Page:EB1911 - Volume 06.djvu/84

 ring system, such as in cinnolene, phthalazine and tolazone. The nitro group has a very important action mainly on account of the readiness with which it can be introduced into the molecule, but its effect is much less than that of the azo group. The colour produced is generally yellow, which, in accordance with a general rule, is intensified with an increase in the number of groups; compare, for example, mono-, di-and tri-nitrobenzene. The nitroso group is less important. The colour produced is generally of a greenish shade; for example, nitrosobenzene is green when fused or in solution (when crystalline, it is colourless), and dinitrosoresorcin has been employed as a dyestuff under the names “solid green” and “chlorine.” The carbonyl group by itself does not produce colour, but when two adjacent groups occur in the molecule, as for example in the -diketones (such as di-acetyl and benzil), a yellow colour is produced. It also acts as a chromogenic centre when double bonds or ethylenic linkages are present, as in fluorene ketone or fluorenone.

A more complex chromophoric group is the triple ethylenic grouping the introduction of which was rendered necessary by the discovery of certain coloured hydrocarbons. As a general rule, hydrocarbons are colourless; the exceptions include the golden yellow acenaphthylene, the red bidiphenylene-ethylene, and the derivatives of fulvene which have been discussed by J. Thiele (Ber., 1900, 33, p. 666). This grouping is not always colour-producing, since diphenyl is colourless.

The most important auxochromes are the hydroxyl (–OH) and amino (–NH2) groups. According to the modern theory of auxochromic action, the introduction of a group into the molecule is accompanied by some strain, and the alteration in colour produced is connected with the magnitude of the strain. The amino group is more powerful than the hydroxyl, and the substituted amino group more powerful still; the repeated substitution of hydroxyl groups sometimes causes an intensification and sometimes a diminution of colour.

We may here notice an empirical rule formulated by Nietzski in 1879:—the simplest colouring substances are in the greenish-yellow and yellow, and with increasing molecular weight the colour passes into orange, red, violet, blue and green. This rule, however, is by no means perfect. Examination of the absorption spectra of coloured compounds shows that certain groupings displace the absorption bands in one direction, and other groupings in the other. If the bands be displaced towards the violet, involving a regression through the colours mentioned above, the group is said to be “hypsochromic”; if the reverse occurs the group is “bathochromic.” It may be generally inferred that an increase in molecular weight is accompanied by a change in colour in the direction of the violet.

Auxochromic groups generally aid one another, i.e. the tint deepens as the number of auxochromes increases. Also the relative position of the auxochrome to the chromophore influences colour, the ortho-position being generally the most powerful. Kauffmann (Ber., 1906, 39, p. 1959) attempted an evaluation of the effects of auxochromic groups by means of the magnetic optical constants. The method is based on the supposition that the magnetic rotation measures the strain produced in the molecule by an auxochrome, and he arranges the groups in the following order:—

The phenomena attending the salt formation of coloured and colouring substances are important. The chromophoric groups are rarely strongly acid or basic; on the other hand, the auxochromes are strongly acid or basic and form salts very readily. Notable differences attend the neutralization of the chromophoric and auxochromic groups. With basic substances, the chromophoric combination with a colourless acid is generally attended by a deepening in colour; auxochromic combination, on the other hand, with a lessening. Examples of the first case are found among the colourless acridines and quinoxalines which give coloured salts; of the second case we may notice the colourless hydrochloride and sulphate of the deep yellow o-aminobenzophenone. With acid substances, the combination with “colourless” metals, i.e. metals producing colourless salts with acids, is attended by colour changes contrary to those given above, auxochromic combination being accompanied by a deepening, and chromophoric by a lessening of the tint.

Mention may be made of the phenomenon of halochromism, the name given to the power of colourless or faintly-coloured substances of combining with acids to form highly-coloured substances without the necessary production of a chromophoric group. The researches of Adolf von Baeyer and Villiger, Kehrmann, Kauffmann and others, show that this property is possessed by very many and varied substances. In many cases it may be connected with basic oxygen, and the salt formation is assumed to involve the passage of divalent into tetravalent oxygen. It seems that intermolecular change also occurs, but further research is necessary before a sound theory can be stated.

