Exciplex and Radical Ion Intermediates in the Photochemical Reaction of α-Phenylcinnamonitrile with 2,5-Dimethyl-2,4-hexadiene

Frederick D Lewis, Robert J. DeVoe, Douglas B. MacBlane

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The photochemical reaction of α-phenylcinnamonitrile with 2,5-dimethyl-2,4-hexadiene has been investigated in several solvents. In nonpolar, nonhydroxylic solvents four isomeric [2 + 2] cycloadducts are formed. Cycloaddition is proposed to occur via a singlet exciplex intermediate. In acetonitrile solution a novel acyclic adduct is formed via an electron transfer-proton transfer-radical coupling mechanism. In alcohol solvents, reduced α-phenylcinnamonitrile, a solvent-incorporated adduct, and an oxidative coupling product of 2,5-dimethyl-2,4-hexadiene are formed. The two latter products are formed via nucleophilic trapping of the diene cation radical by solvent. The difference between electrochemical and photochemical oxidative addition of methanol to dienes and styrenes is discussed.

Original languageEnglish (US)
Pages (from-to)1392-1397
Number of pages6
JournalJournal of Organic Chemistry
Volume47
Issue number8
DOIs
StatePublished - Jan 1 1982

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Photochemical reactions
Ions
Styrenes
Proton transfer
Cycloaddition
Methanol
Cations
Alcohols
Electrons

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Exciplex and Radical Ion Intermediates in the Photochemical Reaction of α-Phenylcinnamonitrile with 2,5-Dimethyl-2,4-hexadiene",
abstract = "The photochemical reaction of α-phenylcinnamonitrile with 2,5-dimethyl-2,4-hexadiene has been investigated in several solvents. In nonpolar, nonhydroxylic solvents four isomeric [2 + 2] cycloadducts are formed. Cycloaddition is proposed to occur via a singlet exciplex intermediate. In acetonitrile solution a novel acyclic adduct is formed via an electron transfer-proton transfer-radical coupling mechanism. In alcohol solvents, reduced α-phenylcinnamonitrile, a solvent-incorporated adduct, and an oxidative coupling product of 2,5-dimethyl-2,4-hexadiene are formed. The two latter products are formed via nucleophilic trapping of the diene cation radical by solvent. The difference between electrochemical and photochemical oxidative addition of methanol to dienes and styrenes is discussed.",
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Exciplex and Radical Ion Intermediates in the Photochemical Reaction of α-Phenylcinnamonitrile with 2,5-Dimethyl-2,4-hexadiene. / Lewis, Frederick D; DeVoe, Robert J.; MacBlane, Douglas B.

In: Journal of Organic Chemistry, Vol. 47, No. 8, 01.01.1982, p. 1392-1397.

Research output: Contribution to journalArticle

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AB - The photochemical reaction of α-phenylcinnamonitrile with 2,5-dimethyl-2,4-hexadiene has been investigated in several solvents. In nonpolar, nonhydroxylic solvents four isomeric [2 + 2] cycloadducts are formed. Cycloaddition is proposed to occur via a singlet exciplex intermediate. In acetonitrile solution a novel acyclic adduct is formed via an electron transfer-proton transfer-radical coupling mechanism. In alcohol solvents, reduced α-phenylcinnamonitrile, a solvent-incorporated adduct, and an oxidative coupling product of 2,5-dimethyl-2,4-hexadiene are formed. The two latter products are formed via nucleophilic trapping of the diene cation radical by solvent. The difference between electrochemical and photochemical oxidative addition of methanol to dienes and styrenes is discussed.

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