Cycloalkene ozonolysis: collisionally mediated mechanistic branching

Master equation calculations on a computational potential energy surface reveal that collisional stabilization at atmospheric pressure becomes important in the gas-phase ozonolysis of endocyclic alkenes for a carbon number between 8 and 15. Because the reaction products from endocyclic ozonolysis are tethered, this system is ideal for consideration of collisional energy transfer, as chemical activation is confined to a single reaction product. Collisional stabilization of the Criegee intermediate precedes collisional stabilization of the primary ozonide by roughly an order of magnitude in pressure. The stabilization of the Criegee intermediate leads to a dramatic transformation in the dominant oxidation pathway from a radical-forming process at low carbon number to a secondary ozonide-forming process at high carbon number. Secondary ozonide formation is important even for syn-isomer Criegee intermediates, contrary to previous speculation. We use substituted cyclohexenes as analogues for atmospherically important mono- and sesquiterpenes, which are major precursors for secondary organic aerosol formation in the atmosphere. Combining these calculations with literature experimental data, we conclude that the transformation from chemically activated to collisionally stabilized behavior most probably occurs between the mono- and sesquiterpenes, thus causing dramatically different atmospheric behavior.     

Complete ozonolysis of alkyl substituted ethenes at -60 degrees C: distributions of ozonide and oligomeric products

The distribution of ozonide and oligomeric structures formed on complete ozonolysis of alkenes in a non-participating solvent at -60 degrees C is governed by the alkyl substitution around the carbon-carbon double bond. The ozonolysis of a 1,1-alkyl substituted ethene generally favours the formation of an ozonide (a 1,2,4-trioxolane). Whereas the ozonolysis of a 1,1,2-alkyl substituted ethene also produces ozonide, a considerable amount of the ozonised products are oligomeric in nature. For example, the ozonolysis of 3-methylpent-2-ene in solution to high conversion in pentane yields oligomers with structural units derived from the fragmentation products of the primary ozonide (a 1,2,3-trioxolane) which are namely butanone carbonyl oxide and acetaldehyde; these can be characterised by electrospray ionisation mass spectroscopy (ESI-MS) under soft ionisation conditions. The predominant oligomers formed are rich in carbonyl oxide units (80 + mol%) and are cyclic in nature. A small proportion of the oligomers formed are open chain compounds with end groups that suggest that chain termination is brought about either by water or by hydrogen peroxide. Residual water in the solvent will react with the carbonyl oxides to produce 2-methoxybut-2-yl hydroperoxide, which we propose readily decomposes generating hydrogen peroxide. A significant yield of oligomers also is obtained from the ozonolysis of a 1,2-alkyl substituted ethene. The ozonolysis of trans-hex-2-ene in pentane yields oligomers containing up to four structural units and are predicted to be mainly cyclic.     

Facile one-pot synthesis of anisaldehyde

At room temperature, anisaldehyde (4-methoxybenzaldehyde) is synthesized based on the ozonolysis of anethole (1-methoxy-4-(1-propenyl)-benzene) in a novel and environmentally friendly system composed of water and ethyl acetate. In the presence of water, ozonolysis of anethole results in the direct formation of anisaldehyde, avoiding the isolation or decomposition of ozonide.     

Kinetics and thermodynamics of limonene ozonolysis

Using density functional methods, the initial reaction steps of limonene ozonolysis have been investigated with a focus on primary ozonide formation and its decomposition to Criegee intermediates and carbonyl compounds. The ozonide formation is highly exothermic, and the decomposition channels have similar free energies of activation, ΔG(?), indicating that there is no primary pathway for ozonide decomposition. Assuming that ozonide formation is the rate limiting step, the theoretical rate coefficient, k = 1.6 × 10(-16) molecule(-1) cm(3) s(-1), evaluated at the CCSD(T)/6-31G(d,p)//BHandHLYP/cc-pvdz level and 298.15 K for d-limonene is in good agreement with the experimental value, k(exp) = 3.3 × 10(-16) molecule(-1) cm(3) s(-1). The theoretical Arrhenius expression is also in good agreement with experimental results.     

