ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The photo-oxidation of [2.2.2]hericene (6) gave successively the endoperoxides 11 (9,10,11,12-tetramethylidene-4,5-dioxatricyclo[6.2.2.02,7]dodec-2(7)-ene), the bis-endoperoxide 16 (15,16-dimethylidene-4,5,11,12-tetraoxatetracyclo[6.6.2.02,7.o9,14]hexadeca-2(7),9(14)-diene), and the tris-endoperoxide 19 (4,5,11,12,17,18-hexaoxapentacyclo[6.6.6.02,7.09,14.015,20]icosa-2(7),9(14),15(20)-triene). The endoperoxides 11, 16, and 19 were formed in the presence or in the absence of a dye sensitizer. The sensitized photo-oxidations of 2,3,5,6-tetramethylidenebicyclo[2.2.2]octane (4), 5,6,7,8-tetramethylidenebicyclo[2.2.2]oct-2-ene (5), 2,3,5,6-tetramethylidenebicyclo[2.2.1]-heptane (7), and 2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane (8) gave successively the corresponding mono-endoperoxides 9, 10, 12, and 13 and the bis-endoperoxides 14, 15, 17, and 18, respectively. Low-temperature NMR spectra of the bis-endoperoxides 14 and 16 indicated that their C2 and Cs conformers have the same stability. Similarly, there was no difference in the enthalpy of the D3 and C2 conformers of the tris-endoperoxide 19. The following reactivity sequence was observed for the sensitized photo-oxidations of 6-8 and 5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene (23): 6 + 1O2→11 〉 7 + 1O2→12〉8 + 1O2→13〉23 + 1O2→24, a trend parallel with that reported for the ethylenetetracarbonitrile (TCNE) cycloadditions to the same polyenes. The rate-constant ratios k1/k2 and k2/k3 for the three successive photo-oxidations of [2.2.2]hericene (6) did not differ significantly from unity, in contrast with the Diels-Alder additions of 6. Similarly, the rate-constant ratios k1/k2 for the two successive photo-oxidations of tetraenes 7 and 8 were significantly smaller than those reported for the successive TCNE cycloadditions to 7 to 8. The endoperoxide formations are not sensitive to the change in the exothermicity of the reactions but they are sensitive to the electronic properties (IP's) of the polyenes.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19860690403
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