The decomposition of acetylenedicarboxylic acid in acetophenone

Hsu, A. M.; Huang, Thomas T. S.

doi:10.1002/kin.550060412

Cited by 3 publications

(1 citation statement)

References 14 publications

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“…In previous work Tommila and Kivinen reported that acetylenedicarboxylic acid decomposed about 30% faster than its monoanion, but did not discuss the dianion. Hsu and Huang determined the rate constant and Arrhenius parameters for decarboxylation of the neutral acid in acetophenone, and reported an unusually small preexponential factor.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopy of Hydrothermal Reactions 20: Experimental and DFT Computational Comparison of Decarboxylation of Dicarboxylic Acids Connected by Single, Double, and Triple Bonds

Brill

2002

J. Phys. Chem. A

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The kinetics and pathways of decarboxylation of aqueous acetylenedicarboxylic acid at pH = 0.97−8.02 were studied in situ at 80−160 °C and 275 bar by using an FT-IR spectroscopy flow reactor with sapphire windows. The first-order (or pseudo first-order) rate constants and corresponding Arrhenius parameters were obtained for the neutral acid, monoanion, and dianion. The decarboxylation rates are in the order: HO2CC⋮CCO2 - > HO2CC⋮CCO2H > -O2CC⋮CCO2 -. The decarboxylation mechanisms of these reactants and the propiolic acid product were analyzed by B3LYP/6-31+G(d) density functional theory. The transition state structures were found for the neutral acids and monoanions. In gas phase the transition state structure is a four-member ring involving C−C(O)−O−H. In aqueous solution a cyclic structure incorporating at least one water molecule forms. A comparison of transition state structures for the decarboxylation of β-saturated (succinic) and β-unsaturated (maleic, fumaric, and acetylenedicarboxylic) aliphatic diacids was made with and without incorporating a water molecule. Consistent with experiment, the calculated activation energy for H-atom transfer to the α carbon atom in the decarboxylation step follows the order C⋮C < CC < C−C.

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Section: Introductionmentioning

confidence: 99%

Spectroscopy of Hydrothermal Reactions 20: Experimental and DFT Computational Comparison of Decarboxylation of Dicarboxylic Acids Connected by Single, Double, and Triple Bonds

Brill

2002

J. Phys. Chem. A

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ChemInform Abstract: THE DECOMPOSITION OF ACETYLENEDICARBOXYLIC ACID IN ACETOPHENONE

Hsu

Huang

1974

Chemischer Informationsdienst

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On the decarboxylation of oxalic acid in solutions

Adams

Franzus

Huang

1978

Int J of Chemical Kinetics

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The first-order kinetics and hydrogen kinetic isotope effect of the decarboxylation of oxalic acid in acetophenone were studied in the temperature range of 109.6"-150.0°C. The rate constants, activation parameters, and hydrogen kinetic isotope effect were calculated. Detailed comparison and discussion of the results were made with the data reported in the literature. Kinetic isotope effects and solvent effects on rates should be considered similar in mechanistic and/or theoretical studies in the sense that kinetic isotope effects result from a small perturbation of the reaction coordinate, while the solvent effect causes a general overall variation on the potential energy surface (thereby resulting in a change in the reaction coordinate).

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The decomposition of acetylenedicarboxylic acid in acetophenone

Cited by 3 publications

References 14 publications

Spectroscopy of Hydrothermal Reactions 20: Experimental and DFT Computational Comparison of Decarboxylation of Dicarboxylic Acids Connected by Single, Double, and Triple Bonds

Spectroscopy of Hydrothermal Reactions 20: Experimental and DFT Computational Comparison of Decarboxylation of Dicarboxylic Acids Connected by Single, Double, and Triple Bonds

ChemInform Abstract: THE DECOMPOSITION OF ACETYLENEDICARBOXYLIC ACID IN ACETOPHENONE

On the decarboxylation of oxalic acid in solutions

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