Solvent isotope effects upon proton transfer from the hydronium ion

1971 ◽  
Vol 93 (1) ◽  
pp. 9-20 ◽  
Author(s):  
Rory A. More O'Ferrall ◽  
Gerald W. Koeppl ◽  
A. Jerry Kresge
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Hydronium Ion ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

Vinyl ether hydrolysis. XXIV. 1-Methoxycyclooctene and the question of reversibility of the carbon protonation step

1991 ◽  
Vol 69 (1) ◽  
pp. 84-87 ◽  
Author(s):  
A. J. Kresge ◽  
Y. Yin
Keyword(s):  
Reaction Mechanism ◽  
Proton Transfer ◽  
Vinyl Ether ◽  
Isotope Effects ◽  
Hydrolysis Rate ◽  
Hydronium Ion ◽  
Mineral Acids ◽  
Dilute Aqueous Solutions ◽  
Solvent Isotope ◽  
Hydrolysis Of

An argument is presented which suggests that hydrolysis of the vinyl ether group of 1-methoxycyclooctene may occur by reversible proton transfer from a catalyzing acid to the β-carbon atom of the substrate, instead of by the conventional reaction mechanism in which this proton transfer is rate determining and not reversible. Hydrolysis of this substrate is then examined by measuring rates of reaction in dilute aqueous solutions of strong mineral acids (perchloric and hydrochloric) as well as in buffer solutions of seven carboxylic acids, biphosphate ion, and 1,1,1,3,3,3-hexafluoro-2-propanol. General acid catalysis is observed and a Brønsted relation with the exponent α = 0.73 is constructed. That, plus the isotope effects kH/kD = 2.9 and 6.0 for catalysis by hydronium ion and acetic acid respectively, as well as the lack of deuterium incorporation into the substrate when the reaction is carried out in D2O with D2PO4−/DPO42− buffer at pD = 8, show that carbon protonation of the substrate is not reversible and that the conventional reaction mechanism is operative. Key words: 1-methoxycyclooctene, vinyl ether hydrolysis, rate-determining proton transfer, Brønsted relation, solvent isotope effect.

Photoredox chemistry of nitrobenzyl alcohols in aqueous solution. Acid and base catalysis of reaction

1986 ◽  
Vol 64 (10) ◽  
pp. 2076-2086 ◽  
Author(s):  
Peter Wan ◽  
Keith Yates
Keyword(s):  
Aqueous Solution ◽  
Isotope Effects ◽  
Base Catalysis ◽  
Quantum Yields ◽  
Hydronium Ion ◽  
Acid And Base ◽  
New Type ◽  
Solvent Isotope ◽  
Catalytic Effects ◽  
Solvent Isotope Effects

The photochemistry of several m- and p-nitrobenzyl alcohols (1–5) has been studied in aqueous solution. These compounds react via an intramolecular photoredox pathway to give reduced and oxidized moieties of the substituent groups. The reaction is an example of a new type of photoreaction of nitro-substituted aromatic derivatives that is not observed in organic solvents, the presence of water being essential. This effect is exemplified by measuring the quantum efficiency as a function of mol% water in aqueous acetonitrile, methanol, and formamide: the reaction efficiency decreases rapidly as water is depleted in the mixture. Catalytic effects due to the hydronium and hydroxide ions were studied: the para derivatives exhibited hydroxide ion catalysis; the meta derivatives exhibited hydronium ion catalysis. Quantum yields, solvent isotope effects, and α-deuterium isotope effects are reported for the parent derivatives.

Kinetics and mechanism of acid-catalyzed hydrolysis of the diazo functional groups of 1-diazo-2-indanone and 2-diazo-1-indanone in aqueous solution

2005 ◽  
Vol 83 (9) ◽  
pp. 1202-1206 ◽  
Author(s):  
Yvonne Chiang ◽  
A Jerry Kresge ◽  
Oleg Sadovski ◽  
Xiaofeng Zeng ◽  
Yu Zhu
Keyword(s):  
Formic Acid ◽  
Isotope Effect ◽  
Isotope Effects ◽  
Diazo Compound ◽  
Acid Buffer ◽  
Buffer Solutions ◽  
Hydronium Ion ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

Rates of hydrolysis of 1-diazo-2-indanone and 2-diazo-1-indanone were measured in dilute aqueous perchloric acid solutions using both H2O and D2O as the solvent, and rates of hydrolysis of the latter substrate were measured in dilute aqueous (H2O only) formic acid buffer solutions as well. The data for 1-diazo-2-indanone gave the hydronium ion catalytic coefficient kH+ = 5.7 × 10–3 (mol/L)–1 s–1 and the isotope effect kH+/kD+ = 2.9. The normal direction (kH/kD > 1) of this isotope effect was taken as evidence for a reaction mechanism involving rate-determining hydron transfer from the hydronium ion to the substrate's diazo carbon atom; followed by rapid displacement of diazo nitrogen by a water molecule, giving the observed 1-hydroxy-2-indanone product. The data for 2-diazo-1-indanone, on the other hand, gave a hydronium ion catalytic coefficient two orders of magnitude greater than the value for 1-diazo-2-indanone (kH+ = 5.9 × 10–1 (mol/L)–1 s–1), and an isotope effect near unity (kH+/kD+ = 1.2). It is argued that this isotope effect represents a situation in which diazo carbon hydronation and displacement of diazo nitrogen are each partly rate determining, a conclusion supported by incipient saturation of buffer catalysis in the formic acid buffer solutions. The 100-fold difference in hydronium ion catalytic coefficients for the two substrates is rationalized in terms of differing electron densities on the diazo carbon atoms.Key words: diazo compound hydrolysis, solution kinetics, acid catalysis, solvent isotope effects, buffer catalysis saturation.

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