3,121,737 United States Patent O? ice Patented Feb. 18, 1964

1 2 lie compounds will vary according to type and structure, 3,121,737 an 50;, complex of the types aforementioned can be FORMATION VIA SULFONA chosen in each instance which is suf?ciently active to TION 0F TRIALKYL AND TRIARYLALKYL ALUMINUM effect the desired reaction at a convenient temperature Alfred J. Rntkowski, Colonia, and Albin F. Turbak, New and at the same time one in which the activity of the S03 Providence, N.J., assignors to Esso Research and Engi is su?‘iciently diminished to enable the reaction to proceed neering Company, a corporation of Delaware smoothly while yielding pure products. Thus, for ex No Drawing. Filed Dec. 24, 1959, Ser. No. 861,744 ample, with a reactive organometallic such as aluminum 7 Claims. (Cl. 260-513) , the (RO)3PO/SO3 complex has sufficiently active 10 S03 for producing the desired sulfonic acids while for This invention relates to a novel process for preparing a relatively inactive metal a complex such as sulfonic acids by reacting organometallic compounds with (RO)3PO/2SO3, (RO)3PO/3SO3, or dioxane/2SO3 con sulfur trioxide. In particular this invention relates to the taining more reactive S03 is necessary for the reaction. production of acids having the general formula The varying reactivities of organometallics and 80;, com 15 plexes are relative and do not limit the scope of the inven tion but merely serve to illustrate the versatility of the wherein R is a C2-C3‘, hydrocarbon radical which may invention. be alkyl, aryl, cycloalkyl, arylalkyl or alkylaryl hydro This control feature when applied to the reaction of carbon radical. More particularly this invention relates 80;, with organometallic compound provides a means of to the production of these acids by reacting an organo 20 selective sulfonation wherein the S03 group is bonded to metallic compound wherein the metallic constituent is a a carbon atom which prior to the reaction was bonded to metal selected from the metals of groups I, II and III of the metal constituent of the organometallic reactant. the periodic table, the metals of the ?rst transition series Thus, where the hydrocarbon radical attached to the of the periodic table, i.e. metals having an atomic num metal constituent is an arylalkyl radical, sulfonation at ber of 21 to 29 inclusive, silicon, germanium, tin and lead 25 the end of the alkyl chain can be effected without sul with a stoichiometric amount of S0,. The process is also fonating the aryl portion. applicable to the production of acids having the formula The metal atoms of the organometallic reactant may above set forth wherein R is a C2—C3[, substituted hydro be either monovalent or mnltivalent. The organic com carbon radical Wherein one or more hydrogen atoms of ponent of such compounds consists of one or more C2 such radical are replaced with a halogen atom or an 30 to C30 hydrocarbon radicals which may be alkyl, aryl, alkoxy radical, e.g. cycloalkyl, arylalkyl or alkylaryl. The alkyl portions of these radicals may be either straight or branched chain groups. The invention is not limited to the use of organo metallic compounds wherein the hydrocarbon radicals 35 attached to the metal constituent are of equal length or Still more particularly, this invention relates to a proc carbon number but may include radicals of varying size ess for producing sulfonic acids as aforedescribed by such as those obtained from growth type reactions. The reacting an organometallic compound with an SOs-organic number of organic radicals in each organometallic com complex which partially reduces the activity of S03 at pound will, of course, be limited by the maximum valence temperatures in the range of —l00° to —|—l00° C., pref 40 of the metal constituent. The number of sulfonic acid erably between 20° and 50° C. molecules which can be prepared from a given organo In the past, attempts to react organometallic com metallic molecule is in turn dependent upon the number pounds with 50;, have resulted in the formation of un~ of such radicals. Although the process of this invention identi?able, tar-like products. It has now been discovered is not limited to organometallic compounds wherein each that good yields of sulfonic acids, which can be recovered valence