Chemical and thermochemical aspects of the ozonolysis of ethyl oleate: Decomposition enthalpy of ethyl oleate ozonide

Cataldo, Franco

doi:10.1016/j.chemphyslip.2013.07.005

Cited by 26 publications

(30 citation statements)

References 39 publications

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“…The ethyl oleate secondary ozonide (EO-SOZ) showed an exothermal decomposition peak at about 150-155 • C. The experimental decomposition enthalpy of EO-SOZ H dec = -243 kJ/mol was found in close agreement with the theoretically calculated value of -278.5 kJ/mol. More refined calculations (Cataldo 2014) considering all possible ozonization products of ethyl oleate (see Figure 1) from the canonical secondary ozonides to the bis-peroxide and all the possible polymeric ozonides (polycarbonyl oxide oligomer, peroxide oligomer) and the resulting decomposition products have led to the conclusion that all the considered products should release a decomposition enthalpy in the narrow range comprised between -278 kJ/mol to -298 kJ/mol, with the former value representing the upper limit, coincident with that obtained by our previous calculation (Cataldo 2013a). The most recent study on the decomposition enthalpy of 1-alkene ozonides (Cataldo 2015) has revealed, for this homologous series, that the H dec values range between −313 kJ/mol for 1-decene ozonide to -347 kJ/mol for 1-octadecene ozonide.…”

Section: Introductionsupporting

confidence: 61%

“…Eur. used in the previous work (Cataldo 2013a). In order to compare our enhanced calculations on the decomposition enthalpy of EO-SOZ (Cataldo 2014), we have ozonized an analytical grade (98.5% pure) ethyl oleate and, for comparison, an analytical grade of ethyl elaidate, both obtained from Aldrich.…”

Section: Decomposition Enthalpy Of Secondary Ozonides Of Ethyl Oleatementioning

confidence: 99%

“…The desired ratio O 3 /C=C was controlled by the amount of ozone introduced in the flask. To control the degree of ozonation, one drop of EO-SOZ or EE-SOZ was taken from the flask and put onto the ZnSe crystal of the FT-IR spectrometer to check the integrated absorptivity of the ozonide band at 1110 cm −1 as already detailed in the previous work (Cataldo 2013a).…”

Section: Ozonization Of Ethyl Oleate and Ethyl Elaidatementioning

confidence: 99%

“…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%

“…In a previous work (Cataldo 2013a), commercial ethyl oleate ozonation was studied by FT-IR spectroscopy and by differential scanning calorimetry (DSC). Both the integrated absorptivity of the ozonide infrared band at 1110 cm −1 and the thermal decomposition enthalpy of the resulting ethyl oleate ozonides gave a linear relationship with of the ozonation time.…”

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: Introductionsupporting

confidence: 61%

Section: Decomposition Enthalpy Of Secondary Ozonides Of Ethyl Oleatementioning

confidence: 99%

Section: Ozonization Of Ethyl Oleate and Ethyl Elaidatementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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Biobased Aldehydes from Fatty Epoxides through Thermal Cleavage of β‐Hydroxy Hydroperoxides**

Miguel

Lemaire

et al. 2020

ChemSusChem

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The ring-opening of epoxidized methyl oleate by aqueous H 2 O 2 has been studied using tungsten and molybdenum catalysts to form the corresponding fatty β-hydroxy hydroperoxides. It was found that tungstic acid and phosphotungstic acid gave the highest selectivities (92-93 %) towards the formation of the desired products, thus limiting the formation of the corresponding fatty 1,2-diols. The optimized conditions were applied to a range of fatty epoxides to give the corresponding fatty βhydroxy hydroperoxides with 30-80 % isolated yields (8 examples). These species were fully characterized by 1 H and 13 C NMR spectroscopy and HPLC-HRMS, and their stability was studied by differential scanning calorimetry. The thermal cleavage of the β-hydroxy hydroperoxide derived from methyl oleate was studied both in batch and flow conditions. It was found that the thermal cleavage in flow conditions gave the highest selectivity towards the formation of aldehydes with limited amounts of byproducts. The aldehydes were both formed with 68 % GC yield, and nonanal and methyl 9-oxononanoate were isolated with 57 and 55 % yield, respectively. Advantageously, the overall process does not require large excess of H 2 O 2 and only generates water as a byproduct.

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Correlation of structural characterization and viscosity measurements with total unsaturation: An effective method for controlling ozonation in the preparation of ozonated grape seed and sunflower oils

Guerra-Blanco¹,

Poznyak²,

Chairez³

et al. 2015

Euro J Lipid Sci & Tech

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Ozonated oils have demonstrated promising results for clinical applications. The reaction of ozone with the unsaturated compounds of oils produces by‐products such as ozonides and poly peroxides. A deeper knowledge of the dynamics of by‐product formation is helpful in determining the required ozonation degree to obtain therapeutic effects. The aim of this paper is to show the relationship between ozonation degree and structural and viscosity changes during the ozonation of grape seed (GS) and sunflower (SF) oils. Structural characterization was done by Fourier transform infrared (FT‐IR) and hydrogen‐1 nuclear magnetic resonance (1H NMR) spectroscopy, with iso‐ozonides being identified. Viscosity showed a significant increase during ozonation, a fact associated with poly peroxide formation. We have made use of the total unsaturation (TU) method to measure the ozonation degree. The TU of non‐ozonated GS oil was found to be higher than for SF oil (5.94 and 4.49 mmol per g of oil, respectively), and their by‐product distributions were also found to differ. In GS oil, three reaction steps were observed for double‐bond conversion into iso‐ozonides and poly peroxides, while the ozonides and poly peroxides were formed in parallel in SF oil. The studies we implemented characterized the differences in the reactivities of these oils with ozone. Practical applications: In this work, we propose using the TU method to measure the ozonation degree of ozonated oils. TU experimental determination is based on the ozonation of the sample, and the ozone‐oxidizable substrate is quantified. Despite GS and SF oils having similar fatty acid compositions, they contain other unsaturated compounds specific to their vegetal sources. These compounds are also reactive with ozone, and are also quantified by the TU method. The differences in distributions of by‐products among ozonated oils from different sources could explain why the ozonation degree need not be the same for different oils. Studies like this represent a feasibility foundation for controlling the therapeutic application of ozonated oils and correctly interpreting their well‐known clinical effects. Ozonated vegetable oils have many interesting applications in the food, cosmetic, and pharmaceutical industries, as well as in medicine. A deeper knowledge of the dynamics of by‐product formation is helpful in determining the required ozonation degree to obtain therapeutic effects. In this work, we propose using the total unsaturation method to measure the ozonation degree of ozonated oils. We showed the relationship between ozonation degree and structural and viscosity changes during the ozonation of grape seed and sunflower oils. The differences in distributions of by‐products among ozonated oils from different sources could explain why the ozonation degree need not be the same for different oils.

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Chemical and thermochemical aspects of the ozonolysis of ethyl oleate: Decomposition enthalpy of ethyl oleate ozonide

Cited by 26 publications

References 39 publications

Ethyl Oleate and Ethyl Elaidate Ozonides: Thermal Decomposition and Photolysis

Ethyl Oleate and Ethyl Elaidate Ozonides: Thermal Decomposition and Photolysis

Biobased Aldehydes from Fatty Epoxides through Thermal Cleavage of β‐Hydroxy Hydroperoxides**

Correlation of structural characterization and viscosity measurements with total unsaturation: An effective method for controlling ozonation in the preparation of ozonated grape seed and sunflower oils

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