US2178353A - High molecular weight tetravalent sulphur compounds and process for their production - Google Patents

Description

Patented Oct. 31, 1939 ,178,353

lED STATES RAENT OFFICE HIGH MOLECULAR WEIGHT TETRAVALENT SULPHUR COMPOUNDS AND PROCESS FOR THEIR PRODUCTION James H. Werntz, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application July 21, 1937,

Serial No. 154,827

. 12 Claims. (01. 260-327) This invention relates to processes for the prowherein R and R1 represent aliphatic radicals,

duction of long chain alkyl derivatives, and more particularly refers to processes for the production of long chain thetine compounds and the products thereof.

It is an object of this invention to produce hydrocarbon derivatives which are of particular value in the many processes wherein surface active materials are required. A further object is to produce long chain alkyl derivatives of sulphur. A still further object is to produce a new class of surface active agents which possess satisfactory wetting, penetrating, dispersing and detergent properties. A still further object is to produce long chain alkyl thetines which are useful in place of or in conjunction with soap and soap substitutes. A still further object is to produce a new class of soap substitutes which may in general be used for all the purposes wherein soap and soap substitutes have been used or are capable of use. Additional objects will become apparent from a consideration of the following description and claims.

This invention is directed to tetravalent sulphur compounds having the following general formula:

have the same definition as in the immediately preceding formula:

In its preferred embodiment this invention is directed to thetine-type compounds which may be designated for the most part by the following general formula:

m cnmc 0 on R2 represents hydrogen or an aliphatic radical, the carboxyl group is separated from S by no more than four carbon atoms, X represents an anion, and one of the aliphatic radicals contains 5 from twelve to eighteen carbon atoms. These products may be produced in accordance with various processes which will hereinafter be described in detail. One illustration of these processes is the reaction of a dialkyl sulphide with a 10 halogenated fatty acid or ester or salt of such acid. One of the aliphatic radicals, represented by R, R1 and R2, should advisably contain from twelve to eighteen carbon atoms, although when R2 is the long chain aliphatic radical it may 15 contain a smaller number of carbon atoms than in the case of R and R1. For instance, R2 might contain from ten to sixteen carbon atoms. The remaining aliphatic radicals are preferably of relatively low molecular weight such as methyl, 2() ethyl, propyl, isopropyl, and the like.

The invention may be more readily understood by a consideration of the following illustrative examples in which the quantities are stated in parts by weight:

Example 1 layers which were present at first have now become compatible and after cooling the product crystallized. After recrystallizing twice from acetone, the crystals softened at 67 C. and 35 melted finally at 108 C. Analysis indicated the product to contain 10.6% sulphur, the theoretical value being 10.3% sulphur. The crystals are very hygroscopic and dissolve in water to give clear solutions which foam. Aqueous solutions are not 40 precipitated by calcium chloride solution and when a strip of soiled felt was stirred around in the hard water solution the felt was cleansed. This compound, when tested in a Launderometer in hard, alkaline, soft and acid water, cleansed soiled felt as well as an alcohol sulphate detergent.

Example 2 by weight of potassium hydroxide. A precipitate 55 formed at once which was filtered oil and the alcohol solution allowed to evaporate slowly. A white crystalline mass soluble in water remained. This is dissolved in 240 parts by weight of hot acetone and filtered. On cooling, needles separated from the acetone solution but the needles soon formed a gum. The acetone solution was allowed to evaporate and the gummy mass dried over sulphuric acid in a vacuum desiccator. It did not contain chlorine and analyzed 12% sulphur, the calculated value being 11.7% sulphur. The product weighed 6 parts by weight. This material dissolves readily in water to form solutions which foam. It is exceptionally efiective as an assistant in the mercerizing of cotton cloth.

Example 3 Bromide of benzyl octadecyl thetine. 33.3 parts by weight of octadecyl bromide and 18.2 parts by weight of benzyl thioglycollic acid were warmed together at about 50 C. with occasional Example 4 Chloride of octadecyl benzyl thetine. 7.5 parts by weight of benzyl octadecyl sulphide and 1.9 parts by weight ofchloroacetic acid were heated on the steam bath for two hours at the end of which time the solution was homogeneous. on cooling, the product crystallized and was only slightly soluble in'water. When the chloride of octadecyl benzyl thetine was heated one hour with an alcoholic solution containing sodium hydroxide, the octadecyl benzyl thetine which formed was soluble iii water and the solution foamed.