Linear-reactor-infrared-matrix and microwave spectroscopy of the cis-2-butene gas-phase ozonolysis

Investigation of the formation of complex products in the gas-phase ozonolysis of cis,-2-butene by linear-reactor-infrared-matrix and linear-reactor-microwave spectroscopy is reported. The following species have been unequivocally detected: secondary 2-butene ozonide, acetic acid, peracetic acid, glycolaldehyde, dimethyl ketene, the simple and mixed anhydrides of formic and acetic acid, 2,3-epoxybutane and 2-butanone, besides polyatomic products already known. In contrast, the primary ozonide has been detectable neither by LR.-MW. nor by LR.-IR. Observation of both stereoisomeric epoxides and kinetic modelling are used to support the intermediate formation of the O'Neal-Blumstein radical CH₃CH(O₂)CH(O)CH₃ and the existence of a reaction channel in which the two carbon atoms of the C, C double bond of the olefin remain connected. As the dominant reaction path a mechanism with a Criegee type split into methyldioxirane (ethylidene peroxide) and acetaldehyde is considered and subsequently proposed to explain formation of many complex products by either unimolecular or bimolecular processes of the peroxide. For the reactions considered, thermochemical estimates of reaction enthalpies and activation data are included. Kinetic modelling for a partial reaction mechanism involving at least two different paths of decay of the O'Neal-Blumstein biradical into Criegee-type intermediates and the 2, 3-epoxybutanes is discussed.     

‘Reductive ozonolysis’ via a new fragmentation of carbonyl oxides

This account describes the development of methodologies for ‘reductive’ ozonolysis, the direct ozonolytic conversion of alkenes into carbonyl groups without the intermediacy of 1,2,4-trioxolanes (ozonides). Ozonolysis of alkenes in the presence of DMSO produces a mixture of aldehyde and ozonide. The combination of DMSO and Et₃N results in improved yields of carbonyls but still leaves unacceptable levels of residual ozonides; similar results are obtained using secondary or tertiary amines in the absence of DMSO. The influence of amines is believed to result from conversion to the corresponding N-oxides; ozonolysis in the presence of amine N-oxides efficiently suppresses ozonide formation, generating high yields of aldehydes. The reactions with amine oxides are hypothesized to involve an unprecedented trapping of carbonyl oxides to generate a zwitterionic adduct, which fragments to produce the desired carbonyl group, an amine, and ¹O₂.     

Gas-phase ozonolysis of alkenes: formation of OH from anti carbonyl oxides

Gas-phase ozone-alkene reactions are known to produce the hydroxyl radical (OH) in high yields. Most mechanistic studies to date have focused on the role of syn carbonyl oxides; however, OH production from ethene ozonolysis indicates a second, poorly understood OH-forming channel, which may contribute to OH production in the ozonolysis of substituted alkenes as well. Using laser-induced fluorescence, we have measured OH and OD yields from the ozonolysis of two partially deuterated alkenes, cis- and trans-3-hexene-3,4-d2. OD is formed from both alkenes, indicating a pathway of hydroxyl-radical formation involving vinylic hydrogens, accounting for one-third of total OH formation from cis-3-hexene. The lack of a significant kinetic isotope effect suggests this pathway is the "hot acid" channel, arising from rearrangement of anti carbonyl oxides. Measured yields also allow for the estimation of syn:anti carbonyl oxide ratios, approximately 50:50 for trans-3-hexene and approximately 20:80 for cis-3-hexene, qualitatively consistent with our understanding of ozonide decomposition pathways.     

Pressure dependent mechanistic branching in the formation pathways of secondary organic aerosol from cyclic-alkene gas-phase ozonolysis

The gas-phase ozonolysis of cyclic-alkenes (1-methyl-cyclohexene, methylene-cyclohexane, α-pinene, β-pinene) is studied with respect to the pressure dependent formation of secondary organic aerosol (SOA). We find that SOA formation is substantially suppressed at lower pressures for all alkenes under study. The suppression coincides with the formation of ketene (α-pinene, 1-methyl-cyclohexene), ethene (1-methyl-cyclohexene) and the increased formation of CO (all alkenes) at lower reaction pressures. The formation of these products is independent of the presence of an OH scavenger and explained by an increased chemical activation of intermediate species in the hydroperoxide channel after the OH elimination. These findings underline the central role of the hydroperoxide pathway for SOA formation and give insight into the gas-phase ozonolysis mechanism after the stage of the Criegee intermediate chemistry.     

