which assumes that in addition to the ordinary valencies, each doubly linked atom has a partial valency, by which the atom first interacts. When applied to benzene, a twofold conjugated system is suggested in which the partial valencies of adjacent atoms neutralize, with the formation of a potential double link. The stability of benzene is ascribed to this conjugation.[1]
Physico-chemical properties have also been drawn upon to decide whether double unions are present in the benzene complex; but here the predilections of the observers apparently influence the nature of the conclusions to be drawn from such data. It is well known that Physico-chemical methods.singly, doubly and trebly linked carbon atoms affect the physical properties of substances, such as the refractive index, specific volume, and the heat of combustion; and by determining these constants for many substances, fairly definite values can be assigned to these groupings. The general question of the relation of the refractive index to constitution has been especially studied by J. W. Brühl, who concluded that benzene contained 3 double linkages; whereas, in 1901, Pellini (Gazetta, 31, i. p. 1) calculated that 9 single linkages were present. A similar contradiction apparently exists with regard to the specific volume, for while benzene has a specific volume corresponding to Claus’ formula, toluene, or methylbenzene, rather points to Kekulé’s. The heat of combustion, as first determined by Julius Thomsen, agreed rather better with the presence of nine single unions. His work was repeated on a finer scale by M. P. E. Berthelot of Paris, and F. C. A. Stohmann of Leipzig; and the new data and the conclusions to be drawn from them formed the subject of much discussion, Brühl endeavouring to show how they supported Kekulé’s formula, while Thomsen maintained that they demanded the benzene union to have a different heat of combustion from the acetylene union. Thomsen then investigated heats of combustion of various benzenoid hydrocarbons—benzene, naphthalene, anthracene, phenanthrene, &c.—in the crystallized state. It was found that the results were capable of expression by the empirical relation CaH2b = 104.3b + 49.09m + 105.47n, where CaH2b denotes the formula of the hydrocarbon, m the number of single carbon linkings and n the number of double linkings, m and n being calculated on the Kekulé formulae. But, at the same time, the constants in the above relation are not identical with those in the corresponding relation empirically deduced from observations on fatty hydrocarbons; and we are therefore led to conclude that a benzene union is considerably more stable than an ethylene union.
Mention may be made of the absorption spectrum of benzene. According to W. N. Hartley (J.C.S., 1905, 87, p. 1822), there are six bands in the ultra-violet, while E. C. C. Baly and J. N. Collie (J.C.S., 1905, 87, p. 1332; 1906, 89, p. 524) record seven. 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.
Stereo-chemical Configurations.—Simultaneously with the discussions of Kekulé, Ladenburg, Claus, Baeyer and others as to the merits of various plane formulae of the benzene complex, there were published many suggestions with regard to the arrangement of the atoms in space, all of which attempted to explain the number of isomers and the equivalence of the hydrogen atoms. The development of stereo-isomerism at the hands of J. Wislicenus, Le Bel and van ’t Hoff has resulted in the introduction of another condition which formulae for the benzene complex must satisfy, viz. that the hydrogen atoms must all lie in one plane. The proof of this statement rests on the fact that if the hydrogen atoms were not co-planar, then substitution derivatives (the substituting groups not containing asymmetric carbon atoms) should exist in enantiomorphic forms, differing in crystal form and in their action on polarized light; such optical antipodes have, however, not yet been separated. Ladenburg’s prism formula would give two enantiomorphic ortho-di-substitution derivatives; while forms in which the hydrogen atoms are placed at the corners of a regular octahedron would yield enantiomorphic tri-substitution derivatives.
The octahedral formula discussed by Julius Thomsen (Ber., 1886, 19, p. 2944) consists of the six carbon atoms placed at the corners of a regular octahedron, and connected together by the full lines as shown in (I); a plane projection gives a hexagon with diagonals (II). Reduction to hexamethylene compounds necessitates the disruption of three of the edges of the octahedron, the diagonal linkings remaining intact, or, in the plane projection, three peripheral linkages, the hexamethylene ring assuming the form (III):
In 1888 J. E. Marsh published a paper (Phil. Mag. [V.], 26, p. 426) in which he discussed various stereo-chemical representations of the benzene nucleus. (The stereo-chemistry of carbon compounds has led to the spatial representation of a carbon atom as being situated at the centre of a tetrahedron, the four valencies being directed towards the apices; see above, and Isomerism.) A form based on Kekulé’s formula consists in taking three pairs of tetrahedra, each pair having a side in common, and joining them up along the sides of a regular hexagon by means of their apices. This form, afterwards supported by Carl Graebe (Ber., 1902, 35, p. 526; see also Marsh’s reply, Journ. Chem. Soc. Trans., 1902, p. 961) shows the proximity of the ortho-positions, but fails to explain the identity of 1·2 and 1·6 compounds. Arrangements connected with Claus’ formula are obtained by placing six tetrahedra on the six triangles formed by the diagonals of a plane hexagon. The form in which the tetrahedra are all on one side, afterwards discussed by J. Loschmidt (Monats., 1890, II, p. 28), would not give stereo-isomers; and the arrangement of placing the tetrahedra on alternate sides, a form afterwards developed by W. Vaubel (Journ. Pr. Chem., 1894[2], 49, p. 308), has the advantage of bringing the meta-positions on one side, and the ortho- and para- on opposite sides, thus exhibiting the similarity actually observed between these series of compounds. Marsh also devised a form closely resembling that of Thomsen, inasmuch as the carbon atoms occupied the angles of a regular octahedron, and the diagonal linkages differed in nature from the peripheral, but differing from Thomsen’s since rupture of the diagonal and not peripheral bonds accompanied the reduction to hexamethylene.
We may also notice the model devised by H. Sachse (Ber., 1888, 21, 2530; Zeit. für phys. Chem., II, p. 214; 23, p. 2062). Two parallel triangular faces are removed from a cardboard model of a regular octahedron, and on the remaining six faces tetrahedra are then placed; the hydrogen atoms are at the free angles. This configuration is, according to Sachse, more stable than any other form; no oscillation is possible, the molecule being only able to move as a whole. In 1897, J. N. Collie (Journ. Chem. Soc. Trans., p. 1013) considered in detail an octahedral form, and showed how by means of certain simple rotations of his system the formulae of Kekulé and Claus could be obtained as projections. An entirely new device, suggested by B. König (Chem. Zeit., 1905, 29, p. 30), assumed the six carbon atoms to occupy six of the corners of a cube, each carbon atom being linked to a hydrogen atom and by single bonds to two neighbouring carbon atoms, the remaining valencies being directed to the unoccupied corners of the cube, three to each, where they are supposed to satisfy each other.
Condensed Nuclei.
Restricting ourselves to compounds resulting from the fusion of benzene rings, we have first to consider naphthalene, C10H8, which consists of two benzene rings having a pair of carbon atoms in common. The next members are the isomers anthracene and phenanthrene, C14H10, formed from three benzene nuclei. Here we shall only discuss the structure of these compounds in the light of the modern benzene theories; reference should be made
- ↑ Victor Meyer and G. Heyl (Ber., 1895, 28, p. 2776) attempted a solution from the following data. It is well known that di-ortho-substituted benzoic acids are esterified with difficulty. Two acids corresponding to the formula of Kekulé and Claus are triphenyl acrylic acid, (C6H5) 2C:C(COOH)·C6H5, and triphenyl acetic acid, (C6H5)3C·COOH. Experiments showed that the second acid was much more difficult to esterify than the first, pointing to the conclusion that Claus’ formula for benzene was more probable than Kekulé’s.
