Sulfonation and Sulfation - ACS Publications

LAUREL HILL RESEARCH LABORATORY, LONG ISLAND CITY, N. Y. Production of sulfonates continuesto expand—notably of dodecyl benzene sulfonate...
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Su lfonatio n and Sulfation


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Production 08 sulfonates continues to expand-notably of dodecyl benzene sulfonate detergents, benzene disulfonic acid (for resorcinol), sulfonate emulsifiers (including petroleum sulfonates), and synthetic tanning agents. A new sulfonating agent-sulfur monoxide-was reported. The most widely useful method for preparing aliphatic sulfonates was shown to b e aqueous chlorination of thiol derivatives. A new series of brilliantly colored naphthalene peri sulFonates was prepared, the color apparently arising from unusual carbon-to-sulfur unsaturation. Two detailed studies were Dublished on the rate and mechanism of aliphatic alcohol sulfation with sulfuris acid.


ET~EL~OPMESTS in this unit process for 1951 are reviewed, follo\~-ingthe scheme used in previous similar review by Lisk (248-50) and the present authors (142). The terms “su1Eo:iation” and “sulfation” have, as in the past, been broadly intrrpreted to include all direct and indirect methods invol\-ing any reagent, for preparation of sulfonat,es of all degrees of k1iow1i composition and purity. A standard reference work, dealing with sulfonation as a unit process, hac been revised and issued as a new edition (165). Increased erraptask le placed in the new edition on reaction kinetics, direct, use of sulfur trioxide as a sulfonating agent, sulfochlorination (vith 5uHw dioxide and chlorine), and sulfoxidation. Frequent reference IE made to the many recently available reports on German industrial sulfonation procedures. Expanded production for several sulfonat,es: detergents (66, 76, 164: ,353). benzene disulfonic acid ( 7 4 ) , syntans (76), emulsifiers ( Y S ) , has been along established lines using direct sulfonation wlt,h a.tit1 or oleum (164). Indirect methods continue to be of inte:es? for more specialized sulfonations; the number of references to siulfochlorination and sulfoxidation has decreased, while sulfon;ei,hyjlation (with aldehyde bisulfite) is being used more wideiy, p;iriicularly to solubilize pharmaceuticals with a minimuin oi lass a n a d v i t y . The continusng shortage of sulfuric acid has led to a decreased allotment far drwrgent manufacture ( 6 7 , 1 6 ) ,and to an improved recovery prorws for spent acids of lower than usual strength (68). ALliPHATlC AND ALICYCLIC SULFONATES DIRECT TREATMENT WITH C O M P O U N D S C O N T A I N ! N G SULFUR TRIOXIDE

Saturated Hydrocarbons. n-Butane and isobutane were not sulfonated by sulfuric acid of 92 to 100% strength a t 25” C. with contact times long as 22 hours. Likewise, no sulfonation occurred with low strength oleum (corresponding to a hypothetical 101% acid) (294). Methanesylfonic acid was noted ( 2 5 ) as a hydrolysis product of l,l,l-tii0metlranePulfonyl) methane derivatives. Sulfonation of petroleum fractions is reviewed below under a separate heading. Olefins and Acetylenes. As indicated schematically in a previous review {gg), direct sulfonation of these unsaturates may yield an olefinic sulfonic acid, a carbyl sulfate, a sulfate-sulfonate, a hydroxy-sulfonat,e or a mixture of these, depending upon conditions. An impro,ve,dprocedure for sulfonating olefins with sulfur trioxide diso!ved in liquid sulfur dioside has been patented by

J. K. Fincke (126). The reactants, both dissolved in sulfur dioxide, are reacted in a nozzle; the heat of reaction is sufficient to remove the solvent completely. I n examples, hexadecene is converted (after neutralization) t o the sodium hydroxy sulfonate, and ethylene to carbyl sulfate. The use of the thioxane-sulfur trioxide adduct for olefin sulfonation, previously patented in the United States (234, 236, 248), has been patented in England (133). Examples are given of the conversion of a variety of comnieicially available olefins to the unsaturated sulfonates, as well as preparation of the adduct by several procedures. The sulfonatioii of a hesadecylene with acetyl sulfate (acetic anhydride-sulfuric acid) has been operated commercially a t Ludwigshafen by I. G. Farbenindustrie to yield the expected hydroxy sulfonate marketed as a textile aid under the trade name “Amphoseife 18” (167). I n practice, the olefin and acetic anhydride are mixed and sulfuric acid is then added gradual13 with stirring a t about 25” C. This is a mild sulfonation which avoids decomposition. Removal of the acetyl group as acetic acid is accomplished by steaming. The sulfonation of 4-cvclohexene-1,2-dicarbox~~lic anhydride with concentrated sulfuric acid or chlorosulfonic acid in the range 80” to 115’ C. has been patented (259). The sulfonic group ii thought to be on an olefin carbon; wetting agents are produced by di-esterification n ith various alcohols. Sulfonation (rather than sulfation) of an olefin with these reagents is unusual possibly the organic anhydride grouping may lead to sulfonation in much the same maimer as ncetic anhydride when used ~ i t h sulfuric acid. Further details have been reported by Terent’ev and coworkers on the sulfonatio~iof styrene and several conjugated diolefini (cyclopentadiene, butadiene, isoprene, 2,3-dimethylbutadlene, and 1-phenylbutadiene) using the pyridine-sulfur trioxide adduct in ethylene dichloride solvent a t about 100’ C. (373-6). Products obtained and yields were reported in a previous review (142). The olefinic sulfonates were convei tetl to a series of derivatives by bromination, hydrogenation, and treatment with phosphorus pentachloride. Sulfonation of rubber (pale crepe) with 9570 sulfuric acid or with oleum yielded sulfonated resins of remarkable cationexchange capacity (890, 291). They were used in a study of desalting sea water. Acetylene was sulfonated a t I. G. Farbenindustrie’s Wolfen works with 50% oleum a t 30” t o 40” C., followed by drowning on ice a t not over 5’ C., removal of sulfuric acid being then accomplished by precipitation with calcium carbonate at 30’ to 40’ C. (306). A 15% solution of acetaldehydedisulfonic acid was thus obtained in 80% yield. Absorption of acetylene was greatly accelerated under moderate pressure using nitrogen as diluent.


September 1952


Acetylene may be sulfonated with sulfur trioxide or oleum of various strengths using liquid sulfur dioxide as solvent, according t o a recent patent (149). An aqueous solution of the reaction mixture is then treated with a water soluble potassium salt (as the chloride) t o precipitate the dipotassium salt of acetaldehydedisulfonic acid. This aldehyde disulfonate salt may be reduced in alkaline medium with formaldehyde by a crossed Cannizzaro reaction to the corresponding ethanol disulfonate (393).

Aldehydes, Ketones, and Acids. A series of aldehydes (eight aliphatic and phenylacetaldehyde) and ketones (three aliphatic, acetophenone, and cyclohexanone) were sulfonated on the alpha carbon atom using dioxane-sulfur trioxide with ethylene dichloride as solvent (977). Mono- or disulfonic acids were obtained depending upon proportions used; they were isolated as barium salts in generally good yields. A similar study by Truce and Alfieri was reviewed previously (142). Sulfur monoxide (prepared from sulfur and sulfur dioxide) sulfonates organic compounds (389), including cyclohexanone and acetophenone to give the corresponding sulfonic acids. Yields and conditions are not given, except that the sulfur monoxide was passed into the organic compound between the temperatures of 2" and 60" C. This interesting new sulfonating agent deserves further study. The sulfonation of hinokitiol (a seven-membered ring ketone of the tropolone series) (.%8.%, %A$), two monobrominated hinokitiols (284), one dibrominated derivative (383),and two monochlorinated hinokitiols (281) was achieved by heating with sulfamic acid for 3 to 6 hours a t 150" t o 170" C. T h e ammonium sulfonates were formed, the sulfonic group entering ortho t o the carbonyl group. Sulfamic acid apparently has not been used previously for sulfonation of a ketone. As reported by A. J. Stirton e2 at., lauric, myristic, palmitic, and stearic acids have been sulfonated with liquid sulfur trioxide in tetrachloroethylene solvent (967), yielding the alpha-monosulfonated acids which were converted t o the mono- and disodium salts, as well as the butyl and amyl esters and the triethanolamine saIt of the monosodium sulfonate. A comparative study was made of the solubility and detergency of several of these products. Disodium alpha-sulfopalmitate is concluded to be potentially inexpensive, has adequate surface active properties, is a good detergent in hard and soft water, but has limited solubility at room temperature (0.25% at 25" (3.). The sulfonation of a technical palmitic-stearic acid mixture (iodine number less than 3), dissolved in 5 parts of carbon tetrachloride, wm conducted on a commercial scale at I. G. Farbenindustrie's Ludwigshafen works with excess gaseous sulfur trioxide at 25" t o 30" C. (167); finally the temperature was raised to 60' C. to complete reaction. The solvent could be recovered with 4 to 5% loss, and the sodium salt-obtained in nearly quantitative yield as an almost white solid by bleaching with sodium hypochlorite-comprised 90% of the monosulfonate with the rest more highly sulfonated. This product was marketed in Germany as textile auxiliaries under the trade names "Amphoseife DN" and "Indigosolseife SP". It is of interest to note that the author stipulated avoidance of sulfur trioxide as liquid during sulfonation, while in the other reference cited above the investigators deliberately used the Iiquid. A similar process for use with fatty acids having 7 t o 9 carbon atoms, obtained by oxidation of paraffins was also developed by I. G. Farbenindustrie a t Ludwigshafen (306). T h e carboxylic group was then esterified with alcohols made from the same fatty acids. Sulfonation of long chain saturated acids with chlorosuifonic acid, previously patented in Switzerland (,949), has also been patented m the United States (4.4). The reaction of acetic anhydride in excess (for example, 1.2 moles) with 99.5% sulfuric acid (0.1 mole)-by allowing the re-


actants t o stand at room temperature until sulfate ion is absentis believed to yield predominately acetyl sulfoacetic acid ( 1 1 1 ) as follows:



This product is used as a catalyst for esterifying mercaptans with acid anhydrides or ketenes. Preparation of the anhydrides of sulfoacetic acid by direct reaction of ketene with sulfur trioxide (as dioxane adduct) at a temperature range of 13" t o 30" C. is revealed in a recent patent (561). The reaction is as follows: CH2=C=O

+ so3 +CHZ-CO o=

Q '



This interesting new product was not isolated as such, but was identified by preparation of the aniline derivative. Other ketenes are stated to react similarly, but no examples are given. It is of further interest t o note that the dioxane-sulfur trioxide adduct used in this work was prepared by the direct addition of liquid sulfur trioxide to the usual dioxane-ethylene dichloride mixture, Previously the sulfur trioxide has been introduced as the milderacting vapor form. Sulfonation of butyrolactone with sulfur trioxide is reviewed below under Heterocyclic Compounds. OXIDATIVE PROCEDURES

Sulfochlorination. ' Direct reaction of paraffinic hydrocarbons and more complex compounds containing paraffinic groupings with sulfur dioxide and chlorine in the presence of a catalyst to yield sulfonyl chlorides continues t o be of some research interest, even though large scale manufacturing use of the process is dormant in the United States because of processing problems (169). A critical discussion of various preparative procedures for alkyl sulfonates, with 74 references, has been published in Hungarian (46). Sulfochlorination has been reviewed briefly, in German, with diagrams of apparatus (968). A brief report by Weissenborn (405) summarizes without details the initial work at the Wolfen works of I. G. Farbenindustrie in 1944 son the use of peroxide catalysts including ozonides. Wide variations in effectiveness were noted. A German patent application of Deutsche Hydrierwerke A,-G. (109) describes sulfochlorination of a chlorinated paraffin fraction (obtained from carbon monoxide and hydrogen) containing 10 to 20 carbon atoms. Several German reports have been published relative to separation and purification of the sodium alkyl sulfonates prepared by sulfochlorination followed by hydrolysis with aqueous caustic. A patent application, dated 1944, describes drum drying under reduced pressure to remove unreacted oil (199). Two others (200,W O l ) , dated 1941, disclose addition of methanol to the sodium alkyl sulfonate to effect separation of sodium chloride and unreacted oil. A fourth German application (365) obtains separation into layers containing products having varying molecular weights and degrees of sulfonation by adding a waterabsorbing electrolyte as a n alkali carbonate. Sulfochlorination always involves only partial conversion of the hydrocarbon treated. A German patent (189) describes USE of this recovered unreacted oil as a cleaning solvent when formulated with a n alkyl sulfate emulsifier. Sulfochlorination reaction mixtures tend to be unstable upon standing. Stabilization is achieved (237) by adding a bicyclic terpene (as pinene) with or without a n olefin oxide (as cyclohexene oxide). Amine (alkylolamine, morpholine) salts of polysulfechlorinated polymerized olefins (examples are given of their preparation from



polymerized ethylene or isobutylene) have been patented (58). The salts are film-forming agents for use in paints. Rust and coworkers have continued thelr studj- of the sulfochlorination of aliphatic peroxides. One patent (325)describes the preparation of the monosulfonyl chloride from di-(tertiarybutyl) peroxide and its reaction with sodium hydroperoxides to yield the persulfonate ester. A second patent (526) describes conversion of the same sulfonyl chloride, its mono-chloro derivative, and the monosulfonyl chloride of cumene peroxide to various sulfonamides by reaction with amines. Sulfoxidation. This field has become nearly inactive, in spite of great previous interest in the process in Germany as indicated in previous reviews (148, 248-60). A German patent discloses sulfoxidation of partially hydroxylated materials (1 to 15%), such as a Fischer-Tropsch hydrocarbon fraction which is air oxidized, treated to remove acids and double bonds, and sulfonated at 50" C. with sulfur dioxide and oxygen using chlorine as catalyst (232). The products are useful as surface active agents. Thiol Derivatives. This category includes oxidation by various procedures not only of thiols proper, but also their derivatives (disulfides, thiosulfates, isothiouronium salts, etc.)-Le., compounds containing the RS-grouping. An excellent recent study (413) details preparation of 38 aliphatic, cycloaliphatic, and aromatic-aliphatic sulfonyl chlorides by chlorination in aqueous acetic acid of the corresponding thiosulfates or thiols (prepared from isothiouronium salts). Yields are generally good. The comparative merits of the two approaches are discussed, and it is pointed out that these procedures are usually more widely applicable than other methods such as sulfochlorination of the hydrocarbon. On the other hand, it is reported (398) that-for the preparation of a series of 17 aliphatic sulfonates-aqueous chlorination of the disulfides to the sulfonyl chlorides, followed by saponification to the metallic sulfonates, is not a satisfactory procedure compared to nitric acid oxidation. Surface tension measurements were made on all compounds a t three concentrations. A new process for preparing nontertiary aliphatic sulfonyl chlorides (3)from the disulfide involves two steps, the first being chlorinolysis below 20' C., the second comprising oxygen oxidation in the presence of nitrogen dioxide catalyst to the sulfonyl chloride. Presumably the following types of reactions are involved:

RSSR -t 2C1+ RSCl


+ 2 0 +RSOZCl

The preparation of high purity n-alkane sulfonic acids containing 8 to 18 carbon atoms can be accomplished, according to a recent patent (124), by oxidation of the corresponding betahydroxyethyl sulfide with concentrated nitric acid, as follows: RSCHgCH2OH

+ 6HN03 +RS03H + 6x02 + 2CO2

Six examples are given using sulfides of varying chain length. Direct nitric oxidation of the parent thiol is btated to yield a product of inferior quality. The usual procedures for preparing aliphatic sulfonic acids by thiol oxidation necessitate isolation from an aqueous reaction mixture. B new process ( 4 1 ) , involving oxidation of the thiol (n-decyl and 5-ethylnonane-2-thiol are given in examples) ivith liquid nitrogen tetroxide, yields the anhydrous sulfonic acids directly in good yield and purity. The reaction is conducted by dropwise mixing of the two liquids a t 0' to 15' C. Crude aliphatic sulfonic acids prepared by the nitrogen dioxide-catalyzed ouygen oxidation of thiols or disulfides can be purified, according t o a recent patent (S10), bv treatment with nitric acid followed by treatment with hydrogen chloride.

