un
II/EGIUnit Processes Review
Sulfonation and Sulfation by Everett E. Gilbert and E. Paul Jones, Allied Chemical Corp., General Chemical Division, Morristown, N . J .
b
SO3 dissolved in liquid SO2 is best for sulfonating long-chain alkylated benzenes and naphthalenes
b
Lignite coal can be sulfonated to effective ion exchange resins
b
Complete H 2 S 0 4 consumption in sulfonating hydrocarbons is effected at room temperature by adding SOC12
FUNDAMENTAL
d
* I
ATTACKS on the basic chemistry of aromatic sulfonation and of alkene sulfation, reported during the past year, helped to fill out these longneglected areas. Kinetic studies were made on benzene and toluene, and temperature-isomer data were developed for toluene and xylene. Heats of reaction and activation energies were also determined for the xylene isomers and for ethylbenzene, as well as the relationship between stirring speed and sulfonation rate. Selection of optimum practical conditions for separating m-xylene resulted from one of these studies. A kinetic study was reported of the sulfation of pure terminal olefins in the range Cc to C ~ C .Another investigation was concerned with the effects of changing process variables, such as pressure, temperature, and agitation, in sulfation of the lower olefins. The sulfation of long-chain alcohols to detergents is commercially important. Two laboratory studies considered the relative suitability of various reagent systems. I n one case, nine were evaluated; in the other, four. Two other investigations reviewed reagents suitable for sulfating ethylene oxide condensates derived from long-chain alcohols and from long-chain alkyl phenols. These two types are of increasing interest for liquid detergents. All four of these studies emphasized that no reagent is perfect and that relative suitability varies from one situation to another. Patents continue to appear on improved devices for continuous sulfation of longchain alcohols. Recent commercial interest in imp r w e d diuretics has led to several publications by Merck, Abbott, and other pharmaceutical companies on the chlorosulfonation of various benzene derivatives, especially halogenated anilines, to the disulfonyl chlorides. Merck's commercial plant for doing this with 3chloroaniline was generally described.
Most of these disulfonyl chlorides were prepared by direct heating with excess ClSOgH, possibly with added NaCl or SOClz to improve yields. In other cases, indirect approaches were developed. I n the monosulfonation of benzene and related aromatics with H2S04, water dilution leads to only partial utilization of the acid. A recent report shows that added SOClz removes the water chemically, thereby giving a good yield of sulfonic acid-free of HzSOdin a short time a t room temperature. T h e major problem in the disulfonation of benzenes-commercially important for producing resorcinol-is undesired sulfone formation. An extended Soviet study has shown that sulfone can best be avoided by adding NaZS04 during sulfonation; correct choice of reagent strength is also important. The sulfation of carbohydrates, and other similar sensitive materials, is of interest to biochemists for producing sulfates with physiological activity. A major problem here is the avoidance of degradation during sulfation. Recent progress has been made by the use of SOS-trimethylamine in dimethylformamide. When employed a t 0' C., this system does not degrade during the introduction of 0.5 to 1.0 sulfate group per glucose unit. The success of this approach results from the inertness of SO3-trimethylamine, combined with the remarkable solvent power of dimethylfor mamide This review includes work published in the calendar year of 1960, with a few reports which appeared in 1959.
.
Sulfonating Agents Liquid so3 is largely trimeric ( 7 4 . Benzoyl sulfate, made from benzoic acid and so^, sulfonates styrene polymers ( 2 4 ; the benzoic acid is recovered and recycled.
Aliphatic and Alicyclic Sulfonates Direct Sulfonation. Surface sulfonation of polyethylene film with 8% oleum a t 50° C. improves its antistatic properties and dye receptivity (4OB). Polybutadiene was sulfonated with concentrated H,S04 in 2 hours at 140" C. (304. Polybutadiene, vulcanized with varying percentages of sulfur, was sulfonated t o ion exchange resins (33B) ; exchange capacity decreased with an increase in the amount of sulfur used. In the a-sulfonation of pelargonic acid with sea, no solvent is needed since the monosodium (or potassium) salt can easily be recrystallized from water to Ijght-colored sulfonates (47B). Chlorosulfonic acid shows no advantage in this sulfonatioil; S03-pyridine does not react, but SO3-dioxane gives unusually light-colored sulfonates (47B). The latter reagent was also used to a-sulfonate phenylstearic and 9,lO-dichlorostearic acids; it is noteworthy that in the former case the ring did not react. Hydrolysis of the reaction product of 5 moles of SO3dioxane with 9,lO-dihydroxystearic acid gave the a-sulfonated dihydroxy acid in 6670 yield (47B); evidently the disulfated sulfonic acid was intermediate. Acetophenone and six 4-substituted acetophenones were sulfonated with SO3-dioxane in 56 to 93% yields (34B). Oxidative Procedures. Aqueous chlorination of trithiane was shown (9B) to give an impure sulfonyl chloride. The same method was used to convert N,N'-diacetylcystine dimethyl ester to the corresponding sulfonyl chloride (72B). A cyclic disulfide, DL-lipoic acid, and its derivatives were oxidized to the disulfonic acids with performic acid (23B). Sulfonation with SOz Compounds. Aliphatic or cycloaliphatic sulfonates result from reaction of organic compounds with Son, often in the presence of chlorine or oxygen, or with its salts. VOL. 53, NO. 6
JUNE 1961
501
a
n
v
d Unit Processes Review
SULFOCHLORINATION. Continuing their study of the sulfochlorination of longchain paraffins, Asinger and others ( I B ) considered factors determining relative degree of mono- and disulfochlorination of n-dodecane and n-tetradecane. Presence of the first group tends to inhibit introduction of the second. Natta and others (22B) have reported on sulfochlorination of polypropylene and ethylene-propylene copolymers and on suitability of the products as elastomers. Sulfochlorination of conjugated diolefin polymers with terminal unsaturation is effected with S02C12 using pyridine as catalyst and alkali metal sulfite as promoter ( 3 B ) . ADDITION TO U ~ ~ S A T U R A TCowED POUKDS.T h e equilibrium constant for the formation of benzaldehyde-KaHS03 was shown to be an order of magnitude smaller than previously thought (31B). The reported existence of an enol form of this compound, with an implied expanded valence shell of 10 electrons for sulfur, was disproved (32B). Xylose and arabinose form mixtures of sulfocarboxylic acids with aqueous sulfite-bisulfite a t 130” C. (6B). Epichlorohydrin forms 8770 of the expected chlorohydroxysulfonate if methyl formate is used as reaction solvent and the temperature is kept below 35” C. ( 5 B ) . Addition of a mole of A-aHS03 to a nitrile group in tricyanoethane derivatives, followed by cyclization, comprises a new preparative procedure for various 5-amino-3-cyano-2-pyrrolesulfonic acids (27B). Addition of NaHS03 to mesityl oxide is the first step for preparing hydantoin sulfonates (77B). STRECKER REACTION. Recent applications of this standard preparative method are listed in Table I. A similar type of reaction, involving replacement of an alcoholic h>-droxyl group by sulfonate, has been applied to epinephrine (26B). A mechanism study of the reaction (73B) has shown that above pH 5 it is a simple SN2 type, but below p H 5 there is a parallel Sy1 reaction. Developments in the sulfonation of lignin. which involves similar reactions, have been reviewed covering the past 10 years (4B). Polymerization a n d Condensation Methods. Two procedures have been used to prepare polyethylenesulfonamides (27B). One involves polymerizing ethylenesulfonyl chloride or fluoride,
Table I.
