Ozone Oxidation of Nucleophilic Substances. I. Tertiary Phosphite Esters<sup>1</sup>

Thompson, Quentin E.

doi:10.1021/ja01465a027

Cited by 98 publications

(28 citation statements)

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“…Upon warming to Ϫ35°C, phosphates are produced, and molecular oxygen evolution is observed. On the basis of 31 P-NMR measurements, it was concluded that the precursor triphenyl phosphite-ozone adduct has a four-membered cyclic structure (42). Furthermore, based on the principle of spin-conservation, in 1964, Corey and Taylor suggested that the molecular oxygen evolved in this reaction is singlet molecular oxygen (43).…”

Section: Discussionmentioning

confidence: 99%

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

Khan

Kovacic

Kolbanovskiy

et al. 2000

Proc. Natl. Acad. Sci. U.S.A.

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The mechanism of decomposition of peroxynitrite (OONO ؊ ) in aqueous sodium phosphate buffer solution at neutral pH was investigated. The OONO ؊ was synthesized by directly reacting nitric oxide with superoxide anion at pH 13. The hypothesis was explored that OONO ؊ , after protonation at pH 7.0 to HOONO, decomposes into 1 O2 and HNO according to a spin-conserved unimolecular mechanism. Small aliquots of the concentrated alkaline OONO ؊ solution were added to a buffer solution (final pH 7.0 -7.2), and the formation of 1 O2 and NO ؊ in high yields was observed. The 1 O2 generated was trapped as the transannular peroxide (DPAO2) of 9,10-diphenylanthracene (DPA) dissolved in carbon tetrachloride. The nitroxyl anion (NO ؊ ) formed from HNO (pKa 4.5) was trapped as nitrosylhemoglobin (HbNO) in an aqueous methemoglobin (MetHb) solution. In the presence of 25 mM sodium bicarbonate, which is known to accelerate the rate of decomposition of OONO ؊ , the amount of singlet oxygen trapped was reduced by a factor of Ϸ2 whereas the yield of trapping of NO ؊ by methemoglobin remained unaffected. Because NO3 ؊ is known to be the ultimate decomposition product of OONO ؊ , these results suggest that the nitrate anion is not formed by a direct isomerization of OONO ؊ , but by an indirect route originating from NO ؊ .nitrosylhemoglobin ͉ diphenylanthracene endoperoxide P eroxynitrite is a potent oxidant formed by the near diffusioncontrolled reaction of nitric oxide (NO ⅐ ) and superoxide ion (O 2 Ϫ ) (1). Both nitric oxide and superoxide are produced by activated macrophages (2, 3), neutrophils (4), and endothelial cells (5, 6). There is evidence that peroxynitrite is formed in significant concentrations in vivo (7-9) and may contribute to an increased risk for cancer (10), artherosclerosis (11), stroke (12), and other diseases (13). Peroxynitrite is a stable anion in alkaline solution (pKa of 6.8); however, once protonated, it decomposes rapidly with a half-life of less than 1 s at physiological pH at 37°C (14), generating reactive species that readily react with biomolecules such as lipids (15), amino acids (16), and DNA (17). Central to the question of the biochemistry of peroxynitrite is the mechanism of decomposition and the identity of the reactive species, a subject of intense research and controversy (18-21). Speculations about the decomposition mechanisms are largely based on kinetic and thermodynamic considerations (22). It has been shown that bicarbonate ion enhances the rate of disappearance of peroxynitrite, leading to the proposal of a nitrosoperoxycarbonate anion adduct, with a distinctly different chemistry from that of OONO Ϫ (19). We reported previously that the mere acidification of an aqueous peroxynitrite solution resulted in chemiluminescence at 1,270 nm characteristic of the deactivation of singlet oxygen (23). By comparing the intensity of this emission to that of 1 O 2 generated by the reaction of hydrogen peroxide (H 2 O 2 ) with hypochlorite anion (OCl Ϫ ), which is known to be stoichiometric (24), it wa...

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Section: Discussionmentioning

confidence: 99%

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

Khan

Kovacic

Kolbanovskiy

et al. 2000

Proc. Natl. Acad. Sci. U.S.A.

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“…The initial product 1 from triphenylphosphite contains pentacovalent phosphorus (,'P n.m.r.) (2) and decomposes slowly at -70°, although triphenylphosphine in contrast does not give a stable adduct (2).…”

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confidence: 98%

“…The reaction of ozone with heteroatom compounds containing free electron pairs or dorbitals has come under increasing study in recent years (1)(2)(3)(4)(5). In most cases the final products do not incorporate all three oxygen atoms of the ozone and variously formulated intermediates have been proposed.…”

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confidence: 99%

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The Rate Constants for the Reactions of Ozone with Triphenylphosphite and Triphenylphosphine

Разумовский¹,

Mendenhall²

1973

Can. J. Chem.

