U.S. patent number 3,719,711 [Application Number 05/082,067] was granted by the patent office on 1973-03-06 for oligomeric quaternary ammonium antibacterial agents.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Robert D. Temple.
United States Patent |
3,719,711 |
Temple |
March 6, 1973 |
OLIGOMERIC QUATERNARY AMMONIUM ANTIBACTERIAL AGENTS
Abstract
Quaternary ammonium compounds of the general formula ##SPC1##
Wherein R and R' are the same and are selected from the group
consisting of R"OCH.sub.2 CH(OH)-- and R"CH(OH)-- wherein R" is an
n-alkyl group of from about four to about 20 carbon atoms, X is a
halide ion, and y has a value of from about 2 to about 4 possess
significantly greater antibacterial activity than the corresponding
monomers, i.e., when y has a value of 1 and there is no R'
group.
Inventors: |
Temple; Robert D. (North
College Hill, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Appl.
No.: |
05/082,067 |
Filed: |
October 19, 1970 |
Current U.S.
Class: |
564/286; 510/384;
510/504; 510/391; 510/133; 510/319 |
Current International
Class: |
C11D
3/48 (20060101); C07c 087/30 () |
Field of
Search: |
;260/567.6R,567.6P |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Mars; Howard T.
Assistant Examiner: Glynn; Michael W.
Claims
What is claimed is:
1. Polymeric antibacterial 2-hydroxyalkyl quaternary ammonium
halide compounds having the structural formula: ##SPC3##
wherein R and R' are the same and are selected from the group
consisting of R"OCH.sub.2 CH(OH)-- and R"CH(OH)-- wherein R" is an
n-alkyl group containing from four to 20 carbon atoms, X is a
halide ion, and y has a value of from 2 to 4.
2. The polymeric antibacterial compound of claim 1 wherein R and R'
are C.sub.8 H.sub.17 -- O -- CH.sub.2 CH(OH)--, X is Br.sup.- and y
has a value of from 2 to 4.
3. The polymeric antibacterial compound of claim 1 wherein R and R'
are C.sub.10 H.sub.21 CH(OH)--, X is Br.sup.-, and y has a value of
from 2 to 4.
Description
BACKGROUND OF THE INVENTION
This invention relates to improved antibacterial compositions. More
particularly, it relates to the discovery that certain polymeric
quaternary ammonium compounds possess antibacterial activity
significantly greater than that possessed by the corresponding
monomers.
THE PRIOR ART
Antibacterial quaternary ammonium halides are known to the art.
See, for example, Rohm & Haas British Patents Nos. 812,140,
granted on Apr. 22, 1959; 815,745, granted on July 1, 1959; and
834,410, granted on May 11, 1960. The latter patent has a U.S.
counterpart, U.S. Pat. No. 2,810,713, granted to Melamed on Oct.
22, 1957. Additional patents include British Pat. No. 1,120,523,
granted on July 17, 1968, and U.S. Pat. No. 3,428,680, granted on
Feb. 18, 1969 to Walker et al. Although the above references
disclose certain polymeric quaternary ammonium compounds as
antibacterials, the specific antibacterial compounds of the present
invention are not disclosed nor suggested.
It is, therefore, an object of this invention to provide polymeric
quaternary ammonium compounds which possess a high degree of
antibacterial activity.
This and other objects will become apparent as the invention is
hereafter described in more detail.
SUMMARY OF THE INVENTION
These objects are achieved by the present invention with is
directed towards polymeric 2-hydroxyalkyl quaternary ammonium
halides with greatly improved antibacterial properties. More
specifically, it has been found that polymeric compounds having the
formula ##SPC2##
Wherein R and R' are the same and are selected from the group
consisting of R"OCH.sub.2 CH(OH)-- and R"CH(OH)-- wherein R" is an
n-alkyl group of from about four to about 20 carbon atoms; X is a
halide ion selected from the group consisting of bromine, chlorine,
iodine and fluorine, and y has a value of from about 2 to about 4,
possess greater antibacterial activity than the corresponding
monomers, i.e., when y has a value of 1, and R' is not present.
The process by which the novel compositions of the present
invention are made is no part of the present invention, as they can
be made by methods known in the art. For purposes of the present
invention, it is preferable to begin with an N-methylated polyamine
of the general formula H[N(CH.sub.3)CH.sub.2 CH.sub.2
].sub.n.sub.-1 NH(CH.sub.3). The amine is reacted with an epoxide
selected from the group consisting of 1,2-epoxy-3-alkoxy-propanes
and 1,2-epoxyalkanes in the presence of a solvent. A benzyl halide
is subsequently added, and the reaction is continued until
completion.