Table 11. Compound Alkylated 2-Hydrazinopropane 1-Aminoanthraquinones Antibiotic polypeptide Long-chain amides
Remarks
Sulfomethylation Hydroxymethane sulfonate Product drug Hydroxymethane sulfonate Photographic chemicals Hydroxymethane sulfonate Tetrasulfonate formed Hydroxymethane sulfonate Improved procedures
2,4-Dichlorophenoxyacetyl
Sulfoethylation Isethionate Isethionate
chloride Long-chain fatty acids
Isethionate ; methyl taurine Improved process
Thiourea Benzylamine
Bromoethane sulfonate
Trithiocyanuric acid Polyvinylpyrrolidone
Higher Sulfoalkylation Propane sulfone Acryloyl taurine ; 2-sulfoethyl acrylate
Acrylic acid
followed by reaction of the polymers with amines. The other comprises direct polymerization of the corresponding ethylenesulfonamide. SULFOALKYLATION. This method uses low molecular weight sulfonates ("suifoalkylating agents”) for reaction with other organic compounds to make more complex sulfonates. A recent study (71B) shows the wide applicability of this approach. Sulfomethylated amines and amides were made as follows :
+
H2NCH(R)SOaNa R’COC1R’CONHCH(R)S03Na
+ HC1
where R = H, methyl, or phenyl; and R’COCI = various acylated amino acid chlorides, and :
+
-
HOCH(R)S03Na C8H5CH2NH2 C6H,CH2NHCH(R)SO3Na HzO
+
where R = H, five alkyl groups, two aryl groups, or benzyl. T h e Grignard sulfomethylating agent CGH5CH(MgCl) S0,n-a also proved versatile, since it reacts with ketones (19B),with benzaldehyde? and with acid chlorides (20B) to form the expected alcoholic and ketone sulfonates. Other recent examples of sulfoalkylation are given in Table 11.
Aromatic Sulfonates Benzene, Toluene, Xylene. Complete utilization of HzS04 in sulfonating aromatic compounds is achieved by
Halide
Remarks
16-hr. reflux. Disulfonate formed 5 to 20 hr., 120°-180D C. 16-hr. reflux
...
Acetylenic sulfonates formed
INDUSTRIAL AND ENGINEERING CHEMISTRY
Product monomer Product herbicide
2-Phenylethane-I-sulfonate 40% yield
Reaction of Alkyl Halides with Sulfites (Strecker Reaction)
2-Bromobutane 1,5-Dibromopentane Chlorofluoromethanes ; chloroform Trichlorobenzyl chloride Allyl bromide Propargyl chloride ; 1,4-dichlor0-2-butyne
502
Sulfoalkylation Reagent
Ref. (36B) (16B1 (SB) UOB)
(26B) (2B)
...