Quinone Theory of Colour.—A theory of colour in opposition to the Witt theory was proposed by Henry Armstrong in 1888 and 1892. This assumed that all coloured substances were derivatives of ortho- or para-quinone (see ), and although at the time of its promotion little practical proof was given, yet the theory found wide acceptance on account of the researches of many other chemists. It follows on this theory that all coloured substances contain either of the groupings



the former being a para-quinonoid, the latter an ortho-quinonoid. While very many coloured substances must obviously contain this grouping, yet in many cases it is necessary to assume a simple intermolecular change, while in others a more complex rearrangement of bonds is necessary. Quinone, which is light yellow in colour, is the simplest coloured substance on this theory. Hydrocarbons of similar structure have been prepared by Thiele, for example, the orange-yellow tetraphenyl-para-xylylene, which is obtained by boiling the bromide C6H4[CBr(C6H5)2]2 with benzene and molecular silver. The quinonoid structure of many coloured compounds has been proved experimentally, as, for example, by Hewitt for the benzene-azo-phenols, and Hantzsch for triaminotriphenyl methane and acridine derivatives; but, at the same time, many substances cannot be so explained. A notable example is provided by the phthaleins, which result by the condensation of phthalic anhydride with phenols. In the free state these substances are colourless, and were assumed to have the formula shown in 1. Solution in dilute alkali was supposed to be accompanied by the rupture of the lactone ring with the formation of the quinonoid salt shown in 2.



Baeyer (Ber., 1905, 38, p. 569) and Silberrad (Journ. Chem. Soc., 1906, 89, p. 1787) have disputed the correctness of this explanation, and the latter has prepared melliteins and pyromelliteins, which are highly-coloured compounds produced from mellitic and pyromellitic acids, and which cannot be formulated as quinones. Baeyer has suggested that the nine carbon atom system of xanthone may act as a chromophore. An alternative view, due to Green, is that the oxygen atom of the xanthone ring is tetravalent, a supposition which permits the formulation of these substances as ortho-quinonoids.

The theories of colour have also been investigated by Hantzsch, who first considered the nitro-phenols. On the chromophore-auxochrome theory (the nitro group being the chromophore, and the hydroxyl the auxochrome) it is necessary in order to explain the high colour of the metallic salts and the colourless alkyl and aryl derivatives to assume that the auxochromic action of the hydroxyl group is only brought strongly into evidence by salt formation. Armstrong, on the other hand, assumed an intermolecular change, thus:—



The proof of this was left for Hantzsch, who traced a connexion with the nitrolic acids of V. Meyer, which are formed when nitrous acid acts on primary aliphatic nitro compounds. Meyer formulated these compounds as nitroximes or nitro-isnitroso derivatives, viz. R·C(NO2)(NOH). Hantzsch explains the transformation of the colourless acid into red salts, which on standing yield more stable, colourless salts, by the following scheme:—



He has also shown that the nitrophenols yield, in addition to the colourless true nitrophenol ethers, an isomeric series of coloured unstable quinonoid aci-ethers, which have practically the same colour and yield the same absorption spectra as the coloured metallic salts. He suggests that the term “quinone” theory be abandoned, and replaced by the Umlagerungs theory, since this term implies some intermolecular rearrangement, and does not connote simply benzenoid compounds as does “quinonoid.” H. von Liebig (Ann., 1908, 360, p. 128), from a very complete discussion of triphenyl-methane derivatives, concluded that the grouping was the only true organic chromophore, colour production, however, requiring another condition, usually the closing of a ring.

The views as to the question of colour and constitution may be summarized as follows:—(1) The quinone theory (Armstrong, Gomberg, R. Meyer) regards all coloured substances as having a quinonoid structure. (2) The chromophore-auxochrome theory (Kauffmann) regards colour as due to the entry of an “auxochrome” into a “chromophoric” molecule. (3) If a colourless compound gives a coloured one on solution or by