' Example 5 Bromide of octadecyl ethyl alpha lauroyl thetine. 3.1 parts by weight oi octadecyl ethyl sulphide and 2.8 parts by weight of alpha bromolauric acid were heated at IO- C. After 1%.

hours heating the product was a clear liquid which solidified on cooling. After warming eight hours, the bromide of octdecyl ethyl alpha lauroyl thetine dissolved. readily in cold dilute sodium hydroxide and the solution formed a persistent foam. On acidification the product continued to foam. The product was refluxed one hour with 10 parts by weight of alcohol containing 0.44 part by weight of sodium hydroxide and a precipitate of sodium bromide separated from the solution,

The alcohol solution was decanted, the alcohol evaporated and the residue which is octadecyl ethyl alpha lauroyl thetine was found to be sparingly soluble in dilute alkali and dilute acid solutions.

Example 6 Bromide oi octadecyl ethyl alpha propionyl thetine. 3.1 parts by weight of octadecyi ethyl sulphide and 1.5 parts by weight of alpha bromopropionic acid were warmed together at 70-80 C. for 1% hours at the end of which time the two materials formed a homogeneous mixture. The bromide of octadecyl ethyl alpha propionyl thetine was refluxed one hour with 10 parts by weight of alcohol containing 0.44 part by weight of sodium hydroxide and a precipitate of sodium bromide separated from the solution. The alcohol solution containing octadecyl ethyl alpha propionyl thetine was decanted and poured into water. It was sparingly soluble in dilute alkali and dilute acid solutions and the solutions foamed very much.

' Example 7 Bromide of dodecyl methyl alpha lauroyl thetine. 2.2 parts by weight of dodecyl methyl sulphide and 2.8 parts by weight of alpha bromolauric acid were heated at '7080 C. for eight hours. The product, the bromide of dodecyl methyl alpha lauroyl thetine, was soluble in cold dilute sodium hydroxide solution and formed a persistent foam. The product was next heated one hour at the reflux temperature with 10 parts by weight of alcohol containing 0.44 part by weight of sodium hydroxide and a precipitate of sodium bromide separated from the solution. The alcohol solution containing dodecyl methyl alpha lauroyl thetine was decanted and poured into water. It was very soluble in both acid and alkaline solutions and the solutions produced a persistent foam when shaken.

Example 8 Bromide of dodecyl methyl thetine. 2.2 parts by weight of methyl dodecyl sulphide and 1;; parts by weight of alpha bromo acetic acid were heated eight hours at 7080 C. at the end of which time the mixture was homogeneous. The product, the bromide of dodecyl methyl thetine, was soluble in dilute sodium hydroxide solution and foamed. When the product was heated one hour at the reflux temperature with 10 parts by weight of alcohol containing 0.44 part by weight of sodium hydroxide a precipitate of sodium bromide separated from the solution. The alcohol solution containing dodecyl methyl thetine was decanted and poured into water. It was very soluble in alkaline solutions which gave persistent teams when shaken.

Example 9 Bromide of dodecyl methyl alpha propionyi thetine. 2.2 parts by weight of dodecyl methyi sulphide and 1.5 parts by weight of alpha bromopropionic acid were heated together two hours at 70-80 C. after which time the reactants were compatible and the product was soluble in water to give foaming solutions. The product, the bromide of dodecyl methyl alpha propionyl thetine, was heated one hour with 10 parts by weight of alcohol containing 0.44 part by weight of sodium hydroxide and a, precipitate of sodium bromide separated from the solution. The alcohol solution containing dodecyl methyl alpha propionyl thetine was decanted and poured into water. It gave perfectly clear solutions in both acid and alkaline solutions. which foamed persistently.

Example 10 Bromide of dodecyl methyl beta propionyl the tine. 2.2 parts by weight of dodecyl methyl sulphide and 1.5 parts by weight of beta brornopropionic acid were heated together at 70-86 6. After warming three hours the product was soluble in water, in dilute sodium hydroxide solution and in dilute hydrochloric acid solution, and foamed in each case. The product was refluxed for one hour with 10 parts by weight of alcohol containing 0.44 part by weight of sodium hydroxide and a precipitate of sodium bromide separated from the solution. The alcohol solution containing dodecyl methyl beta propionyl thetine was decanted and poured into water. It was very soluble in alkaline solutions which foamed when shaken.

