Thermal decomposition of allylbenzene ozonide

Ewing, James C.; Church, Daniel F.; Pryor, William A.

doi:10.1021/ja00197a052

Cited by 26 publications

(22 citation statements)

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“…The results of this investigation on the thermal decomposition of EO-SOZ and EE-SOZ are completely in line with the work of other investigators performed on other ozonides (Bernatek and Hvatum, 1960;Ewing et al 1989;Hull et al 1972;Herron et al 1982;Pryde et al 1966;Razumovskii and Zaikov, 1984;Story et al 1968) as well as the work done on the ozonides of fatty acid esters (Privett and Nickell 1966). The latter authors were among the first to propose that the thermal decomposition of secondary ozonides involves the homolytic cleavage of O-O bond, which is also considered to be the rate-determining step leading to aldehydes, carboxylic acid, and other minor products.…”

Section: Insight In the Thermal Decomposition Of Ethyl Oleate Ozonidesupporting

confidence: 91%

“…Furthermore, secondary ozonides are important intermediates in synthetic organic chemistry (Van Ornum et al 2006) and the thermal (Bernatek and Hvatum 1960;Ewing et al 1989;Hull et al 1972;Razumovskii andZaikov 1984: Story et al 1968) and photochemical (Hawkins et al 1982;Khachatryan et al 1997;Story et al 1969) rearrangement of ozonides has been little investigated although some studies appear very promising (Barrero et al 2000). This has stimulated our interest on the stability and on the thermochemistry of ozonides in general (Cataldo, 2014(Cataldo, , 2015, starting from ethyl oleate ozonide in particular (Cataldo 2013a).…”

Section: Introductionmentioning

confidence: 99%

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Ethyl Oleate and Ethyl Elaidate Ozonides: Thermal Decomposition and Photolysis

Cataldo¹

2015

Ozone: Science & Engineering

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Highly pure ethyl oleate and ethyl elaidate were ozonized to their secondary ozonides (respectively EO-SOZ and EE-SOZ). The decomposition enthalpies of EO-SOZ and EE-SOZ were determined by DSC (Differential Scanning Calorimetry) and found, respectively, at -266 kJ/mol and -264 kJ/mol, a value much closer to the theoretically calculated upper limit of -278 kJ/mol than the decomposition enthalpy of -243 kJ/mol measured on EO-SOZ prepared from an ethyl oleate sample conforming to the European Pharmacopoeia. Although a considerable amount of heat was liberated, EO-SOZ and EE-SOZ cannot be defined as explosive based on their DSC traces at a heating rate of 10 • C/min. Pure EO-SOZ and EE-SOZ show a decomposition peak at the DSCs of 137 • C and 139 • C, respectively. The thermal decomposition of EO-SOZ and EE-SOZ was studied also by FT-IR spectroscopy showing that the decomposition involves the loss of the ozonide infrared band at 1110 cm −1 and the formation of the expected decomposition products (pelargonic acid, pelargonaldehyde, ethyl azelate, etc.). The kinetics of the photochemical decomposition of EO-SOZ and EE-SOZ were studied by FT-IR spectroscopy, and the relative rate constants were determined. EO-SOZ when overozonized forms a spin adduct with nitrosobenzene and the relative nitroxyl radical was clearly detected by the Electron Spin Resonance (ESR). Secondary ozonation products known as trioxides may be responsible for these adducts.

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Section: Insight In the Thermal Decomposition Of Ethyl Oleate Ozonidesupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Ethyl Oleate and Ethyl Elaidate Ozonides: Thermal Decomposition and Photolysis

Cataldo¹

2015

Ozone: Science & Engineering

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“…This is likely due to the slow diffusive exchange of the Criegee zwitterions between two different intermediate pairs on the solid support surface. In contrast, in solution where motion of the fragments is less restricted, such cross-ozonide formation can be significant; While the primary ozonide is not sufficiently stable to be observed, except at low temperatures (43)(44)(45)(46)(47), the secondary ozonides are sufficiently stable that they can be characterized and their rates of decomposition deter- et al (23,24) suggest could be important in the initiation of the autoxidation of lipid in biological systems.…”

Section: Discussionmentioning

confidence: 99%

“…A number of previous studies have reported secondary ozonide formation from the reaction of model compounds for naturally occurring lipids, including those in pulmonary surfactant. For example, Roehm et al (13,14) reported ozonide formation from methyl oleate and methyl linoleate using infrared spectroscopy and thin-layer chromatography, and Ewing et al (23) synthesized and characterized the secondary ozonides of these esters as well as those of the allylbenzene and 1-octene. The mechanism of formation of these secondary ozonides is believed to involve the Criegee mechanism (35,41,42) as shown in Scheme 1.…”

Section: Discussionmentioning

confidence: 99%

Formation of secondary ozonides from the reaction of an unsaturated phosphatidylcholine with ozone

Finlayson-Pitts²,

Wv³

1990

Chem. Res. Toxicol.