is satis?ed by a hydrocarbon radical, organo as pure compounds, can be prepared by reacting an or metallic compounds of this ‘type are preferred. Those ganometallic compound with an SO3-organic complex organometallic compounds containing at least one hydro which partially reduces the activity of 50,. Such com< carbon radical but wherein one or more valances are satis plexes can be prepared by admixing 80;, with an organic ?ed with other radicals or atoms such as hydrogen, halo compound selected from the group consisting of acyclic gen or alkoxy radicals and those wherein one or more , e.g. dibutyl , bis (beta chloroethyl ether) and valences are satis?ed by a substituted hydrocarbon radical any dialkyl ethers of poly alkyl oxide structures such as may also be used. dibutyl carbitol; cyclic ethers, e.g. tetrahydropyran, diox The term “substituted hydrocarbon radical” is here ane and tetrahydrofuran; tertiary nitrogen containing limited to those radicals wherein one or more hydrogen compounds, e.g. trimethyl , dimethyl aniline and atoms on such radical are replaced by a halogen atom or N,N’dimethyl formamide, nitrogen containing hetero~ an alkoxy radical. It is, of course, understood that the cyclic compounds, eg. , picoline, lutidine and reaction of S0; with an organometallic compound having compounds which contain both phosphorus and oxygen. a valence satis?ed by an alkoxy radical, e,g. The phosphorus-oxygen complexing agents are herein after discussed in greater detail. Thus, for example, S08 60 is combined with a phosphorus-oxygen containing com~ pound in an approximately 1:1 to 3:1 mole ratio as desired, whereas the limits of combination with dioxane are within the mole ratio of 1:1 to 2:1. With compounds wherein M is a metal, 0 is oxygen and R is a hydrocar such as pyridine the complex with S03 is an equi-molar bon radical, will result in the production of an organic complex. sulfate, e.g. ethyl sulfuric acid, so far as the alkoxy radi It will be noted that in the aforementioned complexes cal is concerned. the ratio of S0, to the completed complex can be made The reactants may be contacted with each other at a to vary. Thus, by decreasing the proportion of SO; in 70 temperature in the range of —l00° to +100“ C. at pres the complex, the activity of the complex is likewise de sures ranging from 0.5 up to 20 atmospheres or more for creased. Since the reactivity of the various organometal from I second to 1 hour. However, the reaction is pref 3,121,737 4 erably carried out at a temperature in the range of —l0° phorus and oxygen containing organic compounds the to +40° C. under atmospheric pressure. phosphorus may be either trivalent or pentavalent. Vari The reaction may be carried out employing only the ous organic phosphite, , , phos reactants or with the aid of a diluent which will dilute the phate, , phosphonite, pyrophosphate and reaction mixture and thus serve as an additional control metaphosphate compounds may be employed to prepare upon the activity of the S03. Diluents are preferred the complexed product. The compounds may contain which maintain a single phase reaction mixture. Suit from 0 to 3 oxygens in the case of the pentavalent able diluents for use with this invention include halogen phosphorus compounds and l to 3 ester oxygens in the substituted hydrocarbons such as chlorobenzene, 1,2,di case of the trivalent phosphorus compounds. These com chloroethane, carbontetrachloride, chloroform, propylene 10 pounds may, of course, contain oxygen other than the dichloride, butyl chloride, butyl bromide, bromobenzene, aforesaid ester oxygens. The ester oxygens may have 1,2,dibromoethane, carbon tetrabromide, tetrailuoroeth< alkyl, aryl, alkylaryl or arylalkyl groups attached to them ane, di?uorodichloroethane, di?uorodichloromethane, containing 1 to 18 carbon atoms. Similar organic groups tetra?uorodichloroethane, and gaseous diluents such as may be attached to the phosphorus directly. These or nitrogen and the gases of group VIII of the periodic table. 