Nucleophile Versus Base Catalysis

Determine the most probable type of catalysis for these esterification processes, using the reaction of benzoyl chloride and phenol, in dichloromethane (DCM) and in the presence of tertiary amines, as a model. 

The reaction between benzoyl chloride and phenol, catalyzed by amines, follows a third-order overall rate, being first order on each of the reactants. 

The reaction rate does not change noticeably when perdeuterated phenol (CeDsOD) was used as reagent. 

In spite of the fact that both phenol and phenoxide ion have different UV absorptions (Xmax(DCM) phenol = 275 nm Xmax(DCM) tetraethylammonium phenoxide = 250 nm), several UV-visible experiments directed towards the detection of the phenoxide ion were fruitless. 

Table 10.1 collects the values for the tertiary amines used in this problem, the rates of disappearance of benzoyl chloride and the rates of formation of phenyl benzoate. 

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NUCLEOPHILIC Versus GENERAL BASE CATALYSIS BY ACETATE ION OF THE HYDROLYSIS OF ARYL ACETATES IN WATER AT pH 5.0 AND IONIC STRENGTH... 

King, J. A., Jr. Nucleophilic versus general base catalysis in carbonyl substitution reactions the influence of acylpyridinium/acylammonium salt formation on the observed reaction rate. Trends in Organic Chemistry QQ7, 6, 67-89. 

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