Primary isotope effects and general base catalysis in the hydrolysis of trans-dichloro(1,9-diamino-3,7-diazanonane)cobalt(III) cations

1975 ◽  
Vol 14 (1) ◽  
pp. 1-5 ◽  
Author(s):  
Etmina. Ahmed ◽  
Marie L. Tucker ◽  
M. L. Tobe
Keyword(s):  
Isotope Effects ◽  
Base Catalysis ◽  
General Base ◽  
Hydrolysis Of

ChemInform Abstract: PRIMARY ISOTOPE EFFECTS AND GENERAL BASE CATALYSIS IN THE HYDROLYSIS OF TRANS-DICHLORO(1,9-DIAMINO-3,7-DIAZANONANE)COBALT(III) CATIONS

1975 ◽  
Vol 6 (11) ◽  
pp. no-no
Author(s):  
ETMINA AHMED ◽  
MARIE L. TUCKER ◽  
M. L. TOBE
Keyword(s):  
Isotope Effects ◽  
Base Catalysis ◽  
General Base ◽  
Hydrolysis Of

Micellar catalysis of organic reactions. VIII. Kinetic studies of the hydrolysis of 2-acetyloxybenzoic acid (aspirin) in the presence of micelles

1982 ◽  
Vol 35 (7) ◽  
pp. 1357 ◽  
Author(s):  
TJ Broxton
Keyword(s):  
Aqueous Solution ◽  
Cetyltrimethylammonium Bromide ◽  
Cetylpyridinium Chloride ◽  
Kinetic Studies ◽  
Base Catalysis ◽  
Plateau Region ◽  
General Base ◽  
Mechanism Of Hydrolysis ◽  
Ph Range ◽  
Hydrolysis Of

The hydrolysis of 2-acetyloxybenzoic acid in the pH range 6-12 has been studied in the presence of micelles of cetyltrimethylammonium bromide (ctab) and cetylpyridinium chloride (cpc). In the plateau region (pH 6-8) the hydrolysis is inhibited by the presence of micelles, while in the region where the normal BAC2 hydrolysis (pH > 9) occurs the reaction is catalysed by micelles of ctab and cpc. The mechanism of hydrolysis in the plateau region is shown to involve general base catalysis by the adjacent ionized carboxy group both in the presence and absence of micelles. This reaction is inhibited in the presence of micelles because the substrate molecules are solubilized into the micelle and water is less available in this environment than in normal aqueous solution.

scholarly journals General Base Catalysis of Hydrolysis of Alkylaminoethyl Esters of Carboxylic Acids

1967 ◽  
Vol 15 (5) ◽  
pp. 674-681
Author(s):  
Tokuji Suzuki ◽  
Yuichi Tanimura
Keyword(s):  
Carboxylic Acids ◽  
Base Catalysis ◽  
General Base ◽  
Esters Of Carboxylic Acids ◽  
Hydrolysis Of

ChemInform Abstract: SYNERGISM OF THE EFFECT OF SOLVENT AND OF GENERAL BASE CATALYSIS IN THE HYDROLYSIS OF A SCHIFF BASE

1976 ◽  
Vol 7 (13) ◽  
pp. no-no
Author(s):  
RALPH M. POLLACK ◽  
MARGARET BRAULT
Keyword(s):  
Schiff Base ◽  
Base Catalysis ◽  
Effect Of Solvent ◽  
General Base ◽  
Hydrolysis Of

The mechanisms of hydrolysis of alkyl N-alkylthioncarbamate esters at 100 °C

2005 ◽  
Vol 83 (9) ◽  
pp. 1483-1491 ◽  
Author(s):  
Eduardo Humeres ◽  
Maria de Nazaré M. Sanchez ◽  
Conceição ML Lobato ◽  
Nito A Debacher ◽  
Eduardo P. de Souza
Keyword(s):  
Rate Constant ◽  
Order Rate Constant ◽  
Base Catalysis ◽  
Hydrolysis Rate ◽  
Negative Slope ◽  
General Base ◽  
Order Rate ◽  
Basic Hydrolysis ◽  
Rate Profile ◽  
Hydrolysis Of

The hydrolysis of ethyl N-ethylthioncarbamate (ETE) at 100 °C was studied in the range of 7 mol/L HCl to 4 mol/L NaOH. The pH–rate profile showed that the hydrolysis occurred through specific acid catalysis at pH < 2, spontaneous hydrolysis at pH 2–6.5, and specific basic catalysis at pH > 6.5. The Hammett acidity plot and the excess acidity plot against X were linear. The Bunnett–Olsen plot gave a negative slope indicating that the conjugate acid was less hydrated than the neutral substrate. It was concluded that the acid hydrolysis occurred by an A1 mechanism. The neutral species hydrolyzed with general base catalysis shown by the Brønsted plot with β = 0.48 ± 0.04. Water acted as a general base catalyst with (pseudo-)first-order rate constant, kN = 3.06 × 10–7 s–1. At pH > 6.5 the rate constants increased, reaching a plateau at high basicity. The basic hydrolysis rate constant of ethyl N,N-diethylthioncarbamate, which must react by a BAc2 mechanism, increased linearly at 1–3 mol/L NaOH with a second-order rate constant, k2 = 2.3 × 10–4 (mol/L)–1 s–1, which was 10 times slower than that expected for ETE. Experiments of ETE in 0.6 mol/L NaOH with an excess of ethylamine led to the formation of diethyl thiourea, presenting strong evidence that the basic hydrolysis occurred by the E1cb mechanism. In the rate-determining step, the E1cb mechanism involved the elimination of ethoxide ion from the thioncarbamate anion, producing an isothiocyanate intermediate that decomposed rapidly to form ethylamine, ethanol, and COS.Key words: alkylthioncarbamate esters, ethyl N-ethylthioncarbamate, ethyl N,N-diethylthioncarbamate, hydrolysis, mechanism.

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