Aromatic acid esters

Solids. —It may Idc a hydrocM bon (c .g., paraffin wa, naphthalene) highei alcohol eg., cetyl alcohol) aldehyde e.g., z5-hydroxybenzaldehyde) ketone and qiiinonc e.g., benzo-phenone, camphor) acid (higher fatty, e.g., palmitic acid or aromatic acid) ester (of glycerol, phenols or aromatic alcohols) phenol e.g., thymol),... 

Figure 13.1 A shows a conventional high performance reversed-phase separation of a three-component mixture of aromatic acid esters obtained with a standard 4.6 mm x 250 mm octadecyl column and methanol water as the eluent. From the view of chromatographic resolution and ruggedness, this is an excellent separation. However, from a practical standpoint, an assay based on this particular separation would not be satisfactory since it wastes large amounts of time between elutions of the individual components.

Alkylbenzoxazoles were condensed with esters of aromatic acid esters to give 2-phenacylbenzox-azoles (249 equation 138). 2-Alkyloxazoles are acylated by electrophiles, e.g. anhydrides, catalyzed... 

Nakamura, Y, and Higuchi, T. (1978) Ester linkage of p-coumaric acid in bamboo lignin. II. Syntheses of coniferyl p-hydroxyhenzoate and coniferyl p-coumarate as possible precursors of aromatic acid esters in lignin. Cellul. Chem. Technol. 12(2), 199-208. 

NB The same apparent pXa values were measured for four odier substituted alkanoic acid esters propionic butanoic, 2-methylpropanoic and pentanoic. Thirteen other compounds, all alkanoic or aromatic acid esters were too poorly water-soluble to be measured in aqueous solution. They all were reported to have apparent pKg = 8.7 in 90.7% aqueous methanol. 

As shown in Table 13.7, the free energy of reaction of aramid polymerizations is reported to be negative even with aromatic acid, ester, and diamine monomers. In spite of this driving force, the rate of reaction is extremely slow because of the high activation energy of the polymerization reaction [51]. 

Aromatic acid esters hydrolyze more slowly than aliphatic esters. Esters of phthalic acid are more easily hydrolyzed than esters of isophthalic acid (IPA) (1,3-benzenedicarboxylic acid) [121-91-5]. Adipic acid (1,6-hexanedioic acid) [124-04-9] is the most widely used aliphatic dibasic acid. Dimer acids made by dimerization of drying oil fatty acids are also used. 

This is usually considered to be essentially monolayer adsorption with competition between solvent and solute. The non-electiolytes that have been studied are mainly fatty acids, aromatic acids, esters and other single functionless group compounds plus a great variety of more complex species such as porphyrins, bile pigments, carotenoids, lipoids and dyestuffs. 

Method (1) is most frequently used for aliphatic acid amides, while Methods (2a), (2b) and (zc) are used most frequently for aromatic acid amides. Of the last three methods, the Acid Chloride Method (zb) is the most rapid and certain. The Ester Method (za) is practicable only when the amide is insoluble in water, and even then is often very slow unless the ester itself is appreciabb soluble in the aqueous ammonia solution. 

In general the method is more satisfactory with esters of aromatic acids than with esters of aliphatic acids. Esters of alcohols other than methyl and ethyl are best treated by first converting them into methyl esters thus Heat together under reflux i ml. of the higher ester, 5 ml. of methanol and 0-2 g. of sodium methoxide. [In place of the sodium methoxide, it suffices to add o i g. of metallic sodium to the methanol.] After refluxing, distil off the excess of methanol (b.p, 65 ). The residue is then heated under reflux with benzylamine as described above. 

B) Benzylamtdes (see (a) above) can often be prepared directly from the ester, particularly if a methyl or ethyl ester. Usually works best with esters of aromatic acids. (M.ps., pp. 543 545.)... 

NOTE. Many esters reduce Fehling s solution on warming. This reduction occurs rapidly with the alkyl esters of many aliphatic acids, but scarcely at all with similar esters of aromatic acids (f.g., ethyl oxalate reduces, but ethyl benzoate does not). Note also that this is a property of the ester itself thus both methyl and ethyl oxalate reduce Fehling s solution very rapidly, whereas neither oxalic acid, nor sodium oxalate, nor a mixture of the alcohol and oxalic acid (or sodium oxalate), reduces the solution. 

Almost insoluble in cold water. Higher alcohols (including benzyl alcohol), higher phenols (e.g., naphthols), metaformaldehyde, paraldehyde, aromatic aldehydes, higher ketones (including acetophenone), aromatic acids, most esters, ethers, oxamide and domatic amides, sulphonamides, aromatic imides, aromatic nitriles, aromatic acid anhydrides, aromatic acid chlorides, sulphonyl chlorides, starch, aromatic amines, anilides, tyrosine, cystine, nitrocompounds, uric acid, halogeno-hydrocarbons, hydrocarbons. 

Metallic sodium. This metal is employed for the drying of ethers and of saturated and aromatic hydrocarbons. The bulk of the water should first be removed from the liquid or solution by a preliminary drying with anhydrous calcium chloride or magnesium sulphate. Sodium is most effective in the form of fine wire, which is forced directly into the liquid by means of a sodium press (see under Ether, Section II,47,i) a large surface is thus presented to the liquid. It cannot be used for any compound with which it reacts or which is affected by alkalis or is easily subject to reduction (due to the hydrogen evolved during the dehydration), viz., alcohols, acids, esters, organic halides, ketones, aldehydes, and some amines. 

N-Benzylamides are recommended when the corresponding acid is liquid and/or water-soluble so that it cannot itself serve as a derivative. Phe benzylamides derived from the simple fatty acids or their esters are not altogether satisfactory (see Table below) those derived from most hydroxy-acids and from poly basic acids or their esters are formed in good yield and are easily purified. The esters of aromatic acids yield satisfactory derivatives but the method must compete with the equally simple process of hydrolysis and precipitation of the free acid, an obvious derivative when the acid is a solid. The procedure fails with esters of keto, sul phonic, inorganic and some halogenated aliphatic esters. 

From the acid chloride. The interaction of the acid chloride of au aromatic acid with the calculated quantity of an alcohol or a phenol aflFords a good yield of the ester, for example ... 

Trichloroacetic acid K = 0.2159) is as strong an acid as hydrochloric acid. Esters and amides are readily formed. Trichloroacetic acid undergoes decarboxylation when heated with caustic or amines to yield chloroform. The decomposition of trichloroacetic acid in acetone with a variety of aUphatic and aromatic amines has been studied (37). As with dichloroacetic acid, trichloroacetic acid can be converted to chloroacetic acid by the action of hydrogen and palladium on carbon (17). 

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). 

Aluminum chloride [7446-70-0] is a useful catalyst in the reaction of aromatic amines with ethyleneknine (76). SoHd catalysts promote the reaction of ethyleneknine with ammonia in the gas phase to give ethylenediamine (77). Not only ammonia and amines, but also hydrazine [302-01-2] (78), hydrazoic acid [7782-79-8] (79—82), alkyl azidoformates (83), and acid amides, eg, sulfonamides (84) or 2,4-dioxopyrimidines (85), have been used as ring-opening reagents for ethyleneknine with nitrogen being the nucleophilic center (1). The 2-oxopiperazine skeleton has been synthesized from a-amino acid esters and ethyleneknine (86—89). 

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