Solid-state photocyclization of 2,4,6-triisopropyl-4′-(methoxycarbonyl)benzophenone. Evidence for a narrow reaction cavity and a photoenol diradical intermediate

Yoshikatsu Ito, Satoshi Yasui, Jun Yamauchi, Shigeru Ohba, Gentaro Kano

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The origin of the previously observed unusual photostability of 2,4,6-triisopropyl-4′-(methoxycarbonyl)-benzophenone (1-p-CO2Me) in the solid state was investigated. 1-p-CO2Me was found to photocyclize normally to produce the corresponding benzocyclobutenol 2-p-CO2Me when its solid-state photolysis was carried out either (a) after thorough grinding, (b) after solid-solid mixing with 2,4,6-triisopropyl-4′-(ethoxycarbonyl)-benzophenone (1-p-CO2Et), or (c) at elevated temperatures (an estimated energy barrier of 20 kcal/mol). Furthermore, when the photolysis was performed under more carefully deoxygenated conditions (closed argon atmosphere), formation of blue species that are persistent in the absence of oxygen was observed. On the basis of oxygen trapping and ESR experiments, the blue species are regarded as a mixture of a diradical intermediate DR and monoradicals derived thereof. The X-ray study of 1-p-CO2Me had revealed that the distances between the carbonyl oxygen and the o-i-Pr methine hydrogens are within the critical limit for hydrogen abstraction to occur, but a small reaction cavity or the compact crystal packing around both of the o-i-Pr groups is interfering with the photocyclization. The present results are consistent with this X-ray crystal structure; i.e., the photochemical hydrogen abstraction of 1-p-CO2Me to DR can take place, but DR reketonizes back to 1-p-CO2Me under the usual photolysis conditions because there is a high topochemical barrier to cyclization leading to 2-p-CO2Me.

Original languageEnglish
Pages (from-to)5415-5420
Number of pages6
JournalJournal of Physical Chemistry A
Volume102
Issue number28
Publication statusPublished - 1998 Jul 9

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photolysis
Photolysis
solid state
Hydrogen
cavities
oxygen
hydrogen
Oxygen
grinding
X rays
Argon
Cyclization
Energy barriers
x rays
trapping
argon
Paramagnetic resonance
atmospheres
crystal structure
Crystal structure

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Solid-state photocyclization of 2,4,6-triisopropyl-4′-(methoxycarbonyl)benzophenone. Evidence for a narrow reaction cavity and a photoenol diradical intermediate. / Ito, Yoshikatsu; Yasui, Satoshi; Yamauchi, Jun; Ohba, Shigeru; Kano, Gentaro.

In: Journal of Physical Chemistry A, Vol. 102, No. 28, 09.07.1998, p. 5415-5420.

Research output: Contribution to journalArticle

Ito, Yoshikatsu ; Yasui, Satoshi ; Yamauchi, Jun ; Ohba, Shigeru ; Kano, Gentaro. / Solid-state photocyclization of 2,4,6-triisopropyl-4′-(methoxycarbonyl)benzophenone. Evidence for a narrow reaction cavity and a photoenol diradical intermediate. In: Journal of Physical Chemistry A. 1998 ; Vol. 102, No. 28. pp. 5415-5420.
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abstract = "The origin of the previously observed unusual photostability of 2,4,6-triisopropyl-4′-(methoxycarbonyl)-benzophenone (1-p-CO2Me) in the solid state was investigated. 1-p-CO2Me was found to photocyclize normally to produce the corresponding benzocyclobutenol 2-p-CO2Me when its solid-state photolysis was carried out either (a) after thorough grinding, (b) after solid-solid mixing with 2,4,6-triisopropyl-4′-(ethoxycarbonyl)-benzophenone (1-p-CO2Et), or (c) at elevated temperatures (an estimated energy barrier of 20 kcal/mol). Furthermore, when the photolysis was performed under more carefully deoxygenated conditions (closed argon atmosphere), formation of blue species that are persistent in the absence of oxygen was observed. On the basis of oxygen trapping and ESR experiments, the blue species are regarded as a mixture of a diradical intermediate DR and monoradicals derived thereof. The X-ray study of 1-p-CO2Me had revealed that the distances between the carbonyl oxygen and the o-i-Pr methine hydrogens are within the critical limit for hydrogen abstraction to occur, but a small reaction cavity or the compact crystal packing around both of the o-i-Pr groups is interfering with the photocyclization. The present results are consistent with this X-ray crystal structure; i.e., the photochemical hydrogen abstraction of 1-p-CO2Me to DR can take place, but DR reketonizes back to 1-p-CO2Me under the usual photolysis conditions because there is a high topochemical barrier to cyclization leading to 2-p-CO2Me.",
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