A Further Investigation of the Symmetrical Chloride of Paranitroorthosulphobenzoic AcidHenderson, William Edwards
Science
A Further Investigation of the Symmetrical Chloride of Paranitroorthosulphobenzoic Acid
Henderson, William Edwards
Ortho-sulfobenzoic acid; Thesis (Ph. D.)
With orthocresol the reaction proceeds with more difficulty. A higher
temperature was required (135°-145°), and quite an amount of tarry
material was obtained from which very little could be extracted. The
product was warmed repeatedly with dilute alkali, the solution so
obtained neutralized with hydrochloric acid, and distilled with steam
for several hours to free it from cresol. The resulting solution was
then evaporated to small volume, and acidified with hydrochloric acid.
A considerable precipitate was thrown down, which was easily filtered
off and dried. In this condition it is a dark purple-red powder, lumps
of which possessed a yellowish-bronze metallic lustre. In dilute
alkaline solution it forms a deep-bluish purple solution, while in
acids it is crimson, or light yellow if the solution is dilute. It is a
excellent indicator, especially with ammonia.
In the insoluble tarry substance the etherial salt was sought for
and obtained in small quantity only. As this substance is soluble in
alcohol, and separates again on cooling in much the same condition,
the etherial salt could not be isolated be crystallization from this
solvent. By boiling the substance with benzene, purifying the filtrate
with boneblack, and allowing the benzene to evaporate, an almost
colorless gummy substance was obtained, which when dissolved in
alcohol, crystallizes in small colorless needles which melt at 89°-90°.
They were not obtained in quantity sufficient for analysis, but there
was little doubt that they were crystals of the diorthocresol etherial
salt.
Apparently much more decomposition occurred in this reaction than
when paracresol was employed, probably in consequence of the higher
temperature required for the reaction.
3. The Action of Paracresol upon the Symmetrical Chloride of
Paranitroorthosulphobenzoic Acid.
This reaction was conducted in the same manner as with phenol. No
hydrochloric acid was evolved until a temperature of about 110° was
reached, although after melting, the solution had steadily darkened to
a deep reddish-brown color. At 130°, after heating for several hours,
hydrochloric acid ceased to be evolved. The product was treated as in
the last experiment. The alkaline extract did not exhibit any marked
color reactions, such as were observed in most of these experiments,
being dull reddish-brown in both acid and alkaline solution.
The insoluble residue crystallized from alcohol in light brown
transparent crystals, which did not lose their color by repeated
crystallization, and boiling with boneblack, and melted sharply at
117°. From benzene they crystallized in colorless needles or flat,
narrow plates. These become opaque on exposure to the air, apparently
through loss of benzene of crystallization.
Analysis of the needles from alcohol gave the following results:
I. 0.2372 gram of substance gave 0.5137 gram CO₂ and
0.0965 gram H₂O.
II. 0.2223 gram gave 0.1203 gram BaSO₄.
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