A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1938, 18, 3
DOI: 10.15227/orgsyn.018.0003
Submitted by T. W. Abbott, Richard T. Arnold, and Ralph B. Thompson.
Checked by Reynold C. Fuson and W. E. Holland.
1. Procedure
A solution of potassium hydroxide is prepared by dissolving 122 g. (2.2 moles; 1.5 times the theoretical amount) of potassium hydroxide in 700 cc. of 95 per cent methyl alcohol (Note 1) contained in a 2-l. round-bottomed flask provided with a reflux condenser. To this alkaline solution is added 100 g. (0.36 mole) of α,β-dibromosuccinic acid (p. 177), and the mixture is refluxed for one hour and fifteen minutes on a steam bath. The reaction mixture is cooled and filtered with suction. The mixed salts are washed with 200 cc. of methyl alcohol (Note 2) and dried by pressing between filter papers; when dry the product weighs 144–150 g.
This salt mixture is dissolved in 270 cc. of water, and the acid potassium salt is precipitated by adding 8 cc. of concentrated sulfuric acid in 30 cc. of water. After standing for three hours, or overnight, the mixture is filtered with suction (Note 3). The acid salt is then dissolved in 240 cc. of water to which 60 cc. of concentrated sulfuric acid has been added, and the solution is extracted with five 100-cc. portions of ether. The combined ether solutions are evaporated to dryness on a steam bath, leaving pure hydrated crystals of acetylenedicarboxylic acid. After drying for two days over concentrated sulfuric acid in a vacuum desiccator the crystals decompose sharply at 175–176°. The yield is 30–36 g. (73–88 per cent of the theoretical amount).
2. Notes
1. The yield is slightly lower when 95 per cent ethyl alcohol is used.
2. This salt mixture is composed of potassium bromide and potassium acetylenedicarboxylate.
3. This acid salt is practically bromine-free and does not require additional washing.
3. Discussion
The procedure described is essentially that of Bandrowski1 and Baeyer2 as modified by Ruggli.3 The same general method has also been used by Backer and van der Zanden,4 and by Moureu and Bongrand.5
This preparation is referenced from:

References and Notes
  1. Bandrowski, Ber. 10, 838 (1877).
  2. Baeyer, ibid. 18, 677 (1885).
  3. Ruggli, Helv. Chim. Acta 3, 564 (1920).
  4. Backer and van der Zanden, Rec. trav. chim. 47, 776 (1928).
  5. Moureu and Bongrand, Ann. chim. (9) 14, 9 (1920).

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

ethyl alcohol (64-17-5)

sulfuric acid (7664-93-9)

methyl alcohol (67-56-1)

ether (60-29-7)

potassium hydroxide (1310-58-3)

potassium bromide (7758-02-3)

Acetylenedicarboxylic acid (142-45-0)

α,β-Dibromosuccinic acid (526-78-3)

potassium acetylenedicarboxylate