Voi: 44, No. 9'


Addition to Unsaturated Compounds. The unsaturated compounds of this category broadly include olefins, olefin oxides, and carbonyl compounds. A study of the addition of sodium bisulfite to crotonaldehyde (194) showed that addition of one mole to the aldehyde group is rapid, easily reversible, and potentially useful for quantitative estimation of the aldehyde, vhile addition of a second mole to the olefinic linkage is slower and not comparably reversible. Aqueous 30y0 sodium bisulfite reacts slo~vly a t 90" to 100" C. with l-cyanobutadiene-1,3 t o yield the compound Sa03SCH2CH=CHCH2CN ($33). This sulfonate xTas reduced with h j drogen and Raney nickel to the corresponding saturated amino sulfonate, isolated as the benzoyl derivative. The mechanism of bisulfite addition to several salts and derivatives of a, 8-unsaturated acids (sodium acrylate, sodium crotonate, methyl acrylate and acrylonitrile) was investigated and found to proceed ionically to yield the p-sulfonate, while a 8, -/-unsaturated acid salt (ammoniumvinylacetate or 3-butenoate) reacted by a free radical niechanism to yield a ?-sulfonate (338). Position of the sulfonate group mas estsblished unequivocally by comparison with materials prepared alternatively. The addition of one mole of bisulfite to one mole of methylenebis-methacrylamide to yield an olefinic sulfonate has been described in two recent patents (105). It may be polymerized to an insoluble resinous material, presumably a polysulfonate. The low water solubility of the disodium salts of the long chain mono-alkyl esters of sulfosuccinic acid (prepared by the addition of aqueous sodium sulfite t o the corresponding maleate) is overcome by using the more soluble lithium (393), magnesium or beryllium (394), cobalt (395) or chromium (396) salts. The properties and uses of the dialkyl sulfosuccinates have been reviewed in German (369). Three new diesters of sodium sulfosuccinate have been offered commercially in trial lot quantities ( 7 0 ) . These materials prepared from 2-butyloctj-1, tridecyl, and 2-p-tert-butylphenoxyethgl alcohols-presumably by addition of aqueous sodium bieulfite to the corresponding maleates-have greater oil solubility than similar products currently marketed. Details are given in a recent patent (226) of the esterification of aconitic acid with n-butanol, and reaction of the ester R-ith aqueous sodium bisulfite to yield the wetting agent sodium tributyl sulfocarballylate. Such compounds have been patented (138) in England as surface active agents; details are given of the preparation of the tri-bopentyl derivatives. A series of patents ( 1 7 7 ) has appeared on a somewhat similar type of surface active agent prepared by the addition of aqueous sodium bisulfite to a benzoyl acrylic acid ester made by the aluminum chloride catalyzed reaction of an aromatic hydrocarbon with maleic anhydride, followed by esterification with an appropriate alcohol as follows:




SO3Sa (probable) Although the addition of bisulfite to the acid is known ( 5 2 ) addition to the ester is novel. This development has been reviewed generally ( 7 l ) , as well as more comprehensively xith considerable experimental detail using a variety of aromatic hydrocarbons (AH above) and alcohols (ROH above), and including test data on the surface activity of the products (178).

September 1952


A series of p-nitroethane sulfonate salts has been prepared (149) b y the knawn. reaction m m p x i h g additian .Q€ aqueous bisulfites to nitro olefins, and a study was made of conditions required t o obtain good yields. These nitrosulfonates have been converted to a n interesting series of sulfonate derivatives, including the amino sulfonates by reduction (163),various halogenated nitro sulfonates (152) (including a cyano nitro sulfonate by use of cyanogen bromide), aromatic diazo nitro sulfonates (160) by coupling reaction, and the several nitro sulfonyl chlorides (148). The reaction of aqueous sodium bisulfite (1 mole) with ethylene oxide (13.33 moles) t o yield a polyglycol alcohol sulfonate has been disclosed in an example in a recent patent ( 1 4 7 ) . Possibly this reaction proceeds in two steps as follows:




CHpCHz y

0 zCHzCHz ‘ (



HO(CH2CHz0),CHzCH2S03Na Three pyridine aldehydes have been shown (161)t o add aqueous sulfurous acid or sodium bisulfite. The a-hydroxymethane sulfonic acids so obtained are stable, thereby differing from the similar derivatives prepared from benzaldehyde. The alkali metal bisulfite addition compound of 3-(methylmercapto) propanal-1 was prepared as the first step in a n improved process for making the amino acid &-methionine (165). The sodium bisulfite addition compound of 3,4,5-trimethoxybenzaldehyde was prepared (31.9). Crude furfural has been reacted with sodium bisulfite in a kneading machine (170). Washing with methanol yielded a granular, free-flowing product used as a herbicide. Substitution Reactions. Several sulfonates were prepared by the Strecker reaction (heating an alkyl halide with sodium sulfite to yield the corresponding derivative of methanesulfonic acid) as shown in Table I. I n one case an alkyl sulfate was used instead of the halide.





A l k y l Halides with Sodium Sulfite

Halide a-Hexyl, octyl, dodecyl bromides n-Decyl bromide

Conditions Reflux 12 hours


Mix slowl,

amyl benzoyl propionic acid 2-Phenylethyl bromide 8-Phenylethgl chloride Benzyl chloride Substituted benzvl chlorides (nitro, hydroxyl) Chloroacetic aoid ester of esteralcohol Monoethanolamine sulfate Chloromethylnaphthalene

Heat under pressure a t 1502000


Reflux 20 hours

... ... ...







Reflux 8 hours Reflux 48 hours




II. Sulfomethylation on Nitrogen

Amine Salvarsitn base Sulfanilamide Pyrrolidine Ammonia (or hexamethylene tetramine) Methylamine 2-Thenylamine (or equivalent) N,N’-Diphenyl ethylene diamine and related compounds N,N’-Dimethyl paraphenylmediamine Z-[-l-.Irninophenyl G Inethylbenzthiazole and-related compounds 4,4’-Bis [4-aminobenzoylamino]-stilbene disodium sulfonate-(2,2’) and related com ounds 4-Met$l-7-aminocoumarin 4-Methyl-7-aminocoumarin 4-Methyl-7-aminocoumarin 4-Methyl-7-aminocoumarin N-Ethyl derivative of above Orthotoluidine Benzidine Orthotoluidine 5-o-Tolylazo-2-aminotoluene 4-Aminoazobenzene 4-Aminobenzenesulfon-Np yrimidylamides

Aldehyde Formaldehyde Cinnamic Formaldehyde Formaldehyde

Proposed Use Drug Drug



... ... ...

Formaldehyde Formaldehyde Formaldehyde




Formaldehyde Acetaldehyde Benzaldehyde Furfural Formaldehyde Acetaldehyde Benzaldehyde Furfural Benzaldehyde Furfural Formaldehyde Cinnamic Formaldehyde Formaldehyde Formaldehyde Formaldehyde Formaldehyde Formaldehyde




Dyes Dyes Dyes Dyes Dyes Dyes Bactericide Bactericide Bactericide Bactericide Bactericide Drug

hydroxy; 3-methoxy-4-hydroxy-a-methyl.This reaction was studied with a view toward elucidation of the chemistry of lignin sulfonation (see below under heading Lignin). Sulfomethylation. This reaction-involving substitution of a reactive hydrogen on nitrogen or carbon with the grouping --CH(R)SOsNrt using an aldehyde with aqueous bisulfite-continues t o find favor as a mild, convenient method for enhancing water solubility of dyes or pharmaceuticals. (Sulfomethylation with sodium iodomethanesulfonate is discussed below under Sulfoalkylation.) Two references were noted t o sulfomethylation on a carbon atom. I n one case, p-nitro sulfonates were prepared by reacting aldehydes (formaldehyde, butyraldehyde) with a substituted nitromethane (1-nitropropane) and aqueous potassium sulfite (149). The second case involves a modified procedure comprising heating a dimethylaminomethyl compound with aqueous sulfite; the dimethylamino group is replaced by the sodium sulfonate grouping. In this manner the sodium salt of 3-indolylmethanesulfonic acid was obtained in quantitative yield from gramine ( = 3-dimethylaminomethylindole), and 2-hydroxy5-methyl-a-toluenesulfonic acid (as barium salt) was prepared from 2-(dimethylamino)methyI-p-cresol(118,119). Sulfomethylation on nitrogen is being more widely employed. It is of particular value for preparing pharmaceuticals (3067, since therapeutic activity of the products is maintained in contrast to that of the nuclear sulfonates, which are less effective and more toxic. This reaction may be expressed schematically as follows: RzNH

+ R’CHO + NaHS03 -+-

+ HzO


References noted are cited in Table 11. A number of p-nitro sulfonates were prepared by heating the corresponding p-nitro alcohol with aqueous sodium bisulfite (149). Alternatively, an organic ester of the’nitro alcohol can be reacted with a sulfite. (These nitro sulfonates can also be prepared from the nitro olefin, as discuss2d above under Addition t o Unsaturated Compounds.) A series of substituted benzyl alcohols has been reacted with aqueous sodium sulfite (simulated “sulfite cooking acid”) at varying p H under pressure a t 135’ C. resulting in replacement of the alcoholic by a sulfonate grouping (844, 145). Substituted benzyl alcohols so reacted are as follows: 3,4--dimethoxy and its ethyl ether; di(3,4dimethoxybenzyl) ether; 3-methoxy-4


This classification includes preparation of sulfonates from other sulfonates, either by polymerization of a n unsaturated sulfonate, or by reaction with the organic compounds. The new sulfonate is more complex in structure and of higher molecular weight than the starting sulfonate. Polymerization. A method for purification and polymerization of vinyl sulfonic acids, previously patented in the United States (142,205),has now been patented in Canada (122). I n a study of the preparation of ion exchange resins (as), vinyl sulfonic acid prober was found to polymerize with difficulty



in nonionizing solvents, but more readily in aqueous solution. Salts of vinyl sulfonic acid polymerized readily in aqueous solution to high molecular weight polymers, but vinyl sulfonic esters could not be polymerized by standard methods. However, the esters copolymerized well with vinyl acetate and vinyl chloride, although poorly with styrene and divinyl benzene. Two recent patents (106) describe the polymerization of an olefinic sulfonate (the addition product of one mole of sodium bisulfite to one mole of methylene-bis-methacrylamide) with hydrogen peroxide to yield an insoluble resinous material, presumably a polysulfonate. Sulfoalkylation and Sulfoacylation. Sulfomethylation (with aldehyde-bisulfite j was reviewed above under Sulfite Reactions. Use of sodium iodomethanesulfonate tor sulfomethylation of a variety of phenols (as their sodium salts by heating a t 180' t o 200' C. in the presence of copper bronze powder catalyst) has been disclosed in a British patent ( 3 7 ) t o yield compounds of the general structure ROCH2SO3Na. A number of salts and derivatives were prepared. Continuing his work on sulfoethylation of cellulose (for reference to previous work see 198, 260), Time11 uses the following procedure to prepare a fibrous product dissolving in water yielding a clear, viscous solution (382). Air-dry cellulose ( 5 grams) is mercerized with 28% sodium hydroxide for 2 hours and pressed. The sheets aie mixed mith 3.5 grams sulfoethyl chloride in nitrogen a t 54" C. After 20 hours the new product is poured into 757, aqueous methanol, neutralized with acetic acid, extracted with 80% methanol for 30 hours and dried in vacuo a t 74" C. The degree of substitution is 0.38. Alkali cellulose may also be sulfoethylated with vinyl sulfonates in an inert organic solvent, according to Grassie (167). Similarly, cellulose may be reacted under alkaline conditions with vinyl sulfonamides (or with the equivalent 2-haloethane sulfonamide) to yield products with interesting colloidal properties (166). A study was made by I. G. Farbenindustrie a t Lerdingen in 1932 ($(I$) of mono- and disulfoethylation on nitrogen of a series of benzene and naphthalene amines; 39 such derivatives were prepared using sodium chloroethanesulfonate as the sulfoethylating reagent. Long chain amides-hydroxyamines of the structure RCONHC2H4NHC2HdOH prepared by heating fatty acids (for example, stearic) with monohydroxyethyl ethylene-diamine -can be sulfoalkylated on the amino (as opposed to the amido) nitrogen by heating with the following cornpounds in aqueous alkaline solution: sodium 2-chloroethane sulfonate ( C1CH2CH,S03Na), sodium 2-( chloroethoxy) ethane sulfonate ( C1CH2CH20CH&H2S03Na), sodium 3-chloro-2-hydroxypi opane-1-sulfonate (C1CH2CHOHCH2S03Xa) or the equivalent 0


epoxide (CH2CHCH2SO3Ka)(Z19). The sulfonates so obtained are used as textile assistants. Potassium (hydroxymethyl) methionate (HOCH&H( SO8K)2), prepared by reduction of the corresponding aldehyde, may be acylated by reaction with acetic anhydride, caproyl chloride and palmityl chloride-the last two in the presence of pyridine(ass),yielding products of structure RCOOCH2CH(SOaK)z. An interesting new process for rendering diethylstilbestrol water-soluble by sulfoacylation with sulfoacetylchloride (ClCOCH2SOaH) has been patented (191, 390). Both phenolic groups are reacted in pyridine medium at 90' C. by the following general reaction: ROH


The method of preparing sulfoacetylchloride is not discussed. Sulfoacylation has also been used t o pro-duce water soluble azo dyes (93). I n this case, the phenolic group of a water-insoluble

Vol. 44, No. 9

azo dye is esterified in pyridine solution with the acid chloride of chlorosulfoacetic acid made hy treating the free acid with phosgene. Condensation Reactions. Ethylene sulfonyl chloride readily undergoes the Diels-Alder reaction Tvith several dienes (butndiene, isoprene, 2,3-dimethylbutadiene, and cyclopentadiene) to yield the expected types of sulfonyl chlorides in good yields (556). This interesting procedure for preparing hydroaromatic sulfonyl chlorides is new; however, it has been used to prepare a sulfonate ester (119,$b0). The free acid did not condense. A novel series of azo dyes was prepared by coupling variou? aromatic diazonium compounds with aliphatic nitro sulfonates (151), the preparation of which was reviewed above under Bisulfite Reactions. Examples are also given of a similar coupling reaction with an aliphatic keto sulfonate and a cyano sulfonate. Met~hylolmelaminehas been condensed with taurine in aqucou? solution at 50' to 55' C. to yield a product of' structure hIC1-1,KHCH2CH2S03Ka ( M represents methylolmelamine) useful for the treating of leather (106).