Überraschende Ergebnisse bei der Nachprüfung der Bildung und Zersetzung von Tripten‐ozonid

Surprising Results during the Re‐investigation of the Formation and Decomposition of Triptene Ozonide . Revision of the ozonolysis of triptene (=2,3,3‐trimethylbut‐1‐ene; 1 ) revealed that molecular oxygen of an applied ozone/oxygen gas mixture participates as well in the cleavage of the C=C bond as in the ozonide formation. Ozone‐to‐olefin stoichiometry varies in the range of 0.64 – 0.95 : 1 in terms of complete olefin consumption, depending on solvents, on reaction temperature, and on reaction conditions. Thermal decomposition of distilled monomeric triptene ozonide ( 2 ) does not lead to 3,6‐di(tert‐butyl)‐3,6‐dimethyl‐1,2,4,5‐tetroxane ( 5 ), which is formed by formaldehyde extrusion from an unstable oligomeric (probably dimeric) triptene ozonide 2 ′. Acid‐catalyzed decomposition of 2 exclusively yields pinacolone ( 7 ) and formic acid ( 9 ).     

Mass spectrometric characterization of beta-caryophyllene ozonolysis products in the aerosol studied using an electrospray triple quadrupole and time-of-flight analyzer hybrid system and density functional theory

The components of the organic aerosol formed due to gas-phase beta-caryophyllene ozonolysis were characterized by the use of a triple quadrupole and time-of-flight analyzer hybrid system coupled to an electrospray ionization source operated in the negative ion mode. A reversed-phase high-performance liquid chromatography (HPLC) column was used to achieve chromatographic separations at neutral pH which has been proved to induce ionization of organic compounds bearing aldehyde moieties. In addition to the detected oxo- and dicarboxylic acids, isomeric oxidation products, which bear multi-functional groups such as aldehyde, carbonyl and hydroxyl groups, could be differentiated by examining their corresponding collision-induced dissociation (CID) fragmentation pathways. Proposed fragmentation mechanisms were drawn for the experimentally observed fragmentation pathways in all the CID experiments. Cyclic oxidation products could also be discerned and their fragmentation behaviour under low energy collisional conditions was studied in detail. Gas-phase deprotonation potentials were calculated by the use of DFT B3LYP/6-311+G(2d,p)//B3LYP/6-31+G(d) + ZPVE to estimate the most thermodynamically favourable deprotonation site for efficient negative ion formation in the ion source. The optimized gas-phase geometries for the most prominent oxidation products reveal a strong intramolecular interaction between the upper and lower C4 carbon chains, which are formed after the decomposition of the primary ozonide generated by ozone attack of the reactive endocyclic C==C bond.     

Trimethylsilyl group migrations in cryogenic ozonolysis of trimethylsilylethene: evidence for nonconcerted primary ozonide decomposition pathway

The identification of trimethylsiloxy-1,2-dioxetane and 2-trimethylsilyloperoxyacetaldehyde and assignment of trimethylsiloxymethyl formate as products of the low-temperature ozonolysis of trimethylsilylethene demonstrate feasibility of migrations of trimethylsilyl group in a dioxygen-centered (oxyperoxy) diradical produced via a homolytic cleavage of each of both O-O bonds in the primary ozonide. The results provide the first experimental evidence on the nonconcerted decomposition of the primary ozonide.     

Ozonolysis of methyl, amino and nitro substituted ethenes: A semi-empirical molecular orbital study

The three-step ozonolysis reaction is studied for a number of methyl, amino and nitro substituted ethenes (classified as symmetrically, asymmetrically and cis/trans substituted) using the PM3 SCF-MO method. Substituent effects are predicted to generally yield the order NH₂ > Me > NO₂ for the ability to enhance facility of ozonolysis, in line with the electrophilic nature of ozone. Geometry and conformation allow for a variety of different pathways, and the lowest energy pathway is predicted for each case, with consequences for identity of the intermediates preferentially involved. Greater stability of the trans isomer of the carbonyl oxide intermediate is the main factor for its preferred involvement in the second step of the reaction. For the cis/trans substituted ethenes, the major product (the secondary ozonide) is predicted as being the cis ozonide and the trans ozonide for the cis and the trans substituted ethenes, respectively.     

