History of Chemistry, Volume 2 (of 2): From 1850 to 1910Thorpe, T. E. (Thomas Edward)
History
History of Chemistry, Volume 2 (of 2): From 1850 to 1910
Thorpe, T. E. (Thomas Edward)
Chemistry -- History
This conception received a great extension as the result of Kekulé’s
application of his ideas to the explanation of the chemical
constitution of the group of substances of vegetable origin—consisting
of essential oils, balsams, resins, and their products, which, on
account of their characteristic odours, were collectively known to
the older chemists as the _aromatic compounds_. Some of these, like
oil of bitter almonds, gum benzoin, coumarin, oil of wintergreen, oil
of anise, oil of cinnamon, oil of cumin, balsam of tolu, phenol, and
certain of their derivatives, such as benzene, aniline, salicylic acid,
cinnamic acid, toluene, cymene, had already been investigated with
important theoretical results; but as a class they had received far
less attention than the derivatives of the great group of homologous
radicals of which methyl is the initial member. Of course it was part
of the doctrine of Liebig—the discoverer of benzoyl—that the aromatic
compounds also contained specific radicals; but the relation of these
compounds to those we now call aliphatic (fatty) compounds was not
understood, although certain analogies were recognised.
In 1866 Kekulé drew attention to the following significant
peculiarities of the aromatic compounds: (1) All aromatic compounds,
even the simplest, are comparatively richer in carbon than the
corresponding class of fatty (aliphatic) compounds; (2) among the
aromatic substances, as among fatty compounds, numerous homologous
compounds exist; (3) the simplest aromatic substances contain at
least six atoms of carbon; (4) all decomposition products of aromatic
substances show a certain family resemblance; the main product of the
decomposition contains at least six atoms of carbon—_e.g._, benzene
C6H6, phenol C6H6O, etc., which would seem to indicate that all
aromatic substances contain a nucleus or atomic grouping containing
six carbon atoms. Within this nucleus the carbon atoms are in closer
connection or denser combination, from which it follows that all
aromatic compounds are comparatively rich in carbon. More carbon atoms
can then be added to this nucleus according to the same laws that
govern the fatty compounds. In this way the existence of homologous
compounds may be explained.
On the assumption that carbon is tetravalent and that its valency is
constant, Kekulé showed how, by linking together six carbon atoms by
alternate single and double bonds, six affinity units may be left
free. If we assume that six carbon atoms are attached to one another
according to this law of symmetry, we obtain a group which, regarded as
an _open chain_, contains _eight_ unsaturated units of affinity:
——C══C——C══C——C══C——
| | | | | |
By making the further assumption that the two carbon atoms at the
ends of the chain are linked together by one unit of affinity each,
a _closed chain_ (a symmetrical ring) is obtained which now contains
_six_ unsaturated units of affinity:
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