15 ganic groups should be relatively nonreactive, especially The speci?c periodic table referred to is the 1959 revised with the sulfur trioxide used to form the complex. If edition of the table designed in 1924 by Henry D. Hub a reaction does occur between the sulfur trioxide and the bard, revised by William F. Meggers and published by organic group attached to the phosphorus, it will be W. M. Welch Manufacturing Company, of Chicago, Illi necessary to use additional sulfur trioxide to compensate nois. If dioxane, pyridine, or N,N'dimethyl formamide 20 for this loss. is employed as the complexing agent with S03, an excess Among the organic phosphorus and oxygen containing of such compound may be employed as a diluent. Liquid compounds which may be employed to produce the com and gaseous hydrocarbons such as , toluene, and plexes of the present invention are the ‘following: triethyl C1 to C10 hydrocarbons of the para?in series may also , trimethyl phosphate, tripropyl phosphate, tri be used. However, the halogenated hydrocarbon diluents 25 butyl phosphate, triethyl phosphite, trimethyl phosphite, are preferred. Of these the chlorinated hydrocarbons and tripropyl phosphite, tri-butyl phosphite, diethyl hydrogen particularly dichloroethane are most preferred. Thus, phosphate, dimethyl hydrogen phosphate, diethyl hydro the sulfonating complex may be admixed with or dis gen phosphite, dimethyl hydrogen phosphite, ethyl di solved in an inert diluent, e.g. 0.5 to 95 wt. percent solu hydrogen phosphate, methyl dihydrogen phosphate, ethyl tion, prior to admixing it with the organometallic com 30 dihydrogen phosphite, methyl dihydrogen phosphite, tris pound dissolved in the same or a different but compatible (2,4-dichlorophenyl) phosphate, tris (2,4-dichlorophenyl) diluent. While the organometallic compound solution phosphite, bis (2,4Jdichlorophenyl) hydrogen phosphate, may contain as little as 1 wt. percent of organometallic bis (2,4-dichlorophenyl) hydrogen phosphite, tris (p-ni compound, solutions containing as much as 95 wt. per trophenyl) hydrogen phosphate, bis (p-nitrophenyl) hy~ cent may also be used. However, the concentration of 35 drogen phosphite, tris (p-sulfophenyl) phosphate, tris (p organometallic compound in the diluent will depend to a sulfophenyl) phosphite, 2,4-dichlorophenyl dihydrogen large extent on its solubility, and in some instances it may phosphate, 2,4-dichlorophenyl dihydrogen phosphite, be desirable not to use a diluent. Since the sulfonating tetraethyl pyrophosphate, tetramethyl pyrophosphate, di reaction is exothermic a cooling jacket or recycle means methyl diethyl pyrophosphate, ethyl metaphosphate, bis should be employed especially where little or no diluent 40 (2,4»dichlorophenyl) diethyl pyrophosphate, sym-p-ni is present in the reaction zone to dissipate the heat of re trophenyl pyrophosphate, p-nitrophenyl metaphosphate, action. The acid produced by the sulfonation may be neu tris (B-chloroethyl) phosphate, tetra (B-chloroethyl) tralized with an aqueous solution of an alkali or alkaline pyrophosphate, diethyl dihydrogen pyrophosphate, di (2, earth metal hydroxide, e.g. a 40-50 wt. percent solution of 4-dichlorophenyl) dihydrogen pyrophosphate, tris (2,4,6 sodium hydroxide, and the metal salt thus produced may 45 trimethylphenyl) phosphate, tris (3,4,6-trirnethylbenzyl) be dried either by heating it or mixing it with a de phosphate, trilauryl phosphate and tristearyl phosphate. hydrating agent, such as anhydrous sodium sulfate. Any The complexes with pyridine, N,N’dimethyl form excess caustic and salts may be removed by extracting the , dioxane, etc. may be prepared in the same manner reaction product with an , such as isopropanol. as those prepared from phosphorus compounds. The complexes employed in this invention are pref 50 erably prepared separately and admixed with the organo Sulfonic acids which may be prepared by this process metallic reactant. include, by way of example, ethyl sulfonic acid, n-butyl The complexes employed in this invention may be pre sulfonic acid, iso-butyl sulfonic acid, octyl sulfonic acid, pared at conditions such as those hereinbefore set forth iso-octyl sulfonic acid, decyl sulfonic acid, dodecyl sul for reacting the complex with the organometallic com 55 fonic acid, tetradecyl sulfonic acid, octadecyl sulfonic pound, i.e. between —l00° to +100° C., at pressures acid, eicosyl sulfonic acid, cyclopropyl sulfonic acid, ranging from 0.5 up to 20 atmospheres or more for from cyclopentyl sulfonic acid, cyclohexyl sulfonic