Org. Synth. 1940, 20, 23
DOI: 10.15227/orgsyn.020.0023
CYSTEIC ACID MONOHYDRATE
Submitted by H. T. Clarke
Checked by Henry Gilman and H. J. Harwood.
1. Procedure
To a solution of 24 g. (0.1 mole) of cystine in a cold mixture of 150 ml. of water and 50 ml. of concentrated hydrochloric acid is added, dropwise, 80 g. (25 ml., 0.5 mole) of commercial bromine, with occasional stirring, during 40 minutes. The temperature of the mixture rises to about 60°. The resulting solution, which contains a little unreduced bromine, is then evaporated under reduced pressure on a steam bath. The dark-colored crystalline residue is dissolved in 100 ml. of distilled water and filtered from a small quantity of amorphous insoluble matter. The filtrate is concentrated by evaporation on a water bath to 65 ml. and allowed to crystallize by standing overnight in a refrigerator. The crystals are filtered with suction and washed well with about 100 ml. of 95% ethanol in several portions, the washings being collected separately. The crystals are dried under reduced pressure over phosphorus pentoxide. A second crop is obtained by diluting the washings with an equal volume of water, evaporating until free of ethanol (Note 1), adding the residue to the mother liquor, and evaporating the combined solution to dryness on the water bath. The residue is dissolved in 30–40 ml. of water, decolorized with 0.5–1.0 g. of charcoal, concentrated to 15 ml., and, when cold, treated with 30 ml. of 95% ethanol. The crystals so formed are collected, washed with ethanol, and dried as before (Note 2). The total yield is 30.5–33.5 g. of pure cysteic acid monohydrate (81–90%). It melts, with vigorous evolution of gas, at 278° (289° cor.) (Note 3), and shows the rotation [α]54246 + 9.36° (6% in water).
2. Notes
1.
Cysteic acid appears to esterify readily on warming with
ethanol, but the resulting ester is rapidly hydrolyzed by warming with dilute mineral acid.
2.
The final mother liquors, on evaporation to dryness, yield 2–3 g. of a light-brown amorphous product which is readily soluble in water but insoluble in
95% ethanol. In concentrated
hydrobromic acid this by-product forms a dark solution, the color of which is discharged on dilution with water.
3.
The decomposition point of
278° is obtained by placing the capillary in a bath already heated to 260–270°. If the sample is slowly heated, starting at room temperature, a decomposition point of
257–258° is observed.
3. Discussion
The most convenient oxidant for the preparation of
cysteic acid from
cystine is aqueous
bromine.
1 Iodine2 and
hydrogen peroxide3 also bring about the reaction, but with both substances some of the
sulfur is split off as
sulfuric acid.
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
ethanol (64-17-5)
sulfuric acid (7664-93-9)
hydrochloric acid (7647-01-0)
HYDROBROMIC ACID (10035-10-6)
bromine (7726-95-6)
sulfur (7704-34-9)
iodine (7553-56-2)
hydrogen peroxide (7722-84-1)
cystine (56-89-3)
cysteic acid
Cysteic acid monohydrate (23537-25-9)
phosphorus pentoxide (1314-56-3)
Copyright © 1921-, Organic Syntheses, Inc. All Rights Reserved