Crotonic acid

Crotonic acid
Names
	Preferred IUPAC name (2E)-But-2-enoic acid
	Other names (E)-But-2-enoic acid; (E)-2-Butenoic acid; Crotonic acid; trans-2-Butenoic acid; β-Methylacrylic acid; 3-Methylacrylic acid
Identifiers
CAS Number	107-93-7 ;
3D model (JSmol)	Interactive image; Interactive image;
ChEBI	CHEBI:41131 ;
ChEMBL	ChEMBL1213528 ;
ChemSpider	552744 ;
DrugBank	DB02074 ;
ECHA InfoCard	100.003.213
PubChem CID	637090;
UNII	YW5WZZ4O5Q ;
CompTox Dashboard (EPA)	DTXSID30880973 ;
	InChI InChI=1S/C4H6O2/c1-2-3-4(5)6/h2-3H,1H3,(H,5,6)/b3-2+ Key: LDHQCZJRKDOVOX-NSCUHMNNSA-N ; InChI=1/C4H6O2/c1-2-3-4(5)6/h2-3H,1H3,(H,5,6)/b3-2+ Key: LDHQCZJRKDOVOX-NSCUHMNNBH;
	SMILES C/C=C/C(O)=O; O=C(O)/C=C/C;
Properties
Chemical formula	C4H6O2
Molar mass	86.090 g·mol−1
Density	1.02 g/cm3
Melting point	70 to 73 °C (158 to 163 °F; 343 to 346 K)
Boiling point	185 to 189 °C (365 to 372 °F; 458 to 462 K)
Acidity (pKa)	4.69 [1]
Hazards
Safety data sheet (SDS)	SIRI.org
Related compounds
Other anions	crotonate
Related carboxylic acids	propionic acid; acrylic acid; butyric acid; succinic acid; malic acid; tartaric acid; fumaric acid; pentanoic acid; tetrolic acid
Related compounds	butanol; butyraldehyde; crotonaldehyde; 2-butanone
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Crotonic acid ((2E)-but-2-enoic acid) is a short-chain unsaturated carboxylic acid, described by the formula CH₃CH=CHCO₂H. It is called crotonic acid because it was erroneously thought to be a saponification product of croton oil.[2] 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:[3][4]^: 230

CH₃CH=CHCHO + 1/₂ O₂ → CH₃CH=CHCO₂H

A number of other methods exist, including the Knoevenagel condensation of acetaldehyde with malonic acid in pyridine:[3]^: 229

Synthesis of crotonic acid by the Knoevenagel condensation of acetaldehyde and malonic acid

The alkaline hydrolysis of allyl cyanide followed by the intramolecular rearrangement of the double bond:[5][6]

Furthermore, it is formed during the distillation of 3-hydroxybutyric acid:[7]

Properties

Crotonic acid crystallizes in the monoclinic crystal system in the space group P21/a (space group 14, position 3) with the lattice parameters a = 971 pm, b = 690 pm, c = 775 pm and β = 104.0°. The unit cell contains four formula units.[8]

Reactions

Crotonic acid converts into butyric acid by hydrogenation or by reduction with zinc and sulfuric acid.[9]

Upon treatment with chlorine or bromine, crotonic acid converts to 2,3-dihalobutyric acids:[9]

Crotonic acid adds hydrogen bromide to form 3-bromobutyric acid.[9][10]

The reaction with alkaline potassium permanganate solution affords 2,3-dihydroxybutyric acid.[9]

Reaction of crotonic acid with alkaline potassium permanganate solution.

Upon heating with acetic anhydride, crotonic acid converts to the acid anhydride:[11]

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.[12]

Reaction of crotonic acid into 2-chloro-3-hydroxybutanoic acid and subsequent reactions

Crotonic acid reacts with ammonia at the alpha position in the presence of mercury(II) acetate. This reaction provides DL-threonine.[13]

Use

Crotonic acid is mainly used as a comonomer with vinyl acetate.[14] The resulting copolymers are used in paints and adhesives.[4]

Crotonyl chloride reacts with N-ethyl-2-methylaniline (N-ethyl-o-toluidine) to provide crotamiton, which is used as an agent against scabies.[15]

Crotamiton synthesis

Safety

Its LD₅₀ is 1 g/kg (oral, rats).[4] It irritates eyes, skin, and respiratory system.[14]

