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Патент USA US3064058

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United States, Patent ()?iice.
__
3,964,048
Patented Nov. 13, 1952
2
1
3,064,048
PROCESS FOR PREPARENG 3,4',5-TRIBROMO
SALICYLANILIDE IN THE PRESENCE OF A
WETTING AGENT
Charles H. Sehrannn, Easton, Pa., and Henry Lemaire,
Leonia, NJZ, assignors to Lever Brothers Company,
New York, N.Y., a corporation of Maine
It is not desirable to add all of the bromine required
for the reaction to produce the tribromo product at the
start of the reaction, since too high an initial bromine
concentration may lead to the production of a higher
proportion of brominated products containing more than
three bromine atoms per molecule. Thus, the bromine
can be added dropwise or in small increments over a
period of from one-half to three hours. After all of the
bromine has been added, the reaction mixture is held at
10' the reaction temperature for a suf?cient time to allow
The present invention relates to a process for the prep
reaction to proceed to completion, usually in about one
aration of a novel chemical compound, 3,4’,5-tribromo
half to two hours’ time. The reaction mixture then can
No Drawing. Filed July 10, 1958, Ser. No. 747,568
10 Claims. (Cl. 26ti—559)
salicylanilide.
>
be allowed to cool to room temperature, and is ?ltered to
Polyhalosalicylanilides can be made in good yield by
the direct condensation of a halogenated salicylic acid 15
and a halogenated aniline. Although this method is sat
isfactory in the laboratory, it is economically undesirable
commercially because of the necessity for separately halo
genating the salicylic acid and the aniline portions prior
to condensation. However, the halogenation of salicyl 20
remove the desired product which also is insoluble in the
reaction medium.
anilide by methods known in the art results in compara
3,4',5 - tribromosalicylanilide.
tively- poor yields.
quite ?ne particles, i.e., below 200 mesh, others quite
’
Any organic surfactant can be employed. The anionic,
cationic, and nonionic surfactants are the known classes
of surfactants, and any of these, alone or in admixture,
give satisfactory results. The choice of any particular
surfactant will depend upon the particle size desired of the
Some surfactants yield
In accordance with the invention, 3,4',5-tribromosali
coarse particles, i.e., above 20 mesh, and others interme
cylanilide is obtained in a high yield by the bromination
diate these extremes. This phenomenon is at present un
of salicylanilide with three moles of bromine. In this 25 explained.
bromination, it is theoretically possible to obtain a wide
There are many types of anionic surfactants which will
variety of polybrominated products, the bromine being
at once occur to those skilled in this art.
substituted in any of several combinations of one, two
and three positions in the two rings. However, in ac
sulfonates are a class of surfactant well known in the art
under this name. One example thereof are the sulfonated
cordance with the invention the bromine entering the rings
is oriented to give the 3,4’,5-tribromo isomer by effecting
branched chain structure of polypropylene and a tertiary
The alkyl aryl
phenylpolypropylene alkanes, characterized by the
the bromination in a medium composed of from 0.1 to
alkyl'carbon at the benzene ring, and having the following
2% of an organic surfactant and from 99.9 to 98% water.
general structure:
The reaction mixture will contain small amounts not in
excess of about 30% and usually not exceeding 20% of 35
the 3,5 and 4’,5-dibromo derivatives and the 2',3,4’,5
tetrabromo derivative.
The surfactant and water when present in a concentra
tion within the ranges stated by some unknown mecha
nism shift the reaction in favor of the 3,4',5-tribromo 40
derivative.
Bromination in water alone yields a product
SOsM
having a dark color, the reaction proceeds more slowly,
where M is hydrogen, an alkali metal or an organic amine
and the total yield is appreciably lower, due to the forma
cation, and R1 and R2 are alkyl, of the type formula
tion of the tarry products imparting the dark color.
