ChemInform Abstract: SYNTH. EINIGER ALPHA‐ALKOXYALKYLHYDROPEROXIDE

Pospelov, M. V.; Menyailo, A. T.; Bortyan, T. A.; Ustynyuk, Yu. A.; Petrosyan, V. S.

doi:10.1002/chin.197319207

Cited by 5 publications

(8 citation statements)

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“…using TPTD, but the extracted mass spectrum had no satisfactory match in the Wiley Mass Spectral Database. However, on the basis of the results of recent gas-phase studies on ethene, 42 and liquidphase studies on numerous other alkenes, [43][44][45][46] it is expected that the major product of ozonolysis of 1-tetradecene in the presence of excess 2-propanol will be R-isopropoxytridecyl hydroperoxide formed by the mechanism shown in Figure 6E. This compound would most likely have a lower vapor pressure than tridecanoic acid, conforming with the TPTD results.…”

Section: Resultssupporting

confidence: 67%

“…To test this hypothesis, a solution of 1-tetradecene in 2-propanol was ozonated and the product solution was atomized and analyzed by TDPBMS. The liquid-phase reaction is known to produce R-alkoxyalkyl hydroperoxides in near-quantitative yield, [43][44][45][46] so the excellent agreement between the TPTD spectrum of chamber aerosol and the liquid-phase mass spectrum (Figure 5D) is strong evidence that compound B is R-isopropoxytridecyl hydroperoxide. It is worth noting that hydroperoxides such as this may not be amenable to GC analysis (we have observed that they dehydrate to the corresponding esters) and would therefore be overlooked using traditional GC/MS identification procedures.…”

Section: Resultsmentioning

confidence: 99%

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Compound Identification in Organic Aerosols Using Temperature-Programmed Thermal Desorption Particle Beam Mass Spectrometry

1999

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Identification of organic compounds in multicomponent organic aerosols is demonstrated using temperature-programmed thermal desorption particle beam mass spectrometry. Aerosol particles are efficiently sampled into a high-vacuum chamber using aerodynamic focusing techniques followed by impaction onto a cold metal foil. The sample is then slowly heated to achieve temporal separation of components according to their vapor pressures, while evaporating compounds are continuously mass-analyzed using a quadrupole mass spectrometer. Mass spectra of the individual components are then extracted from time-dependent spectra. Measurements made using aerosols containing equal-mass mixtures of various carboxylic acids and dioctyl sebacate indicate that, using this setup and a temperature ramp rate of ∼1 °C/min, useful separation can be achieved for compounds having a factor of 5 or more difference in vapor pressures. The technique is demonstrated for use in laboratory environmental chamber studies of aerosol chemistry by analyzing the secondary organic aerosol generated from the reaction of 1-tetradecene and ozone in excess 2-propanol. Temperature-programmed thermal desorption is shown to be a valuable tool which can be used in conjunction with quantitative thermal desorption particle beam mass spectrometry for chemical analysis of components in secondary organic aerosol formed in laboratory environments.

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Section: Resultssupporting

confidence: 67%

Section: Resultsmentioning

confidence: 99%

Compound Identification in Organic Aerosols Using Temperature-Programmed Thermal Desorption Particle Beam Mass Spectrometry

1999

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“…Liquid‐phase ozonolysis of the alkenes in the presence of carboxylic acids and alcohols is known as a very efficient preparation method of the α‐acyloxy and α‐alkoxy hydroperoxides . For the cyclic alkenes, the resulting α‐acyloxyhydroperoxy aldehydes contain both hydroperoxy and aldehyde moieties; therefore, compounds shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Analysis of α‐acyloxyhydroperoxy aldehydes with electrospray ionization–tandem mass spectrometry (ESI‐MSⁿ)

Witkowski

Gierczak

2013

J. Mass. Spectrom.

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A series of α-acyloxyhydroperoxy aldehydes was analyzed with direct infusion electrospray ionization tandem mass spectrometry (ESI/MS(n)) as well as liquid chromatography coupled with the mass spectrometry (LC/MS). Standards of α-acyloxyhydroperoxy aldehydes were prepared by liquid-phase ozonolysis of cyclohexene in the presence of carboxylic acids. Stabilized Criegee intermediate (SCI), a by-product of the ozone attack on the cyclohexene double bond, reacted with the selected carboxylic acids (SCI scavengers) leading to the formation of α-acyloxyhydroperoxy aldehydes. Ionization conditions were optimized. [M + H](+) ions were not formed in ESI; consequently, α-acyloxyhydroperoxy aldehydes were identified as their ammonia adducts for the first time. On the other hand, atmospheric-pressure chemical ionization has led to decomposition of the compounds of interest. Analysis of the mass spectra (MS(2) and MS(3)) of the [M + NH(4)](+) ions allowed recognizing the fragmentation pathways, common for all of the compounds under study. In order to get detailed insights into the fragmentation mechanism, a number of isotopically labeled analogs were also studied. To confirm that the fragmentation mechanism allows predicting the mass spectrum of different α-acyloxyhydroperoxy aldehydes, ozonolysis of α-pinene, a very important secondary organic aerosol precursor, was carried out. Spectra of the two ammonium cationized α-acyloxyhydroperoxy aldehydes prepared with α-pinene, cis-pinonic acid as well as pinic acid were predicted very accurately. Possible applications of the method developed for the analysis of α-acyloxyhydroperoxy aldehydes in SOA samples, as well as other compounds containing hydroperoxide moiety are discussed.

