Hydroperoxy anion

C-H bond oxygen insertion, 1163 configuration retention, 1163 epoxidation, 1144-50 hydroperoxy anion transfer, 382 Steric effects hydrogen dioxide, 96-7 peroxide dihedral angle, 101, 177 Steric strain... 

The conversion of 3-chloropentafluoropropene to 2-(chlorodifluoromethyI)-2,3,3-trifluoro-oxirane (33) can be carried out64 by heating the mixture of the alkene and oxygen in 1,1,2-trichlorotrifluoroethane (CFC-113) in an autoclave.64 The oxidation with hydrogen peroxide in alkaline solution is negatively influenced by the high nucleophilic reactivity of allylic chlorine.65 66 The reaction is performed at very low temperatures that favor the attack of the hydroperoxy anion in competition with the hydroxy anion. Acceptable yields of 31 -38 % are obtained in the presence of a phase-transfer catalyst.66... 

Methyl aeiylate and acrylonitrile (Eq. 80), on the other hand, wne reported by Yang and i innegan sw to giro no epozidea, but ii) stead the peroxides correeponding to Miehtiel addition of lert butyl hydroperoxi anion to the conjugated systems. 

This method was first described by Weitz and Scheffer. The oxidation begins with a reversible attack by the nucleophilic hydroperoxy anion on the conjugated system, and an oxirane conjugated with an electron-attracting group is formed by ring-closure following the loss of OH from the intermediate enolate anion (Eq. 15). 

Addition of the hydroperoxy anion to the double bond in conjugation is promoted not only by the carbonyl group, but by other electron-attracting groups too. Good yields can be attained from nitroolefins (Eqs. 22 and23). ... 

In a very interesting study which has implications for ionospheric, interstellar, and combustion chemistry, Fehsenfeld [19] reported on the reaction of SO4" with atomic hydrogen. The investigation focussed on the SO2" (O2) complex (Structure I). Two separate channels were observed, both of which resulted in rupture of S02 O2 electrostatic bond and formation of a hydroperoxy anion or radical ... 

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