US1932180A

US1932180A - Sulphuric acid derivatives of amides

Info

Publication number: US1932180A
Application number: US614033A
Authority: US
Inventors: Guenther Fritz; Munz Ferdinand; Haussmann Hans
Original assignee: IG Farbenindustrie AG
Current assignee: IG Farbenindustrie AG
Priority date: 1929-04-12
Filing date: 1932-05-27
Publication date: 1933-10-24
Anticipated expiration: 1950-10-24

Description

Patented Oct. 24, 1933 PATENT OFFICE SULPHURIC ACID DERIVATIVES 0F AMIDES Fritz Guenther, Ludwigshafen-on-the-Rhine,

Ferdinand Miinz, Frankfort-on-the-Main, and Hans Haussmann, Mannheim, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany No Drawing. Application May 2'1, 1932, Serial No. 614,033, and in Germany April 12, 1929 34 Claims.

The present invention relates to the production of assistants for the textile and related industries and particularly of wetting, cleansing, softening and dispersing agents.

We have found that excellent assistants for the textile and related industries and particularly wetting, cleansing and dispersing agents are obtained by reacting an aliphatic, that is aliphatic or cycloaliphatic, compound containing the group in which X is either OH (acid), -O.R (ester) in which X1 denotes hydrogen, an aliphatic open chainor isocyclic aliphatic radicle or aliphaticaromatic radicle and X2 denotes either hydrogen, an aliphatic radicle as denoted by X1, or an arcmatic radicle provided X1 is one of the said organic radicles, which bases are free from aliphatic alcoholic groups and in which any aromatic, that is aryl or aralkyl, radicles connected to nitrogen atoms are free from chromophorous groups, the resulting amides being then reacted with sulphonating agents to form in the said amides sulphuric derivative groups, that is carboxylic amide sulphonic acids or sulphuric esters, or mixtures of both or products which contain both sulphuric ester and sulphonic groups, if the carboxylic amides do not already contain, or only contain an insufiicient quantity of, sulphuric derivative groups, i. e. the said sulphuric ester or sulphonic groups, or both. In any case the components should be so chosen that the resulting amides contain at least 8 carbon atoms, preferably in chains of aliphatic nature.

The basic amides according to the present invention correspond to the general formula in which R denotes an aliphatic open chain or aliphatic-aromatic radicle or a cycloaliphatic radicle containing up to 3 condensed nuclei, X1 denotes hydrogen or a radicle as denoted by R, X2 denotes either hydrogen or a radicle as denoted by R or, if X1 be an organic radicle as denoted by R, X2 may denote an aromatic radicle free from chromophorous groups. X1 and X2 may also form a single aliphatic radicle conjointly so that constitutes a heterocyclic radicle. According to the definition given above the number of carbon atoms of R should be at least '7 if X1 and. X2 be hydrogen atoms, whereas it may be 1 if X1 be a hydrogen atom and X2 contains for example 6 carbon atoms, or if the sum of the carbon atoms in X1 and X2 be 6.

Different specific types of the products according to the present invention will be more clearly exemplified by the following general formula: in which Y denotes a sulphuric ester or sulphonic acid radicle.

Products of Group II prepared from amines instead of ammonia are preferred for many purposes and those of Group III prepared from secondary amines usually have the most valuable properties. The sulphuric ester and sulphonic acid groups need not be in the free state in the final products but may be neutralized by alkalies or organic bases of any kind. We wish it therefore to be understood that the terms sulphuric ester and sulphonic acid groups are intended to embrace the said acid groups in the free state as well as in thesalt form.

In the following we will describe first the initial materials generally employed in our process and then the different methods for the production of the sulphuric derivatives of the amides.

The acid components of the amides may be chosen from any aliphatic open chain saturated or unsaturated fatty acids which may contain hydroxyl or keto groups and/or other substituents, such as aryl radicles as for example acids of the type of Twitchell fatty acids; further from cycloaliphatic carboxylic acids containing up to 3 condensed nuclei, such as hexahydrobenzoic, resinic and naphthenic acids and from heterocyclic aliphatic carboxylic acids, such as the different pyridine carboxylic acids. Carboxylic acids having more than 3 condensed nuclei should not be employed since the resulting products are not very eificient for the purposes in view. Generally, carboxylic acids with at least 6 carbon atoms are preferred as components of the amides though acids with less carbon atoms give also valuable products in many cases. Particularly valuable for the process according to the present invention are acid components chosen from the acids of' oils or fats of vegetal, that is animal or vegetable, origin, such as the acids of coconut, palm kernel and palm oil which contain fatty acids with from 6. to 18 carbon atoms, of soya bean, linseed, olive, rape-seed, cotton-seed, peanut and caster oils which contain large proportions of unsaturated fatty, or unsaturated hydroxy fatty, acids, the acids of tallow, fish or seal oils, whale or shark oils and hydrogenated acids of the said sources; the synthetic high molecular fatty acids, obtainable by the oxidation of parafiin wax and similar high molecular hydrocarbons by means of gaseous oxidizing agents, resinic acids, such as abietic acid, or the different naphthenic acids and long-chain fatty acids having an aromatic hydrocarbon radicle directly connected with the aliphatic chain (Twitchell fatty acids) as are obtainable from oleic, ricinoleic,

linoleic and like unsaturated fatty acids. Instead of mixtures of acids from the oils, fats and resins single acids may be employed as for example caproic, pimelic, heptylic, caprilic,sebacic,undecylic, lauric, myristic, palmitic, stearic, behenic, arachic and cerotic acids as well as similar saturated and/or hydroxylated fatty acids, such as undecylenic, oleic, eruca, linoleic and linolenic acids, ricinoleic and hydroxy-stearic acids. Lower aliphatic carboxylic acids, such as acetic, propionic, butyric, valeric and caproic acids may also be employed but in these cases the amines should contain-such a high number of carbon atoms that the total number of carbon atoms in the amides is at least eight. In the place of these saturated lower acids the corresponding unsaturated and/or hydroxylated acids may be employed as for example acrylic and crotonic acids, lactic acid or pyroracemic acid and the like. As pointed out above sulphuric esters and sulphonic acids of the aforesaid acids may be employed, an extended enumeration of these compounds being not necessary as they are well known in the art, reference being made for example to hydroxy-stearic sulphonic acid or hydroxy-stearic sulphonic methyl ester (obtainable by reacting oleic methyl ester with chrolosulphonic acid in the presence of ethyl ether and washing with alkali), the sulphuric ester of oleic methyl ester (obtainable by acting on oleic methyl ester with sulphuric acid at about 20 0.), ricinoleic sulphuric ester, palmitic sulphonic acid and the like. As described above all the said acids or their esters may be employed as such for the reaction but in most cases the employment of their anhydrides or halides facilitates the reaction if it be carried out in an aqueous medium.