Trisulfonate formed Obtained graft polymer
adding SOC12 to react with the water formed (7C) : RH HzS04 SOCli + RSOIH SO2 2HC1
+
+
+
+
Sulfonate yields of 73 to 99y0 were obtained a t room temperature from benzene, toluene, 0- and p-xylenes, ethylbenzene, fluoro-, chloro-, and bromobenzenes. Paradichlorobenzene, 2-chlorotoluene, and 4-nitrotoluene gave 28% or less: while nitrobenzene and iodobenzene gave no sulfonate. Alternatively, the residual HzS04 can be removed with an anion exchange resin (23C). Study of the rate of sulfonation of benzene with a large excess of concentrated acid showed the reaction to be first order in the hydrocarbon and second order in molecular H2S04 (35C). Continuing their extended study of sulfone formation in the disulfonation of benzene, Shestov and Osipova (60C) drew further conclusions, as follo\vs : Sulfone sulfonic acid is formed both from diphenyl sulfone and from benzenesulfonic acid-benzenedisulfonic acid does not form a sulfone; minimum sulfones result from use of 100% acid in the monosulfonation step and 65Y0oleum for 3 hours a t 90” C. in the disulfonation stage; the most important factor is the addition of NaSS04 “sulfone inhibitor ;” 0.5 mole per mole of benzene lowers sulfone sulfonic acid from 24.3y0 (based on benzene, using no Na2S04) to 1.7%. The normal disulfonation product of benzene is 1,3-benzenedisulfonic acid. However, the 1,4-isomer is the main product if either the 1,3-isomer (as the disodium salt), or the sodium monosulfonate (by disproportionation), is heated a t 300” C. under pressure with a metal catalyst (37C, 32‘2). I n the second reaction, benzene is formed as coproduct. Equilibrium concentrations of para isomer in mixtures of o- and p-toluene-
an 4-
-
sulfonic acid were found to be as follows a t the temperatures given (46C): 81% (80" C.); 83.5% (90' C.); 84.6% (100' C.); 87.0% (110" C.). Kinetics of the reaction were found to be first order. Toluene sulfonates 31 times faster than benzene in concentrated acid and shows the same dependence of rate upon acid concentration (78C). A study of trans-sulfonation was made in the system p-toluenesulfonic acid-oxylene (75C) ; 65% di(o-xylyl) sulfone was formed besides only 34% of the expected tolyl o-xylyl sulfone. Similarly, toluene and p-xylenesulfonic acid formed 45% of the expected sulfone with 28% di(p-tolyl) sulfone. Heats of sulfonation with 96.5% acid at 20' C. of the three xylene isomers and ethylbenzene were determined as follows, as expressed in kilocalories per grammole (4OC): m-, 3.9; p-, 4.1; 0-, 5.5; ethylbenzene, 5.1. A rate study of the same four hydrocarbons, using 70 to 90% acid over the range 60" to 75" C., showed (47C) that: Sulfonation occurs in the acid phase; the rate increases with the rate of stirring to a certain point, and then remains constant; a t 75" C. using 75Oj, acid, the rate of sulfonation, as well as the change of rate, decreases in the order m-, 0-, p-, ethylbenzene. Activation energies were calculated. Results of a study (45C) of the sulfonation of oxylene with concentrated acid are summarized below : 4-Sulfonate, Temp., O C. 10
50 70 100
% 32 93 98.5 99.8
3-Sulfonate,
% 18 17
1.5 0.2
The 3-sulfonate was converted to the 4isomer in as high as 96% conversion by warming in concentrated acid. These results accord with earlier observations that lower temperatures promote o-sulfonation. Detergent Alkylate. A study of the unsulfonated hydrocarbon recovered after the sulfonation of four commercial brands of detergent alkylate using monohydrate acid a t 55" C. and 20% oleum a t 25' and 50" C. (44C) showed that only one of the alkylates gave increasing amounts ofrecovered oil with increasing time of sulfonation. The oil contains both unsulfonatable and unsulfonated sulfonatable hydrocarbons. Both of these were present in the raw materialneither being formed during sulfonation. A "pocket-sized" plant in Israel for making dilute SO8 gas (from sulfur) and using it to sulfonate detergent alkylate has been generally described (77C, 7ZC). Constants for a typical sulfonic acid product are given. Anodic control of corrosion is practical in mild steel oleum storage and in Type 304 stainless steel
neutralization kettles of a sulfonation plant (58C). American patents describe improved work-up procedures for SOa-sulfonated detergent alkylate. By-product anhydride is destroyed by adding water (36C), and inorganic sulfate is greatly reduced with alcohols (79C, 27C). British patents render oleum-based sulfonate salt-free by adding acetone (26C) or an ether (47C). Other Long-chain Alkylated Aromatics. Sulfur trioxide dissolved in liquid SO2 is best for preparing pure sulfonates for cosmetic use from the C16 to CZO long-chain alkyl derivatives of benzene, cyclohexylbenzene, naphthalene, Tetralin, diphenyl, and phenol and from alkylphenyl stearates (4'). Details are given for equipment for laboratory and commercial use. In preparing an oil-soluble sulfonate from "detergent alkylate still bottoms" with 20% oleum, a petroleum white oil is used as reaction solvent, and the desired sulfonate is extracted from it with methanol (3C). Polystyrene a n d O t h e r Aromatic Resins. Water-soluble poly(styrene sulfonate) was prepared with SO3- d'ioxane a t 70' C. in 48 hours (57C) and with concentrated acid in the presence of A g S 0 4 catalyst (33C). I n the second case, 85% sulfonation occurred a t room temperature and 91% a t 100' C. Concentrated acid was also used at 60" C. in 2 hours with 1,2-dichloroethane solvent (29C). Vinylhydroquinone dibenzoate-ol-methylstyrene copolymer was sulfonated to an electron exchange polymer with concentrated acid a t 5" C. in 35 minutes (8C). Usually, polymers are sulfonated in liquid phase; a patent (20C) employs SOs vapor a t 55" C. in 1 hour with very finely divided solid polystyrene or polyvinyltoluene in a fluidized bed operation. Water-insoluble sulfonated resins were also prepared. Vinylhydroquinone-cumethylstyrene-divinylbenzene terpolymer beads, preswollen with hot benzene, were sulfonated with concentrated acid a t 20" C. in 3 hours (8C), as was also a quaternary polymer made of these three monomers plus vinylpyridine. Ion ex-
Table 111. Compound
Unit Processes Review
change membranes are prepared by sulfonating with benzoyl sulfate ( 2 A ); the benzoic acid is recovered and reconverted to the sulfate with S C 3 . Membranes have also been sulfonated with concentrated acid at 100" C. using Ag2S04 catalyst (39C). In the preparation of ion exchange resins from butadiene-styrene copolymers cyith 98% acid a t 100' C., only the benzene rings reacted with a styrene content of 30% or higher; below 3Oy0, aliphatic sulfonation also occurred (63C). Ion exchange membranes were made by grafting styrene monomer onto polyethylene film; the next step was sulfonation with ClSOzH at 50" C. (30C). Simultaneous condensation and sulfonation to an ion exchange resin occur upon treating polystyrene with formaldehyde and ClSOBH (52C). Miscellaneous Benzene Derivatives. Various halogenated benzenes (bromo-, 1,4-dibromo-, l-bromo-4-chloro-, 1,2.4trichloro-, and 1,2,4-tribromo-) were monosulfonated by adding liquid S O 8 (67C); by-product sulfones were formed in all cases. Toluene and 2-bromoethylbenzene were sulfonated with freshly distilled SO3 using methylene chloride as solvent (73C). Data on the sulfonation of other nonhydrocarbon benzene derivatives are given in Table 111. Isomer Separation. Selective sulfonation, followed by selective desulfonation, is often used t o separate isomeric benzene derivatives. A Soviet study (47C)explored conditions for optimum separation of m-xylene, using acid of 70 to 90% strength in the range 60 ' to 75 ' C. Another report (28C) shows 140" C. as optimum for rn-xylene recovery by desulfonation. A patent (62C) reports better yields of rn-xylene if the isomeric sulfonic acids are used as the sulfonation solvent. Naphthalene Derivatives. A Soviet study (68C) on the conversion of 1naphthalenesulfonic acid to the 2-isomer in 91% acid at 160' C. concludes that the reaction is not intramolecular but intermolecular, with intermediate formation of free naphthalene. Sulfonation of
Miscellaneous Benzene Derivatives Comment Conditions 95% yield ClSOaH used Conc. acid used
Ref.
