Acid-promoted reactions of butan-2,3-dione

Alexandropoulou, Ioanna; Crabb, Trevor A.; Patel, Asmita V.; Hudec, J.

doi:10.1016/s0040-4020(99)00249-5

Cited by 5 publications

(7 citation statements)

References 7 publications

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“…The trimer in Figure 1 can react with additional BA to produce a substituted furanone dimer (m/z 199). 42 Fragmentation data for m/z 199 aligns with known fragmentation for methylated furanones, further supporting this assignment. 60 The decrease in pH over the course of the kinetics experiments supports the formation of acetic acid (Table 1), which has a mass too small to be observed by the Notably, m/z 137 is only seen in the BA + AS system and not in reactions when only BA is present, suggesting that quinone formation requires acid catalysis supplied by the ammonium ions in this system.…”

Section: ■ Results and Discussionsupporting

confidence: 54%

“…BA ( m / z 87) oligomerizes to produce dimers and trimers (Figures and ), like the previously mentioned carbonyl + AS systems. − Typical of carbonyl oligomerization reactions, BA readily forms aldol dimers ( m / z 173) via the corresponding enol. , The EIC for m / z 173 showed the presence of two isomers, which are likely to be the cyclic and open-chain forms of the dimer (Figure S1). The cyclic hemiacetal form of m / z 173 can react with hydrated BA to form trimers (Figure ); , however, no trimers were observed via SFC-MS/MS. The trimer in Figure can react with additional BA to produce a substituted furanone dimer ( m / z 199) .…”

Section: Resultsmentioning

confidence: 59%

“…The cyclic hemiacetal form of m / z 173 can react with hydrated BA to form trimers (Figure ); , however, no trimers were observed via SFC-MS/MS. The trimer in Figure can react with additional BA to produce a substituted furanone dimer ( m / z 199) . Fragmentation data for m / z 199 aligns with known fragmentation for methylated furanones, further supporting this assignment .…”

Section: Resultsmentioning

confidence: 99%

“…Atmospheric condensed-phase concentrations of BA are approximately an order of magnitude lower than Gly and MGly and are similar to GAld and HA, ,, and the BA + AS system will likely undergo similar Maillard-type browning reactions. BA can self-react to form aldol and acetal dimers and trimers, − and it is reasonable to assume that the important reaction pathways identified in previously studied carbonyl + AS systems could produce analogous BrC products in the BA + AS system . Although the ketone functional groups make this reaction less favorable than the analogous reaction with an aldehyde, imine formation is possible, as was observed in the HA + AS and MGly + AS reaction systems. , Key structural features of products in the BA + AS system and its reaction kinetics were identified using a combination of experimental methods.…”

Section: Introductionmentioning

confidence: 99%

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Brown Carbon Formation Potential of the Biacetyl–Ammonium Sulfate Reaction System

Grace

Lugos

et al. 2020

ACS Earth Space Chem.

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The contribution of organic aerosol from biomass burning is poorly constrained, and the lack of consensus regarding its overall contribution to global radiative forcing leads to significant uncertainties in climate modeling. Identification of potential brown carbon chromophores from common biomass burning emissions may reduce this uncertainty. Biacetyl (BA) is found in emissions from industry and biomass burning from various ecosystems and shares structural similarities with other small carbonyls that react with ammonium sulfate (AS) to produce brown carbon compounds. Like previous carbonyl + AS studies, the BA + AS system results in the formation of hundreds of different products; these were separated and identified using supercritical fluid chromatography–tandem mass spectrometry, isotopic substitution experiments, and comparisons to standards. Kinetic information was obtained through spectral decomposition of experimentally measured UV–visible absorbance data. Theoretical TDDFT calculations were utilized to extract more information on the light absorbance of identified products and to determine how these individual chromophores would contribute to the light absorbance of organic aerosol. This information could provide insight into unknown organic aerosol behavior by furthering our understanding of the reactivity of a common biomass burning emission product like biacetyl.

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Section: ■ Results and Discussionsupporting

confidence: 54%

Section: Resultsmentioning

confidence: 59%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Brown Carbon Formation Potential of the Biacetyl–Ammonium Sulfate Reaction System

Grace

Lugos

et al. 2020

ACS Earth Space Chem.

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“…Another typical reaction under the present conditions is the acid catalyzed aldol reaction, which leads to C-C-bond formation. 58,59 Consequently, BD/AS did not yield products absorbing at wavelengths 4250 nm within the timescale and conditions of our experiments. Thus the main products in the corresponding reaction systems involve imidazole ring structures, i.e., five membered aromatic rings with two nitrogen atoms.…”

Section: The Chemistry Of the Formation Of Nitrogen Heterocycles In Amentioning

confidence: 50%

Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects

Kampf

Filippi

Zuth

et al. 2016

Phys. Chem. Chem. Phys.

106

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Dicarbonyls are known to be important precursors of so-called atmospheric brown carbon, significantly affecting aerosol optical properties and radiative forcing. In this systematic study we report the formation of light-absorbing nitrogen containing compounds from simple 1,2-, 1,3-, 1,4-, and 1,5-dicarbonyl + amine reactions. A combination of spectrophotometric and mass spectrometric techniques was used to characterize reaction products in solutions mimicking atmospheric particulates. Experiments with individual dicarbonyls and dicarbonyl mixtures in ammonium sulfate and glycine solutions demonstrate that nitrogen heterocycles are common structural motifs of brown carbon chromophores formed in such reaction systems. 1,4- and 1,5-dicarbonyl reaction systems, which were used as surrogates for terpene ozonolysis products, showed rapid formation of light-absorbing material and products with absorbance maxima at ∼450 nm. Synergistic effects on absorbance properties were observed in mixed (di-)carbonyl experiments, as indicated by the formation of a strong absorber in ammonium sulfate solutions containing acetaldehyde and acetylacetone. This cross-reaction oligomer shows an absorbance maximum at 385 nm, relevant for the actinic flux region of the atmosphere. This study demonstrates the complexity of secondary brown carbon formation via the imine pathway and highlights that cross-reactions with synergistic effects have to be considered an important pathway for atmospheric BrC formation.

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1,3-Dioxoles and 1,3-Oxathioles

Aitken

Power

2008

Comprehensive Heterocyclic Chemistry III

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Acid-promoted reactions of butan-2,3-dione

Cited by 5 publications

References 7 publications

Brown Carbon Formation Potential of the Biacetyl–Ammonium Sulfate Reaction System

Brown Carbon Formation Potential of the Biacetyl–Ammonium Sulfate Reaction System

Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects

1,3-Dioxoles and 1,3-Oxathioles

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