Study of the kinetics and mechanism of the acid-base-catalyzed enolization of hydroxyacetaldehyde and methoxyacetaldehyde

Fedoroňko, M.; Temkovic, Peter; Königstein, J.; Kováčik, Vladimı́r; Tvaroŝka, Igor

doi:10.1016/s0008-6215(00)85189-7

Cited by 22 publications

(6 citation statements)

References 25 publications

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“…In the case of glycolic aldehyde, theoretically also enolization could take place, however, in this case, the end product would not be oxalic acid, since the unsaturated bond is oxidized by permanganate with fission of the carbon chain. Fedorenko et al [23] assumed that with oxidation of glycol aldehyde by methylene blue enolization was the rate determining step, however, these authors measured in alkaline medium a rate constant more than three orders of magnitude lower than we did. Thus, this also suggests the inferior role of enolization, and that hydration can rather be expected.…”

Section: Discussioncontrasting

confidence: 88%

Oxidation by Permanganate in strong alkaline medium. Oxidation of ethane‐1,2‐diol, glycol aldehyde, glycollic acid, and glyoxylic acid

Szammer

Jáky

Gerasimov

1992

Int J of Chemical Kinetics

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A study was made on the kinetics and mechanism of the reaction 2Mn042-+ Product 2Mn04-+ S in aqueous solutions of 0.10 to 2.0 mol dm-3 alkaline concentrations. The substrates (S) applied were ethane-l,a-diol (ethylene glycol), glycol aldehyde, glycollic acid, and glyoxylic acid. Glycol aldehyde and glyoxylic acid were present in the form of dihydrate. In each case alkoxy anion is the reactive form and the Kg constant of deprotonation can be calculated from the kinetic data.A mechanism based on electron abstraction is suggested. Manganate reacts with these substrates much slower than permanganate.

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Section: Discussioncontrasting

confidence: 88%

Oxidation by Permanganate in strong alkaline medium. Oxidation of ethane‐1,2‐diol, glycol aldehyde, glycollic acid, and glyoxylic acid

Szammer

Jáky

Gerasimov

1992

Int J of Chemical Kinetics

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“…A dilute solution of tetrachloroauric(III) acid is known [6,11,25] to involve the following equilibria Although GA is known to undergo enolization [29] catalyzed by acids as well as bases, under the present experimental condition, the concentration of the enol form will be very small compared to the keto form. As such the keto form may be presumed to be the predominant reducing species participating in the reaction, although the participation of the enol form can not be ruled out.…”

Section: Discussionmentioning

confidence: 99%

Kinetics and mechanism of the oxidation of glycolaldehyde by tetrachloroaurate(III)

Sen

Bilkis

Gupta

1998

Int. J. Chem. Kinet.

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“…The aldol addition of GA under basic conditions involves an enolization to 1,2‐ethenediol (possibly in its anionic form) upon α‐proton abstraction, which enables the nucleophilic addition of the 1,2‐ethenediol to the carbonyl group of another GA molecule [2a,11] . The equilibrium between GA and 1,2‐ethenediol is strongly shifted towards the aldehyde form [12] .…”

Section: Resultsmentioning

confidence: 99%

Heterogeneous Base‐Catalyzed Conversion of Glycolaldehyde to Aldotetroses: Mechanistic and Kinetic Insight

et al. 2021

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Recent strides towards greater sustainability in materials and energy production have led to a resurgence in the study and utilization of carbohydrates. Opposite to C6 and C5 carbohydrates, C4 carbohydrates (tetroses) are much less accessible from biological sources. A promising approach for the production of C4 carbohydrates is the cracking of C6 carbohydrates to C2 fragments, and the subsequent combination of two C2 fragments to tetroses. Here, we show that the suitable choice of reaction conditions can kinetically stabilize the rare aldotetroses threose (THR) and erythrose (ERY). The latter approach yields THR and ERY at high selectivity under benign conditions, using commercial resins with tertiary amine groups as the catalyst. Isotope incorporation into GA in D2O solvent is introduced as a reference reaction to probe the competitive formation of aldotetroses and deuterated GA from a low‐populated, not directly detected enediol intermediate that is formed in the rate‐determining step. Reaction progress tracked in situ by NMR and ex situ by chromatography validates that the overall conversion is of first order with respect to GA due to the slow initial enolization. Cyclization of the aldotetroses slows their further conversion to thermodynamically more stable erythrulose and C6 sugars.

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Study of the kinetics and mechanism of the acid-base-catalyzed enolization of hydroxyacetaldehyde and methoxyacetaldehyde

Cited by 22 publications

References 25 publications

Oxidation by Permanganate in strong alkaline medium. Oxidation of ethane‐1,2‐diol, glycol aldehyde, glycollic acid, and glyoxylic acid

Oxidation by Permanganate in strong alkaline medium. Oxidation of ethane‐1,2‐diol, glycol aldehyde, glycollic acid, and glyoxylic acid

Kinetics and mechanism of the oxidation of glycolaldehyde by tetrachloroaurate(III)

Heterogeneous Base‐Catalyzed Conversion of Glycolaldehyde to Aldotetroses: Mechanistic and Kinetic Insight

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