Peroxidation singlet oxygen

Methyl-4,5-diphenyloxazole in methanol containing methylene blue as sensitizer irradiated 6 hrs. with a 150 w. floodlamp N-acetyldibenzamide. Y 86%. Also from the isomeric 4-methyl-2,5-diphenyloxazole and f. e. s. H. H. Wasser-man and M. B. Floyd, Tetrahedron SuppL 7, 441 (1966) with 9,10-diphenyl-anthracene peroxide, singlet oxygen reactions, s. Am. Soc. 89, 3073 (1967). 

Hindered amines, such as 4-(2,2,6,6-tetramethylpiperidinyl) decanedioate, serve as radical scavengers and will protect thin Aims under conditions in which ultraviolet absorbers are ineffective. Metal salts of nickel, such as dibutyldithiocarbamate, are used in polyolefins to quench singlet oxygen or elecbonically excited states of other species in the polymer. Zinc salts function as peroxide decomposers. 

The mechanism of chemiluminescence is still being studied and most mechanistic interpretations should be regarded as tentative. Nevertheless, most chemiluminescent reactions can be classified into (/) peroxide decomposition, including biolurninescence and peroxyoxalate chemiluminescence (2) singlet oxygen chemiluminescence and (J) ion radical or electron-transfer chemiluminescence, which includes electrochemiluminescence. 

Classical chemiluminescence from lucigenin (20) is obtained from its reaction with hydrogen peroxide in water at a pH of about 10 Qc is reported to be about 0.5% based on lucigenin, but 1.6% based on the product A/-methylacridone which is formed in low yield (46). Lucigenin dioxetane (17) has been prepared by singlet oxygen addition to an electron-rich olefin (16) at low temperature (47). Thermal decomposition of (17) gives of 1.6% (47). 

Most likely singlet oxygen is also responsible for the red chemiluminescence observed in the reaction of pyrogaHol with formaldehyde and hydrogen peroxide in aqueous alkaU (152). It is also involved in chemiluminescence from the decomposition of secondary dialkyl peroxides and hydroperoxides (153), although triplet carbonyl products appear to be the emitting species (132). 

Phenols with bulky ortho- and para-substituents, eg, phenoHc antioxidants, do not undergo this reaction however, they scavenge radicals generated by thermolysis of diacyl peroxides and other peroxides. Diacyl peroxides react with potassium superoxide, KO2, forming singlet oxygen (207). 

Reaction between oxygen and butadiene in the Hquid phase produces polymeric peroxides that can be explosive and shock-sensitive when concentrated. Ir(I) and Rh(I) complexes have been shown to cataly2e this polymerisation at 55°C (92). These peroxides, which are formed via 1,2- and 1,4-addition, can be hydrogenated to produce the corresponding 1,2- or 1,4-butanediol [110-63-4] (93). Butadiene can also react with singlet oxygen in a Diels-Alder type reaction to produce a cycHc peroxide that can be hydrogenated to 1,4-butanediol. 

This group is prepared by the reaction of the anion of 9-hydroxyanthracene and the tosylate of an alcohol. Since the formation of this group requires an S 2 displacement on the alcohol to be protected, it is best suited for primaiy alcohols. It is cleaved by a novel singlet oxygen reaction followed by reduction of the endo-peroxide with hydrogen and Raney nickel. 

The primary interaction of singlet oxygen, produced by energy transfer from the excited sensitizer, with the diene can give rise to an exciplet that then collapses to peroxide, to a 1,4-biradical or to a 1,4-zwitterion alternatively, the adduct is the result of a concerted action without the involvement of an intermediate. Detailed kinetic Diels-Alder investigations of singlet oxygen and furans indicate that the reactions proceed concertedly but are asynchronous with the involvement of an exciplex as the primary reaction intermediate [63]. 

Fukuzawa, K. et ah. Rate constants for quenching singlet oxygen and activities for inhibiting lipid peroxidation of carotenoids and alpha-tocopherol in liposomes. Lipids, 33, 751, 1998. 

Kellogg, E.W. and Fridovich, I. (1975). Superoxide, hydrogen peroxide, and singlet oxygen in lipid peroxidation by a xanthine oxidase system. J. Biol. Chem 250, 8812-8817. 

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