More emphatic opposition to the dualistic theory of Berzelius was hardly possible; this illustrious chemist perceived that the validity of his electrochemical theory was called in question, and therefore he waged vigorous war upon Dumas and his followers. But he fought in a futile cause; to explain the facts put forward by Dumas he had to invent intricate and involved hypotheses, which, it must be said, did not meet with general acceptance; Liebig seceded from him, and invited Wöhler to endeavour to correct him. Still, till the last Berzelius remained faithful to his original theory; experiment, which he had hitherto held to be the only sure method of research, he discarded, and in its place he substituted pure speculation, which greatly injured the radical theory. At the same time, however, the conception of radicals could not be entirely displaced, for the researches of Liebig and Wohler, and those made subsequently by Bunsen, demonstrated beyond all doubt the advantages which would accrue from their correct recognition.
A step forward—the fusion of Dumas’, type theory and the radical theory—was made by Laurent and Charles Gerhardt. As early as 1842, Gerhardt in his Précis de chimie organique exhibited a marked leaning towards Dumas’ theory, and it is without doubt that both Dumas and Laurent exercised considerable influence on his views. Unwilling to discard the strictly unitary views of these chemists, or to adopt the copulae theory of Berzelius, he revived the notion of radicals in a new form. According to Gerhardt, the process of substitution consisted of the union of two residues to form a unitary whole; these residues, previously termed “compound radicals,” are atomic complexes which remain over from the interaction of two compounds. Thus, he interpreted the interaction of benzene and nitric acid as C6H6 + HNO3 = C6H5NO2 + H2O, the “residues” of benzene being C6H5 and H, and of nitric acid HO and NO2. Similarly he represented the reactions investigated by Liebig and Wöhler on benzoyl compounds as double decompositions.
This rejuvenation of the notion of radicals rapidly gained favour; and the complete fusion of the radical theory with the theory of types was not long delayed. In 1849 C. A. Wurtz discovered the amines or substituted ammonias, previously predicted by Liebig; A. W. von Hofmann continued the investigation, and established their recognition as ammonia in which one or more hydrogen atoms had been replaced by hydrocarbon radicals, thus formulating the “ammonia type.” In 1850 A. W. Williamson showed how alcohol and ether were to be regarded as derived from water by substituting one or both hydrogen atoms by the ethyl group; he derived acids and the acid anhydrides from the same type; and from a comparison of many inorganic and the simple organic compounds he concluded that this notion of a “water-type” clarified, in no small measure, the conception of the structure of compounds.
These conclusions were co-ordinated in Gerhardt’s “new theory of types.” Taking as types hydrogen, hydrochloric acid, water and ammonia, he postulated that all organic compounds were referable to these four forms: the hydrogen type included hydrocarbons, aldehydes and ketones; the hydrochloric acid type, the chlorides, bromides and iodides; the water type, the alcohols, ethers, monobasic acids, acid anhydrides, and the analogous sulphur compounds; and the ammonia type, the amines, acid-amides, and the analogous phosphorus and arsenic compounds. The recognition of the polybasicity of acids, which followed from the researches of Thomas Graham and Liebig, had caused Williamson to suggest that dibasic acids could be referred to a double water type, the acid radical replacing an atom of hydrogen in each water molecule; while his discovery of tribasic formic ether, CH(OC2H5)3, in 1854 suggested a triple water type. These views were extended by William Odling, and adopted by Gerhardt, but with modifications of Williamson’s aspects. A further generalization was effected by August Kekulé, who rejected the hydrochloric acid type as unnecessary, and introduced the methane type and condensed mixed types. Pointing out that condensed types can only be fused with a radical replacing more than one atom of hydrogen, he laid the foundation of the doctrine of valency, a doctrine of incalculable service to the knowledge of the structure of chemical compounds.
At about the same time Hermann Kolbe attempted a rehabilitation, with certain modifications, of the dualistic conception of Berzelius. He rejected the Berzelian tenet as to the unalterability of radicals, and admitted that they exercised a considerable influence upon the compounds with which they were copulated. By his own investigations and those of Sir Edward Frankland it was proved that the radical methyl existed in acetic acid; and by the electrolysis of sodium acetate, Kolbe concluded that he had isolated this radical; in this, however, he was wrong, for he really obtained ethane, C2H6, and not methyl, CH3. From similar investigations of valerianic acid he was led to conclude that fatty acids were oxygen compounds of the radicals hydrogen, methyl, ethyl, &c., combined with the double carbon equivalent C2. Thus the radical of acetic acid, acetyl, was C2H3·C2. (It will be noticed that Kolbe used the atomic weights H=1, C=6, O=8, S=16, &c.; his formulae, however, were molecular formulae, i.e. the molecular weights were the same as in use to-day.) This connecting link, C2, was regarded as essential, while the methyl, ethyl, &c. was but a sort of appendage; but Kolbe could not clearly conceive the manner of copulation.
The brilliant researches of Frankland on the organo-metallic compounds, and his consequent doctrine of saturation capacity or valency of elements and radicals, relieved Kolbe’s views of all obscurity. The doctrine of copulae was discarded, and in 1859 emphasis was given to the view that all organic compounds were derivatives of inorganic by simple substitution processes. He was thus enabled to predict compounds then unknown, e.g. the secondary and tertiary alcohols; and with inestimable perspicacity he proved intimate relations between compounds previously held to be quite distinct. Lactic acid and alanine were shown to be oxy- and amino-propionic acids respectively; glycollic acid and glycocoll, oxy- and amino-acetic acids; salicylic and benzamic acids, oxy- and amino-benzoic acids.
Another consequence of the doctrine of valency was that it permitted the graphic representation of the molecule. The “structure theory” (or the mode of linking of the atoms) of carbon compounds, founded by Butlerow, Kekulé and Couper and, at a later date, marvellously enhanced by the doctrine of stereo-isomerism, due to J. H. van’t Hoff and Le Bel, occupies such a position in organic chemistry that its value can never be transcended. By its aid the molecule is represented as a collection of atoms connected together by valencies in such a manner that the part played by each atom is represented; isomerism, or the existence of two or more chemically different substances having identical molecular weights, is adequately shown; and, most important of all, once the structure is determined, the synthesis of the compound is but a matter of time.
In this summary the leading factors which have contributed to a correct appreciation of organic compounds have so far been considered historically, but instead of continuing this method it has been thought advisable to present an epitome of present-day conclusions, not chronologically, but as exhibiting the principles and subject-matter of our science.
Classification of Organic Compounds.
An apt definition of organic chemistry is that it is “the study of the hydrocarbons and their derivatives.” This description, although not absolutely comprehensive, serves as a convenient starting-point for a preliminary classification, since a great number of substances, including the most important, are directly referable to hydrocarbons, being formed by replacing one or more hydrogen atoms by other atoms or groups. Two distinct types of hydrocarbons exist: (1) those consisting of an open chain of carbon atoms—named the “aliphatic series” (ἄλειφαρ, oil or fat), and (2) those consisting of a closed chain—the “carbocyclic series.” The second series can be further divided
- This must not be confused with the modern acetyl, CH3·CO, which at that time was known as acetoxyl.