A Further Investigation of the Symmetrical Chloride of Paranitroorthosulphobenzoic Acid — John Shaqi
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.)
This same product was sought for when pure symmetrical chloride was
employed, but without success. In every case, crystals of unchanged
chloride separated, or else it was found that it had been completely
converted into the acid etherial salt. In another trial cold water
was carefully added in small portions, since Kastle found that such
treatment facilitated the separation of the substance; the chloride
alone appeared. Still other attempts were made to obtain the substance
by adding a large amount of water to the solution of the chloride
in alcohol, after it had stood for some time. In this way, quite a
precipitate was thrown down, and this was filtered off and crystallized
from ether. It always proved to be the symmetrical chloride, and none
of the other substance was obtained.
Karslake[16] in working with the symmetrical chloride of
orthosulphobenzoic acid, was unable to isolate the analogous compound,
although from the mixed chlorides, by the action of alcohols, Remsen
and Dohme[17] had obtained chloro-etherial salts.
[16] Inaug. Diss. J. H. Univ. 1895.
[17] Am. Ch. Journ. XI, 341.
In as much as the pure symmetrical chloride is relatively stable in
cold alcohol (it can be crystallized from warm alcohol with very
little loss), it is possible that it is more stable than the chloro
etherial salt, and that in consequence the latter, when formed, yields
more readily to the further action of alcohol than does the unacted
on chloride. Hence when the action begins, it at once proceeds to the
limit. The fact that the symmetrical chloride is rather sparingly
soluble in cold alcohol, making the use of concentrated solutions
impossible, may also be a factor in the case. Whatever may be the
cause, this substance could not be obtained under any conditions that
were devised.
Having in my possession a very small specimen of crystallized
unsymmetrical chloride, it was submitted to the action of ethyl
alcohol, under as nearly as possible the conditions employed by Kastle.
Crystals of a colorless substance were obtained, which in every respect
agreed with Kastle’s description of the chloride of the acid ethyl
etherial salt of paranitroorthosulphobenzoic acid. Crystallized from
ether they melted at 68°.
The conditions employed by Kastle in preparing the chloride would
undoubtedly lead to a relatively large proportion of unsymmetrical
chloride, and it is to this chloride that the formation of the chloro
etherial salt is apparently due.
VII. The Action of Phenols upon the Symmetrical Chloride of
Paranitroorthosulphobenzoic Acid.
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