CDHZHH, and at least one R is a polypropylene group, the
Salicylanilide is insoluble in the reaction medium at the 45 Whole
alkyl group containing preferably twelve to ?fteen
reaction temperatures. Stirring therefore is essential
carbon atoms. These are known compounds, whose prep
throughout the reaction in order to keep the system uni
aration and properties are set forth in US. Patent No.
form. Enough of the reaction medium should be used
2,477,383 to Lewis, issued July 26, 1949; they are avail
to ensure complete suspension of the salicylanilide, but
able in commerce under the trade names “Oronite”,
apart from this the amount is in no way critical. The
“Ultrawet” and “Neolene”.
larger‘,- the volume of reaction medium, the more di?icult
Another example thereof are the alkyl aryl sulfonates
the mix is to handle and the more dilute will be the suspen
sion, so that the reaction will proceed more slowly. A
made by chlorinating a keryl hydrocarbon, and condens
ing this with benzene, followed by sulfonating.
reaction medium having a concentration of less than about
These give a ?ne particle size of 3,4’,5-tribromosalicyl
5% salicylanilide thus would not be used. At a concen 55 anilide.
tration in excess of about 12%, the reaction mixture be
Also useful are the aliphatic acyl amino alkane sul
comes quite thick and dif?cult to stir. Usually, a con
fonates of the type described in Patent No. 1,932,180, the
centration of from 8% to 10% is preferred.
sodium alkanoyl and alkenoyl methyl taurides. They
The reaction proceeds smoothly at a temperature with
have the formula:
in the range from about 40° to about 70° C. Preferably, 60
from 50° to 65° C. is employed, since at the more elevated
temperatures the color of the product may be dark. At
temperatures below 40° C. the reaction proceeds too slow
ly to be practical.
where R is an aliphatic hydrocarbon radical, such as alkyl
or alkenyl, having nine to seventeen carbon atoms, R1 is
3,064,048
d.
3
hydrogen or a lower alkyl radical of one to six carbon
unsaturated hydrocarbon group having ‘from eight to
atoms such as methyl, ethyl, propyl, butyl, amyl, and
eighteen carbon atoms or an aralkyl group having a
straight or branched saturated or unsaturated hydro
carbon group of from eight to eighteen carbon atoms at
tached to the aryl nucleus, and attached to A through the
hexyl, and n and X are the same as that de?ned in con
nection with the aminocarboxylates. Examples are lauro
yl, oleoyl and stearoyl taurides, methyl taurides and amino
aryl nucleus, A is selected from the group consisting of
ethereal oxygen and sulfur, carboxylate and thiocar
methane sulfonates.
These give a relatively ?ne particle 3,4',5-tribromo
salicylanilide, about 2% of which is above 200 mesh.
There can also be employed the aliphatic hydrocarbon
boxylate groups and x is a number from eight to thirty.
R can for example be a straight or branched chain octyl,
10 nonyl, decyl, lauryl, myristyl, cetyl, or stearyl group, or
aminocar-boxylates, of the general formula:
an alkyl aryl group such asoctylbenzene, nonylbenzene,
decylbenzene, stearylbenzene, etc.
When R is alkyl it will be evident that the surfactant
can be regarded as derived from an alcohol, mercaptan,
where R is an aliphatic hydrocarbon radical, such as
alkyl or alkenyl, having one to eighteen carbon atoms, 15 oxy or thio fatty acid of high molecular weight, by
condensation with ethylene oxide. Typical of this type
and R1 is hydrogen or the same as R or some other
of alkyl ether are the condensation products of oleyl or
dodecyl alcohol or mercaptan with “Emulfor ON,”
“Nonic 218” and “Sterox SE” and “SK”. Typical alkyl
aliphatic hydrocarbon radical, such as alkyl or alkenyl,
having one to eighteen carbon atoms, the total number
of carbon atoms of R and R1 being not less than eight
esters are “Gl226” and “Renex” (polyoxyethylene ester
and not more than twenty-two, n is a whole number
of one to ?ve, preferably one or two, and x is a salt
of tall oil acids), “Sterox CD”, “Neutronyl 330” and
“331” (higher fatty acid esters of polyethylene glycol).
forming cation, more particularly sodium, potassium,
When R is aralkyl, the surfactant can be derived from
an alkyl phenol or thiophenol.
calcium, magnesium, and amine, an ethanolamine, etc.
