Org. Synth. 1940, 20, 14
DOI: 10.15227/orgsyn.020.0014
D-ARABINOSE
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
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
diphenylhydrazone
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)
arabinose,
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)
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