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{{chembox |
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{{chembox |
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|Watchedfields = changed |
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| verifiedrevid = 415530850 |
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|verifiedrevid = 443859459 |
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|ImageFile=Hydantoin.svg |
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|ImageFileL1 = Hydantoin.svg |
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|ImageSize= |
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|ImageAltL1 = Skeletal formula of hydantoin |
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|IUPACName=imidazolidine-2,4-dione |
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|ImageFileR1 = Hydantoin-3D-balls.png |
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|OtherNames= |
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|ImageAltR1 = Ball-and-stick model of hydantoin |
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|Section1= {{Chembox Identifiers |
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|PIN =Imidazolidine-2,4-dione |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID = 9612 |
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| KEGG_Ref = {{keggcite|correct|kegg}} |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|ChemSpiderID = 9612 |
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| KEGG = C05146 |
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|KEGG_Ref = {{keggcite|correct|kegg}} |
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| InChI = 1/C3H4N2O2/c6-2-1-4-3(7)5-2/h1H2,(H2,4,5,6,7) |
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|KEGG = C05146 |
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| InChIKey = WJRBRSLFGCUECM-UHFFFAOYAD |
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|InChI = 1/C3H4N2O2/c6-2-1-4-3(7)5-2/h1H2,(H2,4,5,6,7) |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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|InChIKey = WJRBRSLFGCUECM-UHFFFAOYAD |
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| ChEMBL = 122334 |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|ChEMBL_Ref = {{ebicite|correct|EBI}} |
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|ChEMBL = 122334 |
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| StdInChI = 1S/C3H4N2O2/c6-2-1-4-3(7)5-2/h1H2,(H2,4,5,6,7) |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChI = 1S/C3H4N2O2/c6-2-1-4-3(7)5-2/h1H2,(H2,4,5,6,7) |
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| StdInChIKey = WJRBRSLFGCUECM-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey = WJRBRSLFGCUECM-UHFFFAOYSA-N |
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| CASNo=461-72-3 |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| PubChem=10006 |
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|CASNo =461-72-3 |
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| ChEBI = 27612 |
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|PubChem =10006 |
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| SMILES = O=C1NC(=O)NC1 |
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|ChEBI_Ref = {{ebicite|correct|EBI}} |
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|ChEBI = 27612 |
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|SMILES = O=C1NC(=O)NC1 |
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|UNII = I6208298TA |
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}} |
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|Section2={{Chembox Properties |
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|C=3|H=4|N=2|O=2 |
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|MeltingPtC = 220 |
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|Solubility = 39.7 g/l (100 °C) |
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}} |
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}} |
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|Section2= {{Chembox Properties |
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| Formula=C<sub>3</sub>H<sub>4</sub>N<sub>2</sub>O<sub>2</sub> |
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| MolarMass=100.076 |
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| Appearance= |
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| Density= |
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| MeltingPt=220°C |
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| BoilingPt= |
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| Solubility=39.7 g/L (100°C) |
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}} |
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|Section3= {{Chembox Hazards |
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| MainHazards= |
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| FlashPt= |
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| Autoignition= |
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}} |
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}} |
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}} |
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'''Hydantoin''', which is also known as '''glycolylurea''', is a ] ] that can be thought of as a cyclic "double-]" product of ] and ]. Its ], shown in the Table of Properties at right, is similar to that of ] except that the ] of hydantoin has ]s in the number 2 and 4 positions in the ring. Imidazolidine is the ]-saturated ] of ]. Imidazole is a heterocyclic ] organic compound. |
