ISSN:
0947-3440
Keywords:
[14]Annulenes
;
[2.2]Metacyclophane-1,9-dienes
;
Photochemistry
;
Photooxidation
;
Endoperoxides
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The photoisomerization of trans-10b,10c-dimethyl-10b,10c-dihydropyrene (1), its 2,7-di-tert-butyl derivative 5 and a series of potassium sulfonate derivatives of 1, in both [D8]1,4-dioxane and [D2]dichloromethane as solvent, has been studied using λ = 420-570 nm irradiation. Irradiation of a deoxygenated solution of 1 in dioxane leads to the exclusive formation of anti-8,16-dimethyl[2.2]metacyclophane-1,9-diene (2), whereas the photoconversion of 1 in a non-degassed solution leads to the successive formation of 2 and 5,8-epidioxy-anti-8,16-dimethyl[2.2]metacyclophane-1,9-diene (7). Similarly, irradiation of the 2,7-di-tert-butyl derivative 5 in oxygen containing [D8]dioxane as solvent leads to the consecutive formation of the corresponding 5,13-di-tert-butyl derivatives 6 and 8. Irradiation of mixtures of potassium sulfonate derivatives of 1 (1-Sn) in D2O as solvent leads to photoisomerization with formation of the correspondingly substituted sulfonate derivatives of 2. Only with the dipotassium 2,4- and 2,5-disulfonates of 1 eventually small amounts of the corresponding epidioxy-bridged products 7 were formed. The photoisomerization 1-Sn → 2-Sn appeared to be most effective for 1-2-S and 1-2,5-S2 and least effective for 1-2,4,7-S3 and 1-2,4,7,10-S4. In the dark, the epidioxy products 7 and 8 reverted to give initially the corresponding metacyclophanes 2 and 6, and subsequently the respective dihydropyrenes 1 and 5, and the dark reactions of the potassium sulfonate derivatives 2-Sn yielded the correspondingly substituted 1-Sn. A quantitative study showed that the dark reactions steps 7 → 2, 8 → 6, and 2-Sn → 1-Sn (n = 1-4) exhibit first-order kinetics. For the deoxygenation of 5,8-epidioxy-anti-8,16-di-methyl[2.2]metacyclophane-1,9-diene (7) the rate coefficient is ca. 2.7 times that of its 5,13-di-tert-butyl derivative (8), and the rate coefficient for the isomerization 2-Sn → 1-Sn follows the order 2-5-S → 2-5,13-S2 〉 2-1,5,10-S3.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.199719970513