acid, cyclo 1 second to 1 hour or more. When the reactants are ad dodecyl sulfonic acid, 4-methyl cyclohexyl sufonic acid, mixed with adequate agitation, such as that obtained with 3-butyl cyclohexyl sulfonic acid; phenyl sulfonic acid; an e?icient stirrer, the reaction is almost instantaneous alkylaryl sulfonic acids such as 2-butyl phenyl sulfonic and therefore the time is principally dependent upon the acid, 4~nonyl phenyl sulfonic acid, 4-dodecyl phenyl rate of addition of the sulfur trioxide substance to the sulfonic acid, 4-tetradecyl phenyl sulfonic acid, 4-hexa phosphorus-oxygen containing compound. Because the decyl phenyl sulfonic acid, 4-octadecyl phenyl sulfonic reaction is accompanied by a rise in temperature in the acid; arylalkyl sulfonic acids such as phenyl methyl sul reaction zone, it may be desirable in some instances to 65 fonic acid, 2-phenyl ethyl sulfonic acid, 3-phenyl butyl employ either an internal cooling system, e.g. recycling, sulfonic acid, 9-phenyl nonyl sulfonic acid, lZ-phenyl or an external coolant in a jacket. The amount of diluent dodecyl sulfonic acid, 14-phenyl tetradecyl sulfonic acid, employed to assist in the dissipation of heat will depend l6-phenyl hexadecyl sulfonic acid, l8-phenyl octadecyl to a large extent on the reaction temperature. For in 70 sulfonic acid, alpha naphthyl sulfonic acid, beta naphthyl stance at very low temperatures the inert diluent may sulfonic acid, and substituted arylalkyl sulfonic acids such contain up to 95 wt. percent of reactants while at tempera as chloro phenyl alkyl sulfonic acids, e.g. 2-o-chloro~ tures approximately that of the room, e.g., 20"-25 ° C., the phenyl ethane sulfonic acid, bromo phenyl alkyl sulfonic solvent may contain as little as 0.1 wt. percent reactants. acids, e.g. 2-o-bromophenyl ethane sulfonic acid, ?uoro In the preparation of the S03 complexes with phos 75 phenyl alkyl sulfonic acids, and methoxyl phenyl alkyl 3,121,737 5 6 sulfonic acids, e.g. 2~p-methoxy phenyl ethyl sulfonic Examples of Compounds of Formula B acid. In addition to the foregoing mono-sulfonic acids, alkyl, aryl, cycloalkyl, arylalkyl or alkylaryl disulfonic acids can be prepared from dimetal alkyl and dimetal aryl com pounds which, by way of example, may be described by the following formulae:

10

15 wherein R, R’, R", and R’” may be hydrogen, C1 to C10 alkyl, aryl, cycloalkyl, arylalkyl or alkylaryl groups and may be the same or different; M and M’ are metals (either the same or different) selected from the metals in groups I, II and III of the periodic table, the metals of the ?rst 20 transition series of the periodic table, i.e. metals having an atomic number of 21 to 29 inclusive, silicon, germani um, tin and lead; n is a positive integer in the range of 2 to 10; x is one less than the valence of M where R" is a monovalent radical and two less than the valence of M where R" is divalent; and y is one less than the valence of M' where R’” is a monovalent radical and two less than the valence of 1V ’ where R'” is divalent. Where M or M‘ are metals from group I, then the corresponding (11")K or (R"')y equals zero. 30 FORMULA B (Rn)xM___Ar__Ml(Rrn)y Examples 0]‘ Compounds of Formula C wherein Ar is a phenylene radical or a divalent poly nuclear aromatic radical and M and MIR")x and (R"’)y have values as de?ned above. Unsaturated sulfonic acids can also be made in ac cordance with the present invention from organometallic 4:0 compounds having the general formula:

FORMULA C The organometallic compound suitable for use in this invention may be prepared according to conventional methods such as reaction of Grignard reagents with metal halides, metal hydrides with ole?ns, and the like, or from growth type reactions such as those discussed in “Kinetics of Polymerization With Aluminum Alkyls,” wherein k is equal to 0 or a positive integer in the range International Symposium on Macromolecular Chemistry, of 1 to 10; R, R’ and R" are selected from hydrogen, C1 50 Milan, Italy, Septmeber 26 to October 2, 1954. More to C10 alkyl, aryl, cycloalkyl, arylalkyl or alkylaryl groups; speci?cally, one method for preparing organometallic M is a metal as de?ned in Formula A and z is equal to the compounds suitable for use with this invention is disclosed valence of M. in Ziegler