General acid catalyzed acetal hydrolysis. The hydrolysis of acetals and ketals of cis- and trans-1,2-cyclohexanediol. Changes in rate-determining step and mechanism as a function of pH

1986 ◽  
Vol 108 (25) ◽  
pp. 8050-8056 ◽  
Author(s):  
Thomas H. Fife ◽  
R. Natarajan
Keyword(s):  
Rate Determining Step ◽  
General Acid ◽  
Acid Catalyzed ◽  
Cis And Trans ◽  
Hydrolysis Of

ChemInform Abstract: An ab initio Calculation of the Acid-Catalyzed Hydrolysis of N-Nitrosoamines. A Hypothesis on the Rate-Determining Step.

ChemInform ◽  
1987 ◽  
Vol 18 (28) ◽  
Author(s):  
NGUYEN MINH THO NGUYEN MINH THO ◽  
A. F. HEGARTY
Keyword(s):  
Ab Initio ◽  
Ab Initio Calculation ◽  
Rate Determining Step ◽  
Acid Catalyzed ◽  
Hydrolysis Of

scholarly journals The mechanism of the hydrolysis of acylimidazoles in aqueous mineral acids. The excess acidity method for reactions that are not acid catalyzed

1997 ◽  
Vol 75 (8) ◽  
pp. 1093-1098 ◽  
Author(s):  
Robin A. Cox
Keyword(s):  
Imidazole Ring ◽  
Carbonyl Oxygen ◽  
Pseudo First Order Reaction ◽  
Acid Media ◽  
Tetrahedral Intermediate ◽  
Reaction Rate Constants ◽  
Rate Determining Step ◽  
Reversible Addition ◽  
Acid Catalyzed ◽  
Hydrolysis Of

The mechanism of the hydrolysis of acetylimidazole in aqueous perchloric, sulfuric, and hydrochloric acid mixtures has been determined. Benzoylimidazole was also studied in the latter two acids. The method of analyzing the available data, pseudo-first-order reaction rate constants as a function of acid concentration and, in one case, temperature, is the excess acidity method, here applied to the same reaction in the three different acid media, allowing their comparison. The reaction is not acid catalyzed; the rates decrease with increasing acidity. The substrate reacts in the form that is monoprotonated on the imidazole ring; it is 100% protonated at acidities much lower than those used here. Acetylimidazole is shown to become diprotonated at high acidity [Formula: see text], protonating on the carbonyl oxygen, but the diprotonated form is not reactive. The hydrolysis involves the reversible addition of one water molecule to the substrate to give a tetrahedral intermediate; at low acidities the decomposition of this hydrate is the rate-determining step, but as the acidity increases and the water activity decreases its formation becomes rate limiting. Hydroxide catalysis was also observed in dilute perchloric acid, but this is swamped by nucleophilic catalysis by the acid anion in HCl and H2SO4. Keywords: acylimidazoles, excess acidity, hydrolysis, protonation, tetrahedral intermediate.

Ortho Esters, Imidic Esters and Amidines. V. General Acid Catalyzed Hydrolysis of Ethyl Orthoformate1

1954 ◽  
Vol 76 (17) ◽  
pp. 4379-4381 ◽  
Author(s):  
Robert H. DeWolfe ◽  
Royston M. Roberts
Keyword(s):  
General Acid ◽  
Acid Catalyzed ◽  
Ortho Esters ◽  
Hydrolysis Of

Hydrolyses of 2- and 4-fluoro N-heterocycles. 3. Nucleophilic catalysis by buffer bases in the general-acid-catalyzed hydrolysis of 4-fluoroquinaldine

1989 ◽  
Vol 54 (1) ◽  
pp. 166-171 ◽  
Author(s):  
Oliver J. Muscio ◽  
Paula G. Theobald ◽  
Denise R. Rutherford
Keyword(s):  
Nucleophilic Catalysis ◽  
General Acid ◽  
Acid Catalyzed ◽  
Hydrolysis Of

Cis- and trans-2,4-dimethoxytetrahydropyran. Models for the study of the anomeric effect

1968 ◽  
Vol 46 (9) ◽  
pp. 1543-1548 ◽  
Author(s):  
F. Sweet ◽  
R. K. Brown
Keyword(s):  
Good Yield ◽  
Methoxy Group ◽  
Equilibrium Mixture ◽  
Anomeric Effect ◽  
Kcal Mole ◽  
Mild Acid Hydrolysis ◽  
Acid Catalyzed ◽  
Cis And Trans ◽  
Hydrolysis Of ◽  
Mild Acid

Acid-catalyzed methanolysis of 2-methoxy-5,6-dihydro-2H-pyran gave, in good yield, a 4.0:1.0 mixture of trans- and cis-2,4-dimethoxytetrahydropyran. Mild acid hydrolysis of 2-methoxy-5,6-dihydro-2H-pyran followed by acid-catalyzed reaction with methanol gave a cis-trans mixture of 4-hydroxy-2-methoxytetrahydropyran in very poor yield.From the equilibrium mixture of trans- and cis-2,4-dimethoxytetrahydropyran (4.0:1.0), the magnitude of the anomeric effect of the 2-methoxy group was calculated to be 1.4 kcal/mole.

A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the Hydrolysis of Aryl N-(Substituted Phenylsulfonyl)carbamates

1994 ◽  
Vol 116 (26) ◽  
pp. 11787-11796 ◽  
Author(s):  
Alain Vigroux ◽  
Michel Bergon ◽  
Catherine Bergonzi ◽  
Pierre Tisnes
Keyword(s):  
General Acid ◽  
Acid Catalyzed ◽  
Hydrolysis Of

Hydrolysis of Orthocarbonates. Evidence for Charge Imbalance in the Transition State for the General Acid Catalyzed Process

1994 ◽  
Vol 116 (13) ◽  
pp. 5601-5606 ◽  
Author(s):  
Pramod Kandanarachchi ◽  
Michael L. Sinnott
Keyword(s):  
Transition State ◽  
Charge Imbalance ◽  
General Acid ◽  
Acid Catalyzed ◽  
Hydrolysis Of
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