Acyclic Forms of [1-13C]Aldohexoses in Aqueous Solution:  Quantitation by13C NMR and Deuterium Isotope Effects on Tautomeric Equilibria

2001 ◽  
Vol 66 (19) ◽  
pp. 6244-6251 ◽  
Author(s):  
Yuping Zhu ◽  
Jaroslav Zajicek ◽  
Anthony S. Serianni
Keyword(s):  
Aqueous Solution ◽  
Isotope Effects ◽  
Tautomeric Equilibria ◽  
Deuterium Isotope Effects

A hydrogen-atom transfer mechanism in the oxidation of alcohols by [FeO4]2− in aqueous solution

2018 ◽  
Vol 47 (1) ◽  
pp. 240-245 ◽  
Author(s):  
Jianhui Xie ◽  
Po-Kam Lo ◽  
Chow-Shing Lam ◽  
Kai-Chung Lau ◽  
Tai-Chu Lau
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Atom ◽  
Dft Calculations ◽  
Isotope Effects ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Bond Dissociation Energies ◽  
Dissociation Energies ◽  
Oxidation Of Alcohols ◽  
Deuterium Isotope Effects

The oxidation of alcohols by [FeO4]2− in aqueous solution is found to proceed via a hydrogen atom transfer (HAT) mechanism based on deuterium isotope effects, correlation between rate constants and bond dissociation energies (BDEs) and DFT calculations.

Kinetic deuterium isotope effects and kinetic solvent isotope effects for the solvolyses in water and in water + acetonitrile mixtures related to a series of substituted benzyl nitrates

1980 ◽  
Vol 58 (20) ◽  
pp. 2142-2145 ◽  
Author(s):  
Mohammed Ahsan ◽  
Ross Elmore Robertson ◽  
Michael Jesse Blandamer ◽  
John Marshall William Scott
Keyword(s):  
Aqueous Solution ◽  
Benzene Ring ◽  
Isotope Effect ◽  
Isotope Effects ◽  
Bond Breaking ◽  
Relative Importance ◽  
Stage Process ◽  
Deuterium Isotope Effects ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

In aqueous solution, the α-deuterium isotope effects in the solvolyses of benzyl nitrates derivatives depend on the nature of the substituent in the benzene ring. In addition, the isotope effect for some derivatives depends on mole fraction of added acetonitrile while for others the isotope effect is insensitive to solvent composition. However, the kinetic solvent isotope effects for para-methyl and meta-trifluoromethyl derivatives remain unchanged when acetonitrile is added. These observations are accounted for in terms of a model which describes the solvolytic reaction as a two-stage process and contrasts the relative importance of bond-making and bond-breaking.

Deuterium Isotope Effects on Degradation of Hydrocortisone in Aqueous Solution

1972 ◽  
Vol 61 (6) ◽  
pp. 918-920 ◽  
Author(s):  
Ian H. Pitman ◽  
T. Higuchi ◽  
M. Alton ◽  
R. Wiley
Keyword(s):  
Aqueous Solution ◽  
Isotope Effects ◽  
Deuterium Isotope Effects

Mechanism of hydration and isomerisation of 4-ethylidene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one. Kinetics, acid-base catalysis and solvent deuterium isotope effects

1979 ◽  
Vol 44 (1) ◽  
pp. 110-122 ◽  
Author(s):  
Jiří Velek ◽  
Bohumír Koutek ◽  
Milan Souček
Keyword(s):  
Aqueous Medium ◽  
Rate Equation ◽  
Kinetic Data ◽  
Isotope Effects ◽  
Base Catalysis ◽  
Quinone Methide ◽  
Reaction Products ◽  
Acid Base ◽  
Deuterium Isotope Effects ◽  
Hydroxybenzyl Alcohol

Competitive hydration and isomerisation of the quinone methide I at 25 °C in an aqueous medium in the region of pH 2.4-13.0 was studied spectrophotometrically. The only reaction products in the studied range of pH are 4-hydroxybenzyl alcohol (II) and 4-hydroxystyrene (III). The form of the overall rate equation corresponds to a general acid-base catalysis. The mechanism of both reactions for three markedly separated pH regions is discussed on the basis of kinetic data and solvent deuterium effect.

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