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
Among the naturally occurring pyridine alkaloids may be named
_piperine_, found in black pepper, and _conine_, the poisonous
principle of hemlock (_conium maculatum_). The latter alkaloid was
prepared synthetically by Ladenburg in 1886; as first obtained
it differed from the naturally occurring product, which is
dextro-rotatory, in being optically inactive. Ladenburg surmised that
the synthetic preparation stood to the naturally occurring compound
in the same relation that racemic acid stood to tartaric acid, and
that, by treatment in the manner employed by Pasteur, the racemic
modification of conine might be separated into its dextro- and
lævo-constituents. This was found to be the case; but the separated
dextro component was now found to be distinctly more optically
active than the pure, natural variety. It was, in fact, an isomeric
modification—_iso_-conine. By heating this to 300° it was transformed
into ordinary conine, identical in all respects with the natural
alkaloid. Ladenburg has also effected the synthesis of piperine by
condensing piperidine and piperinic acid.
_Nicotine_, the alkaloid of tobacco, was discovered by Posselt and
Reimann in 1828. Its constitution was first ascertained by Pinner, and
it was synthetically obtained by Amé Pictet, in 1904, as an inactive
substance, capable of being resolved by the crystallisation of its
tartrates into a dextro- and lævo-modification, the latter of which was
identical with that found in the tobacco leaf.
_Atropine_ and _hyoscyamine_—the poisonous principles of belladonna
and henbane—are isomeric alkaloids, the former of which is optically
inactive, and the latter is lævo-rotatory. Atropine is, in fact, the
racemic modification. The constitution of both alkaloids is known, and
their synthesis is now possible.
The successive steps may be thus indicated:
1. _Synthesis of glycerin_ (Faraday, Kolbe, Melsens, Boerhave, Friedel,
and Silva).
2. _Glycerin to glutaric acid_ (Berthelot and De Luca, Cahours and
Hofmann, Erlenmeyer, Lermantoff, and Markownikoff).
3. _Glutaric acid to suberone_ (Brown and Walker, Boussingault).
4. _Suberone to tropidine_ (Willstätter).
5. _Tropidine to tropine_ (Willstätter, Ladenburg).
6. _Synthesis of tropic acid_ (Berthelot, Fittig and Tollens, Friedel,
Ladenburg, and Rügheimer).
7. _Tropine and tropic acid: atropine_ (Ladenburg).
The alkaloid _cocaïne_, contained in the leaves of _erythroxylon
coca_ and now employed as a local anæsthetic, was discovered by
Niemann in 1860. It has been shown to be closely related to atropine
in constitution, and has now been synthetically prepared in the
dextro-modification.
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