Theoretical investigations of the photochemical isomerizations of indoxazene and isoxazole

Journal of Organic Chemistry

Volumn 74, Issue 16, 2009, Pages 6055-6063

  Su, Ming Der ^a  

^a NATIONAL CHIAYI UNIVERSITY   (Taiwan)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVE SPACES; BASIS SETS; CAS-SCF; CHEMICAL EQUATIONS; CONICAL INTERSECTION; DIAGNOSTIC TOOLS; DIRECT PATHS; EXPERIMENTAL OBSERVATION; FRANCK-CONDON; HETEROCYCLES; ISOXAZOLES; ORBITALS; PHOTOCHEMICAL ISOMERIZATION; PHOTOPRODUCTS; REACTION PATHWAYS; REACTION ROUTES; THEORETICAL INVESTIGATIONS; TOPOLOGY MODEL; TWO MODEL SYSTEMS;

CARBOXYLATION; DIAGNOSTIC PRODUCTS; ELECTRON TRANSITIONS; INTERSECTIONS; ISOMERIZATION; ISOMERS;

PHOTOCHEMICAL REACTIONS;

1,2 BENZISOXAZOLE; BENZENE DERIVATIVE; ISOXAZOLE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; ELECTRON; GEOMETRY; ISOMERIZATION; PHOTOCHEMICAL EFFICIENCY; PREDICTION; THEORETICAL STUDY;

EID: 70349140079     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo901010q     Document Type: Article

References (22)

1. For reviews, see: (a) Horspool, W. In Organic Photochemistry: A Comprehensive Treatment; Simon & Schuster: London, 1992.
2. (b) Kopecky, J. In Organic Photochemistry: A Visual Approach; VCH Publishers: New York, 1992.
3. For instance, see: (a) De Mayo, P. In Rearrangements in Ground and Excited States; Academic Press: New York, 1980; Vol.3.
4. (b) Buchardt, O. In Photochemistry of Heterocyclic Compounds; Wiley: New York, 1976.
5. (a) Ferris, J. P.; Antonucci, F. R.; Trimmer, R. W. J. Am. Chem. Soc. 1973, 95, 919.
6. (b) Ferris, J. P.; Antonucci, F. R. J. Am. Chem. Soc. 1974, 96, 2010.
7. Ferris, J. P.; Antonucci, F. R. J. Am. Chem. Soc. 1974, 96, 2014.
8. Good, R. H.; Jones, G. J. Chem. Soc. C 1971, 1196.
9. For recently excellent reviews, see: (a) Bernardi, F.; Olivucci, M.; Robb, M. A. Isr. J. Chem. 1993, 265.
10. (b) Klessinger, M. Angew. Chem., Int. Ed. Engl. 1995, 34, 549.
11. (c) Bernardi, F.; Olivucci, M.; Robb, M. A. Chem. Soc. Rev. 1996, 321.
12. (d) Bernardi, F.; Olivucci, M.; Robb, M. A. J. Photochem. Photobiol. A: Chem. 1997, 105, 365.
13. (e) Klessinger, M. Pure Appl. Chem. 1997, 69, 773.
14. (f) Klessinger, M.; Michl J. Excited States and Photochemistry of Organic Molecules; VCH Publishers: New York, 1995.
15. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Wallingford CT, 2003.
16. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986.
17. Bearpark, M. J.; Robb, M. A.; Schlegel, H. B. Chem. Phys. Lett. 1994, 223, 269.
18. McDouall, J. J. W.; Peasley, K.; Robb, M. A. Chem. Phys. Lett. 1988, 148, 183.
19. The C-C, C-N, C-H, C-O, and N-O bonds in 1 and 5 are fixed to be 1.35, 1.30, 1.09, 1.30, and 1.30 Å, respectively. Also, the ∠CCC (for six-membered ring), ∠CCC, ∠CNC, ∠HCC, ∠HNC, ∠CON, and ∠CCN bond angles are fixed to be 120°, 108°, 108°, 126°, 126°, 108°, and 180°, respectively.
20. -2. However, experimental data are not available for them.
21. 1 excitation for such compounds. In brief, the present computations can at least give the qualitative results and explanations for understanding their photochemical mechanisms.
22. One reviewer of this paper mentioned the substituent effect of electron-withdrawing 3-carboxylate on the photochemistry. We agree that the influence of substituents may alter the position of the singlet state as well as the Franck-Condon region for such reactant species. This kind of investigation needs a great deal of both experimental and theoretical evidence as well as work. However, as one can see in the Introduction, to the best of our knowledge, no available experimental or theoretical observations about the related study have been reported. It is thus quite difficult for us to test such photochemical isomerization reactions theoretically, since there is no related experimental data available for comparison. Moreover, the theoretical investigations of the substituent effect on such compounds are beyond the scope of the present study. We have a continuing interest in such photochemical transposition reactions and will report computational studies of the substituent effect on such photoorganic systems in future publications.