US3050521A - N-alkylbenzyl-n-dodecenyl quaternary ammonium salts - Google Patents

Description

United States Patent Ofiiee w 3,5 0,521 Patented Aug. 21, 1952 3,05%,521 N-ALKYLBENZYL-N-DODECENYL ONIUM SALTS Warren D. Niederhauser, Huntsville, Ala, assignor to QUATE'RNARY Rohm & Haas Company, Philadelphia, Pa, 21 cor ora.

tion of Delaware N Drawing. Filed Apr. 3, 1959, Ser. No. 303,835 7 Claims. (Cl. 260-247) in which X is preferably a halogen 'having an atomic weight between about 35.5 and 127, R is an alkyl group of six to eight carbon atoms, and the R groups, taken individually, represent alkyl groups of no more than two carbon atoms and, taken collectively,'represent a divalent saturated aliphatic chain of four to five atoms which jointly with the amino nitrogen forms a fiveto six-sided monoheterocyclic amine. Divalent in the above sense is to be construed to mean a, w divalency, that is, one valence at each end of the chain.

The symbol X is preferably chlorine, bromine, or iodine. Chlorine is the preferred representation of X. it will be apparent to one skilled in the art that other anions may be satisfactorily employed such as sulfate, methylsulfate, phosphate, acetate, citrate, tartrate, and the like, which may be supplied directly or by metathesis with the halide form of the present compounds or by the use of an anion exchange resin. Generally, an anion having a group weight of up to about 127 is desired.

The R groups, taken singly, may represent alkyl groups of no more than two carbon atoms, that is, methyl or ethyl groups, in which case the R groups may be the same or different. The R groups, taken collectively and in conjunction with the amino nitrogen, may stand for a morpholino, thiamorpholino, pyrrolidinyl, or piperidino group, and these groups having a lower alkyl substituent, such as a methyl or ethyl group.

The symbol R represents an alkyl group of six to eight carbon atoms, that is, hexyl, heptyl, or octyl. The R" groups may be straight or branched chains in any of the known configurations. For instance, the octyl group may be n-octyl, isooctyl, tert-octyl, 2,4-dimethylhexyl, 1,6-dimethylhexyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, 3-propylpentyl, 2-methyl-4-ethylpentyl, and the like. The R group is preferably in the para position on the benzene ring with respect to the methyl ring group, but it may satisfactorily be in the ortho or meta position.

The dodecenyl group may be a straight or branched chain in any of the known spatial configurations, including n-dodecenyl, isododecenyl, 1,IO-dimethyI-Z-decenyl, 2,7-dimethyl-1-decenyl, 1-ethyl-2-methyl-5-nonenyl, 4- propyl-Z-nonenyl, 5-butyl-2-octenyl, l,2-diethyl-4-octenyl, l-propyl-6-ethyl-3-heptenyl, and the like. The double bond may be at any possible location. A common commercial form of the dodecenyl group that yields a compound of this invention that is particularly eifective for the present purposes is tetramethyloctenyl, in which there are two methyl ,groups on each of the number five and seven carbon atoms, and the double bond is at the number two location.

The present quaternary ammonium compounds may be prepared preferably in one of two equally satisfactory ways. In one case, analkylbenzyldialkylamine is reacted with a dodecenyl halide. Alternatively, the instant compounds may be prepared by reacting a dodecenyldialkylamine with an alkylbenzylhalide. These reactants, set forth above and hereinafter, used for the preparation ofthe quaternary ammonium compounds of this invention are known or prepared by known methods.