XYLSNE, etc. Monocyclic Compounds. BESZEKE,TOLUEXE, Production of benzene disulfonic acid as a resorcinol intermcdittte has increased almost twentyfold since 1937, and is continuing t'o increase ( 7 4 ) . Det'ailed laboratory directions have been published ior the sulfonation of benzene with 8 5 oleum and of t,oluene with concentrated sulfuric acid (397). Isolation of toluene sulfonic acid as such is described, as is also conversion of both tothesodiuni salts. Reactions and characterization are also discussed at length. Benzene was sulfonated with oleum in the course of a study of the mechanism of electrophilic aromatic substitution (264). Inhibition of sulfone formation during monosulfonation of benzene with 207, oleum in a three stage process is accomplished by concurrent addition of 5 to 10 weight per cent (011 total reactants) of sodium benzeiiesulfonat'e ( 2 7 s ) . Green and Carrier (1681, pointing out that up to the present. the continuous sulfonation of aroniatic compounds (in particular benzene) has not been considered commercially practical, have patented such a continuous process involving introduction oi benzene, 987' sulfuric acid, and a portion of the reaction product into a tower through which benzene vapors are simultaneously paseed. Reaction temperature can be about 340" F. Toluene has been sulfonated n-ith sulfur monoxide, a new sulfonating agent (359). S o details are given of this interesting reaction. The yield of pure sodium p-toluenesulfonate on a laboratory scale has been raised from 38 to 6070 (314) by using a waterremoving apparatus, stirring, aud adding excess toluene. The acid used contained some 535 isotope. As part of a patent,ed process for producing dixylyl sulfones ($40)commercial xylene mixtures (containing the three xylene?, ethyl benzene and nonaromatics, possibly of petroleum origin) are sulfonated azeotropically with 9870 sulfuric acid a t 145' to 165" C. as the first step. Considerable experimental detail is given. Sulfonation continues to be of interest as a method for segregating aromatic hydrocarbons and their derivatives by selective reaction. (For other examples, as reviewed previously, see 142.) -4recent paper (75') indicates commercial use of sulfonation t o separate ethyl benzene from meta-xylene in processing crude xylene of petroleum origin; in this case the xylene is sulfonated and then recovered by steaming. -2 reference was noted of the use of sulfonation to purify meta-xylene in the laborat,ory ( 1$8).

September 1952


Elwell (117) patent6 the separation of 3,5-dimethyl-l-ethylbenzene from other ethyl xylenes by sulfonation followed by hydrolysis. (The separation of chlorinated toluenes is reviewed below under Halogenated Hydrocarbons.) A comprehensive study has recently been reported on the purification and several physical properties of sodium benzenesulfonate, sodium p-toluenesulfonate, and related compounds (316). No sulfonations were made in the course of this study. h n improved process for separating sodium sulfate from the sodium sulfonates of benzene, toluene, xylene, and p-cymene has been patented (280). The process comprises treating the crude sulfonate with a relatively small quantity of water such that the organic sulfonate dissolves but the inorganic salt remains undissolved. DETERGENT ALKYLATES.Production of synthetic detergents has continued t o expand a t the expense of solid soap, the great bulk of a n expected 1,500 million pounds of synthetic products for 1951 being of the "dodecyl benzene" sulfonate type (363); further expansion is anticipated for 1952. This required sulfuric acid a t the rate of 15,300 tons per month in the summer of 1951. The history and statistics of petroleum-derived surface-active agents hae been reviewed by Skeen and Snell(Sb0). Production and properties have been generally reviewed by Snell and Reich (355). detailed discussion of dodecyl benzene detergent manufacture on a plant scale has been presented by Snell and coworkers (354). Specific data are given for the following steps: Sulfonation with 20% oleum, spent acid separation, neutralization, building, and drying. Equipment, process requirements, and materials of construction are covered and a flow diagram is included. The relative merits of various strengths of oleum and of sulfur trioxide for the sulfonation step are reviewed briefly. I n another review of synthetic detergents of various types derived from petroleum, Griesinger and Nevison (163),state that the sulfonation of dodecyl benzene is a relatively simple chemical operation which can be carried out using 98% sulfuric acid, fuming sulfuric acid, or any combination of the two. As examples are cited use of 50 volume per cent of 20% fuming acid (based on the alkylate) at 90" F. or 90 volume per cent of 98y0 acid a t 150" F. I n a similar review Griesinger and Hersberger (162) state that commercial equipment for detergent alkylate sulfonation, in order of preference, is made of glass, type 316 stainless steel, nionel, or lead. Three other reviews on synthetic surface active agents have appeared, well documented with references to the patent and chemical literature (166,847,368). A general description has been published of the process for manufacturing a well-known brand of dodecyl benzene sulfonate detergent (Santomerse) as operated in Great Britain (18). The sulfonat,ion is operated continuously, followed by water dilution and layer separation. The spent acid is used for steel pickling. KOfurther details are given of the sulfonation step. Chu and associates (81)made a study of the spray drying of Santomerse. Dodecylbenzene sulfonic acid was prepared (134) in the course of a study of fabsplitting agents. Fincke (126) sulfonated dodecyl benzene, dissolved in liquid sulfur dioxide, in a nozzle apparatus with sulfur trioxide, dissolved in liquid sulfur dioxide, a t 25" to 35" C. The heat of reaction was utilized to distill off all the sulfur dioxide solvent. The process for sulfonating detergent alkylate type hydrocarbons with 30 to SO% oleum using a n inert low molecular weight saturated paraffin hydrocarbon-e.g., butane-as the reaction medium (149)has been patented (50). Several patents mainly concerned with improved procedures €or preparing detergent alkylates also incidentally mention the sulfonation procedures used. Two of these references (208, 279) employ two-step sulfonation, the first with 97 to 100% acid, the A%


second with oleum. The other references (187, 133, 863, 389) employ the conventional one-step procedure with acid or oleum. Deodorization of alkylated aromatic sulfonates may best be accomplished by steaming, according to a Dutch patent (886). POLYSTYRENE. Two references were noted on direct sulfonation of styrene-divinylbenzene bead copolymers to produce experimental ion exchange resins (160,301) using silver sulfate catalyst with excess concentrated sulfuric acid a t 90" to 100" C. at sulfonation times varying from 6 hours to 1 week. A British patent (If&'),primarily concerned with a n improved conditioning procedure for the product, mentions sulfonation of spherical particles of styrene-ethyl vinylbenzene-divinylbenzene copolymer by heating with concentrated sulfuric acid, followed by draining off excess acid. HALOGENATED HYDROCARBONS. A study was made of the sulfonation of chlorobenzene between 5" and 55' C. with sulfuric acid of between 90 and 102% strength from the standpoint of being a side reaction in the preparation of DDT (64). Crude trichlorotoluenes have been sulfonated stepwise, 23% oleum at 70" to 80' C., then 33% oleum at 130' to 140" C.; and then "fractionally desulfonated" with superheated steam to effect separation of the various isomers (60). The purification and physical properties of sodium 4chlorobenzene sulfonate have been studied (316). No sulfonations were made during the course of this work. Details for the laboratory sulfonation of bromobenzene with 8% oleum have been reported (397),the sulfonate being isolated as the sodium salt. Reactions and characterization of the 3bromo- and the 3-chlorobenzene sulfonic acids are considered. Melander ($64)sulfonated bromobenzene with oleum in the course of an investigation of electrophilic aromatic substitution, PHENOLS . ~ N DPHENOLIC ETHERS.Phenol, 0-cresol, and guaiaeo1 were sulfonated by heating with concentrated sulfuric acid for IS hours at 80' t o 90" C. (198). Isolation and purification of the sodium (or potassium) monosulfonates are described. The degree of sulfonation of phenol and the three cresols with concentrated sulfuric acid a t 100' C. for 2 hours, varying the proportions of reagents from excess acid t o 25% excess phenol, was studied (116). For equimolar proportions, the degree of sulfonation, assuming no disulfonation, was: phenol, 94.6; o-cresol, 88.4; m-cresol, 83.6; p-cresol, 76.4. A review of the composition and industrial production of potassium guaiacol sulfonate has been published (268). The preparation of dodecylphenol sulfonic acid, as well as its chloro and iodo derivatives, has been described (134). (The original is in Japanese and the English abstract gives no details.) Sulfonation has been used in German industrial practice ( 4 ) on a pilot plant scale as the basis for a method of separating 2 , 4 dimethylphenol from other xylenols. The xylenol mixture (40 kg.) was sulfonated by heating with 77.7y0 acid (40 kg.) for 4 hours at 100' C. Better results were obtained with 92% acid for 6 1 / 2 hours at 45' C. After separation of the sulfonic acids the pure xylenol was recovered b y steaming. A British patent (38)shows sulfonation of phenol by heating with concentrated sulfuric acid at 90" C. for 0.5 hour as a step incidental to subsequent ortho alkylation with an alcohol followed by dinitration to produce 2,4dinitro-6-sec-butyI phenol, a weedkiller. Simultaneous alkylation-e.g., with polybutylenes-and sulfonation of phenol has been used for the preparation of longchain alkylphenol sulfonates, the salts of which are used as lubricant additives (362). Sulfonation of methyl salicylate with gaseous sulfur trioxide, followed by treatment with a higher alcohol to effect ester interchange, patented in the United States as previously reviewed ( l 4 8 ) ,has now been patented in England (873). The monosulfonation of resorcinol in nitrobenzene solution


2088 Table


Sulfonates Prepared from 1-Naphthol-3,6-disodium Sulfonate

Sulfonate Prepared 1-OH-2,3,4.6 (XII) 1-OH-3,6 1-OH-2,3,6 1-OH-3,4,6 (XI11 b ) 1,3-Di OH-2,4,6 (XXI)

Starting Compound 1-OH-3,6 XI1 XI1 XI1 XI1

1,3-Di OH-4,6 ( X X I X b)


1 3 - D i OH-6 (XXVIII) l:NHz-3-OH-2,4,6 (XXII)


I-XHz-3-OH-6 (XXIV) 1,3-Di "2-6 (XXV)


1.3-Di SHz-2.4.6 ( X X I I I )


l-OH-3-NHz-4,6 (XXVI)


1-OH-3-"1-6 (XXVII) 4-NO-1,3-d! NHz-2,6 (XXX) 4-NO-1,3-d1 "2-6 (XXXI) 4-NO-1,3-di OH-6 ( X X X I I )


4-NH1-1,3-di O H 4 ( X X X I I I )


1,3,4-Tri "2-6





Method 30% Oleum Bqueous acid hydrolysis Hydrolysis with methanolio KzCOa Aaueous ammoniacal hydrolysis Aqueous alkaline hydrolysis Aqueous alkaline hydrolys1s Aqueous acid hydrolysis Aqueous ammonium sulfite ( 5 hours) Hydrolysis Aqueous ammonium sulfite (16 hours) Aoueous ammonium sulfite A q ueous ammoniacal 1iydrolysis Aq ueous acid hydrolysis Nitrous acid Aqueous acid hydrolysis Aqueous alkaline hydrolysis Kitrous acid Stannous chloride reduotion Stannous chloride reduotion

Vol. 44, No. 9

nitrochlorobenzene. The analogous United States patent was previously reviewed ( 1 4 2 ) . 4 surface active agent used for dye leveling, disclosed in a n Austrian patent (137), comprises methylating Iauroyl cyanoguanidine, reacting with aniline (to form a n amidine with the cyano group), followed by sulfonation with 26y0 oleum, presumably in the para position of the benzene ring. 4-Aminobiphenyl was converted to 4'-amino-4-biphenylsulfonic acid by heating 1.5 hours a t 90' C. with an excess of strong sulfuric acid (126). This product was converted t o 4'-hydroxy-4-biphenylsulfonic acid by diazotization and to 4,4'-dihgdroxybiphenyl by caustic fusion. A study has been reported ( S F ) of various procedures for sulfonating l-methy1-2-amino-4-isopropyl-benzene(2-amino p cymene). An 80% yield was obtained by the baking process. Several derivatives were prepared, including a number of new dyes by diazotization and coupling. Benzhydrol, added as a solid t o a large MISCELLANEOUS. o acid, was largely sulfonated in 10 minutes excess of 1 0 0 ~ sulfuric (406). The possible composition of the sulfonate was not discussed. A series of Swiss patents (358, 534) discloses preparation of green dyes by sulfonation of both R groups in the compound

