A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1930, 10, 1
DOI: 10.15227/orgsyn.010.0001
[2-Propanone, 1-hydroxy-]
Submitted by P. A. Levene and A. Walti.
Checked by Frank C. Whitmore and J. Pauline Hollingshead.
1. Procedure
In a 3-l. round-bottomed flask fitted with a 75-cm. Liebig condenser is placed 210 g. of potassium hydroxide (purified with alcohol) dissolved in 1.5 l. of anhydrous methyl alcohol. The solution is cooled to below 50° (Note 1), 300 g. of purified ethyl formate is added, and the mixture is refluxed for two hours (Note 2) and (Note 3).
Then 410 g. (251 cc., 3 moles) of bromoacetone (p. 88) is added, and the mixture is refluxed for sixteen hours on a water bath at 95–97°. At the end of the operation the solution is cooled to 0° in an ice-salt bath. The potassium bromide which settles is filtered on a cooled suction filter, and the filtrate is fractionated.
The fraction boiling at 23–35°/12 mm. is discarded, as it contains very little acetol. The main fraction distils at 35–47°/12 mm. and weighs 160 g. This material is refractionated, and the portion boiling at 40–43°/12 mm. is collected. The yield is 120–130 g. (54–58 per cent of the theoretical amount) (Note 4).
2. Notes
1. It is necessary to cool the mixture below 50° to prevent loss of the volatile ethyl formate.
2. Technical ethyl formate was purified by washing with 3 per cent sodium carbonate solution, then with cold water, drying over anhydrous sodium sulfate, filtering, and fractionating. Compare p. 180. It is very important that all the materials used in the synthesis of acetol be anhydrous, as otherwise condensation products are formed.
3. If commercial potassium formate is used it should be dried under reduced pressure at 80°. One and one-half to two moles should be used per mole of the bromo compound.
4. Acetol polymerizes very readily on standing but remains unchanged when dissolved in an equal volume of methyl alcohol.
3. Discussion
Acetol has usually been prepared by the reaction between bromoacetone and sodium or potassium formate or acetate, followed by hydrolysis of the ester with methyl alcohol.1, 2 Treatment of glycerol3 or propylene glycol4 at 200–300° with a dehydrogenating catalyst leads to the formation of acetol, while the direct oxidation of acetone with Baeyer and Villiger's acetone-peroxide reagent furnishes acetol together with pyruvic acid.5

References and Notes
  1. Nef, Ann. 335, 247, 260 (1904).
  2. Urion, Ann. chim. (11) 1, 78 (1934).
  3. Holmes, Brit. pat. 428,462 [C. A. 29, 6908 (1935)].
  4. Carbide and Carbon Chemicals Corporation, U. S. pat. 2,143,383 [C. A. 33, 2914 (1939)].
  5. Pastureau, Bull. soc. chim. (4) 5, 227 (1909).

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

sodium or potassium formate

Baeyer and Villiger's acetone-peroxide reagent

alcohol (64-17-5)

Acetol (64-19-7)

methyl alcohol (67-56-1)

glycerol (56-81-5)

sodium carbonate (497-19-8)

sodium sulfate (7757-82-6)

acetone (67-64-1)

potassium hydroxide (1310-58-3)

potassium bromide (7758-02-3)

ethyl formate (109-94-4)

Pyruvic acid (127-17-3)

2-Propanone, 1-hydroxy- (116-09-6)

Bromoacetone (598-31-2)

potassium formate

propylene glycol (57-55-6)