Volume 18, Number 3, 333-341, DOI: 10.1007/BF03162147

Application of benzophenones to elucidate the photochemical reaction pathways of hydrogen peroxide with dimethylsulfoxide

J. R. Woodward, T. -S. Lin, Y. Sakaguchi and H. Hayashi

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Abstract

Benzophenone ((C6H5)2CO) and decafluorobenzophenone ((C6F5)2CO) were applied to elucidate the photochemical reaction pathway of hydrogen peroxide (H2O2) with dimethylsulfoxide (DMSO). When a solution of benzophenone in DMSO was excited with the 355 nm laser light, three transient species were observed in the time-resolved electron paramagnetic resonance spectra: benzophenone ketyl (C6H5)2COH, methylCH3, and methylsulfinic methylCH2SOCH3 radicals. However, when decafluoro-benzophenone was used with DMSO, only ketyl and methylsulfinic methyl radicals were observed under the same experimental conditions. When the reaction of benzophenone and DMSO was carried out in the presence of H2O2, different time profiles ofCH3 radicals were observed. In the reaction of decafluorobenzophenone-DMSO-H2O2, the time profiles of the radicals were not affected by the presence of H2O2. Thus, these results verify thatCH3 radicals are regenerated in a cyclic pathway, in whichCH3 radicals attack H2O2. The regeneration pathway allows us to observe f-pair polarization throughout the lifetime ofCH3 radicals, which last several microseconds, an order of magnitude longer than theT 1 relaxation time ofCH3 radicals.

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