Source:http://linkedlifedata.com/resource/pubmed/id/15563191
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
47
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| pubmed:dateCreated |
2004-11-25
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| pubmed:abstractText |
This paper describes the use of a substituent effects study to understand the mechanistic basis for an interfacial Diels-Alder reaction that does not proceed with standard second-order kinetics. Cyclopentadiene (Cp) undergoes a Diels-Alder reaction with a chemisorbed mercaptobenzoquinone to yield an immobilized Diels-Alder adduct. The pseudo-first-order rate constants are not linearly related to the concentration of diene, but they reach a limiting value with increasing concentrations of diene. The results of a substituent effects study support a mechanism wherein the electrochemical oxidation of hydroquinone produces two states of quinone. The first form, Q*, either reacts with Cp or isomerizes to Q, a form that is significantly less reactive with the diene. The interfacial reaction reaches a maximum rate when the concentration of diene is sufficiently high so that Q* undergoes complete Diels-Alder reaction and does not isomerize to Q. This work provides an example of the use of physical organic chemistry to understand an interfacial reaction.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Dec
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| pubmed:issn |
0002-7863
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:day |
1
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| pubmed:volume |
126
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
15613-7
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| pubmed:year |
2004
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| pubmed:articleTitle |
A substituent effects study reveals the kinetic pathway for an interfacial reaction.
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| pubmed:affiliation |
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282, USA. gawalte@duq.edu
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| pubmed:publicationType |
Journal Article
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