Direct measurement of Criegee intermediate (CH2OO) reactions with acetone, acetaldehyde, and hexafluoroacetone

Criegee biradicals, i.e., carbonyl oxides, are critical intermediates in ozonolysis and have been implicated in autoignition chemistry and other hydrocarbon oxidation systems, but until recently the direct measurement of their gas-phase kinetics has not been feasible. Indirect determinations of Criegee intermediate kinetics often rely on the introduction of a scavenger molecule into an ozonolysis system and analysis of the effects of the scavenger on yields of products associated with Criegee intermediate reactions. Carbonyl species, in particular hexafluoroacetone (CF(3)COCF(3)), have often been used as scavengers. In this work, the reactions of the simplest Criegee intermediate, CH(2)OO (formaldehyde oxide), with three carbonyl species have been measured by laser photolysis/tunable synchrotron photoionization mass spectrometry. Diiodomethane photolysis produces CH(2)I radicals, which react with O(2) to yield CH(2)OO + I. The formaldehyde oxide is reacted with a large excess of a carbonyl reactant and both the disappearance of CH(2)OO and the formation of reaction products are monitored. The rate coefficient for CH(2)OO + hexafluoroacetone is k(1) = (3.0 ± 0.3) × 10(-11) cm(3) molecule(-1) s(-1), supporting the use of hexafluoroacetone as a Criegee-intermediate scavenger. The reactions with acetaldehyde, k(2) = (9.5 ± 0.7) × 10(-13) cm(3) molecule(-1) s(-1), and with acetone, k(3) = (2.3 ± 0.3) × 10(-13) cm(3) molecule(-1) s(-1), are substantially slower. Secondary ozonides and products of ozonide isomerization are observed from the reactions of CH(2)OO with acetone and hexafluoroacetone. Their photoionization spectra are interpreted with the aid of quantum-chemical and Franck-Condon-factor calculations. No secondary ozonide was observable in the reaction of CH(2)OO with acetaldehyde, but acetic acid was identified as a product under the conditions used (4 Torr and 293 K).     

Heterogeneous ozone oxidation reactions of 1-pentene, cyclopentene, cyclohexene, and a menthenol derivative studied by sum frequency generation

We report vibrational sum frequency generation (SFG) spectra of glass surfaces functionalized with 1-pentene, 2-hexene, cyclopentene, cyclohexene, and a menthenol derivative. The heterogeneous reactions of ozone with hydrocarbons covalently linked to oxide surfaces serve as models for studying heterogeneous oxidation of biogenic terpenes adsorbed to mineral aerosol surfaces commonly found in the troposphere. Vibrational SFG is also used to track the C=C double bond oxidation reactions initiated by ozone in real time and to characterize the surface-bound product species. Combined with contact angle measurements carried out before and after ozonolysis, the kinetic and spectroscopic studies presented here suggest reaction pathways involving vibrationally hot Criegee intermediates that compete with pathways that involve thermalized surface species. Kinetic measurements suggest that the rate limiting step in the heterogeneous C=C double bond oxidation reactions is likely to be the formation of the primary ozonide. From the determination of the reactive uptake coefficients, we find that ozone molecules undergo between 100 and 10000 unsuccessful collisions with C=C double bonds before the reaction occurs. The magnitude of the reactive uptake coefficients for the cyclic and linear olefins studied here does not follow the corresponding gas-phase reactivities but rather correlates with the accessibility of the C=C double bonds at the surface.     

