Patented Apr. 1, 94 2,236,530 UNITED STATES PATENT OFFICE 2,236,530 suLPHoCARBOXYLIC ACRED ESTERS OF ALCOBO AMNE DERWATWES Albert K. Epstein and Morris Katzaraat, Chicago, l, assignors to Ahe Emulso Corporation, Chi cago, Ill., a corporation of Elinois No Drawing. Application September 28, 1939, Serial No. 296.98 18 Claims. (C. 260-401) Our invention relates to a new class of chemical acid group. A more complete understanding of Substances, and more in particular to a new class what may comprise the lipophile group and the of chemical substances having capillary active particular character of the sulpho-carboxylic or properties and particularly adapted for use as sulpho- group will be had as the de detergents, wetting, penetrating, emulsifying, , tailed description progreSSeS. lathering, fiotation and anti-spattering agents, The function of the sulphonic acid group is to and for frothing purposes. impart hydrophilic properties, that is, water Wet The principal object of the present invention ting or water attracting properties, to the mole is the provision of a new class of chemical Sub cule as a whole. The groups which are esteri stances capable of satisfactory use in connection fied by the sulpho-carboxylic or sulpho-fatty acid with the problems and fields hereinabove and are in general of a lipophile character. At times hereinafter discussed. they may be strongly lipophilic and at other Another object is the provision of a new class times moderately lipophilic. They may be of of chemical substances which are in general of low molecular weight or of moderately high no relatively simple structure and can be cheaply lecular weight, depending upon the purpose for made in commercial quantities. which the substances may be used. Another object is the provision of a new class More specifically, at least most of the Sub of chemical substances having improved Wetting stances of the invention are lower molecular and detergent characteristics. weight sulpho-carboxylic acid esters of alcohol Other objects and features of the invention Will :20 primary or secondary amines, hydrogen attached be apparent from a consideration of the following to nitrogen of the alcohol primary or Secondary detailed description. amines being replaced by an acyl radical con The substances of the invention are in general taining at least four and preferably from eight esters, preferably of lower molecular Weight car to eighteen carbon atoms. boxylic or fatty acids, with at least one unesteri illustrative examples of compounds falling fied sulphonic acid group in the carboxylic or Within the scope of the invention are as follows: fatty acid radical, wherein. the group esterified with the sulpho-carboxylic or Sulpho-fatty acid (1) C-C-NH-CH-O-C-CH -SO3Na contains nitrogen linked to carbon and a lipophile l & radical with at least four carbon atoms. In cera 30 (2) Cish-C-NH-C.E.-O-C-CH-CH-soak tain circumstances there may be more than one nesterified sulphonic acid group in the car boxylic or fatty acid radical or there Inay be sul (3) CH-CO-NH-CH-O-C-CH2-SO3K phonic acid groups that are esterified and other O sulphonic acid groups that are not esterified but 3 (4) C.E.-- N- CH-CH-C-O-C-C-SO3N in all cases there must be at least One unesteria O O fied sulphonic acid group in preferably the lower molecular weight carboxylic or fatty acid radical. The carboxylic or fatty acid radical with the un (5) CE-O-C-C133 esterified sulphonic acid group is, as indicated, 40 C-CO-N-CH-CH-N preferably of relatively low molecular weight and, for best results, should contain not more C.H-0--C H-SO3Na than eight carbons. Considering the compounds from another C.H.OH aspect, the molecule in each instance contains a 45 relatively high molecular weight lipophile group (6) CH-CO-N and a relatively low molecular Weight hydrophile CH-O--CH-SO.Na group which, in the class of compounds to which the present invention relates, are sulphonic acid O radicals or free or unesterified OH groups in con junction with a sulphonic acid radical. From C.H-0--Caha still another angle, the compounds may be con (7) C-CO-N- W sidered as combinations of a higher molecular weight lipophile group and a relatively low no CH-O--chi-sok lecular weight sulpho-Carboxylic or SulphO-fatty 55

8

