Spin-trapping with 2-methyl-2-nitrosopropane: photochemistry of carbonyl-containing compounds. Methyl radical formation from dimethyl sulfoxide

Rosenthal, I.; Mossoba, Magdi M.; Riesz, Peter

doi:10.1139/v82-215

Cited by 48 publications

(14 citation statements)

References 10 publications

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“…Although a literature search allowed us to find some information about the possibility to oxidize PH 3 in the gas phase by ozone (O 3 ) [67] or by interaction with CO 2 [62] or molecular oxygen, [68] we decided to limit our study to the investigation of PH 3 reactivity towards hydrogen peroxide H 2 O 2 (aqueous solution) and CaOCl 2 . Although a literature search allowed us to find some information about the possibility to oxidize PH 3 in the gas phase by ozone (O 3 ) [67] or by interaction with CO 2 [62] or molecular oxygen, [68] we decided to limit our study to the investigation of PH 3 reactivity towards hydrogen peroxide H 2 O 2 (aqueous solution) and CaOCl 2 .…”

Section: Model Processes Of Ph 3 Chemical Oxidationmentioning

confidence: 99%

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

2013

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Electrochemical methods have become important from the viewpoint of the development and creation of new ecologically safe and resource‐saving chemical processes. The use of electrons as a “universal” and “inexhaustible” reagent for chemical reactions is the main advantage of electrochemical tools. Although electrochemical processes have been already successfully applied in the preparation of different classes of practically important chemical compounds, a very limited number of industrially applicable electrochemical processes that involve elemental (white) phosphorus is currently known, except for some examples of the electrochemical production of phosphane PH3. These are mainly associated with the investigation of bulk reactions of the electrochemically activated P4 molecule and phosphorus intermediates derived therefrom; very limited attention has been paid to the electrode surface reactions as a key stage of the electrochemical process. In this Microreview we describe the electrode reactions of elemental (white) phosphorus and phosphane that accompany the electrochemical process of the preparation of some phosphorus compounds starting directly from P4. The important role of the nature of the electrode material, the reactivity of the formed phosphorus intermediates and the surface processes are discussed. Moreover, recently, we succeeded in discovering a new, previously unstable phosphorus compound, phosphane oxide H3PO, which can be easily produced using an electrochemical method by mild anodic oxidation of phosphane PH3 electrochemically formed from P4. In this respect, some attention has been paid to the electrochemically induced processes of PH3 oxidation that result in the selective formation of phosphane oxide, which is of high interest from the viewpoint of the investigation of its properties and reactivity.

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Section: Model Processes Of Ph 3 Chemical Oxidationmentioning

confidence: 99%

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

2013

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“…Alternatively, dimethylsulfoxide (DMSO) as a detector of hydroxyl radicals is possible, but complications from the addition of hydroxide followed by oxidation should not be overlooked (29). Another possible indicator for hydroxyl is sodium formate (preferably NaHi3C02) because spin adduct spectra of C02-(36) are very similar to those of acyl spin adducts from nitrone hydrolysis (30).…”

Section: Radical Conformationsmentioning

confidence: 99%

An EPR/ENDOR study of aminoxyls (nitroxides) capable of intramolecular bonding: hydroxyalkyl radical spin adducts of nitrones

Haire¹,

Kotake²,

Janzen³

1988

Can. J. Chem.

