1911 Encyclopædia Britannica/Fumaric and Maleic Acids

FUMARIC AND MALEIC ACIDS, two isomeric unsaturated acids of composition C4H4O4. Fumaric acid is found in fumitory (Fumaria officinalis), in various fungi (Agaricus piperatus, &c.), and in Iceland moss. It is obtained by heating malic acid alone to 150° C., or by heating it with hydrochloric acid (V. Dessaignes, Jahresb., 1856, p. 463) or with a large quantity of hydrobromic acids (A. Kekulé, Ann., 1864, 130, p. 21). It may also be obtained by boiling monobromsuccinic acid with water; by the action of dichloracetic acid and water on silver malonate (T. Komnenos, Ann., 1883, 218, p. 169); by the cyanide synthesis from acetylene di-iodide; and by heating maleic acid to 210° C. (Z. Skraup, Monats. f. Chemie, 1891, 12, p. 112). It crystallizes in small prisms or needles, and is practically insoluble in cold water. It sublimes to some extent at about 200° C., being partially converted into maleic anhydride and water, the reaction becoming practically quantitative if dehydrating agents be used. Reducing agents (zinc and caustic alkali, hydriodic acid, sodium amalgam, &c.) convert it into succinic acid. Bromine converts it into dibromsuccinic acid. Potassium permanganate oxidizes it to racemic acid (A. Kekulé and R. Anschutz, Ber., 1881, 14, p. 713). By long-continued heating with caustic soda at 100° C. it is converted into inactive malic acid.

Maleic acid is obtained by distilling malic or fumaric acids; by heating fumaric acid with acetyl chloride to 100° C; or by the hydrolysis of trichlorphenomalic acid (β-trichloracetoacrylic acid) [A. Kekulé, Ann., 1884, 223, p. 185]. It crystallizes in monoclinic prisms, which are easily soluble in water, melt at 130° C., and boil at 160° C., decomposing into water and maleic anhydride. When heated with concentrated hydrobromic or hydriodic acids, it is converted into fumaric acid. It yields an anilide; oxidation converts it into mesotartaric acid. Maleic anhydride is obtained by distilling fumaric acid with phosphorus pentoxide. It forms triclinic crystals which melt at 60° C. and boil at 196° C.

Both acids are readily esterified by the action of alkyl halides on their silver salts, and the maleic ester is readily transformed into the fumaric ester by warming with iodine, the same result being obtained by esterification of maleic acid in alcoholic solution by means of hydrochloric acid. Both acids yield acetylene by the electrolysis of aqueous solutions of their alkali salts, and on reduction both yield succinic acid, whilst by the addition of hydrobromic acid they both yield monobromsuccinic acid (R. Fittig, Ann., 1877, 188, p. 98). From these results it follows that the two acids are structurally identical, and the isomerism has consequently to be explained on other grounds. This was accomplished by W. Wislicenus [“Über die räumliche Anordnung der Atome,” &c., Trans, of the Saxon Acad. of Sciences (Math. Phys. Section), 1887, p. 14] by an extension of the van’t Hoff hypothesis (see Stereo-Isomerism). The formulae of the acids are written thus:

HC·CO2H  Maleic acid.  HC·CO2H  Fumaric acid.
HC. .·CO2H HO2C·C. .·H

These account for maleic acid readily yielding an anhydride, whereas fumaric acid does not, and for the behaviour of the acids towards bromine, fumaric acid yielding ordinary dibromsuccinic acid, and maleic acid the isomeric isodibromsuccinic acid.