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, P. Bakó, Erik Van Der Eycken

Research output: Contribution to journalArticle

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
Publication statusPublished - May 8 2000

Fingerprint

Irradiation
irradiation
Photoreactivity
Reaction products
reaction products
Polymers
polymers

Keywords

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

ASJC Scopus subject areas

  • Bioengineering
  • Physical and Theoretical Chemistry

Cite this

Intramolecular ortho and meta photocycloadditions of 4-phenoxybut-1-enes substituted in the arene residue with carbomethoxy, carbomethoxymethyl, and 2-carbomethoxyethyl groups. / Vízvárdi, Kristóf; Toppet, Suzanne; Hoornaert, Georges J.; De Keukeleire, Denis; Bakó, P.; Van Der Eycken, Erik.

In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 133, No. 1-2, 08.05.2000, p. 135-146.

Research output: Contribution to journalArticle

@article{6305aa162bc64381a9dbea37a06679df,
title = "Intramolecular ortho and meta photocycloadditions of 4-phenoxybut-1-enes substituted in the arene residue with carbomethoxy, carbomethoxymethyl, and 2-carbomethoxyethyl groups",
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.",
keywords = "4-Phenoxybut-1-enes, Carbon-carbon bond formation, Intramolecular photocycloaddition, Meta photocycloaddition, Ortho photocycloaddition",
author = "Krist{\'o}f V{\'i}zv{\'a}rdi and Suzanne Toppet and Hoornaert, {Georges J.} and {De Keukeleire}, Denis and P. Bak{\'o} and {Van Der Eycken}, Erik",
year = "2000",
month = "5",
day = "8",
language = "English",
volume = "133",
pages = "135--146",
journal = "Journal of Photochemistry and Photobiology A: Chemistry",
issn = "1010-6030",
publisher = "Elsevier",
number = "1-2",

}

TY - JOUR

T1 - Intramolecular ortho and meta photocycloadditions of 4-phenoxybut-1-enes substituted in the arene residue with carbomethoxy, carbomethoxymethyl, and 2-carbomethoxyethyl groups

AU - Vízvárdi, Kristóf

AU - Toppet, Suzanne

AU - Hoornaert, Georges J.

AU - De Keukeleire, Denis

AU - Bakó, P.

AU - Van Der Eycken, Erik

PY - 2000/5/8

Y1 - 2000/5/8

N2 - 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.

AB - 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.

KW - 4-Phenoxybut-1-enes

KW - Carbon-carbon bond formation

KW - Intramolecular photocycloaddition

KW - Meta photocycloaddition

KW - Ortho photocycloaddition

UR - http://www.scopus.com/inward/record.url?scp=0041287202&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0041287202&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0041287202

VL - 133

SP - 135

EP - 146

JO - Journal of Photochemistry and Photobiology A: Chemistry

JF - Journal of Photochemistry and Photobiology A: Chemistry

SN - 1010-6030

IS - 1-2

ER -