0 with chlorosulfonic acid, previously patented in the United States (650),has now been patented in England (140). Anisole was sulfonated by heating on the steam bath with concentrated sulfuric acid for 0.5 hour (198). With chlorosulfonic acid a t 20' C., anisole gave a water-soluble product; at 60' t o SO" C. a disulfonyl chloride was apparently formed. I n the course of a physical study of the behavior of organic compounds in 1007, sulfuric acid a t 25" C., it was found t h a t 4,4'-dimethoxybenzophenone was completely sulfonated in 1 hour, and the three methoxybenzoic acids in 6 hours (278). An amide of 4-methoxybenzoic acid (the diamide of 3,7diaminobenzothiophene sulfone) has been sulfonated on both methoxybenzoyl rings (position not stated, presumably ortho t o the methoxyl groups) using chlorosulfonic acid as disclosed in a recent patent (337). I n one example, using nitrobenzene as the solvent, the chlorosulfonic acid was added in two portions in the range 10' to 25' C. I n a second example with solvent, the organic compound was added to the acid in the 10" to 10' C. range. The products were fluorescent dyes. Prutton (311) discloses the sulfonation of wax alkylated diphenyl ether with chlorosulfonic acid at 30' to 50" C. to introduce 1 to 1.55 sulfonic groups per mole. In a second patent (612), Prutton sulfonates a monocapryl diphenyl ether with chlorosulfonic acid a t 30' to 60" C. in carbon tetrachloride solution, and dicapryl diphenyl ether with the same reagent a t room temperature using mineral spirits as the solvent. The products are used as lubricant additives. ANINO COMPOUNDS. This category comprises aniline and its derivatives. A laboratory preparative procedure for sulfanilic acid has been described (59);a white product of good purity was obtained directly in 84 t o 96% yield. Aniline was heated with 9370 sulfuric acid stepwise to 200" to 210" C., a t which temperature the reaction is completed in 3 hours. A study was made of the behavior of the anilides of three methylated benzoic acids in 100% sulfuric acid a t 25' C. (878). No sulfonation of the pentamethyl derivative occurred in up to 90 minutes, while the trimethyl compound was 16% sulfonated and the monomethyl (ortho) was 8570 sulfonated in 30 minutes. Hydrolysis also occurred. A British patent ( 6 1 ) has been issued on rrn improved procesv for preparing 2,6-dichloro-4-nitroaniline involving as possible alternative first steps the sulfonation of 4-nitroaniline or 4-


d K h e n R is 5,6,7,8,-tetrahydro-2-naphthylamino, 5 to 10% oleum is used a t 14' t o 45" C. Other R groups similarly sulfonated are: 1,2,3,4-tetrahydro-2-naphthylamino, 4-phenoxyphenyl, 4biphenylyl, 4-benzylphenyl. Similar disulfonates (one sulfonic group on the anthraquinone ring) are described in a British patent ($50). Two other Swiss patents (555)disclose the preparation of similar disulfonate dyes containing no chlorine where one R group is H. Sulfonation of 2-(A%~-phenylacetyl)-amino-l-naphthol occurs on the benzene ring (141). This product is an intermediate for azo dyes. POlyCyCliC. x.4PHTH.4LENE .4SD DERIVLTIVESDetailed lithoratory directions have been published (597) for the sulfonation of naphthalene (100 grams) with concentrated sulfuric acid to the p-monosulfonate. Isolation of the sodium salt is described. The preparation of derivatives of various naphthalene nionoand disulfonic acids for purposes of identification is also discussed and the melting points of 25 such derivatives are tabulated. The sulfonation of naphthalene to the a-sulfonic acid mith thioxane-sulfur trioxide adduct is disclosed in a British patent (159). The United States analog appeared previously (225,248). Sprgskov (359) has published data on the degrees of hydration of the two naphthalene monosulfonic acids using various desiccants. D a t a on the solubilitiee of the two sodium salts in aqueous sodium chloride solutions a t various temperatures are also presented. A recent United States patent (189) discloses a procedure for improved recovery of sodium P-naphthalene sulfonate from the final aqueous solution prepared by the usual process. The process involves addition of a surface active material-e.g., dihexyl sodium sulfosuccinate-to promote crystallization from the supersaturated solution. Sulfonation by the usual procedures of various alkylated naphthalenes is mentioned in recent references primarily concerned with the alkylation step. Thus, a t the Hochst works of I. G. Farbenindustrie naphthalene (alkylated with isohexyleneisoheptylene mixture using boron fluoride-phosphoric acid)

September 1952


was sulfonated in a two-step process, first with monohydrate acid at 5 " t o 10' C., then with 30% oleum t o complete water solubility (203). A Canadian patent (181) claims a naphthalene sulfonic acid containing mixed alkyl groups (C, t o CV). According to a Japanese patent (386) a fat-splitting agent can be prepared by sulfonating with fuming acid a t 40' C. the alkylate prepared from naphthalene and hexadecene-1 in the presence of a n acid clay. An extensive study has been reported of the sulfonation of 2,2'-dinaphthyl sulfone (230). The sulfonation goes with difficulty, requiring concentrated acid (above 87.5%) in large excess. Three sulfonic acids were isolated, one mono (in 5 position), and two di (in 7,7' and 5,5' positions). Several derivatives were prepared. Sulfonation of l-naphthol-3,6-disodium sulfonate with 30% oleum for 4 hours at 125" C. yielded l-naphthol-2,3,4,6-tetrasulfonate (42 ) isolated as the crude sodium salt. Other sulfonates were prepared from i t (Table 111; Roman numerals in the table are as used in the original text). Hydrolytic procedures were used extensively. A detailed study has been made of the polysulfonates of 2naphthol and 2-naphthylamine, two of the sulfonate groups being in the peri position (808); these compounds have not previously been described. The compounds prepared and the methods used are indicated in Table IV; the Roman numerals being as used in Chemical Abstracts.

Table IV. Sulfonation of %Naphthol and %Naphthylamine Sulfonic Acids Sulfonate Prepared

Starting Compound 2-NHa-1,6


VI1 I11

I or I1


VI 2-"2-8-OH-3 6 2-OH-1 3 6 , s CbII) 2-OH-1'3'6 2-0H-1:3:6,8 (VII)


Method 20% Oleum 40% Oleum Aqueous acid hydrolysis Aqueous hydrolysis Diazotization Aqueous acid hydrolysis A ueous hydrolysis A% aline fusion 40% Oleum Aqueous ammoniacal hydrolysis Alkaline fusion

2-OH- 1,6;Z-OH-:

The unusually brilliant colors of several of the peri sulfonates prepared in the above investigation led to a potentiometric study from which i t was concluded t h a t these compounds contain a chromophore group with a sulfur of a sulfonate group doubly bonded to the ring carbon (371). 2-Amino-Ebhydroxynaphthalene was converted t o the corresponding 7- (65y0) and 5-sulfonic acids (16%) (302)by treatment with 96% sulfuric acid a t 0' to 3' C.; a t 20' t o 30" C., the yields were 50 and 35%. These acids were converted t o a series of azo dyes by coupling. Stannous chloride reduction of the l-benzeneazo derivative of the 5-sulfonic acid yielded 1,2-diamino-8naphthol-5-sulfonic acid. The sulfonation of nitrosonaphthol reagents (used for cobalt determination) yields sulfonates useful for colorimetric determination of cobalt (221). A British patent (98) cites preparation of 1-amino-2-hydroxy6-methoxy-4-sulfonic acid by nitrosation of 2-hydroxy-6-methoxynaphthalene, followed by reduction and direct sulfonation. The sulfonate is a n intermediate for metal-containing monoazo dyes. ANTHRACENE DERIVATIVES. 2-Methylanthraquinone was sulfonated with oleum in a two-step procedure, first a t 50' to 60' C., then a t 145' C. for 4 to 5 hours, forming the 3-monosulfonate (17 5 ) . The sulfonation of alizarin yields a more sensitive analytical reagent for determining aluminum (221 ). Anthracene oil is sulfonated with concentrated acid to yield


a sulfonate used as a n ingredient of a rushremoving composition, according t o a German patent (184). MISCELLANEOUS. Three 9-alkyl-fluorenes (butyl, hexyl and heptyl) were sulfonated in the 2-position with excess concentrated sulfuric acid by stirring for 12 hours a t 45" C., followed by 12 hours at 100' C. (23). These sulfonates, prepared as experimental wetting agents, were converted to several derivatives. Water solubilities and surface tensions of the aqueous solutions were measured. A sulfonation study has been made of a styrene dimer, l-methyl3-phenylindane (322). Concentrated sulfuric acid gave excessive disulfonation, but chlorosulfonic acid (10% molar excess added to the hydrocarbon at 30" C. with chloroform as solvent) gave a better yield of mixed monosulfonates from which three isomers were isolated in pure form. Several derivatives were prepared. 6-Sulfodehydroabietic acid was prepared by sulfonation of colophony, and two grades of 2-abietic acid by a n improved procedure using concentrated sulfuric acid (131). Several metallic salts were prepared. Attempts t o convert the carboxyl group to an amino group were not successful. The manufacture, properties and uses of "sulfonated resin oils" have been reviewed in French (18). A tannin extracted with water from the Indian khair tree was treated with concentrated sulfuric acid at 80' C., followed by refluxing for 4 hours with 10% sulfuric acid, t o yield a resin capable of absorbing calcium and magnesium ions from aqueous solution (46); barium was absorbed sparingly and strontium not a t all. According to a recent German patent (31), a dispersing agent may be prepared by treating a coal-tar residue with 9601, sulfuric acid a t a maximum of 120' C., followed by water dilution and neutralization with aqueous ammonia. Sulfonyl Halides. Direct introduction of the sulfonyl halide grouping into the aromatic compound with the appropriate halosulfonic acid is reviewed ia this section. (Oxidative introduction of this group is discussed below the appropriate separate heading.) Procedures starting from the sulfonate-e.g., by use of phosphorus pentachloride or chlorosulfonic acid-are not considered. However, mention should be made of a recent study (360) of the preparation of sulfonyl chlorides by the action of chlorosulfonic acid on the appropriate sodium sulfonate; examples are given, with yields, of its use in a variety of cases. A study of the equilibrium:



has been made at 0' C. where R is 4-methylphenyl (361). The equilibrium state was reached in 4 to 9 hours, the constant being 1.18.



Compound Reacted To1uen e 9-Heptyl fluorene Anis o1e Diphenyl oxide Diphenyl methane 1-Chloronaphthalene N-Acetylaminomethylbenzene A-Phenylvalerio acid Phenyl acetic acid 1-Methyl-1-phenylcyclohexane 4-Chlorotoluene 8-Phenoxyethylhromide p-Anisic acid

Sulfonyl Halides kemarks


4-Sulfonyl chloride obtained Carbon tetrachloride solvent: disulfonyl chloride formed No solvent used at 60: t o SOo C.: disulfonyl chloride formed Disulfon 1chloride exclusively forme$ Disulfonyl chloride formed Monosulfonyl chloride obtained Yield 47% para, 9% ortho of mono compound Mono-sulfonyl fluoride obtained in high yield Mono-sulfonyl fluoride obtained in high ield Carbon tetrachlori& solvent: mixture obtained Chlor-oinn solvent; yield 67

(6) (93) (98) (198)

(260,840) (860) , (gas) (11)

t o 7870

Chloroform solvent No solvent: addition a t 5' to 1 l 0 C.; heat t o 7 5 O C.

(368) ($36)



Laboratory technique for conducting the chlorosulfoiiation reaction, without a solvent or using chloroform as the solvent, has been detailed (397) from the standpoint of identifying the organic compound treated. Sulfonyl halides prepared by the usual procetlure (reaction of the organic compound with excess halosulfoiiic acid a t moderate temperatures) are listed in Table V. 9 Japanese patent (271 ) discloses chlorosulfonation of toluene SO2C12 in the presence of added o- or p-toluenesulfonyl chloride. In the presence of the para-isomer, from 19 kg. of toluene, 24.5 kg. of ortho- and 11 kg. of para-toluenesulfonyi chloride were obtained. When 92 kg. of toluene were reacted with S0~C12in the presence of o-toluenesulfonyl chloride, the para-isomer was the predominant product, the yield being 1.5 kg. of the ortho-isomer and 90 kg. of the para-isomer. A series of azo sulfonyl fluorides, useful as dyes for synthetic fibers, has been prepared by diazotization and coupling of various amino sulfonyl fluorides (698). O X I D A T I V E PROCEDURES

Several w e s were noted of the formation of sulfonates (or sulfonyl halides) by the oxidation of thiol or sulfinic acid derivatives, as indicated in Table VI; oxidizing agents used are of the usual types.

Table VI. Thiol and SulAnic Acid Derivatives Organic Reactant Tetra(4-thiooresy1)ortho


Di(2-trifluoromethyl-4nitrophenyl) disulfide (4-CHaCONHCsH&)


Procedure Perbensoic acid in chloroform solution Fuming nitric acid -4queous chlorine or bromine

~ - C H ~ C O N € I C B H ~ S C O XAqueous H~ chlorine or bromine (3-Cl-4-CHaCONHC~HaS-)p Aqueous chlorine Bromide-bromate titration 30% Hydrogen o-(1-Naphthyl)-benzenesulfinic said peroxide 4-Toluenesulfinic acid (so- Disproportiondium salt) ation by heat2-Toluenesulfinio acid (sodium salt)

Remarks Sulfonic acid formed Sulfonic acid formed; several deriys. prepd. Corresponding sulfonyl halide formed Corresponding sulfonyl halide formed Corresponding sulfonyl halide formed R = CeHs and o , m. p-tolyl; sulfonvl bromides formed Sodium sulfonate formed Sodium sulfonate formed


Aqueous ammoSulfonamide niacal chlorinaformed tion


An improved procedure for introducing a sodium sulfonate group into the 2-position of 1,4-dihydroxy anthraquinone, involving heating the dihydroxy compound with aqueous sodium bisulfite in the presence of an aromatic nitro conipound (nitrobenzene, m-nitrobenzene sulfonic acid are cited), is described in a recent patent (56). Similar examples are also given for two tetrahydroxy anthraquinones. I n a similar case, the reaction of varioue nitrobiphenyls with excess aqueous sodium bisulfite a t 130' to 135" C. has been investigated (126). Although the nitro groups were partially or completely reduced in all cases, only the .%nitro and 4,4'-dinitro compounds were also sulfonated (in the 3-position), yielding 4amino-biphenyl-%sulfonic acid and benzidine-3-sulfonic acid. The latter was converted by diazotization and decomposition of the diazonium salt to biphenyl-3-sulfonic acid, which in turn was converted to several derivatives. Diethyl-p-phenylenediamine is sulfonated (position undetermined) by aeration in aqueous alkaline bisulfite solution (267); traces of copper accelerate the reaction. This observation was made incidentally to a study of photographic developers.