The reaction is carried out using specific mole ratios. The number
of moles of epoxide used is twice the number of moles of amine. The
number of moles of benzyl halide used is the number of moles of
amine multiplied by the number of nitrogen atoms in the amine.
Examples of preferred amines that can be used to produce the
compositions within the scope of the present invention include:
N,N'dimethylethylenediamine; N,N' ,N"trimethylethylenetriamine;
N,N' ,N" ,N'"tetramethylethylenetetramine.
Examples of preferred epoxides that can be used to produce the
novel compositions of the present invention include:
1,2-epoxyhexane; 1,2-epoxyheptane; 1,2-epoxynonane;
1,2-epoxydecane, 1,2-epoxydodecane; 1,2-epoxytetradecane;
1,2-epoxyhexadecane; 1,2-epoxyoctadecane; 1,2-epoxyeicosane;
1,2-epoxy-3-hexyloxypropane; 1,2-epoxy-3-heptyloxypropane;
1,2-epoxy-3-octyloxypropane; 1,2-epoxy-3-nonyloxypropane;
1,2-epoxy-3-decyloxypropane; 1,2-epoxy-3-dodecyloxypropane;
1,2-epoxy-3-tetradecyloxypropane; 1,2-epoxy-3-hexadecyloxypropane;
1,2-epoxyoctadecyloxypropane.
Most preferred are 1,2-epoxy-3-octyloxypropane and
1,2-epoxydodecane.
Examples of suitable solvents for the purposes of the present
invention include methanol, ethanol, isopropanol, butanol, or any
other suitable polar solvent.
Examples of suitable benzyl halides are benzyl bromide, benzyl
chloride, benzyl fluoride and benzyl iodide. Benzyl bromide is most
preferred.
PREFERRED EMBODIMENTS
The following examples set forth and illustrate in more detail the
nature and objects of the present invention but are not limiting
thereof.
EXAMPLE I
Preparation of the diquaternary analog of
2-hydroxy-3-octyloxypropyl dimethylbenzylammonium bromide
2.37 grams (0.0269 moles) of N,N'-dimethylethylenediamine (Aldrich
Chemical Co., Inc.) and 10 grams (0.0538 moles) of
1,2-epoxy-3-octyloxypropane (Chemical Procurement Labs Inc.) were
dissolved in 50 ml of ethanol and heated at reflux temperature for
16 hours. 9 grams (0.0538 moles) of benzyl bromide were
subsequently added and the refluxing was continued for an
additional 24 hours. The mixture was then cooled to about room
temperature and the ethanol subsequently evaporated off to yield a
light-colored, hygroscopic crystalline solid. The residue was
subsequently washed with ether and dried. The result was the
diquaternary analog of 2-hydroxy-3-octyloxypropyl
dimethylbenzylammonium bromide which is effective as an
antibacterial agent, and which possesses significantly greater
effectiveness than the corresponding monomer.
EXAMPLE II
Preparation of the triquaternary analog of
2-hydroxy-3-octyloxypropyl dimethylbenzylammonium bromide
Utilizing substantially the same procedures as in Example I, 1.0 g
(0.00689 moles) of N,N',N"-trimethyldiethylenetriamine, 2.56 g
(0.01378 moles) of 1,2-epoxy-3-octyloxypropane, were reacted in 25
ml of ethanol. 3.53 g (0.02067 moles) of benzyl bromide were
subsequently added as in Example I. The resulting composition was
the triquaternary analog of 2-hydroxy-3-octyloxypropyl
dimethylbenzylammonium bromide, said compound being an effective
antibacterial agent and having significantly greater effectiveness
than the corresponding monomer.
EXAMPLE III
Preparation of the tetraquaternary analog of
2-hydroxy-3-octyloxypropyl dimethylbenzylammonium bromide
Utilizing substantially the same procedures as in Example I, 1.0 g
(0.00494 moles) of N,N',N",N'"-tetramethyltriethylenetetramine,
1.84 g (0.00988 moles) of 1,2-epoxy-3-octyloxypropane, and 3.38 g
(0.01976 moles) of benzyl bromide were reacted in the presence of
25 ml of ethanol. The result was the tetraquaternary analog of
2-hydroxy-3-octyloxypropyl dimethylbenzylammonium bromide, which is
effective as an antibacterial agent possessing significantly
greater activity than the corresponding monomer.
