Isolierung von Dibenzyläther‐hydroperoxid aus den Peroxygenaten von Benzylalkohol und Dibenzyläther

Rieche, Alfred; Seyfarth, Hans Eberhard; Brand, F.A.

doi:10.1002/jlac.19697250112

Cited by 12 publications

(2 citation statements)

References 15 publications

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“…In some other studies of the reactions of β-diketones with hydrogen peroxide, the formation of tetraoxanes was not documented . In the study, presumably bis-tetraoxane was synthesized in high yield from tetraketone (1,1,3,3-tetraacetylpropane) by the sulfuric acid catalyzed reaction with hydrogen peroxide in water at elevated temperature (80 °C). This result is apparently attributed to the specific reactivity of this tetraketone, its good solubility in water, and the relatively high thermal stability of the resulting peroxide.…”

Section: Introductionmentioning

confidence: 98%

Facile and Selective Procedure for the Synthesis of Bridged 1,2,4,5-Tetraoxanes; Strong Acids As Cosolvents and Catalysts for Addition of Hydrogen Peroxide to β-Diketones

et al. 2009

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A facile, experimentally simple, and selective method was developed for the synthesis of bridged 1,2,4,5-tetraoxanes based on the reaction of hydrogen peroxide with beta-diketones catalyzed by strong acids (H(2)SO(4), HClO(4), HBF(4), or BF(3)). The yields of the target products vary from 44% to 77%. 1,2,4,5-Tetraoxanes can easily be separated from other reaction products by column chromatography. A high concentration of a strong acid is a key factor determining the selectivity of formation and the yield of 1,2,4,5-tetraoxanes. Unlike many compounds containing the O-O bond, which undergo rearrangements in acidic media, the resulting cyclic peroxides are quite stable under these conditions.

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Section: Introductionmentioning

confidence: 98%

Facile and Selective Procedure for the Synthesis of Bridged 1,2,4,5-Tetraoxanes; Strong Acids As Cosolvents and Catalysts for Addition of Hydrogen Peroxide to β-Diketones

et al. 2009

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“…Currently, the reaction of ketones or aldehydes with H 2 O 2 and hydroperoxides serves as one of the main synthetic approaches to organic peroxides. − Although many publications describe reactions of hydrogen peroxide and monoketones, − the problem of peroxidation selectivity in the presence of several reactive centers has not found a general solution. For β-dicarbonyl compounds, this issue has been successfully addressed only in a small number of literature reports. − It was shown that β-diketones can be transformed into 1,2,4,5-tetraoxanes, , whereas δ-diketones can be converted into 1,2,4-trioxolanes (ozonides) (Scheme ). , Peroxidation of malonic acids and their esters yields malonyl peroxides (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

et al. 2018

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We have discovered synthetic access to βhydroperoxy-β-peroxylactones via BF 3 -catalyzed cyclizations of a variety of acyclic precursors, β-ketoesters and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals, with H 2 O 2 . Strikingly, independent of the choice of starting material, these reactions converge at the same β-hydroperoxyβ-peroxylactone products, i.e., the peroxy analogues of the previously elusive cyclic Criegee intermediate of the Baeyer− Villiger reaction. Computed thermodynamic parameters for the formation of the β-hydroperoxy-β-peroxylactones from silyl enol ethers, enol acetates, and cyclic acetals confirm that the β-peroxylactones indeed correspond to a deep energy minimum that connects a variety of the interconverting oxygen-rich species at this combined potential energy surface. The target β-hydroperoxy-β-peroxylactones were synthesized from β-ketoesters, and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals were obtained in 30−96% yields. These reactions proceed under mild conditions and open synthetic access to a broad selection of β-hydroperoxy-βperoxylactones that are formed selectively even in those cases when alternative oxidation pathways can be expected. These βperoxylactones are stable and can be useful for further synthetic transformations.

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Approach for the Preparation of Various Classes of Peroxides Based on the Reaction of Triketones with H₂O₂: First Examples of Ozonide Rearrangements

Yaremenko

Terent’ev

Vil

et al. 2014

Chemistry A European J

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The reaction of β,δ-triketones with an ethereal solution of H2O2 catalyzed by heteropoly acids in the presence of a polar aprotic co-solvent proceeds via three pathways to form three classes of peroxides: tricyclic monoperoxides, bridged tetraoxanes, and a pair of stereoisomeric ozonides. The reaction is unusual in that produces bridged tetraoxanes and ozonides with one of the three carbonyl groups remaining intact. In the synthesis of bridged tetraoxanes, the peroxide ring is formed by the reaction of hydrogen peroxide with two carbonyl groups at the β positions. The synthesis of ozonides from ketones and hydrogen peroxide is a unique process in which the ozonide ring is formed with the participation of two carbonyl groups at the δ positions. Rearrangements of ozonides were found for the first time after more than one century of their active investigation. Ozonides are interconverted with each other and rearranged into tricyclic monoperoxides, whereas ozonides and tricyclic monoperoxides are transformed into bridged tetraoxanes. The individual reaction products were isolated by column chromatography and characterized by NMR spectroscopy, mass spectrometry, and elemental analysis. One representative of each class of peroxides was characterized by X-ray diffraction.

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Isolierung von Dibenzyläther‐hydroperoxid aus den Peroxygenaten von Benzylalkohol und Dibenzyläther

Cited by 12 publications

References 15 publications

Facile and Selective Procedure for the Synthesis of Bridged 1,2,4,5-Tetraoxanes; Strong Acids As Cosolvents and Catalysts for Addition of Hydrogen Peroxide to β-Diketones

Facile and Selective Procedure for the Synthesis of Bridged 1,2,4,5-Tetraoxanes; Strong Acids As Cosolvents and Catalysts for Addition of Hydrogen Peroxide to β-Diketones

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

Approach for the Preparation of Various Classes of Peroxides Based on the Reaction of Triketones with H₂O₂: First Examples of Ozonide Rearrangements

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Isolierung von Dibenzyläther‐hydroperoxid aus den Peroxygenaten von Benzylalkohol und Dibenzyläther

Cited by 12 publications

References 15 publications

Facile and Selective Procedure for the Synthesis of Bridged 1,2,4,5-Tetraoxanes; Strong Acids As Cosolvents and Catalysts for Addition of Hydrogen Peroxide to β-Diketones

Facile and Selective Procedure for the Synthesis of Bridged 1,2,4,5-Tetraoxanes; Strong Acids As Cosolvents and Catalysts for Addition of Hydrogen Peroxide to β-Diketones

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF3-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

Approach for the Preparation of Various Classes of Peroxides Based on the Reaction of Triketones with H2O2: First Examples of Ozonide Rearrangements

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Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

Approach for the Preparation of Various Classes of Peroxides Based on the Reaction of Triketones with H₂O₂: First Examples of Ozonide Rearrangements