2 2,286,580 (8) l ', corn oil, cottonseed oil, sardine oil, tallow, soya CH-C-NH-(CH2)-CH-O-C-CH-SOH.NE(('HOH) bean oil, peanut oil, castor oil, seal oil, whale oil, I shark oil, partially or completely hydrogenated animal and vegetable oils such as those men tioned; hydroxy and alphahydroxy higher ali phot phatic and fatty acids such as i-hydroxy stearic (9) Cutta--NH-CH-N--H-CH,- COOK acid, dihydroxy , alpha-hydroxy dok stearic acid, alpha-hydroxy , alpha hydroxy , alpha-hydroxy coconut oil (10) CH-C-NBI-CE-NH-CH-O-C-C-SONa 10 mixed fatty acids, and the like; other substituted fatty acids such as (ii) CH-C-NH-CH-O-CH-O-C-CH-S OK B-C-COO

(12) CiHan-g-NH-CHi-O-g-CH-soH.HN-CHOH 15 Where R is a higher molecular weight hydrocar bon radical; fatty acids derived from various Waxes such as beeswax, spermaceti, montan wax, (13) CH-(CH2)-CH--NH-CH-O-g-CH-s OK and carnauba wax and carboxylic acids derived, by oxidation and other methods, from petrole CH-CH 20 um; cycloaliphatic and hydroaromatic acids such as hexahydrobenzoic acid, resinic acids, naph (14) cá, C-C-NH-C-C-C-O-C-C-SONa thenic acid, and abietic acid; aromatic acids Yoh-cá, such as phthalic acid, benzoic acid, naphtholic O acid, pyridine carboxylic acids; hydroxy aro 25 matic acids such as salicylic acid, hydroxy ben (15) t–NH-CH-O--ch-s ONBI Zoic and naphtholic acids, and the like; and sub stitution and addition derivatives such as amino, halogen, hydroxy, sulphate, sulphonic, phosphate O and the like substitution and addition derivatives 30 of the aforementioned carboxylic substances. It CH-CH-CH-O-(-CH-s O3K will be understood that mixtures of any two or (16) Ciba-C-N, more of said acids may be employed. Yoh-CH-CH-o-c-ch-s OK The alcohol primary and secondary amines or alkylolamines which provide the linkage between the lipophile group and the sulpho-carboxylic Cas group may be selected from a large class and in (17) Culti-c-f-c-b-o-c-CH,- SO3Na clude symmetrical, unsymmetrical, normal and s iso-derivatives, such as monoethanolamine, di O ethanolamine, mono-propanolamine, di-propa 40 nolamine, mono-butanolamine, mono-iso-buta (18) CH-NH--Caha nolamine, mono-pentanolamine, mono-hexanol & HoH amine, mono-decylolamine, mono-laurylolamine, mono-hexadecylolamine, mono-Octodecylolamine, mono-ethyl ethanolamine, mono-butyl ethanol bi-o-on-on-on- OK amine, cyclohexyl ethanolamine, N-cyclohexyl O butanolamine, ethanolandline, alkylolamines of (19) CH-NH-i-Citi, other monovalent or polyvalent alcohols such as glycols, glycerol, sugars, and sugar alcohols such (HoH), as dextrose, sucrose, sorbitol, mannitol and dul CH-0--H-CH, t 50 citol, alkylol polyamines such as alkylol deriva d solk tives of ethylene diamine, diethylene trianine While the above examples represent single and triethylene tetraamine, arylolamines and Substances, it will be understood that, in practice, cyclic hydroxy amines such as N-phenyl ethanol it is, in general, more advantageous to employ amine, p-amino phenol, mixtures of any two or more thereof with or 55 Without diluents. Many different types of compounds may be Ho-ch-{ X-NH. Selected as lipophile groups which are to be re and the like. The alcohol or alkylol radicals of acted with the alcohol primary or secondary the alcohol amines or alkylolamines may contain amines, principally compounds having lipophile 60 substitutent groups such as amino, nitrile, car radicals of relatively high molecular weight. boxyl, hydroxy, halogen, sulphate, Sulphonic, For example, the following materials may be phosphate, and the like and the sequence of car utilized as Sources of lipophile groups: straight bon atoms therein may be interrupted by O, S, chain and branched chain carboxylic, aliphatic, C-O, NH, NR where R is lower alkyl, and the and fatty acids, saturated and unsaturated, such 65 like. as , , , capric From a study of the compounds which are acid, sebacic acid, , , listed hereinabove, those skilled in the art will , , melissic acid, Stearic acid, understand that many different expedients may , ricinoleic acid, , linolenic be employed for forming the compounds in So acid, lauric acid, , palmitic acid, 70 far as the dominant lipophile group and the rel mixtures of any two or more of the above men atively low molecular weight sulpho-carboxylic or tioned acids or other acids, mixed higher fatty fatty acid group are concerned. As stated, how acids derived from animal or vegetable sources, ever, ester linkages are utilized between these for example, lard, COConut oil, rapeseed oil, two portions of the compound, and the skilled sesame oil, palm kernel oil, palm oil, olive oil, 75 chemist will understand in general the most ap a.