Example 11 Bromide of benzyl octadecyl alpha lauroyl thetine. 3.8 parts by weight of benzyl octadecyl sulphide and 2.8 parts of alpha bromolauric acid were warmed together at 70-80 C. After heating eight hours the product, the bromide of benzyl octadecyl .alpha lauroyl thetine, was soluble in dilute sodium hydroxide solution and foamed very much. Itcontinued to be soluble on acidification. The product was refluxed for one hour with 10 parts by weight of alcohol containing 0.44 part-.by weight of sodium hydroxide and a precipitate of sodium bromide separated from the solution. The alcohol solution containing benzyl octadecyl alpha lauroyl thetine was decanted and poured into water. It was slightly soluble in dilute acid and alkali solutions which foamed when shaken.

Example 12 Chlorides of a mixture of Ca to C20 alkyl methyl thetines. The mixture of alcohols obtainable by the catalytic carboxylic hydrogenation of coconut oil and containing approximately 0.5% hexanol, 9.2% octanol, 6.8% decanol, 44.2% dodecanol, 18.2% tetradecanol, 13.1% hexadecanol, 6.3% octadecanol and 1.7% eicosyl alcohol was converted to the bromide, then to the mercaptan and finally to the mixture of methyl alkyl sulphides. 23 parts by weight of the mixture of methyl alkyl sulphides and 9.5 parts by weight of chloroacetic acid wereheated at 60 C. with stirring. The viscous oil representing the chlorides of the mixed alkyl methyl thetines. was soluble in water and gave clear solutions which foam.

32.5 parts by weight of the chlorides of the mixed alkyl methyl thetines was treated in alcohol solution with 5.6 parts by weight of potas sium hydroxide and the precipitate of potassium chloride filtered ofi. The alcohol was evaporated and there remained a viscous oil which represents the mixed alkylthetines. This product dissolves readily in Water to give foaming solutionsthat are efiective as mercerizing assistants.

It is to be understood that the above examples are illustrative merely of a relative few of the processes wherein the products described within the scope of the present invention may be produced. These examples may be varied widely, both with respect to the reactants and the conditions of reaction, without departing from the scope hereof.

It is to be understood that the preferred compounds are tetravalent sulphur derivatives containing a long chain aliphatic radical and an oxygen-containing acid group or derivative thereof, advisably a carboxylic acid group. In these compounds the oxygen-containing group may be present on the same substituent as the long chain aliphatic radical or it may be present on a different substituent. This acid group should preferably be substituted on the radical in such a.

position that it is not separated from the nuclear atom of the resulting compound by more than four carbon atoms.

In producing these compounds one may employ dialkyl sulphides wherein one or both of the alkyl radicals possesses from one to twenty or more carbon atoms. Instances of sulphides of this type are hexadecyl ethyl sulphide, didodecyl sulphide, oleyl methyl sulphide, oleyl isopropyl sulphide, tetradecyl ethyl sulphide and the like. same manner, the alkyl radicals may possesss branched chains and they may be saturated or unsaturated. Likewise, they may be'iurther sub- In the stituted with one or more non-hydrocarbon'radicals which do not interfere with the resulting reaction, for instance, halogen, hydroxyl, sulphate, sulphonate, ester, ether, ketone, and the like groups. The higher aliphatic radicals may correspond to the radicals present in alcohols obtained from natural oils, fats and waxes by saponification or by catalytic or sodium reduction, or they may correspond to the radicals of alcohols isolated from the reaction of water and carbon oxides in the presence of catalysts employed in the methanol synthesis. The alkyl groups may be the same or dissimilar and they may have substituted thereon the same or dissimilar nonhydrocarbon groups. Also, it is contemplated that these radicals may be of cyclic nature, either carbocyclic or heterocyclic. In other words, one or both alkyl groups may be of aryl, heterocyclic, cycloaliphatic or aralkyl derivation, such as for example, phenyl, cyclohexyl, naphthenyl, benzyl, etc.