Examples of such compounds are alkyl or alkenyl
aminopropionates, such as the sodium salt of dodecyl
The oxyethylated alkyl phenols and thiophenols have
the following general formula:
?-alanine, octadecenyl-B-alanine, dodecyl methyl amino
propionate, diamyl aminopropionate, oleyl ethyl amino
propionate, the sodium salt of alkyl or alkenyl glycines,
such as sodium dodecyl glycine, and sodium octadecenyl
30
glycine.
R
These give a fairly coarse particle 3,4',5-tribromo
‘salicylanilide, about 50% of which is above 200 mesh.
Any alkyl sulfate Whose alkyl group has from about
eight to about twenty-two carbon atoms is suitable, for
where R is a straight or branched saturated or un
saturated hylrocarbon group having at least eight carbon
atoms up to approximately eighteen carbon atoms, A is
example, lauryl, myristyl, stearyl and cetyl sulfates, and
oxygen or sulfur and x is a number ‘from eight to thirty.
also sulfates derived from mixed fatty alcohols obtained
from fatty oils, such as coconut oil fatty alcohols and
R can, for example, be a straight or branched chain octyl,
palm oil fatty alcohols.
are the condensation products of octyl and nonyl phenol
with from eight to seventeen moles of ethylene oxide,
nonyl, decyl, lauryl, myristyl, cetyl or stearyl. Typical
'
These give a relatively ?ne particle 3,4',5-tribromo
salicylanilide.
40 available commercially under the trade names “Oronite
Also useful are the sulfated ethoxynated alkyl phenols
having the following general formula:
NIW,” “Antarox A400,” “Igepal CA” and “CO,” “Triton
X—l00,” “Neutronyx 600” and “Tergitol NPX.”
Also useful are the alkyl carboxyamido condensation
products (condensation products of ethanolamine with
fatty carboxylic acids and fatty thiocarboxylic acids)
having the following general formula:
where R is a straight or branched chain saturated or un
saturated hydrocarbon group having at least eight carbon
atoms up to approximately eighteen carbon atoms, A is
The compound has at least one RA or R'A group, usually
one or two, R and R’ are straight or branched chain satu
oxygen or sulfur, x is a number from three to eight, and
rated or unsaturated hydrocarbon groups having from
eight to eighteen carbon atoms, R” is hydrogen, an alkyl
M is hydrogen or an alkali metal, e.g., sodium, potassium,
and ammonium, or_an organic amine cation. The amine
can be any of those listed hereinafter.
group of one to about twenty-four carbon atoms, or a
R is usually a
second
branched chain hydrocarbon group and can, for example,
be a straight or branched chain octyl, nonyl, decyl, lauryl,
cetyl, myristyl or stearyl group.
H
[0112011201 or group
AR’
. These give a relatively ?ne particle 3,4',5-tribrorno
salicylanilide. Exemplifying the amines are water-soluble
strongly basic amines such as triethanolarnine, dietha
nolamiue, monoethanolamine, ethylenediarnine, diethyl
'enetriamine, tetraethanol ammonium hydroxide, morpho
line, mixed isopropanolamines, monoisopropanol amine,
diethylene glycol ‘amine, and amino ethyl ethanolamine.
The
alkylolamines, either mono-,
preferred.
'
1
di- or tri-,‘ ‘are
'
There are many types of nonionic surfactants known
to ‘those skilled in the- art, and any of these or mixtures
thereof could bev employed, including, for example,
alkyl oxy- and thioether and oxy- and thioester surfac
tants having the following general formula:
I
R_A_[cH2cH2O1g—_—CH2CH2-or1
where R is a straight or branched chain saturated or
(if)
A is selected from the group consisting of carbonyl
0:0 and thiocarbonyl (:8 groups, and x is a whole
number equal to the valence of RA or R'A. For example,
if one of RA or R’A is a dicarboxylic acid, x is at least
two, with a possibility of longer chains of amido- and
ester-linked acid and ethylene units. Usually x is from
one to four. R, R’ and R” can, for example, be a straight
or branched chain octyl, nonyl, decyl, lauryl, myristyl,
cetyl or stearyl group.
The Pluronics are a group of nonionic surfactants hav
ing the'formula:
.
