Patent GB-651840-A (GB)
Title: Thioxane sulphur trioxide addition compounds and the use thereof as sulphonating and sulphating agents
Filed: 1947-07-10
Abstract: Thioxane-sulphur trioxide addition compounds, which are sulphonating and sulphating agents, are prepared by reacting 1 : 4-thioxane with sulphur trioxide, oleum, chlorsulphonic acid or fluor sulphonic acid. Thus, a mixture of sulphur trioxide or chlorsulphonic acid and an inert solvent may be added to the thioxane; the sulphonating agent may be added to a mixture of thioxane and the solvent; sulphur trioxide or chlorsulphonic acid may be added to a mixture of the solvent, thioxane and a material to be sulphonated; oleum or floursulphonic acid may be reacted either alone with thioxane or in conjunction with inert hydrocarbons, ethers, polyethers, inorganic and organic acid anhydrides and acid chlorides.  The addition compounds contain one or two molecular equivalents of sulphur trioxide per equivalent of the thioxane and are white solids difficulty soluble in benzene, carbon tetrachloride and ethylene dichloride and are hydrolysed by water.  They may be employed in the sulphation or sulphonation of organic hydroxy compounds such as primary, secondary and tertiary mono- and poly-hydroxy derivatives of substituted or unsubstituted aliphatic and aromatic hydrocarbons, of ether, polyethers, acids, esters and amines; and the sulphonation of olefinic compounds, in particular straight and branched chain olefines and tertiary olefines having a branch chain on an unsaturated carbon atom which may be mixed with saturated hydrocarbons, such as all pentenes, hexenes, heptenes, octenes, nonenes and the like, as well as halogenated olefines; suitable olefinic materials are obtainable by dehydration of various alcohol, partial or complete dehalogenation of halogenated hydrocarbon, cracking of saturated hydrocarbons, polymerization of such olefines as propylene butylenes, isobutylenes, pentenes, hexenes and isohexenes, decarboxylation of unsaturated fatty acids and halogenation of aliphatic unsaturated hydroxy compounds. Olefinic compounds are converted into olefinic sulphonic acids. The preferred olefines have the general formula <FORM:0651840/IV (b)/1> where either R1 or R2 may be hydrogen or both straight or branched chain substituted or unsubstituted hydrocarbon radicals and at least one X or Y radical is hydrogen and the other a hydrogen or straight or branched chain alkyl group but in no case should X, Y and either R1 or R2 be hydrogen atoms at the same time; preferably, the olefins have 4-30 carbon atoms; on sulphonation one of the hydrogen atoms, either on the double bond or in one of the alkyl groups is substituted by a sulphonic group.  The olefinic sulphonic acids in salt form are surface active (see Group IV (c)).  The hydroxy compounds yield sulphuric acid esters which are surface active and may be used as chemical intermediates and as dyestuffs.  The thioxanesulphur trioxide addition compounds may be used for selective sulphonation of unsaturated hydrocarbons, such as aromatic polycyclic compounds, and for sulphonations under mild conditions to reduce by-product formation; hydrocarbon treated may contain halogens, nitro groups, carbonyl groups, free or esterified carboxylic acid groups and ether linkages.  In typical examples: (1) chlorsulphonic acid is gradually added to an agitated solution of 1 : 4-thioxane in carbon tetrachloride with cooling; hydrogen chloride is evolved and a white precipitate of the 1 : 1 ratio addition compound of thioxane and sulphur trioxide is formed; (2) sulphur trioxide is distilled from fuming sulphuric acid into a solution of thioxane in ethylene chloride and carbon tetrachloride respectively to yield in the former case the 1 : 1 ratio addition compound and in the other the 2 : 1 ratio sulphur trioxide-thioxane compound; (3) chlorsulphonic is added to an ethylene chloride solution of thioxane forming the solid addition compound, whereupon a tetra-isobutylene obtained by polymerization of isobutylene over activated clay is added at 40 DEG C. and the product neutralized with caustic soda to yield tetra-isobutylene sodium sulphonate; (4) chlorsulphonic acid is added to a solution of thioxane and naphthalene in benzene at room temperature and on subsequently steam distilling, the naphthalene is recovered as a -naphthalene sodium sulphonate and the benzene is recovered