1911 Encyclopædia Britannica/Esters

ESTERS, in organic chemistry, compounds formed by the condensation of an alcohol and an acid, with elimination of water; they may also be considered as derivatives of alcohols, in which the hydroxylic hydrogen has been replaced by an acid radical, or as acids in which the hydrogen of the carboxyl group has been replaced by an alkyl or aryl group. In the case of the polybasic acids, all the hydrogen atoms can be replaced in this way, and the compounds formed are known as “neutral esters.” If, however, some of the hydrogen of the acid remain undisplaced, then “acid esters” result. These acid esters retain some of the characteristic properties of the acids, forming, for example, salts, with basic oxides. Esters may be prepared by heating the silver salt of an acid with an alkyl iodide; by heating the alcohols or alcoholates with an acid chloride; by distilling the anhydrous sodium salt of an acid with a mixture of the alcohol and concentrated sulphuric acid; or by heating for some hours on the water bath, a mixture of an acid and an alcohol, with a small quantity of hydrochloric or sulphuric acids (E. Fischer and A. Speier, Ber., 1896, 28, p. 3252).

The esters of the aliphatic and aromatic acids are colourless neutral liquids, which are generally insoluble in water, but readily dissolve in alcohol and ether. Many possess a fragrant odour and are prepared in large quantities for use as artificial fruit essences. They hydrolyse readily when boiled with solutions of caustic alkalies or mineral acids, yielding the constituent acid and alcohol. When heated with ammonia, they yield acid amides (q.v.). They form unstable addition products with sodium ethylate or methylate. With the Grignard reagent, they form addition compounds which on the addition of water yield tertiary alcohols, except in the case of ethyl formate, where a secondary alcohol is obtained.

R·CO2C2H5 → R·C	OMgBr	→ R·C	OMgBr	→	R′	C·OH.
	OC2H5		R′		R′
	R′		R′		R′
H·CO2C2H5 → H·C	OMgBr	→ H·C	OMgBr	→ R′ R′ CH·OH.
	OC2H5		R′
	R′		R′

N. Menschutkin (Ber., 1882, 15, p. 1445; Ann., 1879, 195, p. 334) examined the rate of esterification of many acids with alcohols. It was found that the normal primary alcohols were all esterified at about the same rate, the secondary alcohols more slowly than the primary, and the tertiary alcohols still more slowly. The investigation also showed that the nature of the acid used affected the result, for in an homologous series of acids it was found that as the molecule of the acid became more complex, the rate of esterification became less. The formation of an ester by the interaction of an acid with an alcohol is a “reversible” or “balanced” action, for as M. Berthelot and L. Péan de St Gilles (Ann. Chim. Phys., 1862 (3), 65, p. 385 et seq.) have shown in the case of the formation of ethyl acetate from ethyl alcohol and acetic acid, a point of equilibrium is reached, beyond which the reacting system cannot pass, unless the system be disturbed in some way by the removal of one of the products of the reaction. V. Meyer (Ber., 1894, 27, p. 510 et seq.) showed that in benzenoid compounds ortho-substituents exert a great hindering effect on the esterification of alcohols by acids in the presence of hydrochloric acid, this hindering being particularly marked when two substituents are present in the ortho positions to the carboxyl group. In such a case the ester is best prepared by the action of an alkyl halide on the silver salt of the acid, and when once prepared, can only be hydrolysed with great difficulty.

Ethyl formate, H·CO₂C₂H₅, boils at 55° C. and has been used in the artificial preparation of rum. Ethyl acetate (acetic ether), CH₃·CO₂C₂H₅, boils at 75° C. Isoamylisovalerate, C₄H₉·CO₂C₅H₁₁, boils at 196° C. and has an odour of apples. Ethyl butyrate, C₃H₇·CO₂C₂H₅, boils at 121° C. and has an odour of pineapple. The fats (q.v.) and waxes (q.v.) are the esters of the higher fatty acids and alcohols. The esters of the higher fatty acids, when distilled under atmospheric pressure, are decomposed, and yield an olefine and a fatty acid.

Esters of the mineral acids are also known and may be prepared by the ordinary methods as given above. The neutral esters are as a rule insoluble in water and distil unchanged; on the other hand, the acid esters are generally soluble in water, are non-volatile, and form salts with bases. Ethyl hydrogen sulphate (sulphovinic acid), C₂H₅·HSO₄, is obtained by the action of concentrated sulphuric acid on alcohol. The ester is separated from the solution by means of its barium salt, and the salt decomposed by the addition of the calculated amount of sulphuric acid. It is a colourless oily liquid of strongly acid reaction; its aqueous solution decomposes on standing and on heating it forms diethyl sulphate and sulphuric acid. Dimethyl sulphate, (CH₃)₂SO₄, is a colourless liquid which boils at 187°-188° C., with partial decomposition. It is used as a methylating agent (F. Ullmann). Great care should be taken in using dimethyl and diethyl sulphates, as the respiratory organs are affected by the vapours, leading to severe attacks of pneumonia. Ethyl nitrate, C₂H₅·ONO₂, is a colourless liquid which boils at 86.3° C. It is prepared by the action of nitric acid on ethyl alcohol (some urea being added to the nitric acid, in order to destroy any nitrous acid that might be produced in secondary reactions and which, if not removed, would cause explosive decomposition of the ethyl nitrate). It burns with a white flame and is soluble in water. When heated with ammonia it yields ethylamine nitrate, and when reduced with tin and hydrochloric acid it forms hydroxylamine (q.v.) (W. C. Lossen). Ethyl nitrite, C₂H₅·ONO, is a liquid which boils at 18° C.; the crude product obtained by distilling a mixture of alcohol, sulphuric and nitric acids and copper turnings is used in medicine under the name of “sweet spirits of nitre.” Amyl nitrite, C₅H₁₁·ONO, boils at 96° C. and is used in the preparation of the anhydrous diazonium salts (E. Knoevenagel, Ber., 1890, 23, p. 2094). It is also used in medicine.