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“1. Rapid penetration of the substance into the
cell by virtue of its high lipoid solubility.
2. Hydrolysis by the water within the cell, to form
hydrochloric acid and dihydroxyethylsulphide.
3. The destructive effect of hydrochloric acid upon
some part or mechanism of the cell.
“Although hydrochloric acid does not penetrate
cells readily and is easily neutralized by the buffer
action of the fluids of the body, we might expect by
flooding the body with large quantities of acid to
produce some of the characteristic effects of mustard
gas. Stimulation of the respiratory center is a well
known effect of acid. Convulsions and salivation may
be produced by injection of hydrochloric acid and we
have been able to produce slowing of the heart by
rapid injection of this acid.
“The delayed action of mustard gas might be
explained by the formation of some compound with
some constituent of the blood. However, blood taken
from dogs which had been poisoned with mustard
gas and were exhibiting typical symptoms at the time,
injected into normal dogs produced no effect. Serum
treated in vitro with mustard gas and allowed to stand
and then injected into a dog, produced no effect. The
fluid which is formed in the vesicle and blebs
produced by the application of mustard gas to the
skin produces no mustard gas effects.”
In studying the toxicity of mustard gas for dogs, it was observed
that a concentration of 0.01 mg. per liter could be tolerated indefinitely.
If this value is considered as a threshold value, and subtracted from
the toxicity values for varying periods of time, it is found that there is a
definite relation between the toxic concentration and the time of
exposure. This is expressed by the formula
(C - 0.01)t = K
where C is the concentration observed for a given time
t
. K has the approximate value of 1.7, where
t
varies between 7.5 and 480 minutes.
Vesicant Action
In addition to its toxicity mustard gas is highly important because of
its peculiar irritating effect upon the skin. Its value is seen when we
realize that one part in 14,000,000 is capable of causing conjunctivitis
of the eye and that one part in 3,000,000 and possibly one part in
5,000,000 will cause a skin burn in a sensitive person on prolonged
exposure. According to Warthin, the lesions produced by mustard gas
are those of a chemical, not unlike hydrochloric acid, but of much
greater intensity. The pathology of these lesions has been carefully
studied and fully described by Warthin and Weller in their book on The
Pathology of Mustard Gas. Our observations will therefore be confined
to certain striking features of the vesicant action of this substance.
Diphenylchloroarsine
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.
Diphenylchloroarsine
C₆H₅N₂Cl + C₆H₅AsO₃Na₂ +
=
Na₃AsO₃ NaCl + N₂
C₆H₅AsO₃Na₂ + C₆H₅AsO₃H₂ +
=
2HCl 2NaCl
C₆H₅AsO₃H₂ + C₆H₅AsO₂H₂ +
=
SO₂+H₂O H₂SO₄
C₆H₅N₂Cl + (C₆H₅)₂AsO₂Na +
=
C₆H₅AsO₂Na₂ NaCl + N₂
(C₆H₅)₂AsO₂Na + (C₆H₅)₂AsO₂H +
=
HCl NaCl
2(C₆H₅)₂AsO₂H + [(C₆H₅)₂As]₂O +
=
2SO₂ + H₂O 2H₂SO₄
[(C₆H₅)₂As]₂O + 2(C₆H₅)₂AsCl +
=
2HCl H₂O.
“The entire process was carried out at Höchst.
The method used at Höchst was as follows: In
preparing the diazonium solution, 3 kg.-mols of
aniline were dissolved in 3000 liters of water and the
theoretical quantity of hydrochloric acid. The
temperature of the solution was reduced to between
0° and 5° and the theoretical amount of sodium
nitrite added. The reaction was carried out in a
wooden tank of the usual form for the preparation of
diazonium compounds. A solution of sodium
arsenite was prepared which contained 20 per cent
excess of oxide over that required to react with the
aniline used. The arsenous oxide was dissolved in
sodium carbonate, care being taken to have enough
of the alkali present to neutralize all of the acid
present in the solution of the diazonium salt. To the
solution of the sodium arsenite were added 20 kg. of
copper sulfate dissolved in water, this being the
amount required when 3 kg.-mols of aniline are
used. The solution of the diazonium compound was
allowed to flow slowly into the solution of the
arsenite while the temperature was maintained at
15°. The mixture was constantly stirred during the
addition which requires about 3 hrs. After the
reaction was complete, the material was passed
through a filter press in order to remove the coupling
agent and the tar which had been formed.
Hydrochloric acid was next added to the clear
solution to precipitate phenylarsenic acid, the last
portions of which were removed by the addition of
salt.
“The phenylarsenic acid was next reduced to
phenylarsenous acid by means of a solution of
sodium bisulfite, about 20 per cent excess of the
latter over the theoretical amount being used. For
100 parts of arsenic acid, 400 parts of solution were
used. The reaction was carried out in a wooden
vessel and the mixture stirred during the entire
operation. A temperature of 80° was maintained by
means of a steam coil. Phenylarsenous acid
separated as an oil. The aqueous solution was
decanted from the oil, which was dissolved in a
solution of sodium hydroxide, 40° Bé. The solution
of the sodium salt of phenylarsenous acid was
treated with water so that the resulting solution had
a volume of 6 cu. m. when 3 kg.-mols of the salt
were present. Ice was next added to reduce the
temperature to 15° and a solution of benzene
diazonium chloride, prepared in the manner
described for the first operation, was slowly added.
After the coupling, diphenylarsenic acid was
precipitated by means of hydrochloric acid. The acid
was removed by means of a filter press and
dissolved in hydrochloric acid, 20° Bé. For one part
of diphenylarsenic acid, 3 parts of hydrochloric acid
were used. Into this solution was passed 5 per cent
excess of sulfur dioxide over that required for the
reduction. The sulfur dioxide used was obtained
from cylinders which contained it in liquid condition.
“The reduction was carried out in an iron tank
lined with tiles and a temperature of 80° was
maintained. About 8 hrs. were required for the
reaction. The diphenylarsenic acid on reduction by
the sulfur dioxide was converted into
diphenylarsenous oxide which, in the presence of
the hydrochloric acid, was converted into
diphenylchloroarsine, which separated as an oil.
The oil was next removed and heated in the best
vacuum obtainable until it was dry and free from
hydrochloric acid. The compound melted at 34°. It
was placed in iron tanks for shipment. The yield of
diphenylchloroarsine calculated from the aniline
used was from 25 to 30 per cent of the theoretical.
No marked trouble was observed in handling the
materials and no serious poisoning cases were
reported.
Diphenylcyanoarsine
Ethyldichloroarsine