Typical of the reactants that may be employed in the present instance, when an alkylbenzyldialkylamine is reacted with a dodecenyl halide, include oc-tylbenzyldimethylamine, octylbenzyldiethylamine, hexylbenzyldimethylamine, heptylbenzylmethylethylamjne, hexylbenzylmorpholine, heptylbenzylpyrrolidine, octylbenzylpiperidine, octylbenzylthiamorpholine, dodecenyl chloride, dodecenyl bromide, and dodecenyl iodide. When a dodecenyldialkylamine is reacted with an alkylbenzyl halide, as reactants there may be typically employed dodecenyldimethylamine, dodecenyldiethylamine, dodecenylmethy ethylamine, dodecenylmorpholine, dodecenylthiamorpholine, dodecenylpyrrolidine, dodecenylpiperazine, dodecenylpiperidine, hexylbenzyl chloride, heptylbenzyl chloride, octylbeuzyl chloride, octylbenzyl bromide, and octylbenzyl iodide.

The. present quaternary ammonium compounds may be prepared by either of two equally satisfactory methods, as stated heretofore. The choice of either method is purely a matter of convenience. Both methods are conducted under essentially the same conditions. The reactants unite on a substantially equimolccular basis to produce substantially quantitative results.

The present reaction is consummated by bringing the reactants together at a reacting temperature, usually in the range of about 50 to 150 C., with the range of about 60 to C. being preferred. It is often advantageous to use the reflux temperature of the reaction mixture when solvents are used. Reflux temperatures of up to about 225 C. and above are practical. The reactants may be supplied to the reaction mixture in equivalent amounts or either reactant may be slightly or greatly in excess, as desired. An inert volatile solvent may be advantageously employed, if desired. Suitable in this respect are water, acetonitrile, nitromethane, dimethylformamide, toluene, benzene, xylene, isopropanol, butanol, isopropyl ether, and the like, and mixtures thereof.

Reaction times of about two to twenty-four hours are generally employed depending largely on the reaction temperature, solvent, and individual reactants used. The time of reaction is not critical but merely influences the yield. As will be apparent to one skilled in the art, the longer reaction times generally favor higher yields, up to a point, and, of course, some reactants combine more speedily than others. in order to assure completeness of reaction and concomitant substantially quantitative results, if desired, there may be determined the amount of ionizable halide formed in the reaction mixture. When the theoretical amount of ionizable halide is present, the reaction is complete. At the conclusion of the reaction any solvent used is removed preferably by distillation, preferably under reduced pressure. The product is preferably washed with hexane, heptane, or the like, to remove any unused starting material and then isolated by removing volatile components, preferably under reduced pressure or on a steam bath. Recrystallization of the product may be accomplished, if desired, from a suitable solvent, such as ethyl acetate.

It is possible, and frequently advantageous, in the preparation of some of the instant compounds to first prepare the halide form, such as chloride, in a manner already set forth, and then prepare any other desired form Within the present definition by metathesis or ion exchange methods. For instance, any of the present compounds in halide form may be converted to the hydroxide form through the use of silver oxide, or the like, and then converted to any desired anion form by acidifying with an acid of choice such as sulfuric, phosphoric, acetic, and others within the range and spirit of this invention. As an alternative, an anion-exchange resin may be employed. Any of the present compounds, in halide or hydroxide form, may be converted to any desired anion form through the use of an anion-exchange resin in the desired anion form. For instance, there may be used an insoluble, cross-linked, styrene-divinylbenzene copolymeric quaternary ammonium salt in its sulfate, phosphate, or the like, form to convert a present compound in halide or hydroxide form to a desired form, such as sulfate, phosphate, and the like.

