Synthesis, structure, and photoreactions of fluorinated 2,11-diaza[32]paracyclophane: Photochemical formation of cage-diene type benzene dimer

Hideki Okamoto, Tetsuya Kozai, Zenji Okabayashi, Teruo Shinmyozu, Hiromi Ota, Kiichi Amimoto, Kyosuke Satake

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

An octafluorinated 2,11-diaza[32]paracyclophane derivative 12 was prepared, and its photochemical reaction was investigated. Upon irradiation at 300 nm, the fluorinated azacyclophane 12 underwent efficient photodimerization of the benzene cores to afford the corresponding photoisomer 13, which possessed cage diene benzene dimer structure (pentacyclo[6.4.0.0.2,70.3,1206,9]dodeca-4,10-diene skeleton). The cage diene structure was established by single-crystal X-ray diffraction analysis. The cage diene 13 thermally isomerized to a syn-o,o′-dibenzene isomer 22. The activation parameters for the thermal isomerization were determined to be Ea = 121 kJ mol-1, ΔH = 118 kJ mol-1, ΔS (293 K) = 22 J mol-1 K-1, and ΔG (293 K) = 111 kJ mol-1. It was revealed that, by photoirradiation at 300 nm, the syn-o,o′-dibenzene isomer 22 underwent facile intramolecular [π4s + π4s] cycloaddition to reproduce the cage diene isomer 13. Copyright

Original languageEnglish
JournalJournal of Physical Organic Chemistry
DOIs
Publication statusAccepted/In press - 2017

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dienes
Benzene
Isomers
Dimers
benzene
dimers
synthesis
isomers
Cycloaddition
Photochemical reactions
Isomerization
X ray diffraction analysis
Chemical activation
Irradiation
Single crystals
Derivatives
cycloaddition
musculoskeletal system
photochemical reactions
isomerization

Keywords

  • Azacyclophane
  • Benzene dimer
  • Cage compound
  • Cyclophane
  • Photocycloaddition

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Synthesis, structure, and photoreactions of fluorinated 2,11-diaza[32]paracyclophane : Photochemical formation of cage-diene type benzene dimer. / Okamoto, Hideki; Kozai, Tetsuya; Okabayashi, Zenji; Shinmyozu, Teruo; Ota, Hiromi; Amimoto, Kiichi; Satake, Kyosuke.

In: Journal of Physical Organic Chemistry, 2017.

Research output: Contribution to journalArticle

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title = "Synthesis, structure, and photoreactions of fluorinated 2,11-diaza[32]paracyclophane: Photochemical formation of cage-diene type benzene dimer",
abstract = "An octafluorinated 2,11-diaza[32]paracyclophane derivative 12 was prepared, and its photochemical reaction was investigated. Upon irradiation at 300 nm, the fluorinated azacyclophane 12 underwent efficient photodimerization of the benzene cores to afford the corresponding photoisomer 13, which possessed cage diene benzene dimer structure (pentacyclo[6.4.0.0.2,70.3,1206,9]dodeca-4,10-diene skeleton). The cage diene structure was established by single-crystal X-ray diffraction analysis. The cage diene 13 thermally isomerized to a syn-o,o′-dibenzene isomer 22. The activation parameters for the thermal isomerization were determined to be Ea = 121 kJ mol-1, ΔH≠ = 118 kJ mol-1, ΔS≠ (293 K) = 22 J mol-1 K-1, and ΔG≠ (293 K) = 111 kJ mol-1. It was revealed that, by photoirradiation at 300 nm, the syn-o,o′-dibenzene isomer 22 underwent facile intramolecular [π4s + π4s] cycloaddition to reproduce the cage diene isomer 13. Copyright",
keywords = "Azacyclophane, Benzene dimer, Cage compound, Cyclophane, Photocycloaddition",
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T1 - Synthesis, structure, and photoreactions of fluorinated 2,11-diaza[32]paracyclophane

T2 - Photochemical formation of cage-diene type benzene dimer

AU - Okamoto, Hideki

AU - Kozai, Tetsuya

AU - Okabayashi, Zenji

AU - Shinmyozu, Teruo

AU - Ota, Hiromi

AU - Amimoto, Kiichi

AU - Satake, Kyosuke

PY - 2017

Y1 - 2017

N2 - An octafluorinated 2,11-diaza[32]paracyclophane derivative 12 was prepared, and its photochemical reaction was investigated. Upon irradiation at 300 nm, the fluorinated azacyclophane 12 underwent efficient photodimerization of the benzene cores to afford the corresponding photoisomer 13, which possessed cage diene benzene dimer structure (pentacyclo[6.4.0.0.2,70.3,1206,9]dodeca-4,10-diene skeleton). The cage diene structure was established by single-crystal X-ray diffraction analysis. The cage diene 13 thermally isomerized to a syn-o,o′-dibenzene isomer 22. The activation parameters for the thermal isomerization were determined to be Ea = 121 kJ mol-1, ΔH≠ = 118 kJ mol-1, ΔS≠ (293 K) = 22 J mol-1 K-1, and ΔG≠ (293 K) = 111 kJ mol-1. It was revealed that, by photoirradiation at 300 nm, the syn-o,o′-dibenzene isomer 22 underwent facile intramolecular [π4s + π4s] cycloaddition to reproduce the cage diene isomer 13. Copyright

AB - An octafluorinated 2,11-diaza[32]paracyclophane derivative 12 was prepared, and its photochemical reaction was investigated. Upon irradiation at 300 nm, the fluorinated azacyclophane 12 underwent efficient photodimerization of the benzene cores to afford the corresponding photoisomer 13, which possessed cage diene benzene dimer structure (pentacyclo[6.4.0.0.2,70.3,1206,9]dodeca-4,10-diene skeleton). The cage diene structure was established by single-crystal X-ray diffraction analysis. The cage diene 13 thermally isomerized to a syn-o,o′-dibenzene isomer 22. The activation parameters for the thermal isomerization were determined to be Ea = 121 kJ mol-1, ΔH≠ = 118 kJ mol-1, ΔS≠ (293 K) = 22 J mol-1 K-1, and ΔG≠ (293 K) = 111 kJ mol-1. It was revealed that, by photoirradiation at 300 nm, the syn-o,o′-dibenzene isomer 22 underwent facile intramolecular [π4s + π4s] cycloaddition to reproduce the cage diene isomer 13. Copyright

KW - Azacyclophane

KW - Benzene dimer

KW - Cage compound

KW - Cyclophane

KW - Photocycloaddition

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