Page:EB1911 - Volume 01.djvu/572

 formation of secondary alcohols, thus from acetaldehyde and magnesium methyl iodide, isopropyl alcohol is obtained.

The lower members of the aliphatic series are characterized by their power of polymerization (see, and the account of Acetaldehyde below), and also by the so-called “aldol” condensation, acetaldehyde in this way forming aldol, CH3·CHOH·CH2·CHO. These aldols generally lose the elements of water readily and pass into unsaturated compounds; aldol itself on distillation at ordinary atmospheric pressure gives crotonaldehyde, CH3·CH : CH·CHO.

Aldehydes are characterized by the reddish-violet colour which they give with a solution of fuchsine that has been decolorized by sulphurous acid (H. Schiff, Ann., 1866, 140, p. 131). With diazobenzene sulphonic acid in the presence of alkali and a trace of sodium amalgam, a reddish-violet coloration is formed on standing (E. Fischer, Ber., 1883, 16, p. 657). A. Angeli (Gazz. chim. Ital., 1896, 22, ii, 17) has shown that aldehydes in the presence of nitrohydroxylaminic acid form hydroxamic acid. The aldehydes condense readily with acetoacetic ester in the presence of ammonia, to pyridines (see ), whilst O. Doebner and W. v. Miller (Ber., 1892, 25, p. 2864; 1896, 29, p. 59) have shown that in the presence of aniline and sulphuric acid they give substituted quinolines. (See also C. Beyer, Ber., 1887, 20, p. 1908). The chief aldehydes are shown in the following table:—

For formaldehyde see. Acetaldehyde, CH3·CHO, was first noticed by C. Scheele in 1774 and isolated and investigated by J. v. Liebig (Annalen, 1835, 14, p. 133). It is prepared by oxidizing ethyl alcohol with dilute sulphuric acid and potassium bichromate, and is a colourless liquid of boiling point 20·8° C., possessing a peculiar characteristic smell. Its specific gravity is 0·8009 (0° C.). It is miscible in all proportions with alcohol, ether and water. It is readily polymerized, small quantities of hydrochloric acid, zinc chloride, carbonyl chloride, &c. converting it, at ordinary temperatures, into paraldehyde, (C2H4O)3, a liquid boiling at 124° C. and of specific gravity 0·998 (15° C.). Paraldehyde is moderately soluble in water, and when distilled with sulphuric acid is reconverted into the ordinary form. Metaldehyde, (C2H4O)3, is produced in a similar way to paraldehyde, but at lower temperatures (e.g. in presence of a freezing mixture). It is a crystalline solid, which sublimes at 112°—115° C. It is insoluble in water, and is only slightly soluble in alcohol and ether. When heated in a sealed tube at 120° C. it is completely converted into the ordinary form. Paraldehyde is oxidized by dilute nitric acid, with formation of much glyoxal, (CHO)2. (For trichloracetaldehyde see .)

By the action of acetaldehyde on alcohol at 100° C., acetal, CH3·CH(OC2H5)2, is produced. It may also be prepared by oxidizing ethyl alcohol with manganese dioxide and sulphuric acid (A. Wurtz). It is a colourless liquid of specific gravity 0·8314 (20°/4°) (J. W. Brühl) and boiling point 104° C. Dilute acids readily transform it into alcohol and aldehyde, and chromic acid oxidizes it to acetic acid. Chlor- and brom-acetals have been described.

Thioaldehydes are also known, and are obtained by leading sulphuretted hydrogen into an aqueous solution of acetaldehyde. By this means a mixture is obtained which by distillation or the action of hydrochloric acid yields trithioaldehyde, (C2H4S)3. For the constitution of these substances see E. Baumann and E. Fromm (Berichte, 1891, 24, p. 1426). Aldehyde ammonia, CH3·CH(OH)·NH2, is formed when dry ammonia gas is passed into an ethereal solution of acetaldehyde. It crystallizes in glistening rhombohedra, melting at 70°–80° C., and boiling at 100° C. It is completely resolved into its components when warmed with dilute acids.

The higher aldehydes of the series resemble acetaldehyde in their general behaviour. Unsaturated aldehydes are also known, corresponding to the olefine alcohols; they show the characteristic properties of the saturated aldehydes and can form additive compounds in virtue of their unsaturated nature. The simplest member of the series is acrolein, C3H4O or CH2 : CH·CHO, which can be prepared by the oxidation of allyl alcohol, or by the abstraction of the elements of water from glycerin by heating it with anhydrous potassium bisulphate. It is also produced by the action of sodium on a mixture of epichlorhydrin and methyl iodide, C3H5OCl＋CH3I＋2Na＝C3H4O＋NaI＋NaCl＋CH4. It is a colourless liquid, with a very pungent smell, and attacks the mucous membrane very rapidly. It boils at 52·4° C. and is soluble in water. It oxidizes readily: exposure to air giving acrylic acid, nitric acid giving oxalic acid, bichromate of potash and sulphuric acid giving carbon dioxide and formic acid. It combines with bromine to form a dibromide, from which E. Fischer, by the action of baryta water, obtained the synthetic sugars - and -acrose (Berichte, 1889, 22, p. 360). Metacrolein, (C3H4O)3, is a polymer of acrolein. By passing acrolein vapour into ammonia, acrolein ammonia, C6H9NO, is obtained. It is a reddish amorphous mass, insoluble in alcohol, and when distilled yields picoline (methyl pyridine) (A. Baeyer, Ann., 1870, 155, p. 283). Citronellal, rhodinal and geranial are also unsaturated aldehydes (see ).

The aromatic aldehydes resemble the aliphatic aldehydes in most respects, but in certain reactions they exhibit an entirely different behaviour. They do not polymerize, and in the presence of caustic alkalies do not resinify, but oxidize to alcohols and acids (see for Cannizzaro’s reaction). When heated with alcoholic potassium cyanide they are converted into (q.v.). Vanillin does not give the Cannizzaro reaction, but with alcoholic potash forms vanillic acid, HOOC(1)·C6H3·OCH3(3)·OH(4), and vanilloin. With ammonia, benzaldehyde does not form an aldehyde ammonia, but condenses to hydrobenzamide, (C6H5CH)3N2, with elimination of water. Cumic aldehyde (cuminol), (CH3)2CH(1)C6H4·CHO(4), is found in Roman caraway oil and in oil of the water hemlock. It is a liquid, boiling at 235° C., and has a specific gravity of 0·973. On distillation with zinc dust it forms cymene (1·4 methyl isopropyl benzene).

Salicylic aldehyde (ortho-hydroxybenzaldehyde), HO(1)·C6H4·CHO(2), an aromatic oxyaldehyde, is a colourless liquid of boiling point 196° C. and specific gravity 1·172 (15°). It is found in the volatile oils of Spiraea, and can be obtained by the oxidation of the glucoside salicin, (C13H18O7), which is found in willow bark. It is usually prepared by the so-called “Reimer” reaction (Ber, 1876, 9, p. 1268), in which chloroform acts on phenol in the presence of a caustic alkali, C6H5OH＋CHCl3＋4KHO＝3KCl＋3H2O＋KO·C6H4·CHO, some para-oxybenaldehyde being formed at the same time. It