Linked Life Data

18044925

Source:http://linkedlifedata.com/resource/pubmed/id/18044925

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
26
pubmed:dateCreated
2007-12-14
pubmed:abstractText
The reaction chemistry of menthofuran (1), a toxic furan terpenoid from various mint oils, with nitric acid and nitrous acid has been investigated. Treatment of 1 with nitric acid afforded a 1:1 mixture of the bisfuran derivatives 5 and 6, resulting from the unexpected cleavage of the furan into two carbonyl fragments (3-methylcyclohexanone and hydroxyacetone) and their subsequent trapping by unreacted 1. Under conditions of high dilution, the nitrofuran derivative 7 was formed instead as the major reaction product. During investigation of this chemistry, it was found that oxidation of 1 with DDQ led to the important fragrant monoterpenoid 4 [dehydromenthofurolactone (anhydro Woodward-Eastman lactone)] in 44% yield. Exposure of 1 to nitrite ions at pH 3 afforded a completely different type of products, encompassing the known lactone 14, the lactam 15, and the remarkable dimer 16, bearing a N-hydroxy-2-pyrrolinone moiety linked to a nitrooximinofuran unit by an oxygen bridge. By using a combined spectroscopic and DFT approach, the constitution and configuration of 16 could be determined. These results fill a gap in the chemistry of furan compounds and describe routes to menthofuran-derived scaffolds of potential synthetic and biomedical relevance.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Dec
pubmed:issn
0022-3263
pubmed:author
pubmed:issnType
Print
pubmed:day
21
pubmed:volume
72
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
10123-9
pubmed:meshHeading
pubmed:year
2007
pubmed:articleTitle
Nitration versus nitrosation chemistry of menthofuran: remarkable fragmentation and dimerization pathways and expeditious entry into dehydromenthofurolactone.
pubmed:affiliation
Dipartimento di Chimica Organica e Biochimica, Università di Napoli Federico II, Via Cinthia 4, I-80126 Napoli, Italy.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't