The ammonia bases may be chosen from ammonia and primary and secondary aliphatic amines, that is amines containing at least one aliphatic radicle. amines may be mentioned as primary amines: mono-methyl or -ethyl amines, mono-allyl amine, mono-n-butyl, mono-hexyl or -cetyl amines, as cyclo-aliphatic primary amines: cyclohexyl amine or its homologues and bornyl amine, as a primary aliphatic-aromatic amine: benzyl amine; as

secondary aliphatic amines: di-ethylamine, secondary amines containing methyl, ethyl, propyl, butyl, hexyl or cetyl groups, as for example of the type of N-methyl-N-ethyl amine secondary As specific examples of such mixed aliphatic-cycloaliphatic amines containing a group of cyclohexylamine or its homologues, secondary aliphatic-aromatic amines, as for example N-methyl-N-benzyl amine, secondary mixed aliphatic-aromatic amines, such as N-alkyl anilines, N-alkyl naphthyl amines. N-benzyl naphthylamine, and heterocyclic aliphatic bases, such as morpholine and piperidine. In any case it is preferable that these amines do not contain aliphatic alcoholic groups since otherwise esters might be obtained instead of the desired amides depending upon the reaction conditions, and the amines as well as the acid components of the amides must be free from such aromatic nuclei connected to nitrogen atoms as contain chromophorous groups, as for example nitro and azo groups, since otherwise colouring materials might be obtained. The said bases may be employed in the free state or also in the form of their salts when alkaline agents are present during the formation of the amides. As explained above, instead of the acid components, the amines may contain one or more sulphuric ester or sulphonic groups as is the case for example in mono-ethanol amine sulphuric ester (NH2-C2H4OSO:H) and taurine bodies such as ,taurine (NH2-C2H4SO3H), N- methyl, N-butyl, N-cetyl, N-cyclohexyl or N- phenyl taurines or amino methane sulphonic acids, and the aromatic amines may contain sulphonic groups as for example N-ethyl sulphanilic acid and benzyl aniline sulphonic acid and in these cases the subsequent, treatment with 'sulphonating agents may be dispensed with.

The amides containing a lower number of (one or two) sulphuric ester orvsulphonic acid groups are usually particularly suitable as wetting, dispersing, softening, washing and scouring agents and their solubility in water may be increased by introducing further sulphuric ester or sulphonic acid groups. Amides containing a lower number of sulphuric ester or sulphonic acid groups and prepared from unsaturated acids and/0r amines show a particularly high solubility'in water and resistance to precipitation by calcium and magnesium salts. Generally speaking, it is advisable to take higher amines containing at least 6 carbon atoms such as cetyl amine or ethyl aniline for the reaction when lower carboxylic acids (containing less than 6 carbon atoms) are to be employed, and higher carboxylic acids or their derivatives, such as oleic acid and castor oil, when lower amines, such as monoor di-ethyl amine, are to be used. Particularly suitable are in many cases, products which have been prepared from higher carboxylic acids, or their derivatives, and from higher secondary bases. On the other hand products prepared from amines and acids of low molecular weight may, however, find useful application as wetting agents in baths containing large quantities of electrolytes, as for example those employed in mercerizing in alkaline and acid solutions, precipitating baths for the production of artificial silk and impregnating and fireproofing fabrics.

In any case no metal halides having a condensing action must be present during the reaction since otherwise water-insoluble, from oily to rubher-like condensation products mightbe formed. The condensation of the acid compounds with the amines is carried out by the methods usual and known in the art for the production of amides, for example by a condensation of the free acids, with the amines intended for the conversion to amides, by simple heating salts of the acids concerned with the amines intended or by reacting esters of the acids, if desired while heating, with the amines. The tree acids may be replaced by the corresponding anhydrides or halides while employing a quantity of basic agents sufllcient ior neutralizing tree acid formed by the interaction of one acid radlcle with a hydrogen atom connected to nitrogen of the amine chosen; the basic agents may be chosen from aqueous alkali or from inert organic (tertiary) bases, such as tri-alkyl amines, pyridine or dimethylaniline, which then may simultaneously act as diluents.

Products similar to those obtainable in the aforesaid reactions by the use of secondary amines, amino sulphonic acids and sulphuric esters of secondary amines can be obtained by subsequently treating amides obtained with the aid of ammonia, or oi. primary amines, with alkylating or aralkylating agents either before or after the sulphonation. Thus, for example, the well known stearic anilide may be improved by a methylation with the aid of dimethyl sulphate after the anilide has been converted into its sodium salt by means of sodium alcoholate.

The action and results of a desired subsequent treatment sulphonating agent depend on the materials to be sulphonated and on the conditions of the treatment. Sulphuric esters, for example, can be obtained from amides containing oleflnic and/or hydroxyl groups. For the production of sulphuric esters the reaction may be carried out with sulphuric acid or also with stronger sulphonating agents such as fuming sulphuric acid, sulphur trioxide. or chlorsulphonic acid, which latter agents are usually employed in cases when the initial materials contain one or more hydroxyl groups. The reaction may be carried out in the presence of inert diluents such as carbon tetrachloride, trichlor ethylene, nitrobenzene, acetic acid and the like which usually allow of reducing the temperature of the treatment, and/or in the presence of agents removing water, such as anhydrides or chlorides of organic or inorganic acids. At least one molecular proportion of sulphonating agent is usually employed with each molecular proportior of the amides, but in the aforesaid case of acting on compounds containing hydroxyl groups with strong sulphonating agents, such as sulphur trioxide or chlorsulphonic acid, or with mixtures of milder sulphonating agents with the strong sulphonating agents or with agents removing water, the quantity of the strong sulphonating agents, or of the agents removing water, should not exceed one molecular proportion for each hydroxyl group. In most cases, the temperature employed during the sulphonation should not considerably exceed 40 C. when more than one molecular proportion of sulphonating agent is employed for each molecular proportion of amide.

If, however, sulphonic acids are to be produced and when the primary reaction products do not already contain one or more sulphonic groups and no aromatic radicles. the temperature of a sulphonation by means of sulphuric acid monohydrate must exceed 40 C., a temperature of about C. being preferably chosen, since otherwise sulphuric esters are formed or no reaction takes place. When stronger sulphonating agents such as fuming sulphuric acid, sulphur trioxide or chlorsulphonic acid or mixtures of mild sulphonating agents with these or with agents removing water be employed for this sulphonation of compounds containing one or more hydroxyl groups, the quantity of these strong sulphonating agents or of the agents removing water must exceed one molecular proportion per each hydroxyl group present. It is obvious that variations of the conditions described may lead to the production of mixed products. When the amides contain aromatic nuclei the sulphonation will generally lead to sulphonic acids but also sulphuric ester radicles may be introduced into an aliphatic radicle of such an amide when the latter contains olefinic groups in the acid or in the amino radicle of the amide and/or hydroxyl groups in the acid radicle. When working with considerable quantities of strong sulphonating agents, however, sulphonic radicles may be introduced into an aliphatic radicle of such an amide together with a sulphonation of the nucleus.