s 2,286,530 8 proved practices in securing this result. Nu ester of lauric acid may be reacted with mono merous methods are also available for the in ethanolamine at about 150 degrees C. to 80 de troduction of the sulphonic acid group. grees C. until the methyl alcohol or ethyl alco In the case particularly of aliphatic Sulphonic hol, as the case may be, formed in the reaction acids, a reactive halogen may be caused to re is volatilized. act with an alkali Sulphite such as sodium sul (2) To 23 grams of the product obtained in phite, potassium sulphite, ammonium sulphite or part (i) hereof, 4 grams of chloracetic acid lithium sulphite or some other sulphite in aque were added and the mixture was heated for 2 Ous Solution, if desired. to 3 hours at 150 degrees C-190 degrees C. The Another method is to introduce a sulph-hy O resulting product was then washed three times dryl or disulphite or some other suitable sulphur with hot water (80-90 degrees C.) until it was group and then oxidize to the sulphonic acid free of acid. The product was liquid at room with nitric acid or a permanganate or some other temperature. Oxidizing agent. (3) To 66.4 grams of the washed product of The preferred process comprises reacting a 5 part (2), 26.6 grams of potassium meta bisul higher molecular weight carboxylic acid amide phite (K2S2O5), 13.3 grams of potassium hydroxo of an alcohol amine, containing at least one free ide, 0.6 gram of potassium iodide, and 80 cc. or esterifiable hydroxy group, with a halogeno of Water were added and the resulting mixture carboxylic acid such as chloracetic or brom Was heated for 2 hours with stirring at 80 de , or with a halogeno-carboxylic acid 20 grees C.-88 degrees C. halide Such as chlor-acetyl chloride or bron (4) To the product resulting from part (3) acetyl bromide, to form a chloracetate or brom hereof, 6 volumes of isopropyl alcohol were added acetate, and then converting the latter into the aid the mixture was brought to a boil and then Sulphonic acid derivative by reaction with an filtered to remove the inorganic salts. To the alkali Sulphite. Other halogeno-carboxylic acids filtrate 3 more volumes of isopropyl alcohol were or derivatives thereof which may be utilized are added, the solution was cooled in an ice bath, those derived from mono-, di-, and poly-car and the material which crystallized out was ill boxylic acids including, for example, iodo acetic tered off and dried. It was a hard, crystalline acid, alpha-chlor , alpha-chlor. solid, light brown in color and had good wetting butyric acid, alpha-brom , mono-chlor 30 properties and other properties such as those succinyl chloride, di-chlor succinyl chloride, described hereirafter. mono-chlor Succinic acid, di-chlor succinic acid, Eacomple B mono- and di-brom glutaric acid and the cor responding glutaryl bromides, nitro-chloro-ben (1) 25 grams of the coconut oil mixed higher Zoyl chlorides, and the like. Of particular utili fatty acid amides of monoethanolamine (co ity are the halogeno-acetic acids and their hal sisting largely of the lauric acid amide of mono ides. ethanolamine) and 1 grams of maleic anhydride The following examples are illustrative of the were mixed together and heated to 100 degrees preparation of compounds falling within the C. for a few minutes with stirring. scope of the invention. It will be understood, of 40 (2) 10 grams of the product resulting from part course, that said examples are given only by way (l) hereof were mixed with 10 grams of po of illustration and are not to be considered in tassium meta-bi-sulphite dissolved in 40 cc. of any way limitative of the true Scope of the in water (50 degrees. C.) and the mixture was vention. Thus, for example, other methods may Warmed to 60 degrees C.-70 degrees C., with stir be employed, the proportions of reacting ingredi ring, for a few minutes. The mass became clear ents and times and temperatures of reaction may and honogeneous. It was a viscous liquid, solu be varied, and Supplementary processes of puri ble in Water, and had excellent wetting and fication may be resorted to wherever found de foaming properties. The reaction product com sirable or convenient. These and other varia prises essentially a compound having the follow tions and modifications Will be evident to those 50 ing probable formula: skilled in the art in the light of the guiding O principles disclosed herein. R-CO-NH-C-O-C-C-C-COOK. sea EacGimple A Acyl radical O3K of coconut oil mixed (1) One mol of lauric acid and about la mois 5 5 fatty acids of monoethanolamine Were heated for 54 hours Eacample C at a temperature of 150 degrees C.