Effective agents are also obtained by substituting the following
compounds for the 1,2-epoxy-3-octyloxypropane utilized in Examples
I-III: 1,2-epoxyhexane; 1,2-epoxyheptane; 1,2-epoxynonane;
1,2-epoxydecane, 1,2-epoxydodecane; 1,2-epoxytetradecane;
1,2-epoxyhexadecane; 1,2-epoxyoctadecane; 1,2-epoxyeicosane;
1,2-epoxy-3-hexyloxypropane; 1,2-epoxy-3-heptyloxypropane;
1,2-epoxy-3-nonyloxypropane; 1,2-epoxy-3-decyloxypropane;
1,2-epoxy-3-dodecyloxypropane; 1,2-epoxy-3-tetradecyloxypropane;
1,2-epoxy-3-hexadecyloxypropane; 1,2-epoxyoctadecyloxypropane.
Similar results are also achieved by substituting the following
compounds for the benzyl bromide utilized in Examples I-III: benzyl
chloride, benzyl fluoride, and benzyl iodide to form the
corresponding di-, tri-, and tetraquaternary halides. Similar
results are also achieved by substituting the following compounds
for the ethanol utilized in Examples I-III: methanol, isopropanol,
butanol, and other suitable polar solvents.
EXAMPLE IV
Preparation of the diquaternary analog of 2-hydroxy
dodecyldimethylbenzylammonium bromide
1.0 g (0.01136 moles) of N,N'-dimethylethylenediamine and 4.19 g
(0.02272 moles) of 1,2-epoxydodecane were refluxed in 25 ml of
ethanol for about 20 hours. 3.88 g (0.02272 moles) of benzyl
bromide were then added and refluxing continued for about an
additional 2 hours. The ethanol was stripped off by rotary
evaporation, leaving a heavy syrup. The syrup was washed several
times with ether and dried in a desiccator. The resulting
composition was the diquaternary analog of
2-hydroxy-dodecyldimethylbenzylammonium bromide which is an
effective antibacterial agent possessing significantly greater
effectiveness than the corresponding monomer.
EXAMPLE V
Preparation of the triquaternary analog of 2-hydroxy
dodecyldimethylbenzylammonium bromide
Utilizing substantially the same procedures as in Example IV, 1.0 g
(0.00689 moles) of N,N',N"-trimethyldiethylenetriamine, 2.54 g
(0.01378 moles) of 1,2-epoxydodecane, and 3.53 g (0.02067 moles) of
benzyl bromide were reacted in 25 ml of ethanol. The resulting
compound was the triquaternary analog of
2-hydroxy-dodecyldimethylbenzylammonium bromide which is an
effective antibacterial agent possessing significantly greater
antibacterial effectiveness than the corresponding monomer.
EXAMPLE VI
Preparation of the tetraquaternary analog of 2-hydroxy
dodecyldimethylbenzylammonium bromide
Utilizing substantially the same procedures as in Example IV, 1.0 g
(0.00494 moles) of N,N',N",N'"-tetramethyltriethylenetetramine,
1.82 g (0.00988 moles) of 1,2-epoxydodecane, and 3.38 g (0.01976
moles) of benzyl bromide were reacted in 25 ml of ethanol. The
resulting compound was the tetraquaternary analog of 2-hydroxy
dodecyldimethylbenzylammonium bromide, which is an effective
antibacterial agent possessing significantly greater effectiveness
than the corresponding monomer.
Effective agents are also obtained by substituting the
1,2-epoxydodecane utilized in Examples IV-VI with 1,2-epoxyhexane;
1,2-epoxyheptane; 1,2-epoxynonane; 1,2-epoxydecane,
1,2-epoxytetradecane; 1,2-epoxyhexadecane; 1,2-epoxyoctadecane;
1,2-epoxyeicosane; 1,2-epoxy-3-hexyloxypropane;
1,2-epoxy-3-heptyloxypropane; 1,2-epoxy-3-octyloxypropane;
1,2-epoxy-3-nonyloxypropane; 1,2-epoxy-3-decyloxypropane;
1,2-epoxy-3-dodecyloxypropane; 1,2-epoxy-3-tetradecyloxypropane;
1,2-epoxy-3-hexadecyloxypropane; 1,2-epoxyoctadecyloxypropane.
Similar results are also achieved by substituting the following
compounds for the benzyl bromide utilized in Examples IV-VI: benzyl
chloride, benzyl fluoride, and benzyl iodide to form the
corresponding di-, tri-, and tetraquaternary halides. Similar
results are also achieved by substituting the following compounds
for the ethanol utilized in Examples IV-VI: methanol, isopropanol,
butanol, and other suitable polar solvents.
