Perfluorobutyryl peroxide

In reaction of 2-Me- and 2-(chloro)bromothiopenes with bis(perfluorobutyryl) peroxides heptafluoropropyl group was introduced into a 5-position. In the analogous reaction of 3-bromothiophene, a heptafluoropropyl group was introduced into both 2- and 5-position in the yields 49% and 30%, respectively. ... 

In contrast, it is well known that styrene is a useful radical polymerizable monomer, and diacyl peroxide such as benzoyl peroxide and alkanoyl peroxide are widely used as conventional radical initiators. Since the interaction between theLUMO of diacyl peroxide (e.g., butyryl peroxide) and the HOMO of styrene become extremely weak compared to that of perfluorobutyryl peroxide (see Figure 4.3), the interaction of the SOMO of acyloxy radicals, which produce in the radical decomposition of diacyl peroxides, should interact with the HOMO of styrene to afford the radical polymerization of styrene. In contrast, styrene reacted with fluoroalkanoyl peroxides to afford not the radical polymerizable products but 1 1 adducts [PhCH(OCORp)CH2Rp] via... 

FIGURE 43 LUMO energy levels of perfluorobutyryl peroxide and butyryl peroxide, together with the HOMO-LUMO interactions. 

SCHEME 4 J Reaction of perfluorobutyryl peroxide with styrene. 

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See also in sourсe #XX -- [ ]

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