et al., U.S. Patent 2,781,410. In this process A few of the compounds represented by the foregoing ethylene and aluminum alkyl such as aluminum triethyl general formulas are as follows: unite to form higher alkyls of aluminum. The prepara tion of aluminum triethyl from aluminum hydride and Examples of Formula A Compounds ethylene is also described in this patent. The preparation of trisubstitutcd boranes of the type R3B wherein R is a hydrocarbon radical which can be aliphatic, alicyclic or 60 aromatic is described in British Patent 804,341. Sulfonic acids have various uses. These include by way of example, catalysts for esteri?cation, antistatic agents for fibers and fabrics when combined with high molecular weight , dyeing aids and for use in deter gent manufacture. The alkyl aryl sulfonic acids prepared by this invention having 3 to 24, preferably 11 to 18, carbon atoms in the alltyl chain are particularly valuable for use in ‘detergent manufacture. For example, the so dium salts of such acids have good detergent properties. 70 This sulfonate detergent in commercial practice may, of course, be combined with various detergent builders such as sodium sulfate, carboxy methyl cellulose, various so dium and the like. The following examples are given to more fully illus— 75 trate how the present invention may be carried out. 3,121,737 8 EXAMPLE 1 additional water. Two layers separated, the upper layer Into a 500 ml. 4-neck ?ask ?tted with a 250 ml. drop was extracted with petroleum ether. The lower layer was ping funnel, cold heptane condenser, thermowell and air put on a steam bath and the dichloroethane removed. driven stirrer was placed 5 grams (0.0136 mole) of tri The residue of the upper layer after removal of the octylaluminum diluted with 250 ml. of 1,2-dichlorocthane. petroleum ether was neutralized with aqueous sodium The dichloroethane was dried prior to use, and the appa hydroxide. A large amount of solid appeared. The solid ratus was heated with dry nitrogen passing through prior was extracted with a 50/ 50 isopropyl alcohol-water mix to use. Into the drapping funnel was placed 7.5 grams ture. The water layer was salted out with potassium (0.041 mole) of triethyl phosphate diluted with 99 ml. carbonate, and the layer which formed was separated after of 1,2-dichloroethane and 3.3 grams (0.041 mole) of 10 heating the alcohol-water solution to 50° C. The iso liquid S03. This complex of triethyl phosphate and 503 propyl alcohol solution was separated and the alcohol was added over 77 minutes, and was accompanied by a was evaporated. The original lower layer after removing rise in temperature from 25 ° C. to 282° C. The reaction the dichloroethane was neutralized with aqueous NaOH mixture was then heated to 30°—33° C. for 2 hours. and a solid, sodium 2 phenyl ethyl sulfonate, was obtained When the reaction mixture cooled to room temperature in the amount of 39.6 grams (71% yield). 4 cc. of cone. HCl diluted to 10 ml. with water was added EXAMPLE 4 slowly with a temperature rise from 25° to 27° C. The Into a 500 ml. four-neck ?ask, ?tted with a cold hep reaction mixture was washed with 70 nil. of water and tane condenser, stirrer, thermowell, and a 125 ml. drop 150 m1. of ethyl ether. The ether layer was dried over 20 ping funnel was placed 38.9 grams (0.05 mole) of tri K2CO3 and the ether and dichloroethane were removed. octadecylborane diluted with 300 ml. of dichloroethane. The residue on distillation gave 6.1 grams triethyl phos— Into the dropping tunnel was placed 39.5 grams (0.15 phate, B.P. 75—78° C./3.0—3.8 mm. mole) of triethyl phosphate/S03 complex diluted to 50 The water layer after concentration to 40 ml. was ml. with dichloroethane. The S03 complex was added neutralized with aqueous sodium hydroxide during which to the boron alkyl with stirring and reaction temperature time a solid settled out. The liquor was diluted with was kept at 25° C. with cooling. Total addition time Water to 50 ml. and 50 ml. of isopropyl alcohol was was 1 hour. The reaction mixture was stirred for an added. This solution was heated to about 50° C. and additional hour. The reaction mixture was a clear yellow saturated with Na2CO3. The upper alcohol layer was color and exhibited some foaming tendency. The reac separated and the alcohol evaporated. There was ob tion mixture was neutralized with aqueous NaOH and tained 5.3 grams of solid product, a 66 mole percent yield. 