The quaternary ammonium compounds of this invention are gene-rally white to gray waxy or solid materials that are outstanding in bacteriostatic and bactericidal activity. The present compounds are especially effective in controlling Micrococcus pyogenes var. aureus and Salmonella typhosa, as determined by the standard AOAC phenol coefiicient test. The present compounds give values in the range of about 300 to 650 and above against Salmonella typhosa and 715 to 1100 and above against Micrococcus pyogenes var. aareas; For instance, N octylbenzyl N dodecenyl N,N dimethylammonium chloride gives a value of 430 against Salmonella typhosa and 715 against Micrococcus pyogenes var. aareus and, correspondingly, N-hexylbenzyl-N-dodecenyl-N,N-dimethylarnmonium chloride gives values of 625 and 1000. Similar results are obtained with the other compounds of this invention. The compounds of this invention are also effective in controlling Escherichia coli in hard water as evaluated by the standard Chambers Modification of the Weber-Black Test (Journal of the Association of Official Agricultural Chemists, volume 41, No. 3, August 1958). The values obtained in the Chambers Modification of the Weber-Black Test indicate, in parts per million as calcium carbonate, the greatest water hardness at which the tested compound will kill in 30 seconds at least 99.999% of the defined amount of Escherichia coli used. The 99.999% standard is that set by the United States Department of Public Health and is a very rigid one to achieve. The compounds of this invention in the Standard Chambers Modification of the Weber-Black Test consistently achieve values of 700 and more. lllustratively, N-dodecenyl N,N dimethyl N octylbenzylammonium chloride gives values of 700 to 750 in this test. The very high values in this test against Escherichia coli in hard water are surprising in the light of the known diminution of bactericidal properties of quaternary ammonium compounds in the presence of hard water It is unexpected and quite advantageous that the present compounds exhibit such Superior activity against Micrococcas pyogenes var. aareus, Salmonella typhosa, and Escherichia coli in hard water. Because of such superior bactericidal activity, one may employ a single compound of this invention to control at least these three bacteria at the same time, whereas the closest prior art compounds require at least two for somewhat comparable, although actually inferior, activity. Therefore, the compounds of this invention provide a means for treating contaminated Waters, premises, and equipment by the use of a single bactericide, particularly when the three aforementioned bacteria are considered.

The compounds of this invention also exhibit strong bacteriostatic and bactericidal activity toward S. fecalis, N. catarrhalis, B. suis, and C. welchii, among others, in a wide range of dilutions.

The compounds of this invention are useful fungicides in dilutions down to /2 ounce in 100 gallons of water and lower, particularly against Stemphyliam sarcinaeforme and Monilinia fructicola. These compounds exethanol, to 40% soda ash, 20 to 40% sodium metasilicate, and the remainder sodium tripolyphosphate. One ounce of this formulation is used per gallon of water. For sanitizing citrus fruit there is preferably used one part of a present compound in 5000 parts. of water. For use in dairy farms, there may be used 10% of a quaternary ammonium compound of this invention, 10% of octylphenoxypolyethoxyethanol, 7% of trisodium phosphate, and 73% of Water. One ounce of this solution is used per four gallons of water. The instant compounds in aqueous solution in amounts of about 0.5 to one ounce to one hundred pounds of dry fabric, are excellent as a final diaper rinse to prevent diaper rash. These compounds are also excellent premise sanitizers where they may be employed in concentrations of about 0.1 to 2.0% in aqueous cleaning solutions.

This application is a continuation-in-part of application Serial No. 549,515, filed November 28, 1955, now abandoned.

The quaternary ammonium compounds of this invention and the method for their preparation may be more fully understood from the following examples which are presented by way of illustration and not by way of limitation. Parts by weight are used throughout.

Example 1 There are added to a reaction vessel 15.5 parts of hexylbenzyldimethylamine, 17 parts of dodecenyl chloride, and 9 parts of acetonitrile. The reaction mixture is stirred and heated at reflux for twelve hours. The acetonitrile is removed by distillation atreduced pressure. The product is washed with hexane. The hexane is removed by distillation at reduced pressure leaving the product. The product contains 8.7% chlorine (9.1% theoretical), is identified as N-hexylbenzyl-N-dodecenyl- N,N-dimethylammonium chloride, and has a formula corresponding to CH3 011 In like manner, there is prepared from dodecenyl bromide and heptylbenzyldiethylamine, the compound having the formula A mixture of 26.1 parts of hexylbenzylmorpholine, 29.4 parts of dodecenyl iodide, and 40 parts of isopropanol is heated at reflux for sixteen hours. The isopropanol is stripped off, leaving as the residue the product which corresponds to the compound having the formula The same result is obtained by similarly reacting hexylbenzyl iodide and dodecenylmorpholine.