-222 degrees C. While continuously passing steam through the 216 grams of the naleic acid ester of the coco reaction mixture While maintaining the latter nut oil mixed fatty acid anides of monoethanola under reduced pressure, until the free fatty acids 60 nine, 150 grams of sodium sulphite and 400 cc. were decreased to 0.3%. The resulting product of water were heated and stirred at a temperature contained about 95% of the lauric acid amide of from 60 degrees C. to 65 degrees C. for a period monoethanolamine. The product was washed of about 10 minutes. The reaction mass was a free of the excess monoethanolanine with hot paste which contained a substantial proportion Water, three Washings being employed and each 65 of a compound having the following probable time the product was salted out with sodium formula: R-CO-N-CI-O-C-C-C-COONa chloride. An excess of ether was then added - . thereto, the maSS Was heated to the boiling point Acyl radical O SON of coconut of the ether, anhydrous sodium sulphate was oil mixed added thereto, the ether layer was poured of O fatty acids and the ether was then evaporated. In order to make an effective hair shampoo (l-a) In order to obtain essentially complete from this composition, 690 cc. of water were add amidification. With little or no ester formation ed thereto, the product was cooled to 20 degrees and to form light-colored compositions at some C. and 55 cc. of a 30% solution of hydrogen what lower temperatures, the methyl or ethyl peroxide Were added in order to remove the ex 4. 2,236,530 cess sodium sulphite. The product was neutral Eacample F ized to a pH of 6.8 by adding 12.5 cc. of a 20% (1) 25 grams of diethanolamine were dissolved solution of sodium hydroxide. The final product in 25 cc. of Water and then 23 grams of lauroyl was a clear solution which had excellent foam chloride were added dropwise, with stirring, the ing and detergent properties. If desired, the mass being cooled so that the temperature did product may be substantially diluted with water. not rise above about 30 degrees C. To the re Eacample D Sulting reaction product, 1000 cc. of water were added and the mass was heated to 80 degrees C., 78.8 grams of the caprylic acid amide of mono common Salt being added to the point of Satura ethanolamine and 20 grams of maleic anhydride O tion. An oily layer formed on the top of the re were slowly heated for 10 minutes to 100 degrees action mixture and was removed and then dis C. and then heated to 230 degrees C. for about Solved in ether. Anhydrous sodium sulphate was one hour, under vacuum, whereby a compound then added to the ether Solution, the mass was having the following probable formula was pro filtered, and the ether evaporated. The residue duced: 5 contained predominantly the lauric acid amide O O of diethanolamine. CH-i-NH-CH-O- (2) 9.9 grams of lauric acid amide of diethanol N amine, obtained as described in part (1) herein above, and 3.6 grams of maleic anhydride were 20 heated to 80 degrees C., with stirring, after which the temperature spontaneously rose to 90 de grees C., the reaction mixture then being heated to 100 degrees C. and kept at such temperature 10 grams of this product were then heated for between 5 and 10 minutes. with 20 grams of sodium bisulphite and 40 cc. (3) 12 grams of the reaction product from of water for between 10 and 15 hours at a tem part (2) hereinabove, 20 cc. of water and 10 perature of about 90 degrees C. until the mix grains of Sodium bisulphite were heated at a ture became water soluble. The resulting prod temperature of 55 degrees C.