Diacyl peroxides, peroxycarboxylic acids and peroxy esters

Bouillon, Gnter; Lick, Carlo; Schank, Kurt

doi:10.1002/9780470771730.ch10

Cited by 9 publications

(5 citation statements)

References 189 publications

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“…This conclusion, of a high sensitivity to polar effects by acylperoxy radicals, was in striking contrast with previous reports stating that primary and secondary alcohols are unreactive with peracids (perbenzoic acid decomposes in ethanol solution in two months at room temperature 39 ). In fact, hydrogen abstraction from C−H bonds in the α-position of alcohols is particularly sensitive to the electrophilic character of the abstracting radical, due to the particular stability of the α-hydroxy carbonium ion.…”

Section: Discussioncontrasting

confidence: 98%

Radical versus “Oxenoid” Oxygen Insertion Mechanism in the Oxidation of Alkanes and Alcohols by Aromatic Peracids. New Synthetic Developments

et al. 1996

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Evidences concerning a novel free-radical mechanism for the oxidation of alkanes by aromatic peracids are reported. The mechanism involves hydrogen abstraction from the OH group of peracids by an aroyloxyl radical; the acylperoxyl radical thus generated is responsible for the selective oxidation. The reaction is affected by the presence of oxygen and it is inhibited by TEMPO and by solvents forming hydrogen bonds with peracids. A more simple and effective synthetic procedure has been developed, on the basis of the autoxidation of aliphatic and aromatic aldehydes in the presence of alkanes. It is also shown that the previously reported inertness of alcohols toward peracids must be ascribed to solvent effects, due to the formation of hydrogen bonds; in suitable solvents alcohol oxidation smoothly occurs.

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Section: Discussioncontrasting

confidence: 98%

Radical versus “Oxenoid” Oxygen Insertion Mechanism in the Oxidation of Alkanes and Alcohols by Aromatic Peracids. New Synthetic Developments

et al. 1996

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“…Although this can be explained by the Dakin-like (Dakin 1901) and Baeyer-Villiger (Bouillon et al 1983) reactions, it most likely arises from the elimination of acetic acid or acetaldehyde respectively, via the addition of ΗΟΟ·/·Ο 2~ and subsequent Reverse Aldol Addition (Kratzl et al 1967 Figure 4 shows the rate of formation of methoxyhydroquinone C4 (+) during the degradation of acetoguaiacone (O). Also include is the degradation of C4 in identical conditions.…”

Section: Reaction Of Cyanamide-peroxide With Apocynol and Acetoguaiaconementioning

confidence: 99%

Reactions of Lignin with Cyanamide Activated Hydrogen Peroxide. Part 2. The Degradation Mechanism of Phenolic Lignin Model Compounds

Kadla¹,

Chang²,

Chen³

et al. 1998

Holzforschung

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The reactions of monomeric phenolic lignin model compounds with cyanamide activated hydrogen peroxide were studied. Analyses of the various reaction products indicate four main reactions occur; aromatic hydroxylation, demethoxyiation, radical coupling and oxidative ring opening. The predominate products from apocynol and acetoguaiacohe were dicarboxylic acid compounds, maleic/fumaric, oxalic, and succinic acid derivatives, consistent with degradation by Superoxide. In the degradation of creosol, 3-hydroxy-4-methoxy-6-methyl-N-methylaniline was the major compound isolated, providing evidence of a cyanamide radical. Finally, plausible pathways to the formation of Superoxide anion and cyanamide oxidation products from alkaline hydrogen peroxide and cyanamide are proposed and their impact on delignification is discussed.

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“…Photochemical dissociation of peroxides in the solid state has been the subject of various studies . Although esters generated from tert -alkyl hydroperoxides are comparatively stable, crystal structure data on peroxides and peresters are rather limited . This is undoubtedly due to the decay that often occurs when their crystals are exposed to the X-ray radiation .…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Crystal Structures, and Laser Flash Photolysis oftert-Butyl Aroylperbenzoates¹

Shah

Neckers

2003

J. Org. Chem.

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tert-Butyl aroylperbenzoates (1-7) were synthesized. Single-crystal structures for 2 and 5 show that the perester and benzophenone carbonyl groups are almost coplanar in each. Laser flash photolysis (LFP, lambdaex = 355 nm) of 1-5 in CCl4 produces the corresponding aroylphenyl radicals (9-13). The lifetimes of the para aroyl-substituted phenyl radicals (9-12) are similar (approximately 0.4 micros), but each is shorter lived than the meta aroyl-substituted phenyl radical (13). LFP of 2, 6, and 7 also produces different (tert-butyldioxycarbonylbenzoyl)benzyl radicals (8, 14, and 15, lambdamax approximately 320 nm). The lifetimes of each in CCl4 have been found to be approximately 17-18 micros. The effect of substituents on the quantum yield of decomposition of 1-7 and the lifetimes of 9-13 is discussed.

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Diacyl peroxides, peroxycarboxylic acids and peroxy esters

Cited by 9 publications

References 189 publications

Radical versus “Oxenoid” Oxygen Insertion Mechanism in the Oxidation of Alkanes and Alcohols by Aromatic Peracids. New Synthetic Developments

Radical versus “Oxenoid” Oxygen Insertion Mechanism in the Oxidation of Alkanes and Alcohols by Aromatic Peracids. New Synthetic Developments

Reactions of Lignin with Cyanamide Activated Hydrogen Peroxide. Part 2. The Degradation Mechanism of Phenolic Lignin Model Compounds

Synthesis, Crystal Structures, and Laser Flash Photolysis oftert-Butyl Aroylperbenzoates¹

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Diacyl peroxides, peroxycarboxylic acids and peroxy esters

Cited by 9 publications

References 189 publications

Radical versus “Oxenoid” Oxygen Insertion Mechanism in the Oxidation of Alkanes and Alcohols by Aromatic Peracids. New Synthetic Developments

Radical versus “Oxenoid” Oxygen Insertion Mechanism in the Oxidation of Alkanes and Alcohols by Aromatic Peracids. New Synthetic Developments

Reactions of Lignin with Cyanamide Activated Hydrogen Peroxide. Part 2. The Degradation Mechanism of Phenolic Lignin Model Compounds

Synthesis, Crystal Structures, and Laser Flash Photolysis oftert-Butyl Aroylperbenzoates1

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Synthesis, Crystal Structures, and Laser Flash Photolysis oftert-Butyl Aroylperbenzoates¹