Mechanism of Diacyl Peroxide Decomposition

Linhardt, Robert J.
Murr, B.L.
Montgomery, E.
Osby J.
Sherbine, J.
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Biology , Chemistry and chemical biology , Chemical and biological engineering , Biomedical engineering
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Mechanism of Diacyl Peroxide Decomposition, R.J. Linhardt, B.L. Murr, E. Montgomery, J. Osby and J. Sherbine, The Journal of Organic Chemistry, 47, 2242-2251 (1982).
The presence of ion-pair intermediates in diacyl peroxide decomposition has been established. Various substituted (4-X·pOOiyl)phenylaoetyl Y·benzoyl peroxides and three corresponding 4·X-bemhydryl-4·nitrobenzolc carbonic anhydride& (X • CH3, H, CU were prepared. All compounds decompo1ed in 90% acetone-water (v/ v), giving the ionic product. eater, alcohol, and acid. The fraction of ester (R) was similar to that found in the solvolysis of substituted benzhydryl·N·nitroeoe.mides, indicating a similar spectrum of ion-pair intermediates. The yield of ester product could be increased markedly by the addition of common ion. The mixed carbonic carboxylic an.hydrides were not productl of peroxide decomposition in either nucleophillc or nonnucleophiUc aolventa and abowtd a lowe1 deoompoei;ion raU. than the peroxide. Lastly, both the peroxide and the mixed carbonic carboxylic Anhydride decompoMd in chloroform with net retention. Neither CIDNP nor any radical abstraction product was detected.
The Journal of Organic Chemistry, 47, 2242-2251
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