Ketone peroxides, cyclic

The cyclic trimer ketone peroxides (eg, methyl ethyl ketone peroxide cyclic trimer [24748-23-0]) have been selectively prepared in dilute solution (in a safety solvent due to the shock sensitivity of the pure peroxide) for use as impromoted, thermal initiators (124,125). They have been shown to effectively modify polyolefins under certain conditions in a manner similar to dialkyl peroxides. 

Cyclic stresses/strains, 13 481-483 Cyclic stress-strain curves, 13 491 Cyclic structures, nonaromatic, 15 5 Cyclic thermomechanical characterization, of shape-memory polymers, 22 358-362 Cyclic trimer ketone peroxides, 14 292 Cyclic trioxides, 18 448 Cyclic voltammetry, 9 580 Cyclitols, 4 710 Cyclization(s)... 

See CYCLIC PEROXIDES, KETONE PEROXIDES Lead, Trioxane... 

H202 added slowly at 20-30° to a mixture of cyclohexanone and 10%-perchloric in glacial acetic acid, after stirring 15-20 min. at 40-45° more glacial acetic acid added, and the soln. warmed 0.5-1 hr. at 55-60° -> crude tricyclo-hexylidene triperoxide. Y 83%. F. e. s. J. R. Sanderson, K. Paul, and P. R. Story, Synthesis 1975, 275 mixed cyclic ketone peroxides cf. ibid. 1975, 388 J. Org. Chem. 41, 1283 (1976) cyclic ketone diperoxides in acetonitrile-methylene chloride in the presence of methanesulfonic acid s. ibid. 40, 2239 (1975) tricyclohexylidene triperoxide s. a. M. J. C. Harding and D. M. Whalen, Ind. Eng. Chem., Prod. Res. Dev. 14, 232 (1975). 

N-Bromosuccinimidelbenzoyl peroxide Cyclic ketones from cyclic alcohols with ring expansion... 

Aromatic aldehydes and cyclic perfluoroketones are oxidized to a-hydroxy hydroperoxides or bis(a-hydroxy) peroxides, aliphatic ketones are converted to esters, and ketenes are converted to a-lactones... 

Both dimeric and trimeric cycloaikylidine peroxides can be synthesized by treatment of the corresponding cyclic ketones with H2O2 in acid solution. The trimeric peroxide is formed first and is subsequently converted to the dimeric compound. ... 

The effect of the nitric acid/hydrogen peroxide mixture on acetone when it is hot gives rise to an explosive oxidation, especially when the medium is confined. This situation also applies to a large number of ketones, and in particular, cyclic ketones. Cyclic di- and triperoxides form compounds that detonate, if there is no strict and very delicate thermal control. Accidents have been reported with butanone, 3-pentanone, cyclopentanone, cyclohexanone and methylcyclo-hexanones. 

For the oxidation of ketones, Baeyer-Villiger oxidation of cyclic ketones with monopersuccinic acid in water gives lactones in good results (Eq. 8.22).47 Peroxy species generated from borax in 30% hydrogen peroxide is effective for the Baeyer-Villiger oxidation of... 

Another useful oxidative reaction in aqueous medium is the cleavage of cyclic ketones by hydrogen peroxide in the presence of Fe(II) salts (Eq. 8.25). The reaction proceeds through an a-hydroxy hydroperoxide, leading to a variety of products.50 The presence of Fe(II) salts decomposes the intermediate, generating a radical. In the presence of halide ions, the radical leads to synthetically useful halocarboxylic acids.51... 

Hydrogen peroxide Ketones, Nitric acid Ozone Citronellic acid See other cyclic peroxides... 

The carbon templated tin incorporated mesoporous silicalite catalysts with MFI structure were successfully synthesized using microwave and well characterized using all the physico-chemical techniques. The catalytic activity of these catalysts was studied for liquid phase Baeyer-Villiger oxidation of various cyclic ketones using hydrogen peroxide. All the catalyst showed high conversion ( 100%) for bicyclic ketones with 100% selectivity to the corresponding lactone. 

Cyclic enone, 12 185 Cyclic ethers, 10 567, 569 12 663 polymerization, 14 271 Cyclic fatigue, in ceramics, 5 633-634 Cyclic gas generators, 6 786-787, 789, 827 Cyclic halides, 19 56 Cyclic hexakis(thio-l,4-phenylene), melt polymerization of, 23 705 Cyclic hydrocarbons, 13 687 Cyclic hydroxyalkyl alkyl peroxide, 18 454 Cyclic ion exchange operation, 14 408-413 Cyclic ketones, 12 176, 177 14 590-592. See also Cyclic 1,2-diketones physical properties of, 14 591t hydroxyalkyl hydroperoxides from, 18 450... 

Peroxides, per-acids. Note Numerous unsaturated hydrocarbons, aldehydes, ketones, ethers and some cyclic hydrocarbons (e.g. Dekalin) tend to form peroxides in the presence of air... 

Halogens are frequently used as oxidation agents and, under two-phase conditions, they can either be employed as ammonium complex halide salts [3], or in the molecular state with or without an added quaternary ammonium catalyst [4]. Stoichiometric amounts of tetra-n-butylammonium tribromide under pH controlled conditions oxidize primary alcohols and low-molecular-weight alkyl ethers to esters, a,cyclic ethers produce lactones [3], and secondary alcohols yield ketones. Benzoins are oxidized to the corresponding benzils (80-90%) by the tribromide salts in acetonitrile in the presence of benzoyl peroxide [5]. 

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