100 ml. of isopropyl alcohol-water (50/50) was added. Analysis of the solid gave 10.2% Na, 13.10% S, as com The reaction mixture was washed with two portions (100 pared with 10.6% Na, and 14.8% S, calculated for so ml.) of petroleum ether and formed two distinct layers. dium octyl sulfonate. The lower aqueous layer was salted out with KZCOS and EXAMPLE 2 35 the alcohol layer was removed. After removal of the alcohol and the petroleum ether from the respective layers Into a 1 liter 4-neck ?ask with a cold heptane con~ 33.5 grams of sodium octadecyl sulfonate were obtained. denser, 500 ml. dropping funnel, thermowell and stirrer was placed 31.5 grams (0.058 mole) tridodecylaluminum EXAMPLE 5 in 250 ml. of 1,2-dichloroethane. The dichloroethane was 40 Into a 5 00 ml. four-neck ?ask equipped as in Example 4 previously dried and the apparatus was heated with dry is placed 40.3 grams (0.1 mole) of tetraisoamyl tin diluted N2 passing through. Into the dropping funnel was placed with 100 ml. of dichloroethane. Into the dropping funnel 27.0 grams (0.147 mole) triethyl phosphate in 150 ml. is placed 68.4 grams (0.2 mole) of a complex made up dichloroethane and 14.5 grams (‘0.18 mole) S03 in 50 ml. of 1 equivalent of triethyl phosphate to two equivalents dichloroethane. The temperature was maintained be of S03 diluted with 100 ml. of dichloroethane. The re tween 30°—35° C. by regulating the rate of addition. 45 action is carried out in accordance with Example 4. From After complete addition the reaction mixture was heated the reaction sodium isoamyl sulfonate is obtained. at 64° C. for 45 minutes. Then, 300 ml. of water was added and a large amount of solid appeared. On neu EXAMPLE 6 tralization a voluminous amount of solid appeared. The A sulfonic acid is produced as in Example 4 except for solid was acidi?ed to a slightly acidic stage by adding 50 the following differences: Dicyclohexyl berryllium, 17.5 dilute HCl and the free sulfonic acid was taken up in grams (0.1 mole) diluted to 100 ml. with carbon tetra petroleum ether. After evaporation of the petroleum chloride, is reacted with 52.4 grams (0.2 mole) of a 1:1 ether the free acid was converted to the sodium salt with triethylphosphate S03 complex diluted with 100 ml. of aqueous NaOH. The sodium salt was washed with diethyl carbon tetrachloride. The temperature is kept between ether and a white solid product, sodium dodecyl sulfonate 55 25°—35° C. by regulating the rate of addition. From the was obtained. Analysis of the solid gave 8.52% Na and reaction mixture there is obtained upon neutralization 11.34% S, as compared with 8.46% Na and 11.75% S, sodium cyclohexyl sulfonate. calculated for sodium dodecyl sulfonate. The yield ob tained was 45 mole percent. EXAMPLE 7 EXAMPLE 3 60 A sulfonic acid is produced as in Example 4 except for the following differences: Into the ?ask is placed 34.3 Into a 1 liter four-neck ?ask equipped with a 150 ml. grams (0.1 mole) of tri (p-ethylphenyl) aluminum diluted dropping funnel, cold heptane condenser, thermowell, and with 100 ml. of dichloroethane. Into the dropping fun stirrer was placed 34.3 grams (0.1 mole) of tri-styryl nel are placed 78.6 grams (0.3 mole) of a 1:1 complex aluminum diluted to 200 ml. with 1,2-dichloroethane. of triethyl phosphate and S03. From the reaction mix Into the dropping funnel was placed 78.6 grams (0.3 ture there is obtained after neutralization sodium p-ethyl mole) of a 1/1 complex of triethylphosphate and S03 benzene sulfonate. diluted to 130 ml. with dichloroethane. The complex was EXAMPLE 8 added to the aluminum styryl over a 1 hour period. The temperature was kept between 30°-45° C. by regulating 70 A sulfonic acid is produced as in Example 4 except the addition. After complete addition of the complex for the following differences: About 27.8 grams (0.1 mole) the ?ask was heated to 60° C. for 45 minutes, and allowed of di-a-naphthyl-magnesium is reacted with 33.6 (0.2 to stand overnight. To the reaction mixture was added mole) of a dioxane/SO3 complex. There is obtained from 100 ml. of distilled water with stirring. After 25 ml. was the reaction mixture after neutralization sodium-a-naph added, a solid came out of solution which dissolved with 75 thyl sulfonate. 