| 词条 | Boekelheide reaction |
| 释义 |
| Name = Boekelheide reaction | Type = Rearrangement reaction | NamedAfter = Virgil Carl Boekelheide }} The Boekelheide reaction is a rearrangement of α-picoline-N-oxides to hydroxymethylpyridines. It is named after Virgil Boekelheide who first reported it in 1954.[1] Originally the reaction was carried out using acetic anhydride, which typically required a period at reflux (~140°C). The reaction can be performed using trifluoroacetic anhydride (TFAA), which often allows for a room temperature reaction.[2] MechanismThe mechanism of the Boekelheide reaction begins by an acyl transfer from the trifluoroacetic anhydride to the N-oxide oxygen. The α-methyl carbon is then deprotonated by the trifluoroacetate anion. This sets the molecule up for a [3.3]-sigmatropic rearrangement which furnishes the trifluoroacetylated methylpyridine. Hydrolysis of the trifluoroacetate releases the hydroxymethylpyridine. {{Commonscat|Boekelheide reaction}}References1. ^{{cite journal|last1=Boekelheide|first1=V.|last2=Linn|first2=W. J.|title=Rearrangements of N-Oxides. A Novel Synthesis of Pyridyl Carbinols and Aldehydes|journal=Journal of the American Chemical Society|date=March 1954|volume=76|issue=5|pages=1286–1291|doi=10.1021/ja01634a026}} 2. ^{{cite journal|last1=Fontenas|first1=C.|last2=Bejan|first2=E.|last3=Haddou|first3=H. Aït|last4=Balavoine|first4=G. G. A.|title=The Boekelheide Reaction: Trifluoroacetic Anhydride as a Convenient Acylating Agent|journal=Synthetic Communications|date=23 September 2006|volume=25|issue=5|pages=629–633|doi=10.1080/00397919508011399}} 3 : Chemical reactions|Organic reactions|Name reactions |
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