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Phosphatidylcholines are significant components of pulmonary surfactant in the alveolar region of the lung, where they play a major role in lung function due to their surface tension reducing properties. However, separation and the direct identification of many of the primary products of reaction of phosphatidylcholines with inhaled pollutant gases has not been possible until recently due to the lack of suitable analytical techniques, so that compounds such as fatty acid methyl esters generally have been used as analogues for the phospholipids. We report here the first isolation and identification of the products of reaction of ozone with one of the unsaturated components of lung surfactant, beta-oleoyl-gamma-palmitoyl-L-alpha-phosphatidylcholine (OPPC), using a combination of high-performance liquid chromatography, fast atom bombardment mass spectrometry, and Fourier transform infrared, ultraviolet absorption, and nuclear magnetic resonance spectrometry as well as gas chromatography. The products are shown to be the cis and trans secondary ozonides of the parent phosphatidylcholine, analogous to those previously observed by other researchers in the reactions of the simple fatty acid methyl esters with ozone. This also appears to be the first report of fast atom bombardment mass spectra of these phospholipid secondary ozonides. The implications of this work for the inhalation of ozone, formed in photochemical smog, are discussed.

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“…The intermediacy of the biradical is also consistent with a variety of other products observed upon ozonide activation. While it is well known that ozonolysis of alkenes produces hydroxyl radicals [ 26 – 30 ], work by Pryor and co-workers investigating the thermal decomposition of the secondary ozonide of allylbenzene found evidence for the formation of carbon- and oxygen-centered radicals [ 21 ]. UV-photolysis of secondary ozonides has also been reported with several studies observing spectroscopic signatures consistent with products of biradical decomposition [ 17 , 24 , 31 – 33 ].…”

Section: Introductionmentioning

confidence: 99%

Radical Generation from the Gas-Phase Activation of Ionized Lipid Ozonides

Ellis

Panhuis

Trevitt

et al. 2017

J. Am. Soc. Mass Spectrom.

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Reaction products from the ozonolysis of unsaturated lipids at gas–liquid interfaces have the potential to significantly influence the chemical and physical properties of organic aerosols in the atmosphere. In this study, the gas-phase dissociation behavior of lipid secondary ozonides is investigated using ion-trap mass spectrometry. Secondary ozonides were formed by reaction between a thin film of unsaturated lipids (fatty acid methyl esters or phospholipids) with ozone before being transferred to the gas phase as [M + Na]+ ions by electrospray ionization. Activation of the ionized ozonides was performed by either energetic collisions with helium buffer-gas or laser photolysis, with both processes yielding similar product distributions. Products arising from the decomposition of the ozonides were characterized by their mass-to-charge ratio and subsequent ion-molecule reactions. Product assignments were rationalized as arising from initial homolysis of the ozonide oxygen–oxygen bond with subsequent decomposition of the nascent biradical intermediate. In addition to classic aldehyde and carbonyl oxide-type fragments, carbon-centered radicals were identified with a number of decomposition pathways that indicated facile unimolecular radical migration. These findings reveal that photoactivation of secondary ozonides formed by the reaction of aerosol-bound lipids with tropospheric ozone may initiate radical-mediated chemistry within the particle resulting in surface modification. Graphical Abstractᅟ Electronic supplementary materialThe online version of this article (doi:10.1007/s13361-017-1649-4) contains supplementary material, which is available to authorized users.

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Thermal decomposition of allylbenzene ozonide

Cited by 26 publications

References 1 publication

Ethyl Oleate and Ethyl Elaidate Ozonides: Thermal Decomposition and Photolysis

Ethyl Oleate and Ethyl Elaidate Ozonides: Thermal Decomposition and Photolysis

Formation of secondary ozonides from the reaction of an unsaturated phosphatidylcholine with ozone

Radical Generation from the Gas-Phase Activation of Ionized Lipid Ozonides

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