Naming carboxylic acid derivatives

Nitriles are classified as carboxylic acid derivatives because they are converted to carboxylic acids on hydrolysis. The conditions required are similar- to those for the hydrolysis of amides, namely, heating in aqueous acid or base for several hours. Like the hydrolysis of amides, nitrile hydrolysis is ineversible in the presence of acids or bases. Acid hydrolysis yields fflnmonium ion and a carboxylic acid. 

Simple carboxylic acids derived from open-chain alkanes are systematically named by replacing the terminal -e of the corresponding alkane name with -oic acid. The —C02H carbon atom is numbered Cl. 

As noted in the preceding section, one of the most general methods of synthesis of esters is by reaction of alcohols with an acyl chloride or other activated carboxylic acid derivative. Section 3.2.5 dealt with two other important methods, namely, reactions with diazoalkanes and reactions of carboxylate salts with alkyl halides or sulfonate esters. There is also the acid-catalyzed reaction of carboxylic acids with alcohols, which is called the Fischer esterification. 

Namely, allyl alcohol is successively treated with diethylzinc, (R,R) dipropyl tartrate, and 4-methoxybenzohydroximinoyl chloride (163) to afford the enantiomeric isoxazoline alcohol 166, which under the Jones oxidation conditions affords the corresponding carboxylic acid derivative (167). Treatment of compound 167 with hydroxylamine-O-triflate followed by tri-fluoroacetic acid gives rise to the desired enantiomeric 165 in high excess enantiomeric yield. The synthesis of other isosteric analogues of 165 was reported in the same paper. None of the isosteric analogues exhibits LpxC inhibitory and antibacterial activities [103]. 

In humans, ca. 10% of the urinary metabolites of epicainide (4.29, Fig. 4.3), an antiarrhythmic agent, is accounted for by the carboxylic acid derivative 4.32. Three distinct pathways are possible for the formation of this metabolite, namely direct hydrolysis of the secondary amide function of epicainide (Fig. 4.3, Pathway a), hydrolysis of the primary amide (4.30) resulting... 

Carboxylic acids and their derivatives like esters, amides, anhydrides, and acyl halides are formally synthesized from olefins, carbon monoxide, and compounds represented by Nu-H such as H2O, ROH, RNH2, RCOOH (Equations (4) and (5)). Alkynes also react under similar conditions to afford the corresponding unsaturated carboxylic acid derivatives. These reactions have been named hydrocarboxylation, hydroalkoxycarbonylation, and hydroaminocarbonylation. 

The IUPAC rules name esters as alkyl alkanoates. That is, the portion of the ester derived from the alcohol is named as an alkyl group. The portion of the ester that is derived from the carboxylic acid is named as the conjugate base of that acid. It is easy to distinguish these parts. The half derived from the carboxylic acid has the carbonyl group. Pentyl ethanoate, or pentyl acetate, is one ester used as artificial banana flavoring. Figure 11.51 shows three ester nomenclature examples. 

Carboxylic acid derivatives are all named by using the same root as the carboxylic acid from which they are derived. Note that the root always begins with the carbon of the carbonyl group and this carbon is always given the number 1. 

Draw and name carboxylic acid derivatives, and use spectral information to determine their structures. 

Name the following carboxylic acid derivatives, giving both a common name and an IUPAC ... 

Name carboxylic acid derivatives, and draw the structures from their names. 

We analyze one system, the photoisomerization of 2,3-diphenylcyclopropane-l-carboxylic acid derivatives, in detail to illustrate the role of alkali ions during the asymmetric induction process within zeolites [282,296]. All other systems investigated here could be analyzed on the basis of the same model. Computational results have been used to gain an insight into the interaction among the reaction site, the chiral auxiliary, and the cation. While the computations provide information about interactions in the gas phase, the reactions that we are concerned with occur in much more complex environments, namely zeolites. In spite of this severe limitation, the computational results serve to build a preliminary model that can be used to plan further experiments. 

Table 21.1 lists the suffixes for naming carboxylic acid derivatives. The suffixes used... 

Into this group fall the named oxidation rearrangement reactions which proceed with carbon-carbon bond cleavage and 1,2-transfer of an alkyl group to a heteroatom, such as the Baeyer-Villiger reaction (discussed in Chapter 5.1, this volume) and the Beckmann reaction (found in Chapter 5.2, this volume) of ketones, as well as the Hofmann reaction/Schmidt reaction/Curtius reanangement of carboxylic acid derivatives. The two examples discussed here involve related reactions of alcohols. 

To form a ketone fiom a carboxylic acid derivative, a less reactive organometallic reagent— namely an organocuprate—is needed. Acid chlorides, which have the hest leavii group (CO of the carboxylic acid derivatives, react with R 2CuLi, to give a ketone as product. 

The names of carboxylic acid derivatives are formed from the names of the parent carboxylic acids discussed in Section 19.2. Keep in mind that the common names formic acid, acetic add, and benzoic acid are virtually always used for the parent acid, so these common parent names are used for their derivatives as well. 

Symmetrical anhydrides are named by changing the acid ending of the parent carboxylic acid to the word anhydride. Mixed anhydrides, which are derived from two different carboxylic acids, are named by alphabetizing the names for both acids and replacing the word acid by the word anhydride. 

In contrast to the carboxylic acid derivatives, nitriles are named as alkane derivatives. To name a nitrile using lUPAC rules ... 

---