1993
DOI: 10.1021/ja00058a006
|View full text |Cite
|
Sign up to set email alerts
|

Structure-reactivity correlations for reactions of substituted phenolate anions with acetate and formate esters

Abstract: The reactions of substituted phenolate anions with m-nitrophenyl, p-nitrophenyl, and 3,4-dinitrophenyl formates follow nonlinear Bransted-type correlations that might be taken as evidence for a change in the rate-limiting step of a reaction that proceeds through a tetrahedral addition intermediate. However, the correlation actually represents two different Bronsted lines that are defined by meta-and para-substituted phenolate anions and by meta-and para-substituted o-chlorophenolate anions. A concerted mechani… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
3
1
1

Citation Types

10
113
0
3

Year Published

1998
1998
2019
2019

Publication Types

Select...
8

Relationship

0
8

Authors

Journals

citations
Cited by 131 publications
(126 citation statements)
references
References 2 publications
10
113
0
3
Order By: Relevance
“…Especially, the ΔH ≠ values are somewhat lower and the ΔS ≠ values are higher negative values than other aminolysis systems. 13 The expulsion of ArO − anion in the rate determining step (an endoergic process) is assisted by the hydrogen-bonding with an amino hydrogen of the benzylammonium ion within the intermediate, T…”
Section: Resultsmentioning
confidence: 99%
“…Especially, the ΔH ≠ values are somewhat lower and the ΔS ≠ values are higher negative values than other aminolysis systems. 13 The expulsion of ArO − anion in the rate determining step (an endoergic process) is assisted by the hydrogen-bonding with an amino hydrogen of the benzylammonium ion within the intermediate, T…”
Section: Resultsmentioning
confidence: 99%
“…Investigating the reaction of p-nitrophenylacetate and phenolate ions, Buncel 35 described the process as a multi-step reaction and proposed the rate-limiting step to be the intermediate formation, regardless of whether the leaving group departure is synchronized with the nucleophilic attack or not. On the other hand, Williams 6a and Jencks 7 , studying the same reaction have proposed a concerted mechanism based on a constant β NU value even for ∆pKa= 0 when phenolate acts as both the nucleophile and the leaving group. This suggestion is supported by Hengge following his kinetic isotope effect studies of reactions between p-nitrophenylacetate and several oxyanions, such as, the hydroxyl anion, phenolates, hexafluormethylisopropoxide and aliphatic oxyanions.…”
Section: Methodsmentioning
confidence: 99%
“…[1][2][3][4][5][6][7][8][9] Besides describing the structural relationships which lead to the reactivity of carboxylic acid derivatives, the search for nucleophiles able to cleave selectively peptide and ester bonds is still a challenge in many areas of chemistry and biochemistry. [10][11][12] The development of such stable and highly reactive nucleophiles has a wide range of applications in chemical detoxification, e.g., where quantitative phosphate bond cleavage is the target.…”
Section: Introductionmentioning
confidence: 99%
“…[4][5][6][7][8][9][10][11][12][13] The first is the concerted mechanism. The acyl-group transfer reactions of aryl phenyl carbonates with phenoxides and 4-nitrophenyl acetate with phenoxides have been concluded to be of this type.…”
Section: Introductionmentioning
confidence: 99%
“…The acyl-group transfer reactions of aryl phenyl carbonates with phenoxides and 4-nitrophenyl acetate with phenoxides have been concluded to be of this type. [7][8][9] The aminolysis can also proceed via a zwitterionic tetrahedral intermediate. [14][15][16][17] In contrast, much less is known about the corresponding acyl transfer reactions involving heterocyclic aromatic compounds.…”
Section: Introductionmentioning
confidence: 99%