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.)
Analysis of this product for sulphur showed that in this galleïn, as
in the case of the hydroquinone phthaleïn more than two pyrogallol
residues had entered the acid residue. The indications were that
six had entered into one of the chloride. This also agrees with the
observation of Lyman[23], who describes a hexapyrogallol galleïn of
orthosulphoparatoluic acid.
Probably a mixture of varying composition was obtained, and little
importance was attached to the results save as they showed that no
etherial salt is formed in the reaction.
[23] Am. Ch. Journ. XVI-527.
7. The Action of β-Naphthol upon the Symmetrical Chloride of
Paranitroorthosulphobenzoic Acid.
It was hoped that here, as in the case of the monohydroxy phenols an
etherial salt would be obtained. It was found, however, that very
little action occurred, save such as was indicated by the development
of a bright carmine color in the melted mixture, until a temperature of
about 160° was reached. At this point hydrochloric acid was evolved,
but the chloride itself undergoes decomposition. Nothing definite could
be isolated among the reaction products, save unchanged β-Naphthol.
VIII. The Action of Aniline upon the Symmetrical Chloride of
Paranitroorthosulphobenzoic Acid.
As has been pointed out in the Introduction, it was in connection
with the aniline derivatives of orthosulphobenzoic acid, that the
isomerism of the chlorides was first noticed, two anilids being
obtained. Accordingly, when Gray began his study of the chlorides
of paranitroorthosulphobenzoic acid, his first effort was to obtain
evidence of the existence of two anilids. These were not obtained,
however, until after the chlorides themselves had been isolated, as
their properties made their isolation and preparation a matter of
difficulty.
Some points still remained in doubt after Gray’s study, and a further
investigation was thought to be desirable to clear these up.
Some time was spent in an endeavor to obtain a method by which a good
yield of fusible, or symmetrical, anilid could be obtained. The yield
in all cases tried, is not a good one. The presence of the nitro group
appears to complicate the reaction, leading to secondary reactions
whose course could not be followed. Upon bringing aniline and the
chloride together, a very vivid red color was always observed, and the
same was true when it was necessary to employ alkali. The fact that
such colors develop when nitro compounds are treated with alkali has
been noticed in many instances and some progress has been made in the
study of these compounds. Jackson and Ittner[24] have lately reviewed
this subject.
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