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Publication numberUS3361794 A
Publication typeGrant
Publication dateJan 2, 1968
Filing dateApr 3, 1964
Priority dateApr 3, 1964
Publication numberUS 3361794 A, US 3361794A, US-A-3361794, US3361794 A, US3361794A
InventorsCoates Joseph F, Wakeman Reginald L
Original AssigneeMillmaster Onyx Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Microbiologically active quaternary ammonium compounds
US 3361794 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

v ing 3,361,794 MlCROBlOLOGICALLY ACTIVE QUATERNARY AMMONIUM COMPOUNDS Reginald L. Wakeman, Philadelphia, Pa, and Joseph F.

Coates, Washington, D.C., assignors, by niesne assignments, to Millmaster Onyx Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Apr. 3, 1964, Ser. No. 357,263 8 Claims. (Cl. 260--501.15)

The present invention has for its object the prepara tion of relatively water-insoluble, microbiologically active compounds by reaction of certain quaternary ant-- monium hydroxides or their Water-soluble salts with alkylsubstituted aromatic carboxylic acids or their water-soluble salts.

The quaternary ammonium compounds used in the process of this invention are all bacteriologically active, having a phenol coefiicient of at least 100 with respect to both Staphylococcus aureus and Salmonella iyp'hosa at 20 C., when determined by the standard method given in the United States Department of Agriculture Circular No. 198. They contain at least one carbon chain having from 8 to 22 carbon atoms and also possess at least one benzyl radical attached to the quaternary nitrogen atom. The benzyl radical may, if desired, be substituted by alkyl groups or halogen atoms. The quaternary ammonium compounds, moreover, possess only non-heterocyclic nitrogen atoms. In general, the quaternary ammonium compounds used in the present invention comply with the formula:

where R is an alkyl radical containing from 8 to 22 carbon atoms, an alkyl benzyl radical in which the benzyl group may contain a substituent methyl radical and in which the alkyl group contains 8 to 22 carbon atoms, or an alltyl phenoxy ethoxy ethyl radical in which the phenyl group'may contain a substituent methyl radical and R is a benzyl or substituted benzyl radical, or a methyl group if R is an all-:yl benzyl radical containing eight or more on )Ol'l atoms in its alkyl substituent. X in the above formula is chlorine, bromine, iodine, sulfate, methosulfate, ethosulfate and the like.

Typical examples of these quaternary ammonium compounds are alkyl dimethyl benzyl ammonium chloride in which the alkyl group may have from 8 to 22 carbon atoms, alkyl dimethyl substituted benzyl ammonium chlorides, in which the alkyl radical contains from 8 to 22 carbon atoms and in which the benzyl radical is substituted with one or more side chains Containing from 1 to 5 carbon atoms such, for example, as methyl, dimethyl, trimethyl, tetramethyl, ethyl, diethyl, isopropyl, tertiary butyl and isoamyl or with one, two, or more, halogen atoms such as chlorine or bromine, alkyl dimethyl menaphthyl ammonium chloride and alkyl dimethyl tctrahydromenaphthyl ammonium chloride in which the alkyl radical contains from 8 to 22 carbon atoms, alkyl benzyl trimethyl ammonium chloride in which the alkyl radical contains from 8 to 22 carbon atoms and in which the aromatic nucleus of the benzyl radical may, if desired, be substituted by one or more methyl or other lower alkyl groups, alkyl phenoxy ethoxy ethyl dimethyl benzyl ommonium chloride in which the alkyl radical may be isooctyl or nonyl, and mixtures of the aforesaid quaternary ammonium compounds.

The alkyl-aromatic monocarboxylic acids which are :d Jan. 2, i968 used in the present invention correspond. to the general formula RZCO H where n is any number from zero to four.

Typical examples of the alkyl-aryl. carboxylic acids which may be used in the practice of this in ention. in clude o, mand ptoluic acids, the various isomer:z at dimethyl benzoic acid and trimethyl benzoic acid, o ill" and p ethyl or isopropyl benzoic acid, hexyl, octyl, or decyl benzoic acid and the like, methylor ethylcinnamic acid or hydrocinnamic acid, the various isomers of meth, l== naphthoic acid the like.

