Kinetics of the acid dissociation of oligopeptide complexes of copper(II) and nickel(II): a study on general-acid catalysis with "noncoordinating" 2,6-lutidine type buffers

1989 ◽  
Vol 28 (4) ◽  
pp. 736-742 ◽  
Author(s):  
Maria Hauroeder ◽  
Monika Schuetz ◽  
Klaus J. Wannowius ◽  
Horst Elias
Keyword(s):  
Acid Catalysis ◽  
Acid Dissociation ◽  
General Acid ◽  
Kinetics Of

Reaction kinetics of 1,2-diaminobenzene with ethyl 2-oxopropanoate and 2,3-butanedione

1988 ◽  
Vol 53 (12) ◽  
pp. 3154-3163 ◽  
Author(s):  
Jiří Klicnar ◽  
Jaromír Mindl ◽  
Ivana Obořilová ◽  
Jaroslav Petříček ◽  
Vojeslav Štěrba
Keyword(s):  
Reaction Kinetics ◽  
Acid Catalysis ◽  
Reaction Pathway ◽  
Hydroxide Ion ◽  
Tetrahedral Intermediate ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
General Acid ◽  
Rate Limiting ◽  
Kinetics Of

The reaction of 1,2-diaminobenzene with 2,3-butanedione is subject to general acid catalysis in acetate and phosphate buffers (pH 4-7). The rate-limiting step of formation of 2,3-dimethylquinoxaline consists in the protonation of dipolar tetrahedral intermediate. In the case of the reaction of 1,2-diaminobenzene with ethyl 2-oxopropanoate, the dehydration of carbinolamine gradually becomes rate-limiting with increasing pH in acetate buffers, whereas in phosphate buffers a new reaction pathway makes itself felt, viz. the formation of amide catalyzed by the basic buffer component and by hydroxide ion.

Kinetics of the hydrolysis of the dichromate ion. V. General acid catalysis

1969 ◽  
Vol 73 (12) ◽  
pp. 4391-4394 ◽  
Author(s):  
R. Baharad ◽  
Berta Perlmutter-Hayman ◽  
Michael A. Wolff
Keyword(s):  
Acid Catalysis ◽  
General Acid ◽  
Kinetics Of ◽  
Hydrolysis Of

Kinetics and mechanism of cyclization of N-(2-methoxycarbonylphenyl)-N’-methylsulphonamide to 3-methyl-(1H)-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide

1991 ◽  
Vol 56 (8) ◽  
pp. 1701-1710 ◽  
Author(s):  
Jaromír Kaválek ◽  
Vladimír Macháček ◽  
Miloš Sedlák ◽  
Vojeslav Štěrba
Keyword(s):  
Potassium Hydroxide ◽  
Acid Catalysis ◽  
Potassium Hydroxide Solution ◽  
Hydroxide Solution ◽  
General Base ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Cyclization Kinetics ◽  
Rate Limiting ◽  
Kinetics Of

The cyclization kinetics of N-(2-methylcarbonylphenyl)-N’-methylsulfonamide (IIb) into 3-methyl-(1H)-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide (Ib) has been studied in ethanolamine, morpholine, and butylamine buffers and in potassium hydroxide solution. The cyclization is subject to general base and general acid catalysis. The value of the Bronsted coefficient β is about 0.1, which indicates that splitting off of the proton from negatively charged tetrahedral intermediate represents the rate-limiting and thermodynamically favourable step. In the solutions of potassium hydroxide the cyclization of dianion of the starting ester IIb probably becomes the rate-limiting step.

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