CH3
HO[CH?CH20]m[OHaéHOLJCIIzCHzOhUH
These are fully described in US. Patent No. 2,674,619
to L. G. Lundsted, dated April 6, 1954; see especially
‘seems
.
.
.
.
5
.
.
column 3, lines 55 to 71. See
2,677,700 to D. R. Jackson et al.,
m and m’ represent the average
units, and n the average number
also U.S. Patent No.
dated May 4, 1954.
number of oxyethylene
of oxypropylene units.
See U.S. Patent No. 2,674,619.
The sum of m and m’ 5
Typical compounds are those where R is oleyl, stearyl and
palmityl.
The following examples are illustrative:
EXAMPLES 1 TO 6
Salicylanilide (213 g., one mole) was suspended in 2.5
liters of water containing 2 g. (basis active) surfactant
preferably is within the range from ?fteen to forty-one,
and n preferably is within the range from seventeen t0
thirty-one.
and brought to 55° C. The surfactant was as listed in
These give a ?ne particle 3,4’,5-tribr0m0salicylanilide.
the table below. The suspension was stirred and 480 g.
The process of the invention as stated also can be based 10 (three moles) of bromine was added dropwise while
upon cationic surfactants. These are characterized by
maintaining a temperature from 55° to 60° C. The
the fact that the hydrophobic group forms part of cation
bromine addition required ninety minutes, and the mix
when the compound is dissolved in water. The amines
and quaternary ammonium salts are the preferred groups
ture was held at 55 ° C. for an additional hour. At the
end of this time the product was cooled to room tem
of cationic surface active agents, but any such agents 15 perature, neutralized, and ?ltered. The ?lter cake was
known to those skilled in the art can, of course, be used.
washed twice with methanol and dried. The yield in
The quaternary ammonium compounds are soluble in both
all cases was about 95—98% of material containing 70
basic and acidic media. The primary, secondary, and
to 79% 3,4’,5-tribromosalicylanilide, from 1 to 4% 4',5
tertiary amines containing a hydrophobic group suf?dibromosalicylanilide, from 12 to 17% 3,5-dibromo
ciently large to be in the surface active range are less 20 salicylanilide and from 4 to 15% 2’3,4’,5-tetrabromo
soluble in water and in alkaline solutions, and usually
Salicylanilide. The yields and particle sizes obtained are
require solubilization with an organic solvent. They are,
listed in Table I:
Table 1
Percent Yield
Percent
'
Example
No.
1
Surfactant
Retained
Percent
on 200
Mesh
Bromine 5
Percent
3,4/,& 1
Percent
435 2
Percent
3,5 3
Percent
2’3,4’.=. 4
78
1
13
8
2.31
52.63
79
4
13
4
70.57
51.21
70
3
12
15
43. e3
52. 82
74
2
12
12
2.92
52.23
17
9
3. 37
51. 20
14
6
0. 27
51. 53
Igepon T (sodium oleyl methyl
taurideip ______________________ __
Cetyltritnethylammonium
bromide (Ce-tab) ______________ __
Sodium salt of coco~beta~alanine
(Deriphat- XD-151) _ _
__
Sodium lauryl sulfate. _
Ammonium saltofsulin
dn0u_ -
phenol-4 mole ethylene oxide
condensate
6 _______ __
(Alipal
00-436,
NPES-4) _ _
Sodium salt of dodeeylbenzene
sullonate ______________________ -.
74
75
5
l 3,4’,s-tribromosalicylanilide.
2 4’,5-dibromosalicylanilide.
3 3,S-dibromosalicylanilide.
4 2'3,4’5-tetrabromosalicylnnilide.
_
_
I
_
5 Analysis based on entire mixture; theoretleal for 3,4’,?-tribromosal1cylani11de—5329%.
however, soluble in acidic solutions where the pH is low
enough to convert the bases to their amine salts. In
addition to these classes of materials, there are the surface
active agents based upon guanidines, hydrazines, amine
oxides and nitrogen-containing heterocyclic substances, as
well as sulfonium compounds containing long-chain
hydrophobic groups.
