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United States Patent Office Patented Dec 3,16,257 United States Patent Office Patented Dec. 31, 963 2 These and other objects and features of the invention 3,15,257 will be described or become apparent as the specification SURFACTANT COMPOSTECBNS CONTANNG proceeds. SATS OF WNYESULFCNANLDES In order to demonstrate the invention, a number of Bolaaid L. Kass, Barrington, ., assignor to The Praire 5 non-limiting examples are given: (Oil Company, Chicago, ii., a corporation of Ohio Example 1 No Brawing. Fied Dec. 19, 1960, Ser. No. 76,566 9 Caiaas. (C. 252-355) A 3.0-g. portion of the anilinium salt of 2-hydro Sulfato-1-dodecanesulfonanilide, previously prepared by This invention relates to a new class of surfactants reacting dodecene with dioxane-sulfur trioxide complex characterized as metallic salts of vinylsulfonamides. More O and aniline, was dissolved in 25 ml. of 1 N sodium hy particularly this invention relates to the discovery that droxide solution, and the resulting solution was heated vinylsulfonamides or sulfonanilides per se are not sur on a steam bath for 1/2 hours. During this period, the face active, but their salts possess surface activity provided Viscosity of the clear solution increased appreciably. the organic portion of the molecule contains at least 8 Then the mixture was cooled in an ice bath and neutral carbon atoms. ls ized with 10% hydrochloric acid solution, yielding 1 In accordance with this invention I have discovered dodecene-1-sulfonanilide having the formula that the alkali and alkaline earth metal salts of vinyl-sul fonamides derived from olefins containing at least 8 () CH3(CH2)CH=CHSONHg) carbon atoms have excellent surface-active properties. After the product had been filtered and recrystallized, The vinylsulfonamides per se and the metallic salts of 20 it was in the form of white flakes which had a melting vinylsulfonamides derived from lower-molecular-weight point of 55-57.5° C. The product was soluble in hexane olefins, i.e., having from 2 to 7 carbon atoms, do not and warn oil, contained nitrogen and sulfur (qualitative possess this surface activity. The surfactants of this elemental analysis), decolorized bromine solution in invention may be represented by the formula: acetic acid, and consumed an equivalent of alkali when 25 titrated, thereby indicating that it was as shown above. R1 R2 The infrared analysis was in accord with the structure - soner Mineb shown. wherein R, R, R2, and R3 are hydrogen or hydrocarbon Example 2 radicals containing from 1 to 20 carbon atoms and may 30 Example 1 was repeated, using hexene to form 1 be of the same or different configuration, i.e., alkyl, alk hexene-1-sulfonanilide, having the formula aryl, aryl, aralkyi, cr cycloparaffinic radicals containing from 1 to 20 carbon atoms, the total number of carbon (II) CH3(CH2)3CH=CHSONH atoms in R, R', and R is at least 6, or R3 contains at Example 3 least 6 carbon atoms or is an aryl group (e.g., phenyl), M 35 A 45-mg. portion of product () of Example 1 was is an alkali metal, i.e., sodium, potassium, lithium, treated with 1.34 ml. of 0.1035 N potassium hydroxide rubidium, or cesium, or an alkaline earth metal, i.e., solution to prepare the potassium salt of 1-dodecene-1- barium, calcium, strontium, and magnesium, and n is the valence of M. The organic portion of the molecule sulfonanilide, having the formula, comprises the olefinic carbon atoms along with R, R and 40 (III) ICH3(CH2)CH=CHSONebK(D R2, or the olefinic carbon atoms and R3, to constitute The volume of the resulting mixture was increased to a total of at least 8 carbon atoms. 50 ml. by adding distilled water, yielding a 0.1% aqueous The process by which the above-defined vinylsulfon suspension of compound III. amides are prepared comprises reacting about 1 mol of an olefia having at least 8 carbon atoms with about 45 Example 4 2 mois of sulfur trioxide in complexed form, treating A 40.5-mg. portion of product (II) of Example 2 was the reaction product with about 2 mols of a primary treated with 1.63 ml. of 0.1035 N potassium hydroxide amine per mc of olefin reactant, reacting the resulting Solution to prepare the postassium salt of 1-hexene-1-sul product with a sufficiently strong base to eliminate the fonanilide, having the formula, amine and the sulfato group to form the vinylsulfon 50 arinide, and reacting the vinylsulfonamide with an oxide or (IV) CH3(CH2)3CH=CHSONegblKICD hydroxide of an aikali or alkaline earth metal to form The volume of the resulting mixture was increased to 50 the surface-active salt. ml. by adding distilled water, yielding a 0.1% aqueous It becomes then a primary object of this invention to solution of (IV). provide surfactants of the general formula supra. 