(71C) 3-(Trifluoromethyl) aniline N-(4-nitrO) and (4-chloro(16C) phenyl) amides (55C) 2-Hydroxy-3-methoxybenzal- 15% oleum, 10 min., 80' C. 35% yield dehyde 95% acid, 30 min., 90' C. Sulfonate nitrated (2C) Resorcinol Phenolic ring monosul- (26C) Hydroxyphenylazoindanfonates diones Monosulfonate formed (65C) Conc. acid, 6 hr. 2-Phenyl-3-(4-tolyl) indandiones Mono- and disulfonates ( 5 9 0 e . . 4-Ethylbenzdc acid formed
...
...
VOL. 53, NO. 6
JUNE 1961
503
Unit Processes Review
an
1,4 - endoethylene - 1.2,3,4 - tetrahydronaphthalene is best accomplished with SO8-dioxane in 1,2-dichloroethane solvent (34C). Separation of 1-naphthalenesulfonic acid from contaminating 2-isomer can be achieved by precipitation as the p toluidine salt (66C). At 300' C. under pressure, naphthalene-2,7-disulfonate rearranges to the 2,6-disulfonate in the presence of metal catalysts (32C). Under the same conditions, the 2-sulfonate disproportionates to naphthalene and the 2,6-disulfonate (37C). Sulfonation of 2-phenyl-3-naphthylindanone occurred in 2 minutes with concentrated acid
(65C). Direct Preparation of Aromatic Sulfonyl Chlorides (Chlorosulfonation). Dichlorosulfonation of halogenated anilines has recently been of special interest because of the activity of their derivatives as diuretics. Anilines m-substituted by fluorine, chlorine, bromine, niethoxy, nitro, amino, trifluoromethyl, and methyl have been so reacted (QC,42C, 50C, 54C, 70C), usually by heating with excess ClSO3H for 2 to 4 hours at 115' to 180" C.; yields are improved by adding NaCl or SOC12. Dichloro- and chloroiodoanilines have likewise been converted to the disulfonyl chlorides (50C, 67C). Aniline and acetanilide form the trisulfonyl chloride in preference (50C); N-methylaniline, however, yields the expected di-compound (9C). A commercial plant for conxierting m-chloroaniline to the disulfonyl chloride has been generally described (582). Substituted anilines have also been converted to monosulfonyl chlorides, usually under milder conditions. Included are the chlorotoluidines (70C, 50C), 3,4-dichloroaniline (50C), 4chloroanthranilic acid (70C), and a series of anilides p-substituted by various types of alkyl groups ( 4 8 2 ) . The last group of compounds was reacted in 1 hour at 60" C. Fluorobenzene and m-oriented fluoro-, chloro-, and bromotoluenes, as well as the corresponding chlorofluoro, chlorobromo, and dibromobenzenes, were also dichlorosulfonated in 20 hours a t 170' C. using pentachloroethane as reaction solvent (6C). The three tri-
Table IV. Sulfonate Prepared
Aromatic Sulfonates via Oxidation Compound Oxidized
Benzene-1,4-di Disulfide, thiol Pentachloroben- Xanthate zene Chloronitroben- Disulfide zene 2-(TrifluoroDisulfide methy1)benzene 1-Amino-4-nitro- Furoxan disulfide naphthalene
504
chlorobenzenes and two tetrachlorosoluble resins used in tanning and benzenes (1,2,3,4 and 1,2,4,5) were conwater-insoluble resins employed as ion verted to the mono compounds in 3 exchange resins. Recent examples are hours at 100' C. (70B). noted in Table V. Benzene is converted in 70% yield to Heterocyclic Compounds the disulfonyl chloride by heating a t 160' C. with 2-mole quantities of SO8 Nitrogen Heterocyclics. Sulfonation of 2,6-di-tert-butylpyridine, and its 4(as 65% oleum) and 8 moles of C l S 0 3 H chloro derivative, is easily achieved in (37C). Separation from by-product dithe 3-position with SO%,which is surphenyl sulfone disulfonyl chloride can be easily effected with carbon tetraprising on steric grounds ( 7 2 0 ) . The chloride. corresponding 4-sulfonate was made by Several phenol derivatives were chloro"03 oxidation of the thiol (720), as sulfonated. These include 2,4-dimethwas also the 4-sulfonate of pyridine ylanisole (69C), l-chloro-2,5-dimethoxyoxide (7D)-likewise prepared by reecbenzene ( 70B), l-methyl-3,4-dimethoxytion of 4-chloropyridine oxide with NazSOa. Pyridine oxide is sulfonated benzene (69C), and methyl and ethyl (64C). Diphenylin the 3-position a t 230' C. with oleum in phenoxyacetates methane was dichlorosulfonated in the presence of mercury ( 7 7 0 ) . thep-positions a t 80' C. (77C). In sulfonating quinoline with oleum in the 3-position, spent HzS04 is advanPreparation of sulfonyl chlorides by the action of SO2 on the diazonium tageously removed by adding methyl isobutyl ketone ( 7 3 0 ) . Nitrogen heterocompound is discussed below. Oxidative Methods. Recent prepcyclics converted to sulfonyl chlorides aration of aromatic sulfonates by this with ClS08H include uracil, to the monostandard procedure is summarized in sulfonyl chloride ( 2 0 ) ; dibenzotetra-azaTable IV. cyclo-octatetraene, to the tri- ( 3 0 ) ; and copper phthalocyanine to the tetraSulfonation with SO2 Compounds. Treatment of diazonium compounds ( 7 0 ) . Oleum was used to convert 6with SO2 in the presence