The Effect of Iodine on the Peroxidation of Carbonyl Compounds

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Abstract

Peroxidation of ketones and aldehydes with iodine as a catalyst was studied. Ketones reacted with 30% aq hydrogen peroxide in the presence of 10 mol % of iodine to yield gem-dihydroperoxides in acetonitrile and hydroperoxyketals in methanol. The yield of hydroperoxidation of various cyclic ketones was 60−98%, including androstane-3,17-dione, while acyclic ketones were converted with a similar efficiency. Aromatic aldehydes were also converted to gem-dihydroperoxides with hydrogen peroxide and iodine as catalyst in acetonitrile and to hydroperoxyacetal in methanol, while the reactivity of aliphatic ones remained the same as in noncatalyzed reactions. tert-Butylhydroperoxide reacted in a similar manner, giving the corresponding perether derivatives. A study was also made of the relative kinetics of dihydroperoxidation from which the Hammet equation gave a reaction constant (ρ) of −2.76, indicating the strong positive charge development in the transition state and the important role of rehybridization in the conversion of hydroperoxyhemiketal to gem-dihydroperoxide. In acetonitrile, the iodine catalyst is apparently able to discriminate between the elimination of a hydroxy, methoxy, and hydroperoxy group and addition of water, methanol, and H₂O₂ to a carbonyl group.

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This article has been cited by 3 ACS Journal articles (3 most recent appear below).

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  Selective Synthesis of Cyclic Peroxides from Triketones and H₂O₂

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  The Journal of Organic Chemistry2012 Article ASAP

  • Selective Synthesis of Cyclic Peroxides from Triketones and H₂O₂

    Alexander O. Terent’ev, Ivan A. Yaremenko, Vladimir V. Chernyshev, Valery M. Dembitsky, and Gennady I. Nikishin
    The Journal of Organic Chemistry2012 Article ASAP

    A method for the assembly of tricyclic structures containing the peroxide, monoperoxyacetal, and acetal moieties was developed based on the acid-catalyzed reaction of β,δ-triketones with H2O2. Tricyclic compounds are formed selectively in yields from 39% ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Ring Contraction of 1,2,4,5,7,8-Hexaoxa-3-silonanes by Selective Reduction of COOSi Fragments. Synthesis of New Silicon-Containing Rings, 1,3,5,6-Tetraoxa-2-silepanes

  Alexander O. Terent’ev, Maxim M. Platonov, Anna I. Tursina, Vladimir V. Chernyshev and Gennady I. Nikishin
  The Journal of Organic Chemistry2009 74 (5), 1917-1922

  • Ring Contraction of 1,2,4,5,7,8-Hexaoxa-3-silonanes by Selective Reduction of COOSi Fragments. Synthesis of New Silicon-Containing Rings, 1,3,5,6-Tetraoxa-2-silepanes

    Alexander O. Terent’ev, Maxim M. Platonov, Anna I. Tursina, Vladimir V. Chernyshev and Gennady I. Nikishin
    The Journal of Organic Chemistry2009 74 (5), 1917-1922

    The reducing agents Ph3P, (C8H17)3P, or NH2C(S)NH2 promote the ring contraction of nine-membered triperoxides, viz., 1,2,4,5,7,8-hexaoxa-3-silonanes, giving rise to seven-membered rings belonging to the previously unknown class of monoperoxides, viz., 1,...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Chemical Stability of the Peroxide Bond Enables Diversified Synthesis of Potent Tetraoxane Antimalarials

  Igor Opsenica, Dejan Opsenica, Kirsten S. Smith, Wilbur K. Milhous and Bogdan A. Šolaja
  Journal of Medicinal Chemistry2008 51 (7), 2261-2266

  • Chemical Stability of the Peroxide Bond Enables Diversified Synthesis of Potent Tetraoxane Antimalarials(1)

    Igor Opsenica, Dejan Opsenica, Kirsten S. Smith, Wilbur K. Milhous and Bogdan A. Šolaja
    Journal of Medicinal Chemistry2008 51 (7), 2261-2266

    Of 17 prepared 1,2,4,5-tetraoxacyclohexanes stable to reductive and acidic conditions, 3 of them were more active than artemisinin against CQ and MFQ resistant strain TM91C235 and all compounds were more active in vitro against W2 than against D6 strain. ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

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