Org. Synth. 1931, 11, 74
DOI: 10.15227/orgsyn.011.0074
MESACONIC ACID
Submitted by R. L. Shriner, S. G. Ford, and L. J. Roll.
Checked by C. R. Noller
1. Procedure
A mixture of 100 g. (0.89 mole) of citraconic anhydride (Note 1) 100 cc. of water, and 150 cc. of dilute nitric acid (1 part of concentrated nitric acid to 4 parts of water by volume) is evaporated in a 500-cc. Erlenmeyer flask until the appearance of red fumes (Note 2). The solution is cooled and the mesaconic acid is collected on a filter. The mother liquor is evaporated to 150 cc., cooled, and the crystalline solid which separates is collected on a filter. Further concentration of the mother liquor to 50 cc. yields more product (Note 3). The entire product is recrystallized from 100 cc. of water. The yield of mesaconic acid melting at 203–205° is 50–60 g. (43–52 per cent of the theoretical amount).
2. Notes
1.
An equivalent amount of
citraconic acid can be used. Directions for preparing
citraconic acid and anhydride are given on
p. 140.
2.
It is necessary to carry the evaporation to the point where red fumes appear in order for the rearrangement to take place. The volume is usually about 250 cc.
3.
The concentration of the mother liquor must be carried out in steps in order to obtain an efficient separation of
mesaconic acid.
3. Discussion
Mesaconic acid has been prepared by heating
citraconic acid with dilute
nitric acid,
1 with
hydriodic acid,
2 or with concentrated
sodium hydroxide solution;
3 by heating a concentrated water solution of
itaconic or citraconic acid at 180–200°;
4 by treating
citradibromopyrotartaric acid and
mesodibromopyrotartaric acid with
potassium iodide and
copper at 150°;
5 and by heating
citraconic anhydride with
nitric acid.
6
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
citraconic acid and anhydride
itaconic or citraconic acid
citradibromopyrotartaric acid
sodium hydroxide (1310-73-2)
nitric acid (7697-37-2)
potassium iodide (7681-11-0)
copper (7440-50-8)
hydriodic acid (10034-85-2)
Citraconic anhydride (616-02-4)
Citraconic acid (498-23-7)
Mesaconic acid (498-24-8)
mesodibromopyrotartaric acid
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