Carboxylic esters with carboxylate ions

Animal fats and vegetable oils are triacylglycerols, or triesters, formed from the reaction of glycerol (1,2, 3-propanetriol) with three long-chain fatty acids. One of the methods used to characterize a fat or an oil is a determination of its saponification number. When treated with boiling aqueous KOH, an ester is saponified into the parent alcohol and fatty acids (as carboxylate ions). The saponification number is the number of milligrams of KOH required to saponify 1.000 g of the fat or oil. In a typical analysis, a 2.085-g sample of butter is added to 25.00 ml of 0.5131 M KOH. After saponification is complete, the excess KOH is back titrated with 10.26 ml of0.5000 M HCl. What is the saponification number for this sample of butter ... 

Reaction of carboxylate ion with nitrophenyl sulfites gives the carboxylate -nitrophenyl esters. If the -nitrophenyl sulfite is unsymmethcal (02NCgH40S(0)0R, where R is ethyl or phenyl), carboxylate attacks the -nitrophenyl side (69). Some amino acids react with methyl and benzyl sulfites in the presence of -toluenesulfonic acid to give methyl and benzyl esters of the amino acids as -toluenesulfonate salts (70). With alcohols, the conversion of henzil to a monoacetal upon addition of sulfuric acid to the henzil in methanol and dimethyl sulfite proceeds in high yield (71). 

The SEM ester was used to protect a carboxyl group where DCC-mediated esterification caused destruction of the substrate. It was formed from the acid and SEM chloride (THF, 0°, 80% yield) and was removed solvolytically. The ease of removal in this case was attributed to anchimeric assistance by the phosphate group. Normally SEM groups are cleaved by treatment with fluoride ion. Note that in this case the SEM group is removed considerably faster than the phenyl groups from the phosphate. ... 

The Dppe group was developed for carboxyl protection in peptide synthesis. It is formed from an N-protected amino acid and the alcohol (DCC, DMAP, 3-12 h, 0°, It). It is most efficiently cleaved by quatemization with Mel followed by treatment with fluoride ion or K2CO3. The ester is stable to HBr/AcOH, BF3 Et20, and CF3CO2H. ... 

The effect of a carboxy group is illustrated by the reactivity of 2-bromopyridine-3- and 6-carboxylic acids (resonance and inductive activation, respectively) (cf. 166) to aqueous acid under conditions which do not give hydroxy-debromination of 2-bromopyridine and also by the hydroxy-dechlorination of 3-chloropyridine-4-car-boxylic acid. The intervention of intermolecular bifunctional autocatalysis by the carboxy group (cf. 237) is quite possible. In the amino-dechlorination (80°, 4 hr, petroleum ether) of 5-carbethoxy-4-chloropyrimidine there is opportunity for built-in solvation (167) in addition to electronic activation. This effect of the carboxylate ion, ester, and acid and its variation with charge on the nucleophile are discussed in Sections I,D,2,a, I,D,2,b, and II,B, 1. A 5-amidino group activates 2-methylsulfonylpyridine toward methanolic am-... 

Methyl esters (RCO2CH3) undergo a cleavage reaction to yield carboxylate ions plus iodomethane on heating with Lil in dimethylformamide ... 

Reagents that provide UV adsorptive derivatives of carboxylic acids are fairly numerous. The preparation of the simple benzyl esters by reacting the carboxylic ion with alkyl halides or diazo compounds has been unsuccessful due to their having unacceptable toxicity. The... 

The above results pertain to reactions in solution. In the gas phase reactions can take a different course, as illustrated by the reaction of carboxylic esters with MeO, which in the gas phase was shown to take place only by the Bal2 mech-anism, ° even with aryl esters, ° where this means that an Sn2 mechanism takes place at an aryl substrate. However, when the gas-phase reaction of aryl esters was carried out with MeO ions, each of which was solvated with a single molecule of MeOH or H2O, the Bac2 mechanism was observed. 

The reaction of alkyl sulfates with alkoxide ions is quite similar to 10-12 in mechanism and scope. Other inorganic esters can also be used. One of the most common usages of the reaction is the formation of methyl ethers of alcohols and phenols by treatment of alkoxides or aroxides with methyl sulfate. The alcohol or phenol can be methylated directly, by treatment with dimethyl sulfate and alumina in cyclohexane. Carboxylic esters sometimes give ethers when treated with alkoxides (Bal2 mechanism, p. 473) in a very similar process (see also 10-24). 

A series of substituents meta to the nitrogen atom and para to the functionalized methylene were then introduced. The hydrophobic electron-attracting ester substituents (26 Z = C02 Bu, C02C6H13, C02(CH2)3 or C02rBu Fig. 11.14) decreased the inhibitory efficiency. The acid ester 26 (Z = C02(CH2)3C02H) was prepared in the hope that the anionic charge of the corresponding carboxylate ion would interact with... 

Transesterifications, of neutral carboxylate and organophosphate esters with transition metal ion and Ln3+ catalysts, 284-288 alcoholysis of carboxylate esters, 288-294 alcoholysis of neutral phosphate esters, 294-308... 

B Castro, J-R Dormoy, G Evin, C Selve. Peptide coupling reagents. Part VII. Mechanism of the formation of active esters of hydroxybenzotriazole in the reaction of carboxylate ions on the BOP reagent for peptide coupling. A comparison with Itoh s reagent. J Chem Res (S) 82, 1977. 

The saponification (the base-catalyzed hydrolysis of an ester) of fats has been important since ancient times. This process frees the glycerin and releases the fatty acids as carboxylate ions. The carboxylate ions, along with sodium or potassium ions from the base, create a soap (refer to Figure 16-28). 

The reaction of a-haloketones (chloro, bromo or iodo) with alkoxide ions to give rearranged esters is called Favorskii rearrangement. For example, 2-chlorocyclohexanone is converted to the methyl ester of cyclopentane carboxylic acid by treatment with sodium methoxide in ether. 

The axial or equatorial nature of a substituent has a bearing on its reactivity, or ability to interact with its environment. Equatorial substituents are more stable and less reactive than their axial counterparts. For example, equatorial carboxyl groups are stronger acids than axial ones because of the higher stability of the carboxylate ion, whereas equatorial esters are hydrolyzed more slowly than axial ones because they are less accessible to protons or hydroxyl ions during acid- or base-catalyzed hydrolysis. 

Amides. Metal ions catalyze the hydrolysis of a variety of amides, including acylamino acids, dipeptides and tripeptides, and amino acid amides. In all these compounds it is possible for a metal ion to complex with one or more ligand groups, either amine or carboxylate ion functions, in addition to the amide group. Thus the structural prerequisites for the metal ion catalysis of amide hydrolysis are the same as those for ester hydrolysis. 

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