Meta toluene sulphonic acid and related compounds — John Shaqi
Meta toluene sulphonic acid and related compoundsAllen, C. F. H. (Charles Francis Hitchcock)
Science
Meta toluene sulphonic acid and related compounds
Allen, C. F. H. (Charles Francis Hitchcock)
Organic compounds -- Synthesis; Sulfonic acids
A portion of the dry diazo compound was placed in a flask connected
with a reflux condenser, and solid sodium carbonate and n-butyl
alcohol added. No reaction took place at ordinary temperature so heat
was applied. Decomposition started at 65° and evolution of hydrogen
proceeded evenly and smoothly until all the diazo compound had
disappeared. The alcohol, at first colorless, became an orange and
finally a brown color. The solution was then refluxed an hour to ensure
complete decomposition of the diazo compound. The smell of an aldehyde
was evident indicating that the hydrogen reaction was taking place; the
solution was tested with Schiff’s reagent and with ammoniacal silver
nitrate with distinct positive results in both cases, showing aldehyde
was present. The alcoholic solution was filtered from the sodium
carbonate remaining, and the alcohol distilled off on an oil bath. A
yellowish-orange porous solid was left in such a small amount that
no derivatives could be made and studied. It was free from the diazo
compound, shown by its giving no color with an alkaline solution of H
acid.
(2) With n-Butyl Alcohol alone.
The previous experiment showed that n-butyl alcohol would decompose
the diazo compound in the presence of sodium carbonate and replace
the amino group by hydrogen, so this time a decomposition with the
alcohol alone was tried. Decomposition took place evenly and smoothly
as before at the same temperature, and the solution became a clear
brownish-orange. Aldehyde was given off and tested for as before with
positive results. The alcohol was removed by distillation and a thick
brownish syrupy liquid was left. This was easily soluble in water,
so was dissolved, filtered, and the solution used in the following
experiments. At this point it is similar in every way to the solution
obtained by Griffin (loc. cit.) from the diazo compound of para
toluidine meta sulphonic acid.
Subsequent preparations of this syrup were made in the above way with
similar results in every case. The only precaution to be observed is
that no part of the flask containing the reaction mixture be allowed
to become too hot as the diazo compound is then decomposed violently
leaving a grayish ash.
A STUDY OF THE SOLUTION OBTAINED BY THE DECOMPOSITION OF THE DIAZO
COMPOUND
The syrup which remained after distilling off the n-butyl alcohol was
a thick brown viscous fluid in all cases. It has an acid reaction and
is completely soluble in water. On testing it showed the presence of
sulphur in quantity and the absence of nitrogen. Some was dissolved in
water, filtered, and evaporated on the water bath. After its volume had
been considerably reduced it turned a very dark brown, then blackish,
and smelled very tarry. It did not crystallize at all, finally becoming
very black. To a drop on a watch glass, a drop and then an excess of
concentrated hydrochloric acid was added but with no apparent result.
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