Org. Synth. 1940, 20, 14
DOI: 10.15227/orgsyn.020.0014
Submitted by Géza Braun
Checked by H. T. Clarke and S. M. Nagy.
1. Procedure
A solution of 100 g. (0.26 mole) of pentaacetyl glucononitrile (p. 690) in 150 ml. of chloroform in a 1-l. Erlenmeyer flask is chilled to −12°. A chilled (−12°) solution of 16 g. (0.7 gram atom) of sodium in 250 ml. of anhydrous methanol is added with continual shaking and chilling to the chloroform solution of the nitrile. The mixture soon solidifies to a pale yellow gelatinous mass. After 10 minutes at −12° this is broken up with a heavy glass rod and dissolved in 600 ml. of a suspension of ice in water. The resulting solution is acidified with an ice-cold mixture of 33 g. (18 ml., 0.32 mole) of 95% sulfuric acid, 5 ml. of acetic acid, and 45 g. of ice. The aqueous layer is separated, washed once with 50 ml. of chloroform, and evaporated without delay (Note 1) under reduced pressure. The residual heavy syrup is dissolved in 300 ml. of water and again evaporated as completely as possible under reduced pressure, in order to remove residual hydrogen cyanide (Note 2). The highly viscous residue, which contains some crystals of sodium sulfate, is dissolved in 500 ml. of hot methanol. After about 10 minutes the sodium sulfate is filtered with suction and washed with two 25-ml. portions of methanol. The filtrate is concentrated under reduced pressure at 40° to a heavy syrup which is poured while warm into a 200-ml. Erlenmeyer flask. The distilling flask is rinsed twice with 20-ml. portions of hot ethanol, and this rinse is added to the filtrate. The resulting ethanol solution soon begins to deposit crystals of arabinose; it is stirred by hand during the crystallization and gradually diluted with more ethanol until 100 ml. in all has been added during the course of an hour. The mixture is allowed to stand for 4–5 hours; the crystals are then filtered, washed with two 25-ml. portions of ethanol, and dried at 40°. The yield of colorless D-arabinose, m.p. 158–158.5°, [α]D20 −105° (final value), is 23.5–26.3 g. (61–68%) (Note 3).
2. Notes
1. After the reaction mixture has been dissolved in water and acidified, the hydrogen cyanide should be removed as soon as possible, for the arabinose tends to react with it even in dilute solution.
2. A slightly higher yield of crystalline arabinose is obtainable by removing the hydrogen cyanide with silver acetate. The procedure then consists in acidifying with acetic acid in place of sulfuric acid, adding an excess of silver acetate, shaking for an hour, filtering, saturating with hydrogen sulfide, again filtering, and adding sulfuric acid as indicated above. The rest of the procedure is the same. The yield of crystalline arabinose so obtained is 27.1 g. (70%).
3. A further quantity of arabinose may be isolated from the mother liquors by the use of diphenylhydrazine: to a solution of 22 g. of diphenylhydrazine hydrochloride in 100 ml. of absolute methanol is added a solution of 3.3 g. of sodium in 50 ml. of methanol. After 15 minutes' standing the sodium chloride is removed by filtration and washed with methanol. The filtrate, which contains approximately 18 g. of free diphenylhydrazine, is added to the alcoholic mother liquor from the arabinose, and the mixture is inoculated with diphenylhydrazone prepared from some of the crystalline arabinose. The mixture is allowed to stand overnight, and the crystalline diphenylhydrazone is filtered, washed with 95% ethanol, and dried in a vacuum desiccator. In a preparation in which the yield of crystalline arabinose had been 23.5 g., the yield of diphenylhydrazone was 16.5 g., corresponding to 7.8 g. of the sugar. Arabinose can be recovered from the diphenylhydrazone by treatment with formaldehyde in aqueous solution. In view of the high cost of diphenylhydrazine, however, it is doubtful whether its use for this purpose is profitable.
3. Discussion
D-Arabinose was first prepared by Wohl,1 by treating pentaacetyl glucononitrile with ammoniacal silver nitrate. It has also been obtained from d-gluconic acid in various ways: by oxidation of the calcium salt by means of hydrogen peroxide in the presence of ferric acetate;2,3,4,5 by boiling an aqueous solution of the mercuric salt;6 by electrolysis;7 by the action of sodium hypochlorite upon the amide.8 It has also been obtained by the electrolytic reduction of D-arabonic acid lactone.9 The present method, developed by Zemplén and Kiss,10 furnishes better yields than that of Wohl.
A modification of the Ruff method,2 using ion-exchange resins for the removal of salts, has been published.11

References and Notes
  1. Wohl, Ber., 26, 730 (1893).
  2. Ruff, Ber., 32, 553 (1899).
  3. Hockett and Hudson, J. Am. Chem. Soc., 56, 1632 (1934).
  4. Jones, Kent, and Stacey, J. Chem. Soc., 1947, 1341.
  5. Berezovskii and Kurdyukova, Zhur. Priklad. Khim., 22, 1116 (1949) [C. A., 45, 5628 (1951)].
  6. Guerbet, Bull. soc. chim. France, (4) 3, 427 (1908).
  7. Neuberg, Biochem. Z., 7, 527 (1908).
  8. Weermann, Rec. trav. chim., 37, 16 (1918).
  9. Swiss pat. 258,581 [C. A., 44, 4352 (1950)].
  10. Zemplén and Kiss, Ber., 60, 165 (1927).
  11. Fletcher, Diehl, and Hudson, J. Am. Chem. Soc., 72, 4546 (1950).

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


ammoniacal silver nitrate

ethanol (64-17-5)

sulfuric acid (7664-93-9)

acetic acid (64-19-7)

methanol (67-56-1)

formaldehyde (50-00-0)

chloroform (67-66-3)

sodium chloride (7647-14-5)

hydrogen sulfide (7783-06-4)

hydrogen cyanide (74-90-8)

sodium sulfate (7757-82-6)

d-ARABINOSE (28697-53-2)

sodium (13966-32-0)

hydrogen peroxide (7722-84-1)

sodium hypochlorite (7681-52-9)

silver acetate (563-63-3)

pentaacetyl glucononitrile

diphenylhydrazine (530-50-7)

diphenylhydrazine hydrochloride (530-47-2)

ferric acetate

d-arabonic acid lactone

d-gluconic acid (526-95-4)