Reactions with Singlet Oxygen

The fact that singlet oxygen ene-reactions with ds-olefins have less negative activation entropies and about 2-8 times larger reaction rates (e.g., for ds-2-butene AS = -32 e.u., AH =1.6 kcal/mol for trans-2-butene AS = -42 e.u., AH = 0.3 kcal/mol) than with trans-olefins implies that the transition states... 

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). 

Characteristic reactions of singlet oxygen lead to 1,2-dioxetane (addition to olefins), hydroperoxides (reaction with aHyhc hydrogen atom), and endoperoxides (Diels-Alder "4 -H 2" cycloaddition). Many specific examples of these spectrally sensitized reactions are found iu reviews (45—48), earlier texts (15), and elsewhere iu the Engchpedia. 

Dithiolylium-4-olate, 2,5-diphenyl-reactions with singlet oxygen, 6, 831... 

B. Ranby and J. F. Rabek (eds.) Singlet Oxygen Reactions with Organic Compounds and Polymers, Wiley, Chichester, 1978, 331 pp. 

Dihydro-2f/-pyran-2-one has been prepared by reductive cycliza-tion of 5-hydroxy-2-pentynoic acid [2-Pentynoic acid, 5-hydroxy-], which is obtained in two steps from acetylene [Ethyne] and ethylene oxide [Oxirane] 3 and by the reaction of dihydropyran [277-Pyran, 3,4-dihydro-] with singlet oxygen [Oxygen, singlet].4,5 2ff-Pyran-2-one has been prepared by pyrolysis of heavy metal salts of coumalic acid [2//-Pyran-5-carboxylic acid, 2-oxo-],8 by pyrolysis of a-pyrone-6-carboxylic acid [211 - Pyran-6-carboxyl ic acid, 2-oxo-] over copper,7 and by pyrolysis of coumalic acid over copper (66-70% yield).8... 

Consequently, the antioxidant activity of GA in biological systems is still an unresolved issue, and therefore it requires a more direct knowledge of the antioxidant capacity of GA that can be obtained by in vitro experiments against different types of oxidant species. The total antioxidant activity of a compound or substance is associated with several processes that include the scavenging of free radical species (eg. HO, ROO ), ability to quench reactive excited states (triplet excited states and/ or oxygen singlet molecular 1O2), and/or sequester of metal ions (Fe2+, Cu2+) to avoid the formation of HO by Fenton type reactions. In the following sections, we will discuss the in vitro antioxidant capacity of GA for some of these processes. 

The ability of carotenoids to act as antioxidants is closely related to their long-chain conjugated polyene structures (see Section 2.2 in Chapter 2). Two main types of antioxidant actions can be distinguished singlet oxygen quenching and reactions with radicals. The first mechanism occurs in vivo in plants and has been extensively studied in vitro. Reactions with radicals of different types have also been extensively studied in vitro under different conditions but their occurrence in vivo is still a matter of discussion. 

Analogs of conduritols from toluene cA-dihydrodiol by reaction with singlet oxygen followed by scission with thiourea (Figure 8.7d) (Carless et al. 1989). 

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