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In a more general sense, hydantoins can refer to ]s that have substituent ] bonded to a hydantoin ring ''skeletal structure''. For example, ] (mentioned below) has two ] groups substituted onto the number 5 carbon in a hydantoin molecule.<ref>''The Chemistry of the Hydantoins.''Elinor Ware ]; '''1950'''; 46(3) pp 403 - 470; {{DOI|10.1021/cr60145a001}}</ref> |
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'''Hydantoin''', or '''glycolylurea''', is a ] ] with the formula CH<sub>2</sub>C(O)NHC(O)NH. It is a colorless solid that arises from the reaction of ] and ]. It is an oxidized derivative of ]. In a more general sense, hydantoins can refer to ] or a class of compounds with the same ring structure as the parent compound. For example, ] (mentioned below) has two ] groups substituted onto the number 5 carbon in a hydantoin molecule.<ref name= Konnert>{{cite journal |doi=10.1021/acs.chemrev.7b00067|title=Recent Advances in the Synthesis of Hydantoins: The State of the Art of a Valuable Scaffold |year=2017 |last1=Konnert |first1=Laure |last2=Lamaty |first2=Frédéric |last3=Martinez |first3=Jean |last4=Colacino |first4=Evelina |journal=Chemical Reviews |volume=117 |issue=23 |pages=13757–13809 |pmid=28644621 |s2cid=23653941 |url=https://hal.archives-ouvertes.fr/hal-02385289/file/Hal-126.pdf }}</ref> |
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==Synthesis== |
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==Synthesis== |
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Hydantoin was first isolated in 1861 by ] in the course of his study of ]. He obtained it by ] of ], hence the name. Urech in 1873 <ref>Urech, Ann., 165, 99 (1873).</ref> synthesized the derivative 5-methylhydantoin from ] ] and ] in what is now known as the ]: |
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Hydantoin was first isolated in 1861 by ] in the course of his study of ]. He obtained it by ] of ], hence the name. |
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] |
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{{clear left}} |
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The 5,5-dimethyl compound can also be obtained from ] (also discovered by Urech: see ]) and ].<ref>], Coll. Vol. 3, p.323 (1955); Vol. 20, p.42 (1940) and Steiner, J. prakt. Chem., 140, 291 ('''1934''').</ref><ref>Bergs, Ger. pat. 566,094 ('''1929''') .</ref> |
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Friedrich Urech synthesized 5-methylhydantoin in 1873 from ] ] and ] in what is now known as the ].<ref>{{cite journal|first = Friedrich|last = Urech|journal = ]|title = Ueber Lacturaminsäure und Lactylharnstoff|language = de|volume = 165|issue = 1|pages = 99–103|year = 1873|doi = 10.1002/jlac.18731650110|url = https://zenodo.org/record/1427313}}</ref> The method is very similar to the modern route using alkyl and arylcyanates. The 5,5-dimethyl compound can also be obtained from ] (also discovered by Urech: see ]) and ].<ref>{{OrgSynth|collvol = 3|collvolpages = 323|volume = 20|pages = 42|year = 1940|prep = CV3P0323|doi = 10.15227/orgsyn.020.0042|title = 5,5-Dimethylhydantoin|first1 = E. C.|last1 = Wagner|first2 = Manuel|last2 = Baizer}}</ref> This reaction type is called the ].<ref>{{cite journal|last1 = Bucherer|first1 = H. T.|author-link1 = Hans Theodor Bucherer|last2 = Steiner|first2 = W.|language = de|title = ]|volume = 140|page = 291|year = 1934}}</ref><ref>Bergs, Ger. pat. 566,094 ('''1929''') .</ref> |
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According to the ], hydantoin can also be synthesized either by heating ] with ] or by "heating bromacetyl urea with alcoholic ammonia". |
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Hydantoin can also be synthesized either by heating ] with ] or by "heating bromacetyl urea with alcoholic ammonia".<ref>{{cite EB1911 |wstitle=Hydantoin |volume=14 |pages=29–30}}</ref> The cyclic structure of hydantoins was confirmed by ] 1913.<ref>{{cite encyclopedia| title = Encyclopedia of World Scientists|last = Oakes|first = Elizabeth H.|publisher = ]|year = 2007|isbn = 9780816061587|pages = 298}}</ref> |
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Of practical importance, hydantoins are obtained by condensation of a ] with ]. Another useful route, which follows the work of Urech, involves the condensation of amino acids with cyanates and isocyanates: |
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==Uses== |
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:] |
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===Chemical=== |
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When hydantoin reacts with hot, dilute ], ] is one of the products. |
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==Uses and occurrence== |
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===Medicine=== |
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====Derivatives==== |
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===Pharmaceuticals=== |
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The hydantoin group can be found in several medicinally important compounds.<ref name= Konnert/> In pharmaceuticals, hydantoin ] form a class of ];<ref>{{cite web | url = https://www.drugs.com/drug-class/hydantoin-anticonvulsants.html | title = Hydantoin anticonvulsants | publisher = ]}}</ref> ] and ] both contain hydantoin moieties and are both used as anticonvulsants in the treatment of seizure disorders. The hydantoin derivative ] is used as a muscle relaxant to treat ], ], ], and ] intoxication. ] is an example of an ] hydantoin. |
