Intramolecular ortho and meta photocycloadditions of 4-phenoxybut-1-enes substituted in the arene residue with carbomethoxy, carbomethoxymethyl, and 2-carbomethoxyethyl groups

Kristóf Vízvárdi, Suzanne Toppet, Georges J. Hoornaert, Denis De Keukeleire, Péter Bakó, Erik Van Der Eycken

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19 Citations (Scopus)

Abstract

On irradiation of 4-phenoxybut-1-enes substituted with a carbomethoxy group in the arene, only the ortho compound 1 led to no-table ortho photocycloaddition, while the meta regioisomer 2 furnished meta and ortho photocycloadducts albeit in low yield, and the para-substituted compound 3 resulted only in intractable polymers. On irradiation of the carboxymethyl- and 2-carboxyethyl homologues 4-9, the photoreactivity altered dramatically. The highest yields of meta photocycloadducts were observed on irradiation of the ortho-substituted compounds 4 and 7. Due to steric hindrance, only one of the two possible regioisomers 18 and 19, respectively, was formed. The meto-substituted compounds 5 and 8 gave significant amounts of meta photocycloadducts as mixtures of regioisomers 13+16 and 14+17, respectively. The intramolecular meta photocycloaddition was directed exclusively to the 2′,6′-positions of the arene and only 1,5-bridged dihydrosemibullvalenes were formed. On irradiation of the ortho- and para-substituted compounds 4 and 7, and 6 and 9, respectively, considerable amounts of reaction products derived from initial ortho photocycloaddition were detected.

Original languageEnglish
Pages (from-to)135-146
Number of pages12
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume133
Issue number1-2
DOIs
Publication statusPublished - May 8 2000

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Keywords

  • 4-Phenoxybut-1-enes
  • Carbon-carbon bond formation
  • Intramolecular photocycloaddition
  • Meta photocycloaddition
  • Ortho photocycloaddition

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Physics and Astronomy(all)

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