Abstract
The first part of this study is an application of nuclear magnetic resonance to the determination of the sign and magnitude of the long range nuclear-electron spin-spin couplings in the free radical nitroxide derived from piperidine. It has been shown that the coupling constants of the protons {gamma} to the nitrogen atom have a pronounced spatial dependence as do the protons in the {beta} position, a point which has not been brought out by previous investigations. Conformational analysis of these compounds has been carried out by measurement of the effect of temperature on the NMR spectra at 310 MHz. The synthesis of di-t-Bu nitroxide labelled with C{sup 13} in the {alpha}-position made possible the unambiguous determination of the corresponding {sup 13}C nuclear-electron spin-spin coupling constant, a parameter which had not previously been measured. The coupling constants measured in the 2,2,6,6-tetramethyl piperidine series could then be attributed to the {sup 13}C atoms in the {beta}-position and their variation related to the conformations of the heterocycles. This constitutes the second part of the work reported here. The final section is devoted to a study of the decomposition of an unstable nitroxide having a hydrogen atom in the p-position. This decomposition is bimolecular
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Briere, R
[1]
- Commissariat a l'Energie Atomique, Grenoble (France). Centre d'Etudes Nucleaires
Citation Formats
Briere, R.
A study of the conformation and stability of nitroxide free radicals; Etude de la conformation et de la stabilite de radicaux libres nitroxydes.
France: N. p.,
1969.
Web.
Briere, R.
A study of the conformation and stability of nitroxide free radicals; Etude de la conformation et de la stabilite de radicaux libres nitroxydes.
France.
Briere, R.
1969.
"A study of the conformation and stability of nitroxide free radicals; Etude de la conformation et de la stabilite de radicaux libres nitroxydes."
France.
@misc{etde_20552661,
title = {A study of the conformation and stability of nitroxide free radicals; Etude de la conformation et de la stabilite de radicaux libres nitroxydes}
author = {Briere, R}
abstractNote = {The first part of this study is an application of nuclear magnetic resonance to the determination of the sign and magnitude of the long range nuclear-electron spin-spin couplings in the free radical nitroxide derived from piperidine. It has been shown that the coupling constants of the protons {gamma} to the nitrogen atom have a pronounced spatial dependence as do the protons in the {beta} position, a point which has not been brought out by previous investigations. Conformational analysis of these compounds has been carried out by measurement of the effect of temperature on the NMR spectra at 310 MHz. The synthesis of di-t-Bu nitroxide labelled with C{sup 13} in the {alpha}-position made possible the unambiguous determination of the corresponding {sup 13}C nuclear-electron spin-spin coupling constant, a parameter which had not previously been measured. The coupling constants measured in the 2,2,6,6-tetramethyl piperidine series could then be attributed to the {sup 13}C atoms in the {beta}-position and their variation related to the conformations of the heterocycles. This constitutes the second part of the work reported here. The final section is devoted to a study of the decomposition of an unstable nitroxide having a hydrogen atom in the p-position. This decomposition is bimolecular and the primary isotope effect shows that the rupture. of the C-H bond is involved. From this one can conclude that a nitroxide is stable when the different groups attached to the nitrogen atom cannot give rise to a decomposition either intra molecularly, if the molecular geometry is suitable, or inter molecularly by dimerisation through attack on a different center of a neighbouring molecule thus leading to a fragmentation or a disproportionation. (author) [French] La premiere partie est une application de la resonance magnetique nucleaire a la determination du signe et de la grandeur des couplages a longue distance dans des radicaux libres nitroxydes piperidiniques. Il est montre que les constantes de couplage des protons situes en {gamma} de l'azote ont une dependance spatiale tres marquee au meme titre que les protons situes en {beta}, ce que les etudes anterieures n'avaient pu preciser. Une analyse conformationnelle est effectuee par RMN a 310 MHz, en temperature variable. La synthese du di-t-butyl nitroxyde marque au carbone 13 en position {alpha} du groupement nitroxyde a permis de determiner avec certitude la constante d'interaction hyperfine electron carbone 13 quaternaire, grandeur