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
The synthesis of the alkaloids _conine_, _atropine_, _cocaïne_,
_piperine_, and _nicotine_ has been already referred to[5] as also that
of _vanillin_, the aromatic principle of the dried fermented pods of
certain orchids; _coumarin_, the odoriferous principle of woodruff and
of the tonka bean; of _salicylic acid_, _oil of wintergreen_, _oil of
mustard_, _bitter-almond oil_, and _camphor_. _Acetic_, _succinic_,
_tartaric_, and _citric acids_ have also been artificially obtained,
and may, indeed, be built up from their elements.
[5] P. 133.
No synthesis of recent years created more widespread interest than that
of _alizarin_, first effected by Graebe and Liebermann in 1868. Its
successful commercial manufacture by Sir William Perkin in this country
and by Caro in Germany created nothing less than a revolution in one
of our leading industries, and completely destroyed a staple trade of
France, Holland, Italy, and Turkey. To procure alizarin, anthraquinone
is treated with sulphuric acid, and the product is fused with alkali
and potassium chlorate.
The remarkable industrial results attending the synthetical formation
of this madder-product naturally led to attempts to procure other
important vegetable dye-stuffs artificially, notably _indigo_.
The synthetical production of indigo has been accomplished by
the joint labours of many chemists, notably Baeyer, Heumann, and
Heymann, and the substance is now prepared on an industrial scale.
The starting-point is _naphthalene_, obtained from coal-tar. This
is converted into _phthalic acid_, which is then transformed into
_phthalimide_. The last-named substance is converted into _anthranilic
acid_, which, on treatment with monochloracetic acid, is changed into
_phenylglycin_-ortho-_carbonic acid_. On melting this with caustic
potash it yields _indoxyl acid_, which is transformed into _indoxyl_,
and thence into _indigo_.
Another method is to treat the sodium salt of phenylglycin with
sodamide, whereby _indoxyl_ is at once obtained, and this by
condensation yields _indigo blue_:
C6H5.NH.CH2.COONa + Na.NH2
Sodium salt of Sodamide.
phenylglycin.
CO
/ \
→C6H4 CH2
\ /
NH
Indoxyl.
CO CO
/ \ / \
→C6H4 C:C C6H4
\ / \ /
NH NH
Indigo blue.
Phenylglycin is obtained by the action of monochloracetic acid
on aniline, which in its turn is obtained through nitrobenzene
from benzene. Since benzene can be synthetically prepared by the
condensation of acetylene, which can be obtained by the direct union of
carbon and hydrogen at a high temperature, it is theoretically possible
to build up indigo blue from inorganic materials.
Public-domain text, read in full here on John Shaqi.
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