Acyl peroxides halides

A facile conversion of several aliphatic and aromatic acyl peroxides, halides, and anhydrides to the "per" acids has been effected by treatment with H2O2 and a threefold excess of base in the presence of a soluble magnesium saltl > The magnesium salt Is proposed to stabilize the "per" acid as it is formed, and to prevent its decomposition. 

By the reaction between a solution of an acyl halide in a dry organic solvent, such as toluene, with a cold solution of sodium peroxide, for example ... 

Diacyl peroxides and acyl hydroperoxides can similarly be prepared from acyl halides or anhydrides... 

Similar additions have been successfully carried out with carboxylic acids, anhydrides, acyl halides, carboxylic esters, nitriles, and other types of compounds. These reactions are not successful when the alkene contains electron-withdrawing groups such as halo or carbonyl groups. A free-radical initiator is required, usually peroxides or UV light. The mechanism is illustrated for aldehydes but is similar for the other compounds ... 

Reaction between alkyl or acyl halides and hydrogen peroxide... 

Reaction of alkyl and acyl halides with peroxide ion... 

See other acyl halides, diacyl peroxides, oxidants... 

Decomposition of azo compounds and peroxides provides the alkoxyamine by the nitroxide-trapping of the primary radicals [29]. The radicals produced by hydrogen abstraction with oxy radicals are also trapped by the nitroxide [242, 243]. In the photoreaction, alkoxyamines were isolated with high yields [244]. The reactions of Grignard reagents with nitroxides [215] and the coupling reaction of sodium nitroxides with bromo compounds [234,235] are also used. The hydrolysis of 56 followed by the reaction with acyl or alkyl halides afforded alkoxyamines with various functional groups,63 (Eq. 68) [245-251] ... 

Anderson, L. R. et al., J. Fluorine Chem., 1976, 7, 481-500 Five derivatives, including the 0-0 lithium or sodium salts of the hydrogen peroxide adduct of hexafluoroacetone (2-hydroxyhexafluoro-2-propyl hydroperoxide), and their reaction products with acyl halides, are less flammable or explosive than their hydrocarbon analogues, though less stable than the parent hydroperoxides. Relevant entries are ... 

It is possible to decarbonylate acyl halides in another way, to give alkanes (RCOC1 - RH). This is done by heating the substrate with tripropylsilane Pr,SiH in the presence of t-butyl peroxide.464 Yields are good for R = primary or secondary alkyl and poor for R = tertiary alkyl or benzylic. There is no reaction when R = aryl. (See also the decarbonylation ArCOCl — ArAr mentioned in 4-38.)... 

Reduction of carboxylic acids 9-42 Reduction of carboxylic esters 9-43 Reduction of carboxylic esters with titanocene dichloride 9-44 Reduction of anhydrides 9-45 Reduction of acyl halides 9-53 Reduction of nitriles 9-57 Reduction of hydroperoxides 9-60 Reduction of peroxides 9-69 Reaction between aldehydes and base (Cannizzaro)... 

See other ACYL HALIDES, DIACYL PEROXIDES, OXIDANTS... 

In titanium acylates, the carboxylate ligands are unidentate, not bidentate, as shown by ir studies (333,334). The ligands are generally prepared from the halide and silver acylate (335). The benzoate is available also from a curious oxidative addition with benzoyl peroxide (335—338) ... 

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