词条 | Hofmann rearrangement |
释义 |
| Name = Hofmann rearrangement | Type = Rearrangement reaction | NamedAfter = August Wilhelm von Hofmann | Section3 = {{Reactionbox Identifiers | RSC_ontology_id = 0000410 }} The Hofmann rearrangement is the organic reaction of a primary amide to a primary amine with one fewer carbon atom.[1][2][3] The reaction is named after its discoverer – August Wilhelm von Hofmann. This reaction is also sometimes called the Hofmann degradation, and should not be confused with the Hofmann elimination. MechanismThe reaction of bromine with sodium hydroxide forms sodium hypobromite in situ, which transforms the primary amide into an intermediate isocyanate. The formation of an intermediate nitrene is not possible because it implies also the formation of a hydroxamic acid as a byproduct, which has never been observed. The intermediate isocyanate is hydrolyzed to a primary amine, giving off carbon dioxide.[2]
VariationsSeveral reagents can substitute for bromine. sodium hypochlorite,[4] lead tetraacetate,[5] N-bromosuccinimide, (bis(trifluoroacetoxy)iodo)benzene,[6] and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) can affect a Hofmann rearrangement. In the following example, the intermediate isocyanate is trapped by methanol, forming a carbamate.[7] In a similar fashion, the intermediate isocyanate can be trapped by tert-butyl alcohol, yielding the tert-butoxycarbonyl (Boc)-protected amine. The Hofmann Rearrangement also can be used to yield carbamates from α,β-unsaturated or α-hydroxy amides[2][8] or nitriles from α,β-Acetylenic amides[2][9] in good yields (≈70%). For amiloride, hypobromous acid was used to effect Hofmann rearrangement. Applications
See also
References1. ^{{cite journal|last1=Hofmann|first1=A. W.|title=Ueber die Einwirkung des Broms in alkalischer Lösung auf Amide|trans-title=On the action of bromine in alkaline solution on amides|journal=Berichte der Deutschen Chemischen Gesellschaft|date=1881|volume=14|issue=2|pages=2725–2736|doi=10.1002/cber.188101402242}} 2. ^1 2 3 {{cite book|last1=Everett|first1=Wallis|last2=Lane|first2=John|title=The Hofmann Reaction|journal=Organic Reactions|date=1946|volume=3|issue=7|pages=267–306|isbn=9780471005285|doi=10.1002/0471264180.or003.07}} 3. ^{{cite book|last1=Shioiri|first1=Takayuki|title=Degradation Reactions|journal=Comprehensive Organic Synthesis|date=1991|volume=6|pages=795–828|isbn=9780080359298|doi=10.1016/B978-0-08-052349-1.00172-4}} 4. ^{{cite journal|last1=Mohan|first1=Ram S.|last2=Monk|first2=Keith A.|title=The Hofmann Rearrangement Using Household Bleach: Synthesis of 3-Nitroaniline|journal=Journal of Chemical Education|date=1999|volume=76|issue=12|page=1717|doi=10.1021/ed076p1717|bibcode=1999JChEd..76.1717M}} 5. ^{{cite journal|author1=Baumgarten, Henry |author2=Smith, Howard |author3=Staklis, Andris |title=Reactions of amines. XVIII. Oxidative rearrangement of amides with lead tetraacetate|journal=The Journal of Organic Chemistry|year=1975|volume=40|issue=24|pages=3554–3561|doi=10.1021/jo00912a019}} 6. ^{{cite journal|last1=Almond|first1=Merrick R.|last2=Stimmel|first2=Julie B.|last3=Thompson|first3=Alan|last4=Loudon|first4=Marc|title=Hofmann Rearrangement under Mildly Acidic Conditions using [I,I-Bis(Trifluoroacetoxy)]iodobenzene: Cyclobutylamine Hydrochloride from Cyclobutanecarboxamide|journal=Organic Syntheses|date=1988|volume=66|page=132|doi=10.15227/orgsyn.066.0132}} 7. ^{{cite journal|last1=Keillor|first1=Jeffrey W.|last2=Huang|first2=Xicai|title=Methyl Carbamate Formation via Modified Hofmann Rearrangement Reactions: Methyl N-(p-Methoxyphenyl)carbamate|journal=Organic Syntheses|date=2002|volume=78|page=234|doi=10.15227/orgsyn.078.0234}} 8. ^{{cite journal|last1=Weerman|first1=R.A.|title=Einwirkung von Natriumhypochlorit auf Amide ungesättigter Säuren|journal=Justus Liebigs Annalen der Chemie|date=1913|volume=401|issue=1|pages=1–20|doi=10.1002/jlac.19134010102}} 9. ^{{cite journal|last1=Rinkes|first1=I. J.|title=De l'action de l'Hypochlorite de Sodium sur les Amides D'Acides|journal=Recueil des Travaux Chimiques des Pays-Bas|date=1920|volume=39|issue=12|pages=704–710|doi=10.1002/recl.19200391204}} Bibliography
3 : Rearrangement reactions|Degradation reactions|Name reactions |
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