-60 degrees C. for uct, which was in paste form, had excellent foam about 10 minutes, with stirring; the resulting re ing properties and comprised a substantial pro 30 action product had good foaming and wetting portion of a compound having the following prob properties. able formula: (4) In order to eliminate excess sulphite pres O O ent in the reaction product, 6 grams of a 30% so lution of hydrogen peroxide were added drop chi--NH-CH-O- CE-SO3Na Wise, with stirring, the mass being maintained in bH, an ice bath in order to prevent the temperature / rising above about 35 degrees C. The reaction C-Hit--NH-C E-O-C product was then neutralized with 8 cc. of a 20% Solution of sodium hydroxide. The final product, Eacample E 40 which had good foaming and wetting properties, (1) 1051 grams of monostearin and 200 grams contained a substantial proportion of a com of monoethanolamine were mixed together and pound or a mixture of compounds having the heated from 174 degrees C. to 250 degrees C. for following probable formulae: a period of about 2 hours. The reaction product thus obtained was washed twice, in each instance O SON a with 20 pounds of boiling water, to remove excess C.H.-0--chi-bh-coona or unreacted monoethanolanine and the glycerin (a) cha-i-N which was set free in the reaction. In the first CHOH washing step, 45 cc. of concentrated hydrochloric O S ONa acid were added to the wash water in order to 50 O CH-0--0 H.-l E-COONa neutralize the excess monoethanolamine and to facilitate the removal thereof by Washing. In (b) CEas- -N each instance, about 1 pound of common Salt was added to the wash water in order to aid in CH-0--CH-H-c OON salting out the compound. The resulting amide O oNa was dried at 150 degrees C-160 degrees C. in an Those substances which are freely soluble in OWe Water may be recovered from their solutions in (2) 36 grams of the dried amide resulting from the customary manner by concentration and part (1) hereof were mixed with 11 grams of crystallization. As stated hereinabove, as the maleic anhydride and the mixture was heated 60 maSS of the lipophile radical increases, solubility up to 140 degrees C., with stirring, for a period decreases and affinity for water is manifested by of about 10 minutes. the dispersibility in water. From these disper (3) 11 grams of the reaction mass resulting Sions, the Substances may be readily recovered from part (2) herein, 20 cc. of water, and 7.5 by "salting out' with suitable soluble electrolytes. grams of sodium sulphite were heated at 70 de Common salt is very satisfactory for this pur grees C.-80 degrees C. for about 10 minutes, with pose in most cases. When salted out of an aque stirring. The resulting product comprised a white ous dispersion at temperatures ranging from 60 paste, soluble in water and having good foaming to 95 degrees C., the substances are obtained in and surface tension reducing properties. It con the form of a paste with a water content rang tained a Substantial porportion of a compound 70 ing from approximately 25 to 75%. The more having the following probable formula: hydrophilic the Substance, the greater the wa ter content, and, of course, the salt is present in O O the Water of the paste in approximately the same critis-e-NH-CH-O-(-CH-CH-C OONa concentration in which it existed in the disper soNa sion from which the paste was salted out. 2,236,530 5. Many of the compounds of the present inven like of arsenical and similar sprays. They pos tion may be represented by the general formula, sess marked utility in the ore dressing industry Wherein they function effectively in froth flota tion processes. Their interface modifying prop 5 erties also permit their use in lubricating oils and s the like enabling the production of effective bor Wherei ing oils, cutting oils, drilling oils, wire drawing O oils, extreme preSSure lubricants and the like. R-C- They may also be used with effect in the prep O a ration of metal and furniture polishes, as pick denotes an aliphatic acyl radical containing at ling inhibitors in metal cleaning baths, in shoe least six carbon atoms and preferably from 12 to polishes, in rubber compositions, for breaking or 18 carbon atoms, alk is alkylene, or (alkylene-O- demulsifying petroleum emulsions such as those alkylene), it being one, two three or more and of the Water-in-oil type Which are encountered in --x 5 oil-field operations, and for various other pur O poses which will readily occur to those versed in the art in the light of our disclosure herein. is a carboxylic acyl radical containing at least As detergents, they may be employed for the One sulphonic group. preparation of shampoos, dentifrices and the like. Many of the compounds of the invention may 20 In general, they may be dissolved in water or also be represented by the general formula, aqueous media, and utilized in that form or, in O the case of solid products, they may be packaged 2 and sold in Such form preferably mixed. With R -o-c-X-so Y