of CuCl is often aminoindazole to mixtures of mono- and the best procedure for preparing certain disulfonates ( 9 0 ) . Phenothiazine, and aromatic sulfonyl chlorides. This apits 5-oxide, were converted to 3,7-disulfoproach was used recently with 2-(triphenazathionium hydroxide in 93% fluoromethy1)aniline (77C) and with 4yield with ClS03H ( 6 0 ) . The same reagent gave the 3,7-disulfonic acid from (su1famyl)aniline (27C, 37C). A 3570 yield of 2-hydroxy-4-aminobenzene-l- phenothiazine dioxide. sodium sulfonate resulted from treatSulfur-, Oxygen-, and MetalContaining Heterocyclics. Adding ment of the corresponding nitrophenol with N a H S 0 3 (IC). PCls improves the yield of 2-sulfonyl chloride from thiophene and ClS03H Condensation Reactions (Sulfoarylation). This approach is analogous to (50). Likewise, SOClz improves the sulfoalkylation in the aliphatic series, yield of 3,5-disulfonyl chloride from 2since aromatic sulfonates are reacted chlorothiophene (40). Dibenzo-p-diwith other organic compounds to form oxin forms the 2,8-disulfonic acid with new sulfonates with modified properClS03H a t room temperature (70D) ; the 3,7-dimethyl derivative reacts similarly. ties. Styrene-4-sulfonate is a useful comonomer for preparing polymers with Ferrocene carboxylic acid, and its methyl improved dyeability, water-sensi tivity, ester. were sulfonated at 0' C. with so$dioxane ( 8 0 ) ; as expected, reaction and resistance to static build-up, or with occurred in the ring without a carboxyl modified ion exchange or polyelectrolyte properties. Its purification has been group. described (24C), as has its grafting onto Petroleum, Coal polyvinylpyrrolidone ( 7 4 ' ) . Further data are available on the Sulfoarylation by condensation of Soviet process for preparing detergents aromatic sulfonic acids with formaldefrom the aromatics in kerosine, gas oil, hyde is important for making water-
Reagent "03
"03
Ref. WC) UOB)
Aqueous Cln
(@C, 49C)
Aqueous Clz
(71'2)
Internal oxida(6C) tion-reduction
INDUSTRIAL AND ENGINEERING CHEMISTRY
Table V.
Aromatic Sulfonic Acid-Formaldehyde Condensates
Sulfonic Acid from Phenol Phenol 2-Naphthol m-Cresol a
Remarks
TypeQ
Aniline added Temperature, reactant ratio studied Dihydroxydiphenylsulfone added Disulfonated tetramer formed
I I
I = water-insoluble; S
=
water-soluble.
s s
Ref. (5x3
(I4C) (66C,67C) (RX)
anp4and solar oil using SO3 a t 50" to 60" C. ( ?E). Twelve treatment combinations were studied in the preparation of ion exchange resins from lignite coal with 20% oleum ( 2 E ) . Preliminary heating at 100" to 110" C. for 1 to 25 hours was followed by sulfonation for 1 to 8 hours. The best exchangers were made by heating 1 hour a t 110" C., followed by sulfonation for 8 hours a t 90" to 100" C. I
*
Fatty Oils and Acids Sulfonated copra and palm oils do not foam, are stable to hydrolysis and oxidation, and are superior in wetting properties to sulfonated or sulfated cod and other fish oils, neat's foot oil, and spermaceti ( 2 F ) . Further study of the preparation of sulfonated oils by adding bisulfite to olefinic bonds (7F) has shown that oils with isolated double bonds (such as dehydrated castor oil or ricinoleic acid) react, but only in the presence of oxygen, while oils with conjugated double bonds do not react. Butyl oleate was '.sulfonated" with concentrated acid a t 15" C. in 2.5 hours ( 3 F ) . Sulfation Alkenes. Continuing their kinetic study of alkene sulfation, Butcher and Nickson have determined heats of sulfation a t room temperature with 85% acid for 1-hexene, I-heptene, 1-octene, and 1-decene (4G) ; no dialkyl sulfates or polymers were formed under these mild conditions. T h e kinetic results indicate a carbonium ion intermediate. Another basic study (78G) was concerned with the effect of varying agitation, pressure, temperature, and acid concentration in the sulfation of ethylene, propylene, 1and 2-butene, and isobutylene. A fluosulfonate is formed from hexafluoropropylene and H z S 0 4 a t 350" C. ( 7 7G), via F S 0 3 H formed by side reactions. Propylene and cyclohexene react with H & 0 4 in the presence of tert-butyl hypochlorite to give chlorinated ethyl sulfates (28G) : 2CHz:CHCHI
+ HZSO, + Cl+
+
[ CICH&H( CH,)],SO, Monohydric Alcohols. Nine reagent systems (concentrated acid with and without carbon tetrachloride, 20% oleum with and without ether, CIS03H with and without ether, sulfamic acid, so3 vapor, and SO, in liquid SO,) were compared for sulfating a mixture of 1dodecanol and I-tetradecanol (26G). Chlorosulfonic acid without ether is best for laboratory use (5G). Four reagents (SO3 vapor, ClSOsH, 20% oleum, and sulfamic acid) were compared for sulfating tridecyl (Oxo) alcohol (8G). The first two reagents gave 97 to 99% yield of sulfates with similar performance, but the last two reagents gave poor results.