The compounds of this invention may be prepared by mixing an aqueous solution of the quaternary ammonium salt or hydroxide ot the kind defined above with an aqm ous solution of the acid in question or with any of water-soluble salts.

After thorough mixing, the organic product layer arated from the aqueous layer (as with a separatory fun nel) since two distinct phases are formed. Separation may be facilitated by the addition of an organic solvent; im-- miscible with water. The product layer may be washed with water to remove any residual by-product salt r unreacted materials. The solvent, if any, may be evaporated and the product air or vacuum dried to a paste, wax; oil or solid.

It is not necessary to use an aqueous medium. A vent or solvent mixture in which the starting materia soluble will be satisfactory. Non-acqueous solvents facilitate the separation of by-product inorganic salt and rcduce the need for vacuum drying to get an anhydrous product. When a non-aqueous medium is employed, it usually necessary to add a small amount or; water to tacilitate ionic reaction.

The product may be used, if desired, without drying since any entrapped water is irrelevant to the microbiological activity of the compounds. In other applications, removal of Water may be essential for reasons not related to biological activity.

An alternative method for the preparation of cont pounds especially applicable to the treatment: of fabric, ropes, net, woven and non-woven fabric and reticulated or convoluted materials, involves a twostep process. in the first step, the material is passed through a bath con taining the anionic moiety. Excess solution is removed by methods well known to those skilled in the art. The treated material is then passed through a, second bath wherein the concentration of quaternary ammonium compound is such that the material pickup will result in an. equivalent amount of quaternary ammonium compound reacting with the anionic moiety, depositing the product in the most intimate way on the surface and in the interstices, convolutions and reticulations of the material.

The method of adjustment of solution concentration to achieve the required pickup is well known to those skilled in the art. The order of treatment may be reversed with out atfecting the biological activity or durability of the product on the material. The products of this invention may be formulated as Water dispersions by dissolving them in a water-miscible organic solvent such as acetone or methanol and diluting with water or by dissolving them in emulsifiable oils such, for example, as sulfonated castor oil or pine oil and diluting with water. In preparing aqueous dispersions, emulsifying agents such, for example.

as ethylene oxide condensates of alkyl phenols may be used with or without organic solvents.

It is surprising that the compounds of this invention exsolubility in water. Because of their unusual combnation of physical and microbiological properties, they can be used to impart laundry-resistant anti-microbial characteristics to textiles. They can also be used as the active agent in antimildew finishes for textiles which are resistant to leaching with water.

Although the compounds have low water solubility, they are compatible with various organic solvents, plasticizers and high molecular weight compounds. Consequently, they may be incorporated as anti-microbial agents in synthetic resins and plastics. The compounds are compatible with natural and synthetic rubber latices. Therefore, they may be used to prepare bactcriostatic illms and molded objects deposited from such latices.

The compounds can be incorporated into cutting and grinding fluids without precipitation. Also, they blend well with non-ionic and anionic surface active agents. In such compositions they retain their microbiological activity.

It will be understood that the properties of the products described herein will vary depending upon the nature of the quaternary ammonium compound used in their prep-- aration as well as the aromatic carboxylic acid or salt reacted therewith.

The chemical, physical and biological properties of the products of our invention make them especially approlpriate for the following applications when. suitably incororated in active amounts in an appropriate vehicle, bind- };rer, medium or substrate:

(I) Mildewproofing fabric, canvas, ropes, textiles, awn" ings, sails, tcnting and other woven and non-woven reticulated materials.

I (2) Paint inildewstats.

i (3) let plane fuel additive to control growth of micro- I organisms.

(4) Odor preservative agents for clothes and shoes.

(5) Mildew retardant and odor suppressant for shoes and other leather products.

(6) Topical antiseptics.

(7) Antidandrufl agents.

(8) Disinfection agents for hair and gut of man and beast.

(9) Bacteriostatic furniture dressing.

(10) Surface finishes for stone, plaster, tile, cement. brick and other inorganic building materials. to retard growth of microorganisms, fungi, mold and algaev l l) Wool preservative.

(12) Plant and tree spray to combat fungi.

(l3) Antimycotic agents for soap wrappers.

(i-l) Self-sanitizing brushes.

( l5) Mildewproofing agent in and on plastic and film.

(16) h lildewproofing of cellulosics, cardboard. fibre board. paper and corclage.

