Dynamics of reaction of [5,10,15,20-tetrakis(2,6-dimethyl-3-sulfonatophenyl)porphinato]iron(III) hydrate with tert-butyl hydroperoxide in aqueous solution. 3. Comparison of refined kinetic parameters and D2O solvent isotope effects to those for [5,10,15,20-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphinato]iron(III) hydrate and iron(III) hydrate

1991 ◽  
Vol 113 (12) ◽  
pp. 4657-4665 ◽  
Author(s):  
Enona Gopinath ◽  
Thomas C. Bruice
Keyword(s):  
Aqueous Solution ◽  
Kinetic Parameters ◽  
Isotope Effects ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

The radical versus ionic mechanisms of reduced cobalamin inactivation by tert-butyl hydroperoxide and hydrogen peroxide in aqueous solution

2021 ◽  
Author(s):  
Denis S. Salnikov ◽  
Sergei V. Makarov ◽  
Oscar I. Koifman
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Ionic Mechanisms

It was demonstrated that antioxidants cannot protect reduced cobalamin against its modification by hydrogen peroxide.

Ketonization of the unusually acidic elongated enol generated by flash photolytic decarboxylation of p-formylphenylacetic acid in aqueous solution

2008 ◽  
Vol 86 (2) ◽  
pp. 101-104 ◽  
Author(s):  
Yvonne Chiang ◽  
Kirill Kolmakov ◽  
A Jerry Kresge
Keyword(s):  
Aqueous Solution ◽  
Acetic Acid ◽  
Sodium Hydroxide ◽  
Perchloric Acid ◽  
Flash Photolysis ◽  
Isotope Effects ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

Rates of photolysis of p-formylphenylacetic acid were measured flash photoytically in perchloric acid and sodium hydroxide solutions, and also in acetic acid, biphosphate ion, and tris-(hydroxymethyl)methaneammonium ion buffers, using H2O and D2O as solvents. The results provide rate profiles and solvent isotope effects, which indicate that photolysis occurs through an elongated enol intermediate. This enol is unusually strongly acidic, by some two to three pQa units, when compared with simple non-elongated enols.Key words: flash photolysis, elongated enols, rate profiles, solvent isotope effects.

Generation of 6-methylene-2,4-cyclohexadienylidene ketene by flash photolysis of benzocyclobutenone in aqueous solution and study of the reactions of this ketene in that medium

2003 ◽  
Vol 81 (6) ◽  
pp. 607-611 ◽  
Author(s):  
Y Chiang ◽  
A J Kresge ◽  
H -Q Zhan
Keyword(s):  
Aqueous Solution ◽  
Ring Opening ◽  
Flash Photolysis ◽  
Isotope Effects ◽  
Buffer Solutions ◽  
Product Identification ◽  
Rate Profile ◽  
Solvent Isotope ◽  
Rates Of Decay ◽  
Solvent Isotope Effects

Flash photolysis of benzocyclobutenone in aqueous solution produced a transient species with a microsecond lifetime whose rates of decay were measured in perchloric acid, sodium hydroxide, and buffer solutions over the acidity range [H+] 1 × 10–13 – 100 M. This produced a rate profile, isotope effects, and buffer behaviour typical of ketene reactions, and that, together with product identification, served to identify this transient as 6-methylene-2,4-cyclohexadienylidene ketene, formed by electrocyclic opening of the four-membered ring of benzocyclobutenone. Comparison of rates of reaction of this ketene with those of its saturated analog, pentamethyleneketene, produced some expected as well as some unexpected results. Key words: cyclobutenone chemistry, electrocyclic ring opening, ketene hydration, rate profile, solvent isotope effects.

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