Oxidation of nitroxides by -chloroperbenzoic acid

Cella, James A.; Kelley, James A.; Kenehan, Edward F.

doi:10.1016/s0040-4039(00)75017-9

Cited by 21 publications

(10 citation statements)

References 3 publications

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“…24, 25 1-Benzyl-3,3,5,5-dicyclohexyl-4-(1-phenyl-ethoxy)piperazine-2,6-dione (4). Ethylbenzene (25 mL), BODAZ (5) (830 mg, 2.33 mmol), and di-tert-butyl peroxide (0.49 mL, 390 mg, 267 mmol) were combined, and the same procedure as 1 was followed.…”

Section: Methodsmentioning

confidence: 99%

Rate Constants for the Trapping of Various Carbon-Centered Radicals by Nitroxides: Unimolecular Initiators for Living Free Radical Polymerization

Skene¹,

Scaiano²,

Listigovers³

et al. 2000

Macromolecules

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The recapping kinetics of a series of unimolecular initiators for free radical polymerization were investigated. The rate constants for the trapping of various carbon-centered radicals were analyzed as a function of structurally different nitroxides in order to determine suitable candidates for living free radical polymerization (LFRP). The technique of laser flash photolysis was used to determine the trapping rate constants for the radicals in the presence of various amounts of nitroxide and to also gain insight into the properties of the LFRP process.

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Section: Methodsmentioning

confidence: 99%

Rate Constants for the Trapping of Various Carbon-Centered Radicals by Nitroxides: Unimolecular Initiators for Living Free Radical Polymerization

Skene¹,

Scaiano²,

Listigovers³

et al. 2000

Macromolecules

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“…83). 150,287,288 The decomposition is especially prominent in the presence of a 4-keto function in the piperidine framework.…”

Section: 28mentioning

confidence: 99%

“…10,252,289 The so-called doxyl radical 45 decomposes on oxidation with m-CPBA, and the pyrroline and pyrrolidine radicals 46, 47, and 48 do not react with alcohols in the presence of a peracid 150 or in electrochemical reactions in the presence of bromide. 223 However, similar nitroxides have been converted to oxoammonium salts such as 7 and used for oxidations.…”

Section: 28mentioning

confidence: 99%

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

2009

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The discovery in 1959 of stable nitroxide‐based free radicals such as the prototypical 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) led to their use as electron spin resonance (ESR) spin labels in chemistry, biomedicine, and materials science. These nitroxides are prepared by the oxidation of secondary amines that contain no hydrogen atoms on the alpha‐carbons. The unique redox properties of nitroxides enable their use as oxidants in organic synthesis. The varied preparation and uses of oxoammonium salts as stoichiometric oxidants for alcohols are one subject of this review. Oxoammonium ions as oxidants for alcohols have a number of advantages, for example, the method is heavy‐metal free and some of the reactions can be performed in water or aqueous mixtures. A few side reactions are associated with these oxidations. The most serious is the fast reaction of the oxoammonium ion with free amines The several ways these oxidation reactions can be carried out are discussed in detail. They are: Oxidations using stoichimetric quantities of preformed oxoammonium salts carried out in either acidic, neutral, or basic conditions; reactions in which stoichiometric quantities of oxoammonium salts are generated in situ by disproportionation of a nitroxide in the presence of a strong acid; nitroxide‐catalyzed oxidations using a secondary oxidant; efficient nitroxide‐catalyzed oxidations of primary alcohols to carboxylic acids; and oxidations of primary alcohols or hemiacetals that can lead to lactones.

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“…Another important factor is the stability of the N -oxo ammonium ion, the actual oxidant in the catalytic cycle. Both di- tert -butyl nitroxide and the doxyl radicals do not form stable N -oxo ammonium ions, and are not effective catalysts for this reason . These are not the only structural requirements for effective catalysis.…”

Section: Discussionmentioning

confidence: 99%

AM1-SM2 Calculations Model the Redox Potential of Nitroxyl Radicals Such as TEMPO

et al. 1999

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Nitroxyl radicals can be oxidized to N-oxo ammonium salts that are themselves useful oxidants for primary and secondary alcohols. Several computational methods were investigated in order to predict the redox potential of nitroxyl radicals and to better understand the behavior of different nitroxides as catalysts for alcohol oxidation. The difference in calculated heats of formation for N-oxo ammonium ions and nitroxyl radicals using AM1 did not lead to a useful correlation with experimental redox potential as measured by cyclic voltammetry. However, when both the N-oxo ammonium ion and the nitroxyl radical were evaluated using the Cramer-Truhlar solvation model (SM2), a linear correlation was observed between the difference in heats of formation and the experimental redox values. This correlation may be used to correctly predict the redox potential of new nitroxyl radicals.

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Oxidation of nitroxides by -chloroperbenzoic acid

Cited by 21 publications

References 3 publications

Rate Constants for the Trapping of Various Carbon-Centered Radicals by Nitroxides: Unimolecular Initiators for Living Free Radical Polymerization

Rate Constants for the Trapping of Various Carbon-Centered Radicals by Nitroxides: Unimolecular Initiators for Living Free Radical Polymerization

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

AM1-SM2 Calculations Model the Redox Potential of Nitroxyl Radicals Such as TEMPO

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