Acid-catalyzed esterification, mechanism

The most apparent chemical property of carboxylic acids their acidity has already been examined m earlier sections of this chapter Three reactions of carboxylic acids—con version to acyl chlorides reduction and esterification—have been encountered m pre vious chapters and are reviewed m Table 19 5 Acid catalyzed esterification of carboxylic acids IS one of the fundamental reactions of organic chemistry and this portion of the chapter begins with an examination of the mechanism by which it occurs Later m Sec tions 19 16 and 19 17 two new reactions of carboxylic acids that are of synthetic value will be described... 

An important question about the mechanism of acid catalyzed esterification concerns the origin of the alkoxy oxygen For example does the methoxy oxygen m methyl benzoate come from methanol or is it derived from benzoic acid s... 

Section 19 14 The mechanism of acid catalyzed esterification involves some key fea tures that are fundamental to the chemistry of carboxylic acids and then-derivatives... 

FIGURE 19.7 The mechanism of acid-catalyzed esterification of benzoic acid with methanol. 

Problem 16.16 Give the mechanism for the acid-catalyzed esterification of RCOOH with R OH. ... 

Like the AVADA and the AlkyClean processes, these two processes also replace the liquid acid/base catalysts with solid acids and bases [192]. Although the reaction mechanism for the heterogeneous acid-catalyzed esterification is similar to the homogeneously catalyzed one [207,208], there is an important difference concerning the relationship between the surface hydrophobicity and the catalyst s activity. This is especially true for fatty acids, which are very lipophilic compounds. One can envisage three cases First, if there are isolated Bronsted acid sites surrounded by a... 

The Aac2 mechanism (Figure 6.22) of ester hydrolysis represents an SN reaction at the carboxyl carbon, which follows the general mechanism of Figure 6.5. Acid-catalyzed hydrolyses of carboxyhc esters that are derived from primary or from secondary alcohols take place according to the Aac2 mechanism. The reverse reactions of these hydrolyses follow the same mechanism, namely, the acid-catalyzed esterifications of carboxylic acids with alcohols. In the esterifications, the same intermediates are formed as during hydrolysis, but in the opposite order. 

The widely accepted mechanism of the acid-catalyzed esterification is designated as the Aac2 process (A = acid catalysis, AC = acyl transfer, 2 = bimolecular). As shown in Schemes la and lb the rate-deter-... 

Esters react by both acid and nucleophile initiated mechanisms. Hydrolysis of esters by acid catalysis is exactly the reverse of the mechanism for the acid-catalyzed esterification of a carboxylic acid. Base-catalyzed hydrolysis of esters is called saponification. Hydroxide attacks to form a tetrahedral intermediate. Loss of alkoxide ion then occurs. The alkoxide neutralizes the resulting carboxylic acid to form the salt. 

This pattern of increased reactivity resulting from carbonyl group protonation has been seen before in nucleophilic additions to aldehydes and ketones (Section 17.6) and in the mechanism of the acid-catalyzed esterification of carboxylic acids (Section 19.14). Many biological reactions involve nucleophilic acyl substitution and are catalyzed by enzymes that act by donating a proton to the carbonyl oxygen, the leaving group, or both. 

A methacrylate terpolymer containing 35 mol% methacrylic acid units was mixed with diepoxides (Fig. 131) and triphenylsulfonium triflate and imaged in a negative mode by exposure to ArF excimer laser followed by development with 0.06% (weak) TMAH solution [383]. The aromatic epoxide was selected for imaging because the more transparent aliphatic epoxide was liquid and thus lowered the Tg of the resist film to an unacceptable level. The insolubilization mechanism was speculated to be crosslinking through acid-catalyzed esterification between the carboxylic acid and epoxide. 

To obtain rate equations for the esterification reactions (1) and (2), a detailed knowledge of the underlying mechanisms is necessary. For the acid-catalyzed esterification of carboxylic acids with alcohols, the mechanism was proposed (Figure 5.2). 

---