The gas-phase ozonolysis reaction of methylbutenol: A mechanistic study

The gas-phase ozonolysis reaction of methylbutenol through the Criegee mechanism is investigated. The initial reaction leads to a primary ozonide (POZ) formation with barriers in the range of 10–28 kJ mol⁻¹. The formation of 2-hydroxy-2-methyl-propanal (HMP) and formaldehyde-oxide is more favorable, by 10 kJ mol⁻¹, than the syn-CI and formaldehyde. The unimolecular dissociation of the more stable syn-CI via 1,5-H transfer into an epoxide is more favored than the epoxide and ³O₂ formation. The ester channel led to the formation of the acetone and formic acid favorably from the anti-CI. The hydration of the anti-CI with H₂O and (H₂O)₂ is significantly barrierless with a higher plausibility to the latter, and thus they may lead to the formation of peroxides and ultimately OH radicals, as well as airborne particulate matter. Reaction of anti-CI with water dimers enhances its atmospheric reactivity by a factor of 28 in reference to water monomers.     

Ozonolysis of 1,4-cyclohexadienes in the presence of methanol and acid. Mechanism and intermediates in the conversion of 1,4-cyclohexadiene derivatives to beta-keto esters

Conditions for the preparation of beta-keto esters directly from 1,4-cyclohexadiene derivatives are described. This procedure is a further step in the application of the synthetic methodology, which consists of the combination of Birch reduction of available benzene derivatives followed by ozonolysis. In this work, the syntheses of derivatives of dimethyl gamma-keto-alpha-aminoadipate and dimethyl beta-keto glutamate from the corresponding 1,4-cyclohexadiene derivatives are described. The latter compounds are prepared from phenylalanine and phenylglycine, respectively. The study of the ozonolysis of simple alkyl derivatives of 1,4-cyclohexadiene in the presence of methanol, both in the presence and absence of acid, helped to establish the mechanism of this reaction. The proximity of the two double bonds, which are cleaved, leads to the intermediate formation of 1,2-dioxolane derivatives that could be identified by NMR spectroscopy. It is shown that regardless of the regioselectivity of the cleavage of the primary ozonide, which is formed, all 1,2-dioxolane derivatives can lead to beta-keto esters. This is due to the equilibrium between these dioxolanes in the presence of methanol and acid.     

Ozonolysis of naphthoquinones—I Ozonolysis of 1:4-naphthoquinone in chloroform

During ozonisation of 1:4-naphthoquinone in chloroform at −5 to −8° about 70 per cent undergoes anomalous ozonolysis forming phenylglyoxal-o-carboxylic acid and probably carbon monoxide. The remaining 30 per cent forms a normal ozonide which rearranges to a mixed anhydride of formic acid and phenylglyoxal-o-carboxylic acid. Sodium iodide reduction of the normal ozonide produces o-phenylenediglycolaldehyde. An intramolecular benzoin condensation of this substance is discussed.     

Intramolecular Oxygen Transfer on the Ozonolysis of a Diphenylcyclopentene Derivative

The ozonolysis of cis-3,4a,7,7a-tetrahydro-3,3-dimethyl-6,7a-diphenylcyclopenta[1,2,4]trioxine ( 1 ) in CH₂Cl₂ at ?78° gave the secondary endo ozonide 2 (43% yield) and an acetal 3 (27% yield) derived from O-insertion at the ortho position of the C(7a) phenyl substituent. Both structures were elucidated by X-ray. Repetition of the ozonolysis in MeOH/CH₂Cl₂20:3 at ?78° also gave the same two products in 12 and 15% yields, repectively, together with the hemiperacetal 4 (54% yield) formally derived from the secondary ozonide by addition of MeOH.     

Ring-closing double reductive amination route to aza-heteroannulated sugars

1,4-Dicarbonyl derivatives of glycosides are produced by ozonolysis or Wacker oxidation. A stable ozonide is isolated and a carbonyl group reduced whilst maintaining the ozonide functionality. The 1,4-dicarbonyl compounds are converted to various N-substituted pyrrolidines by diastereoselective double reductive amination The resulting aza-heteroannulated sugars no significant inhibition of any glycosidase, with the exception of compound 12g, which is a weak inhibitor of β-galactosidase.     

Conclusive evidence of the trapping of primary ozonides

[reaction: see text] Anomalous ozonolysis of strained bicyclic allylic alcohols yields alpha-hydroxymethyl ketones. The proposed mechanism involves an unusual trapping of the primary ozonide that undergoes a Grob-like fragmentation instead of dissociating into the Criegee intermediates.