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2,411,815
Patented Nov. 26, 1946
UNITED STATES PATENT OFFICE
2,411,815
SOLUTIONS OF ORGANIC MERCURY
COMPOUNDS
Frank J. Sowa, Cranford, N. J.
No Drawinga, Application May 31, 1943,
Serial No. 489,244
(Cl. 167-30)
5 Claims.
1
This invention relates to solutions of organic
mercury compounds and to methods for produc
ing and using such solutions.
It is well known that the aryl and aralkyl'mer
2
latex solutions, and they may be added to dis
persions and emulsions of water proo?ng or
fabric treating compositions. They also may be
used in carrying out various chemical reactions
wherein high concentrations of mercury com
cury hydroxides and salts are relatively insolu
pounds are desirable or of advantage. The solu
ble in water. Thus, for example, phenyl mer
tions may be caused to penetrate into ?bers, or
curic acetate is soluble in water to the extent of
pores in material or they may be applied as a
about 1 part in 600 parts of water while phenyl
constituent of ?lm forming, coating or impreg
mercuric chloride only. dissolves to the extent of
nating compositions. Furthermore, the concen
about 1 part to 20,000 parts of water. All known 10 tration of organic mercury compounds in medic
compounds having the general formula Rr—Hginal and industrial formulae may be materially
X, wherein R is an aryl, aralkyl, alkaryl, or
increased by practice in accordance with the
heterocyclic group, Hg is mercury, and X is an
present invention. '
anion, exhibit similar low solubility in water and
The principal objects of the present invention
in many water miscible solvents such as alco 15 are to increasethe solubility or concentration of
hols, glycerols and the like.v
organic mercury compoundsv in aqueous solu
Many, if not all, of these organic mercury
tions; to provide new types of mercury‘contain
compounds have high toxicity to bacteria and
ing germicidal compositions and products; to in
fungi and have other important uses in indus
crease the resistance of products to the action of
try and medicine. However, because of their 20 bacteria, fungi, mildew and the like; and to pro
relatively low solubility it is not economically
practical to ship the product in the form of a
vide novel methods of producing and using solu
tions of organic mercury compounds having the
solution and it frequently is di?icult or impos
general formula R—Hg-X, in which R is an
sible for the user to produce solutions having the
aryl, aralkyl,‘ alkaryl or heterocyclic group, Hg is
25
desired concentration of the mercury compound
mercury and X is an anion.
therein. Moreover, in many applications of such
Particular objects of the invention are to pro
solutions it is impossible to use suf?cient water
vide relatively concentrated solutions of phenyl
or solvent for the mercury compound to obtain
mercury compounds and to provide methods for
the required concentration thereof in the product
using such solutions in the treatment of fabrics,
30
without undesired dilution or unbalancing of a
leather and other ?brous, porous or textile
formula.
products to render them bacterlostatic, fungi
I have discovered that the solubility of mer
static and mildew resistant.
cury compounds of the R—Hg-X type, in water
These and other objects and features of the
and in mixtures of water with solvents such as
present invention will appear from the following
alcohols, glycerols and the like, can be materially
description thereof in which speci?c examples
increased provided ammonium hydroxide and a
are cited to indicate the nature of the invention
soluble ammonium salt are present in the solu
and , typical applications and. embodiments
tion. Some of the ammonium salts may be used
thereof, but without intending to limit the scope
for this purpose without adding ammonium hy
of the invention thereby.
40
droxide to the solution, whereas in at least one
My investigations indicate that all of the or
instance I have found it possible to dissolve a
ganic mercury compounds which have the gen
relatively water insoluble organic mercury com
eral formula R.—Hg-A-X will dissolve to a greater
pound in a solution of ammonium hydroxide
extent in aqueous solutions containing an am
alone. However, in most instances it is necessary
45 monium compound than they will in water'or
ammonium
hydroxide
and
an
am-_
to use both
the solvent alone. It appears in most instances
monium salt in order to dissolve substantial
that the solubility of the mercury compound in
amounts of the mercury compounds in aqueous
aqueous solvents is markedly increased when the
solutions. It is also found in general that the
solution also contains both an ammonium salt
pH value of the solution should be above 7 and
and ammonium hydroxide. I am unable at this
50
preferably in the range of about ‘7.2 to 9.0.
time to state exactly what chemical or physical
Solutions of this character may contain up to
reactions account for the increase in solubility of
50% or more by weight of the aryl, aralkyl or
the mercury compound in aqueous solutions
alkaryl mercury compound and can be used to
when ammonium compounds are present, but it
apply such compounds to fabrics, leather, paper,
is my belief that some addition compound or co
sheets or films, or for admixture with paints or 55
2,411,815
4
ordination complex is produced during solution,
acetate so that the apparent result when using
ammonium chloride and ammonium thiocyanate
or similar compounds, is to decrease the amount
of the phenyl mercury acetate in solution. Such
reactions, however, are to be avoided in the prac_
and that the resulting compound or complex is
itself relatively soluble or exerts an in?uence on
the mercury compound which serves to increase
its solubility in water.