(17) Contact biostat for application to film, waxes and cloth to preserve cheese. meats and Vegetables and other food products.

(18) Algal inhibition, especially on surfaces and in solution where low foaming is desirable.

(19) Paper pulp slime control.

(20) Sanitizing agent for rug, carpet, curtains.

(21) Egg preservation.

(22) Adhesive preservation.

(23) Preservation of latex paints.

(24) Preservation of metalworking compounds.

(25) Additives for soap and for both anionic and non-= ionic detergents in liquid, bar, powder, bead, solution and other forms to impart bacteriostatic and fungistatic properties thereto.

The microbiological activity of our compounds has been evaluated for microbiological stasis by the Standard Tube Dilution Test, the technique for which is common knowledge to those skilled in the art. A Difco Bacto 4 CSMA Broth #0826 was used in the study. This test is used to determine the lowest concentration of microbiologically active compounds which will inhibit the growth of. the organism in question. For a wide range of applications, the inhibition of growth rather than outright kill is satisfactory.

Briefly put, the Tube Dilution Test consists in placing 9 cc. of the CSMA Broth in a test tube which is then sterilized in an autoclave. One cc. solution of the microbiologically active compound at an appropriate concentration is added to the test tube which is then inoculated with 0.l cc. of a twenty-four hour old culture of the organism under study. The test tube is then incubated at 37 C. for forty-eight hours and observed 'Qor bacterial growth.

The same procedure is followed for fungi. i such tests. however, the tubes are incubated for fourteen days at a temperature suitable for optimum fungal growth, usual ly 25 C.

The invention is illustrated by, but not restricted to, the following examples:

Example I A stock solution was prepared containing 5% by weight of the sodium salt of p-toluic acid. To a vigorously agitated aliquot of this solution containing 0.04l equivalent weight of the compound was added the chemical y equiv alent amount of an 11% solution of a commercial grade of alkyl dimethyl ethyl-benzyl ammonium chloride (Onyx Chemical Corporation, BTC471, in which the alkyl diStributiOn is C12, C14, C16, C18) The agitated mixture was poured into a separatory funnel and separated into two phases. The organic product layer was removed and vacuum dried to a yellow paste, in. theoretical yield, of alkyl dimethyl ethyl-benzyl ammonium p-toluate.

Similar products were prepared by replacing the ptoluic acid with m-toluic acid and otoluic acid.

Example 11 The solution of sodium p-toluate of Example l was treated in the same manner and in the same amount with a chemically equivalent amount of a solution of a com mercial grade of; alkyl dimethyl benzyl ammonium chloride (Onyx Chemical Corporation, ETC-824," in which the alkyl distribution is 60% C 30% C 5% C 5% C The agitated mixture was transferred to a separatory funnel and separated into two phases. The separated or ganic compound layer on vacuum drying yielded a white paste, in theoretical yield, of alkyl dimethyl benzyl ammonium, p-toluate.

Similarly, by substituting m-toluic acid for p-toluic acid, the alkyl dimethyl benzyl ammonium m-toluate was obtained in theoretical yield.

Example I]! A stock solution was prepared containing 5% by weight of the sodium salt of octyl-benzoic acid. An aliquot con taining 0.064 equivalent weight of the compound was agitated vigorously, while adding the chemically equiv alcnt amount of an ll% solution of the alkyl dimcthyl benzyl ammonium chloride of Example ll. The agitated mixture was separated in a separatory funnel. The organic product. layer was vacuum dried to a yellow paste. in theoretical yield, of alkyl dimethyl benzyl ammonium octyl-benzoate.

Example I V The products of: Example I and ll were tested by the Standard Tube Dilution Test described above against Staphylococcus (Ill/(HIS (8.4.), Sa/nm/zellu Iyp/mm (St) and Aspergillus nigcl (A .15.). Results are shown in Table l.

We claim: 1. A compound having the structure:

wherein R is a member of the group consisting of alkyl, alkyl benzyl, alkyl methyl-benzyl, alkyl phenoxy ethoxy ethyl and alkyl phenoxy ethoxy ethyl having a methyl substituent on the phenyl group, the alkyl in each case having 8 to 22 carbon atoms, R" is a member of the group consisting of benzyl, lower alkyl-substituted benzyl and methyl, R" being methyl when R is alkyl benzyl, R is a member of the group consisting of alkyl substituted benzene, alkyl substituted naphthalene, alkyl substituted diphenyl and alkyl substituted diphenyl oxide, said alkyl having 1 to 22 carbon atoms, and Z is a member of the group consisting of (CH and (CH ),,-2H wherein n is a number from to 4.