Long-chain alcohols can be sulfated in a device with revolving plates which throw the product on a cooling wall (ICG). Another scheme (22G) involves continuous atomization of 120 kg. of long-chain alcohol per hour with ClSO3H onto a rotating cone which likewise throws the product toward the wall. The equipment operates in vacuo to remove H C l ; this obviates corrosion and gives a product low in inorganic salts. Color formation during sulfation of dodecanol with HzS04 a t 70' C. is inhibited by adding thioamides (75G). Sulfation of 9, IO-dichloro-octadecanol to a good detergent is accomplished with ClSO3H (6G). By-product alcohols from synthetic acid manufacture can be sulfated with H2S04, 3Oy0 oleum, or ClSOsH in the range IO" to 28" C. (2OG). Sulfation of 7-(2-hydroxyethyl) theophylline or 1-(2-hydroxyethyl) theobromine can be done with SO3-pyridine or with ClSOBH (7G). Glycol Esters and Ethers. Pure oleic and linoleic monoglycerides were sulfated with excess SO,-pyridine in 30 minutes a t 10" C. (3G); monoglycerides from the ' 2 1 2 , C14, (216, and Clg saturated acids were sulfated with CISOaNa. Six detergency factors were studied with the sulfates. Tridecyl alcohol, ethoxylated with 4 to 5 moles of ethylene oxide, is sulfated in 94 to 100% yields with SO3 vapor (at 35" C.), ClSO3H (at 25" C.), 20% oleum (at 20" C.) and sulfamic acid (at 150' C.) (7G, 8G, 23G). Product performance is the same for all four reagents. Sulfur trioxide vapor was compared with sulfamic acid for sulfating nonylphenol plus 4 or 9 moles of ethylene oxide, octylphenol plus 3, 5, or 12 moles, and dodecylphenol plus 6 moles (72G). The former reagent is cheaper but gives appreciable ring sulfonate, whereas sulfamic acid forms none. This difference is reflected in a foamretention test in dishwashing (7G) but not in other performance tests (72G). Poly(viny1 alcohol) was completely sulfated with SOB-pyridine in 1 hour a t 110" C. (QG). Ethylene sulfate was prepared from ethylene oxide (74G) as follows : CHgCHlO r
-
1
+ SOZ-dioxane-, Table VI.
CHzO )SO2 CHzO
1
Unit Processes Review
Carbohydrates. T h e sulfation of these, and similar polymeric polyhydroxy and polyamino compounds, is of interest for preparing synthetic blood anticoagulants. A basic problem in preparing such sulfates is finding extremely mild conditions to avoid degradation. A recent report (27G) recommends use of SO3-trimethylamine (a mild reagent) in dimethylformamide (an excellent solvent) at 0" C. for 24 hours for sulfating polysaccharides. iVo degradation occurs until 0.5 to 1.0 group per anhydroglucose unit has reacted; substitution begins a i position 6. The properties and possible uses of the new industrial product cellulose sulfate acetate have been reviewed (79G). Glucose and galactose give a poor yield of glucose-6-sulfate with aqueous N a H S 0 3 a t 100" C. (1GG). Recent reports on the sulfation of other similar compounds are summarized in Table VI. Cyclic Sulfates. Sulfation of trans(2-aminocycloheptanol) and the corresponding cyclo-octanol was achieved with 95% acid a t 140" C. in 45 minutes a t reduced pressure (77G, 25G). Sulfur trioxide-pyridine was used to prepare hydrocortisone semisulfate (24G) and sulfates of four steroids of the pregnane series (JOG). Sulfamation (N-Sulfonation) I n the preparation of sulfamic acid from urea and oleum, a purer product is obtained by using tetrachloroethylene as reaction medium (ZH). I n sulfamating cyclohexylamines with sulfamic acid, the reaction temperature can be reduced from 180" to 140" C. if a tertiary amine is added ( 7 H ) . With S03-pyridine a t 6OoC., 2-aminoethanol gives 7270 sulfatesulfamate ( 5 H ) . Insulin was sulfamated to varying degrees with SO3-pyridine, but products of lowered biological activity resulted (4H). T h e dinitrobenzoate of testosterone yielded the water-soluble disulfamate with aqueous N a H S 0 3 ( 3 H ) . literature Cited (1A) Gillespie, R. J., Oubridge, J. V., Proc. Chem. Soc. (London) 1960, p. 308. (2A) McRae, W. A., Alexander, S. S. (to Ionics, Inc.), U. S. Patent 2,962,454 (Nov. 29, 1960). Aliphatic a n d Alicyclic Sulfonates
(1B) Asinger, F., Breitag, G., J. Prakt chem. 7, 320 (1959).
Sulfation of Carbohydrates with S03-Pyridine
Materials Sulfated
Comments
Ref.
Cyclohexa- and heptaamyloses 6 hr., 85' C. Saponin, tannin heterosides 1000 c. N-Deacetylated chondroitin sulfate 64y0 yielda 2 5 O C. for 48 hr. ; 5 5 O C. for 3.5 hr. n-Galactose derivative SOs-dimethylformamidegave an 8Sy0 yield.