The resulting products are generally distinguished by excellent wetting properties, in neutral, acid or also alkaline baths. The products also possess high stability in hard water or solutions made therewith. Consequently the products according to the present invention constitute highly valuable assistants for all the branches of 'the textile and allied industries. The amides and anilides prepared from unsaturated or hydroxyl bearing fatty or resinic acids, and treatment with sulphonating agents, may generally find useful application especially as wetting agents, whereas amides prepared from olefinic or mixed aliphatic-aromatic secondary amines and fatty acids free from hydroxyl groups or from mixed (secondary) aliphatic-aromatic amines, and treatment with sulphonating agents, are particularly valuable washing, scouring and emulsifying agents, as well as the products prepared by the condensation of high molecular carboxylic acids and amines containing sulphonic acid or sulphuric ester groups or by the condensation of higher amines with carboxyllc acids containing sulphonic acid or sulphuric ester groups. The wetting, emulsifying and washing power of the amides, in which both hydrogen atoms of the amide group are substituted by alkyl, cycloalkyl, aralkyl or aryl groups according to the definition given above, is considerably higher than that of the amides which contain one or two hydrogen atoms connected with the nitrogen atom of, the amide group. They are particularly stable even in hot alkaline baths, have a particularly high emulsifying and levelling power and a far reaching power for dispersing water-insoluble or difiicultly watersoluble solid substances such as alkaline earth metal soaps, water-insoluble dyestuffs or other water-insoluble colouring materials, fats, waxes and the like.

The amides containing sulphuric derivative groups according to the present invention may be employed as such or in conjunction with other wetting or emulsifying agents such as soaps, products of the type of Turkey red oils, sulphonic acids from mineral oils or sulphonic acids of aromatic, and especially of polynuclear aromatic compounds or their salts, with hydroxy-alkyl amines, quaternary ammonium bases or their salts, or with protective colloids, such as glue, gelatine or vegetable mucilages or gums. Salts as for example sodium carbonate, sodium bicarbonate, waterglass, common salt, neutral or acid sodium sulphates may be added, or organic solvents, such as ethylene glycol monocresyl ether. trichlorethylene or bleaching agents such as perborates, percarbonates or para-toluene sulphonic chloramide sodium. The said agents are employed in quantities depending on the desired purpose and several of them may be added conjointly. Thus for example the quantity of these additions may be the same as that of the sulphonated amides or considerably higher depending on the purposes of emulsifying, wetting, washing, cleaning or dispersing solid water-insoluble materials in water. In baths for the treatment of textiles the quantity of the sulphonated amides may be as low as a few per cent or even a few per thousand of the whole liquors.

The present application is a continuation-in part of the application Ser. No. 441,717, filed April 4, 1930.

The following examples will further illustrate how the said invention may be carried out in practice, but the invention is not restricted to these examples. The parts are by weight.

The following Examples 1 to 7 show the production of sulphuric esters containing sulphuric ester radicles in the carboxylic acid radicles of the amides.

Example 1 202 parts of oleic acid are converted, in the usual manner, into oletic amide, and this, by treatment with about 350 parts of concentrated sulphuric acid at about 35 C. in the presence of 500 parts of trichlorethylene, is converted into the acid sulphuric ester of olec amide. The resulting product freed from trichlorethylene possesses excellent wetting properties, even in alkaline baths and especially after conversion into a salt thereof with an alkaline or organic base such as sodium, potassium, ammonia, methylamine, butylamine, pyridine or ethanol amines such as mono, dior tri-ethanol amine or mixtures thereof when no solvent is employed the sulphonation is carried out at about 100 C. The product corresponds to the formula CmHmOSOaH) CO --NH$.

Ezample 2 932 parts of castor oil are dissolved in 1000 parts of'ethyl alcohol and the solution is saturated with gaseous ammonia. After standing for some time the castor oil is converted practically completely into the amide. The remainders of ammonia are then removed and the alcohol is distilled off. The mixture of the amide and glycerol is then suspended in 3000 parts of ethyl ether and 696 parts of chlorsulphonic acid are then added at from 0 to 10 Q. After the evolution of hydrochloric acid has ceased a mixture of the sulphuric ester of ricinoleid amide- (CuHmOSOfl-I) -CONH2) with glycerol monosulphuric ester and free mineral acid is obtained. This mixture is poured onto ice, then rendered neutral with the aid of caustic soda solution and the reaction product is allowed to settle. Three layers are formed, the upper of which consists of the main quantity of the ether, the middle layer of the reaction product, whereas the lower layer is an aqueous salt solution. The middle layer is separated and the ether is evaporated therefrom by warming. Instead of ethyl ether, ethyl acetate or another inert diluent may be employed. The product obtained possesses a very high wetting capacity and wets quickly diflficultly wettable unbucked cotton goods.

Example 3 31 parts of ricinoleic methyl ester are treated with a mixture of 10 parts of ethyl ether and 10 parts of chlorsulphonic acid. As soon as a sample is soluble in water the reaction product is neutralized with gaseous ammonia and the ether is distilled off in vacuo. The product is then heated in a closed vessel together with 100 parts of ammonia for 10 hours to 100 C. After removal of remainders of ammonia and methyl alcohol the product is treated with water and the aqueous solutions show a good wetting, cleansing and emulsifying eflfect.

The product has the same structure as that described in Example 2 but is prepared by first introducing the sulphuric ester radicle into the carboxylic acid, or its ester respectively, and then converting the sulphuric ester into the amide.

Example 4 100 parts of hydroxystearic methyl ester are heated in a pressure-tight vessel with 200 parts of ammonia for 4 hours at 150 C. The product obtained is then freed from ammonia and methyl alcohol and led at from 10 to 15 0. into a mixture of parts of acetic anhydride and 50 parts of sulphuric acid monohydrate. After stirring for 2 hours at room temperature the reaction product is poured onto ice, rendered neutral with the aid of caustic soda solution and salted out. The product corresponds to the formula CnHmOSOaNa) CONH2.

Example 5 100 parts of oleic ethylamide obtainable by boiling under reflux a solution in ethyl alcohol of oleic methyl ester and ethyl amine, are dissolved in 300 parts of trichlorethylene and then treated with parts of sulphuric acid monohydrate preferably at a temperature below zero centigrade. After dilution with water containing some ice the lower layer formed is separated and then neutralized with the aid of caustic soda solution. The solution obtained which generally is quite clear becomes turbid by adding more water and separates after standing for some time into two layers, the lower layer of which contains the trichlorethylene and the constituents which have not reacted with the sulphuric acid, and is drawn off. The upper layer which still contains some trichlorethylene and water is evaporated to the desired concentration. The product obtained, which corresponds to the formula possesses a high wetting power which is superior to that of the product obtained according to the foregoing example. Each 0.4 gram of the product obtained is dissolved in 1 liter each of water. Even with this low concentration the bath shows an excellent wetting effect.

Example 6 100 parts of oleic di-ethylamide (obtainable by boiling under reflux a solution in ethyl alcohol of layers, the layer of which contains the trichlorethylene and the constituents which have not reacted with the sulphuric acid, and is drawn off. The upper layer which still contains some trichlorethylene and water is evaporated "to the desired concentration. The product obtained, which corresponds to the formula 01H! possesses a particularly high wetting power which is superior to that of the product obtained from oleic amide and is also superior to that of a sulphuric ester of an oleic mono-alkyl-amide. Each 0.4 gram of the product obtained is dissolved in 1 litre of water. Even with this low concentration the bath shows an excellent wetting effect which is about 3 times that of sulphonated oleic amide and. about 4 to 5 times that of sulphonated oleic acid.

