Imidazole Catalysis. VI.1The Intramolecular Nucleophilic Catalysis of the Hydrolysis of an Acyl Thiol. The Hydrolysis of n-Propyl γ-(4-Imidazolyl)-thiolbutyrate

1959 ◽  
Vol 81 (20) ◽  
pp. 5444-5449 ◽  
Author(s):  
Thomas C. Bruice
Keyword(s):  
Nucleophilic Catalysis ◽  
Hydrolysis Of ◽  
Imidazole Catalysis

Nucleophilic catalysis of the hydrolysis of phenyl acetates by the succinimide anion in aqueous solution

1982 ◽  
Vol 47 (19) ◽  
pp. 3687-3691 ◽  
Author(s):  
Robert W. Huffman
Keyword(s):  
Aqueous Solution ◽  
Nucleophilic Catalysis ◽  
Hydrolysis Of

Nucleophilic catalysis in the hydrolysis of 2,4-dinitrophenyl dibenzyl phosphate

1977 ◽  
Vol 99 (7) ◽  
pp. 2258-2263 ◽  
Author(s):  
David G. Gorenstein ◽  
Yue-Guey Lee
Keyword(s):  
Nucleophilic Catalysis ◽  
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

Efficient intramolecular nucleophilic catalysis in the base-catalyzed hydrolysis of o-(1-hydroxyalkyl)-N,N-dimethylbenzenesulfonamides

1986 ◽  
Vol 27 (21) ◽  
pp. 2423-2426 ◽  
Author(s):  
Jan-Wouter Drijfhout ◽  
Anno Wagenaar ◽  
Jan B.F.N Engberts
Keyword(s):  
Nucleophilic Catalysis ◽  
Hydrolysis Of

Vinylogous nucleophilic catalysis. Tertiary amine promoted hydrolysis of 1-alkene-1-sulfonyl chlorides

1984 ◽  
Vol 62 (10) ◽  
pp. 1977-1995 ◽  
Author(s):  
James Frederick King ◽  
John Henry Hillhouse ◽  
Stanisław Skonieczny
Keyword(s):  
Sulfonyl Chloride ◽  
Tertiary Amines ◽  
Nucleophilic Catalysis ◽  
Product Composition ◽  
Similar Product ◽  
Substituted Pyridines ◽  
Solvent Isotope ◽  
Zwitterionic Intermediate ◽  
Hydrolysis Of ◽  
Concerted Reaction

We present evidence that the reactions of ethenesulfonyl chloride (1) and trans-1-propene-1-sulfonyl chloride (3) with water in the presence of pyridine, trimethylamine, and a number of other tertiary amines proceed primarily by way of an initial vinylogous substitution reaction to form the cationic sulfene, [Formula: see text], which subsequently reacts with water either by addition (and deprotonation) to form the betaine [Formula: see text], or by vinylogous substitution (and deprotonation) to give the alkenesulfonate anion, [Formula: see text] (R = H or CH3). Formation of the latter represents the first well-supported example of vinylogous nucleophilic catalysis. These conclusions are drawn from kinetic and product composition observations, including (a) α-monodeuteration in the betaine and lack of deuteration of the ethenesulfonate [Formula: see text] from the reaction in D2O, (b) rate lowerings of up to 2000-fold for 2- (and 6-) substituted pyridines from those expected from Brønsted-type relationships shown by "unhindered" pyridine bases, (c) lack of a kinetic solvent isotope effect in the reaction of 1 with 3-cyanopyridine, (d) a lower rate of reaction of 3 vs. 1 not directly correlated with product composition, and (e) formation of similar product mixtures from either 1 or Pyr+CH2CH2SO2Cl Cl− (18a) with aqueous pyridine. For the initial formation of the sulfene, [Formula: see text], the available evidence does not distinguish between a two-step mechanism via an intermediate zwitterion and a closely related concerted reaction, but for the further reaction of the sulfene a process involving a zwitterionic intermediate common to both products is favoured. For the reaction of 1 or 3 in the absence of tertiary amines evidence is presented for a direct displacement on sulfur mechanism leading to the alkenesulfonate anion, plus a small proportion (up to 15%) of formation of the 2-hydroxy-1-alkanesulfonate anion by way of the sulfene HOCHRCH=SO2 (R = H or CH3).

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