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] is used in ], ], ], and ] intoxication. |
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===Pesticides=== |
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Some N-Halogenated derivatives of hydantoin are used as chlorinating or brominating agents in ]/sanitizer or ] products. The three major N-halogenated derivatives are dichlorodimethylhydantoin (]), bromochlorodimethylhydantoin (]), and dibromodimethylhydantoin (]). |
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The hydantoin derivative ] is a pyrethroid ]. ] is a popular fungicide containing the hydantoin group.<ref name = Ullmann>{{cite encyclopedia|encyclopedia = ]|doi = 10.1002/14356007.a02_057.pub2|first1 = Karlheinz|last1 = Drauz|first2 = Ian|last2 = Grayson|first3 = Axel|last3 = Kleemann|first4 = Hans-Peter|last4 = Krimmer|first5 = Wolfgang|last5 = Leuchtenberger|first6 = Christoph|last6 = Weckbecker|year = 2007|isbn = 978-3527306732|chapter = Amino Acids}}</ref> |
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===Synthesis of amino acids=== |
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===Pharmaceutical Industry=== |
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Hydrolysis of hydantoins affords amino acids: |
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Hydantoin is used to synthesize the following ]: |
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:<chem>RCHC(O)NHC(O)NH + H2O -> RCHC(NH2)COOH + NH3</chem> |
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* ] |
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Hydantoin itself reacts with hot, dilute ] to give ]. Methionine is produced industrially via the hydantoin obtained from ].<ref name = Ullmann/> |
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* ] |
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* ] |
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* ] |
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===Methylation=== |
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==DNA Oxidation to hydantoins after cell death== |
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] of hydantoin yields a variety of derivatives. '''Dimethylhydantoin''' (DMH) <ref>{{Cite web | url=https://www.tappi.org/21969/ | title=5,5-Dimethylhydantoin (DMH) a Highly Effective, Halogen Stabilizer for Wet End Applications, PaperCo}}</ref> may refer to any dimethyl derivative of hydantoin, but especially '''5,5-dimethylhydantoin'''.<ref>{{Cite web | url=https://pubchem.ncbi.nlm.nih.gov/compound/5_5-dimethylhydantoin | title=5,5-Dimethylhydantoin}}</ref> |
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A high proportion of ] and ] bases in ] are oxidized to hydantoins over time after the death of an organism. Such modifications block DNA polymerases and thus prevents ] from working. Such damage is a problem when dealing with ancient DNA samples.<ref>Hofreiter M., Serre D., Poinar H.N., Kuch M., and Paabo S. ''Nature Reviews Genetics'' (2001) '''2''':353.</ref> |
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==External links== |
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===Halogenation=== |
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Some ''N''-halogenated derivatives of hydantoin are used as chlorinating or brominating agents in ]/sanitizer or ] products. The three major ''N''-halogenated derivatives are '''dichlorodimethylhydantoin''' (DCDMH), ] (BCDMH), and ] (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. |
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] is a popular fungicide containing the hydantoin group.]] |
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===DNA oxidation to hydantoins after cell death=== |
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A high proportion of ] and ] bases in ] are oxidized to hydantoins over time after the death of an organism. Such modifications block DNA polymerases and thus prevents ] from working. Such damage is a problem when dealing with ancient DNA samples.<ref>{{cite journal|last1 = Hofreiter|first1 = Michael|last2 = Serre|first2 = David|last3 = Poinar|first3 = Hendrik N.|last4 = Kuch|first4 = Melanie|last5 = Pääbo|first5 = Svante|title = Ancient DNA|journal = ]|year = 2001|volume = 2|issue = 5|pages = 353–359|doi = 10.1038/35072071|pmid = 11331901|s2cid = 205016024}}</ref> |
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==External links and further reading== |
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{{wiktionary|dimethylhydantoin}} |
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* {{cite journal|title = The Chemistry of the Hydantoins|first = Elinor|last = Ware|journal = ]|year = 1950|volume = 46|issue = 3|pages = 403–470|doi = 10.1021/cr60145a001|pmid = 24537833}} |
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* {{Webarchive|url=https://web.archive.org/web/20201018004942/https://www.mjlphd.net/translations.html |date=2020-10-18 }} English Translation of 1926 German review article on the Preparation of hydantoins by Heinrich Biltz and Karl Slotta |
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==References== |
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==References== |
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{{reflist}} |
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{{reflist}} |
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{{1911}} |
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{{Anticonvulsants}} |
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{{Anticonvulsants}} |
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