Stereochemistry of free-radical oxidations at trivalent phosphorus

Bentrude, W. G.; Hargis, J. H.; Rusek, Paul E.

doi:10.1039/c29690000296

Cited by 20 publications

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“…In this regard, the n.m.r. results J, = 20.2 and J, = 4.14 Hz, have recently been published (30) for the thermodynamically stable isomer Q.…”

mentioning

confidence: 99%

Studies of Organophosphorus Derivatives. Part I. Nuclear Magnetic Resonance Studies of the 2-Oxo-1,3,2-dioxaphosphorinane System

Hall¹,

Malcolm²

1972

Can. J. Chem.

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The n.m.r. spectra of a series of simple derivatives of the 2-0x0-l,3,2-dioxaphosphorinane system are discussed in terms of the favored conformations of the derivatives and the stereospecific dependencies of vicinal 31P-O-C-' H couplings. Attention is drawn to a type of "deceptively-simple" ABX spectrum which is commonly found for the n.m.r. spectra of substances containing one or more heteronuclear species.Les spectres r.m.n. d'une strie de dtrivts simples du systtme 2-0x0-l,3,2-dioxaphosphorinane sont discutts a la IumiBre des conformations priviligites des dtrivts et des dtpendances stbr6ospkifiques des couplagesL'accent est mis sur un type de spectre ABX "anormalement simple" que I'on retrouve dans les substances qui contiennent une ou plusieurs espkes hettronucltaires.

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“…In this regard, the n.m.r. results J, = 20.2 and J, = 4.14 Hz, have recently been published (30) for the thermodynamically stable isomer Q.…”

mentioning

confidence: 99%

Studies of Organophosphorus Derivatives. Part I. Nuclear Magnetic Resonance Studies of the 2-Oxo-1,3,2-dioxaphosphorinane System

Hall¹,

Malcolm²

1972

Can. J. Chem.

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“…The methylenic H a and 4,5 The classical method (selective irradiation and shift correlation) was applied and the results are given in Table 1.…”

Section: Methodsmentioning

confidence: 99%

13C,31P and1H NMR of some dioxaphosphinopyridines and pyridoazaphosphinines

1999

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“…However, Denney et al 55 believe that th£ formation of an ion pair of a different structure, [(RO) 3 P-OH, "OR'], converted into the products (phosphate and alcohol) by proton transfer, is more likely. This last hypothesis is based on the fact that, in the first place, the reduction of hydroperoxides by phosphines in ethanol-H 2 18 O solution yields a phosphine oxide and an alcohol, both without 18 O, which can be accounted for by the absence of free OH" ions and their isotope exchange with the solvent 18 OH~ ions and, in the second place, by the fact that the optical activity of the initial hydroperoxide is retained in the alcohol formed 58 . However, these arguments put forward by Denney in favour of a nucleophilic mechanism can also be accommodated within the framework of the one-electron mechanism.…”

Section: ιπ Kinetics and Mechanism Of Reactions Of Phosphitesmentioning

confidence: 99%

“…ί Recently Bentrude 58 established that the transfer of an oxygen atom from the R'O radicals to the optically active phosphines R 1 R 2 R 3 P takes place with retention of the configuration, i.e. the optical activity also does not disappear from the phosphoranyl radical R 1 R 2 R 3 P-OR'.…”

Section: ίη''mentioning

confidence: 99%

Kinetics and Mechanism of the Reaction of Peroxy-compounds with Phosphites, Sulphides, and Aromatic Amines

Pobedimskii¹

1971

Russ. Chem. Rev.

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The studies dealing with the elucidation of the detailed mechanism and quantitative kinetics of the reactions of peroxycompounds with phosphites, sulphides, and aromatic amines are reviewed. It is shown how evidence has been obtained, by ESR of the existence of the one-electron amine oxidation stage, i.e. the stage involving the formation of radicalcations. The consecutive reactions of the radical-cations formed initially and their relation to the behaviour of the amines as polymerisation initiators are analysed. The characteristics of the detection of free radicals in reactions of phosphites and sulphides with hydroperoxides are examined and certain criteria of the latent, radical nature of these reactions are formulated. In the last section correlations of the Hammett equation type for rates of the reactions under consideration and also the correlation between the rate constants on the one hand and the ionisation potentials and electron affinities on the other are discussed within the framework of the one-electron oxidation-reduction mechanism. The bibliography includes 96 references. CONTENTS

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Stereochemistry of free-radical oxidations at trivalent phosphorus

Cited by 20 publications

References 0 publications

Studies of Organophosphorus Derivatives. Part I. Nuclear Magnetic Resonance Studies of the 2-Oxo-1,3,2-dioxaphosphorinane System

Studies of Organophosphorus Derivatives. Part I. Nuclear Magnetic Resonance Studies of the 2-Oxo-1,3,2-dioxaphosphorinane System

13C,31P and1H NMR of some dioxaphosphinopyridines and pyridoazaphosphinines

Kinetics and Mechanism of the Reaction of Peroxy-compounds with Phosphites, Sulphides, and Aromatic Amines

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