References

Dawson, R. M. C.; et al. (1959). Data for Biochemical Research. Oxford: Clarendon Press.
Chisholm, Hugh, ed. (1911). "Crotonic Acid" . Encyclopædia Britannica. Vol. 7 (11th ed.). Cambridge University Press. p. 511.
Beyer, Hans; Walter, Wolfgang (1984). Organische Chemie (in German). Stuttgart: S. Hirzel Verlag. ISBN 3-7776-0406-2.
Schulz, R. P.; Blumenstein, J.; Kohlpaintner, C. (2005). "Crotonaldehyde and Crotonic Acid". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a08_083.
Rinne, A.; Tollens, B. (1871). "Ueber das Allylcyanür oder Crotonitril" [On allyl cyanide or crotononitrile]. Justus Liebigs Annalen der Chemie. 159 (1): 105–109. doi:10.1002/jlac.18711590110.
Pomeranz, C. (1906). "Ueber Allylcyanid und Allylsenföl" [On allyl cyanide and allylic mustard oil]. Justus Liebigs Annalen der Chemie. 351 (1–3): 354–362. doi:10.1002/jlac.19073510127.
Beilstein, F. (1893). Handbuch der organischen Chemie (in German). Vol. 1 (3rd ed.). Verlag Leopold Voss. p. 506.
Shimizu, S.; Kekka, S.; Kashino, S.; Haisa, M. (1974). "Topochemical Studies. III. The Crystal and Molecular Structures of Crotonic Acid, CH₃CH=CHCO₂H, and Crotonamide, CH₃CH=CHCONH₂". Bulletin of the Chemical Society of Japan. 47 (7): 1627–1631. doi:10.1246/bcsj.47.1627.
Heilbron (1953). "Crotonic acid". Dictionary of Organic Compounds. 1: 615.
Lovén, J. M.; Johansson, H. (1915). "Einige schwefelhaltige β-Substitutionsderivate der Buttersäure" [Some sulfur-containing β-substitution derivatives of butyric acid]. Berichte der deutschen chemischen Gesellschaft. 48 (2): 1254–1262. doi:10.1002/cber.19150480205.
Clover, A. M.; Richmond, G. F. (1903). "The Hydrolysis of Organic Peroxides and Peracids". American Chemical Journal. 29 (3): 179–203.
Beilstein, F. (1893). Handbuch der organischen Chemie (in German). Vol. 1 (3rd ed.). Verlag Leopold Voss. p. 562.
Carter, H. E.; West, H. D. (1955). "dl-Threonine". Organic Syntheses.; Collective Volume, vol. 3, p. 813
Entry on Butensäuren. at: Römpp Online. Georg Thieme Verlag, retrieved January 7, 2020.
Kleemann, A.; Engel, J. Pharmazeutische Wirkstoffe: Synthesen, Patente, Anwendungen. Vol. 5 (2nd rev. and updated ed.). Stuttgart & New York: Georg Thieme Verlag. p. 251. ISBN 3-13-558402-X.

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[1] Dawson, R. M. C.; et al. (1959). Data for Biochemical Research. Oxford: Clarendon Press.

[2] Chisholm, Hugh, ed. (1911). "Crotonic Acid" . Encyclopædia Britannica. Vol. 7 (11th ed.). Cambridge University Press. p. 511.

[Beyer-3] Beyer, Hans; Walter, Wolfgang (1984). Organische Chemie (in German). Stuttgart: S. Hirzel Verlag. ISBN 3-7776-0406-2.

[Schulz-4] Schulz, R. P.; Blumenstein, J.; Kohlpaintner, C. (2005). "Crotonaldehyde and Crotonic Acid". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a08_083.

[Tollens-5] Rinne, A.; Tollens, B. (1871). "Ueber das Allylcyanür oder Crotonitril" [On allyl cyanide or crotononitrile]. Justus Liebigs Annalen der Chemie. 159 (1): 105–109. doi:10.1002/jlac.18711590110.

[Pomeranz-6] Pomeranz, C. (1906). "Ueber Allylcyanid und Allylsenföl" [On allyl cyanide and allylic mustard oil]. Justus Liebigs Annalen der Chemie. 351 (1–3): 354–362. doi:10.1002/jlac.19073510127.

[Beilstein-7] Beilstein, F. (1893). Handbuch der organischen Chemie (in German). Vol. 1 (3rd ed.). Verlag Leopold Voss. p. 506.

[Shimizu-8] Shimizu, S.; Kekka, S.; Kashino, S.; Haisa, M. (1974). "Topochemical Studies. III. The Crystal and Molecular Structures of Crotonic Acid, CH₃CH=CHCO₂H, and Crotonamide, CH₃CH=CHCONH₂". Bulletin of the Chemical Society of Japan. 47 (7): 1627–1631. doi:10.1246/bcsj.47.1627.

[DOC-9] Heilbron (1953). "Crotonic acid". Dictionary of Organic Compounds. 1: 615.

[Loven-10] Lovén, J. M.; Johansson, H. (1915). "Einige schwefelhaltige β-Substitutionsderivate der Buttersäure" [Some sulfur-containing β-substitution derivatives of butyric acid]. Berichte der deutschen chemischen Gesellschaft. 48 (2): 1254–1262. doi:10.1002/cber.19150480205.

[Clover-11] Clover, A. M.; Richmond, G. F. (1903). "The Hydrolysis of Organic Peroxides and Peracids". American Chemical Journal. 29 (3): 179–203.

[Beilstein2-12] Beilstein, F. (1893). Handbuch der organischen Chemie (in German). Vol. 1 (3rd ed.). Verlag Leopold Voss. p. 562.

[13] Carter, H. E.; West, H. D. (1955). "dl-Threonine". Organic Syntheses.; Collective Volume, vol. 3, p. 813

[:0-14] Entry on Butensäuren. at: Römpp Online. Georg Thieme Verlag, retrieved January 7, 2020.

[15] Kleemann, A.; Engel, J. Pharmazeutische Wirkstoffe: Synthesen, Patente, Anwendungen. Vol. 5 (2nd rev. and updated ed.). Stuttgart & New York: Georg Thieme Verlag. p. 251. ISBN 3-13-558402-X.