3,121,737 10 EXAMPLE 9 All percentages expressed herein unless otherwise desig A sulfonic acid is produced as in Example 4 except for nated are to be construed as percentage by weight. the following differences: Into a ?ask is placed 8.4 grams The term “inert” as used herein refers to a substance (0.1 mole) of phenyl lithium. To this is added 15 grams that is essentially chemically inert to the reactants, in_ (0.1 mole) of an SOS/pyridine complex. The reaction termediates and products of the reaction of an organo mixture is stirred for 1 hour after complete addition. metallic compound with an SO3-organic complex such as After neutralization there is obtained from the reaction hereinbefore described under the conditions of reaction mixture sodium phenyl sulfonate. herein set forth. EXAMPLE 10 What is claimed is: 10 l. A process for producing C2 to C30 sulfonic acids A sulfonic acid is produced as in Example 4 except for which comprises contacting an aluminum compound se the following differences: Into a ?ask are placed 53.1 lected from the group consisting of aluminum trialkyls grams (0.1 mole) of an aluminum alkyl growth product having 2~30 carbon atoms per alkyl group and tri(aryl corresponding to Al[(CH2)11CH3]3 diluted to 200 ml. alkyl) aluminurns having 7-30 carbon atoms per aryl with N,N'dimethyl formamide. To this is added 24 grams alkyl group with a complex of S03 and a trialkyl phos (0.3 mole) of S03 with 50 ml. of N,N'dimcthyl form phate wherein each alkyl group contains 1 to 18 carbon amide. After neutralization there is obtained from the atoms in an inert diluent selected from the group con reaction mixture an alkyl sodium sulfonate corresponding sisting of liquid hydrocarbons and chlorinated hydrocar to (C12H35)SO3NZL bons at a temperature in the range of about —100 to EXAMPLE 11 20 +100° C. To 18.3 grams (0.1 mole) of tricthyl phosphate dis 2. A process in accordance with claim 1 wherein said solved in 250 cc. of dichloroethane is slowly added 8.0 temperature is in the range of about 20° to 50° C. grams (0.1 mole) of S03. The solution is stirred during 3. A process in accordance with claim 1 wherein the the addition and the temperature rises from 25° to 37° mole ratio of $03 to said trialkyl phosphate in said com C. The solvent is removed by heating to 35° C. at 5 plex is in the range of about 1:1 to 3:1. mm. pressure. A 1:1 SO3-triethyl phosphate complex is 4. A process in accordance with claim 1 wherein said recovered. aluminum compound is an aluminum trialkyl. EXAMPLE 12 5. A process in accordance with claim 1 wherein said To 6.1 grams (0.033 mole) of triethyl phosphate dis trialltyl phosphate is triethyl phosphate. solved in 250 cc. of dichloroethanc is slowly added 8.0 30 6. A process in accordance with claim 1 wherein said grams (0.1 mole) of 503. The solution is stirred and inert diluent is a chlorine substituted hydrocarbon. the temperature rises from 25° C. to 34° C. A 3:1 SO3 7. A process in accordance with claim 1 wherein said triethyl phosphate complex is recovered. diluent is 1,2-dichloroethane. EXAMPLE 1 3 References Cited in the ?le of this patent To 8.8 grams (0.1 mole) of dioxane dissolved in carbon UNITED STATES PATENTS tetrachloride is slowly added 8.0 grams (0.1 mole) of 50;, at —5° C. A white solid separates which can be 2,268,443 Crowder ______Dec. 30, 1941 stored as such or redissolved in carbon tetrachloride at 2,807,642 Bloch et al ______Sept. 24, 1957 room temperatures. A 1:1 SOg-dioxane complex is thus 40 3,072,618 Turbak ______Jan. 8, 1963 prepared. A 2:1 SO3-dioxane complex is prepared in the OTHER REFERENCES same manner by adding 8.0 grams (0.1 mole) of 50;; to Turbak: Chem. and Eng. News, vol. 41, Mar. 18, 1963, 4.4 grams (0.05 mole) of dioxane. page 43. EXAMPLE 14 45 Groggins, op. cit, pages 326—328. To 7.9 grams (0.1 moie) of pyridine dissolved in Rochow et al.: The Chemistry of Organometallic Com propylene dichloride is slowly added 8.0 grams of S03 pounds (1957), pages 279—280. to form a 1:1 SOs-pyridine complex. Heat evolved in Groggins: Unit Processes in Organic Synthesis, 5th edi the addition may be controlled by the rate 01803 addition. tion (1958), pages 306, 341L350.