PHTHALIC ACIDS, or Benzene Dicarboxylic Acids, CmH 4 (CO 2 H) 2.
Orientation of Substituent Groups.-The determination of the relative positions of the substituents in a benzene derivative constitutes an important factor in the general investigation of such compounds.
Markownikov, Ann., 1898, 302, p. I); and many other cases of the conversion of six-carbon rings into fivecarbon rings have been recorded (see below, Decompositions of the Benzene Ring) .
Those substituted in the benzene nucleus are obtained by condensing two molecules of a substituted benzyl and benzal chlorides.
It occurs naturally in some resins, especially in gum benzoin (from Styrax benzoin), in dragon's blood, and as a benzyl ester in Peru and Tolu balsams. It can be prepared by the oxidation of toluene, benzyl alcohol, benzaldehyde and cinnamic acid; by the oxidation of benzene with manganese dioxide and concentrated sulphuric acid in the cold (L.
These bands are due to molecular oscillations; Hartley suggests the carbon atoms to be rotating and forming alternately single and double linkages, the formation of three double links giving three bands, and of three single links another three; Baly and Collie, on the other hand, suggest the making and breaking of links between adjacent atoms, pointing out that there are seven combinations of one, two and three pairs of carbon atoms in the benzene molecule.
The relative merits of the formulae of Kekule, Claus and Dewar were next investigated by means of the reduction products of benzene, it being Baeyer's intention to detect whether double linkages were or were not present in the benzene complex.
Soc. 61, p. 367): If the hydrogen compound of the substituent already in the benzene nucleus can be directly oxidized to the' corresponding hydroxyl compound, then meta-derivatives predominate on further substitution, if not, then orthoand paraderivatives.
Prior to 1830, little was known of the process other than that organic compounds generally yielded tarry and solid matters, but the discoveries of Liebig and Dumas (of acetone from acetates), of Mitscherlich (of benzene from benzoates) and of Persoz (of methane from acetates and lime) brought the operation into common laboratory practice.
The former, based on Kekule's symbol for benzene, explains the decompositions and syntheses of the ring, but the character of naphthalene is not in keeping with the presence of five double linkages, although it is more readily acted upon than benzene is.