Vol. 44, No. 9


The introduction of a sodium sulfonate group into di- and tetrahydroxy-anthraquinones by react,ion with sodium sulfite in thc; presence of an oxidizing agent was cited above under Oxidative Procedures. A similar reaction, involving formation of aminobiphenyl sulfonic acids, was revien-ed under the same heading. The chemical struct'ure of the sulfonate prepared by reacting 1,4-naphthoquinone with 2 moles of sodium bisulfite continue? to be a matter of controversy (51). This product, possessing vitamin Kactivitg andalreadypateiited in Switzerland (65,I.@), has now been patented in Sweden (SO). C O N D E N S A T I O N REACTIONS

Under this heading are discussed t,he reactions of aromatic sulfonic acids with other organic compounds to yield new iulfonic. acids. These may be polymeric in nature, as when fornialdehyde reacts with phenolic sulfonic acids to yield ion exchange resins or tannin agents. (Preparation of sulfonated polystyrene by direct sulfonation is discussed above under the heading Pol>-styrene.) The production of synthetic tanning agents (by the reaction of formaldehyde with various phenolic sulfonic acids) has bren increasing in the United States ( 7 6 ) a t the expense of less uniform natural products. An extensive general review in Creriiiai1 ( 3 6 4 ) discusses the preparation, composition, and action of synthetic tanning agents. Abstracts of 500 synt,an patenB over the pcriod 1911 to 1950 have been collected in one volume (77j. The chemistry of the p-cresolsulfonic acid-formaldehyde condensation in relation to tanning properties has been investigated by t'he Swedish Tanning Research Institute (116). Pure p-cresolsulfonic acid x-ith formaldehyde yields solely 2.2'dihydroxy- 5,5' - dimethyldiphenylmethane- 3,3' - disulfonic acid, n-hich has no t'anning properties. IIov-ever, p-cresolsulfonic acid mixed with unsulfonated pcresol yields with formaldehydr. an effective tanning agent marketed as Xeradol D. Heating under specified conditions, with some decomposition noted, conferred tanning properties upon the above disulfonic acid, and enhanced those of Xeradol D. However, such heating of similar sulfonic acids (p-cresolsulfonic acid or rn-xylenolsulfonic ac,itl) yielded sulfones devoid of tanning properties. The sulfonatiaii rates of several phenols were determined (reported above unt1c.r iiromatic Phenolic Compounds). A German patent (26) describes the preparation of improved tanning agents involving primary partial sulfonation (as indicated by the lack of complete water solubility) of a commercial polyhydric phenol, followed by condensation with an aldehyde. I n a United States patent Miglarese (269)describes simultaneous sulfonation and condensation of phenol with vanillin. Thomaen (379) prepared a tanning agent -:1 sulfonating a mixture of @-naphtholand colophony with 10OGG acid and then condensing the product with phenol-formaldehyde. Tanning agenk, prepared by sulfonating naphthalene with an excess of rmlfuric acid and condensating the naphthalene sulfonic acid with formalti+ hyde, are described in a brochure ( 7 ) . Incorporation of mercury into the syntan molecule has led to an interesting new type of water-dispersible fungicide useful for preserving cloth (193, 309). In preparative examples (508), naphthalenesulfonic acids are first reacted rvit,h phenylmercui y acetate, followed by reaction with formaldehyde. Several studies have been noted on the preparation of ion eschange resins by reaction of phenolic sulfonic acids with iormaldehyde. Physical properties, chemical analysis, and exchange capacity of the Italian cation exchanger Dakation-K-7, prepared by acid-catalyzed condensat'ion of alkali-p-hydroxyphenylsulfonate with trioxymethylene, have been reported (300). d Japanese worker has described (19g) preparation of resin from pure pphenolsulfonic acid, a number of variables in $he condensa-

September 1952


tion being considered. About two-thirds of the sulfonic groups were lost during condensation. Absorption of cobalt complexes on the resin was studied. Another Japanese investigator (347) has described details of the preparation of a similar resin with a capacity, against 0.5 N caustic soda and sodium chloride, of about 70% of theory. Moralli (274) reports conclusions from the preparation of several resins from sulfonated mono- and polyhydric phenol as follows: (1) exchange capacity in acid medium increases linearly with sulfonic group content; (2) the exchange reaction is of the equilibrium type; (3) resins having the sulfonate group para to the hydroxyl group have lower eschange capacity than theory, while the ortho compounds have greater capacity than theory (exception: the resin from hydroquinone). In a British patent ( l l d ) , concerned with an improved procedure for conditioning ion exchange resins, examples are given of their preparation from phenolsulfonic acid and formaldehyde, and from phenol, sulfuric acid, and formaldehyde. Four patents were noted relating to the condensation of "methylol aminoplastd' (such as methylol melamine or methylol urea) with aromatic sulfonic acids (monomeric or polymeric) to yield leather-conditioning or tanning agents. In one case ( S I ) , the sulfonic acid was a soluble sulfonated polystyrene produced by a procedure reviewed previously ( 1 4 2 ) . In the second patent (106), methylol melamine was reacted with sulfanilic acid to yield products of the general formula MCH2NHCeHaSOsKa (M is methylol melamine). I n a third example (63) p-naphthalene-sulfonic acid is reacted a i t h urea-formsldehyde, while the fourth patent (54) discloses sulfonation with 98% sulfuric acid of a phenol-formaldehyde novolak, followed by reaction with a condensation product of formaldehydc, ammonia, and urea. Complex alkylated naphthalene sulfonates, useful in breaking petroleum emulsions, have been prepared by reacting amyl naphthalenes, after sulfonation with 98yo sulfuric acid in the presence of isopropanol, with petroleum diolefin polymer (as "Gray tower polymer") (227). Optical bleaching compounds have been prepared by condensing 4-methyl-7-aminocoumarin with benzylchloride-4-sulfonate or with benzaldehyde-2,4-disulfonate(83). Reaction occurred via the amino group in both cases.


Sulfonation of y-butyrolactone in chloroform solution a t 0" C . with sulfur trioxide yields the a-monosulfonic acid (231 ). The disulfonio acid is obtained a t 100" C. without a solvent. The sodium salt of the mono-sulfonate was also prepared by reacting the a-bromo lactone with sodium sulfite (30). 1,4-Benzodioxane was sulfonated in the 6-position with 95% sulfuric acid at 140" C. in 67% yield (179); 6-nitro-1,Pbenzodioxane wae similarly sulfonated in an unknown position in 57% yield. Derivatives were prepared from both sulfonates. 2-(Cyanoacetyl) coumarone was treated at 40" C. for 5 hours with excess chlorosulfonic acid to yield 78% of the 5-sulfonyl chloride (367). Several derivatives were prepared. Several Pmethyl-7-aminocoumarin derivatives were sulfonated in a series of Swiss patents (84-90) on the preparation of dyes for optical bleaching of wool. The 7-benzylamino derivative was treated with concentrated sulfuric acid a t 70" to 150' C. (86); the 7-be~zylethylamino compound at 0" C. with oleum (87); the 7-ethylamine derivative with chlorosulfonic acid a t 90' t o 95' C. (88); the 3-benzyl-7-ethylamino analog with monohydrate acid at room temperature (90). Sulfonation probably also occurred on the benzyl groups. Sulfomethylation may also be used on these compounds (p.0.). An ion exchange resin may be prepared by reacting furfural with petroleum acid sludge, followed by sulfonation with oleum (59).

209 1

Preparation of the diaminodibenzothiophene sulfonates (mono-, di-, tri-) by simultaneous sulfonation and sulfone formation, with 25 to 35% oleum, of the corresponding benzidine derivatives (diacetyl dianisidine, benzidine, tolidine) has been detailed (336). The diacylated derivatives are effective optical bleaches. (Similar compounds containing sulfonate groups in the nonheterocyclic portion of the molecule are described above under Monocyclic Phenolic Compounds). Sulfonation of anilino substituted fluoranes may be accomplished with 1 0 0 ~acid o or 37, oleum (128, $14, 817) to yield violet dyes for wool. NITROGEN COMPOUNDS

2-Chloropyrrole and 2-phenylazopyrrole were sulfonated in the 5-position with pyridine-sulfur trioxide in ether a t 60" to 70" C. in 4 hours (378). Several derivatives were prepared. Patents continue to appear on improved procedures for sulfonating pyridine. G d a t (135) heats the pyridine-sulfur trioxide adduct with mercuric sulfate catalyst, while Segool and Tryon (344)use the same catalyst at 250" to 300" C., but employ a vacuum to maintain the sulfonating acid a t 96 t o 100~c strength. Tisza and Duesel (383) periodically add oleum and a metallic catalyst (mercury, aluminum, magnesium, or vanadium) t o pyridine sulfate in oleum a t 250" to 320' C. 8-Hydroxyquinoline was sulfonated in the 5-position by gradual addition to oleum at not over 10' C., followed by standing a t the same temperature for 24 hours (251). Several metallic derivatives were prepared. Isoquinoline was sulfonated by addition to s O ~ coleum a t below 80" C., followed by heating 2 hours a t 90" to 95' C. Similarly, 8-phenylquinaldine and benzalquinaldine \+ere sulfonated with 1.570 oleum, presumably on the benzene rings (123). The products are improved electroplating additives. The quinophthalone from 4-methylquinoline was sulfonated with 25Yc oleum (position unspecified) to yield a light brown dye for wool and silk (18). Indigo has been sulfonated, according to a Hunganan patent (.bo), with acid prepared by diluting 10% oleum with 78y0sulfuric acid in such a manner that the acid is not heated above 60" to 70" C. The sulfonation of carbazole with chlorosulfonic acid in nitrobenzene solution a t 10' C. was studied by Borodkin (57). Depending upon mole ratio, but independent of reaction time, 80 to 95% yields of the 3-monosulfonic acid or the 3,6-disulfonic acid could be obtained. Small quantities of the 1,3,6trisulfonic acid were formed a t higher temperatures. The N-sulfonic acid was obtained in some cases, as reviewed below under Sulfamation. Carbazole was sulfonated to the 1,3,6-trisulfonate a t Hochst by I. G. Farbenindustrie on a commercial scale intermediate to preparation of a tetranitrocarbazole fungicide (580). The carbazole was added to 95% sulfuric acid, the temperature being 50" C. a t the end of the addition. The exothermic reaction carried the temperature to 95' to 100' C., a t which point it was maintained for 1hour. I n a discussion of this process, the folloning points were brought out: (1) oleum gives more isomers than 95% acid; (2) a better product and yield can be obtained if the reaction is carried out at 0" C., but for practical purposes the rate of reaction is too slow and too much cooling is required; (3) a better yield is also obtained when the process is carried out in two phases, the first phase at 40" to 45" C. yielding the 3,6-disulfonate, and the second phase at 70" C., introducing the third sulfonate group in the 1-position by the use of additional acid. Sulfonated carbazoles of the anthraquinone series, useful as yellow-brown dyes, have been prepared by combined ring closure and sulfonation of various 1-acylamino-5-arylaminoanthraquinones (64, 369, 331, 333). The preparation of similar products was reviewed previously (143).



4-Amino indazole was sulfonated (306)below 35" C. with monohydrate acid followed by 65YG oleum to yield the 7-sulfonateJ a s part of a study of the variation in acidity of the sulfonate group caused by other substituents in the ring. The isomeric sulfonates were prepared by indirect methods (diazonium reaction, Curtius degradation). The same investigators (304) have prepared an extensive series of isoindazole sulfonic acids and derivatives, the substituents in all cases being on the benzenoid ring. This study is of interest for the variety of preparative techniques used. The sulfonates prepared, the raw materials, and the techniques used are indicated in Table VII. (The Roman numerals used are taken from ChemicaE Abstracts.)

Table VII. lsoindazole Sulfonates Raw Material

7-XHz-5 (XL)

Method Deamination (zinc and alcohol) Deamination (diazonium) VI1 h-itration. reduction. sul7-CHaCOSH fonation, deamination Sitration, sulfite reduc7-CHsCONH-5-CI tion, acetylation, deamination NazS2, then nitric oxida5,6-Di NOe tion, reduction, deamination Sulfonation with 20% Isoindaeole oleum 25yo Oleum. then deam6-NHz ination . ~ ~ ~ . ~ Sulfuric acid: also, aque5-NOz-4-Cl ous sodium sulfite Nitric oxidation Corresp. disulfide Aqueous chlorination Corresp. disulfide Aqueous sulfite 5,6-Di SO1 Aqueous sulfite 6-NOz-7-Cl Nitric oxidation Corresp. disulfide Reduction x Sulfuric acid, then 6 5 % 5-NH2 oleum Iron and hydrochloric acid xxxv Iron and acetic acid 5-N0z-z Iron and acetic acid 6-S02-r Sulfonation with acid and 6-NHz oleum 6-NHz Sulfonation with acid and oleum Iron and acetic acid XXV 4-NOz Aqueous bisulfite Sulfuric acid, then 65% 7-NHs oleum: also, aqueous bisulfite 6-NHz-7-CHzCONH-5 Deamination (diazonium), then hydrolysis 4-NHz-7-CHKOSH-5 Deamination and hydrol-

7-NHz-4,6 (VIII)


7-NH2-4,6 (VIII)


4-N0z-7-"2-5 (XLII) 4-NO?-7-OH-5

4-h-02-5-C1-7-NHd (XLII)



Sulfonate Prepared 4 (XII) 4 (XII)

5 (11) 5 (11) 6 (111)

7 (XIII) 7 (XIII)

X I : 6-"2-4;



5-NOc-4 (X) s-h-Oz-6 (XXXV) 5-Noz-6 (chloride) 5-NOz-7 6-NO?-7 7-N0z-4 (XXV) 5-NHz-4 (XI) 5-XHz-4 (XI)

6-h-Hz-5,7 (XVII) 7-"2-4 7-"2-4 7-"2-4

(7711) (VI11 (VII)




Aqueous bisulfite (along with 4-monosulfonate) Sulfuric acid, then 65% oleum Aqueous sodium sulfide Potassium hydroxide fusion Sulfonation with acid and oleum

The direct sulfonation of phenazine has been studied with several reagents under a variety of conditions (354). This sulfonation, which goes with difficulty, could be controlled t o give a fair yield of the 2-sulfonate, as summarized in Table VIII. Several derivatives were prepared.

Table VIII. Sulfonation of Phenazine Gtrength oleum, % Oleum to organic, wt. ratio Sulfuric acid (on organic), wt. % Yield 2-monosulfonate, 70 Yield polysulfonic acids, %

40 5 5 18 Trace

40 5

10 20


40 40 45 10 10 5 5 1 0 5 25 25 24 3 3 4




33 5

50 70 10 5 5 5 41 44 10 10

Sulfonated dyestuffs, yielding red shades on wool, have been prepared (401) by reacting certain 6-arylamino-2-aryl-l ': 9'-anthrapyrimidines with sulfuric acid or oleum. Position of the sulfonic group is not stated. A phthalocyanine derivative, prepared by heating 3,3',4,4'tetracyanobenzophenone with cuprous chloride, has been sul-

Vol. 44, No. 9

fonated with 25% oleum a t 160" C. to yield a green wool dye of unspecified structure (83). 2-Aminobenzthiazole may be sulfonated in the 6-position (164) by heating the acid sulfate for 1 to 2 hours a t 210" C., preferably under reduced pressure. The product is of therapeutic value.

