The Ozonolysis of Terpenoids, a Pandora's Box of by-Products

Hanson, James R.

doi:10.3184/174751917x15064232103029

Cited by 11 publications

(5 citation statements)

References 85 publications

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“…In non-polar organic solvents, the aromatic aldehyde product was further oxidized by ozone to the corresponding perbenzoic acid, which subsequently decomposed to benzoic acid. 31 When using a mixture of water and organic solvent, 32 the formal dehydration of the hydroxy hydroperoxide intermediate via Baeyer−Villiger-type fragmentation yields benzoic acid instead of the desired aldehyde (Scheme 1, blue pathway). 4a, 16,33 Having optimal conditions in hand for the aqueous ozonolysis of alkene 1 in the presence of Coolade as the most suitable surfactant, the scope of alkene substrates was examined with other aliphatic and aromatic alkenes (Table 2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

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Surfactant-Assisted Ozonolysis of Alkenes in Water: Mitigation of Frothing Using Coolade as a Low-Foaming Surfactant

et al. 2022

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Aqueous-phase ozonolysis in the atmosphere is an important process during cloud and fog formation. Water in the atmosphere acts as both a reaction medium and a reductant during the ozonolysis. Inspired by the atmospheric aqueous-phase ozonolysis, we herein report the ozonolysis of alkenes in water assisted by surfactants. Several types of surfactants, including anionic, cationic, and nonionic surfactants, were investigated. Although most surfactants enhanced the solubility of alkenes in water, they also generated excessive foaming during the ozone bubbling, which led to the loss of products. Mitigation of the frothing was accomplished by using Coolade as a nonionic and low-foaming surfactant. Coolade-assisted ozonolysis of alkenes in water provided the desired carbonyl products in good yields and comparable to those achieved in organic solvents. During the ozonolysis reaction, water molecules trapped within the polyethylene glycol region of Coolade were proposed to intercept the Criegee intermediate to provide a hydroxy hydroperoxide intermediate. Decomposition of the hydroxy hydroperoxide led to formation of the carbonyl product without the need for a reductant typically required for the conventional ozonolysis using organic solvents. This study presents Coolade as an effective surfactant to improve the solubility of alkenes while mitigating frothing during the ozonolysis in water.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Surfactant-Assisted Ozonolysis of Alkenes in Water: Mitigation of Frothing Using Coolade as a Low-Foaming Surfactant

et al. 2022

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“…Under these conditions, the ozonation of 2 was fast; however, a mixture of products was obtained (Scheme ). , Careful separation of the reaction mixture and analysis of the isolated products revealed that four compounds were obtained in this reaction. It must be noted that the composition of the mixture and the yields of the products changed significantly from batch to batch.…”

Section: Resultsmentioning

confidence: 99%

Oxidative Functionalization of Trinor-18α-olean-17(22)-ene Derivatives. Annulation of the E-Ring by an Intramolecular Aldol Reaction

et al. 2021

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cis -Dihydroxylation of trinor-18α-olean-17(22)-ene 2 with osmium tetroxide led to diol 9 . Its cleavage with lead tetraacetate gave tetracyclic ketoaldehyde 10 . By comparison, the ozonation of trinor-18α-olean-17(22)-ene 2 in the presence of p -toluenesulfonic acid gave the corresponding ketoacetal 12 . Both products were subjected to an intramolecular aldol reaction under the acidic conditions and yielded unusual triterpenes bearing a bicyclo[4.3.1]decane fragment ( 22 ). Further manipulation of the protective groups afforded compounds useful in triterpene synthesis, especially in the preparation of potentially biologically active saponins based on a tetracyclic terpene core.

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“…It has been proven that firstly, terpene is attacked by ozone in the place of double bonding, and a primary ozonide (PO) is formed. PO is then decomposed to form the so-called "Criegee intermediate", which is highly reactive and will undergo further reactions, which are still under investigation [8][9][10][11][12]. Some terpenes' oxidation products may remain in a gaseous phase, while others may undergo homogeneous nucleation or condensation on preexisting particles.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Dynamism of Nanosized SOA Particle Formation in Indoor Air by a Scanning Mobility Particle Sizer and Proton-Transfer-Reaction Mass Spectrometry

2020

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Terpenes are VOCs of particular importance, since they are emitted from a wide range of indoor sources and are considered to be precursors of Secondary Organic Aerosol (SOA) formation. It has been proven that SOA particles, especially nanosized ones, pose a threat to human health. In this research, experiments with the application of an environmental chamber and real-time measurement techniques were carried out to investigate in a complimentary way the formation of monoterpene oxidation products and nanosized SOA particles initiated by monoterpene ozonolysis. Proton-Transfer-Reaction Mass Spectrometry with a Time-Of-Flight analyzer (PTR-TOF-MS) and a Scanning Mobility Particle Sizer (SMPS) were applied to determine in real time the dynamism of the formation of the corresponding terpene ozonolysis products and submicron SOA particles. Results proved that firstly, oxidation products were formed, and then, they underwent nucleation and condensation, forming particles whose diameters grew with time. The oxidation products formed were different depending on the type of terpenes applied. The comparison of the results obtained during the experiments with gaseous standard mixtures and real samples commonly present and used in indoor air revealed that the diversified chemical composition of the emission source had implications for both the particle formation initiated by the oxidation of essential oil components and the chemical reactions occurring via the oxidation process. With the instrumentation utilized, the concentration changes at the level of a few ppbv could be monitored.

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The Ozonolysis of Terpenoids, a Pandora's Box of by-Products

Abstract: The ozonolysis of terpenoids is described and the origins of some by-products are discussed.

Cited by 11 publications

References 85 publications

Surfactant-Assisted Ozonolysis of Alkenes in Water: Mitigation of Frothing Using Coolade as a Low-Foaming Surfactant

Surfactant-Assisted Ozonolysis of Alkenes in Water: Mitigation of Frothing Using Coolade as a Low-Foaming Surfactant

Oxidative Functionalization of Trinor-18α-olean-17(22)-ene Derivatives. Annulation of the E-Ring by an Intramolecular Aldol Reaction

Investigation of the Dynamism of Nanosized SOA Particle Formation in Indoor Air by a Scanning Mobility Particle Sizer and Proton-Transfer-Reaction Mass Spectrometry

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