diluents. They may also be utilized for commer O O W 25 cial cleansing, laundering and Washing operations wherein R is a radical of an alcohol amine amidi with marked advantage. fied with a carboxylic acid acyl group having at The products of the present invention may be least four carbon atoms and preferably from employed alone or together With lesser or greater twelve to eighteen carbon atoms, X is the carbon quantities of inorganic or organic compounds. hydrogen residue of the sulpho-carboxylic acid, 30 Thus, for example, they may be employed to Y is a cation, and w is a small whole number, gether with salts such as sodium chloride, al at least one. kali metal phosphates including pyrophosphates At least many of the compounds of the present and tetraphosphates, sodium sulphate, alums, invention have utility in various arts in which perborates such as sodium perborate, and the interface modifying agents are employed. Many like. They may be utilized in alkaline or acid of them are resistant to precipitation by calcium media, in the presence of sodium carbonate, so and magnesin Salts and are compatible With diur bicarbonate, dilute acids Such as hydro acid and alkali media. They may, in general, be chloric, sulphurous, acetic and similar in Organic utilized in Washing and laundering and in the and organic acids. They may also be employed textile and related industries wherein they func 40 in the presence of such diverse substances as hy tion for softening, wetting, detergent, emulsify drophilic gums including pectin, tragacanth, ing, penetrating, dispersing, frothing and foam karaya, locust bean, gelatin, arabic and the like, ing purposes. The textiles, various treatments glue, vegetable, animal, fish and mineral oils, Sol of which in the presence of the agents of the vents such as carbon tetrachloride, monoethyl present invention are rendered effective, com- 45 ether of ethylene glycol, monobutyl ether of prise natural products such as cotton, Wool, linen ethylene giycol, monoethyl and monobutyl ethers and the like as well as the artificially produced of diethylene glycol, cyclohexanol, and the like. fibres (and fabrics), such as rayon, cellulose ace They may be used together with wetting, emul tates, cellulose ethers and similar artificial prod sifying, frothing, foaming, penetrating and de ucts. It will be understood, of course, that the 60 tergent agents such as the higher molecular agents may be used in aqueous and other media. weight alcohol or alkyl sulphates, phosphates, either alone or in combination with other Suit pyrophosphates and tetraphosphates as, for ex able salts of organic or inorganic character or ample, laury sodium sulphate, myristy sodium with other interface modifying agents. In the pyrophosphate, cetyl sodium tetraphosphate, octyl dyeing of textiles they may be employed as as 5 5 sodium sulphate, oley sodium sulphate, and the sistants in order to bring about even level shades. like; higher molecular weight sulphonic acid de They may be used in the leather industry as Wet rivatives such as cetyl sodium sulphonate and ting agents in soaking, dyeing, tanning and the laury sodium sulphonate; sulphocarboxylic acid softening and other treating baths for hides and esters of higher molecular weight alcohols Such skins. Their utility as emulsifying agents en- 60 as laury sodium sulphoacetate, dioctyl sodium ables them to be employed for the preparation of sulphosuccinate, dilauryl potassium sulpho-glu emulsions which may be used for insecticidal, tarate, laury monomethanolamine Sulpho-ace fungicidal and for similar agriculture purposes. tate, and the like; sulphuric and Sulphonic de They have utility in the preparation of cosmetic rivatives of condensation products of alkylol creams such as cold creams, vanishing creams, 63 amines and higher fatty acids; Turkey-red oils; tissue creams, shaving creams of the brushless compounds of the type of isopropyl naphthalene and lathering type and similar cosmetic prepara sodium sulphonate, and other classes of Wetting tions. Another use to which the agents of our agents. invention may be placed is for the treatment of It will be understood that the products may be paper where they may be employed, for example, employed in the form of impure reaction mix as penetrating agents in the cooking of the paper tures containing substantial proportions of the pulp or the like. Their capillary