Example 7 100 parts of oleic ethylanilide (obtainable by heating oleic acid and ethyl aniline until the distillation of water has ceased) are dissolved in 200 parts of trichlorethylene and are then treated at about zero centigrade with '75 parts of sulphuric acid monohydrate. The reaction mixture is then incorporated with water containing some ice, the sulphonated layer is then drawn oil, neutralized with caustic potash solution and freed from trichlorethylene by distillation. The properties of the product obtained, which corresponds to the formula CaHt CzHu

When cotton is dyed with a bad-levelling vat dye with an addition of 2 grams per litre of the vat of the first mentioned product very uniform dyeings are obtained even in pale shades, the

levelling effect and particularly the wetting effect of the sulphonation product being superior to that from oleic anilide.

The following Examples 8 to 11 show the production of a sulphuric ester in which-the sulphuric ester radicle is connected to the amino radicle of the amide either by the introduction of the ester radicle into the amide or by condensing the carboxylic compound with an amino sulphuric ester.

Example 8 I 2'74 parts of palmitic chloride are slowly introduced at from 0 to 10 C. into an aqueous, solution of 120 parts of allyl amine sulphate, the reaction mixture being continuously kept alkaline by adding an aqueous caustic soda solution. The resulting palmitic allyl amide is filtered ofl', dried 15o and then worked with 300 parts of sulphuric acid monohydrate at from 35 to 40 C. until a sample is soluble in water. 'Ehe reaction product is then poured on ice and rendered neutral with the aid of aqueous caustic soda or aqueous ammonia. A pasty mass is obtained from which the aqueous solution of Glaubers salt separates after some settling. The product is particularly valuable for scouring and levelling purposes.

The same product can be obtained by first converting the allyl amine sulphate into its sulphuric ester and then reacting the sulphuric ester with palmitic chloride as described above. The product corresponds to the formula Ci5H31CONHCH2-CH (OSOsH) CH3 Example 9 95 parts of mono-ethanol amine sulphuric ester are dissolved in 200 parts of water. After adding 110 parts of a 50 per cent aqueous caustic-soda solution, 190 parts of stearic chloride are slowly introduced while stirring continuously, whereby the temperature is kept at about 10 C. by cooling. The paste of the sodium salt of stearic acid hydroxy-ethylamide sulphuric ester obtained after the reaction is completed may be directly employed as a wetting, washing or softening agent for artificial silk or cotton and like textile purposes.

The product obtained in the said manner corresponds to the formula If 2 grams of the product be added to each litre of a dyeing bath for dyeing artificial silk, the dyed and dried silk shows a soft and supple touch.

Example 10 900 parts of oleic chloride are added at 20 C., while stirring, to a solution of 500 parts of aminomono-ethanol sulphuric ester and 250 parts of caustic soda solution in 1300 parts of water. The reaction mixture is then stirred for 1 hour whereby an about 40 per cent paste of the sodium salt of oleic mono-ethanol amide sulphuric ester (C1'1H33-CO-NHCzH4O SOaNa) is obtained which may be directly employed, even with hard water, as a highly eflicient washing and wetting agent.

Example 11 66 parts of caustic soda and 150 parts of water are added to 260 parts of an aqueous solution of n-butyl-amino-ethanol sulphuric ester (obtainable by acting with ethylene oxide on n-butylamine and by treating the resulting N-n-buty1-, N-ethanol amine with chlorosulphonic acid). 120 parts of coconut oil fatty acid chloride are added to the solution at about 35 C. A viscous emulsion is formed which is readily soluble in water and which is suitable as a wetting agent in acid and alkaline baths, the product corresponding to the formula CHr-CHz-OS OaNa in which R-CO denotes the radicles of the fatty acids of coconut oil.

The following example shows the production of a compound which is presumably a di-sulphuric ester, the sulphuric ester radicles of which are situated in the carboxylic and the amine radicles both.

eearao Example 12 100 parts of oleic N-allyl-meta-toluidide obtainable from oleic chloride and N-allyl-metatoluidine) are mixed with 100 parts of sulphuric acid monohydrate while cooling and then stirred therewith after adding 100 parts of trichlorethylene. After neutralizing with concentrated aqueous potash solution (1:1) and, if desired removing the solvent, the product is diluted with water up to 300 parts. The viscous liquid, containing the compound presumably corresponding to the formula constitutes an eflicient wetting and emulsifying agent.

The following Examples 13 to 18 show the production of sulphonic acids containing the sulphonic acid radicle in the carboxylic acid radicle of the amides either by the condensation of sul- 1 phonated carboxylic acid compounds with ammonia, or amines, or by the sulphonation of amides.

Example 13 1 1" parts of the sodium salt of the methyl ester 0 of palmitic sulphonic acid (C15H3o(SO3Na)-- COOCHs) are heated with 375 parts of concentrated ammonia for 3 to 4 hours at 150 C. in an autoclave. The remainders of ammonia and 1 methyl alcohol are evaporated and the sodium salt of the sulphonic acid of palmitic amide (C15H3o(SO3Na)CONH2) is dried in vacuo.

Example 14 CrzHss (OH) (SOsNa) CONH2.

Example 15 V 100 parts of oleic acid are boiled under refiux with 900 parts of cyclohexyl amine until splitting off of water has ceased whereupon remainders of the amine are distilled off. 10 parts of the oleic cyclohexylamide are stirred while cooling into 35 parts of chlorsulphonic acid whereupon the mixture is stirred for 8 to 10 hours, then heated to from 50 to 60 C. until the product is soluble in water and poured onto ice. The solution is rendered neutral with caustic soda solu- 1.10

tion and inspissated, the main product corresponding to the formula Example 16 10 parts of oleic Ndimethyl-amide are stirred with 50 parts of ethyl ether, whereupon 29 parts of chlorsulphonic acid are added while stirring. Stirring is continued for five hours at about 30 C. The sulphonic acid can be separated from the reaction mixture in the form of an alkali metal salt for example as described in Example 14. The reaction product corresponds to the formula CnHaKOHXSOaNifl-CO-N Example 17 ,ably to the formula DOC-CH:

SOaNa DOC-CH3 SOaNa The acetyl radicles may be split off by any usual method of saponification with the aid of aqueous alkali or acids.

Example 18 100 parts of phenyl-stearic chloride (Twitchel acid chloride) are stirred with 100 parts of n-butyl amine dissolved in ethyl ether; remainders of butyl amine and of its hydrochloric salt are removed by washing with water and the ether is distilled off. 10 parts of the phcnyl-stear-ic butyl amide are dissolved in 90 parts of sulphuric acid iii) ' monohydrate and stirred with 40 parts of fuming sulphuric acid containing 23 per cent of S0: at from 100 to 105 C. until the product is soluble in water. The reaction mixture is then poured onto ice, rendered neutral with caustic soda solution and inspissated. The product corresponds presumably to the formula The following Examples 19 to 21 show the production of a mixture of a sulphuric ester with a sulphuric acid, or of products which contain both sulphuric ester and sulphuric acid radicles in the carboxylic acid radicles of the amides.

Example 19 C11H21(0H) (OSOaNa) -CO-NH2 C11H32(OSOaNa)--CONH: C17H32(OH) 2(SO3Na) -CO-NH: and probably some CnHaa (OSOaNa) POO-NH: Ci'zHa:(OSO3Na) (OH) (SOaNa) 'CONH2.