The aforesaid and related sulphides may be reacted with hydrocarbon derivatives having substituted thereon an oxygen-containing acid group or derivative thereof and an anion, in order to produce the desired tetravalent sulphur compounds. The hydrocarbon radical of this reactant may contain from one to twenty carbon atoms, as in the case of the alkyl or other hydrocarbon radicals of the sulphur containing reactant. This hydrocarbon grouping may also be a straight chain alkyl group or it may contain branched chains, it may be saturated or unsaturated, or may be further substituted with one or more non-hydrocarbon groups which do not interfere with the resulting reaction, and it may be or may have substituted thereon aryl, heterocyclic, cycloalkyl, aralkyl and the like groups. This hydrocarbon group should have substituted thereon, as previously stated, an oxygen-containing acid group or derivative thereof. Among the groups coming within this category mention may be made of carboxyl, sulphonic acid, sulphuric acid, phosphoric acid, and their salts, esters, amides, ureas, thioureas, nitriles and related derivatives. It is to be understood that the carboxylic acid group is preferred for this purpose. The hydrocarbon group of the reactant under consideration should also have substituted thereon an anion such as bromine, chlorine, iodine, sulphuric acid, hydroxyl, sulphuric acid ester, sulphonic acid, sulphonic acid ester, etc. In this connection it might be mentioned that the preferred anion substituents are chlorine and bromine.

In accordance with the aforesaid instructions the reactions set out may be, for example, between a cyclic sulphide such as diethylene disulphide, thiophene, or tetrahydrothiophene and a halogenated fatty acid containing from one to twenty carbon atoms. A mercaptan such as mercaptobenzothiazole may be reacted with a long chain halogen compound such as dodecyl bromide to obtain a sulphide for further reaction with bromoacetic acid to form a thetine bromide which may be ring closed with an alkaline condensing agent such as sodium carbonate or silver oxide to form the thetine. Thioglycollic acid may be reacted with a long chain halide such as octadecyl bromide to form octadecyl thioglycollic acid which, upon treatment with dimethyl sulphate will form the methyl sulphate of methyl octadecyl thetine, and this compound upon treatment with an alkaline condensing agent will cause ring closure to form methyl octadecyl thetine. Long mercaptan to obtain the sulphide, which may be further condensed with bromoacetic acid to form a thetine bromide. Likewise, a sulphide such as CuHsaCONI-ICl-IzCHzSCHs may be reacted with chloroacetic acid. An alternative process in= volves the treatment or thioglycollic acid with dioctadecyl sulphate to obtain the octadecyl sulphate of di-octadecyl thet'ine, which on treatment with sodium carbonate or sodium hydroxide forms a mixture of dl-octadecyl thetine and sodium octadecyl sulphate. Another illustration of the many reactions contemplated herein concerns the condensation of methyl thioglycollic acid with dodecyl para toluene sulphonate to obtain the para toluene sulphonate of dodecyl methyl thetine.

as is clear from the preceding description, the preferred embodiment of this invention pertains to tetravalent sulphur compounds which contain an aliphatic radical of between twelve and eighteen carbonatoms, two alkyl groups of lower molecular weight, an anion such as chlorine or bromine, and a carboxyl group. These compounds may advisably be obtained by the reaction of an organic sulphide, preferably a dialkyl sulphide, with a halogenated carboxylic acid, and

in this reaction either the sulphide or the carboxylic acid may contain an aliphatic chain of at least six carbon atoms and preferably from twelve to eighteen carbon atoms. In the same manner, a thio ether oi thioglycollic acid may be reacted with a suitable organic halide or sulphate. One of these preferred products is obtained by a class reaction involving the heating of octyl methyl sulphide and chloroacetic acid with the production of a material which dissolves readily in water and gives clear solutions that foam persistently. This reaction product may be further treated with an aqueous or alcoholic alkali solution thereby causing the alkali salt of the carboxylic acid to form and subsequently split d an alkali halide with the production of cyclic octyl methyl thetine having the following formula:

It is to be understood that in the preesnt specification and claims when reference is made to long chain thetines this term is intended to include both the uncondensed tetravalent sulphur compounds previously described and their condensation products which correspond to true thetines.

The products of the present invention are of particular value as surface active agents. For this purpose, they may be substituted for or used in admixture with surface active agents of the prior art in the various processes wherein these agents have heretofore been used or are capable of use. As the uses or these agents are legion it is deemed unnecessary to'refer to them in detail herein. However, for purposes of illustration a few of these uses will hereafter be given. I

A few illustrative uses of these compounds depend.- upon the excellent wetting, penetrating, detergent, dispersing, emulsifying, irothing,

arrests roaming and kindred characteristics evidenced by these materials.