or interfacial effective interface modifying agent or agents or, tension reducing properties enables then to be if desired, for any particular purposes, purifica employed in the fruit and vegetable industry in tion procedures may be employed to produce pure order to effect the removal from fruits and the or substantially pure products. Those versed in 6 2,236,580 the art are familiar with the types of purifica 1. An alcohol amine in which amine hydrogen tion methods which may be employed with ad is replaced by an aliphatic carboxylic acyl radical vantage herein, particularly in the light of the containing at least four carbon atoms, and in disclosures made hereinabove. which hydroxyl hydrogen is replaced by an ali In the event that the compounds of the inven 5 phatic Sulpho-carboxylic acid radical. tion are made by reacting the halogen derivatives 2. An alkylolamine in which one hydroxyl hy With alkali Sulphites or other soluble sulphites drogen is substituted by an aliphatic sulpho as well as thio-Sulphates, the corresponding als carboxylic acid acyl radical containing from four kali Sulphonic acid derivative will be produced. to eight carbon atoms, and in which one amine The term alkali is employed to include the am O hydrogen is substituted by a straight chain ali monium radical (NH4) When prepared by oth phatic carboxylic acid acyl radical containing er methods so that the compounds contain the from twelve to eighteen carbon atoms. sulphonic acid group (-SO3H), the hydrogen 3. An alkyloamine in Which one hydroxyl hy thereof may be replaced by other cations such drogen is substituted by a sulpho-monocarboxylic as calcium, magnesium, aluminum, zinc, amines, acid acyl radical and in which One annine hydro alkylolamines such as mono, di- and triethanol gen is substituted by a fatty acid acyl radical con amine and mixtures thereof, other organic ni taining from twelve to eighteen carbon atoms. m trogenous bases such as pyridine and piperidine, 4. An alkylolamine in which hydroxyl hydrogen tertiary amines, quaternary ammonium bases is substituted by a lower molecular weight sulpho such as tetra-methyl ammonium hydroxide, etc., fatty acid acyl radical, and in which amine hy as described, for example, in the application of 20 drogen is Substituted by a straight chain aliphatic Morris B. Katzman, Serial No. 219,358, filed July carboxylic acid acyl radical containing from 15, 1938, Patent No. 2,184,770, issued December 26, tWelve to eighteen carbon atons. 1939. It will be understood that by the term 5. An alcohol amine in which amine hydrogen “cation,' as used throughout the specification is replaced by an aliphatic carboxylic acyl radical and claims, is meant hydrogen and such other containing from twelve to eighteen carbon atoms, elements as are mentioned herein, and, in gen , and in which hydroxyl hydrogen is replaced by an eral, atoms or radicals which are regarded as aliphatic sulpho-carboxylic acid acyl radical con bearing a positive charge or capable of replacing . ... taining not more than eight carbon atoms. acidic hydrogen. 30 6. Monoethanolamine in which one amine hy It will be understood that the Selection of the drogen is replaced by an aliphatic carboxylic acyl particular halogen derivatives which may be uti radical containing from twelve to eighteen carbon lized in the preparation of the products will de atoms, and in which the hydroxyl hydrogen is pend upon certain factors. Thus, while bromo replaced by an aliphatic Sulpho-carboxylic acid and iodo- derivatives, in general, react slightly radical containing not more than eight carbon more rapidly than do the chloro- derivatives, the atoms. relatively cheaper cost of the latter will generally 7. Monoethanolamine in which one amine hy justify their use from a purely economic stand drogen is Substituted by coconut oil mixed fatty point. acid acyl radicals and wherein hydroxyhydrogen The term “residue,' as used throughout the speci 40 is replaced by a sulpho fatty acid acyl radical fication and claims, is employed in its ordinarily containing from two to four carbon atons. understood chemical significance. For example, 8. Monoethanolamine in which one amine hy where the hydroxyl groups of monoethanolamine drogen is Substituted by a straight chain fatty is esterified with a sulpho-carboxylic acid and a acid acyl radical containing at least eight carbon hydrogen of the amino