Example 20 100 parts of fused ricinoleic amide are incorporated at to C. with a mixture of 300 parts of ethyl ether. and 430 parts of chlorsulphonic acid in a vessel provided with a stirring device and a reflux condenser. The temperature decreases to about 40 C. and the mixture is stirred for 2 hours whereupon the reaction mixture is poured onto ice, rendered neutral with the aid of aqueous caustic soda and freed from the ether. The upper oily layer contains the desired sodium salt of the sulphonation product, the main constituent of which corresponds presumably to the formula C1'rH32(OSOaNa) (OH) (SOaNa) -CONH2 together with some of the other bodies referred to in the foregoing example.

Example 21 100 parts of fused ricinoleic N-diethyl amide are incorporated at from 70 to 75 C. with a mixture of 300 parts of ethyl ether and 430 parts of chlorsulphonic acid in a vessel provided with a stirring device and a reflux condenser. The temperature decreases to about 40 C. and the mixture is stirred'for'2 hours whereupon the reaction mixture is poured onto ice, rendered neutral with the aid of aqueous caustic soda and freed from the ether. The upper oily layer contains the desired sodium salt of the sulphonation product.

The following Examples 22 to 26 show the production of amides which contain sulphonic acid radicles in the amino radicles by sulphonation of amides.

Example 22 150 parts of caproic allyl amide are introduced into a mixture of 120 parts of sulphuric acid monohydrate and 130 parts of acetic anhydride, prepared at from 10 to 15C., whereupon the whole is stirred at from 20 to 25 C. for from 6 to 8 hours. The resulting product is heated to boiling with an equal quantity of water while passing through steam so that acetic acid is split oif. The mixture is then rendered neutral with the aid of caustic soda solution and evaporated to dryness. The resulting product, the caproic amide of amino-hydroxy propane sulphonic sodium salt, can be employed as wetting agent in aqueous solutions containing large quantities of electrolytes such as acid or alkaline baths as for example in mercerizing cotton with sulphuric acid.

Example 23 100 parts of commercial naphthenic acid mixture are boiled for 10 hours under reflux with 200 100 to 105 C. with 90 parts of fuming sulphuric acid containing 23 per cent of S03 until the product is soluble in water. The reaction mixture is poured onto ice, rendered neutral with caustic soda solution and inspissated. The product corresponds to the formula in which R-CO denotes the radicles of the acids of the initial naphthenic acid mixture.

Example 24 1000 parts of a mixture of fatty acids obtained by the oxidation of parafiin with the aid of air while warming and separating the acids from unattacked initial material, are heated under reflux with 2000 parts of N-methyl aniline for 1'7 hours to from 180 to 190 C., the water formed during the reaction being continuously distilled off. The remainders of free aniline are then distilled off in vacuo and the residue is distilled in 4750 parts of sulphuric acid monohydrate. 2200 parts of fuming sulphuric acid containing 23 per cent of sulphur trioxide are then introduced into the solution at about 10 C. and the mixture is stirred for about 20 hours at 20 to 25 C. The reaction product is then poured onto a mixture of ice and common salt and filtered. The product which is a mixture of amides of the different fatty acids may be employed as such or after neutralization with caustic soda, if desired after removal of the nYineral acid salts. It possesses a high resistance to acid and a high scouring power superior to that of soaps and is not precipitated from aqueous solutions by means of alkaline earth metals. The product corresponds to the general formula CuH4-S03N3 R-CON in which RCO denotes the radicles of the different fatty acids in the said oxidation products.

Example 25 284 parts of stearic acid are heated under reflux for 24 hours with N-mono-ethyl-e-naphthylamine,

- whereupon remainders of the amine are removed with aqueous dilute hydrochloric acid. The product is then dried and dissolved in 400 parts of sulphuric acid monohydrate while warming, whereupon 400 parts of fuming sulphuric acid with a content of 23 per cent of sulphur trioxide are gradually added and the mixture is heated to 100 C. The reaction mixture is kept at this temperature until the product is soluble in water, and is then poured onto ice and neutralized with lime,

- a sodium salt being then prepared from the calcium salt by means of sodium carbonate. The product corresponds presumably to the formula Example 26 460 parts of benxy -a-naphthylamine are brought into reaction with 190 parts of lauric chloride the reaction being completed by heating to 100 C. By washing with acid and alkali solution the reaction product is freed from remainders of initial material and is then dried and subsequently sulphonated at 100 C. with the aid of 400 parts of fuming sulphuric acid containing 12 per cent of sulphur trioxide until the product is watersoluble. The reaction product is then poured onto ice, incorporated with lime and after removal of gypsum the sodium salt is prepared in the usual manner with the aid of soda. The sodium salt which corresponds presumably to the formula SO3Nii is soluble even in acid baths and possesses a good wetting power.

The following Examples 27 and 42 show the production of amides containing sulphonic radicles connected to the amino radicles by a condensation of carboxylic acid compounds with amino-sulphonic acids.

Example 27 200 parts of ethylaniline-meta-sulphonic acid are treated with 250 parts of oleic chloride in a weak aqueous caustic soda solution, the reaction mixture being constantly kept slightly alkaline by gradually adding caustic soda. After the reaction the mass is rendered slightly acid, so that litmus paper is coloured red and oleic acid formed is separated, whereupon the product is recovered from the solution by salting out and shows a very good wetting power. The product corresponds to the formula (uni-some H3iC0N Example 28 10 parts of p-aminobenzyl sulphonic acid with sodium chloride constitutes a valuable washing and scouring agent.

Example 29 148 parts of the sodium salt of taurine (N H2C2H4SO3Na) in 1000 parts of water, 40 parts of caustic soda are added and 300 parts of oleic chloride are gradually introduced at from 20 to 25 C. After from 1 to 2 hours the solution solidifies to a liquid paste which may be employed as such for wetting and scouring purposes. The product corresponds to the formula Emample 30 300 parts of coconut oil fatty acid chloride are introduced into a solution of 300 parts of sodium taurine in 3000 parts of water at from 0 to 10 C. The mixture is then stirred at room temperature until a sample is soluble in water. The product obtained is a highly efiicient washing and scouring agent and corresponds to the formula R.CONHCzH4SO3Na, R-CO denoting the radicles of the fatty acids of coconut oil.