The quaternary ammonium compounds have at least
one long aliphatic chain having from about twelve to
about eighteen carbon atoms, and the remaining valences
of the nitrogen are taken with short-chain aliphatic radi
cals usually having from one to ?ve carbon atoms, or by
hydrogen. These compounds have the general formula
EXAMPLE 7
Salicylanilide (213 g., one mole) was suspended in
2.5 liters of water containing 5 g. (40% active) of an
aqueous sodium dodecylbenzenesulfonate paste. The
suspension was stirred and heat was applied to bring the
temperature of the mixture to 55 ° C. Two-thirds (320 g.,
two moles) of the bromine was added during this period
and the remaining one-third (160 g., one mole) was added
at 55—60° C.
The bromine addition required ninety
minutes, and the reaction temperature was held at 65° C.
for an additional hour. At the end of this time, the
product was cooled to room temperature and 175 cc. of
an aqueous 10% sodium bisul?te solution was added.
R1R2R3R4NX, wherein one R is a long-chain aliphatic
radical as described, and the remaining R’s are additional 60 After neutralization with 130 g. (in 500 cc. of water) of
sodium hydroxide to pH 4, the crude, 3,4’,5-tribromo
long-chain or short-chain aliphatic radicals, or hydrogen,
Salicylanilide was ?ltered and dried. The yield was
and X is an anion such as halogen, for example halide or
440 g. (98%) of material containing 77% 3,4',5-tribrom0
bromide, sulfate, nitrate, and the like. Typical quaternary
ammonium compounds having surface active properties
are palmityl trimethyl ammonium chloride, stearyl di
methyl benzyl ammonium chloride, oleyl trimethyl am~
monium chloride, cetylpyridinium bromide, and coconut
fatty alkyl dimethyl benzyl ammonium chloride (Roccal,
Triton K60). These give a quite coarse particle 3,4’,5
tribromosalicylanilide.
Salicylanilide, 4% 4’,S-dibromosalicylanilide, 13% 3,5
dibromosalicylanilide and 6% 2',3,4’,5-tetrabromosalicyl
anilide. The material was vcomposed of ?ne particles
below 200 mesh.
EXAMPLE 8
Salicylanilide (213 g., 1 mole) was suspended in' 2.5
70 liters of water containing 2 g. Pluronic F68. The sus
pension was stirred vand heat was applied to bring the
temperature of the mixture to 55° C. Two-thirds (320 g.,
two moles) of the bromine was added during this period
has from nine to seventeen carbon atoms. These com
and the remaining one-third (160 g., one mole) was
pounds are available under the trade name “Sapamines.” 75 added at 5 5—610‘‘ C. The bromine addition required ninety
Another well known class of cationic detergents have
the formula RCONHC2H4N(C2H5)2, where R is a long
chain hydrophobic group derived from a fatty acid and
aoeacas
" 7
minutes, and the reaction temperature was held :at 65° C.
is therefore no need to free the 3,4',5-tribromosalicyl
for an additional hour. At the end of this time, the
anilide of these di- andjtetrabromo. derivatives. The mix
product was cooled to room temperature and 1775 cc. of
tures of di-, tri- and tetrabromo derivatives can be used
an aqueous 10% sodium bisul?te solution was added.
directly in soap and nonsoap compositions, and these
After neutralization with 130 g. (in 500 cc. of water) of 5 compositions show excellent germicidal effectiveness.
sodium hydroxide to pH 4, the crude 3,4',5-tribromo
The following example is illustrative:
salicylanilide was ?ltered and dried. The yield was 440
EXAMPLE ll
g. (98%) of material containing 77% 3,4',5-tribrorno
Soap-synthetic chips (30 lbs.) containing 24.9% so
salicylanilide, 3% 4',5-dibromosalicylanilide, 16% 3,5
dibromosalicylanilide and 4% 2’,3,4’,5-tetrabromosalicyl
dium tallow soap, 35% sodium coconut oil soap, 18%
acyl methyl taurate prepared from 40—I.V. tallow fatty
acids, 5% miscellaneous unidenti?ed matter from the
soap and taurate, 10% stearic acid, 0.02% butylated hy
anilide. The material was composed of gritty particles.
