This and other facts connected with the stability of benzenoid compounds are clearly shown when we consider mixed aliphatic-aromatic hydrocarbons, i.e.
X u x?X x x HZ which exist between aliphatic and benzenoid compounds make the transformations of one class into the other especially interesting.
Methane, tetrachlormethane, &c., to yield aromatic compounds when subjected to a high temperature, the so-called pyrogenetic reactions (from Greek 7rup, fire, and - yon, fco, I produce); the predominance of benzenoid, and related compounds-naphthalene, anthracene, phenanthrene, &c.-in coal-tar is probably to be associated with similar pyrocondensations.
Certain a-diketones condense to form benzenoid quinones, two molecules of the diketone taking part in the reaction; thus diacetyl, CH 3 CO CO CH 3, yields p-xyloquinone, C 6 H 2 (CH 3) 2 0 2 (Ber., 1888, 21, p. 1411), and acetylpropionyl, CH 3 CO CO C 2 H 5, yields duroquinone, or tetramethylquinone, C 6 (CH 3) 4 0 2, Oxymethylene compounds, characterized by the grouping > C:CH(OH), also give benzene derivatives by hydrolytic condensation between three molecules; thus oxymethylene acetone, or formyl acetone, CH 3 CO.
Hitherto we have generally restricted ourselves to syntheses which result in the production of a true benzene ring; but there are many reactions by which reduced benzene rings are synthesized, and from the compounds so obtained true benzenoid compounds may be prepared.
The transformation is not one of the oxidation of a hexamethylene compound to a benzenoid compound, for only two hydrogen atoms are removed.
The stronger argument against the ethylenoid linkages demanded by Kekule's formula is provided by the remarkable stability towards oxidizing and reducing agents which characterizes all benzenoid compounds.
From the fact that reduction products containing either one or two double linkages behave exactly as unsaturated aliphatic compounds, being readily reduced or oxidized, and combining with the halogen elements and haloid acids, it seems probable that in benzenoid compounds the fourth valencies are symmetrically distributed in such a manner as to induce a peculiar stability in the molecule.
It is difficult to determine which configuration most accurately explains the observed facts; Kekule's formula undoubtedly explains the synthetical production of benzenoid compounds most satisfactorily, and W.
Thomsen then investigated heats of combustion of various benzenoid hydrocarbons - benzene, naphthalene, anthracene, phenanthrene, &c. - in the crystallized state.
The molecule is aromatic but not benzenoid; however, by the reduction of one half of the molecule, the other assumes a benzenoid character.
Bamberger's observations on reduced quinoline derivatives point to the same conclusion, that condensed nuclei are not benzenoid, but possess an individual character, which breaks down, however, when the molecule is reduced.
Benzenoid rings as represented by the symbols: - Anthracene Phenanthrene In both cases the medial ring is most readily attacked; and various formulae have been devised which are claimed by their authors to represent this and other facts.
For general purposes, however, the symbol (2), in which the lateral rings are benzenoid and the medial ring fatty, represents quite adequately the syntheses, decompositions, and behaviour of anthracene.
(7) (2) Phenanthrene is regarded by Armstrong as represented by (3), the lateral rings being benzenoid, and the medial ring fatty; Bamberger, however, regards it as (4), the molecule being (3) (4) entirely aromatic. An interesting observation by Baeyer, viz.
Meyer (Ber., 18 94, 2 7, p. 510 et seq.) showed that in benzenoid compounds ortho-substituents exert a great hindering effect on the esterification of alcohols by acids in the presence of hydrochloric acid, this hindering being particularly marked when two substituents are present in the ortho positions to the carboxyl group. In such a case the ester is best prepared by the action of an alkyl halide on the silver salt of the acid, and when once prepared, can only be hydrolysed with great difficulty.
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."
Thus ortho-phenylene diamine yields the following products: N H N ./`N; Xn NZ In some cases oxidation of condensed benzenoid-heterocyclic nuclei results in the rupture of the heterocyclic ring with the formation of a benzene dicarboxylic acid; but if the aromatic nucleus be weakened by the introduction of an amino group, then it is the benzenoid nucleus which is destroyed and a dicarboxylic acid of the heterocyclic ring system obtained.
Systems which are generally unsaturated compounds, often of considerable stability, and behave as nuclei; these compounds constitute a well-individualized class exhibiting closer affinities to benzenoid substances than to the open-chain series.