group of the monoethanol-. atoms and in which one hydroxyl hydrogen is amine is replaced by the carboxylic acyl group of replaced by an aliphatic sulpho-mono-carboxylic a higher fatty acid, that which remains of the acid acyl radical Containing not more than eight monoethanolamine molecule, for example carbon atoms. --HN-CHA droxyl9. A hydrogenmono-hydroxy is substituted alkylamine by in an which aliphatic hy is the “residue' of the alcohol amine, in this case sulpho-carboxylic acid acyl radical containing monoethanolamine. not more than eight carbon atoms, and in which Similarly, the term 'carbon-hydrogen residue' one amine hydrogen is substituted by a carboxylic of a Sulpho-carboxylic acid is employed as in con acyl radical containing at least eight carbon ventional chemical nomenclature. Thus, for ex atoms. ample, if sulpho-acetic acid 10. A sulpho-carboxylic acid derivative in the (HOOC-CH -SO3H) form of a reaction product of a salt of sulphurous is esterified with monoethanolamine, the group acid and the product resulting from the inter -CH2- is to be considered as the 'carbon action of an aliphatic halogeno-carboxylic acid hydrogen residue' of the Sulpho-acetic acid. with a fatty acid amide of an hydroxy alkyl Unless otherwise indicated, the term “higher,' 60 amine, the fatty acid radical containing at least wherever employed in the claims, will be under eight carbon atoms. stood to mean at least eight carbon atoms and, 1. Chemical compounds having the formula conconitantly, the term 'lower' will mean less than eight carbon atoms. Whenever the term sulpho-carboxylic ester, sulphO-acetate, or the like expression is employed wherein in the claims, it will be understood to cover the O compounds irrespective of whether the hydrogen R-C of the sulphonic acid is present as such or re is an acyl radical containing at least eight carbon placed by another cation. atoms, alk is a member selected from the group This application is a continuation-in-part of consisting of alkylene and alkylene-O-alkylene, our application Serial No. 222,150, fled July 30, 1938, Patent No. 2,178,139, issued October 3, 1939. it is a Whole number, and What we claim as new and desire to protect by -Ca-X Letters Patent of the United States is 75 2,236,580 7 is a carboxylic acid acyl radical containing at the fatty acid radical of which contains from least one sulphonic group. twelve to eighteen carbon atoms, with a halogeno 12. Chemical compounds having the formula acetic acid or acyl halide thereof, and then re acting the resulting compound with an alkali sui cha-i-NH-CH-CH-O--CH-s OY phite. 16. The process which comprises reacting an hy wherein Y is a cation selected from the group droxy amine to introduce a carboxylic acid acyl consisting of alkali metals, ammonia, and ethanol radical containing at least four carbon atoms in amines. place of amine hydrogen of the hydroxy amine, 13. The process which comprises reacting a O and an aliphatic sulpho-carboxylic acid acyl fatty acid amide of an hydroxy amine, the fatty radical in place of hydroxyl hydrogen of the hy acid radical containing from twelve to eighteen droxy amine. carben atoms, by means of a member selected 17. The process. Which comprises reacting from the group consisting of lower molecular monoethanolamine to introduce therein, in place weight aliphatic halogeno-carboxylic acids and of one amine hydrogen, a fatty acid acyl radical their acyl halides, and then reacting the resulting containing from twelve to eighteen carbon atoms, compound with a salt of sulphurous acid. and, in place of hydroxy hydrogen of the mono 1. The process which comprises reacting a ethanolamine, an aliphatic Sulpho-carboxylic member of the group consisting of chloracetic acid acyl radical containing not more than eight acid, bromacetic acid, chloracetyl chloride, and 20 carbon atoms. bromacetyl bromide, with a carboxylic acid amide 18. An alcohol amine in which amine hydrogen of an hydroxy aliphatic amine, the carboxylic is replaced by an aliphatic carboxylic acyl radical radical containing a chain of at least four carbon containing at least eight carbon atoms and in atons, and then reacting the resulting ester with which hydroxyl hydrogen is replaced by a sulpho an alkali sulphite, 25 carboxylic acid radical. 15. The process which comprises reacting a ABER 3, EPSEN. higher fatty acid amide of monoethanolamine, MORRIS KATZMAN.