(2G) (21G) (g9 G) (1W
Q
VOL. 53, NO. 6
JUNE 1961
505
a
n
r
a Unit Processes Review
(2B) Badische Anilin- und Soda-Fabrik, Ger. Patent 1,086,693 (Aug. 11, 1960). (3B) Borunsky, J. (to Polymer Corp., Ltd.). T;. S. Patent 2,962,480 (Nov. 29, 1960). (4B) Brauns, F. E., Brauns, D. A., “The Chemistry of Lignin (1949-1958),” 2nd ed., Academic Press, New York, 1960. (5B) Chemische Fabrik Duren G.m.b.H.. Ger. Patent 1,075,596 (Feb. 18, 1960). (6B) Cordingly, R . H.. TapfIi 42, 645 (1959). f7B) Dehvdar Deutsche Hvdrierwerke ‘ G.ni.b.H., “Brit. Patent 847,841 (Sept. 14, 1960). (r 3B) Dow Chemical Co.. Ibzd., 849,063 (Sept. 21, 1960). (9B) Farrar, W. V.. J . Chem. Soc. (London) 1960, p. 3058. (10B) Ibid., p. 3063. illB1 Frankel. M.. Moses. P., Tetra‘ hedron 9 , 288 (1960). (12B) Heymann, H., Ginsherg, P.: others, J. Am. Chem. Soc. 81. 5125 119591. (13B) Higuchi, T.. ’Schroetkr, L. C.: Zbid., 82, 1904 (1960). (14B) Horsley, L. H., Sexton, A . H. (to Dow Chemical Co.), U. S. Patent 2,945,056 (July 12, 1960). (15B) Johnston, T. F.. Kussner. C. L., Holum. L. B., J . Ore. Chem. 25, 399 (1960).’ (16B) Kodak Ltd., Brit. Patent 830,003 (March 9, 1960) (17B) Levy, W. F., Seubert, G. A., Jr. (to Argus Chemical Gorp.), U. S. Patent 2,945,045 (July 12, 1960). (18B) Logemann, W.:Lauria, F., Artini, D., Nature 185, 532 (1960). (19B) Marekov, S.: Comnpt. rend. acad. bulgare sei. 12, 231 (1959). (20B) Zbid., p. 325. (21B) Middleton, W. J. (to E. I . du Pont de Nemours & Co.), U. S. Patent 2,940,977 (June 14, 1960). (22B) Natta, G., Crespi, G., Bruzzone, M., Chim. e ind. (Milan) 42, 463 (1960). (23B) Nawa, H.: Brady, W.T., others, J . Am. Chem. SOC.82, 896 (1960). (24B) Petrun’kin, V. E., Tiolovye Soedinen. v Med., Ukrain. Nauch.Issledovatel. Sanit.-Khim. Inst., Trudy Nauch. Konf., Kiev, 1957, 7-18 (Pub. 1959). (25B) Rogers, A. 0. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,934,561 (April 26, 1960). (26B) Schroeter, L. C.? Higuchi, T., J . Am. Pharm. Assoc., Sci. Ed. 49, 331 (1960). (27B) Schulz, R. C.; Schlesmann, H., Angew. Chem. 72, 579 (1960). (28B) Sheetz, D. P. (to Dow Chemical Co.). U. S. Patent 2,923,734 (Feb. 2, 1960). (29B) Shoji, J., Hamada, M., others, J. Antibiotics ( J a f u n ) Ser. B 12, 365 (1959). (30B) Solomon, P. 1%‘. (to Phillips Petroleum Co.), U. S. Patent 2,909,572 (Oct. 20, 1959). (31B) Sousa, J. A . , Margerum, 3. D., J . Am. Chem. SOC.82, 3013 (1960). (32B) Sousa, J. A., Margerum, J. D., J . Org. Chem. 25, 638 (1960). (33B) Starobinets, G. I., Sevost’yanova, L. I., Bulatskaya, G. iV.,Zhur. Priklad. Khim. 33, 690 (1960). (34B) Terent‘ev, A. P., Potapov, V. M., Dem’yanovich, V. M., Zhur. Obshcher Khim. 29, 949 (1959). (35B) Unilever Ltd., Brit. Patent 830,054 (March 6, 1960). (36B) Zbid., 848,463 (Sept. 14, 1960). (37B) Ibid., 848,633 (Sept. 21, 1960). (38B) Zbid., 853,590 (Kov. 9,1960). (39B) Unilever N. V., Ger. Patent 1,089,767 (Sept. 29, 1960). I
,~
506
(40B) Walles, W‘. E. (to Dow Chemical C o . ) , U. S. Patent 2,937,066 (May 17, 1960). (41B) Weil, J . K., Stirton; A . J., others, J . Am. Oil Chemists‘ Sac. 37, 769 (1960). Aromatic Sulfonates (1C) Aguado, L.: Lora-tamayo, >I., others, Anales Teal sac. espaA. fi‘s. y quim. (Madrid) 55b, 523 (1959). (2C) Allan: I V . G. (to Imperial Chemical Industries, Ltd.), U. S. Patent 2,945,890 (July 19: 1960). (3C) Anderson, R. L., McDonald, H.; Zbid., 2,924,618, (Feb. 9, 1960). (4C) Artozoul, J., Parfums, cosme‘t., sacons 3, 88 (1960). (5C) Bagdanol-, S. V.: Tabachinkov, N. I., Russ. Patent 127,661 (April 12, 1960). (6C) Boggiano, B. G., Condon, S., others, J . Pharm. and Pharmacol. 12, 419 (1960). (7C) Bradley, J. A , , Perkins: P., Polisin, J . J., Division of Organic Chemistry, 138th Meeting, ACS, New York, September 1960. (8C) Cassidy, H. G., Ezrin, M. (to Research Gorp.), U. S. Patent 2,900,353 (Aug. 18, 1959). (9C) Close, W. J., Swett, L. R., others, J . Am. Chem. Soc. 82, 1132 (1960). (1OC) Cohen, E., Klarberg; B., Vaughan, J. R.. Jr.. Zbzd.. 82. 