55 Example 5 Another object of the invention is to provide a process for preparing surfactants of the general formula supra The procedure of Examples 3 and 4 were repeated, by the steps outlined above. using sodium hydroxide in place of potassium hydroxide, Ancther object of the invention is to provide surfactants to obtain clear 0.1% aqueous solutions of the following comprising alkali metal salts of vinylsulfonamides where 60 products: in the organic portion of the molecule contains at least (V) 8 carbon atoms. Still another object of the invention is to provide sur (VI) (CH3(CH2)3CH=CHSO.Ned Naj9 factants comprising alkaline earth metal salts of vinyl The 0.1% solutions of compounds (I), (II), (III), sulfonamides wherein the organic portion of the molecule 65 Erlenmeyer contains at least 8 carbon atoms. (IV) were shaken 25 times in a 250 ml. 3 3,116,257 flask to determine the amounts of suds formed, with 4. the following results: Cesium salt of 1-tridecene-1-sulfonanilide Lithium salt of 1-tridecene-1-sulfonanilide Suds Barium salt of 1-tridecene-1-sulfonanilide Appearance of Rating Time to Calcium salt of 1-tridecene-1-sulfonanilide Compound Solution at Room Suds disap 5 Temper- pearance Strontium salt of 1-tridecene-1-sulfonanilide ature I Magnesium salt of 1-tridecene-1-sulfonanilide (I)------------------------ 10 Sodium salt of 1-tetradecene-1-sulfonanilide (II)------- O Potassium salt of 1-tetradecene-1-sulfonanilide (III)-------------- 10 (IIIa) (excess base 1 2 hours. 0. Cesium salt of 1-tetradecene-1-sulfonanilide (IV)- 9 Lithium salt of 1-tetradecene-1-sulfonanilide (V). i 2 hours. Barium salt of 1-tetradecene-1-sulfonanilide (VI)------ 9 10 minutes. Calcium salt of 1-tetradecene-1-sulfonanilide 1 The suds-forming properties were rated according to an arbitrary Strontium salt of 1-tetradecene-1-sulfonanilide scale wherein a rating of 1 was assigned when the 250 ml. Erlenmeyer Magnesium salt of 1-tetradecene-1-sulfonanilide flask was filled with suds, and a rating of 10 was assigned when no suds 5 formed. Thus, a rating of 3 indicates that 70% of the flask was filled with Sodium salt of 1-pentadecene-1-sulfonanilide suds, a rating of 4 indicates that 60% of the flask was filled, etc. Potassium salt of 1-pentadecene-1-sulfonanilide Example 6 Cesium salt of 1-pentadecene-1-sulfonanilide One mol of undecene-1 is reacted with 2 mols of sulfur Lithium salt of 1-pentadecene-1-sulfonanilide trioxide-dioxane complex at 0° C. in a solution of 200 ml. 20 Barium salt of 1-pentadecene-1-sulfonanilide of ethylene dichloride with stirring over a period of about Calcium salt of 1-pentadecene-1-sulfonanilide 1 hour. The resulting light yellow mixture is maintained Strontium salt of 1-pentadecene-1-sulfonanilide at -15 C. for two days, after which it is warmed to 10 Magnesium salt of 1-pentadecene-1-sulfonanilide C. and 186 g. (2 moles) of aniline in 200 ml. of ethylene Sodium salt of 1-octene-1-N-methyl sulfonamide dichloride are added. The resulting solution is maintained 25 Potassium salt of 1-octene-1-N-ethylsulfonamide at -15° C. for two days, during which time a compound Cesium salt of 1-octene-1-N-propylsulfonamide of the formula, Lithium salt of 1-octene-1-N-isopropylsulfonamide Barium salt of 1-octene-1-N-butylsulfonamide Calcium salt of 1-octene-1-N-t-butylsulfonamide 30 Strontium salt of 1-octene-1-N-amylsulfonamide is precipitated, namely, the anilinium salt of 2-hydrosul Magnesium salt of 1-octene-1-N-amylsulfonamide fato-1-undecanesulfonanilide. The precipitate is filtered Sodium salt of 1-nonene-1-N-benzylsulfonamide by use of a vacuum and air-dried. The product is dis Potassium salt of 1-nonene-1-N-naphthylsulfonamide solved in excess of 1 N sodium hydroxide solution and 35 Cesium salt of 1-nonene-1-N-anthrylsulfonamide heated on a steam bath for 2 hours. An increase in vis Lithium salt of 1-nonene-1-N-cyclohexylsulfonamide cosity of the solution occurs. The mixture is cooled on an Barium salt of 1-nonene-1-N-cyclopentylsulfonamide ice bath and neutralized with 10% hydrochloric acid, yield Calcium salt of 1-nonene-1-N-phenylethylsulfonamide ing 1-undecane-1-sulfonanilide of the formula Strontium salt of 1-nonene-1-N-phenylbutylsulfonamide 40 Magnesium salt of 1-nonene-I-N-phenylbutylsulfonamide C9H19-CH= CHSONHCH Sodium salt of 1-dodecene-1-N-pentylsulfonamide A 45-mg. portion of this product is treated with 1.46 ml. Potassium salt of 1-undecene-1-N-eicosylsulfonamide of 0.1 N sodium hydroxide to prepare the sodium salt of Cesium salt of 1-undecene-1-N-nonadecylsulfonamide 1-undecene-1-sulfonanilide: Lithium salt of 1-undecene-1-N octadecylsulfonamide 45 Barium salt of 1-undecene-1-N-heptadecylsulfonamide CH19-CH= CHSON-CHNa+ Calcium salt of 1-undecene-1-N-dodecylsulfonamide By following the foregoing examples, the various salts Calcium salt of 1-undecene-1-N-anthrylsulfonamide of this invention
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