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.
Polycrystalline 2,4,6-triisopropyl-4′-methoxycarbonylbenzophenone was photo-irradiated in vacuo and the colored solid obtained exhibited intense ESR signals which are attributable to mono-radical and radical pair species. These are intermediates after the hydrogen abstraction by photo-excited carbonyl from isopropyl group.
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