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 language | English |
|---|---|
| Pages (from-to) | 5415-5420 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry A |
| Volume | 102 |
| Issue number | 28 |
| Publication status | Published - 1998 Jul 9 |
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- Physical and Theoretical Chemistry
Cite this
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 journal › Article
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TY - JOUR
T1 - Solid-state photocyclization of 2,4,6-triisopropyl-4′-(methoxycarbonyl)benzophenone. Evidence for a narrow reaction cavity and a photoenol diradical intermediate
AU - Ito, Yoshikatsu
AU - Yasui, Satoshi
AU - Yamauchi, Jun
AU - Ohba, Shigeru
AU - Kano, Gentaro
PY - 1998/7/9
Y1 - 1998/7/9
N2 - 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.
AB - 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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M3 - Article
VL - 102
SP - 5415
EP - 5420
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 28
ER -