether, whereas the β-isomer is insoluble. In some cases the entire product dissolves, but the β-isomer separates when the solution is allowed to stand.
6. The submitters state that the yield of purified product varies from 148 g. to 180 g.
3. Discussion
These directions are modifications of the methods used by Helferich and Klein for the original preparation of the substance,1 although it had apparently previously been obtained by Oldham by hydrolysis of tetraacetylglucose-6-mononitrate.2

References and Notes
  1. Helferich and Klein, Ann., 450, 219 (1926); Helferich, Moog, and Junger, Ber., 58, 877 (1925).
  2. Oldham, J. Chem. Soc., 127, 2840 (1925).

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

D-Glucose, β-1,2,3,4-tetraacetyl-

ethanol (64-17-5)

acetic acid (64-19-7)

ether (60-29-7)

acetic anhydride (108-24-7)

chloroform (67-66-3)

hydrogen bromide (10035-10-6)

sodium sulfate (7757-82-6)

pyridine (110-86-1)

glucose (492-62-6)

trityl chloride (76-83-5)

trityl bromide (596-43-0)

tetraacetylglucose-6-mononitrate

β-D-Glucose-1,2,3,4-tetraacetate (13100-46-4)

6-trityl-β-d-glucose-1,2,3,4-tetraacetate