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The stoichiometry and rate constants for the reaction of triphenylphosphite and triphenylphosphine with ozone were measured at several temperatures. The rate was first order in each reactant, with k = (3f 1) x lo4 and ( 5 f 2 ) x lo3 M -' s-' , respectively, for the reaction of ozone with triphenylphosphine and triphenylphosphite (2,4-dimethylhexane, -9 0 ) . The reaction of ozone with triphenylphosphite has a low activation energy in carbon tetrachloride. The stoichiometry was 1:l for both compounds under these conditions. La stoechiomCtrie et les constantes de vitesse de la reaction entre le triphCnylphosphite et la triphinylphosphine avec I'ozone ont Bte mesurees a diverses temptratures. La vitesse est du premier ordre pour chaque reactant avec k = ( 3 i 1) x loJ et ( 5 2 2) x lo3 M -' s-' respectivement pour la triphCny1-phosphine et le triphCnylphosphite (dimithyl-2,4-hexane, -90"). La reaction de I.ozone sur le triphinylphosphite possede une faible energie d'activation dans le tCtrachlorure de carbone. La stoechiometrie est de 1 :1 pour les deux composes dans ces conditions.[Traduit par le journal]Can.

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“…Le bilan de I'action des ozonides sur ces capteurs peut s'Ccrire selon les reactions [2], [3] et [4] (23,24). Ce resultat confirrne que la voie d'oxydation la plus probable obtenue par l'ozonide l a est celle qui passe par la gtneration d"02 (25) (voie (ii), schema 1).…”

Section: Resultatsunclassified

Ozonides de phosphite source d'oxygène singulet: rendement, mécanisme

Caminade¹,

Khatib²,

Koenig³

et al. 1985

Can. J. Chem.

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Chem. 63, 3203 (1985). Nous avons fait rCagir dans le dichloromethane les ozonides de plusieurs phosphites sur differents capteurs d'oxygkne singulet ('0,): le rubrkne 2, la tCtraphenylcyclopentadienone 4 et le diphenyl-9.10-anthrackne 6. Ces ozonides riagissent lors de leur dCcomposition (-47°C < t < 30°C) sur ces capteurs. Les droitcs de Foote obtenues en faisant varier les concentrations respectives d'ozonides et de capteurs conduisent aux mtmes parametres que ceux obtenus lors de la photooxydation par '0, de ces capteurs. Cela confirme I'aptitude de ces ozonides B engendrer 'O?. La valeur trouvCe du rendement absolu en 'O? est de 100% (p = 1). Les rtsultats confirment aussi la grande efficacitd "is-B-vis de '0, du rubrene (y = 1) et la valeur moyenne de la tCtraphCnylcyclopentadienone (y = 0,46). La valeur faible (y = 0.3) de I'efficacitC du diphtnyl-9,lO-anthrackne 4 est par contre inattendue.ANNE MARIE CAMINADE, FAYEZ EL KHATIB, MAX KOENIG, and JEAN MARIE AUBRY. Can. J. Chem. 63, 3203 (1985). The ozonides of several phosphites in solution in dichloromcthane have been reacted with some scavengers of singlet oxygen ('04 like rubrene (2), tetraphenylcyclopentadienone (4). and 9,IO-diphenylanthracene (6). These ozonides react on the scavengers (-47°C < t < 30°C) upon their decomposition. The Foote curves obtained by varying the respective concentrations of ozonides and of scavengers lead to parameters similar to those obtained upon the photooxidation of the scavengers by 'Oz.Results confirm that these ozonides can lead to the formation of lo2. The absolutc yield of 'Oz is 100% (p = I). These results also confirm the high efficiency of the rubrene toward '02 (y = I ) and the lower efficiency of the tetraphenylcyclopentadienone (y = 0.46). However, the low value (y = 0.3) for the efficiency of the 9,lO-diphenylanthracene (4) is unexpected.[ ' Auteurs B qui adresser la correspondance. ResultatsNous avons fait reagir dans le dichloromCthane les differents ozonides la-cl sur trois capteurs classiques d'oxygkne sin-

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Ozone Oxidation of Nucleophilic Substances. I. Tertiary Phosphite Esters¹

Cited by 98 publications

References 4 publications

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

The Rate Constants for the Reactions of Ozone with Triphenylphosphite and Triphenylphosphine

Ozonides de phosphite source d'oxygène singulet: rendement, mécanisme

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Ozone Oxidation of Nucleophilic Substances. I. Tertiary Phosphite Esters1

Cited by 98 publications

References 4 publications

The decomposition of peroxynitrite to nitroxyl anion (NO − ) and singlet oxygen in aqueous solution

The decomposition of peroxynitrite to nitroxyl anion (NO − ) and singlet oxygen in aqueous solution

The Rate Constants for the Reactions of Ozone with Triphenylphosphite and Triphenylphosphine

Ozonides de phosphite source d'oxygène singulet: rendement, mécanisme

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Product

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Ozone Oxidation of Nucleophilic Substances. I. Tertiary Phosphite Esters¹

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution