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Publication numberUS3578667 A
Publication typeGrant
Publication dateMay 11, 1971
Filing dateMar 26, 1968
Priority dateMar 26, 1968
Publication numberUS 3578667 A, US 3578667A, US-A-3578667, US3578667 A, US3578667A
InventorsReginald L Wakeman, Joseph F Coates
Original AssigneeMillmaster Onyx Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Quaternary ammonium alicyclic carboxylates
US 3578667 A
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Description  (OCR text may contain errors)

3,578,667 QUATERNARY AMMONIUM ALICYCLIC CARBOXYLATES Reginald L. Wakeman, Philadelphia, Pa, and Joseph F. Coates, Washington, D.C., assignors to Millmaster Onyx Corporation, New York, N.Y.

No Drawing. Continuation-impart of application Ser. No. 563,388, July 7, 1966. This application Mar. 26, 1968, Ser. No. 715,963 The portion of the term of the patent subsequent to July 19, 1983, has been disclaimed Int. Cl. C07d 35/24 U.S. Cl. 260-286 10 Claims ABSTRACT OF THE DISCLOSURE A quaternary ammonium alicyclic dicarboxylate wherein the quaternary ammonium cation is the cationic residue of a quaternary ammonium compound having one alkyl group of 8 to 22 carbon atoms attached to the quaternary nitrogen and having a phenol coeflicient of at least 100 with respect to Staphylococcus awreus and Salmonella ryphosa at C., and wherein the anion is the anionic residue of an alicyclic dicarboxylic acid containing at least one ring of five or six carbon atoms, or the chlorine substitution product thereof.

This invention relates to microbiocidally active, relatively water-insoluble, compounds prepared by the reaction of water-soluble, microbiocidally active quaternary ammonium compounds with alicyclic dicarboxylic acids having at least one ring of five or six carbon atoms and having a total of not more than ten carbon atoms, preferably not more than nine carbon atoms, or the salts of such acids.

This is a continuation-in-part of co-pending application Ser. No. 563,388, filed July 7, 1966, now abandoned.

The quaternary ammonium compounds utilized in this invention as starting materials are preferably those that have one alkyl group of 8 to 22 carbon atoms attached to the quaternary nitrogen and which have a phenol coefficient of at least 100 with respect to Staphylococcus aureas and Salmonella typhosa at 20 C.

Typical examples of these quaternary ammonium compounds are alkyl trimethyl ammonium chloride, alkylbenzyl trimethyl ammonium chloride, and alkyl dimethyl benzyl ammonium chloride in which the alkyl group may have from 8 to 22 carbon atoms; alkyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride in which the alkyl radical may be isooctyl or nonyl and in which the phenyl radical may be substituted with a methyl group; 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, amyl, ethyl, diethyl, isopropyl, and tertiary butyl or with one, two or more halogen atoms such as chlorine; and alkyl dimethyl menaphthyl or tetrahydro menaphthyl ammonium chloride in which the alkyl radical contains from 8 to 22 carbon atoms; and quaternary ammonium compounds in which the nitrogen atom may be a member of a heterocyclic ring such as pyridine, isoquinoline, morpholine, and pyrrolidine, if desired and the alkyl group may have from 8 to 22 carbon atoms. Various other analogs of these quaternaries may be employed such, for example, as cetyl dimethyl ethyl ammonium bromide or oleyl dimethyl ethyl ammonium bromide.

It has generally been thought that quaternary ammonium compounds such, for example, as those of the prenited States Patent 0 ceding types which are microbiocidally active are not compatible, that is to say, lose their microbiocidal activity in the presence of anionic materials which render them insoluble in water.

It has now been found that highly germicidal and substantially water-insoluble compounds are formed by the reaction of microbiocidal water-soluble quaternary ammonium compounds with alicyclic dicarboxylic acids containing at least one ring having six carbon atoms, or with the chlorine substitution products of such alicyclic acids. This reaction may either be directly with the acids or with the water-soluble salts thereof depending on the solvent medium used. The reaction takes place upon mixture.

When using an aqueous medium, after thorough mixing, the organic product layer is separated from the aqueous layer (as with a separatory funnel) since two distinct phases are formed. Separation may be facilitated by the addition of an organic solvent immiscible with water. The product layer may be washed with water to remove any residual by-product salt or unreacted materials. The solvent, if any, may be evaporated and the product air or vacuum dried to a paste, wax, oil or solid.

As indicated above, it is not necessary to use an aqueous medium. Any solvent or solvent mixture in which the starting materials are soluble will be satisfactory. Nonaqueous solvents facilitate the separation of by-product inorganic salt and reduce the need for vacuum drying to get an anhydrous product. When a non-aqueous medium is employed, it is usually necessary to add a small amount of water to facilitate 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.

Exemplifying, but not limitative of the alicyclic dicarboxylic acids, generally, which may be utilized in this invention are such acids as tetrahydrophthalic acid, endomethylene tetrahydrophthalic acid, hexahydrophthalic acid, camphoric acid and the like, as well as their chlorinated derivatives, for example, chlorendic anhydride and the like.

An alternative method for the preparation of com pounds especially applicable to the treatment of fabric, ropes, net, woven and non-woven fabric and reticulated or convoluted materials, involves a two-step process. In the first step, the material is passed through a bath containing 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 without affecting 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 exhibit high microbiological activity despite their relative insolubility in water. Because of their unusual combination 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 anti-mildew 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 bacteriostatic films and molded objects deposited from such latices.

The compounds of this invention also possess effective antistatic properties and may be incorporated in or used as a coating upon any product that is subject to static electricity. For example. they may be used to coat or impregnate wood, paper, ceramics, natural or synthetic polymers, etc. They may be coated upon the surface of such products or intermixed with the components of a molded, cast or extruded product.

The compounds can be incorporated into cutting and grinding fiuids 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 cationic quaternary ammonium compound used in their preparation as well as the anionic compound reacted therewith.

The chemical. physical and biological properties of the products of our invention make them especially appropriate for the following applications when suitably incorporated in active amounts in an appropriate vehicle, binder, medium or substrate:

(1) Mildewproofing fabric, canvas, ropes, textiles, awnings, sails, tenting and other woven and non-woven reticulated materials.

(2) Paint mildewstats.

(3) Jet plane fuel additive to control growth of microorganisms.

(4) Odor preservative agents for clothes and shoes.

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

(6) Topical antiseptics.

(7) Antidandruff agents.

(8) Disinfection agents 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 algae.

(11) Wool preservative.

(12) Plant and tree spray to combat fungi.

(l3) Antimycotic agents for soap wrappers.

(l4) Self-sanitizing brushes.

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

(16) Mildewproofing of cellulosics, cardboard, fibreboard, paper and cordage.

(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 metal-working compounds.

(25) Additives for soap and for both anionic and nonionic detergents in liquid, bar, powder, bead, solution for hair and gut of man and and other forms to impart bacteriostatic and fungistatic properties thereto. (26) Antistatic oating and impregnants.

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 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 0.1 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 for bacterial growth.

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

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

EXAMPLE I A stock solution of the monosodium salt of d-camphoric acid was prepared. 60 ml. of this solution containing 0.027 chemical equivalents was mixed with 90 m1. of a solution containing the chemically equivalent amount of a commercial grade of alkyl dimethyl ethyl-benzyl ammonium chloride (Onyx Chemical Corporation's BTC- 471 in which the alkyl distribution is C 30% C 17% C 3% C The well agitated mixture was separated in a separatory funnel; the yellow oily layer was removed and dried to a yellow paste in 94% theoretical yield of alkyl dimethyl ethyl-benzyl ammonium camphorate.

EXAMPLE II To the same amount of the stock solution of the sodium camphorate as in Example I, was added 90 ml. of a solution of alkyl dimethyl benzyl ammonium chloride in stoichiometric proportions (Onyx Chemical Companys ETC-824 in which the alkyl distribution is C 30% C 5% C 5%C plus a small amount of henzene. The thoroughly agitated mixture was transferred to a separatory funnel and the oil layer was removed and dried in vacuo to yield a yellow paste in theoretical amount of alkyl dimethyl benzyl ammonium camphorate.

