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Org. Synth. 1931, 11, 50
DOI: 10.15227/orgsyn.011.0050
dl-GLYCERALDEHYDE
Submitted by E. J. Witzemann, Wm. Llloyd Evans, Henry Hass, and E. F. Schroeder.
Checked by Frank C. Whitmore and Harry T. Neher.
1. Procedure
A mixture of 50 g. (0.3 mole) of dl-glyceraldehyde acetal (p. 307) and 500 cc. of 0.1 N sulfuric acid is allowed to stand for one week at about 20° (Note 1). Thirty cubic centimeters of glacial acetic acid is added; the mixture is neutralized carefully with barium hydroxide solution (Note 2), stirred with 5 g. of decolorizing carbon, and filtered. The filtrate is evaporated at 10 mm. pressure (Note 3). When no more water can be removed, the residue is treated with an equal volume of absolute alcohol to hasten crystallization. The crystals are collected on a filter and dried in a vacuum desiccator over soda-lime and calcium chloride. The yield of product melting at 137–139° is 22 g. (80 per cent of the theoretical amount).
2. Notes
1. During the entire preparation, including the evaporation, the temperature should be kept below 30°. If this precaution is rigidly observed, the glyceraldehyde crystallizes readily.
2. Samples of the filtered solution should give only a very slight opalescence when tested with barium hydroxide and with sulfuric acid.
3. The use of 10 mm. instead of 20 mm. pressure for the evaporation improves the quality of the glyceric aldehyde, making the difference between a syrup which may or may not crystallize and a product which crystallizes even from the concentrated solution.
3. Discussion
dl-Glyceraldehyde has been obtained by the oxidation of glycerol with nitric acid,1 with bromine and sodium carbonate,2 and with hydrogen peroxide in the presence of ferrous salts;3 by the action of ultraviolet light on glycerol in neutral solution;4 by the action of sunlight on glycerol in the presence of uranium sulfate;5 by electrolysis of dl-erythronic acid;6 by the hydrolysis of dl-glyceraldehyde acetal;7 by the oxidation of acrolein;8 by the oxidation of benzal-1,3-propenediol followed by hydrolysis;9 and by the alkaline condensation of formaldehyde.10
This preparation is referenced from:

References and Notes
  1. Kiliani, Ber. 54, 467 (1921); Fischer and Tafel, ibid. 20, 3385 (1887).
  2. Fischer and Tafel, ibid. 20, 3385 (1887).
  3. Fenton and Jackson, Chem. News 78, 187 (1898); J. Chem. Soc. 75, 5 (1899); Witzemann, J. Am. Chem. Soc. 36, 2227 (1914).
  4. Bierry, Henri, and Ranc, Compt. rend. 152, 535 (1911).
  5. Neuberg, Biochem. Z. 13, 307 (1908).
  6. Neuberg, Scott, and Lachmann, ibid. 24, 157 (1910).
  7. Wohl, Ber. 31, 1800, 2395 (1898); Wohl and Neuberg, ibid. 33, 3100 (1900); Evans and Hass, J. Am. Chem. Soc. 48, 2706 (1926); Witzemann, ibid. 36, 1913 (1914); Spoehr and Young, Carnegie Inst. Washington Yearbook, 25, 177 (1925–1926); Exp. Sta. Record, 57, 817 (1927) [C. A. 22, 2368 (1928)].
  8. Neuberg, Biochem. Z. 221, 492 (1930); 255, 1 (1932).
  9. Fischer, Ahlström, and Richter, Ber. 64, 611 (1931).
  10. Kuzin, J. Gen. Chem. (U.S.S.R.) 8, 592 (1938) [C. A. 33, 1271 (1939)].

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

soda-lime

alcohol (64-17-5)

calcium chloride (10043-52-4)

sulfuric acid (7664-93-9)

acetic acid (64-19-7)

formaldehyde (50-00-0)

Acrolein (107-02-8)

glycerol (56-81-5)

nitric acid (7697-37-2)

sodium carbonate (497-19-8)

bromine (7726-95-6)

decolorizing carbon (7782-42-5)

hydrogen peroxide (7722-84-1)

barium hydroxide (17194-00-2)

glyceraldehyde,
glyceric aldehyde,
DL-Glyceraldehyde (56-82-6)

uranium sulfate

benzal-1,3-propenediol

DL-Glyceraldehyde acetal

dl-erythronic acid