EXAMPLE VII
Agar Incorporation Minimal Inhibitory Concentration Test
The antibacterial efficacies of the antibacterial compositions of
the present invention were established and can be demonstrated by
determining the bacteriostatic breakpoint also known as the minimal
inhibitory concentration (MIC). The test is designed to determine
the minimum concentration of an antibacterial composition which
just prevents the growth of a test organism through incubation.
This is expressed as the "MIC" or "Bacteriostatic Breakpoint" and
is expressed in parts per million (ppm).
In this test, plates containing a medium of trypticase soy agar
(TSA) and varied concentrations of the antibacterial agents to be
tested were prepared. The plates were subsequently inoculated with
prepared trypticase soy broth (TSB) cultures of an inoculum. In the
present test, the inoculum against which the compounds of the
present invention were tested were Staphylococcus aureus (Gm +) and
Escherichia coli (Gm -). The inoculated plates were incubated for
about 48 hours at 37.degree.C. and subsequently examined for
growth. The lowest concentration of the antibacterial agent being
tested which shows no growth of the inoculum is the MIC expressed
in parts per million. In this test, 2-hydroxy-3-octyloxypropyl
dimethylbenzylammonium bromide and the corresponding di-, tri-, and
tetraquaternary analogs were evaluated. Also evaluated was
2-hydroxy dodecyldimethylbenzylammonium bromide and the
corresponding di-, tri-, and tetraquaternary analogs thereof. The
results of tests are disclosed below in Table I wherein y.sub.1
denotes the monomer, y.sub.2 the diquaternary analog, y.sub.3 the
triquaternary analog, and y.sub.4 the tetraquaternary analog.
Table I
(MIC) (MIC) Compound Staphylococcus aureus ppm Escherichia coli ppm
Broth Broth
__________________________________________________________________________
A.sup.1 pH 5.8 pH 6.8
__________________________________________________________________________
Y.sub.1 > 10 >10 >20 Y.sub.2 2.5 2.5 20 Y.sub.2 2.5 2.5 20
Y.sub.3 10 10 20 Y.sub.4 2.5 2.5 5
__________________________________________________________________________
B.sup.2
__________________________________________________________________________
Y.sub.1 10 >10 >20 Y.sub.2 2.5 0.6 >20 Y.sub.3 2.5
<0.15 20 Y.sub.4 10 2.5 20 Y.sub.4 2.5 0.6 >20 1. A --
2-hydroxy-3-octyloxypropyl dimethylbenzylammonium bromide 2. B --
2-hydroxy dodecyldimethylbenzylammonium bromide
From the above table, it can be seen that the higher analogs, i.e.,
di- (y.sub.2), tri- (y.sub.3), and tetraquaternary (y.sub.4)
analogs, generally exhibit lower MIC values than the corresponding
monomers (y.sub.1) indicating greater antibacterial
effectiveness.
EXAMPLE VIII
Bactericidal Test
This test is designed to determine bactericidal effectiveness of
antibacterial agents. A stock solution of the antibacterial agent
being tested and dimethyl formamide (DMFA) was prepared, the
concentrations of antibacterial agent being 10 ppm and 100 ppm.
After the tubes were heated in a water bath for about 20 minutes at
about 37.degree.C., they were inoculated by a trypticase soy broth
culture containing the test organisms, Staphylococcus aureus and
Escherichia coli. Aliquots were removed from the samples and were
put into Petri plates containing molten trypticase soy agar
containing 5 percent Tween 80 and 1 percent horse serum. The plates
were allowed to harden and were subsequently incubated for 48 hours
at 37.degree.C. The plates were then examined and the number of
bacterial colonies formed were counted using a Quebec Colony
Counter. The results of the tests expressed as percent cidal kill
are found in Table II below, wherein y.sub.1 indicates the monomer,
y.sub.2 the diquaternary analog, y.sub.3 the triquaternary analog,
and y.sub.4 the tetraquaternary analog.
