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
Organic chemistry has been largely developed by the discovery from time
to time of special reagents and special types of reactions which have
shown themselves to be capable of extensive application. Such, for
example, was Frankland’s discovery, in 1852, of zinc-ethyl—the first of
the organo-metallic compounds, and the type of a series of substances
of great theoretical importance, and of great practical value by reason
of their reactive powers. They led to the synthesis of the paraffins,
the secondary and tertiary alcohols, and ketones. A few years later
Wurtz introduced the use of metallic sodium as a condensing agent, and
showed thereby how the hydrocarbon _butane_ could be produced from
ethyl iodide:
2C2H5I + Na2 = C4H10 + 2NaI.
Use was made of the same agent by Fittig, in 1863, in effecting the
synthesis of the homologues of benzene by the action of an alkyl iodide
upon bromobenzene:
C6H5Br + CH3I + Na2 = C6H5.CH3 + NaI + NaBr.
In like manner Kekulé, in 1866, obtained benzoic acid by the action of
carbon dioxide upon bromobenzene:
C6H5Br + CO2 + Na2 = C6H5COONa + NaBr.
The readiness with which magnesium can now be obtained, mainly as the
result of Sonstadt’s efforts to develop its metallurgy, has led to its
application, at the suggestion of Barbier, in 1899, in place of zinc.
The particular form of magnesium compound now employed as a reagent was
prepared by Grignard in 1900, and is known by his name. It is obtained
by bringing an ethereal solution of an alkyl iodide or bromide into
contact with magnesium, when the metal is dissolved, forming, in the
case of methyl iodide,
MgCH3I.(C2H5)2O.
Grignard’s reagent has shown itself to be extraordinarily reactive, and
a great number of condensations—of hydrocarbons, alcohols, aldehydes,
acids, ketones, amides, and additive compounds—have been effected by
means of it.
Other condensing reagents of value are aceto-acetic ester, sodium
amalgam, sodamide, sodium ethoxide, dimethyl sulphate, zinc chloride,
aluminium chloride, fused caustic potash, hydrogen chloride,
phenyl-hydrazine, hydrogen peroxide in presence of a ferrous salt
(Fenton’s reagent), ammonia, and various amines. The application of
these reagents has led to the discovery of a variety of new compounds,
the mode of origin of which has served to elucidate their constitution.
The great majority of organic syntheses, especially when they start
by the use of inorganic materials, consist in passing from simple to
complex molecular groupings by condensation processes. An interesting
example of the reverse process is seen in the production of _carbon
suboxide_, or _carbon carbonyl_, C3O2, obtained from various malonyl
compounds, but most conveniently prepared by the action of phosphoric
oxide on malonic acid under diminished pressure, or by treating an
ethereal solution of dibromomalonyl chloride with zinc:
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