2. The compound as defined in claim 1, wherein the carboxylic acid is selected from the group consisting of o-, m, and p-toluic acids, dimethyl benzoic acid, trimethyl benzoic acid and its isomers, 0-, mand p-ethyl benzoic acids, o-, mand p-isoproyl benzoic acid, o-, mand p-hexyl benzoic acid, o-, mand p-octyl benzoic acid, o-, mand p-decyl benzoic acid, o-, m and p-methyland ethyl-cinnamic and hydrocinnamic acids, and methyl naphthoic acids, and its isomers.

3. Alkyl dimethyl ethyl-benzyl ammonium p-toluate wherein the alkyl has 12 to 18 carbon atoms.

4. Alkyl dimethyl ethyl-benzyl ammonium p-toluate wherein the alkyl has 12 to 18 carbon atoms.

5. Alkyl dimethyl ethyl-benzyl ammonium o-toluate wherein the alkyl has 12 to 18 carbon atoms.

6. Alkyl dimethyl benzyl ammonium p-toluate wherein the alkyl has 12 to 18 carbon atoms.

7. Alkyl dimethyl benzyl ammonium m-toluate where in the alkyl has 12 to 18 carbon atoms.

8. Alkyl dimethyl benzyl ammonium octyl-benzoate wherein the alkyl has 12 to 18 carbon atoms,

References Cited UNITED STATES PATENTS 2,108,765 2/1938 Domagk 260-567 2,676,986 4/1954 Wakeman et a1. 260567 2,695,840 11/1954 Leppla 260-501 OTHER REFERENCES Ishidate et 211.: J. Pharm. Soc., Japan 69, 518-52 (1949), CA. relied on, vol. 44, column 4202b (1950),


M. WEBSTER, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2108765 *Apr 7, 1934Feb 15, 1938 Preserving and disinfecting media
US2676986 *Feb 15, 1950Apr 27, 1954Onyx Oil & Chemical CompanyEthylbenzyl, lauryl, dimethyl ammonium salts
US2695840 *Nov 21, 1951Nov 30, 1954 Methods and compositions for killing
Referenced by
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US4804492 *Dec 16, 1987Feb 14, 1989Sterling Drug Inc.Liquid sanitizing and cleaning compositions with diminished skin irritancy
US5346725 *Aug 18, 1993Sep 13, 1994Targosz Eugene FTreatment for nylon and other textiles
US5458737 *Jul 27, 1993Oct 17, 1995Hoechst Celanese CorporationQuaternary compounds as brightness enhancers
US5560805 *Jul 27, 1993Oct 1, 1996Hoechst Celanese CorporationEnhanced decolorization of waste paper with selected amines
US5580422 *Jul 27, 1993Dec 3, 1996Hoechst Celanese CorporationBrightening color dyed wastepaper with a bleaching agent and a quaternary compound
US5833741 *Jan 16, 1997Nov 10, 1998Lonza Inc.Waterproofing and preservative compositons for wood
US20040115249 *Dec 8, 2003Jun 17, 2004Raczek Nico N.Ionic compounds of quaternary ammonium cations with anions of preservation acids, preparation thereof, and use thereof for preservation
WO1996005916A1 *Aug 17, 1994Feb 29, 1996Targosz Eugene FTreatment for nylon and other textiles
U.S. Classification562/493, 504/158, 252/8.57, 162/72, 106/18.32, 562/495, 562/490, 44/408, 106/18.34, 504/142, 504/160, 162/161, 504/157, 44/369, 44/422, 562/475, 162/5, 162/76
International ClassificationC07C63/00, A01N33/00, B65D81/28, A01N33/12, A23L3/3463, C07C63/04
Cooperative ClassificationC07C63/04, B65D81/28, A23L3/3463, A01N33/12
European ClassificationA23L3/3463, A01N33/12, B65D81/28, C07C63/04
Legal Events
Jun 9, 1983ASAssignment
Effective date: 19821222
Effective date: 19830407