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 these assumptions was first given by A. Ladenburg in 1874 (see Ber., 1874, 7, p. 1684; 1875, 8, p. 1666; Theorie der aromatischen Verbindungen, 1876). These results may be graphically represented as follows: numbering the hydrogen atoms in cyclical order from 1 to 6, then the first thesis demands that whichever atom is substituted the same compound results, while the second thesis points out that the pairs 2 and 6, and 3 and 5 are symmetrical with respect to 1, or in other words, the di-substitution derivatives 1.2 and 1.6, and also 1.3 and 1.5 are identical. Therefore three di-derivatives are possible, viz. 1.2 or 1.6, named ortho- (o), 1.3 or 1.5, named meta- (m), and 1.4, named para- compounds (p). In the same way it may be shown that three tri-substitution, three tetra-substitution, one penta-substitution, and one hexa-substitution derivative are possible. Of the tri-substitution derivatives, 1.2.3.-compounds are known as “adjacent” or “vicinal” (v), the 1.2.4 as “asymmetrical” (as), the 1.3.5 as “symmetrical” (s); of the tetra-substitution derivatives, 1.2.3.4-compounds are known as “adjacent,” 1.2.3.5 as “asymmetrical,” and 1.2.4.5 as “symmetrical.”



Here we have assumed the substituent groups to be alike; when they are unlike, a greater number of isomers is possible. Thus in the tri-substitution derivatives six isomers, and no more, are possible when two of the substituents are alike; for instance, six diaminobenzoic acids, C6H3(NH2)2COOH, are known; when all are unlike ten isomers are possible; thus, ten oxytoluic acids, C6H3·CH3·OH·COOH, are known. In the case of tetra-substituted compounds, thirty isomers are possible when all the groups are different.

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. Confining our attention, for the present, to di-substitution products we see that there are three distinct series of compounds to be considered. Generally if any group be replaced by another group, then the second group enters the nucleus in the position occupied by the displaced group; this means that if we can definitely orientate three di-derivatives of benzene, then any other compound, which can be obtained from or converted into one of our typical derivatives, may be definitely orientated. Intermolecular transformations—migrations of substituent groups from one carbon atom to another—are of fairly common occurrence among oxy compounds at elevated temperatures. Thus potassium ortho-oxybenzoate is converted into the salt of para-oxybenzoic acid at 220°; the three bromphenols, and also the brombenzenesulphonic acids, yield m-dioxybenzene or resorcin when fused with potash. It is necessary, therefore, to avoid reactions involving such intermolecular migrations when determining the orientation of aromatic compounds.



Substitution of the Benzene Ring.—As a general rule, homologues and mono-derivatives of benzene react more readily with substituting agents than the parent hydrocarbon; for example, phenol is converted into tribromphenol by the action of bromine water, and into the nitrophenols by dilute nitric acid; similar activity characterizes aniline. Not only does the substituent group modify the readiness with which the derivative is attacked, but also the nature of the product. Starting with a mono-derivative, we have seen that a substituent group may enter in either of three positions to form an ortho-, meta-, or para-compound. Experience has shown that such mono-derivatives as nitro compounds, sulphonic acids, carboxylic acids, aldehydes, and ketones yield as a general rule chiefly the meta-compounds, and this is independent of the nature of the second group introduced; on the other hand, benzene haloids, amino-, homologous-, and hydroxy-benzenes yield principally a mixture of the ortho- and para-compounds. These facts are embodied in the “Rule of Crum Brown and J. Gibson” (Jour. Chem. 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 ortho- and para-derivatives. By further substitution of ortho- and para-di-derivatives, in general the same tri-derivative [1.2.4] is formed (Ann., 1878, 192, p. 219); meta-compounds yield [1.3.4] and [1.2.3] tri-derivatives, except in such cases as when both substituent groups are strongly acid, e.g. m-dinitrobenzene, then [1.3.5]-derivatives are obtained.

Syntheses of the Benzene Ring.—The characteristic distinctions