Singlet from hypochlorite

Benzene oxide (86), on reaction with singlet oxygen generated either from hypochlorite-hydrogen peroxide or ozone-triphenyl phosphite, forms peroxide 87 in 37% yield. This peroxide on heating in chloroform is quantitatively isomerized to anti-benzene trioxide (42)46 The endoperoxide 88 is similarly... 

In the case of chemiluminescence occurring on treatment of di-benzanthrone with hypochlorite, as mentioned above, an endo peroxide might well be a key intermediate formed from 4 and singlet oxygen. The emitting species, however, is trichloro-dibenzanthrone, not 4 itself 70h... 

Excited singlet oxygen generated in situ by oxidising hydrogen peroxide with sodium hypochlorite, produces results chemically indistinguishable from photo-sensitised auto-oxidation of olefins [70]. 

The thermal generation of singlet oxygen from hydrogen peroxide and hypochlorite presumably involves the chloroperoxy anion other synthetically useful examples involve decomposition of phosphite ozonides or endoperox-ides, as indicated in Scheme 67 (cf. Murray, 1979). 

In this expression, Y102 is the yield of singlet oxygen produced from a given amount of hypochlorite, and the other terms have the same meaning as stated previously. 

HOCl is a strong oxidizing agent ( hoci/ci- = 1-49 V, pH = 0) in acid but not in alkaline solution. Hence, oxidation goes only from HOCl or its protonized form HOCIH" with the direct transfer of Cl (chlorination), similar to the reaction of HOBr and HOI. It disproportionates into chloride and chlorate singlet oxygen is then partly formed, which can oxidize organic compounds (the biocide application of hypochlorite is based on this) ... 

Electron transfer reactions Of biological interest, the enzyme myeloperoxidase, present in neutrophiles, can catalyze the formation of hypochlorite from Cf and H Oj The further reaction of hydrogen peroxide (H O ) with formed HOCl yields singlet oxygen ( o ) ... 

Sodium hypochlorite hydrogen peroxide Ketones from thioketones by singlet oxygen... 

Recently, a clever approach was used by Foote and Wexler (1964a, b) which further substantiates the excitation transfer mechanism. The chemiluminescence produced upon reaction of hydrogen peroxide with sodium hypochlorite in aqueous solution has been, tentatively, identified as phosphorescence from a low-lying singlet state of molecular oxygen (Khan and Kasha, 1963, 1964). In preliminary studies, Foote and Wexler (1964a, b) have shown that the species produced from this thermal reaction in the presence of several substrates yields the same products as are formed in the photosensitized oxidations, e.g., Eqs. (174)-(176). 

Sodium hypochlorite hydrogen peroxide Oxidations with singlet oxygen Ethyleneperoxides from 1,3-dienes... 

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