PETROLEUM FRACTIONS Several recent reviews discussed generally the manufacture, constitution and uses of petroleum sulfonates (73, 136, 163, 342). One of these covers the preparation of sulfonates from the kerosene fraction of Pennsylvania grade crude oil (136). The increasing petroleum sulfonate market is estimated ( 7 8 ) a t 19 million pounds per year, which corresponds to over half of all sulfonate emulsifiers and over 6% of emulsifiers of all types. Two patents describe the preparation of improved sulfonation stocks. I n one case, a German patent ( 2 7 ) cites sulfonation, with monohydrate acid a t 50" C., of an oil prepared by catalytically aromatizing paraffinic hydrocarbons. A British patent (404)obtains improved sulfonates from shale oil by chlorinating the oil before sulfonation; on treatment with concentrated sulfuric acid, -C1 is replaced by -SOaH. With regard to improvements in the sulfonation step proper, the use of a '.Votator" is noteworthy (408). This machine is especially designed for rapid heat removal from viscous materials on a continuous basis. The examplc cited involves sulfonation of "spray oil distillate" (boiling from 500" t o 800" F.) x i t h a 3minute residence time. Snother patent (144) discloses sulfonation of an aromatic lubrirant extract with the acid sludge from a previous batch. This process, previously patented in the United States ( 7 7 , 260), suggests that the acid sludge is a satisfactorily mild reagent, while direct treatment of such extracts with virgin acid may cause excessive sludging. One patent application (391)was noted relative to the indirect sulfonation of petroleum oils. This involved chlorination to about 2y0 chlorine content, followed by reaction with a metallic sulfite (or with potassium hydrosulfide followed by oxidation with nitric acid or permanganate) t o the desired sulfonate. The purification and separation of petroleum sulfonates, especially procedures involving the use of extractive methods, are of continuing interest. In one case, (408) a nearly white, freeflowing substantially odorless sulfonate of 817 ' active ingredient content is obtained from "spray oil distillate" using a two-step extraction process; the first step comprises extraction of the sulfonation mass with a n aromatic hydrocarbon, and the second, extraction of the sulfonate so obtained with petroleum naphtha. A second patent (161 ) separates oil-soluble petroleum sulfonates from water and inorganic salts in a two-step process involving mixing with a hydrocarbon naphtha, and then contacting the solution so obtained with a lower aliphatic alcohol. Cone and Comeaux (104) fractionally separate oil-soluble petroleum sulfonates by successive extractions of the acid sludge with brines of diminishing salt content. Another patent (223) separates oil-soluble sulfonates from unsulfonated oil by extracting with water under pressure above 212' F., the oil-soluble sulfonates being water-soluble under these conditions. A Canadian patent (408)describes an improved procedure for preparing a barium sulfonate concentrate involving treatment of the acid oil with excess solid barium hydroxide in the presence of a minor proportion of water. A United States patent (238), assigned t o the same group, describes a similar process for preparation of the calcium salt. hlonoethanolamine, in excess of t h a t required t o neutralize the oil-soluble sulfonic acids in the oil layer, is an efficient extractant for such amine sulfonate salts (319). Pointing out that the yield of oil-soluble sulfonates obtained by standard practice averages 5 t o 9% on the weight of the oil treated, Anderson, Samson, and Clark (9) obtain improved yields (10 to By0)by addition of water immediately after sulfonation to yield 60 to 65y0 spent sulfuric acid. Previous prac-

September 1952


tice involved addition of too much water (causing corrosion), or too little (resulting in difficult handling). A German patent (243) improves the color of petroleum sulfonates by catalytic hydrogenation in the presence of a tungsten sulfide catalyst; under the specified conditions, no splitting of the sulfonate group occurs. Chemical derivatives of petroleum sulfonates have been described in two patents. I n one case, (3.94) ricinoleic acid (or castor oil) is condensed with an oil-soluble sulfonic acid through their nonacid functions (possibly by alkylation) to yield carboxylic-sulfonic dibasic acids, the metallic salts of which are lubricant additives. Harlan describes (17 2 ) nitration of petroleum sulfonic acids and reduction of the nitrosulfonates to the corresponding amino compounds; the products are useful for de-emulsifying crude oil emulsions. Helmore (280)describes the preparation of tin and chromium petroleum sulfonates by double decomposition of the sodium sulfonate with the tin and chromium inorganic salts. They are used in compound lubricants. The reaction of petroleum acid sludge with furfural to produce ion-exchange resins was reviewed above under Heterocyclic Oxygen Compounds. An analysis of the white oil acid sludge from a heavy fraction of a Mid-Continent crude is given.


similar to those which were prepared from sprucewood by t h e same procedure. According to a recent patent (d56), a tanning agent can be prepared by heating sulfite cellulose waste lye with caustic soda below IO@’ C. It is stated that hydroxyl groups are thus substituted for some sulfonic groups in sulfolignin and t h a t polymerization also occurs, yielding a product with tanning properties. The production of tanning agents from lignin sulfonic acid was studied by I. G. Farbenindustrie at Wolfen in 1940-44 (206). A procedure was developed which gave a product free of ash, iron, and mineral acids using Wofatite ion exchange resin


This category includes the so-called “sulfonated oils” prepared by empirical methods involving direct treatment of t h e oil, acid, or ester with sulfuric acid or related sulfonating agents thereby introducing hydrophilic sulfate and/or sulfonate groups. (The sulfonation of pure saturated fatty acids is reviewed &bove under Aliphatic Compounds.) The annual market for sulfonated oil emulsifiers (animaI, vegetable, marine, tall) has been estimated at 16 million pounds ( 7 3 ) ; this represents about 5’30 of the total emulsifier market. A German review on aetergents (568) contains a brief section on LIGNIN direct sulfonation of natural fats and oils; references are given t o patents on various procedures. A review of the patent literaThe production of lignosulfonic acid has been discussed as ture on sulfonated esters has been published in Spanish (166). part of a general review on lignin (19). A review on emulsiA British publication by Schwitzer on continuous processing fiers ( 7 3 )indicates that sulfonated lignin is used, in comparatively of fats (343) reviews the chemistry of fatty oil sulfonation, small total volume, chiefly as a n ingredient of polish and insectidetails several types of apparatus proposed for continuous operacide formulations. tion, and concludes that the small scale of production has generChemical studies on the formation and composition of lignoally favored batch rather than continuous sulfonation of fatty sulfonic acid have continued. Erdtman (fdo), in a study of oils. Sulfonated lecithin has recently been advertised as a new the sulfonation with aqueous sodium sulfite (“sulfitecookingacid”) product (8). The British standards for cod oil suitable for of low-sulfonated ethoxylated lignosulfonic acids a t varying s u l f o n a t i o n h a v e redegrees of acidity, cently been revised (68). found that a t low p H Two grades of erucic the ethoxyl groups acid, isolated from rapeare replaced more or seed oil, were sulfated less completely by with sulfuric acid a t a sulfonate groups, preferred ratio of 1 part while a t higher p H t o 2, the weight ratios few ethoxyl groups being the critical variare removed. Similar able (166). The sulfates studies by Lindgren were hydrolyzed to crude (244, 245) involved monohydroxy b e h e n i c reaction a t varying acids. pH of sulfite cooking Hirschmann made a acid with veratryl study of the sulfonation alcohol and other refor varying lengths of lated substituted time of linseed oil at four b e n z y l alcoholstemperatures (4O, 15”, these substances being taken as lignin 25”, and 35’ C.), using models; at 135’ C. 98% sulfuric acid a t a weight ratio of 100 parts these compounds formed derivatives of oil to 20 parts acid (190). 3,4-dihydroxyphenylThis author concluded m e thanesulfonic t h a t the lowest temperaacid, the rate varying ture gave the best results with pH. ( w h i t e , s t a b l e emulAnother group sions), and that the raw (13d)-using as lignin and refined grades of oil models, coniferin and were equivalent. a dehydrogenation A French patent (341) polymer of coniferyl describes sulfonation of alco h o 1-0 b t a i n e d the ethyl esters of satuwith sulfite cooking COURTESY MARATHON CORP. rated or slightly unsatua c i d , sulfonates rated fatty acids (cocoEvaporator Used for Processing Lignosulfonates



nut and palm) with 9370 sulfuric acid below 10" C. It appears questionable whether saturated esters would be sulfonated under these mild conditions. Sperm oil or wool fat, alcoholized with a lower aliphatic alcohol to yield a mixture of esters and higher alcohols, can be sulfonated to yield surface-active products, according to a n'orwegian patent (280). Oil extracted from olive residues has been sulfonated by Spanish investigators (188) with 93pc sulfuric acid in an effort to prepare substitutes for sulfonated coconut or palm oil. The final product analyzed 23,6y0 fatty acids, 3,5% bound sulfate, 2.8y0free sulfate and 54.59" n-atel Sericano (345) discusses the changes in the properties of fatty acids produced by sulfonation and concludes that it is not possible to identify the original oil by eyamining the sulfonated acids, especially by color reactions. Three Japanese patents described procedures for producing odorless detergenta from fish or vegetable oils (387, 588). The oils are pretreated (by heating, air blowing, or distillation) before sulfonation. -1Japanese patent (384)describes the preparation of the copper or mercury salts of sulfonated acids of esters for use as agricultural sprays. Another Japanese patent (218) discloses the preparation and use of a sinall quantity of sulfonated animal or vegetable oils for purifying in waste mineral lubricating oil.


Sulfonation of olefins (to pioduce sulfonic acids) is reviewed above under Aliphatic Sulfonates. The sulfation of ethylene-intermediate to ethanol production-has increased in use a t the expense of nonsynthetic methods (418). In the process for absorbing ethylene in 97.7% sulfuric acid to produce the sulfates, an improved procedure (175), giving more efficient absorption, comprises using a temperature gradient varying from about 90" C. a t the bottom of the tower to about 70" C . at the top. Recovery of the spent acid from ethJ lene sulfation is facilitated by a preliminary extraction with hydiocarbon oil to remove carbon (174). Isopropyl sulfate solutions of the type obtained in industrial piactice by absorbing propylene in sulfuric acid were simulated by mixing isopropanol, water, and sulfuric acid in the course of studying the hydrolysis of the sulfate to isopropanol (342). Howlett and Wood (196, 197) have disclosed an improved propylene sulfation process, N hich is noncorrosive to mild steel, involving absorption in 65 to 80% acid between 55" and 70" C. The sulfation of normal butenes a t 25" C. with 83% sulfuric acid, and of secondary amylenes with 88% acid at the same temperature, is cited in a patent ( 1 7 ) on an improved procedure for preparing a purified sulfation stock involving selective polymerization of tertiary olefins and dienes over a solid catalyst. The sulfates are hydrolyzed to the alcohols. Selective sulfation of isobutylene to effect its removal from mixtures with other olefins has been disclosed in a Canadian patent (8M).The hydrocarbon mixture is first extracted at 90" to 110' F. with sulfuric acid containing isobutylene, then with fresh 60 to 7070 acid a t 55' to 75" F. The second stage acid is then used for the first stage. Sulfation of a hexene-heptene fraction is described (289) in a patent on an improved step" ise process for hydrolyzing the sulfates to the alcohols. The process for producing "Teepol" (a higher alkyl sulfate detergent made by sulfating cracked paraffin wax olefins) has been generally described as operated in a new plant in France (65, 69, 79). Production of higher alkyl sulfate detergents has been briefly reviewed (368)with emphasis on Teepol. A study of the effect of reaction time, sulfuric acid concentration, and ratio of acid t o olefins was made with 1-hewadecene

Vol. 44, No. 9

and 1-dodecene ( g a g ) relative to formation of monoalkyl sulfate, dialkyl sulfate, and polymer. At 20" C. with a 5 minute reaction time using acid of greater than 90% strength, optimum dialkyl sulfate is obtained a t an acid t o olefin mole ratio of 1:2, while opt'imum monoalkyl sulfate is obtained a t a ratio of 3 : 4. Patents have appeared on improved processes for sulfating higher olefine t,o yield detergents. An annular chamber rezctor (285, 288) efficiently removes the heat' of renction, thereby giving improved results in the sulfation of cracked paraffin wax olefins. Rubin (313) sulfates CIO-,Solefins (from carbon monoxide and hydrogen) a,t below 0" C. in a two-stage process, the first stage employing excess olefin and the second stage excess acid over the remaining unreacted olefin. Shale oil olefins boiling from 150" to 350" C. are sulfated below 20" C. (196). Another patent (386) describes sulfation of shale oil olefins boiling from 270" t.o 360" C. with 96 to 100To acid (12 to 13Ye basis weight of olefins) at 5" to 10" C., the sulfates being finally rendered oil-free by alcohol extraction. In another case ( I O ) , shale oil ol.'fins are solvent ext>racted-e.g., with phenol and furfural-before sulfation a t 10' C. with 9Sye acid. A German patent application dated 1944 from I. G. Farbenindustrie, Ludwigshafen (200) describes removal of oily paraffinic impurities from a sodium alkyl sulfate (madc from olefins prepared from carbon monoxide and hydrogen) by drying under reduced pressure on a drum drier. A Japanese patent (26'3) prepares a detergent by "sulfonation" of pine oil. it'-Alkylmyristamide was sulfated in good yield with sulfuric acid containing 2 t o 2270 of free sulfur trioxide (321). The sodium salt shows good surface activity in neutral, acidic, and salt solution, but not in alkaline solution. ALIPHATIC A L C O H O L S

Several reviews of general scope have appeared on the manufacture, properties, uses, and analysis of primary fatty alcohol sulfates, in particular lauryl sulfate (78, 826, 307, 368, 372). One review (368) gives a diagram of sulfates prepared from secondary alcohols. Lindner (246) has described sulfation of alkylphenolpolyglycol ethers.

Table IX. Sulfation of Alcohols Solvent


Sulfating Agent Pyridine-SO3

Dodecyl Coconut alcohols



Octadecyl. oleyl




... ~ . .