Example 31 354 parts of gaseous sulphuric anhydride are introduced at from 30 to C. into 100 parts of ethyl alcohol whereupon 1000 parts of an aqueous 47 per cent solution of methylamine are introduced at 20 C. The mixture is then heated for 4 hours in an autoclave to 150 C. After cooling the reaction mixture, 900 parts of aqueous caustic soda solution of B. strength are added and the remainders of methylamine are distilled oif. After neutralizing with aqueous sulphuric acid and evaporating the solution N- methyl taurine is crystallized out, after sodium sulphate has crystallized and is separated. 150 parts of oleic chloride are then introduced, while stirring, into a solution of 85 parts of the N- methyl taurine in 300 parts of water and parts of an aqueus caustic soda solution of 40 B. strength at 30 C. while stirring and keeping the solution continuously slightly alkaline, whereupon stirring is continued for from 6 to 8 hours at room temperature, the mixture is rendered neutral, evaporated and finally dried in vacuo. About 250 parts of a, mixture of the sodium salt of oleic N-methyl tauride and some sodium chloride are obtained. The solutions of this mixture possess an extremely high wetting and washing power and are entirely stable to alkaline earths and acids and are capa- Example 32 300 parts of coconut fatty acid chloride are introduced into a solution of 300 parts of N-methyl taurine sodium (CH3-NHCH2CHSO3Na) in 3000 parts of water at from 0 to 10 C. The mixture is then stirred at room temperature until a sample is soluble in water. The product obtained is a highly efficient washing and scouring agent and softening agent for fabrics from artificial silk and corresponds to the formula CzH4SO3NB RCON - cm in which R-CO denotes the radicles of the acids of coconut oil.

Erample 33 10 parts of palmitic acid are dissolved in about 100 parts of tri-n-butyl amine, whereupon the solution is introduced into 10 parts of N-methyl taurine. The mixture is then heated to boiling while stirring and passing through a slow current of air if desired while reducing the pressure in the reaction vessel, the butylamine distilled off being replenished until the splitting off of water has ceased. The butyl amine is then removed for example by adding water, rendering the solution acid and adding some ethyl alcohol and di-ethyl ether or another water-insoluble organic solvent and sufficient common salt for salting out. 3 layers are formed, the central of which contains the reaction product. This latter corresponds to the formula and is separated and freed from remainders of the solvents by evaporation. A product is obtained, which either-in the form of the free acid or after conversion of the original butylamine salt into an alkali metal salt constitutes a highly valuable assistant for the textile industries.

Example 34 A product having properties similar to those of the product according to Example 32 can be obtained by the interaction of 100 parts of lauric acid methyl ester with 90 parts of powdered anhydrous sodium salt of N-methyl taurine at 180 C., while stirring and passing through a slow current of nitrogen for the removal of methyl alcohol split off. The resulting product is taken up with some water, rendered slightly acid with the aid of hydrochloric acid and mixed with ethyl ether. The aqueous layer is drawn off whereupon, after some standing, lauric N-methyl tauride sodium'salt crystallizes in the mixture and is filtered off by suction.

Example 35 10 parts of cetyl taurine (obtainable from cetyl amine and chlorethane sulphonic acid) are dissolved in 10 parts of an aqueous caustic soda 1 solution of 40 B. strength and about 30 parts of water and stirred, while cooling, with 20 parts of acetic anhydride until a sample is completely soluble in water in contrast to the cetyl taurine which is soluble only in alkaline solutions. The product obtained is rendered neutral with the aid of caustic soda solution and evaporated to dryness. The acetyl-, n-cetyl amino-ethane sulphonic sodium salt (CHa-CO-N Cm as possesses a good wetting and washing power.

Example 36 300 parts of oleic chloride are introduced at from 15 to 20 G. into a suspension in 1,000 parts of water of 300 parts of the sodium salt of N- cyclohexyl taurine sodium salt Ill: I

is completely soluble in water and is then rendered neutral with the aid of aqueous caustic soda solution of 40 B. strength. The oleic N-cyclohexyl tauride sodium salt C|H-SOaNa i1Hsa possesses a very good foaming power.

Example 37 245 parts of the sodium salt of N-methyl taurine (HNCH2. CH2. SOsH) are dissolved in 1,000 parts of water and 250 parts of acetone and 450 parts of oleic chloride are added. While intimately stirring 650 parts of 10 per cent aqueous caustic soda solution are then gradually introduced in such a manner that the reaction mixture is continuously kept alkaline, the temperature being preferably kept at from 30 to 40 C. The resulting clear solution is rendered neutral with the aid of hydrochloric acid and inspissated. A colourless product consisting mainly of oleic N -methyl tauride sodium salt together with some common salt is obtained. The product resembles commercial soap powder in its touch and dissolves easily to a clear solution in cold water. The solutions of the sodium salt in water show a neutral reaction and possess a high foaming power, the solutions being neither rendered turbid by the addition of calcium salts or of acids nor is their foaming power reduced by the presence of such additions and the solutions possess a considerable wetting and emulsifying power independently on the presence of alkalies or acids.

Example 38 A mixture of 500 parts of oleic chloride and 200 parts of stearic chloride is gradually stirred at from 30 to 40 C. into a solution of 385 parts of the sodium salt of N-methyl taurine while 100 parts of an aqueous 10 per cent caustic soda solution are added in such a manner that the reaction mixture is continuously kept alkaline and that the temperature remains within the aforesaid range. The product is worked up as described in the foregoing example, the properties and the appearance of the mixture of tauride sodium salts corresponding to that of the oleic tauride.

Example 39 30 parts of the sodium salt of N -phenylaminoethane sulphonic acid are introduced into a solution of 42 parts of stearic chloride in 11 parts of pyridine, the mixture being stirred while raising the temperature to C., until the reaction product gives a clear solution with water. The resulting mixture of stearic N-phenyl tauride sodium and pyridine salts C2H4-SOaN8 (CnHss-C 0-N CaHs is a useful assistant in dyeing, especially of woolen goods with acid dyestuffs, and is preferably employed for this purpose in the form of a 50 per cent aqueous solution.

Example 40 25 parts of an aqueous caustic soda solution of 40 B. strength are added to an aqueous solution of 40 parts of the sodium salt of piperidine sulphonic acid (mainly EN Hz I2 SOaH) in 100 parts of water. While intimately stirring 60 parts of phenylstearic chloride are slowly added at from 15 to 20 C. The reaction mixture is then stirred for from 3 to 4 hours and neutralized with hydrochloric acid, whereby, after adding some cormnon salt, a salve-like reaction product separates at the top of the aqueous solution. After removal of the aqueous layer the product which mainly consists of the amide Hz Hg H, S0 Na may be employed as a softening agent for textile materials especially for those from artificial silk.

Example 41 A commercial naphthenic acid mixture is converted into the corresponding chloride with the aid of phosphorous trichloride. 200 parts of this chloride are then stirred into an aqueous solution of 180 parts of horny] amine sulphonic acid sodium salt obtainable by the reduction of camphor oxime sulphonic acid) dissolved in about 1000 parts of water and of 150 parts of caustic soda while keeping the reaction mixture at from 15 to 20 C. and continuously alkaline by adding an aqueous caustic soda solution. After the reaction, the whole is stirred for 1 hour at about 35 C. The reaction product is then allowed to settle and is separated from the mother liquid, the product being then take up in a little warm Water. A 10 per cent aqueous solution of the product is a viscous liquid.

In the place of the N-bornyl amine sulphonic acid sodium salt salts of other amino sulphonic acids, as for example the alkali metal salts of amino cyclohexyl sulphonic acids (such as or of the amino sulphonic acids from hydrocarbons of the resinic or naphthenic acid series may be employed, the naphthenic acid being replaced for example by a resinic acid or by a mixture containing the same such as tall oil, which is a mixture of resinic and vegetable long chain fatty acids obtained as a by-product in the production of paper pulp by the sulphate process.

