Hydantoin,orglycolylurea,is aheterocyclicorganic compoundwith the formula CH2C(O)NHC(O)NH. It is a colorless solid that arises from the reaction ofglycolic acidandurea.It is an oxidized derivative ofimidazolidine.In a more general sense, hydantoins can refer togroupsor a class of compounds with the same ring structure as the parent compound. For example,phenytoin(mentioned below) has twophenylgroups substituted onto the number 5 carbon in a hydantoin molecule.[1]
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| Preferred IUPAC name
Imidazolidine-2,4-dione | |||
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3D model (JSmol)
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| ECHA InfoCard | 100.006.650 | ||
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CompTox Dashboard(EPA)
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| Properties | |||
| C3H4N2O2 | |||
| Molar mass | 100.077g·mol−1 | ||
| Melting point | 220 °C (428 °F; 493 K) | ||
| 39.7 g/l (100 °C) | |||
Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).
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Synthesis
editHydantoin was first isolated in 1861 byAdolf von Baeyerin the course of his study ofuric acid.He obtained it byhydrogenationofallantoin,hence the name.
Friedrich Urech synthesized 5-methylhydantoin in 1873 fromalaninesulfateandpotassium cyanatein what is now known as theUrech hydantoin synthesis.[2]The method is very similar to the modern route using alkyl and arylcyanates. The 5,5-dimethyl compound can also be obtained fromacetone cyanohydrin(also discovered by Urech: seecyanohydrin reaction) andammonium carbonate.[3]This reaction type is called theBucherer–Bergs reaction.[4][5]
Hydantoin can also be synthesized either by heatingallantoinwithhydroiodic acidor by "heating bromacetyl urea with alcoholic ammonia".[6]The cyclic structure of hydantoins was confirmed byDorothy Hahn1913.[7]
Of practical importance, hydantoins are obtained by condensation of acyanohydrinwithammonium carbonate.Another useful route, which follows the work of Urech, involves the condensation of amino acids with cyanates and isocyanates:
Uses and occurrence
editPharmaceuticals
editThe hydantoin group can be found in several medicinally important compounds.[1]In pharmaceuticals, hydantoinderivativesform a class ofanticonvulsants;[8]phenytoinandfosphenytoinboth contain hydantoin moieties and are both used as anticonvulsants in the treatment of seizure disorders. The hydantoin derivativedantroleneis used as a muscle relaxant to treatmalignant hyperthermia,neuroleptic malignant syndrome,spasticity,andecstasyintoxication.Ropitoinis an example of anantiarrhythmichydantoin.
Pesticides
editThe hydantoin derivativeImiprothrinis a pyrethroidinsecticide.Iprodioneis a popular fungicide containing the hydantoin group.[9]
Synthesis of amino acids
editHydrolysis of hydantoins affords amino acids:
Hydantoin itself reacts with hot, dilutehydrochloric acidto giveglycine.Methionine is produced industrially via the hydantoin obtained frommethional.[9]
Methylation
editMethylationof hydantoin yields a variety of derivatives.Dimethylhydantoin(DMH)[10]may refer to any dimethyl derivative of hydantoin, but especially5,5-dimethylhydantoin.[11]
Halogenation
editSomeN-halogenated derivatives of hydantoin are used as chlorinating or brominating agents indisinfectant/sanitizer orbiocideproducts. The three majorN-halogenated derivatives aredichlorodimethylhydantoin(DCDMH),bromochlorodimethylhydantoin(BCDMH), anddibromodimethylhydantoin(DBDMH). A mixed ethyl-methyl analogue, 1,3-dichloro-5-ethyl-5-methylimidazolidine-2,4-dione (bromochloroethylmethylhydantoin), is also used in mixtures with the above.
DNA oxidation to hydantoins after cell death
editA high proportion ofcytosineandthyminebases inDNAare oxidized to hydantoins over time after the death of an organism. Such modifications block DNA polymerases and thus preventsPCRfrom working. Such damage is a problem when dealing with ancient DNA samples.[12]
External links and further reading
edit
- Ware, Elinor (1950). "The Chemistry of the Hydantoins".Chem. Rev.46(3): 403–470.doi:10.1021/cr60145a001.PMID24537833.
- [1]Archived2020-10-18 at theWayback MachineEnglish Translation of 1926 German review article on the Preparation of hydantoins by Heinrich Biltz and Karl Slotta
References
edit- ^abKonnert, Laure; Lamaty, Frédéric; Martinez, Jean; Colacino, Evelina (2017)."Recent Advances in the Synthesis of Hydantoins: The State of the Art of a Valuable Scaffold"(PDF).Chemical Reviews.117(23): 13757–13809.doi:10.1021/acs.chemrev.7b00067.PMID28644621.S2CID23653941.
- ^Urech, Friedrich (1873)."Ueber Lacturaminsäure und Lactylharnstoff".Liebigs Ann.(in German).165(1): 99–103.doi:10.1002/jlac.18731650110.
- ^Wagner, E. C.; Baizer, Manuel (1940)."5,5-Dimethylhydantoin".Organic Syntheses.20:42.doi:10.15227/orgsyn.020.0042;Collected Volumes,vol. 3, p. 323.
- ^Bucherer, H. T.;Steiner, W. (1934). "J. Prakt. Chem."(in German).140:291.
{{cite journal}}:Cite journal requires|journal=(help) - ^Bergs, Ger. pat. 566,094 (1929) [C. A., 27, 1001 (1933)].
- ^Chisholm, Hugh,ed. (1911)..Encyclopædia Britannica.Vol. 14 (11th ed.). Cambridge University Press. pp. 29–30.
- ^Oakes, Elizabeth H. (2007).Encyclopedia of World Scientists.Facts on File.p. 298.ISBN9780816061587.
- ^"Hydantoin anticonvulsants".drugs.com.
- ^abDrauz, Karlheinz; Grayson, Ian; Kleemann, Axel; Krimmer, Hans-Peter; Leuchtenberger, Wolfgang; Weckbecker, Christoph (2007). "Amino Acids".Ullmann's Encyclopedia of Industrial Chemistry.doi:10.1002/14356007.a02_057.pub2.ISBN978-3527306732.
- ^"5,5-Dimethylhydantoin (DMH) a Highly Effective, Halogen Stabilizer for Wet End Applications, PaperCo".
- ^"5,5-Dimethylhydantoin".
- ^Hofreiter, Michael; Serre, David; Poinar, Hendrik N.; Kuch, Melanie; Pääbo, Svante (2001). "Ancient DNA".Nature Reviews Genetics.2(5): 353–359.doi:10.1038/35072071.PMID11331901.S2CID205016024.