EXAMPLE 9
Salicylanilide (213 g., one mole) was suspended in
droxy toluene, 0.8% perfume, 0.0022% dye (FD&C
2.5 liters of water containing 2 g. of the condensation 15 Red #4), 0.3% TiO2, and the balance water, were
weighed into a chip mixer. All percentages shown above
product of an average of 12 moles ethylene oxide with
are expressed on the weight of the whole mixer com
decanol. The suspension was stirred and heat was ap
position. To these chips were added 0.5% (whole-com
position basis) of a mixture containing 76% 3,4’,5-tzi
bromosalicylanilide, 2% 4',5-dibromosalicylanilide, 10%
3,S-dibromosalicylanilide and 12% 2’3,4’,5-tetrabromo
salicylanilide. The batch was mixed, milled, and plodded
plied to bring the temperature of the mixture to 55° C.
Two-thirds (320 g., two moles) of the bromine was added
‘during this period and the remaining one-third (160 g.,
one mole) was added at 55-605 C.
The bromine addi
tion required ninety minutes, and the reaction tempera
into bars.
8% aqueous solutions were prepared from one of
these soap bars and subjected to the Finger Imprint Test.
ture was held at 65° ,C. for an additional hour. At the
end of this time, the product was cooled to room tempera~
ture and 175 cc. of an aqueous l0% sodium bisul?te
solution was added. After neutralization with 130 g.
The mixture composed‘predominantiy of the 3,4’,5-tri
bromosalicylanilide gave a rating of 3.2. In contrast,
4’,5-dibromosalicylanilide in a germicidal soap bar pre
crude 3,4’,5-tribromosalicylanilide was ?ltered and dried.
pared in the same way and of the same composition
The yield was 440 g. (98%) of material containing 80%
3,4’,5 - tribromosalicylanilide, 4% 4',5 - dibromosalicyl 30 gave a rating of 0.9. A bar prepared in the same way
and of the same composition but containing no germicide
anilide,, 10% 3,S-dibromosalicylanilide and 3% 2’,3,4',5
had a rating of 0.
tetrabromosalicylanilide. The material was composed of
Only small amounts of 3,4’,S-tribrornosalicyanilide are
?ne particles below 200 mesh.
required to render soap germicidal. An amount as low
EXAMPLE 10
35 as 0.01% based on the weight of the soap produces a
soap composition having excellent antibacterial potency.
Salicylanilide (213 g., one mole) was suspended in
As much as 5% has been used to advantage. There is no
2.5 liters of water containing 2 g. of the condensation
need to employ more than is required to give the de
product of tridecyl alcohol with an average of 10 moles
sired germicidal effect, and in general for this reason
ethylene oxide. The suspension was stirred and heat was
‘applied to bring the temperature of the mixture to 55 ° C. 40 from 0.2 to 2% would be preferred. Increasing the con
centration of the compound beyond 5% merely increases
Two-thirds (320 g., two moles) of the bromine was added
(in 500 cc. of water) of sodium hydroxide to pH 4, the
during this period vand the remaining one-third ( 160 g.,
' the cost of the soap and might tend to reduce the de
one mole) was added at 55-60“ C. The bromine addi
tergent properties of the composition.
tion required ninety minutes, and the reaction tempera
be seen that the concentration is not critical, but would
It will readily
ture was held at65° C. for an additional hour. At the
end of this time, the product was cooled to room tem
perature and 175 cc. of an aqueous 10% sodium bisul?te
solution was added. After neutralization with 130 g. (in
be determined from a consideration of these factors as
' long as enough is used to give the desired antibacterial
effect.
In the quantities in which the compound or mixture
thereof with di- and tetrabromo salicylanilides is used
500 cc. of water) of sodium hydroxide to pH 4, the crude
in soaps, it does not produce skin irritation, is not toxic,
3,4’,S-tribromosalicylanilide was ?ltered and dried. The
yield was 440 g. (98%) of material containing 77% 50 and is compatible with the usual soap components.
The term “soap” as used herein refers to alkali met?