Many uses of these new compositions are connected with treatments for processing and improving natural and synthetic textile materials. A few representative uses of these new products as textile assistants will be mentioned in order that the importance and widespread applicability or these new products in the textile industries may be fully appreciated. They may be used alone or in combination with other suitable detergents for cleansing and scouring vegetable and animal fibers when removing fatty or oily materials. They may be used as penetrants in acid solutions which are used for carbonizing vegetable matter in wool. When added to flax retting .baths, they function as wetting and penetrating agents. They may be employed as assistants in fulling and felting processes. They may be used in sizing preparations in combination with the usual materials such as starches or gelatine or their equivalents, clays, tales or their equivalents, weighting salts such as magnesium sulphate or calcium chloride, oils and oils processed by oxidation, polymerization, sulphonation, etc. The penetrating power of these new compositions is utilized with advantage when they are added to baths containing starch ferments which are employed for removing sizing from textile materials. These products function as useful wetting, cleansing, and penetrating agents in bleaching liquors such as those used in the kier boiling of cotton goods. They may be added-to the lye liquors used for mercerizing cotton goods. They improve the absorption capability of fibrous materials when such materials are subjected to treatments for finishing, softening, stiffening, coloring, impregnating, water-proofing, and mildewproofing. They may be used alone or incombination with other materials for lustering or delustering fabrics. They may be employed to oil or lubricate textile materials and as assistants in processes of Weighting or loading fabrics. They may be used as assistants in silk degumming liquors and silk soaking solutions. They can also be used to assist in twist setting in yarn and in processes of stripping colors. The compounds may be used as assistants in processes at stripping dyes from dyed textile materials.

Another important class of uses of these new compositions is as assistants in the preparation and application of dyestuffs. They may be used in the preparation of dyestuffs in readily dispersible. form and for the production 01- inorganic pigments or pigments of azo, basic, acid, vat, and sulphur dyes in a finely divided condition. As penetrants and wetting agents they as ist in producing level d'yeings in neutral, acid, or alkaline dyeing baths. They facilitate dyeing with developed dyes, the dyeing of animal fibers with vat dyes, the dyeing of cellulose acetate fibers with insoluble dyes, dyeing and printing with aniline black, and the dyeing of leather. In printing pastes they assist in the dispersion of the dye or dye component and facilitate its penetration into the natural or synthetic fiber. Solutions of these compounds are useful for increasing the fastness of dyeings on textile materials. Solutions of these compounds may be used for increasing the aflinity of textile fibers of vegetable origin for acid-chrome dyestuffs. These compounds may be used as assistants in resist printing processes.

In the leather industry these compositions function as useful wetting agents in soaking, deliming, hating, tanning, and dyeing baths. They are useful in softening and treating baths for hides and skins, particularly in baths used for fatliquoring leather and in processes of water-proofing leather. Solutions of these compounds are useful for pretreating leather'prior to dyeing.

The dispersing and emulsifying powers of these new compositions give rise to many interesting uses. They may be utilized for converting liquid or solid substances normally insoluble in water, such as hydrocarbons, higher alcohols, pitches and pitchy substances into clear solutions or stable emulsions or dispersions. They are useful in preparing emulsions of wax .and wax-like compositions which are used as leather dressings or fioor polishes. They may be used to prepare artificial dispersions of crude, vulcanized, or reclaimed rubber. They may be used as emulsifiers in the manufacture of cosmetic preparations such as cold creams and lip -sticks. They may be employed for preparing emulsions of the water-in-oil type such as emulsions of water in such organic solvents as are used in the dry cleaning industry. They are also of value in the breaking .of petroleum emulsions, such as those naturally occurring in nature or produced during the refining of petroleum.

These compositions may also be used alone as bactericides and contact insecticides and for enhancing the spreading and penetrating power of other parasiticides. They may be employed in agricultural sprays in combination with the ordinary insecticides and fungicides. They are useful for promoting the penetrating power of wood preservatives.

In the paper industry these products may be used as penetrants in the liquors used for cooking rags and pulp, and as assistants in paper softening, filling, and processes to increase absorbency.

