US3719711A - Oligomeric quaternary ammonium antibacterial agents - Google Patents

Oligomeric quaternary ammonium antibacterial agents Download PDF

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Publication number
US3719711A
US3719711A US00082067A US3719711DA US3719711A US 3719711 A US3719711 A US 3719711A US 00082067 A US00082067 A US 00082067A US 3719711D A US3719711D A US 3719711DA US 3719711 A US3719711 A US 3719711A
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Prior art keywords
oxide
antibacterial
hydroxy
epoxy
bromide
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US00082067A
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English (en)
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R Temple
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Procter and Gamble Co
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Procter and Gamble Co
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • 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'dimethylethylenedi amine; 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; l,2-epoxy-3-heptyloxypropane; 1,2- epoxy-3-octyloxypropane; l ,2-epoxy-3-nonyloxypropane; l,2-epoxy-3-decyloxypropane; 1,2-epoxy-3- dodecyloxypropane; 1 ,2-epoxy-3-tetradecyloxypropane; l,2-epoxy-3
  • Suitable solvents for the purposes of the present invention include methanol, ethanol, isopropanol, butanol, or any other suitable polar solvent.
  • Suitable benzyl halides are benzyl bromide, benzyl chloride, benzyl fluoride and benzyl iodide. Benzyl bromide is most preferred.
  • Effective agents are also obtained by substituting the following compounds for the 1,2-epoXy-3-0ctyloxypropane 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; l,2-epoxy-3hexyloxypropane; 1,2-epoxy-3- heptyloxypropane; l,2-epoxy-3nonyloxypropane; 1,2- epoxy-3-decyloxypropane', 1,2-epoxy-3-dodecyloxypropane; l,2-epoxy-3tetradecyloxypropane; 1,2- epoxy-3-hexadecyloxy
  • Effective agents are also obtained by substituting the 1,2-epoxyd0decane 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-3hexyloxypropane; 1,2-epoxy-3- heptyloxypropane; l,2-epoxy-3octyloxypropane; 1,2- epoxy-3-nonyloxypropane; 1,2-epoxy-3-decyloxypropane; l,2-epoxy-3dodecyloxypropane; 1,2-epoxy- 3-tetradecyloxypropane; 1,2-epoxy-3-hexadecyloxypropane; 1,2epoxyoct
  • 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).
  • 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 ppm and 100 ppm.
  • DMFA dimethyl formamide
  • 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 saponifica' tion of the fats and oils or by the neutralization of the fatty acids which are prepared in a separate manufacturing process.
  • Suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C C 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.
  • an alkali metal e.g., sodium and potassium
  • substituted ammonium e.g., lower alkyl ammonium
  • 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 to about 14 carbon atoms, especially those of the types described in U.S.
  • 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.
  • nonionic synthetic detergents are made available on the market under the trade name ofPluronic. 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.
  • nonionic synthetic detergents include:
  • 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.
  • 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.
  • R R R N Long chain tertiary amine oxides corresponding to the following general formula, R R R N 0, wherein R 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 and R 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.
  • 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.
  • phosphine oxides examples include dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, 3,6,9-trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl)phosphine oxide, stearyldimethylphosphine oxide,
  • Examples include:
  • 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:
  • R 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 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 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-l-carboxylate; -[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-l -sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetracoxylphosphonio1-2- hydroxypropane-l-phosphate; 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-l-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)propane-lsulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropanel -sulfonate; 4-[N,N-di(2-hydroxyeth
  • 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.
  • 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-B- 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 US. Pat. No. 2,438,091, and the products sold under the trade name Miranol" and described in US. Pat. No. 2,528,378.
  • Detergent formulations containing the antibacterial compositions of the present invention can also contain from about 0 to about 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 US. 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.
  • 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 fullers 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.
  • a milled toilet detergent bar is prepared in accordance with methods known and used in the art and having the following composition:
  • 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.
  • 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.
  • R cm-l i-cm lt' wherein R and R are the same and are selected from the group consisting of R"OCH 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.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00082067A 1970-10-19 1970-10-19 Oligomeric quaternary ammonium antibacterial agents Expired - Lifetime US3719711A (en)

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DE (1) DE2151719A1 (enExample)
FR (1) FR2111700B1 (enExample)
GB (1) GB1322636A (enExample)
IT (1) IT1050150B (enExample)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0737702A3 (en) * 1995-04-11 1998-03-25 Air Products And Chemicals, Inc. Partially methylated polyamines as epoxy curing agents
US6017561A (en) * 1997-04-04 2000-01-25 The Clorox Company Antimicrobial cleaning composition
US6080387A (en) * 1998-07-15 2000-06-27 The Clorox Company Aerosol antimicrobial compositions
US6849581B1 (en) 1999-03-30 2005-02-01 Bj Services Company Gelled hydrocarbon compositions and methods for use thereof
US20100081844A1 (en) * 2005-11-04 2010-04-01 Charles Little Polycationic organic compounds
US8486427B2 (en) 2011-02-11 2013-07-16 Kimberly-Clark Worldwide, Inc. Wipe for use with a germicidal solution
US20140116690A1 (en) * 2012-10-26 2014-05-01 Basf Se Process for mineral oil production using surfactants at least comprising a secondary alkanesulfonate as a cosurfactant
WO2015069760A1 (en) * 2013-11-05 2015-05-14 Temple University Of The Commonwealth System Of Higher Education Biscationic and triscationic amphiles as antimicrobial agents
US10136639B2 (en) 2013-11-05 2018-11-27 Villanova University Polycationic amphiphiles as antimicrobial agents
US10398142B2 (en) 2013-11-05 2019-09-03 Temple University Of The Commonwealth System Of Higher Education Polycationic amphiphiles as antimicrobial agents

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0737702A3 (en) * 1995-04-11 1998-03-25 Air Products And Chemicals, Inc. Partially methylated polyamines as epoxy curing agents
US6017561A (en) * 1997-04-04 2000-01-25 The Clorox Company Antimicrobial cleaning composition
US6270754B1 (en) 1997-04-04 2001-08-07 The Clorox Company Antimicrobial cleaning composition
US6080387A (en) * 1998-07-15 2000-06-27 The Clorox Company Aerosol antimicrobial compositions
US6482392B1 (en) 1998-07-15 2002-11-19 The Clorox Company Aerosol antimicrobial compositions
US6849581B1 (en) 1999-03-30 2005-02-01 Bj Services Company Gelled hydrocarbon compositions and methods for use thereof
US20100081844A1 (en) * 2005-11-04 2010-04-01 Charles Little Polycationic organic compounds
US8486427B2 (en) 2011-02-11 2013-07-16 Kimberly-Clark Worldwide, Inc. Wipe for use with a germicidal solution
US20140116690A1 (en) * 2012-10-26 2014-05-01 Basf Se Process for mineral oil production using surfactants at least comprising a secondary alkanesulfonate as a cosurfactant
WO2015069760A1 (en) * 2013-11-05 2015-05-14 Temple University Of The Commonwealth System Of Higher Education Biscationic and triscationic amphiles as antimicrobial agents
US10136639B2 (en) 2013-11-05 2018-11-27 Villanova University Polycationic amphiphiles as antimicrobial agents
US10398142B2 (en) 2013-11-05 2019-09-03 Temple University Of The Commonwealth System Of Higher Education Polycationic amphiphiles as antimicrobial agents

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FR2111700A1 (enExample) 1972-06-09
IT1050150B (it) 1981-03-10
DE2151719A1 (de) 1972-04-20
GB1322636A (en) 1973-07-11
FR2111700B1 (enExample) 1975-06-06

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