Photoinduced Reactions. XLII. Homolytic Expulsion of 4-Substituent in the Photochemical Reaction of 2,5-Cyclohexadienones
- 1 October 1970
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 43 (10) , 3181-3187
- https://doi.org/10.1246/bcsj.43.3181
Abstract
Irradiation of 2,4,6-tri-t-butyl-4-bromo-2,5-cyclohexadienone (X) in various solvents yielded 2,4,6-tri-t-butylphenol (XIII) in high yields. It was shown that 2,4,6-tri-t-butylphenoxy radical (XII) was formed as an intermediate and that the light of shorter wavelengths than 450 mμ accelerated the hydrogen abstraction of XII. The rate of the photochemical decomposition of X decreased in the order: n-hexane, N,N-dimethylformamide and acetic acid. This and the sensitized reaction suggest that the formation of XII from X may result from the n-π* triplet state of X. On the other hand, irradiation of 2,4,6-tri-t-butyl-4-nitro-2,5-cyclohexadienone (XI) afforded 2,6-di-t-butyl-p-quinone (XV) and 2,4,6-tri-t-butylphenol (XIII), indicating a homolytic cleavage of the C–NO2 bond.Keywords
This publication has 15 references indexed in Scilit:
- Photoinduced Reactions. XLI. Stereochemical Course in the Photochemistry of a 2,5-CyclohexadienoneBulletin of the Chemical Society of Japan, 1970
- Photochemistry of 4-methyl-4-trichloromethyl-2,5-cyclohexadienone. II. Mechanistic studies and characterization of the excited stateJournal of the American Chemical Society, 1968
- Photochemistry of 4-methyl-4-trichloromethyl-2,5-cyclohexadienone. I. The nature of the productsJournal of the American Chemical Society, 1968
- Photochemical Rearrangements of Conjugated Cyclic Ketones: The Present State of InvestigationsPublished by Wiley ,1966
- The Photolysis of Spiro[2.5]octa-1,4-dien-3-one in Ethyl Ether. A Note on the Mechanism of Photolysis of 2,5-CyclohexadienonesJournal of the American Chemical Society, 1964
- The Photochemical Transformation of Some p-Quinol EthersBulletin of the Chemical Society of Japan, 1964
- Photochemische Reacktionen. 19. Mitteilung. Die UV.‐Bestrahlung von 3‐Oxo‐10β‐hydroxy‐17β‐acetoxy‐Δ1;4‐östradienHelvetica Chimica Acta, 1963
- Photochemische Reaktionen 7. Mitteilung. Zum photochemischen Zerfall von 3‐Keto‐10β, 17β‐diacetoxy‐Δ1,4‐östradienHelvetica Chimica Acta, 1960
- Über ein stabiles Sauerstoffradikal, das 2.4.6–Tri–tert–butyl–phenoxyl–(1), II. Mitteil.): Weitere Herstellungsmethoden und Lebensdauer des AroxylsEuropean Journal of Inorganic Chemistry, 1954
- Oxidation of Hindered Phenols. II. The 2,4,6-Tri-t-butylphenoxy RadicalJournal of the American Chemical Society, 1953