Example 3 There are introduced into a reaction vessel 23.9 parts of octylbenzyl chloride, 26.5 parts of dodecenylpiperidine, and 50 parts of nitromethane. The mixture is heated at 75 to 85 C. for twenty hours. The nitromethane is removed by distillation under reduced pressure. The product is washted with heptane and then dried by stripping off the volatile components. The product corresponds to the formula.

01 S I TCH2Cs 17 lir zs Analogously, there is prepared, from dodecenyl bromide and hexylbenzylthiamorpholine, the compound having the formula Example 4 CH CH In like manner, there is prepared, from octylbenzylmethethylamine and dodecenyl bromide, the compound having the formula CH3 Cr s Example 5 There are added to a reaction vessel 26.9 parts of heptylbenzyl bromide, 23.7 parts of dodecenylpyrrolidine, and 60 parts of dimethylformamide. The reaction mixture is held at 140 to 146 C. for twelve hours. The dimethylformamide is removed by distillation under reduced pressure leaving the product which has the formula The identical result is obtained by similarly reacting dodecenyl bromide and heptylbenzylpyrrolidine.

Example 6 A mixture of 21.1 parts of hexylbenzyl chloride, 24 parts of dodecenylmethylethylamine, and 50 parts of water is heated at reflux for ten hours. The Water is removed by evaporation on a steam bath. The product is washed with hexane and dried by distillation'under reduced pressure. The product corresponds to the formula In like manner, there is made, from octylbenzyl bromide and dodecenyldiethylamine, the quaternary ammonium compounds N-octylbenzyl-N-dodecenyl-N,N-diethylammonium bromide.

Example 7 There is prepared N-hexylbenzyl-N-dodecenyl-N,N-dimethylammonium phosphate by passing the corresponding halide form of the quaternary ammonium compound through a bed of chloromethylated and aminated styrene divinylbenzene anion-exchange resin in free base form and then titrating with phosphoric acid. The same compound is prepared by first converting the anion-exchange resin to the phosphate form and then passing the chloride form of the quaternary ammonium compound through a bed of the anion-exchange resin in phosphate form. The compound N-octylbenzyl N dodecenyl-N,N-diethylammonium sulfate is prepared in a similar Way.

I claim:

1. As a new composition of matter, the quaternary ammonium compound having the formula in which R is an alkyl group of six to eight carbon atoms, the R groups taken singly represent alkyl groups of no more than two carbon atoms and taken collectively represent a saturated aliphatic chain of a,w-divalency having four to five atoms which jointly with the amino nitrogen atom forms a fiveto six-sided monoheterocyclic amine from the class consisting of morpholino, thiamorpholino, piperidino, and pyrrolidinyl, and X is an anion from the group consisting of chloride, bromide, iodide, sulfate, methylsulfate, phosphate, acetate, citrate, and tartrate.

2. As a new composition of matter, the quaternary ammonium compound having the formula 5. As a new composition of matter, N-octylbenzyl-N- dodecenyl-N,N-dimethylammonium chloride.

6. As a new composition of matter, N-octylbenzyl-N- dodecenyl-N,N-diethylammonium sulfate.

7. As a new composition of matter, N-heptylbenzyl-N dodecenylpyrrolidinium bromide.

No references cited.

Claims (2)

1. AS A NEW COMPOSITION OF MATTER, THE QUARTERNARY AMMONIUM COMPOUND HAVING THE FORMULA

4. AS A NEW COMPOSITION OF MATTER, N-HEXYLBENZYL-NDODECENYLMORPHOLINIUM IODIDE.