v
Among the ammonium salts I have used to in
crease the solubility of phenyl mercuric acetate
in water, I may mention speci?cally ammonium
tice of my invention and ammonium salts se
lected which will not react with the mercury com
sulphate, ammonium carbonate, tri-ammonium
phosphate, di-ammonium phosphate, ammonium
borate, ammonium tetraborate, ammonium ci
trate, ammonium oxalate, ammonium lactate,
pound.
pound to produce a less soluble mercury com- '
10
ammonium formate and ammonium acetate. A
5% solution of any one of these salts has been
found to be capable of dissolving from 4 to 12%
of phenyl mercuric acetate provided some am
monium hydroxide is also present in the solution
and preferably is added in sufficient quantities
In choosing an ammonium salt to increase the
solubility of ammonium compounds ‘of the
R-Hg—-X type it also appears that the action
of ammonium salts of nitrogen containing acids
are much less eifective than are other salts. Thus
the increase in solubility of phenyl mercuric
acetate in an ammoniacal solution of ammonium
nitrate is less than might have been expected.
Similarly, the action of a few other ammonium
to give a ?nal solution having a pH value above 7
salts is limited and relatively poor or negligible
and preferably in the range of from about ‘7.2 20 results are obtained when using ammonium ?uo
to 9.0. Of these salts it has been found that am
ride, ammonium ?uo-silicate, ammonium chlo
monium carbonate, di-ammonium phosphate, tri
ride and ammonium linolate. Nevertheless, the
ammonium phosphate and ammonium borate are
great majority of the ammonium salts appear to
capable of use by themselves in increasing the
increase the solubility of the mercury compounds
solubility of phenyl mercuric acetate. No am
enormously and even the less active salts men
monium hydroxide need be added when using
tioned above appear to have some in?uence on
these salts.
the‘ solubility of the R--Hg-X type of com
Other compounds having the general formula
pounds.
R—Hg-—X exhibit the same property of in
In order to indicate typical and preferred solu
creased solubility in water containing ammonium 30 tions using ammonium salts in ammoniacal water
compounds. Thus, phenyl mercuric hydroxide,
solutions, having a pH valve above 7 the follow
phenyl mercuric borate, phenyl mercuric
ing examples are cited.
phthalate, phenyl mercuric gluconate, benzyl
100 cc. of 5% salt
mercuric acetate and pyridyl mercuric acetate are
soluble to a greater extent in aqueous solutions 35 solution:
of ammonium salts containing ammonium hy
droxide, than they are in water alone.
Phenyl mercuric hydroxide is soluble in solu
tions of ammonium acetate or ‘ammonium sul
phate alone but this probably is due to a reaction 40
of the hydroxide with the acetate 'or sulphate to
produce some ammonium hydroxide in the solu
tion. I have also discovered that phenyl mercuric
gluconate is soluble in ammonium hydroxide
- alone. Solutions containing 75 grams of phenyl
mercuric gluconate in 100 cc. of water are ob
tained by simply adding enough ammonium hy
droxide to keep the pH value around 8. Similarly,
Grams of phenyl mer
curic acetate dissolved
(NHUzSO-i __________________________ __ 8-12
NH4H2PO4 _
6-8
(NH4)2HPO4 ________________________ _._ 6-8
(NH4)3PO4
__
‘
6-8
NHdHCOG ___________________________ __ 4-6
(NH4) 3B0: __________________________ __ 6-8
(NH4)HB4O7 ________________________ __ 8-10
Ammonium oxalate______-._.._.______.____ 7-9
Ammonium citrate ___________________ __ M
Ammonium lactate _______ ._‘_ __________ __ 8-12
Ammonium formate __________________ __ 6-7
Ammonium acetate __________________ -_ 6-8
Alcoholic solutions and mixtures of water with
20 grams of phenyl mercuric hydroxide may be
other water miscible solvents such as triethanol
dissolved in 100 cc. of water containing 40 grams 50 amine also exhibit the same ability to dissolve
of ammonium gluconate and having a pH value
increased amounts of organic mercury com
of approximately 9.