Remarks S o attack of double bond Temperatbre 30' C. Temperature 2.5' C. Product performance comparable to "Aerosol OT"

Cia residue from OXO ClSOsH reaction on hexene-1


OXO alcohols from Cv-s olefins Polyesters of adipic acid with glycols 2-(2,4-Diohloro he noxy) ethanoy CI-s secondary alcohols from ketone reduction F a t t y acid monoethanolamides (from capric, lauric, myriptic, palmitic, stearic, oleic) Lauric isopropanolamide





Einulsifying agents





Product used as herbicide New sulfating agent



Lauric derivative best foaming and wetting properties




Stability studied in alkaline medium Yield quantitative Amine salts of monosulfate prepared, Dispersing agents


B(HS0a)s added


Monoethanolamine Conc. acid Polyethylene glycol SOs (molecular weight 600) Ci-s fluorinated CISOaH, 6 5 % straight chain aloooleum 601s 60% oleum Sperm oil alcohol





September 1952


Examples noted of various alcohol sulfations run under the usual conditions are listed below in Table IX. A careful and detailed study has been made (381) of thc rates and degrees of esterification of lower aliphatic alcohols (methyl; ethyl; normal and isopropyl; normal, secondary, and isobutyl) With sulfuric acid. Ratios used varied from 1.8 moles acid: 0.2 mole alcohol to 0.1 mole acid: 1.9 moles alcohol, most of the measurements being made at 0' C. The effect of added water was also considered. It is concluded that the reaction is accelerated by sulfuric acid beyond what would be expected from the catalytic influence of hydlogen ions alone. Den0 and Newnian (107) have also studied the mechanism and rate of primary and secondary alcohol sulfations with sulfuric acid, attempted preparation of a tertiary alkyl sulfate having been unsuccessful. d-2-Butanol was also sulfated with pyridine-sulfur trioxide. Primary alcohols sulfated tenfold faster than secondary; the reaction is postulated as proceeding without alkyl-oxygen cleavage in a manner similar to carboxylic acid esterification. Henry (187) has disclosed an improved process for sulfating fatty hydroxyamides with concentrated sulfuric acid or chlorosulfonic acid. The amide is added as finely divided solid, and emphasis is placed upon rapidity of reaction (less than 10 minutes) rather than upon maintenance of a constant low temperature by external cooling. A patent review has been published in Spanish on sulfonated amides (166). Clark and Malkemus (94), continuing their study of the sulfation of various alcoholic materials with sulfamic acid (for previous references, see references 59, 60 in I @ ) , have patented the shbilization of the sulfates so prepared with buflers such as dipotassium tartrate. CYCLIC C O M P O U N D S ' A recent review on detergents (568) cites several references on sulfation of cyclic compounds (steroids, hydrogenated lanolin, naphthenic alcohols, and substituted cyclohexanols). Sulfation of the steroid equilin with chlorosulfonic acid in a dry organic solvent-e. g., chloroform or pyridine-is described in two Swedish patents (21, 22). The sulfate obtained has enhanced hormone action. A little-used oxidative procedure for direct introduction of the sulfate group into monohydric phenols with potassium persulfate has been successfully applied by Smith (552) to preparation of potassium monosulfates of 4-nitrocatechol and 2-nitrohydroquinone. The method is a convenient one; yields are not given. Improved methods for preparing the sulfates of leuco vat dyes continue to appear in quantity, Imperial Chemical Industries being particularly active. This firm has shown continued interest in the use of the sulfur trioxide adducts with the amides of disubstituted organic amines (especially dimethylforniamide) as sulfating agents for this purpose. One patent ( 9 5 ) describes preparation of these adducts, with or without use of organic solvents. The use of these adducts preparing leuco sulfates of various types is covered in several patents (96,98-102,

608,210,212,216,407). Modifications (97, 211) involve sulfation in the presence of an amide and a base (organic or inorganic) with a dissociation constant not less than l o + a t 25" C., or a base which coordinates with copper (320). Imperial Chemical Industries has obtained patents involving the use of methyl chlorosulfonate (209, 613, 216) or a metallic chlorosulfonate (207)for leuco dye sulfation. Ogilvie and Genta (292) facilitate production of leuco sulfates by precipitating the vat dye in finely divided form from a solution in sulfuric acid by addition t o excess organic tertiary base. Hardy (171) uses chlorosulfonic acid and pyridine to prepare the leuco sulfate of a benzanthrone-anthraquinone dye of unknown composition.



Sulfation of a variety of polymeric polyhydroxy compounds continues of interest for producing blood anticoagulants and "synthetic water-soluble gums." (The sulfoethylation of cellulose is reviewed above under Aliphatic Condensation Reactions, Sulfoalkylation. ) Sodium cellulose sulfate, as produced by the Tennessee Eastman Co. recently in experimental quantities (reviewed previously I@?), has been discussed (386) from the standpoint of properties and possible uses. It is stated that the sulfation process used produces substantially no degradation of the cellulose. Malm and Crane (266), of the same organization, have patented a process for cellulose sulfation involving the use of 9570 sulfuric acid in the presence of a lower aliphatic alcohol (as propyl, butyl, amyl) and ammonium sulfate, for 45 t o 90 minutes a t -4" t o 15' C. Two other patents were noted on the preparation of fibrous cellulose sulfate (129, 235) using alcohols (normal butyl is cited in examples in both patents) with concentrated sulfuric acid a t 15' to 20' C. A Japanese patent (16) combines sulfation and esterification of rellulose by use of an acid anhydride (as acetic or propionic) with sulfuric or chlorosulfonic acid. The product is then treated with alkali to selectively hydrolyze the organic acid groups, leaving pure cellulose sulfate. Wagner and coworkers have prepared a water-dispersible cellulose sulfate, which however is stated not to form salts or to ionize (4OO), by reacting alkali cellulose with sulfuryl chloride in benzene suspension. The same workers (399) prepared ionizable cellulose sulfate using pyridine and chlorosulfonic acid, and starch sulfate with sulfuric acid and pyridine ($87). These products are used as drilling mud additives, the starch sulfate being employed as the lithium salt. Dextrin and other materials were sulfated by Kazal and coworkers ($24) using pyridine and chlorosulfonic acid t o yield experimental blood anticoagulants; the dextrin derivative was one-fifth as active as heparin. Dextrin, used as a blood plasma substitute, and its hydrolysis products of varying molecular weight, were sulfated to varying degrees with pyridine and chlorosulfo~iic acid (318), and the various sulfates were tested for anticoagulant activity and toxicity. Berger and Lee (46 j reviewed briefly the status of polysulfate anticoagulants and report preparation of sulfated polyuronic acids (polygalacturonic acid methyl ester methyl glucosides), using chlorosulfonic acid and pyridine, and compare activities and toxicities with similar products. Degradation was found to occur during sulfation. Simultaneous desulfation and acetylation of heparin, chondroitinsulfuric and mucoitinsulfuric acids have been studied (409) using absolute sulfuric acid and acetic anhydride. The properties and chemical structures of the bisulfites of the "most important" sugars have been studied in some detail (256).

SULFAMATION Three aliphatic sulfamic acids (ethyl, normal, and isopropyl) were prepared by reacting the corresponding hydroxylamine with sulfur dioxide (388) in chloroform solution. The correspon ding N-hydroxysulfamic acids were prepared by reacting the hydroxylamines with solid sulfur trioxide in chloroform suspension. n-Butylsulfamic acid was prepared by reacting the amine with dioxane-sulfur trioxide in the cold or with sulfamic acid at 185' t o 190' C. (853); the n-butylammonium salt was first isolated in both cases. Potassium sulfamate was reacted with aqueous formaldehyde a t 0" t o 20" C. to yield 50q7b of tripotassium 1,3,5-triazacyclohex-



ane-1,3,5-trisulfonate (47). This product was nitrated to yield *‘RDX.” Glucosamine was sulfonated on nitrogen (266) with liquid sulfur trioxide dissolved in liquid sulfur dioxide in a 24-hour reaction period a t -20” C. The product vas isolated as the aninioniuni salt. Substituted phenylsulfamic acids were prepared by treating the bases [2-(4-amino-phenyl)-6-methyl-benzthiazole j and its N-methyl derivative with chlorosulfonic acid and pyridine a t 40’ to 95’ C. (1). A similar procedure was used to introduce two nitrogen sulfonate groups into a diaminostilbene derivative (2). The products are used as optical bleaches. Borodkin (66) sulfonated carbazole on nitrogen with chlorosulfonic acid in the presence of dimethylaniline using chlorobenzene as solvent a t 10” to 15’ C. for a 2-hour reaction period. Dichloroethane was also used as a solvent. This reaction was employed by the same author (57) as the basis for separating carbazole from crude anthracene. (Other conditions yielded carbon sulfonate, as reviewed under Heterocyclic Sitrogen Compounds. ) In the course of a fundamental study to determine the probablr chemical structure of the aromatic diazosulfonates, Freeinan and Le Fevre (130)prepared the stable and unstable isomers in ten cases (five new) by the usual procedure. These authors ran a series of physical and chemical tests, concluding in favor of the Hantzsch cis-trans sulfonate structure. Sulfamation of aminonitroheterocyclic compounds (2-amino5-nitro derivatives of pyridine, thiazole, and pyrimidine) vim3 conducted with triethylamine-sulfur t r i o d e in ethylene dichloride as solvent (299).


A petroleum oil was sulfonated with the “\?otator” ( 4 0 Q a machine specially designed for rapid heat removal from viscous materials on a continuous basis. Although this appears to be its first recorded use for this purpose, this apparatus shou2d be well adapted to a variety of sulfonations. The specific esample cited refers t o sulfonation of a “spray oil distillate” (boilingpoint 500” to 800” F.) with a 3-minute residence time. A series of specially designed annular reactors gives rapid, intimate mixing, short contact time, and good temperatuir control on a continuous basis in the sulfation of olefins (285, ass), Diagrams of the apparatus are given in the patent. Several proposed methods for continuously sulfonating fatty oils are reviewed and discussed in a recent book on continuous processing of fats (343). .4 spray apparatus for adiabatic sulionatlon of aiomatic hydrocarbons or olefins with sulfur trioxide uiing sulfur d i o d e as the solvent for both reactants ( 1 8 6 ) has been propoqed l)y Fineke -1diagram of the apparatus is given in the patent. The continuous sulfation of lauryl alcohol, involving simultaneous feeding of the alcohol and concentrated acid t o a revolving disk as operated in Germany by the Henkel Works on a 400-tonmonthly alcohol basis, has been detailed, x i t h a diagram, in a recent review in German (368). This process has also been reviewed in English (148). An improvement, comprising uae of a disk with six concentric walls, has been patented 111 Smedeii (186). The basic process (182,185)has been patented in Sweden 2nd Belgium. A French patent (370) describes the use of a Icrause or X r o spray drier for direct neutralization to a dry poxder of sulfonated coconut oil using ammonia gas in admixture with air. IDENTIFICATION AND ANALYSIS Experimental procedures for identifying aromatic sulfonic acids as sulfonamides (via the chloride), S-benzyl-iso-thiourea, salts, and sulfonacetamides (via the sulfonarnicle) are given ia

Vol. 44. No. 9

a recent organic chemistry text (397), and the melting pointci of a number of such derivatives are tabulated. Analytical schemes for detergent formulations are of continued interest. Gilby and Hodgson (246)have developed a modified Linsennieyer procedure for determination of the active ingredient in a mixture of unknown composition; various types of sulfonatey, sulfates, and sulfonated oils are included, Balthazar ( 3 4 ) and Simmons (349) have also reported systematic analytiral procedures for commercial detergents. Reutenauer (327), continuing hi^ comprehensive study ,of detergent analysis as previously I eviewed ( I @ ) , reports procedures for determining phosphates and carboxyniethylcellulose. Rf arconi (857) has also ieported a modification of her previously published systematic proredure for deteigent analysis. Eckhardt ( 1 1 5 ) has reported work a t the Rlereeburg Korks of I. G. Farbenindustrie in 1941 on sulfate determination in detergents. Miller et al. (2’70) have found n-butanol to be preferred for extraction of the active ingredient from its mixtures. Compton and Liggett (IOJ), reviewing procedures for moistui e determination, prefer the Karl Fisrher method. A study has been published in German ( 2 4 ) on assay of licrsolate (sodium sulfonate from sulfochlorination of paraffinic hydrocarbons) in detergent mixtures. Quantitative estimation of sulfonyl chlorides in a recent method (113) is based on their reaction with water and pyridine: the method may be used in the presence of other saponifiable substances. Several commercial ammonium ichthyol sulfonates have been compared bv analysis (316).

LITERATURE CITED (1) -4ckerriiarin. F.(to Ciba. Ltd.). U. R. Patent 2,660,321 (April2.2, 1951). (2) Ibid., 2,587,796 (Sept. 11, 1951). (3) ddams, C. E., a i d Proell, IT. A. (to Standard Oil Co. of Indiana), ‘c. 9.Patent 2,573,874 (Xov. 6, 1951). (4) Adanis, D. A. I\-., and Baird, IT.,C . 5 . Dept. Commerce, DTS Rept., PB 80401 (1946) [BIOS Final Rept. 11541. (6) Aktieselskabet, Alfred Benzon, and Anderaen, F.. Brit. I’atent 845,429 ( S o v . 1, 1950). (6) Amagasa. VI.,Hida, M., and Kanioi, I-.,J . Cl~e7n.SOC. .Ircpmz, I?ad. Chem. Sect., 52, 114-6 (1949). (7 j American Cyanamid Co., “‘Tanak’Synthetic Tanning Agent,sKaphthalene Sgntans,” 15 p p , , 1950. (8) American Lecithin Co., Inc., Oil, Pnilzt R. I l m y Repti.., 160, Xo. 26, 85 (1951). (9) Anderson, €1. X,, Samson, 0 and Clark, A. JT. (to Shell Development Co.). U. 9. Patent 2,578,857 (Dec. 18, 1951). (10) Anglo-Iranian Oil Co.. Ltd., Fr. Patent 989,177 (Dee. 15, 1950). (11) Angyal. S.J., and Jeukin, S.R., Azistrcilian .T. Sci., 3A, 4 6 b 5 (1960). (12) Anon., .Ind. Chemist, 27, 355-8 (1951). (13) Anon., M o n d e industrial, 76, S o . 450, 9-21 (1950j. (14) .ban., SeiSen-Oele-Fette-m’achse, 76, 574-8 (1950). (15) Anon.. S o a p Sanit. Chemicals, 27, S o . 11, 37 ( S o v . 1931 1. (18) Araki, T. (to Tokyo Industrial Research Institnte), Japan. Patent 178,243 (May 18, 1948). (17) .Archibald. F. 11..and Xlottern, H. 0. (to Standard Oil lhvelopment Co.), U. S. Patent 2,543,820 (3iarcli 0 , 1951). (18) Ardaachcr, B. I., J . Gen. Chem. ( U . S . S . R . ) , 20,462-5 ( 1 9 X ) . (19) -hies, R. S., and Pollak, A , , Papeterie. 72, 121-31 (19.50). (20) Ibid., pp. 188-93. (21) Aperst, McKenna Br Harrison Ltd. ( G , -1.Grant and J\.. 1,. Glen, inventors), Swed. Patent 127,427 ( F r h . 21, 1950). (22) I b i d . , 128,079 (May 2, 1950). (33) Bachman, G. B., and Polansky, S,,.T. O r g . CiLern., 16, 1690-6 (1951). (24) Backer, H. J., Rec. trau. chim., 70, 254-9 (1951). (25) Backer, H. J., and Bos, H., Ibid., pp. 93-100. (26) Badische Anilin- & Soda-Fabrik (I. G. Farhenilidilstric A.-O. “In Auslosung”) (Richard hlles, inventor), Ger. Patent 803,848 (April 12, 1951). (27) I b i d . , (Gerhard Free, inrentor), Ger. Patent S04,571 (Apr. 28, 1951). ( 2 8 ) Ibid., (Friedrich H6lscher. inwiltor), Ger. Patent 801,991 (Feb. I , 1951).

