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Peroxide synthesis from alkyl halides, alcohols and alkenes
Author(s) -
Foglia Thomas A.,
Silbert Leonard S.
Publication year - 1992
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/bf02540566
Subject(s) - chemistry , alkyl , peroxide , oxidizing agent , trifluoromethanesulfonate , halide , organic chemistry , catalysis , photooxygenation , singlet oxygen , oxygen
New and improved methods of peroxide synthesis have been developed along with advances in peroxide analyses. Hydroperoxides were obtained by one of three methods: i) perhydrolysis of alkyl mercury tetrafluoroborates (RHgBF 4 ); ii) perhydrolysis of alkyl trifluoromethanesulfonates (triflates, ROSO 2 CF 3 ); and iii) photooxygenation of unsaturated fatty esters (methyl oleate) with sensitizer in a phase transfer catalysis (PTC) system. Dialkyl peroxides also were prepared by three methods: hydroperoxidation of the mercury and triflate intermediates and an innovation of the reaction of superoxide anion with alkyl halides in a PTC system. Chromatographic—gas‐liquid chromatography (GLC) and high‐performance liquid chromatography (HPLC)—methods were examined in detail for compositional analysis of hydroperoxides and dialkyl peroxides in reaction mixtures and for purity determinations. Dialkyl peroxides were further analyzed by an improved rapid iodometric method by using strong non‐oxidizing acid (HCLO 4 ) and iron catalysis.