EXAMPLE III The same amount of the stock solution of sodium cam phorate as in Example I, was treated in a separatory funnel by mixing vigorously with ml. of a solution of a commercial grade of lauryl isoquinolinium bromide in stoichiometric proportion. The orange colored organic layer was dried in a vacuum oven to a brown paste. The yield was 86% of the theoretical of lauryl isoquinolinium camphorate.

EXAMPLE IV Chlorendic anhydride was hydrolyzed with aqueous sodium hydroxide to the di-sodium salt. A stock solution of about 11% concentration was prepared from this. 300 ml. of this solution containing 0.0783 equivalent was mixed vigorously with a chemical equivalent amount of a 10% solution of a commercial grade of the alkyl dimethyl ethyl-benzyl ammonium chloride of Example I. The mixture was transferred to a separatory funnel and the two layers were separated. The organic layer was dried in a vacuum oven to yield 83 grams of a yellow syrup or 97% of the theoretical of di(alkyl dimethyl ethyl-benzyl ammonium) chlorendate.

EXAMPLE V 300 ml. of the stock solution of the di-sodium salt of chlorendic acid of Example IV was reacted with 585 m1. of a chemically equivalent amount of the aqueous solution of alkyl dimethyl benzyl ammonium chloride used in Example H. The oily phase separated therefrom was vacuum dried to a yellow syrup amounting to 85 grams or 101% of the theoretical yield of di(alkyl dimethyl benzyl ammonium) chlorendate.

EXAMPLE VI 300 ml. of the stock solution of di-sodium chlorendate of Example IV and 630 ml. of a 10% solution in water and isopropanol of a commercial grade of lauryl isoquinolinium bromide were mixed vigorously. A small amount of benzene was added to facilitate separation. The organic phase was dried in a vacuum oven and 78 grams of a dark brown syrup was obtained or 98% of the theoretical yield of di(lauryl isoquinolinium) chlorendate.

EXAMPLE VII EXAMPLE VIII In a similar manner to that of Example VII, di-sodium hexahydrophthalate was reacted with the alkyl dimethyl ethyl-benzyl ammonium chloride of Example I. The product was a yellow paste and the yield was the theoretical of di(alkyl dimethyl ethyl-benzyl ammonium) hexahydrophthalate.

EXAMPLE ]X The results of static dilution tests performed upon the products of Examples I to VIII are shown in the following table wherein S.a. indicates Staphylococcus aureus, S.t. is Salmonella typhosa and A.n. is Aspergillus niger.

TABLE I Reciprocal of static dilution of product vs.

Product of quaternary Acid S.a. SJ. Am.

10 10 Aikyl ethyl-benzyl dimethyl {@fifigfifff: ammonium chloride Hexahydrophthalic- 10 10 10 Alkyl benzyl dimethyl am- {d-camphoric 10 10 10 monlum chloride. ghlorergiigfu 1%: it]; Lamyl imquinoumum {dliifitinci'f .II 10 10 104 Hexahydrophthalic- 10 10 1m Obviously, many modifications and variations of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

The invention claimed is:

1. A monoor di-salt of a quaternary ammonium cation, selected from the group consisting of alkyl isoquinolinium, alkyl dimethyl benzyl ammonium or alkyl dimethyl ethyl-benzyl ammonium in which alkyl has 8 to 22 carbons and an anion selected from the group consisting of tetrahydrophthalate, endomethylene tetrahydrophthalate, camphorate and chlorendate.

2. The compound of claim 1 wherein the quaternary ammonium cation is alkyl dimethyl ethyl-benzyl ammonium wherein the alkyl has 8 to 22 carbon atoms, and the dicarboxylate anion is camphorate.

3. The compound of claim 1 wherein the quaternary ammonium cation is alkyl dimethyl benzyl ammonium wherein the alkyl has 8 to 22 carbon atoms, and the dicarboxylate anion is camphorate.