Table II
Compound Staphylococcus aureus Escherichia coli
__________________________________________________________________________
Cidal % Kill Cidal % Kill A.sup.1 10 ppm 100 ppm 10 ppm 100 ppm
Y.sub.1 64.0 52.0 Y.sub.2 99.998 >99.99 99.86 >99.99 Y.sub.2
99.94 99.994 96.4 99.9998 Y.sub.3 98.5 99.999 <50 99.97 Y.sub.4
99.973 99.999 53.0 99.993 B.sup.2 Y.sub.1 <50 99.99 59 99.99
Y.sub.2 99.99 99.99 99.98 Y.sub.3 99.997 99.997 94.2 99.998 Y.sub.4
99.99 99.99 84.3 99.99 Y.sub.4 99.8 99.99 71.2 99.99 1. A --
2-hydroxy-3-octyloxypropyl dimethylbenzylammonium bromide 2. B --
2-hydroxy dodecyldimethylbenzylammonium bromide
From the above table, it can be seen that the higher analogs, i.e.,
the di- (y.sub.2), tri- (y.sub.3), and tetraquaternary (y.sub.4)
analogs show greater cidal kill percentages at lower concentrations
indicating greater antibacterial effectiveness than the
corresponding monomers (y.sub.1).
It has also been found that the above-disclosed polymeric
quaternary ammonium antibacterial agents possess antibacterial
properties whereby a lasting antibacterial effect is obtained
particularly in soap and non-soap synthetic detergent compositions,
and other products where an antibacterial action is desired. Such
compositions containing combinations of the present invention in
amounts of from about 0.1 to about 5 percent, preferably about 2
percent, are particularly effective.
The term "soap" as used herein is meant to designate alkali metal
soaps such as the sodium and potassium salts of the higher fatty
acids of naturally occurring plant or animal esters, e.g., palm
oil, coconut oil, babassu oil, soybean oil, castor oil, tallow,
whale and fish oils, grease and lard and mixtures thereof. Sodium
and potassium soaps can be made by direct saponification of the
fats and oils or by the neutralization of the fatty acids which are
prepared in a separate manufacturing process. Examples of suitable
soaps are the sodium, potassium, ammonium and alkylolammonium salts
of higher fatty acids (C.sub.10 - C.sub.20). Particularly useful
are the sodium and potassium salts of the mixtures of fatty acids
derived from coconut oil and tallow, i.e., sodium or potassium
tallow and coconut soap.
Anionic synthetic detergents which can be used with the
antibacterial combinations of the present invention can be broadly
defined as the water-soluble salts, including the alkali metal,
ammonium and substituted ammonium salts, of organic sulfuric
reaction products having in their molecular structure an alkyl
radical containing from about eight to about 22 carbon atoms and a
radical selected from the group consisting of sulfonic acid and
sulfuric acid ester radicals.
Important examples of the synthetic detergents which can be used
with the compositions of the present invention are the following:
an alkali metal (e.g., sodium and potassium) ammonium and
substituted ammonium (e.g., lower alkyl ammonium) salts; alkyl
sulfates, especially those obtained by sulfating the higher
alcohols produced by reducing the glycerides of tallow or coconut
oil; random paraffin sulfonates, in which the alkyl group contains
from about eight to about 22 carbon atoms, prepared by treating
random paraffin hydrocarbons in sulfur dioxide and chlorine in the
presence of light followed by treating with a base; branched or
linear alkyl benzene sulfonates, in which the alkyl group contains
from about eight to about 18 carbon atoms, preferably from about 10
to about 14 carbon atoms, especially those of the types described
in U.S. Pat. Nos. 2,220,099, and 2,477,383; sodium alkyl glyceryl
ether sulfonates, especially those ethers of the higher alcohols
derived from tallow and coconut oil; coconut oil fatty acid
monoglyceride sulfates and sulfonates; sulfuric acid esters of the
reaction product of one mole of a higher fatty alcohol (e.g.,
tallow or coconut alcohols) and from about 1 to about 6, preferably
about 3 moles of ethylene oxide; alkyl phenol ethylene oxide ether
sulfates with about 4 units of ethylene oxide per molecule and in
which the alkyl radicals contain about nine carbon atoms; the
reaction product of fatty acids esterified with isethionic acid and
neutralized with sodium hydroxide where, for example, the fatty
acids are derived from coconut oil; fatty acid amides of the methyl
taurine in which the fatty acids, for example, are derived from
coconut oil; sulfonated olefins of U.S. Pat. No. 3,332,880; and
others known in the art, a number being specifically set forth in
U.S. Pat. Nos. 2,486,921, 2,486,922 and 2,396,278.
The nonionic synthetic detergents which can be used with the
antibacterial combinations of the present invention may be broadly
defined as compounds produced by the condensation of alkylene oxide
groups (hydrophilic in nature) with an organic hydrophobic compound
which may be aliphatic or alkyl-aromatic in nature. The length of
the hydrophilic or polyoxyalkylene radical which is condensed with
any particular hydrophobic group can be readily adjusted to yield a
water-soluble compound having the desired degree of balance between
hydrophilic and hydrophobic elements.