_
pounds of the R-Hg-X type provided an am
The amount of the ammonium salt used ap
monium compound is present. Thus, for example,
pears to influence the solubility of the mercury
when forming solutions of phenyl mercuric ace
compound and solutions containing from 1 to 20% 55 tate in water and triethanol amine in accordance
of ammonium sulphate indicate that the maxi
with the process of my copending application Se
mum solubility of the mercury compound in such
rial No, 443,304, ?led May 16, 1942, it is sometimes
solutions is possible when about 4 % of ammonium
di?lcult to produce solutions of the desired con
sulphate is used.
centration. The addition of ammonium sulphate
In producing solutions in accordance with my 80 and ammonium hydroxide to such solutions over
invention it is of course desirable to choose am
comes this di?lculty and not only increases the
monium salts which will not react with the mer
amount of the mercury compound which may be
cury compound to produce a more insoluble mer
dissolved but greatly speeds up solution and re
cury compound. Thus, when endeavoring to in
sults in the formation of solutions which are clear
crease the solubility of phenyl mercuric acetate. 85 and very stable.
if ammonium chloride is used the relatively less
Solutions produced in accordance with the
soluble phenyl mercuric chloride will be produced
present invention may be applied directly or after
and may even precipitate from the solution. Sim
dilution with water, to fabrics, leather, paper or
ilarly, if ammonium thiocyanate is 'used the al
the like by spraying the solution thereon or by
most completely insoluble phenyl mercuric ,thio 70 dipping or immersing material therein and the
cyanate will precipitate. While these less soluble
solution may be applied under pressure to insure
compounds are themselves dissolved to some ex
the desired penetration of the solution into the
tent in the ammoniacal ammonium'salt solution,
pores or ?bers of the articles being treated. They
although almost completely insoluble in water,
also may be added to textile treating baths or‘
they are not soluble to the same extent as the 75 ?nishes such as alkaline solutions of cellulose
2,411,815
,
ethers, suspensions of waxes, resins or other sim
ilar materials. The ammoniacal or alkaline vna
ture of solutions embodying my invention renders
them particularly suitable for admixture with
latex dispersions, and suspension of rubber, col
loids, waterproo?ng or fireproo?ng agents; or
products such as casein paints and aqueous coat
ing and impregnating compositions.
Products thus treated are rendered bacterio
static, fungistatic, mildew resistant and germicid
6
-
acetate, and ammonium gluconate, together with
sufficient ammonium hydroxide to maintain the
pH value of thesolution above '7, the amount of
the phenyl mercury compound. in solution ex
ceeding the amount soluble in the aqueous sol
vent of the solution.
‘
2. A solution containing phenyl mercury ace
tate dissolved in an aqueous solvent containing
an ammonium salt selected from the group con
10 sisting of ammonium sulfate, ammonium car
bonate, tri-ammonium phosphate, di-ammonium
phosphate, mono-ammonium phosphate, ammo
nium borate, ammonium tetra-borate, ammoni
The amount of the solution used in any partic
um citrate,‘ ammonium oxalate, ammonium lac
ular application will vary considerably but when
employed to treat textile fabrics the weight 01' 15 tate, ammonium formate, ammonium acetate,
and ammonium gluconate, together with sufli
the mercury compound in the treated material
cient ammonium hydroxide to maintain the pH
should'generally equal about 0.02 to 1.0% and
value of the solution above 7, the amount of the
preferably about 0.5% of the weight of the fabric.
phenyl mercury acetate in solution exceeding the
While I have suggested numerous composi
tions and uses for solutions produced in accord 20 amount soluble in the aqueous solvent of the so
al by reason of the mercury compound deposit
ed on or in the product or admixed therewith.
ance with the present invention it will be under
stood that many other uses and formulae will
suggest themselves to those ‘skilled in the art and »
lution.
»
Y
3. An aqueous solution having a pH value not
less than 7 and containing a phenyl mercury
compound, triethanolamine, ammonium hydrox
be apparent from the foregoing description of the
invention. In view thereof it is intended that 25 ide ‘and ammonium sulfate, the amount of the
phenyl mercury compound in solution being in
the particular composition and uses of solutions
excess'of that soluble in the water of the solution.
speci?cally described above be considered as il
4. An aqueous solution having a pH value not
lustrative only since the scope of my invention is
less than 7 and containing phenyl mercury ace
de?ned by the followim claims.
I claim:
'
1. A solution of a phenyl mercury compound
in an aqueous solvent containing from about 1
to 20 parts by weight of a salt selected from the
group consisting of ammonium sulfate, ammo
tate,,triethanolamine, ammonium hydroxide and
ammonium sulfate, the amount of the‘ phenyl
mercury compound in solution being in excess of
that soluble in the water of the solution.
5. A method of increasing the stability of an
nium carbonate, tri-ammonium phosphate, (11 35 aqueous solution containing phenyl mercury ace
tate and triethanolamine which comprises the
ammonium phosphate, mono-ammonium phos
step of adding ammonium hydroxide and ammo
phate, ammonium borate, ammonium tetra-b0
nium sulfate thereto.
.
rate, ammonium citrate, ammonium oxalate, am
monium lactate, ammonium formate, ammonium
FRANK J. SOWA.
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