Spontaneous cyclo-trimerization of propionaldehyde in aqueous solution

Corrochano, Pablo; García‐Río, Luis; Poblete, F. J.; Rodríguez‐Dafonte, Pedro

doi:10.1016/j.tetlet.2010.01.099

Cited by 7 publications

(4 citation statements)

References 29 publications

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“…The equilibrium between propionaldehyde, propane‐1,1‐diol, and 2,4,6‐triethyl‐1,3,5‐trioxane has been characterized by using the NMR technique. The mol% at different temperatures (5–55°C) has also been reported 49. …”

Section: Resultsmentioning

confidence: 77%

“…The formation of gem‐diols by reversible hydration of the carbonyl group of ketones and aldehydes is well known. There is also literature evidence 49 that spontaneous cyclotrimerization of aldehydes occurs in the aqueous solution. 1,3,5‐Trioxane is formed by cyclotrimerization of aliphatic aldehydes such as acetaldehyde, propionaldehyde, and isobutyraldehyde.…”

Section: Resultsmentioning

confidence: 99%

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Outer‐sphere reduction of hexacyanoferrate(III) by enolizable and nonenolizable aldehydes in alkaline medium

Bera¹,

Pal²,

Gupta

2012

Int J of Chemical Kinetics

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Outer‐sphere reduction of hexacyanoferrate(III) by some enolizable/nonenolizable aldehydes (viz., aliphatic, heterocyclic, and aromatic aldehydes) in alkaline medium has been studied spectrophotometrically at λmax = 420 nm. The reactions are first order each in [aldehyde] and [Fe(CN)63−]. The rate increases with an increase in [OH−] in the oxidation of aliphatic and heterocyclic aldehydes, whereas it is independent of [OH−] in the reaction with aromatic aldehydes. The intervention of free radicals in the reaction mixture was carried out using both acrylonitrile and acrylamide scavenger in two different experiments. The kinetic results indicate that the oxidation of benzaldehyde in aqueous medium proceeds at a slower rate than the aliphatic aldehydes (other than formaldehyde) and furfural. The values of third‐order rate constant (k3) at 308 K in the oxidations of some aliphatic aldehydes and furfural follow the order (CH3)2CH > CH3CH2 > CH3 > C4H3O > H. The rate constants correlate with Taft's σ* value, the reaction constant being negative (–9.8). The pseudo–first‐order rate constants in the oxidations of benzaldehyde and substituted benzaldehydes follow the order NO2 > H > Cl > OCH3. The Hammett plot is also linear with a ρ value (0.6488) for meta‐ and para‐substituted benzaldehydes. The kinetic isotope effect for benzaldehyde (kH/kD = 1.93 at 303 K) was obtained. The rate‐determining step is the outer‐sphere formation of Fe(CN)64− and free radicals, which is followed by the rapid oxidation of free radicals by Fe(CN)63− to give products. The kinetic data and hence thermodynamic parameters have been used to distinguish enolizable and nonenolizable aldehydes. An attempt has also been made to correlate kinetic data with hydration equilibrium constants of some aliphatic aldehydes. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 494–505, 2012

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Section: Resultsmentioning

confidence: 77%

Section: Resultsmentioning

confidence: 99%

Outer‐sphere reduction of hexacyanoferrate(III) by enolizable and nonenolizable aldehydes in alkaline medium

Bera¹,

Pal²,

Gupta

2012

Int J of Chemical Kinetics

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“…In both studies, aldol condensation products were also observed. Furthermore, propanal has been shown to form a trioxane in aqueous solution ( Corrochano et al, 2010 ) and to form a mixture of aldol condensation products, hemiacetals and acetals in the presence of an anion-exchange resin catalyst ( Pyo et al, 2011 ).…”

Section: Introductionmentioning

confidence: 99%

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

et al. 2015

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Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface.

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“…Trioxane formation via cyclotrimerization is also possible and is shown for propanal in Scheme 2e. 41,42 Finally, organosulfate formation can occur when diols formed from carbonyls (Scheme 1a) react directly with sulfuric acid to produce sulfate esters (Scheme 2f). [43][44][45][46] Products of propanal aldol condensation reactions have been reported in previous studies in sulfuric acid (60-96 wt.…”

Section: Potential Reactions Of Organics In Sulfuric Acid Aerosolsmentioning

confidence: 99%

Formation of Organic Films on Sulfuric Acid Solutions at Upper Troposphere and Lower Stratosphere Aerosol Acidities

Perez¹

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The effects of atmospheric aerosols on climate remain uncertain, especially where aerosol chemical composition is not well known. Chemical analysis of aerosols in the upper troposphere (UT) and lower stratosphere (LS) show sulfuric acid (40-80 wt. %) and water as the major components. However, recently, the presence of organic molecules was also reported in UT/LS aerosols which could produce a broad spectrum of chemical reactions that have the potential to alter the aerosol climate properties, so experiments were performed to examine these reactions. Propanal, individually or in mixtures with glyoxal and/or methylglyoxal, combined with sulfuric acid formed highly colored surface films. Since surface films would control aerosol climate properties, the goals of this work are to determine the chemical composition of the films and to determine the effects of aging, organic mixture, and acidity on film composition and formation rates. Films and solutions were analyzed by attenuated total reflectance-FTIR, 1 H NMR and UV-Vis spectroscopies. Results show that aldol condensation products (mainly 2-methyl-2-pentenal and 1,3,5-trimethylbenzene) and acetals (mainly 2,4,6triethyl-1,3,5-trioxane and longer-chain linear polyacetals) are the major species in films formed from propanal. In mixtures of multiple organics, cross-reactions between propanal and glyoxal and/or methylglyoxal were also observed. These results are used to assess the potential for organic films to affect the climate properties of UT/LS aerosols. v 1.

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Spontaneous cyclo-trimerization of propionaldehyde in aqueous solution

Cited by 7 publications

References 29 publications

Outer‐sphere reduction of hexacyanoferrate(III) by enolizable and nonenolizable aldehydes in alkaline medium

Outer‐sphere reduction of hexacyanoferrate(III) by enolizable and nonenolizable aldehydes in alkaline medium

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

Formation of Organic Films on Sulfuric Acid Solutions at Upper Troposphere and Lower Stratosphere Aerosol Acidities

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