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    The Mechanism of Diacyl Peroxide Decomposition

    Author
    Linhardt, Robert J.
    ORCID
    https://orcid.org/0000-0003-2219-5833
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    Linhardt Dissertation.pdf (6.185Mb)
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    Date Issued
    1979
    Subject
    Biology; Chemistry and chemical biology; Chemical and biological engineering; Biomedical engineering
    Degree
    PhD;
    Terms of Use
    In Copyright : this Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s). https://rightsstatements.org/page/InC/1.0/;
    Full Citation
    The Mechanism of Diacyl Peroxide Decomposition, R.J. Linhardt, Ph.D. Dissertation, The Johns Hopkins University, 1979.
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    URI
    https://hdl.handle.net/20.500.13015/5023
    Abstract
    Various substituted 4-X-diphenylacetyl Y-benzoyl peroxides have been prepared and characterized in situ by low temperature NMR and IR spectroscopy. These peroxides decompose in non-nucleophilic solvents below -20°C, with net retention(13%, X^H^, Y=N02 in methylene chloride), formingester in high yields. No evidence of radical in­volvement, such as solvent-derived products, radicalcoupling products or CIDNP, was observed in thisdecomposition. The corresponding carboxy inversion compounds (benzhydryl4-nitrobenzoic carbonic carboxylic anhydrides) were not obtained as products of, nor were they intermediates in, diacyl peroxidedecomposition.Three 4-X-benzhydryl 4-nitrobenzoic carboniccarboxylic: anhydrides (X=C1, H, CH^) were preparedand characterized. These compounds decompose with net retention (29%; X=CH^; methylene chloride) in nonnucleophilic solvents to afford ester in high yield. Decomposition in chloroform at 26°C occurs with a Hammett -a+ p = -3.84 and innitromethane-dg with p = -4.36iiR eproduced with permission of the copyright owner. The activation parameters for these decompositionsin chloroform-d,- were calculated for X=H and X=C1:6 *AEact 13-14 Kcal/mol, Asl6 = 37-39 cal/°mol.The decomposition of these diacyl peroxidesin 90$ aqueous acetone afforded only alcohol,acid and ester. The fraction ester (R) producedwas similar to that obtained in the solvolysis ofsubstituted benzhydryl-N-nitrosoamides, indicatinga similar spectrum of ion pair intermediates. TheR value could be increased by the addition ofcommon ion (.Jj-NOg-benzoate) from R=0.54 to R=0.95.This common ion effect, coupled with the formationof alcohol as a major product, is conclusiveevidence for the intermediacy of ion pairs in thisdecomposition. Preliminary results obtained in thephotodecomposition of diphenylacetyl 4-nitrobenzoylperoxide in methanol-tetrahydrofuran suggests somedecomposition is occurring via a. radical pathway.The mixed carbonic carboxylic anhydrides under­went two modes of decomposition in 90$ aqueousacetone: 1) decomposition to ion pair intermediateswhich gave alcohol, acid, and ester as products;and 2) decomposition by nucleophilic attack at the carbonyl giving alcohol and 4-nitrobenzoic;
    Department
    The Linhardt Research Labs;
    Publisher
    Johns Hopkins University
    Relationships
    The Linhardt Research Labs Online Collection; Rensselaer Polytechnic Institute, Troy, NY; https://harc.rpi.edu/;
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