Cyclic organic peroxides

A. I. Canizo, G. N. Eyler and G. P. Barreto, Determination of the enthalpies of vaporization of cyclic organic peroxides by correlation of changes in gas chromatographic retention times, Chromatographia, 2007, 65, 31-34. 

LC-MS is also used to detect cyclic organic peroxides, a class of compounds that contain the liquid explosives TATP, and HMTD [154-155]. Analysis of cyclic organic peroxides is problematic due to their thermolability and easy degradation, making any analysis challenging for both LC-MS and GC-MS. LC-MS/MS identifies degradation products from these compounds [154]. Considerable work is stiU needed to successfully detect these compounds and their degradation products by MS methods [154-155]. 

Linear peroxides of acetraie have never been used as primary explosives and therefore we have decided to focus exclusively on cyclic organic peroxides in the following sections. 

Cyclic organic peroxides (including DADP) further form by ozonolysis of alkenes. Ozonide forms at first and cyclic organic peroxide is the final product of these reactions which typically yields many by-products [15, 16, 33-36]. 

Pena, A.J., Pacheco-Londono, L., Figueroa, J., Rivera-Montalvo, L.A., Romm-Velazquez, F. R., Hemandez-Rivera, S.P. Characterization and differentiation of high energy cyclic organic peroxides by GC/FT-IR, GC-MS, FT-IR, and Raman microscopy. Proc. SPIE 5778, 347-358 (2005)... 

Pena-Quevedo, A.J. Cyclic organic peroxides identification and trace analysis by Raman microscopy and open-air chemical ionization mass spectroscopy. University of Puerto Rico, PhD thesis, Puerto Rico (2009)... 

The variation of a with potential according to equation (13) may also be used to estimate the value of E°, from which the value of D may be inferred. This approach has been applied to organic peroxides,44 including endoperoxides of biological interest.37 Here again, convolution voltammetry proved to be more precise than plain cyclic voltammetry. 

The PET-oxidative cyclization of unsaturated O-alkyl-O-trimethylsilyl ketene acetals 23 and 27 yields cyclic esters 24, 25, and 28, accompanied by the formation of considerable amounts of non-cyclic esters 26 and 29, respectively [89], The cyclization mode is found to be in accordance with free radical cyclizations of the appropriate esters 26 and 29, performed by heating with organic peroxides [90]. Since organic electrochemistry can be used to oxidize... 

This sequel on contemporary dioxirane chemistry should leave little if any doubt in the interested reader s mind that these fascinating and entertaining three-membered-ring cyclic peroxides are very popular oxidants and stUl in much demand, as witnessed by the current intensive research activities. Since the last Patai volume on Organic Peroxides some twenty years ago , which could have hardly featured a chapter on this subject since it was then in its infancy, dioxirane chemistry has literally exploded and become established as a prominent field in peroxide chemistry, as manifested by the now well over a thousand publications on this subject. ... 

On the basis of mechanistic studies, mainly on these isolable cyclic four-membered peroxides (1 and 2), two main efficient chemiexcitation mechanisms can be defined in organic peroxide decomposition (i) the unimolecular decomposition or rearrangement of high-energy compounds leading to the formation of excited-state products, exemplified here in the case of the thermal decomposition of 1,2-dioxetane (equation l)11-15-19 and (ii) the decomposition of a peroxide, catalyzed by the interaction with a second compound, which is ultimately formed in its electronically excited state. 

Peracids -acetic acid as by-product of [ACETIC ACID AND DERIVATIVES - ACETIC ACID] (Vol 1) -as disinfectant piSINFECTANTS AND ANTISEPTICS] (Vol 8) -10 hHLT [PEROXIDES AND PEROXIDE COMPOUNDS - ORGANIC PEROXIDES] (Vol 18) -for propylene oxide mfg [PROPYLENE OXIDE] (Vol 20) -as bleach [BLEACHING AGENTS - SURVEY] (Vol 4) -reactions of [IMINES, CYCLIC] (Vol 14)... 

COMMERCIAL ORGANIC PEROXIDES CRYSTALLINE HYDROGEN PEROXIDATES CYCLIC PEROXIDES... 

Adam, W., Heil, M., Mosandl, T. and Saha-Moeller, C.R. (1992) Dioxetanes and a-peroxy lactones, four-membered ring cyclic peroxides, in Organic Peroxides (ed. W. Ando), John Wiley Sons, Chichester, UK, pp. 221-254. 

Figure 9 describes a proposed mechanism for the dioxygenase reaction based on enzymatic and structural studies. It is proposed that the substrate binds as a dianion, which ligates the metal ion. Oxygen would then react to form an organic peroxide anion, which would then form a eyerie peroxide intermediate. Trie different reaction specificity is proposed to result from attack of the peroxide oxygen on alternative carbons. For example, the Ni-ARD would direct attack of the peroxide anion at the C3 carbonyl to form a five-membered peroxide intermediate, while the Fe-ARD would attack at carbon 2 to form a four-membered cyclic peroxide. 

Thermolysis of organic peroxides including dioxiranes, dioxetanes, and cyclic trioxides 03UK1055. 

Aral and co-workers [432] reported also a direct route for the preparation of cyclic styrene carbonate from styrene, which avoids the preliminary synthesis and isolation of styrene oxide. A catalyst system consisting of Au/Si02, zinc bromide and tetrabutylammonium bromide (Bu4NBr) was applied to the one-pot synthesis of styrene carbonate from styrene, organic peroxide and CO2. Au/Si02 is active for the epoxidation of styrene, and zinc bromide and Bu4NBr cooperatively catalyse the subsequent CO2 cycloaddition to epoxide. 

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