The best known of the arsenicals, however, is diphenylchloroarsine or
sneezing gas. Although this is an old compound (having been prepared
by German chemists in 1885), there was no method for its preparation
on a large scale when, first introduced into chemical warfare. It
was finally discovered that the interaction of triphenyl arsine with
arsenic trichloride was fairly satisfactory and a plant was erected for
its manufacture.
When pure, diphenylchloroarsine is a colorless solid, melting at 44°.
Because of this, it was always used in solution in a toxic gas or in
a shell which contained a large amount of explosive so that on the
opening of the shell the material would be finely divided and scattered
over a wide territory.
Its value lay in the fact that the fine particles readily penetrated
the ordinary mask and caused the irritation of the nose and throat,
which resulted in sneezing. This necessitated the perfection of special
smoke filters to remove the particles, after which the other toxic
materials were removed by the absorbent in the canister.
It causes sneezing and severe burning sensations in the nose, throat
and lungs in concentrations as slight as 1 part in 10 million. In
higher concentrations, say 1 in 200 to 500 thousand it causes severe
vomiting. While neither of these effects are dangerous or very lasting,
still higher concentrations are serious, as in equal concentrations
diphenylchloroarsine is more poisonous than phosgene.
Various other arsenical chemicals were developed in the laboratory,
but with one or two exceptions they were not as valuable as
diphenylchloroarsine and methyldichloroarsine and were therefore
discarded.
GERMAN METHODS FOR MANUFACTURING ARSENICALS[23]
DIPHENYLCHLOROARSINE
[Footnote 23: Norris, _J. Ind. Eng. Chem._, =11=, 825 (1919).]
“This substance (Blue Cross) was a famous gas of the
Germans and was made in large quantities. The method
used by the Germans was different from the one worked
out by the Allies, and on account of the fact that the
German method could be carried out without specially
designed apparatus and required as raw materials
substances readily obtainable, it was probably
preferable. It is doubtful, however, whether the Allies
would have made this gas, for as the result of its
use no fatalities were reported. The German process
consisted in preparing phenylarsenic acid by condensing
benzene diazonium chloride with sodium arsenite.
The acid was next reduced by sulfur dioxide to
phenylarsenous acid, which was, in turn, condensed with
the diazonium compound to form diphenylarsenic acid.
This acid was reduced to diphenylarsenous oxide, which
with hydrochloric acid yielded diphenylchloroarsine.
The chemical equations for the reactions will make
clearer the steps involved.
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