Source:http://linkedlifedata.com/resource/pubmed/id/15932298
Switch to
| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
12
|
| pubmed:dateCreated |
2005-6-3
|
| pubmed:abstractText |
1,2-dideuterio-cyclohexene, 1,2-dideuterio-cyclooctene, and trans-3,4-dideuterio-hex-3-ene were reacted with three >NO* radicals: 4-hydroxyTempo, di-tert-butyliminoxyl, both used as the actual radicals, and phthalimide-N-oxyl (PINO) generated from N-hydroxyphthalimide (NHPI) by its reaction with tert-alkoxyl radicals (t-RO*) and with lead tetraacetate. In all cases, except the NHPI/Pb(OAc)4 system, only mono >NO-substituted alkenes were produced. The 2H NMR spectra imply that 88-92% of monoadducts were formed by the initial abstraction of an allylic H-atom, followed by capture of the allylic radical by a second >NO*, while the remaining 12-8% appear to be formed by an initial addition of >NO* to the double bond followed by H-atom abstraction by a second >NO*. A substantial and sometimes the major product formed with the NHPI/Pb(OAc)4 system has two PINO moieties added across the double bond. Since such diadducts are not formed with the NHPI/t-RO* system, a heterolytic mechanism is proposed, analogous to that known for the Pb(OAc)4-induced acetoxylation of alkenes. A detailed analysis of the NHPI/Pb(OAc)4/alkene products indicates that monosubstitution occurs by both homolytic and heterolytic processes.
|
| pubmed:language |
eng
|
| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
|
| pubmed:month |
Jun
|
| pubmed:issn |
0022-3263
|
| pubmed:author | |
| pubmed:issnType |
Print
|
| pubmed:day |
10
|
| pubmed:volume |
70
|
| pubmed:owner |
NLM
|
| pubmed:authorsComplete |
Y
|
| pubmed:pagination |
4629-36
|
| pubmed:year |
2005
|
| pubmed:articleTitle |
Mechanisms of reaction of aminoxyl (nitroxide), iminoxyl, and imidoxyl radicals with alkenes and evidence that in the presence of lead tetraacetate, N-hydroxyphthalimide reacts with alkenes by both radical and nonradical mechanisms.
|
| pubmed:affiliation |
National Research Council, Ottawa, ON, K1A 0R6, Canada. coseris@icmpp.ro
|
| pubmed:publicationType |
Journal Article
|