These compositions may be employed as detergents in several different relations. They may be used in the washing of fruits and vegetables for spray residue removal. They may be used in combination with metal cleaning compounds in neutral, acid, or alkaline liquors. They may be used for paint, varnish, and lacquer cleaners. They may advantageously be employed as cleansing agents in hard water and where a fatty or oily film resists the ordinary cleansing media. They may be added to soap in acid or hard water baths, since these compositions do not form precipitates so readily in hard and acid waters as soaps and Turkey red oils.

These compositions may be used as aids in vari ous chemical reactions. They may be used to conrol particle size and shape during precipitation or crystallization of compounds from reaction mixtures. They may be used'to decrease the particle size of insoluble amine hydrochlorides just before these amines are to be diazotized.

These compositions also have several miscellaneous uses. They may be employed as foam stabilizing agents, especially for use in air-foam fire extinguishing compositions. They may be used to stabilize rubber latex. They may also be used as frothing and collecting agents in ore fiotation processes, and in other processes such as the recovery of fixed oil from the oil sands. The uses mentioned will suggest many similar ones.

By means of the present invention a large class of new and commercially feasible surface active materials has been rendered availablejfor use. These compounds possess satisfactory colloidal properties and are of particular value for use in place of or in combination with soap and soap substitutes. This invention is of considerable interest in that the reactants which enter into it are for the most part readily available at a relatively low cost. The large variety of reactions which may be relied upon permit considerable latitude in the selection of reactants and the conditions of reaction. Likewise, the large number of compounds embraced within this category permit the selection of individual members thereof for a wide variety of purposes. In other words, where high wetting and dispersing properties are of paramount importance the molecular weight of these compounds may be lowered. On the other hand, where detergent properties are of primary interest the molecular weight of the compounds may be increased.

As many apparently widely different embodiments of this invenion may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. A process for producing tetravalent sulphur compounds which comprises reacting a dialkyl sulphide with a halogenated fatty acid, one of the aforesaid reactants containing an alkyl group of from twelve to eighteen carbon atoms.

2. A process for producing tetravalent sulphur compounds which comprises reacting a dialkyl sulphide with an alpha brom fatty acid, one of the aforesaid reactants containing an alkyl group of from twelve to eighteen carbon atoms.

3. Aprocess for producing tetravalent sulphur compounds which comprises reacting dodecyl methyl sulphide with chloroacetic acid.

4. Compounds having in their uncondensed form the following general formula:

R1 oH'moooH wherein R andRr represent aliphatic radicals, R2 represents a. member of the group consisting of hydrogen and an aliphatic radical, X represents an anion, and one of the aliphatic radicals contains from twelve to eighteen carbon atoms.

6. Compounds having in their uncondensed form the following general formula:

R1 CHRsOO OH wherein R and R1 represent aliphatic radicals,

R2 represents an aliphatic radical containing from ten to sixteen carbon atoms, the carboxyl that it is not separated from the sulphur nucleus by more than four carbon atoms, and X repregroup being substituted thereon in such manner sents a member of the group consisting of chicrine and bromine.

7. compounds having in their uncondenecd form the iollowing general formula:

121 onmooon wherein R and R1 represent aliphatic radicals at least one of which contains from twelve to eighteen carbon atoms, R2 represents a. member of the group consisting of hydrogen and an aliphatic radical containing less than four carbon atoms, and X represents a member of the group consisting of chlorine and bromine.

8. A compound having in its uncondensed form the following formula:

CHa(CH2)n CHaCOOH 10. The compounds taken from the class consisting of the open chain and inner cnium salts oi the free acids oi the following general formula:

31 oHmY wherein R and R1 represent hydrocarbon radicals which may be externally Joined, Ra represents a member of the group consisting of hydrogen and a hydrocarbon radical, X represents an ani0n,Y represents an oxygen-containing acid group, and one of the hydrocarbon radicals is an aliphatic radical of at least twelve carbon atoms. a

11. Tetravalent sulphur compounds selected from the class consisting of the open chain free acids oi the following general iormula and the inner onium salts of the free acids oi the toll-=- lowing general formula:

wherein R and R1 represent aliphatic radicals at least one of which contains from twelve to eighteen carbon atoms, R2 represents a member of the grounconsisting of hydrogen and an allphatic redicai containing less than four carbon atoms, and X represents a member of the group consisting of chlorine and bromine.

12. A halide of henayi octadecyl thetine.