September 1952


(29) Ibid., (Friedrich Holscher, inventor), Ger. Patent 803,535 (April 12, 1951). (30) Ibid., (Hans Krzikalla and Arnold Tartter, inventors), Ger. Patent 801,992 (Feb. 1, 1951). (31) Ibid., (Walter Simon and George Grassl, inventors), Ger. Patent 500,667 (Nov. 27, 1950). (32) Baer, M. (to Monsanto Chemical Co.), U. S. Patent 2,550,271 (Dec. 25, 1951). (33) Baker, W‘.,Coates, G. E., and Glockling, F., J . Chem SOC., 1951, 1376-7. (34) Balthazar, J., Ing. chim.,32, No. 182, 169-96. (35) Ibid., 33, NO. 183, 3-16 (1951). (36) Bamberber, C., and Orelup, J . W.(to Patent Chemicals Inc.) U. S.Patent 2,575,155 (Nov. 13, 1951). (37) Barber, H. J. (to May & Baker Ltd.), Brit. Patent 647,214 iDec. 6 . 1950). (35) Barker, C: H., and Pound, D. W. (to Pest Control Ltd.), Ibid., 650,906 (March 7, 1951). (39) Baumhardt, G. C., Engenharia e quim. (Rio de Janeiro), 3, 5-9 (1951). (40) Beck, J., Hungarian Patent 139,261 (Feb. 2, 1949). 141) Beck. L. W.. Gilbert. A. R.. and Wolfe. J. K.. U. S. Patent ’ 2,559,585 (July 10, 1951). (42) Berger, L., and Lee, J., X I I Intern. Congr. Pure Applied Chem., Abstracts of Papers 1951, 343-4. (43) Berry, K. L., and Bittles, J. A., Jr. (to E. I. du Pont de Kernours & Co.), U. S.Patent 2,559,751 (July 10, 1951). (14) Bert, L., Procofieff, M., and Blinoff, V. (to SociBtB d’ innovations chimiques dite: Simmova ou Sadic),Ibid., 2,460,965 (Feb. 8, 1949). (45) Berty, J., Oltay, E., and Schnitta, A., Magpar Chem. L a p j a , 4, 617-28 (1949). (46) Bhatnagar, M. S., and Singh, B. P., J . Sei. I n d . Research ( I n d i a ) , 10B, 25-6 (1951). (17) Binnie, W. P., Cohen, H. L., and Wright, G. F., J . Am. Chem. SOC.,72, 4457-9 (1950). (15) Bladwin, D. E., Overberger, C. G., and Gregor, H. P., U. 9. Dept. Commerce, OTS Rept., PB 105,014 (1949). (49) Blangey, L., Fierz-David, H. E., Ulrich, J. C., and Bretscher, H., Helv. Chim. Acta, 34, 501-21 (1951). (50) Bloch, H. 6, and Mammen, H. E. (to Universal Oil Products Co.), U. S.Patent 2,573,675 (Nov. 6, 1951). (51) Bochvar, D. A., Chernyshev, A. S., and Shemyakin, M. M., J. Gen. Chem. (U.S.S.R.), 20, 211-20 (1950). (52) Bogert, M. T., and Ritter, J. J., J . Am. Chem. Soc., 47, 526-35 (1925). (53) Bolgar, L., Brit. Patent 644,451 (Oct. 11, 1950). (54) Ibid., 649,516 (Jan. 31, 1951). (55) Bordwell, F. G., McKellin, W. H., and Babcock, D., J . Am. Chem. SOC.,73, 5566-8 (1951). (56) Borodkin, W. F., J . Applied Chem. (U.S.S.R.), 23, 759-62 (1950). (57) Ibid., 23, 763-6 (1950). (55) Bradley. H. W. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,570,094 (Oct. 2, 1951). (59) Braithwaite, D. G. (to National Aluminate Corp.), Ibid., 2,535,553 (Jan. 16, 1951). (60) Brimelow, H. C., Jones, R. L., and Rietcalfe, T. P., J . Chem. SOC.,1951, 1208-12. (61) British Celanese Ltd., Brit. Patent 639,367 (June 28, 1950). (62) Brit. Standards, 868, 15 pp. (1950). (63) Caldwell, W.T., and Sayin, A. N., J . Am. Chem. Soc., 73, 51257 (1951). (64) Cannon, M. R., and Mosher, H. S., U. S. Dept. Commeice, OTS Rept., PB 103,625 (1944). !65) Chem. A g e (London), 65, 684 (1951). (66) Chem. Eng. News, 29, 2020 (1951). 167) Ibid., pp. 3473-4 (1951). (68) Ibid., p. 4453 (1951). (69) Ibid., p. 5462 (1951). (70) Ibid., p. 5470 (1951). (71) Chem. Inds., 62, 907 (1948). (72) Chem. Ind8. Week, 68, No. 11, 17-19 (1951). (73) Ibid., NO. 19, 19-30 (1951). (74) Chem. Week, 68, No. 22, 43-4 (1951). (75) Ibid., 69, No. 7, 34 (1951). (76) Ibid., 69, No. 16, 35 (1951). (77) Chen, P. S.,“500 Syntan Patent Abstracts, 1911-1950,” South Lancaster, Mass., Chemical Elements, 1950. (78) Chimie & industrie, 66, 725 (1951). (79) Ibid., p. 729 (1951). (50) Chinoin Gyogyszer es Vegyesaeti Termekelr Gyara R. T. (Kereszty and Wolf), Swed. Patent 125,903 (July 1, 1950). (81) Chu, J. C., Stout, L. E., and Busche, R . M., Chem.”Eng. Progress, 47, 29-38 (1951).


(82) Ciba A.-G., Fr. Patent 965,218 (Sept. 6, 1950). (83) Ciba A.-G. (F. Ackermann, inventor), Swed. Patent 127,805 (Apr. 4, 1950). (84) Ciba A.-G., Swiss Patents 265,707 (March 16, 1950). (85) Ibid., 265,708. (86) Ibid., 265,709. (87) Ibid., 265,710. (88) Ibid., 265,712. (89) Ibid., 265,713. (90) Ibid., 265,714. (91) Ibid., 270,447-9 (Nov. 16, 1950). (92) Ibid., 270,831 (Jan. 3, 1951). (93) Ciba Ltd., Brit. Patent 648,364 (Jan. 3, 1951). (94) Clark, J. R., and Malkemus, J. D., (to Colgate-Palmolive-Peet Co.), U. S. Patent 2,513,549 (July 5, 1950). (95) Coffey, S.,Driver, G. W., Fairweather, D. A. W., Irving, F., and Imperial Chemical Industries, Ltd., Brit. Patent 642,206 (Aug. 30, 1950). (96) Coffey, S., Fairweather, D. A. W., Hathway, D. E., and Imperial Chemical Industries, Ltd., Brit. Patent 633,486 (Dec. 19, 1949). (97) Ibid., 633,493 (Dec. 19, 1949). (98) Coffey, S.,Fairweather, D. A. W., Hathway, D. E., Slinger. F. H., and Imperial Chemical Industries, Ltd., Brit. Patent 633,483 (Dec. 19, 1949). (99) Coffey, S.,Fairweather, D. A. W., Hathway. D. E., and Slinger, F. H. (to Imperial Chemical Industries, Ltd.), U. 8. Patent 2,563,819 (Aug. 14, 1951). (100) Coffey, S., Fairweather. D. A. W., and Imperial Chemical Industries, Ltd., Brit, Patent 633,480 (Dec. 19, 1949). (101) Coffey, S., Fairweather, D. A. W., Slinger, F. H., and Imperial Chemical Industries, Ltd., Brit. Patent 633,484 (Dec. 19, 1949). (102) Ibid.. 633.485 (Dec. 19. 1949). (103j Compton; J. W., and Liggett; L. M., J . Am. Oil Chemists’ SOC., 28, 81-4 (1951). (104) Cone, J. H., and Comeaux, R. V. (to Standard Oil Development Co.), U. S.Patent 2,556,256 (June 12, 1951). (105) Dalton, P. D. (to Sun Chemical Cow.). U. S.Patents 2.576.501-2 (Nov. 27. 1951). (106) Dawson, .W. 0. (to American Cyanamid Co.), U. S. 2,550,639 (April 24, 1951). S.,J . Am. Chem. Soc., 72,3852(107) Deno, N. C., and Newman, 6 (1950). (108) Desnuelle, P., and Micaelli, 0.. Bull. SOC. chim. France. 17, 671-3 (1950). (109) Deutsche Hydrierwerke A.-G., U. S. Dept. Commerce, OTS Rept., PB 83253, Frames 701-3 (1940). (110) Donovan, T. S. (to Eastman Kodak Co.), U. S.Patent 2,578,292 (Dec. 11, 1951). (111) Doumani, T. F., and Cueno, J. F., U. S. Patent 2,550,141 (April 24, 1951). ‘(112) Dow Chemical Co., Brit. Patent 659,775 (Oct. 24, 1951). (113) Drahowzal, F., and Klamann, D., Monatsh., 82, 470-2 (1951). (114) Du Pont de Nemours, E. I., & Co., “Pyrrolidine,” 5 pp. (1950) [New Products Bulletin KO,251. (115) Eckhardt, U. 8. Dept. Commerce, OTS Rept., PB 103306 (1941). (116) EkstrBm, G., Svensk Kem. Tid., 62,113-20 (1950). (117) Elwell, W. E. (to California Research Corp.), U. S. Patent 2,541,959 (Feb. 13, 1951). (115) Erdtman, H. G. H. (to Karnbolaget Aktiebolag), Swed. Patent 130,523 (Jan. 16, 1951). (119) Erdtman, H., and Pettersson, T., Acta Chem. Scand., 3, 904-5 (1949). (120) Ibid., 4, 971-7 (1950). (121) Ettel, V., and Hebky, J., Collection Czechoslov. Chem. Communs., 15,65-72 (1950). (122) Evans, R. F., and Smith, J. C., J . Inst. Petroleum, 37, 50-90 (1951). (123) Faust, C. L., Bearse, A. E., and Liger, A. W. (to The Meaker Co.), U. S.Patent 2,543,545 (Fob. 27, 1951). (124) Fincke, J. X. (to Monsanto Chemical Go.), Ibid., 2,547,9013 (Apr. 3, 1951). (125) Ibid., 2,572,605 (Oct. 23, 1951). (126) Finzi, C., and Leandri, G., Ann. chim. ( R o m e ) , 40, 334-44 (1950). (127) Flett, L. H. (to Allied Chemical & Dye Corp.), Can. Patent 471,278 (Feb. 6, 1951). (128) France, H., and Haddock, N. H. (to Imperial Chemical Industries Ltd.), Brit. Patent 652,943 (May 2, 1951). (129) Frank, G., U. S.Patent 2,559,914 (July 10, 1951). (130) Freeman, H. C., and Le Fevre, R. J. W., J. Chem. SOC.,1951, 4 15-25. (131) Frejka, J., and Zenisek, A., Chem. Listy, 44, 3-10 (1950).

INDUSTRIAL AND ENGINEERING CHEMISTRY Freudenberg, K., and Heimberger, IT., Chem. Bel.., 83, 519-30 (1950).

Friedman, B. S., and Hervert, G. L. (to Universal Oil Products Co.), Can. Patent 471,087 (Jan. 23, 1951). Fukuzmi, K., and Oaaki, S.,J . Chem. SOC.J a p a n , I n d . Chem. Sect., 52, 154-5 (1949).

Galat, A. (to Pyridium Corp.), Can. Patent 472,364 (March 20, 1951).

Garin, T. J., Prodztcem Illonthly, 15, 27-31 (Sept. 1951). Geigy, J. R., A.-G., Austrian Patent 165,059 (Jan. 10, 1950). General Aniline 8: Film Corp., Brit. Patent 654,654 (June 27, 1951).

General Aniline 8r Film Corp., (P. iianiasky and G. E. Sprenger, inventors), Brit. Patent 651,840 (Apr. 11, 1951). General Aniline 8r Film Corp., (\T. D. Peterson, inventor), Brit. Patent 663,552 (Dee. 27, 1951). H. von Glahn and L. N . General Aniline 8: Film Corp., (W, Stanley, inventors), Brit. Patent 650,046 (Feb. 14, 1951). Gilbert, E. E., and Jones, E. P., IND. ESG. CHEY.,43, 20222052 (1951).

Gilbert, E. E., and Otto, J. A. (to -4llied Cheni. 6r Dye Corp.) U. S. Patent 2,552,421 (May 8, 1951). Gilbert, G. R. (to Standard Oil Development C o . ) , Can. Patent 473,485 (May 8, 1951). Gilby, J. a.,and Hodgson, H. \Y.,Mfg. Chemist, 21, 371-6 (1950).

Gluesenkamp, E. TV, (to RIonsanto Chemical Co.), U . S. Patent 2,498,618 (Feb. 21, 1950). Gluesenkanip, E. TY., and Kosmin, RI. (to RIonsanto Chemical Co.), Ihid., 2,498,619 (Feb. 21, 1950). Gold, R f . H., and Druker, L. J., J . Orp. Chem., 16, 1530-2 (1951).

Gold, 11.H., Druker, L. J., Yotter, R., Thor, C. J. B., and Lang, G., Ihid., 16, 1495--9 (1951). Gold, 11.H., and Levine, H. H., Ibid., pp. 1507-9. Gold, 1!I,H.. and Levine, H. H. (to S'isking Corp.), C . S.Patent 2,526,218 (Oct. 17, 1950). Gold, RI. H., Lerinc, H. H., and Polen, P.B., J . Ova. Chem., 16, 1503--6 (1951).

Gold, Xi. H., Skehelsliy, >I., and Lang, G., Ibid., 16, 1500-2 (1951).

Goldschmidt, Th., 8.-G. (Albert Sander, inventor), Cer. Patent 809,198 (July 23, 1951). Grace, K.H., and Zuckerman, A,, Can. J . Technol., 29, 276--89 (1951).

Grassie, S'. R. (to Hercules Polder C o . ) , U. S. Patent 2,580,351 (Dec. 25, 1951). Ihid.; 2,580,352 (Dee. 25, 1951). Green, A. D., and Carrier, E. \T-. (to Standard Oil Dcvelopment Go.), U. 8. 2,540,519 (Feh. 6, 1951). Gregg, D. C., and Blood. C. A,, Jr.. J . Ovg. C l ~ c n ~16, . , 1255-8 (1951).

Gregor, H. P., Bregnien, J. I., Gutoff, F., Broadley. 1%.D., Baldwin, D. E., and Overherger, C. G., J . Colloid Cliem.: 6 , 20-32 (1951).

Griesinger, TT. I