The mechanism of thermal eliminations part XXIII: [1] The thermal decomposition of pyruvic acid

Taylor, Roger

doi:10.1002/kin.550190804

Cited by 35 publications

(43 citation statements)

References 5 publications

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“…Earlier work on gas-phase elimination kinetics of pyruvic acid showed that the acid decomposes into carbon dioxide and acetaldehyde [1]. The mechanism proposed for this reaction involves a four-membered cyclic transition state with partial negative charge being developed at the ␣-carbonyl carbon, eq.…”

Section: Introductionmentioning

confidence: 98%

Pyrolysis of ?-hydroxyketones and ?-ketoesters: Gas-phase elimination kinetics of 3-hydroxy-3-methyl-2-butanone and methyl benzoylformate

Al‐Awadi

El‐Dusouqui

1997

Int. J. Chem. Kinet.

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The rates of gas-phase elimination reactions of methyl benzoylformate (1) and 3-hydroxy-3-methyl-2-butanone (2) were obtained at T ϭ 600 K. The two substrates undergo unimolecular first-order elimination for which the Arrhenius equations are, respectively, log k ϭ 13.2 Ϫ 53270/(4.574 ϫ 600) for (1) and log k ϭ 12.4 Ϫ 53060/(4.574 ϫ 600) for (2). The products of pyrolysis of (1) are benzaldehyde, formaldehyde and CO, while those of (2) are acetaldehyde and acetone. The kinetics of the elimination reactions show benzoylformic acid to be 10 6 -fold more reactive than (1), and pyruvic acid ca. 10 5 -fold more reactive relative to (2); an indication of the rate-controlling part played by the acidity of the hydrogen atom involved in the elimination process of the present compounds in this particular type of reaction.

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Section: Introductionmentioning

confidence: 98%

Pyrolysis of ?-hydroxyketones and ?-ketoesters: Gas-phase elimination kinetics of 3-hydroxy-3-methyl-2-butanone and methyl benzoylformate

Al‐Awadi

El‐Dusouqui

1997

Int. J. Chem. Kinet.

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“…[5][6][7] In this paper, we report on the thermal gas-phase elimination of a-substituted propanoic acid and b-substituted 1-propanol, the substituent in both systems being an aryl moiety. Relative rate factors of 10 2 -10 7 have been observed, indicative of the major contribution to reactivity by the mesomerically electron-accommodating phenoxy group and its thio and amino analogues.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of thermal gas-phase elimination of ?-substituted carboxylic acids: role of relative basicity of ?-substituents and acidity of incipient proton

Al‐Awadi

Kaul

El‐Dusouqui

2000

J. Phys. Org. Chem.

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“…PA undergoes decarboxylation in the gas and aqueous phases by means of different mechanisms. Decarboxylation of gas phase PA has been seen to occur thermochemically, through IR multiphoton pyrolysis, as well as through UV and visible excitation (13,(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36). The main removal pathway of gas phase PA from the troposphere is UV photolysis, with reaction with OH radical providing a minor contribution (31).…”

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confidence: 99%

Photochemistry of aqueous pyruvic acid

Griffith

Carpenter

Shoemaker³

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

124

289

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The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH 3 COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH 3 CHOHCOCH 3 ), lactic acid (CH 3 CHOHCOOH), acetic acid (CH 3 COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols.

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The mechanism of thermal eliminations part XXIII: [1] The thermal decomposition of pyruvic acid

Cited by 35 publications

References 5 publications

Pyrolysis of ?-hydroxyketones and ?-ketoesters: Gas-phase elimination kinetics of 3-hydroxy-3-methyl-2-butanone and methyl benzoylformate

Pyrolysis of ?-hydroxyketones and ?-ketoesters: Gas-phase elimination kinetics of 3-hydroxy-3-methyl-2-butanone and methyl benzoylformate

Kinetics and mechanism of thermal gas-phase elimination of ?-substituted carboxylic acids: role of relative basicity of ?-substituents and acidity of incipient proton

Photochemistry of aqueous pyruvic acid

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