3,4’,5 - tribromosalicylanilide, 2% 4’,5 - dibromosalicyl
soaps of the saturated and unsaturated higher fatty acids
anilide, 18% 3,S-dibrornosalicylanilide and 3% 2',3,4',5
having from about eight to about twenty-six carbon atoms,
tetrabromosalicylanilide. The material was composed of
such as capric, caprylic, lauric, myristic, palmitic, stearic,
oleic, linoleic, linoienic, arachidic, behenic, margaric,
?ne particles below 200 mesh.
3,4’,S-tribromosalicylanilideis a novel compound hav
ing the structure:
Br
OH
l
I
tridechoic, and cerotic acids and the mixtures of such
acids naturally occurring in fats, oils, waxes, and rosins,
such as the soaps of coconut oil fatty ‘acids, tallow fatty
acids, pig fat, ?sh oil fatty acids, beeswax, palm oil fatty
60
I
Br
3,4’,5rtiibromosalicylanilide is a white compound, solid
acids, sesame oil fatty acids, peanut oil fatty acids, olive
oil fatty acids, palm kernel oil fatty acids, cottonseed oil
fatty acids, soyabean oil fatty acids, corn oil fatty acids,
babassu oil fatty ‘acids, rosin acids, abietic ‘acid, and
at room temperature, insoluble in water, soluble in hot
acetone and ,very soluble in dimethylformamide. This
greases.
compound has extraordinary bactericidal properties, and
those skilled in the art in order to achieve this result,
these properties are retained in the presence of soap.
the following procedure is recommended: The soap chips
'are weighed into the mixer and followed immediately
by addition of the remaining components of the mix, for
example, perfume and dye, in the form of a solution
if desired, and mixing is continued for a long enough
Soap and nonsoap compositions containing 3,4',5-tri
bromosalicylanilider'have shown excellent germicidal ef
fectivenessr'when subjected to standardized tests.
The 3,4’,S-tribrornosalicylanilide as obtained by the
process of the invention will contain small amounts of
the 3,5 and 4’,S-dibromosalicylanilide and the 2’3,4’,5
tetrabromosalicylanilides. These also have germicidal
properties, particularly the tetrabromo isomer, and there
While several mixing procedures will be apparent to
period to ensure a thorough dispersion. Thereafter the
3,4',5-tribromosalicylanilide or mixture thereof with di~
and tetrabromo salicylanilides is added with complete and
adequate mixing only for the time to ensure uniformity
3,064,048
of dispersion. The ?nal mix then can be treated in
the ‘conventional ways to produce the desired soap. To
form a bar, for example, the mix can be plodded and
extruded using conventional equipment.
The 3,4’,5-tribromosalicylanilide soaps in accordance:
with the invention can be formed as bar soaps, powdered
soaps, chip soaps, ?ake soaps, bead soaps, bar and cake
soaps and soap compositions intended for toilet, wash
10
ethylene oxide, and the higher fatty acid esters of sorbitan
ethylene oxide condensates, such as sorbitan monostearate
ester of polyoxyethylene glycol. They may be in any of
the forms described heretofore, including cakes or pow
ders, and may include various ?llers, sudsing agents and
ingredients conventionally employed in detergent formu
lations. They may be compounded for various purposes,
such as for shampoo, dishwashing, textile laundering,
toilet soaps and similar preparations.
ing and disinfectant purposes in addition to their use
as detergents. The compositions can be dried in any 10
The 3,4’,S-tribromosalicylanilide or mixture thereof
desired way; ‘spray drying is convenient in many in
with di- and tetrabromo salicylanilides may be included
stances. It is desirable to hold the temperature to which
in compositions which contain soap or other surface active
the mix is subjected during conversion into its ?nal form
agents not intended primarily for detergent use, such as
below the temperature at which the 3,4',5-tribromo
salicylanilide would be decomposed. Soap mixtures in 15
accordance with the invention have been subjected to
temperatures up to 215° F. for periods of up to one hour
without disadvantage.
various powdered cosmetics.
This application is a continuation-in-part of applica
tion Serial No. 700,732, ?led December 5, 1957, and
now abandoned.