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. Can. J . Chem. 66, 1901Chem. 66, (1988. A comparison of the effect of solvent and 13c labeling (of the radical addend) on the EPR (electron paramagnetic resonance) spectra of hydroxyalkyl vs. alkyl radical adducts of a-phenyl-N-tert-butyl nitrone (PBN) and 5,5-dimethyl-1-pyrroline-1-oxide (DMPO) has been investigated. The solution ENDOR spectra in toluene and in ethanol are the first examples studied of aminoxyls with hydroxyl substituents in close proximity to the free radical centre. Diastereomeric mixtures of hydroxyalkyl radical adducts are clearly resolved by ENDOR spectroscopy. Conformations of these radicals have been assigned based on the 'H and I3c hyperfine splittings (HFS's) and by differential optimum ENDOR temperatures. Definitive assignments of carbon-centered radical adducts of DMPO and PBN are shown to be feasible by monitoring the p-I3C HFS's of the radical addend. Long-range y-H HFS's from the added radical group can be observed when the deuterated spin trap PBN-d,, is used. The production of 13c labeled hydroxyalkyl adducts of nitrones (e.g., DMPO-'3CH20H, from the reaction of hydroxyl radicals with added I3CH30H) is shown to be useful as an improved EPR spectroscopic method for the verification of the presence of hydroxyl radicals.D. LARRY HAIRE, YASHIGE KOTAKE et EDWARD G. JANZEN. Can. J. Chem. 66, 1901Chem. 66, (1988. On a effectue une Ctude comparative de l'effet de solvant et du marquage au I3C (du radical qui s'ajoute) sur les spectres en rksonance paramagnktique Clectronique d'adduits alkylCs vs. hydroxy-alkylts de l'a-phinyl N-tert-butyl nitrone (PBN) et de l'oxyde de la dimethyl-5,5 pyrroline (DMPO). Les spectres ENDOR, en solutions dans le toluene et dans l'ethanol, sont les premiers exemples de spectres de radicaux aminoxyles portant des substituants hydroxyles i proximite du centre radicalaire. La spectroscopic ENDOR permet de resoudre sans ambigui'tt les melanges diastCr6omeres des adduits radicalaires hydroxy-alkylCs. On a attribut les conformations de ces radicaux en se basant sur les couplages hyperfins du 'H et du I3C et sur les temperatures differentielles ENDOR optimales. On a dtmontrC que, si on determine les couplages hyperfins du p-l3C du radical ajoutC, il est possible de faire des attributions dtfinitives des adduits, du DMPO ainsi que du PBN, qui portent des centres radicalaires sur le carbone. Lorsqu'on utilise le piege i spin PBN-d14, on peut observer les couplages hyperfins du y-H i longue distance du groupement radicalaire qui a Ct C ajoutC. On a dkmontre que la formation d'adduits hydroxy-alkylCs des nitrones qui sont marquees au I3c (par exemple, le D M P O -~~C H~O H qui provient de la reaction de radicaux hydroxyles avec du ajoutC) est une mtthode en resonance paramagnttique Clectronique amCliorCe pour la verification de la presence de radicaux hydroxyles.[Traduit par la revue]

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“…4) recorded in 2-propanol in the presence of MNP showed a radical which is assigned to the trapped 3-phenyl-2,3-dioxopropyl radical 5 from a comparison of its parameters with those of the known trapped benzoylmethyl radical. [15] Other radicals observed were the trapped benzoyl radical 7, [16] the trapped phenyl radical 8, [17] and as usual, when using MNP, the trapped tbutyl radical 9. [18] The sulphonates 1 b -d were capable of crosslinking the melamine formulation when irradiated prior to baking in much the same way as sulphonates 2 b-d of a-hydroxymethylbenzoin which were included for comparison.…”

Section: Resultsmentioning

confidence: 88%

Photoinitiators and photoinitiation, 16. The photodecomposition of some 1-phenyl-3-sulphonyloxy-1,2-propanediones

Hageman¹,

Oosterhoff

2000

Macromol. Chem. Phys.

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Spin-trapping with 2-methyl-2-nitrosopropane: photochemistry of carbonyl-containing compounds. Methyl radical formation from dimethyl sulfoxide

Cited by 48 publications

References 10 publications

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

An EPR/ENDOR study of aminoxyls (nitroxides) capable of intramolecular bonding: hydroxyalkyl radical spin adducts of nitrones

Photoinitiators and photoinitiation, 16. The photodecomposition of some 1-phenyl-3-sulphonyloxy-1,2-propanediones

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Spin-trapping with 2-methyl-2-nitrosopropane: photochemistry of carbonyl-containing compounds. Methyl radical formation from dimethyl sulfoxide

Cited by 48 publications

References 10 publications

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH3

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH3

An EPR/ENDOR study of aminoxyls (nitroxides) capable of intramolecular bonding: hydroxyalkyl radical spin adducts of nitrones

Photoinitiators and photoinitiation, 16. The photodecomposition of some 1-phenyl-3-sulphonyloxy-1,2-propanediones

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Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