unchanged; (5) a mixture of secondary alcohols, of the probable general formula RCH(OH)R1, where R and R1 are alkyl radicals containing 7-9 carbon atoms, and having an average hydroxyl value of 240, is added to the reaction product of (1) yielding a mixture which is neutralized and worked up to yield a paste of sodium alkyl sulphates; (6) the solid products of (1) is added to methallyl chloride in carbon tetrachloride at 50 DEG  C. and chlor-methallyl sulphonic acid is recovered in the form of its sodium salt; (7) higher olefinic hydrocarbons are prepared by treating the copolymers, obtained by polymerization of isobutylene with n-butylenes, at 10 DEG C. with aluminium chloride, steam distilling the treated oil to remove lower olifines and then fractionating in vacuo and a fraction boiling up to 150 DEG  C. at 10 mms. is added to the reaction mixture obtained by adding chlorsulphonic acid to a solution of thioxane in ethylene chloride, and after neutralizing with caustic soda and working up, a soap-like mass soluble in organic solvents and water is obtained which is highly active; in like manner diamylenes are polymerized at 0 DEG  C. with aluminium chloride and a fraction of the product B.P. 110-130 DEG  C. at 10 mms. is reacted with the product obtained on mixing thioxane and sulphur trioxide in carbon tetrachloride. Other products mentioned are the sodium sulphonates of di- and tri-isobutylene, 2-pentene, diamylene, 1-chlor-9-octadecylene, and heptadecylene and the sodium salts of 2-pentene di-sulphonic acid. In comparative tests, (a) olefines such as are obtained by dehydrating the alcohols used in (5) above are added to chlorsulphonic acid in diethyl ether yielding a product containing only small quantities of olefinic sulphonic acids, and (b) tetraisobutylene in ethylene chloride is added to a mixture of 1 : 4-dioxane, chlorsulphonic acid and ethylene chloride yielding tetra and di-isobutylene sulphonic acids in apparently lower yield than in (3) above.  The Specification as open to inspection under Sect. 91 refers to the preparation of 1 : 4-thioxane addition compounds with sulphuric acid derivatives in general and to the sulphonation of organic compounds with a sulphonating agent in the presence of thioxane.  An example describes the treatment of benzene with a mixture of thioxane and chlorsulphonic acid in carbon tetrachloride at room temperature and shows the benzene to be unattacked.  This subject-matter does not appear in the Specification as accepted.ALSO:Surface active agents are prepared by the sulphonation or sulphation of organic hydroxy compounds and olefinic compounds by means of an addition compound of 1 : 4-thioxane and sulphur trioxide (see Group IV (b)).  The hydroxy compounds may be primary, secondary or tertiary mono- and poly-hydroxy derivatives of substituted or unsubstituted aliphatic or aromatic hydrocarbons, ethers, polyethers, acids, esters and amines.  The olefinic compounds may be straight or branched chain olefines, tertiary olefines in which a branched chain is attached to an unsaturated carbon atom, and halogenated olefines. The preferred sulphonic acids have the general formula <FORM:0651840/IV (c)/1> where either R1 or R2 may be hydrogen or both be straight or branched chain substituted or unsubstituted hydrocarbon radicals and at least one of X and Y is hydrogen and the other hydrogen or a straight or branched chain hydrocarbon group but in no case should X and Y and one of the R's be hydrogen atoms at the same time, one of the hydrogen atoms either on the double bond or in one of the alkyl groups being substituted by a sulphonic group; preferably the parent olefine has 4-30 carbon atoms.  The olefinic sulphonic acids may be used in the form of their sodium, potassium ammonium or other monovalent base salts in wetting, penetrating, deterging, emulsifying, de-emulsifying, frothing, foaming, dispersing, softening and like processes, alone or in combination with other surface active or treating agents. Typical compounds mentioned are the sodium salts of the sulphonic acids derived from di-, tri- and tetra isobutylene, 2-pendene, diamylene, methallyl chloride and oleyl chloride and the sodium salts of the sulphuric acid esters of a mixture of secondary alcohols, having the probable general formula RCH(OH)R1, where R and R1 are alkyl radicals containing 7-9 carbon atoms, and having an average hydroxyl value of 240.