qui n'avait pas ete mesuree jusqu'alors. Les constantes de couplage mesurees dans les radicaux piperidiniques tetramethyles en 2,2,6,6 ont pu etre ensuite attribuees a des carbones 13 situes en {beta} de l'azote, et leur variation a pu etre reliee a la conformation des cycles. C'est l'objet de la seconde partie. Dans un dernier chapitre, l'etude cinetique d'un radical nitroxyde instable, ayant un hydrogene en {beta}, met en evidence une decomposition bimoleculaire qui met en jeu la rupture de la liaison C-H; ceci est demontre par effet isotopique primaire. On peut conclure de cette etude qu'un nitroxyde est stable lorsque les differents groupes attaches a l'atome d'azote ne peuvent provoquer une decomposition du radical, soit intramoleculairement, si la geometrie de la molecule le permet, soit intermoleculairement par dimerisation sur un autre centre d'une molecule voisine, conduisant ainsi a une fragmentation ou a une disproportionation. (auteur)}
place = {France}
year = {1969}
month = {Mar}
}
title = {A study of the conformation and stability of nitroxide free radicals; Etude de la conformation et de la stabilite de radicaux libres nitroxydes}
author = {Briere, R}
abstractNote = {The first part of this study is an application of nuclear magnetic resonance to the determination of the sign and magnitude of the long range nuclear-electron spin-spin couplings in the free radical nitroxide derived from piperidine. It has been shown that the coupling constants of the protons {gamma} to the nitrogen atom have a pronounced spatial dependence as do the protons in the {beta} position, a point which has not been brought out by previous investigations. Conformational analysis of these compounds has been carried out by measurement of the effect of temperature on the NMR spectra at 310 MHz. The synthesis of di-t-Bu nitroxide labelled with C{sup 13} in the {alpha}-position made possible the unambiguous determination of the corresponding {sup 13}C nuclear-electron spin-spin coupling constant, a parameter which had not previously been measured. The coupling constants measured in the 2,2,6,6-tetramethyl piperidine series could then be attributed to the {sup 13}C atoms in the {beta}-position and their variation related to the conformations of the heterocycles. This constitutes the second part of the work reported here. The final section is devoted to a study of the decomposition of an unstable nitroxide having a hydrogen atom in the p-position. This decomposition is bimolecular and the primary isotope effect shows that the rupture. of the C-H bond is involved. From this one can conclude that a nitroxide is stable when the different groups attached to the nitrogen atom cannot give rise to a decomposition either intra molecularly, if the molecular geometry is suitable, or inter molecularly by dimerisation through attack on a different center of a neighbouring molecule thus leading to a fragmentation or a disproportionation. (author) [French] La premiere partie est une application de la resonance magnetique nucleaire a la determination du signe et de la grandeur des couplages a longue distance dans des radicaux libres nitroxydes piperidiniques. Il est montre que les constantes de couplage des protons situes en {gamma} de l'azote ont une dependance spatiale tres marquee au meme titre que les protons situes en {beta}, ce que les etudes anterieures n'avaient pu preciser. Une analyse conformationnelle est effectuee par RMN a 310 MHz, en temperature variable. La synthese du di-t-butyl nitroxyde marque au carbone 13 en position {alpha} du groupement nitroxyde a permis de determiner avec certitude la constante d'interaction hyperfine electron carbone 13 quaternaire, grandeur qui n'avait pas ete mesuree jusqu'alors. Les constantes de couplage mesurees dans les radicaux piperidiniques tetramethyles en 2,2,6,6 ont pu etre ensuite attribuees a des carbones 13 situes en {beta} de l'azote, et leur variation a pu etre reliee a la conformation des cycles. C'est l'objet de la seconde partie. Dans un dernier chapitre, l'etude cinetique d'un radical nitroxyde instable, ayant un hydrogene en {beta}, met en evidence une decomposition bimoleculaire qui met en jeu la rupture de la liaison C-H; ceci est demontre par effet isotopique primaire. On peut conclure de cette etude qu'un nitroxyde est stable lorsque les differents groupes attaches a l'atome d'azote ne peuvent provoquer une decomposition du radical, soit intramoleculairement, si la geometrie de la molecule le permet, soit intermoleculairement par dimerisation sur un autre centre d'une molecule voisine, conduisant ainsi a une fragmentation ou a une disproportionation. (auteur)}
place = {France}
year = {1969}
month = {Mar}
}