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“…The gas- () and liquid-phase () reactions of alkenes with O 3 have been widely studied, and the general reaction mechanisms are reasonably well-established and apparently similar in the two phases. Of particular relevance to the work presented here are recent investigations of gas-phase ozonolysis of ethene ( − ) and liquid-phase reactions of normal alkenes ( − ) carried out in the presence of alcohols and carboxylic acids. Ozonolysis of 1-tetradecene [CH 3 (CH 2 ) 11 CHCH 2 ] in the presence of the alcohols and carboxylic acids used here apparently occurs by the following pathways: The initial step in the reaction involves addition of O 3 to the alkene double bond, resulting in the formation of a 1,2,3-trioxolane (primary ozonide).…”

Section: Resultsmentioning

confidence: 99%

“…Ozone from a Welsbach T-408 O 3 generator (∼2% O 3 /O 2 ) was then bubbled through the solutions at ∼0.15 L/min for 60 s, which was sufficiently long to ozonize nearly all the alkene, without adding excess O 3 . This method should produce α-alkoxyalkyl and α-acyloxyalkyl hydroperoxides in nearly quantitative yields ( − ). All reacted solutions were atomized in a Collison atomizer using dry, clean air as the carrier gas.…”

Section: Methodsmentioning

confidence: 99%

Thermal Desorption Mass Spectrometric Analysis of Organic Aerosol Formed from Reactions of 1-Tetradecene and O₃ in the Presence of Alcohols and Carboxylic Acids

Tobias

Ziemann

2000

Environ. Sci. Technol.

174

214

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The chemistry of secondary organic aerosol formation from reactions of 1-tetradecene and O3 in dry air in the presence of excess alcohols and carboxylic acids was investigated in an environmental chamber using a thermal desorption particle beam mass spectrometer. Temperature-programmed thermal desorption of collected aerosol shows that in each reaction two major aerosol products are formed. The more volatile compounds in each pair of products are α-alkoxytridecyl or α-acyloxytridecyl hydroperoxides, which were identified by comparison of mass spectra with those of standard compounds generated by the corresponding liquid-phase ozonolysis reactions. The formation of organic hydroperoxides in the gas and liquid phases is consistent with a mechanism involving reactions of the alcohols and carboxylic acids with stabilized Criegee biradicals generated in the alkene−O3 reaction. The less volatile compounds are α-alkoxy-α‘-hydroxyditridecyl or α-acyloxy-α‘-hydroxyditridecyl peroxides (peroxyhemiacetals) formed by reactions of the hydroperoxides with tridecanal, which is generated along with formaldehyde during biradical formation. The vapor pressures of these compounds estimated from their desorption temperatures are ∼10-7−10-14 Torr. These types of reactions could play a role in atmospheric aerosol nucleation and growth and provide a mechanism for creating fine-particle organic peroxides, which are currently of interest because of their potential for adversely impacting human health.

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ChemInform Abstract: SYNTH. EINIGER ALPHA‐ALKOXYALKYLHYDROPEROXIDE

Abstract: Durch Ozonierung der Olefine (I) in entsprechenden Alkanolen (II) bei ‐70°C werden die Hydroperoxide (III) dargestellt.

Cited by 5 publications

References 0 publications

Compound Identification in Organic Aerosols Using Temperature-Programmed Thermal Desorption Particle Beam Mass Spectrometry

Compound Identification in Organic Aerosols Using Temperature-Programmed Thermal Desorption Particle Beam Mass Spectrometry

Analysis of α‐acyloxyhydroperoxy aldehydes with electrospray ionization–tandem mass spectrometry (ESI‐MSⁿ)

Thermal Desorption Mass Spectrometric Analysis of Organic Aerosol Formed from Reactions of 1-Tetradecene and O₃ in the Presence of Alcohols and Carboxylic Acids

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ChemInform Abstract: SYNTH. EINIGER ALPHA‐ALKOXYALKYLHYDROPEROXIDE

Abstract: Durch Ozonierung der Olefine (I) in entsprechenden Alkanolen (II) bei ‐70°C werden die Hydroperoxide (III) dargestellt.

Cited by 5 publications

References 0 publications

Compound Identification in Organic Aerosols Using Temperature-Programmed Thermal Desorption Particle Beam Mass Spectrometry

Compound Identification in Organic Aerosols Using Temperature-Programmed Thermal Desorption Particle Beam Mass Spectrometry

Analysis of α‐acyloxyhydroperoxy aldehydes with electrospray ionization–tandem mass spectrometry (ESI‐MSn)

Thermal Desorption Mass Spectrometric Analysis of Organic Aerosol Formed from Reactions of 1-Tetradecene and O3 in the Presence of Alcohols and Carboxylic Acids

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Product

Resources

About

Analysis of α‐acyloxyhydroperoxy aldehydes with electrospray ionization–tandem mass spectrometry (ESI‐MSⁿ)

Thermal Desorption Mass Spectrometric Analysis of Organic Aerosol Formed from Reactions of 1-Tetradecene and O₃ in the Presence of Alcohols and Carboxylic Acids