Example 42 200 parts of abietic acid are converted into abietic acid chloride by means of phorphorus trichloride in excess over the amount theoretically necessary and, if desired, in the presence of an inert liquid diluent such as carbon tetrachloride. Any solvent and unaltered phosphorus trichloride are then removed by distillation in vacuo and the resin-like residue is suspended in a small quan- SOaNa lot) tity of acetone. The suspension is introduced at 30 C. into a solution of 500 parts of the potassium salt of N-methyl taurine in 2000 parts of aqueous, 50 per cent acetone which is continuously kept alkaline by means of caustic soda. After about 1 to 2 hours the mixture is neutralized with aqueous sulphuric acid, the acetone is distilled off and the residue is evaporated to dryness. A product is thus obtained which may be ground readily and is an excellent wetting agent.

What we claim is:-

1. The process for the production of amides containing sulphuric derivative radicals which comprises reacting an aliphatic compound containing the grouping in which X is either halogen,

R being an aliphatic radical which radical may contain sulphuric derivative groups, in the absence of a metal halide having a condensing action, with an ammonia base corresponding. to the formula in which X denotes hydrogen or an aliphatic open chain-, an isocyclic aliphatic-, or an aliiphatic aromatic radical which radicals are free from aliphatic alcoholic groups, and X2 denotes hydrogen or a radical as denoted by X- or an aromatic radical free from chromophorous groups provided X is one of the aformentioned organic radicals, or X and X2 denote a conjoint aliphatic chain, all of which radicals may contain sulphuric derivative groups, and if the above initial reacting components do not contain sulphuric derivative groups reacting the resulting amide with a sulphonating agent, the carbon containing reacting components being so selected that the total carbon atoms in the resulting amide is at least 8.

2. The process for the production of amides containing sulphuric derivative groups, which comprises reacting an aliphatic compound, containing the grouping a metal halide, having a condensing action, with an ammonia base corresponding to the formula in which X1 denotes hydrogen or an aliphatic open chain-, an isocyclic aliphatic-, or an aliphatic-aromatic radicle, which radicles are free from aliphatic alcoholic groups, and X2 denotes in which X is either halogen or o -OH, O.R, 0-c

B. being an aliphatic radicle, in the absence of a metal halide, having a condensing action, with an amino-sulphonic acid, the carbon containing reacting components being so selected that the total number of carbon atoms in the resulting amide is at least 8.

4. The process for the production of amides containing sulphuric derivative groups, which comprises reacting an aliphatic compound, containing the grouping o n-c in which X is either halogen or R being an aliphatic radicle, in the absence of a metal halide, having a condensing action, with a secondary amino sulphonic acid, the carbon containing reacting components being so selected that the total number of carbon atoms in the, resulting amide is at least 8.

5. The process for the production of amides containing sulphuric derivative groups, which comprises reacting an aliphatic compound, containing the grouping o RC in which X is either halogen or o OH, O.R, -o-c B being an aliphatic radicle, in the absence of a metal halide, having a condensing action, with a secondary amino-alkyl sulphonic acid, the carbon containing reacting components being so selected thatthe total number of carbon atoms in the resulting amide is at least 8.

6. The process for the production of amides containing sulphuric derivative groups, which comprises reacting an aliphatic compound, con- 143 taining the grouping in which X is either halogen or 0 OH, -0.R, o-c

R being an aliphatic radicle, with a taurine, body, the carbon containing reacting components being so selected that the total number of carbon atoms in the resulting amide is at least 8.

7. The process for the production of amides containing sulphuric derivative groups, which comprises reacting an aliphatic compound, containing the grouping 0 RO-\ X in which X is either halogen or 0 OH,O.R,OC

in which R denotes an aliphatic open chain-,

a heterocyclicor aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or an aliphatic open chain, an aliphatic aromaticor an isocyclic aliphatic radicle and X2 denotes hydrogen or a radicle as denoted by X1, or an aromatic radicle provided X1 is one of the said organic radicles, or X1 and X2 form a conjoint aliphatic chain, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei connected to nitrogen are free from chromophorous groups and at least one sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, is connected to a carbon atom.

9. Amides containing sulphuric derivative radicals corresponding to the formula X1 n-co-N in which R denotes an aliphatic open chain-, heterocyclicor aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or an aliphatic open chain-, an aliphatic aromaticor an isocyclic aliphatic radicle and X2 denotes hydrogen or a radicle as denoted by X1, or an aromatic radicle provided X1 is one of the said organic radicles, or X1 and X2 form a conjoint aliphatic chain, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei connected to nitrogen, are free from chromophorous groups and several sulphuric derivative radicles, selected from the group consisting of sulphuric ester and sulphonic acid groups, are connected to carbon atoms of the said organic radicles.

10. Amides containing sulphuric derivative radicals corresponding to the formula in which R denotes an aliphatic open chainor isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or an aliphatic open chain-, or aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei, and X2 denotes hydrogen or a radicle as denoted by X1, or an aromatic radicle provided X1 is one of the said organic radicles, or X1 and X2 form a conjoint aliphatic chain, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei connected to nitrogen are free from chomophorous groups and at least one sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, is connected to a carbon atom.

11. Amides containing sulphuric derivative radicals, corresponding to the formula in which RCO denotes a radicle of a fatty acid of vegetal origin, X1 denotes hydrogen or an aliphatic open chain, or aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei, and X2 denotes hydrogen or a radicle as denoted by X1, or an aromatic radicle, provided X1 is one of the said organic radicles, or X1 and X2 form a conjoint aliphatic chain, in which amides any aromatic nuclei connected to nitrogen are free from chromophorous groups and at least one sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, is connected to a carbon atom.

12. Amides containing sulphuric derivative radicals, corresponding to the formula derivative radicle, selected from the group con-' sisting of sulphuric ester and sulphonic acid groups, is connected to a carbon atom.

13. Amides containing sulphuric derivative radicals, corresponding to the formula in which R-CO denotes a radicle of a fatty acid of vegetal origin, X1 denotes hydrogen or an aliphatic open chain-, or aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei and X2 denotes groups, are connected to carbon atoms of the said organic radicles.

14. Amides containing sulphuric derivative radicals, corresponding to the formula in which R denotes an aliphatic open chainor an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or an aliphatic open chain-, or aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei, and X2 denotes hydrogen or a radicle as denoted by X1, or an aromatic radicle provided X1 is one of the said organic radicles,v or X1 and X2 form a conjoint aliphatic chain, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei are free from chromophorous groups and at least an amino radicle of said amide contains a sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, connected to a carbon atom.

15. Amides containing sulphuric derivative radicals, corresponding to the formula in which R denotes an aliphatic open chainor an isocyclic aliphatc radicle containing up to three condensed nuclei, X1 denotes an aliphatic open chain, or aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei, X2 denotes a radicle as denoted by X1, or an aromatic radicle, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei are free from chromophorous groups and at least an amino radicle of said amide contains a sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, connected to a carbon atom.

16. Amides containing sulphuric derivative radicals, corresponding to the formula in which R denotes an aliphatic open chainor an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes an aliphatic radicle and X2 denotes an aliphatic open chain or isocyclic aliphatic radicle or aliphatic-aromatic radicle, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei are free from chromophorous groups, and at least an amino radicle of said amide contains a sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, connected to a carbon atom.

