Crotonic acid explained

Crotonic acid ((2E)-but-2-enoic acid) is a short-chain unsaturated carboxylic acid described by the formula CH3CH=CHCO2H. The name crotonic acid was given because it was erroneously thought to be a saponification product of croton oil.[1] It crystallizes as colorless needles from hot water. With a cis-alkene, Isocrotonic acid is an isomer of crotonic acid. Crotonic acid is soluble in water and many organic solvents. Its odor is similar to that of butyric acid.

Production

Crotonic acid produced industrially by oxidation of crotonaldehyde:[2]

A number of other methods exist, including the Knoevenagel condensation of acetaldehyde with malonic acid in pyridine:[2]

The alkaline hydrolysis of allyl cyanide followed by the intramolecular rearrangement of the double bond:[3] [4]

Furthermore, it is formed during the distillation of 3-hydroxybutyric acid:[5]

Properties

Crotonic acid crystallizes in the monoclinic crystal system in the space group P21/a (space group 14, position 3) with the lattice parameters,, and . The unit cell contains four formula units.[6]

Reactions

Crotonic acid converts into butyric acid by hydrogenation or by reduction with zinc and sulfuric acid.[7]

Upon treatment with chlorine or bromine, crotonic acid converts to 2,3-dihalobutyric acids:[7]

Crotonic acid adds hydrogen bromide to form 3-bromobutyric acid.[7] [8]

The reaction with alkaline potassium permanganate solution affords 2,3-dihydroxybutyric acid.[7]

Upon heating with acetic anhydride, crotonic acid converts to the acid anhydride:[9]

Esterification of crotonic acid using sulfuric acid as a catalyst provides the corresponding crotonate esters:

Crotonic acid reacts with hypochlorous acid to 2-chloro-3-hydroxybutyric acid. This can either be reduced with sodium amalgam to butyric acid, can form with sulfuric acid 2-chlorobutenoic acid, react with hydrogen chloride to 2,3-dichlorobutenoic acid or with potassium ethoxide to 3-methyloxirane-2-carboxylic acid.[10]

Crotonic acid reacts with ammonia at the alpha position in the presence of mercury(II) acetate. This reaction provides -threonine.

Use

Crotonic acid is mainly used as a comonomer with vinyl acetate. The resulting copolymers are used in paints and adhesives.

Crotonyl chloride reacts with N-ethyl-2-methylaniline (N-ethyl-o-toluidine) to provide crotamiton, which is used as an agent against scabies.[11]

Safety

Its is 1 g/kg (oral, rats). It irritates eyes, skin, and respiratory system.

See also

Notes and References

  1. Crotonic Acid. 7. 511.
  2. Book: Hans. Beyer. Wolfgang. Walter. Organische Chemie. de. S. Hirzel Verlag. Stuttgart. 1984. 3-7776-0406-2.
  3. A.. Rinne. Bernhard Tollens. B.. Tollens. Ueber das Allylcyanür oder Crotonitril. On allyl cyanide or crotononitrile. Justus Liebigs Annalen der Chemie. 1871. 159. 1. 105–109. 10.1002/jlac.18711590110.
  4. C.. Pomeranz. Ueber Allylcyanid und Allylsenföl. On allyl cyanide and allylic mustard oil. Justus Liebigs Annalen der Chemie. 1906. 351. 1–3. 354–362. 10.1002/jlac.19073510127.
  5. Book: F.. Beilstein. Handbuch der organischen Chemie. de. 3rd. 1. Verlag Leopold Voss. 1893. 506.
  6. S.. Shimizu. S.. Kekka. S.. Kashino. M.. Haisa. Topochemical Studies. III. The Crystal and Molecular Structures of Crotonic Acid, CH3CH=CHCO2H, and Crotonamide, CH3CH=CHCONH2. Bulletin of the Chemical Society of Japan. 1974. 47. 7. 1627–1631. 10.1246/bcsj.47.1627. free.
  7. Heilbron. Dictionary of Organic Compounds. Crotonic acid. 1. 1953. 615.
  8. J. M.. Lovén. H.. Johansson. Einige schwefelhaltige β-Substitutionsderivate der Buttersäure. Some sulfur-containing β-substitution derivatives of butyric acid. Berichte der deutschen chemischen Gesellschaft. 1915. 48. 2. 1254–1262. 10.1002/cber.19150480205.
  9. A. M.. Clover. G. F.. Richmond. The Hydrolysis of Organic Peroxides and Peracids. American Chemical Journal. 1903. 29. 3. 179–203.
  10. Book: F.. Beilstein. Handbuch der organischen Chemie. 3rd. 1. de. Verlag Leopold Voss. 1893. 562.
  11. Book: A.. Kleemann. J.. Engel. Pharmazeutische Wirkstoffe: Synthesen, Patente, Anwendungen. 2nd rev. and updated. 5. Georg Thieme Verlag. Stuttgart & New York. 3-13-558402-X. 251.