For example, a well-known class of nonionic synthetic detergents is
made available on the market under the trade name of "Pluronic."
These compounds are formed by condensing ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide with
propylene glycol. The hydrophobic portion of the molecule which, of
course, exhibits water insolubility has a molecular weight of from
about 1,500 to about 1,800. The addition of polyoxyethylene
radicals to this hydrophobic portion tends to increase the water
solubility of the molecule as a whole and the liquid character of
the products is retained up to the point where polyoxyethylene
content is about 50 percent of the total weight of the condensation
product.
Other suitable nonionic synthetic detergents include:
1. The polyethylene oxide condensates of alkyl phenols, e.g., the
condensation products of alkyl phenols having an alkyl group
containing from about six to 12 carbon atoms in either a straight
chain or branched chain configuration, with ethylene oxide, the
said ethylene oxide being present in amounts equal to 10 to 60
moles of ethylene oxide per mole of alkyl phenol. The alkyl
substituent in such compounds may be derived from polymerized
propylene, diisobutylene, octane, or nonane, for example.
2. Those derived from the condensation of ethylene oxide with the
product resulting from the reaction of propylene oxide and ethylene
diamine -- products which may be varied in composition depending
upon the balance between the hydrophobic and hydrophilic elements
which is desired. For example, compounds containing from about 40
to about 80 percent polyoxyethylene by weight and having a
molecular weight of from about 5,000 to about 11,000 resulting from
the reaction of ethylene oxide groups with a hydrophobic base
constituted of the reaction product of ethylene diamine and excess
propylene oxide, said base having a molecular weight of the order
of 2,500 to 3,000, are satisfactory.
3. The condensation product of aliphatic alcohols having from 8 to
18 carbon atoms, in either straight chain or branched chain
configuration, with ethylene oxide, e.g., a coconut alcohol
ethylene oxide condensate having from 10 to 30 moles of ethylene
oxide per mole of coconut alcohol, the coconut alcohol fraction
having from 10 to 14 carbon atoms.
4. Long chain tertiary amine oxides corresponding to the following
general formula, R.sub.1 R.sub.2 R.sub.3 N.fwdarw.O, wherein
R.sub.1 contains an alkyl, alkenyl or monohydroxy alkyl radical of
from about eight to about 18 carbon atoms from 0 to about 10
ethylene oxide moieties, and from 0 to 1 glyceryl moiety, and
R.sub.2 and R.sub.3 contain from one to about three carbon atoms
and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl,
hydroxy ethyl, or hydroxy propyl radicals. The arrow in the formula
is a conventional representation of a semi-polar bond. Examples of
amine oxides suitable for use in this invention include
dimethyldodecylamine oxide, oleyldi(2-hydroxyethyl)amine oxide,
dimethyloctylamine oxide, dimethyldecylamine oxide,
dimethyltetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine
oxide, di(2-hydroxyethyl)-tetradecylamine oxide,
2-dodecoxyethyldimethylamine oxide,
3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl)amine oxide,
dimethylhexadecylamine oxide.
5. Long chain tertiary phosphine oxides corresponding to the
following general formula RR'R"P.fwdarw.O, wherein R contains an
alkyl, alkenyl or monohydroxyalkyl radical ranging from eight to 18
carbon atoms in chain length, from 0 to about 10 ethylene oxide
moieties and from 0 to 1 glyceryl moiety and R' and $" are each
alkyl or monohydroxyalkyl groups containing from one to three
carbon atoms. The arrow in the formula is a conventional
representation of a semipolar bond. Examples of suitable phosphine
oxides are:
dodecyldimethylphosphine oxide,
tetradecyldimethylphosphine oxide,
tetradecylmethylethylphosphine oxide,
3,6,9-trioxaoctadecyldimethylphosphine oxide,
cetyldimethylphosphine oxide,
3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl)phosphine oxide,
stearyldimethylphosphine oxide,
cetylethylpropylphosphine oxide,
oleyldiethylphosphine oxide,
dodecyldiethylphosphine oxide,
tetradecyldiethylphosphine oxide,
dodecyldipropylphosphine oxide,
dodecyldi(hydroxymethyl)phosphine oxide,
dodecyldi(2-hydroxyethyl)phosphine oxide,
tetradecylmethyl-2-hydroxypropylphosphine oxide,
oleyldimethylphosphine oxide,
2-hydroxydodecyldimethylphosphine oxide.
