X-ray-induced transformation of o-vinylbenzaldehyde and 2-methylbenzocyclobutenone to an o-quinoid ketene and its radical cation

Journal of the American Chemical Society

Volumn 119, Issue 12, 1997, Pages 2825-2831

  Huben, Krzysztof ^a,b   Zhu, Zhendong ^b   Bally, Thomas ^b   Gebicki, Jerzy ^a  

^a LODZ UNIVERSITY OF TECHNOLOGY   (Poland)

^b UNIVERSITY OF FRIBOURG   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; QUINONE DERIVATIVE;

ARTICLE; DRUG STRUCTURE; IN VITRO STUDY; INFRARED SPECTROPHOTOMETRY; PHOTOCHEMISTRY;

EID: 0030887949     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja964243w     Document Type: Article

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28. ‡) 8.3 ± 0.2 kcal/mol (Lunazzi, L.; Macciantelli, D.; Baicelli, A. C. Tetrahedron Lett. 1975, 1205). Note that there is a discrepancy between the rotational barrier of benzaldehyde from NMR and from IR measurements, the latter giving much lower values which are, however, in disaccord with all calculations (cf.: Head-Gordon, M.; Pople, J. A. J. Phys. Chem. 1993, 97, 1147).
29. 6 would have sufficed to make up for the endothermicity, but perhaps the "funnels" on the excited state surface are ill disposed for relaxation to HVA. Also, our calculations show that the vinylic proton remains coordinated to the incipient allenic π-bond after its transfer to the carbonyl group (i.e. formation of HVA). This may cause the barrier for re-ketonization to be too small for HVA to persist after photolytic formation. A calculation of the corresponding reaction path could elucidate this possibility.
30. •+, which is not observed in this experiment. They are probably due to an allenic product of ring-opening that may be formed in a single step.
31. •+, but as the SCF procedure invariably converged to a σ-state we could not evaluate the π-electronic structure by this method.
32. Asmis, K.; Zhu, Z.; Bally, T. Unpublished. We thank Dr. Asmis (University of Fribourg) for recording this spectrum for us.
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35. See also: Fülscher, M. P.; Matzinger, S.; Bally, T. Chem. Phys. Lett. 1995, 236, 167. Truttmann, L.; Asmis, K. R.; Bally, T. J. Phys. Chem. 1995, 99, 17844.