4. The compound of claim 1 wherein the quaternary ammonium cation is alkyl isoquinolinium wherein the alkyl has 8 to 22 carbon atoms, and the dicarboxylate anion is camphorate.

5. The compound of claim 1 wherein the quaternary ammonium cation is di(alkyl dimethyl ethyl-benzyl ammonium) 'wherein the alkyl has 8 to 22 carbon atoms, and wherein the dicarboxylate anion is chlorendate.

6. The compound of claim 1 wherein the quaternary ammonium cation is di(alkyl dimethyl benzyl ammonium) wherein the alkyl has 8 to 22 carbon atoms, and wherein the dicarboxylate anion is chlorendate.

7. The compound of claim 1 wherein the quaternary ammonium cation is di(lauryl isoquinolinium), and wherein the dicarboxylate anion is chlorendate.

8. The compound of claim 1 wherein the quaternary ammonium cation is di(alkyl dimethyl ethyl-benzyl ammonium) wherein the alkyl has 8 to 22 carbon atoms, and wherein the dicarboxylate anion is hexahydrophthalate.

9. The compound of claim 1 wherein the quaternary ammonium cation is di(alkyl dimethyl benzyl ammonium) wherein the alkyl has 8 to 22 carbon atoms, and wherein the dicarboxylate anion is hexahydrophthalate.

10. The compound of claim 1 wherein the quaternary ammonium cation is di(lauryl isoquinolinium), and wherein the dicarboxylate anion is hexahydrophthalate.

References Cited UNITED STATES PATENTS 2,295,504 8/1942 Shelton 260-286X 3,024,283 3/ 1962 Metcalfe et a1. 260-567.6 3,147,182 9/1964 Masci et a1 260-286X 3,261,838 7/1966 Wakeman et al 260-286 3,299,094 1/1967 Weil 2605l4 3,403,170 9/ 1968 Corson et a1 2605l4 3,479,406 11/ 1969 Wakeman 2605 67.6

DONALD G. DAUS, Primary Examiner US. Cl. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3954846 *Dec 23, 1974May 4, 1976Agence Nationale De Valorization De La Recherche (Anvar)New quaternary ammonium salts of malic acid and their application in cosmetics
US3956271 *Feb 6, 1974May 11, 1976Sandoz Ltd.One step
US4038303 *Feb 20, 1976Jul 26, 1977Colgate-Palmolive CompanyQuaternary ammonium carbamide compounds
US4046873 *Feb 25, 1974Sep 6, 1977Colgate Palmolive CompanyAlicyclic amido-quaternary ammonium anti-bacterial agents
Classifications
U.S. Classification546/151, 162/161, 510/390, 544/108, 507/920, 106/18.31, 562/509, 252/8.57, 510/391, 8/188, 162/8, 523/122, 507/240, 510/133, 524/239, 546/347, 510/384, 562/502, 106/3, 510/477
International ClassificationC07D217/10
Cooperative ClassificationC07D217/10, Y10S507/92
European ClassificationC07D217/10
Legal Events
DateCodeEventDescription
Sep 2, 1986ASAssignment
Owner name: STEPAN COMPANY, NORTHFIELD, IL 60093 A CORP. OF DE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:MILLMASTER ONYX GROUP, INC., A CORP. OF DE.;REEL/FRAME:004606/0309
Effective date: 19860815
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MILLMASTER ONYX GROUP, INC., A CORP. OF DE.;REEL/FRAME:004606/0309
Jun 9, 1983ASAssignment
Owner name: BARCLAYS AMERICAN, 1 BUSINESS CREDIT, INC. 111 FOU
Free format text: SECURITY INTEREST;ASSIGNOR:MILLMASTER ONYX GROUP, INC., A DE CORP.;REEL/FRAME:004139/0941
Effective date: 19821222
Owner name: MILLMASTER ONYX GROUP, INC., A DE CORP.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KEWANEE INDUSTRIES, INC.;REEL/FRAME:004139/0909
Effective date: 19830407