6. Long chain dialkyl sulfoxides containing one short chain alkyl
or hydroxy alkyl radical of one to about three carbon atoms
(usually methyl) and one long hydrophobic chain which contains
alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing
from about eight to about 20 carbon atoms, from 0 to about 10
ethylene oxide moieties and from 0 to 1 glyceryl moiety. Examples
include:
octadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide,
3,6,9-trioxaoctadecyl 2-hydroxyethyl sulfoxide,
dodecyl methyl sulfoxide,
oleyl 3-hydroxy propyl sulfoxide,
tetradecyl methyl sulfoxide,
3-methoxytridecyl methyl sulfoxide
3-hydroxytridecyl methyl sulfoxide,
3-hydroxy-4-dodecoxybutyl methyl sulfoxide.
The zwitterionic synthetic detergents useful with the antibacterial
agents of the present invention can be broadly described as
derivatives of aliphatic quaternary ammonium, phosphonium, and
sulfonium compounds, in which the aliphatic radicals can be
straight chain or branched, and wherein one of the aliphatic
substituents contains from about eight to 18 carbon atoms and one
contains an anionic water solubilizing group, e.g., carboxy,
sulfonate, sulfate, phosphate, or phosphonate. A general formula
for these compounds is:
wherein R.sup.2 contains an alkyl, alkenyl, or hydroxy alkyl
radical of from about eight to about 18 carbon atoms, from 0 to
about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y
is selected from the group consisting of nitrogen, phosphorous, and
sulfur atoms; R.sup.3 is an alkyl or monohydroxyalkyl group
containing one to about three carbon atoms; x is 1 when Y is a
sulfur atom and 2 when Y is a nitrogen or phosphorous atom, R.sup.4
is an alkylene or hydroxyalkylene of from one to about four carbon
atoms and Z is a radical selected from the group consisting of
carboxylate, sulfonate, sulfate, phosphonate, and phosphate
groups.
Examples include:
4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate;
5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;
3-[P,P-diethyl-P-3,6,9-trioxatetracoxylphosphonio]-2-hydroxypropane-1-phosp
hate;
3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-1-phosphonate;
3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate;
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane-1-carboxylate
;
3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;
3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; and
5-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]2-hydroxypentane-1-sulfate.
The amphoteric synthetic detergents useful in the present invention
can be broadly described as derivatives of aliphatic secondary and
tertiary amines in which the aliphatic radical can be straight
chain or branched and wherein one of the aliphatic substituents
contains from about eight to about 18 carbon atoms and one contains
an anionic water solubilizing group, e.g., carboxy, sulfonate,
sulfate, phosphate, or phosphonate. Examples of compounds falling
within this definition are sodium 3-dodecylaminopropionate, sodium
3-dodecylaminopropane sulfonate, dodecyl-.beta.-alanine,
N-alkyltaurines such as the one prepared by reacting dodecylamine
with sodium isethionate according to the teaching of U.S. Pat. No.
2,658,072, N-higher alkyl aspartic acids such as those produced
according to the teaching of U.S. Pat. No. 2,438,091, and the
products sold under the trade name "Miranol" and described in U.S.
Pat. No. 2,528,378.
Detergent formulations containing the antibacterial compositions of
the present invention can also contain from about 0 to about 90
percent, preferably from about 10 to about 90 percent of
water-soluble alkaline detergency builder salts, either of the
organic or inorganic types. Examples of such builder salts can be
found in U.S. Pat. No. 3,336,233, issued Aug. 15, 1967, column 9,
lines 29-66, which is incorporated herein by reference.
The detergent formulations can also contain any of the usual
adjuvants, diluents, and additives, for example, perfumes,
anti-tarnishing agents, anti-redeposition agents, dyes,
fluorescers, suds builders, suds depressors and the like without
detracting from the advantageous properties of the antibacterial
compositions of the present invention.
Examples of diluents which may be incorporated into a synthetic
detergent bar in amounts of up to about 80 percent of the bar
include soaps, especially heavy metal insoluble soaps, (metallic
salts of higher fatty acids); starches such as cornstarch; and
clays such as china clay or fuller's earth. Other diluents include
inorganic salts such as sodium and potassium chlorides and
sulfates. Such diluents add bulk to the bar and improve its
cosmetic properties without impairing its detergent or cohesive
properties.