17. Amides containing sulphuric derivative radicals, corresponding to the formula in which R denotes an aliphatic open chainor an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes a hydroxyalkyl radicle in which a hydrogen atom is substituted by a SO3H radicle and X2 denote's hydrogen or an aliphatic open chain-, or aliphaticaromatic radicle or an isocyclic aliphatic radicle, in which amides the total number of carbon atoms is at least 8 and any aromatic nuclei are free from chromophorous groups.

18. Amides containing sulphuric derivative radicals, corresponding to the formula in which R. denotes an aliphatic open chainor an isocyclic aliphatic radicle containing up to three condensed nuclei and X1 and X denote aliphatic radicles, in which amides the total number of carbon atoms is at least 8, and at least an .amino radicle of said amide contains a sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, connected to a carbon atom.

19. Amides containing sulphuric derivative radicals, corresponding to the formula in which R denotes an aliphatic open chainor an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes an aliphatic radicle and X2 denotes hydrogen or an aliphatic open chain, or aliphatic-aromatic radicle or an isocyclic aliphatic radicle, in which amides the total number of carbon atoms is at least 8 and a sulphonic acid radicle connected to a carbon atom of an aliphatic amino radicle.

20. Amides containing sulphuric derivative radicals, corresponding to the formula Xx R-CON/ X: in which R-CO denotes a radicle of a fatty acid of vegetal origin, X1 denotes an aliphatic radicle and X2 denotes hydrogen or an aliphatic open chain, or aliphatic-aromatic radicle or an isocyclic aliphatic radicle, in which amides the total number of carbon atoms is at least 8 and a sulphonic acid radicle is connected to a carbon atom of an aliphatic amino radicle.

21. Amides containing sulphuric derivative radicals, corresponding to the formula in which R-CO denotes a radicle of a fatty acid of vegetable origin, X1 and X2 denote aliphatic 145 radicles and in which amides the total number of carbon atoms is at least 8, and at least one of the radicles X1 and X2 contains a sulphonic acid radicle connected to a carbon atom of said radicles.

22. Taurides containing sulphuric derivative radicals, corresponding to the formula X1 ii-oo-N in which R denotes an aliphatic open chain-, heterocyclicor aliphatic-aromatic radicle, or an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or an aliphatic open chain-, an aliphatic aromaticor an isocyclic aliphatic radicle or an aromatic radicle, in which tauridies the total number of carbon atoms is at least 8 and any aromatic nuclei are free from chromophorous groups.

23. Taurides containing sulphuric derivative radicals corresponding to the formula CzIhSOaH in which R denotes an aliphatic open chain--, heterocyclicor aliphatic-aromatic radicle, or an isocyclic aliphatic radicle containing up to three condensed nuclei, and R1 denotes an aliphatic radicle, in which taurides the total number of carbon atoms is at least 8 and any aromatic nuclei are free from chromophorous groups.

24. Taurides containing sulphuric derivative radicals corresponding to the formula CzTIrSOaH in which R-CO denotes a radicle of a fatty acid of vegetable origin and R1 denotes an alkyl radicle, in which taurides the total number of carbon atoms is at least 8 and any aromatic nuclei connected to nitrogen are free chromophorous groups.

26. Oleic N-methyl tauridehodies corresponding to the formula CH3 C|7Haa-C0N C2H SOzOX in which X denotes hydrogen or a radicle of an organic or inorganic base.

27. Amides containing sulphuric derivative radicals corresponding to the formula X2 in which R denotes an aliphatic open chain-, heterocyclicor aliphatic-aromatic radicle, or an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or an chromophorous groups, and at least one sulaliphatic open chain-, an aliphatic aromaticor an isocyclic aliphatic radicle, X2 denotes hydrogen, a radicle as denoted by X1 or an aromatic radicle provided X1 is one of the said organic radicles, or X1 and X2 form a conjoint aliphatic chain, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei are free from chromophorous groups and at least one sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, is connected to a carbon atom of R.

28. Amides containing sulphuric derivativeradicals corresponding to the formula in which R denotes an aliphatic open chain-,

heterocyclicor aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or an aliphatic open chain, an aliphatic aromaticor an isocyclic aliphatic radicle,Xzdenotes an organic radicle as denoted by X1, or an aromatic radicle provided X1 is one of the said organic radicles, or X1 and X2 form a conjoint aliphatic chain, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei are free from phuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, is connected to a carbon atom of R and of at least one of the organic radicles denoted by X1 and X2.

29. Amides containing sulphuric derivative radicals corresponding to the formula in which R denotes an aliphatic open chainor an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or an aliphatic open chain-, or aliphatic-aromatic radicle or an isocyclic aliphatic radicle containing up to three condensed nuclei, and X2 denotes hydrogen or a radicle as denoted by X1 or an aromatic radicle provided X1 is one of the said organic radicles, or X1 and X2 form a conjoint aliphatic chain, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei are free from chromophorous groups and at least one sulphuric derivative radicle selected 3 from the group consisting of sulphuric ester and sulphonic acid groups, is connected to a carbon atom of R.

30. Amides containing sulphuric derivative radicals corresponding to the formula sulphuric ester radicle is connected to a carbon atom of R.

31. Amides containing sulphuric derivative radicals, corresponding to the formula in which R denotes an aliphatic open chain or an isocyclic aliphatic radicle containing up to three condensed nuclei, X1 denotes hydrogen or a radicle as denoted by R and X2 denotes hydrogen or a radicle as denoted by R, or an aromatic radicle provided X1 is one of the said organic radicles, or X1 and X2 form a conjoint aliphatic chain, in which amides the total number of carbon atoms is at least 8, any aromatic nuclei are free from chromophorous groups and at least one sulphuric derivative radicle, selected from the group consisting of sulphuric ester and sulphonic acid groups, is connected to a carbon atom besides a sulphuric ester radicle connected to a carbon atom of R.

32. An amide corresponding to the formula in which R-CO is the radicle of a fatty acid of vegetal origin, X1 is an alkyl radicle and X2 is an aromatic radicle free from chromophorous groups and at least one sulphuric ester radicle is connected to a carbon atom of R.

33. A carboxylic amide of hydroxy-stearic sulphuric ester and N-ethyl aniline.

34. The sodium salt of the carboxylic amide corresponding to the formula FRITZ GUENTHER.

FERDINAND MU Z. HANS HAUSSMANN.

Certificate of Correction Patent No. 1,932,180.

numbered patent requiring FRITZ GUENTHER ET AL.

It is hereby certified that errors appear in the correction as follows:

printed specification of the above Page 9, line 58, strike out the formula and insert instead (UH --NHC'H CH SO NA); page 10, line 124, for f take read taken; page 13 line 43, claim 15, for aliphate read aliphatic; page 15, lines 90 to 95, claim 34, strike out the formula and insert instead:

and that the said Letters Patent should be-read with these corrections therein that the same may conform to the record of the'case in the Patent Office.

Signed and seaied thislst day of May, A. D 1934.

[SEAL] BRYAN M. BATTEI, Acting Oowwm'ssz'omr of Patents.

October 24, 1933.,