Cyclic diperoxides

Cyclic compounds, unnatural, 24 59 Cyclic cooligomerization, 16 238 Cyclic corrosion tests, 16 218 Cyclic diacyl peroxides, 18 473, 477 Cyclic dimethylsiloxanes, 22 575 Cyclic diperoxides, 18 461 Cyclic diperoxyketals, 18 457 Cyclic disulfides, antimicrobial properties of, 23 713... 

Hydroxyalkyl Hydroperoxyalkyl Peroxides. There is evidence that hydroxyalkyl hydroperoxyalkyl peroxides (2, X = OH, Y = OOH) exist in equilibrium with their corresponding carbonyl compounds and other o -oxygen-substituted peroxides. Thermal decomposition of hydroxyalkyl hydroperoxyalkyl peroxides produces mixtures of starting carbonyl compounds, mono and dicarboxylic acids, cyclic diperoxides, catbon dioxide, and water. 

By-products include ozonides (13). Other peroxidic products including polymeric peroxides and polymeric ozonides can form, depending on reaction conditions, solvent, and olefin used. A variety of cyclic diperoxides (4) have been obtained by ozonolysis of olefins. Boiling point data lor several 1,2,4-trioxanes are listed in Table. 8. 

The rates for the thermolysis of cyclic peroxides are also only slightly solvent-dependent. For example, the first-order decomposition of acetone cyclic diperoxide (3,3,6,6-tetramethyl-l,2,4,5-tetroxane) increases only 21-fold on going from n-octane to acetic acid as solvent, corresponding to homolytic 0-0 bond rupture [824],... 

Cyclic Peroxides. CycHc diperoxides (4) and triperoxides (5) are soHds and the low molecular weight compounds are shock-sensitive and explosive (151). The melting points of some characteristic compounds of this type are given in Table 5. They can be reduced to carbonyl compounds and alcohols with zinc and alkaH, zinc and acetic acid, aluminum amalgam, Grignard reagents, and warm acidified iodides (44,122). They are more difficult to analyze by titration with acidified iodides than the acycHc peroxides and have been sucessfuUy analyzed by gas chromatography (112). 

Interaction of alkenes with ozonised oxygen tends to give several types of products or their polymers, some of which show more pronounced explosive tendencies than others [1]. The cyclic ge/n-diperoxides are more explosive than the true ozonides [2], It has been calculated that ozonisation of the endothermic /rara-stilbene (AH°f +135.4 kJ/mol, 0.78 kJ/g) would give, in the event of decomposition of the unstable ozonide, an exothermic release of 1.41 kJ/g which would attain an adiabatic decomposition temperature approaching 750°C with a 27-fold pressure increase in a closed vessel [3],... 

Dipentaerythritol, 2 46, 47 economic aspects, 2 52 manufacture, 2 51—52 physical properties of, 2 48t Dipentene, 24 491—492 uses for, 24 492 Diperoxides, cyclic, 18 459 Diperoxyacetals, 18 456 Diperoxycarboxylic acids, 18 464 Diperoxydodecanedioic acid, 4 62 Diperoxyketals, 14 281 18 456 boiling points of, 18 457t as free-radical initiators, 14 287-288 Diphasic solids, connectivity patterns for, 11 101... 

Feldhues, M. and Schafer, H.J. (1986) Selective mixed coupling of carboxylic acids- III. Synthesis of cyclopenta-decanone from cyclic tetraacyl diperoxides. Tetrahedron, 42, 1285-1290. 

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). 

Acetylhydroperoxides, cyclic 1,1-Diperoxides Monoperoxycarbonic acid esters... 

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