EXAMPLE IX
A milled toilet detergent bar is prepared in accordance with
methods known and used in the art and having the following
composition:
Percent Sodium alkyl glyceryl ether sulfonate 8.0 (alkyl group
derived from the middle- cut.sup.1 of alcohols obtained by
catalytic reduction of coconut oil) Potassium alkyl sulfate (alkyl
group 20.0 derived from the middle cut.sup.1 of alcohols obtained
by catalytic reduction of coconut oil) Magnesium soap of 80:20
tallow: 17.0 coconut fatty acids Inorganic salts (sodium and
potassium 32.0 chlorides and sulfates) Diquaternary analog of
2-hydroxy-3- 2.0 octyloxypropyl dimethylbenzylammonium bromide
Water and minors balance to 100 .sup.1 Middle-cut coconut alcohols
having a chain length distribution substantially as follows: 2%
C.sub.10, 66% C.sub.12, 23% C.sub.14, and 9% C.sub.16.
this bar cleans well and exhibits good odor reducing properties
evidencing antibacterial effectiveness. It reduces the number of
bacteria on the skin and does not discolor significantly.
Substantially equivalent results are achieved when the diquaternary
analog of 2-hydroxy-3-octyloxypropyl dimethylbenzylammonium bromide
is substituted by the tri-, and tetraquaternary analogs thereof.
Similar desirable antibacterial effectiveness is also achieved when
the diquaternary analog of 2-hydroxy-3-octyloxypropyl
dimethylbenzylammonium bromide is replaced by the di-, tri-, and
tetraquaternary analogs of 2-hydroxy dodecyldimethylbenzylammonium
bromide.
EXAMPLE X
A granular built synthetic detergent composition having the
following formulation can be prepared and the antibacterial
compositions of the present invention can be incorporated
therein.
Percent Sodium dodecylbenzene sulfonate 17.5 Sodium
tripolyphosphate 50.0 Sodium sulfate 14.0 Sodium silicate
(SiO.sub.2 :Na.sub.2 O=2:1) 7.0 Diquaternary analog of 3.0
2-hydroxy dodecyl- dimethylbenzylammonium bromide Water and minors
balance to 100
This composition, in addition to performing well in its cleaning
capacity, imparts considerable antibacterial activity to fabrics
cleansed in its solution.
Substantially equivalent results are obtained when the diquaternary
analog of 2-hydroxy dodecyldimethylbenzylammonium bromide is
replaced with the tri-, and tetraquaternary analogs thereof.
Substantially equivalent results are also obtained when the
diquaternary analog of 2-hydroxy dodecyldimethylbenzylammonium
bromide of Example X is replaced by the di-, tri-, and
tetraquaternary analogs of 2-hydroxy-3-octyloxypropyl
dimethylbenzylammonium bromide.
Substantially equivalent results are obtained, i.e., good cleaning
and good odor reducing properties, when the sodium dodecylbenzene
sulfonate of Example X is replaced, on an equal weight basis, by
the following:
sodium tallowalkyl sulfate;
potassium coconutalkyl glyceryl ether sulfonate;
sodium salt of randomly sulfonated paraffin containing an average
of 15.2 carbon atoms;
ammonium tridecyl sulfate;
condensation product of octyl phenol with 15 moles of ethylene
oxide per mole of octyl phenol;
dimethyldodecylamine oxide,
dodecyldimethylphosphine oxide;
tetradecyl methyl sulfoxide;
3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate;
3-dodecylaminopropionate; and
dodecyl-.beta.-alanine.
EXAMPLE XI
A granular built synthetic detergent composition having the
following formulation can be prepared and the antibacterial
compositions of the present invention incorporated therein.
Percent The reaction product of coconut alcohol 9.0 and about 30
moles of ethylene oxide Sodium tripolyphosphate 58.5 Sodium sulfate
14.0 Sodium silicate (SiO.sub.2 :Na.sub.2 O=2:1) 7.0 Diquaternary
analog of 1.0 2-hydroxy-3-octyl- oxypropyl dimethylbenzylammonium
bromide Water 10.5
The composition possesses good cleaning capacity and desirable
antibacterial effectiveness on fabrics cleansed in the
solution.
Substantially equivalent results are achieved when the diquaternary
analog of 2-hydroxy-3-octyloxypropyl dimethylbenzylammonium bromide
is substituted by the tri-, and tetraquaternary analogs thereof.
Similar desirable antibacterial effectiveness is also achieved when
the diquaternary analog of 2-hydroxy-3-octyloxypropyl
dimethylbenzylammonium bromide is replaced by the di-, tri-, and
tetraquaternary analogs of 2-hydroxy dodecyldimethylbenzylammonium
bromide.
The foregoing description of the invention has been presented
describing certain operable and preferred embodiments. It is not
intended that the invention should be so limited, since variations
and modifications thereof will be obvious to those skilled in the
art, all of which are within the scope and spirit of the
invention.
* * * * *