Esterification salts

The chemical reactivity of resin acids is determined hy the presence of hoth the double- bond system and the COOH group [5], The carboxylic group is mainly involved in esterification, salt formation, decarboxylation, nitrile and anhydrides formation, etc. These reactions are obviously relevant to both abietic- and pimaric-type acids (Rgs 4.1 and 4.3, respectively). The olefinic system can be involved in oxidation, reduction, hydrogenation and dehydrogenation reactions. Given the conjugated character of this system in the abietic-type acids, and the enhanced reactivity associated with it, much more attention has been devoted to these stractures. In terms of industrial applications, salt formation, esterification, and Diels-Alder additions are the most relevant reactions of resin acids. 

The method is generally applicable when other modes of esterification are either slow, inefficient, or likely to cause isomerisation it is, however, time-consuming and expensive. Small quantities of acid impurities are sometimes produced, hence it is advisable to wash the ester with saturated sodium bicarbonate solution. The silver salt can usually be prepared by dissolving the acid in the calculated quantity of standard ammonium hydroxide solution and... 

The exchange resins 6nd application in (i) the purification of water (cation-exchange resin to remove salts, followed by anion-exchange resin to remove free mineral acids and carbonic acid), (ii) removal of inorganic impurities from organic substances, (iii) in the partial separation of amino acids, and (iv) as catalysts in organic reactions (e.g., esterification. Section 111,102, and cyanoethylation. Section VI,22). 

Adipic acid undergoes the usual reactions of carboxyflc acids, including esterification, amidation, reduction, halogenation, salt formation, and dehydration. Because of its biflmctional nature, it also undergoes several industrially significant polymerization reactions. 

In general, the reactions of the perfluoro acids are similar to those of the hydrocarbon acids. Salts are formed with the ease expected of strong acids. The metal salts are all water soluble and much more soluble in organic solvents than the salts of the corresponding hydrocarbon acids. Esterification takes place readily with primary and secondary alcohols. Acid anhydrides can be prepared by distillation of the acids from phosphoms pentoxide. The amides are readily prepared by the ammonolysis of the acid haUdes, anhydrides, or esters and can be dehydrated to the corresponding nitriles (31). 

Ester cmde glycerol is usually of high quality however, salt residue from the esterification catalyst is typically present at a concentration of one... 

As a dibasic acid, malic acid forms the usual salts, esters, amides, and acyl chlorides. Monoesters can be prepared easily by refluxing malic acid, an alcohol, and boron trifluoride as a catalyst (9). With polyhydric alcohols and polycarboxyUc aromatic acids, malic acid yields alkyd polyester resins (10) (see Alcohols, polyhydric Alkyd resins). Complete esterification results from the reaction of the diester of maUc acid with an acid chloride, eg, acetyl or stearoyl chloride (11). 

Hand in hand with this research on finding a suitable carboxyUc acid chemical for cross-linker has been the search for an economical catalyst system. The catalyst found to be most effective for the esterification reaction was sodium hypophosphite (NaH2P02). This material was also costiy and out of range for the textile industry. Because weak bases function as catalyst, a range of bases has been explored, including the sodium salts of acids such as malic acid. 

The toluenesulfonic acid prepared as an iatermediate ia the preparation ofpara-cmso also has a modest use as a catalyst for various esterifications and condensations. Sodium salts of the toluenesulfonic acids are also used ia surfactant formulations. Annual use of toluene for sulfonation is ca 100,000-150,000 t (30-45 x 10 gal). 

Reactions of the carboxyl group include salt and acid chloride formation, esterification, pyrolysis, reduction, and amide, nitrile, and amine formation. Salt formation occurs when the carboxyUc acid reacts with an alkaline substance (22)... 

Zinc chloride is a Lewis acid catalyst that promotes cellulose esterification. However, because of the large quantities required, this type of catalyst would be uneconomical for commercial use. Other compounds such as titanium alkoxides, eg, tetrabutoxytitanium (80), sulfate salts containing cadmium, aluminum, and ammonium ions (81), sulfamic acid, and ammonium sulfate (82) have been reported as catalysts for cellulose acetate production. In general, they require reaction temperatures above 50°C for complete esterification. Relatively small amounts (<0.5%) of sulfuric acid combined with phosphoric acid (83), sulfonic acids, eg, methanesulfonic, or alkyl phosphites (84) have been reported as good acetylation catalysts, especially at reaction temperatures above 90°C. 

Esterification. Chlorohydrins can react with salts of carboxyUc acids to form esters. For example, 2-hydroxyethyl benzoate [134-11-2] was prepared ia 92% yield by heating sodium benzoate [532-32-1] with an excess of ethylene chlorohydrin ia the presence of a small amount of diethylamine... 

Catalysts. The choice of the proper catalyst for an esterification reaction is dependent on several factors (43—46). The most common catalysts used are strong mineral acids such as sulfuric and hydrochloric acids. Lewis acids such as boron trifluoride, tin and zinc salts, aluminum haHdes, and organo—titanates have been used. Cation-exchange resins and zeoHtes are often employed also. 

In laboratory preparations, sulfuric acid and hydrochloric acid have classically been used as esterification catalysts. However, formation of alkyl chlorides or dehydration, isomerization, or polymerization side reactions may result. Sulfonic acids, such as benzenesulfonic acid, toluenesulfonic acid, or methanesulfonic acid, are widely used in plant operations because of their less corrosive nature. Phosphoric acid is sometimes employed, but it leads to rather slow reactions. Soluble or supported metal salts minimize side reactions but usually require higher temperatures than strong acids. 

Although it is seldom used, esterification of pyrimidinecarboxylic acids proceeds normally. Conditions are illustrated by the conversion of pyrimidine-4-carboxylic acid (181 R = H) into its methyl ester (181 R = Me) by methanol/sulfuric acid (47%), methanol/hydrogen chloride (80%), or by diazomethane (ca. 100%) (60MI21300). The isomeric methyl pyrimidine-2-carboxylate is formed by treatment of the silver salt of the acid with methyl iodide. Higher esters, e.g. (182 R = Bu), are usually made by warming the acid (182 R = H) with the appropriate alcohol and sulfuric acid (60JOC1950). 

This method with some slight modihcations is applied in the synthesis of to-bromo esters from Cs to Cn. Methyl 5-bromovalerate has been prepared by treating the silver salt of methyl hydrogen adipate with bromine. The ethyl ester has been prepared from the acid by esterification or through the acid chloride. ... 

The esterification reaction may be carried out with a number of different anhydrides but the literature indicates that acetic anhydride is preferred. The reaction is catalysed by amines and the soluble salts of the alkali metals. The presence of free acid has an adverse effect on the esterification reaction, the presence of hydrogen ions causing depolymerisation by an unzipping mechanism. Reaction temperatures may be in the range of 130-200°C. Sodium acetate is a particularly effective catalyst. Esterification at 139°C, the boiling point of acetic anhydride, in the presence of 0.01% sodium acetate (based on the anhydride) is substantially complete within 5 minutes. In the absence of such a catalyst the percentage esterification is of the order of only 35% after 15 minutes. 

The most important single reactions produced in the carboxyl functionality of the resin acids are salt formation, Diels-Alder additions, and esterification. Other reactions, such as disproportionation and polymerization, are less important. For some specific applications, rosins are subjected to a combination of these reactions. 

---