Sulfonyl peroxides

Wheieas the BPO—DMA ledox system works well for curing of unsaturated polyester blends, it is not a very effective system for initiating vinyl monomer polymerizations, and therefore it generally is not used in such appHcations (34). However, combinations of amines (eg, DMA) and acyl sulfonyl peroxides (eg, ACSP) are very effective initiator systems at 0°C for high conversion suspension polymerizations of vinyl chloride (35). BPO has also been used in combination with ferrous ammonium sulfate to initiate emulsion polymerizations of vinyl monomers via a redox reaction (36). 

Acetyl cyclohexane sulfonyl peroxide, 7 Acetyl Iodide, 7 Acetyl thiourea, 8 Acetylaminofluorene, 7 Acetylene, 7... 

Most of the isolated diacyl (including sulfonyl) peroxides are solids with relatively low decomposition temperatures, and are explosive, sensitive to shock, heat or friction. Several, particularly the lower members, will detonate on the slightest disturbance. Autocatalytic (self-accelerating) decomposition, which is promoted by tertiary amines, is involved [1]. Solvents suitable for preparation of safe solutions of diacetyl, dipropionyl, diisobutyryl and di-2-phenylpropionyl peroxides are disclosed [2], The class is reviewed, including hazards and safety measures [3], Cyclic diacyl peroxides are more stable, but scarcely to be trusted. Individually indexed compounds are ... 

Numerous sulfur and phosphorus peroxy compounds such as monopersulfuric acid (Caro s acid, la), monopersulfate (Oxone, Ib), ammonium monopersulfate Ic, tetra n-butyl-ammonium monopersulfate Id, peroxydisulfates 2a and 2b", tetra n-butylammonium peroxydisulfate 2c, symmetrical bissulfonyl peroxide 3 , acyl sulfonyl peroxide 4 , unsymmetrical sulfonyl peroxide 5 , sulfinyl peroxy intermediates 6a, sulfonyl peroxy intermediate 6b, sulfonimidoyl peroxy intermediate 7, bis(diphenyl phosphinyl) peroxide 8 , unsymmetrical phosphorus peroxide 9 and phosphoranyl peroxy intermediate 10" are known. Recently, many researchers have shown interest in the preparation and... 

Thermal decomposition in three different ways, i.e. homolytic, polar and radical induced decomposition, as well as intermolecular reaction of sulfonyl peroxides are the main reactions displayed by sulfonyl peroxides. When bis(arylsulfonyl) peroxides are allowed to decompose at 25-40 °C in chloroform, homolytic 0—0 bond fission followed by hydrogen abstraction from the solvent results in the formation of the corresponding arylsnlfonic acids. Mixed acyl sulfonyl peroxides undergo complicated thermal decomposition in solution, and have been used commercially as polymerization initiators, since they provide a source of free radicals at a relatively low temperature . 

Electron-donating substituents make the aromatic subsU ate more reactive than benzene and lead to o,/ -orientation, while electron-withdrawing substituents decrease the reactivity and give mostly m-orientation products. The detailed mechanism of the formation of the a complex has been studied by oxygen-18 labeling of the sulfonyl oxygen in p-nitrobenzenesulfonyl peroxide. The ionic mechanism for aromatic substitution by sulfonyl peroxides has been confirmed by carrying out the substitution reaction in the presence of redox catalysts such as copper and cobalt salts and aluminum chloride. Small differences in the rate of the products can be found in the presence or absence of these additives, and it has been concluded that the ionic mechanism accounts satisfactorily for these results. ... 

Hoffman and coworkers have extensively studied the reactions between amines and sulfonyl peroxides. When primary amines reacted with arylsulfonyl peroxides at —78 °C in ethyl acetate, A-alkyl-O-arylsulfonyl hydroxylamine derivatives were obtained (equation 8), whereas when various primary and secondary amines reacted with sulfonyl peroxides, oxidative deamination was observed. ... 

Electron-deficient olefins, asymmetric epoxidation, 386-91 Electron diffraction dialkyl peroxides, 713 ozonides, 721, 723 1,2,4-trioxolanes, 740 see also Gas electron diffraction Electron-donating substituents ene reactions, 841 sulfonyl peroxides, 1005-7 Electronegative functional groups,... 

Polymer immobilization. Mo-peroxide, 427 Polymerization agents, 621, 622 peroxide value, 661, 662 peroxycarboxyUc acids, 698 radical polymerization, 697, 707 styrene, 697, 720 sulfonyl peroxides, 1005 thermochemistry, 155 Polymers aging, 685 autoxidation, 623 hydroperoxide determination, 685 Poly(methacrylonitrile peroxide)... 

C-H bond unreactive to insertion, 1160 dioxirane oxidation, 1156 Sulfonic acids, C-H bond unreactive to insertion, 1160 Sulfonyl endoperoxides parasiticidal activity, 1309 synthesis, 1306-9, 1332 Sulfonyl peroxides, 1001-2, 1004-7 Sulfonylperoxy radical, superoxide reactions, 1035-9 Sulfoxidation... 

Wagner-Meerwein rearrangement, sulfonyl peroxides, 1006 Wastewaters... 

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