We claim:
The compositions of the invention meet all of the re
1. A process for preparing a mixture of brominated
quirements for germicidal soaps, as is evident from tests 20 derivatives composed predominantly of 3,4',5-tribromo
which have been carried out on them, and are indis
salicylanilide which comprises brominating one mole of
tinguishable in appearance from ordinary soaps. They
salicylanilide with three moles of bromine in a reaction
can be used as ordinary detergent soaps and are especially
medium consisting essentially of from 99.9 to 98% water
recommended for uses in which both detergent ‘and de
and from 0.1 to 2% of an organic surfactant.
germing characteristics are desired. The test results show 25
2. A process in accordance with claim 1, the bromine
that the compositions used routinely for a period of from
being added dropwise.
one to two weeks lower the bacterial ?ora of the skin to
3. A process in accordance with claim 1, in which the
a very low level. The compositions are particularly
surfactant is anionic.
valuable for routine surgical and hospital use ‘and gen
4. A process in accordance with claim 3, in which the
erally useful in the prevention of infections arising from 30 surfactant is an alkylaryl sulfonate.
skin bacteria.
5. A process in accordance with claim 3, in which the
Those skilled in the art will perceive many variations
surfactant is an aliphatic hydrocarbon acyl amino alkaue
in the compositions of the invention. For example, the
sulfonate.
6. A process in accordance with claim 3, in which the
and tetrabromo salicylanilides need not be the only 35 surfactant is an alkyl sulfate.
germicidal agent; other germicides, such as 2,2'-dihy
7. A process in accordance with claim 1, in which the
droxy halogenated diphenyl methanes, can be included, if
surfactant is cationic.
desired.
8. A process in accordance with claim 7, in which the
The soap compositions, in addition to the soap and
surfactant is a quaternary hydrocarbon substituted am
germicide, will also usually contain ?llers, coloring ma 40 monium compound.
terials and perfumes, as desired, as is familiar to those
9. A process in accordance with claim 1, in which the
skilled in the art.
surfactant is nonionic.
The compositions containing the 3,4’,5-tribromosalicyl-'
10. A process in accordance with claim 9, in which the
anilide or mixture thereof with di- and tetra-bromo
surfactant is an alkyl oxyethylene condensation product.
salicylanilides may contain mixtures of detergents, such 45
as soap and anionic nonsoap, or soap and a nonionic non
References Cited in the ?le of this patent
soap. Typical satisfactory anionic nonsoaps are the alkyl
UNITED STATES PATENTS
3,4’,5-tribromosalicylani1ide or mixture thereof with di
sulfates, typi?ed by sodium lauryl sulfate, known in the
trade as Duponol C, the alkyl aryl sulfonates, typi?ed by
2,511,784
O’Neal ______________ __ June 13, 1950
the sodium polypropylene benzene or toluene sulfonates, 5 O
and the sodium keryl benzene or toluene sulfonates, the
2,675,409
2,802,029
Orlotf et a1 ___________ _.. Apr. 13, 1954
Schuler ______________ __ Aug. 6, 1957
180,961
516,037
Austria ______________ .._. Nov. 19, 1954
Belgium _____________ __ Dec. 31, 1952
937,646
Germany ____________ __ June 12, 1956
sulfated ethoxynated phenols, typi?ed by the ammonium
salt of sulfated ethoxynated nonyl phenol, prepared by
condensation of nonyl phenol with ?ve moles of ethylene
oxide, and the sodium fatty acid esters of taurine, typi?ed 55
by sodium palmitic or oleic methyl tauride or mixtures
thereof, and the esters of higher fatty acids and hydroxy
ethane sulfonates such as oleic acid ester of hydroxy
ethane sodium sulfonate. Also useful are nonionic non
soaps, such as the polyethylene glycol esters of the higher 60
fatty acids, typi?ed by polyoxylene ethylene and propyl
ene glycol stearates, the polyethylene glycol ethers of a1
kyl phenols, typi?ed by the condensation product of
octyl and nonyl phenol with ?ve to twelve moles of
FOREIGN PATENTS
OTHER REFERENCES
Hirwe et al.: Proc. Ind. Acad. Sci., vol. 5A, pages
321-325 (1937).
Hirwe et al.: J. Indian Chem. Soc., vol. 16, pages 281
284 (1939).
Judhev et _al.; I. University of Bombay, vol. 20, See. A,
pt. 3, pages 97—100 (1951).
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