2731 119601. (11C) Davldsohn’, A,‘, SoaF Chem. ‘Sfiecialties 36, 215, 219 (March 1960). (12C) Davidsohn, A , , Manor, J. (to “Dahila” Kibbutz Hashomer Hazair) , Israeli Patent 12,536 (Nov. 22, 1959). (13C) Dow Chemical Co., Belg. Patent 583,999 (Oct. 26, 1959). (14C) Dow Chcmical Co., Brit. Patent 849,063 (Sept. 21, 1960). (13C) Drews: H., Meyerson, S . , others, Angew. Chem. 72, 493 (1960). (16C) Duffy, J. A,, Leisten, J. .4.,J . Chem. Soc. (London) 1960, p. 545. (17C) Dykhanov, N. N., Shevchenko, Z . N., Russ. Patent 124,451 (Dec. 12, 1959). (18C) Eaborn. C., Taylor, R., J . Chem. Sac. (London) 1960, p. 1480. (19C) Eccles, E. J.: O’Neill, R. J., (to Monsanto Chemical Co.), U. S. Patent 2,926,142 (Feb. 23, 1960). (20C) Eichorn, J., Steinmetz, J. M. (to Dow Chemical C o . ) , Zbid., 2,945,842 (July 19, 1960). (21C) Fike, E. A. (to Monsanto Chemical C o . ) , Zbid., 2,940,936 (June 14, 1960). (22C) Gedeon, J., Bok, K . (to BykGulden Lomberg Chemische Fahrik G.m.b.H.), U. S. Patent 2,953,597 (Sept. 20,‘1960). (23C) Glogau, R. C., Halvorson, D. O., Sloan. 1%’. J.. Division of Industrial and Engineering Chemistry, 138th Meeting, ACS, h’ew York, September 1960. (24C) Grabiel, C. E., Morris, L. R., others, IND.ENG.CHEY.52, 845 (1960). (25C) Gudriniece, E., Jevins, A., others, Latvzjas P S R Zznitnu Akad. Vhstis 1959, No. 10,107. (26C) Hedley, T., & Co. (P. J. Pengilly, inventor), Brit. Patent 820,340 (Sept. 16, 1959). (27C) Holland, G. F., Laubach, G. D., others, Division of Medicinal Chemistry, 137th Meeting. ”, ,4CS. Cleveland, Ohio, April 1960. (28C) Iliesco, G., Cormilesco, A., Compt. rend. congr. intern. chim. ind. 31e, Liege, 1958 1, 601-3 (1959). (29C) Imperial Chemical Industries, Ltd., Brit. Patent 829,704 (March 2, 1960). (30C) Imperial Chemical Industries, Ltd. Ger. Patent 1,082,412 (May 25, 1960). (31C) Imperial Chemical Industries, Ltd. (I. Goodman and R. A. Edington, inventors), Brit. Patent 834,250 (May 4, 1960.)
INDUSTRIAL AND ENGINEERING CHEMISTRY
(32C) Zbzd., 834,251 (May 4, 1960). (33C) Kato, M., Nakagawa, T.. Xkamatsu, H.. Bull. Chem. Soc. J a j a n 33, 322 (1960). (34C) Kazanakii, B. A , , Svirskaya. P. I., Zhur. Obshchei Khim. 29. 2588 (1959). (35C) Kilpatrik. M., hkyer. M. W., Kilpatrick, AM. L., J . Phys. Chem. 64, 1433 (1960). (36C) Kirk, i. C.; Miller, E. L. (to Continental Oil Co.), U. S. Patent 2,928,8.;7 (March 15, 1960). (37C) Kirsanov, A. V.. Kirsanova, N. A,. Zhur. ObshchelKhim. 29, 1802 (1959). (38C) Labine, R. -4.. Chem. Eng. 66, 60 (Nov. 2, 1959). (39C) Lagos, A. E., Kitchener: J. A , Trans. Faraday SOC.5 6 , 1243 (1960). (40C) Leitman. Ya. I., Pevzner: M. S., J . Gen. Chem. U.S.S.R. 29, 2640 (1959). (41C) Leitman, Ya. I., Pevzner, M. S., Zhur. Priklad. Khim. 32, 1842 (1959). (42C) Logemann, W.. Giraldi, P., Galimberti, S., -47271.623, 157 (1959). (43C) Merck & Co., Inc., Ger. Patent 1,088,504 (Sept. 8, 1960). (44C) Mctzger, A , , Kclchner, G., Gennert, M., Fette, Seqen, Anstrichmittel 61, 1131 (1959). (45C) Muramoto, Y., YGki Gdsei Kagaku Ktdkai Shi 18. 644 11960). (46C) Muramdto. Y . , k a g a k u t o KdqyyG (Osaka) 33, 293 (1959). (47C) N. V. DeBataafsche Petroleum Maatschappii. Brit. Patent 849,183 (Sept. 21, 1960):(48C) N. V. Philips Gloeilampenfabrieken, Zbid., 822,237 (Oct. 21, 1959). (49C) Novello, F. C. (to Merck & Go.\: U. S. Patent 2,965,556 (Dec. 20, 1960). (50C) Novello, F. C.. Bell, S. C., others, J. Org. Chem. 25, 965 (1960). (51C) Painter, T. J., Chem. f3Ind. (London) 1960, p. 1214. (52C) Patterson. J . X., Abrams. I . M. (to Chemical Process Co.), U. S. Patent 2,900,352 (Aug. 18, 1959). (53C) Peakes, L. V.: Orlando, A. A . , Johnson, A. I.. ISD. ENG. CHEM.51, 1045 (1959). (54C) Pelayo, C., Iriarte, J., Bingold, H. I.. J . Orp. Chem. 25. 1067 (19601. (55C) Profft,“E., Geislek, E. J., J.’prakt. C h ~ m 9. . 136 (1959). Reich, G.‘, Led& IO, 261 (1959). Reich, G., Ges. Abhandl. deut. Lederznst. FreiberglSa. No. 15, 54 (1959). (58C) Riggs, 0. L., Hutchinson, M., Conger, N. L.. Corroszon 16, 58T-62T (1968). (59C) Schulz, J. C. F., C’niv. Microjlms nn Arbor, Mich.) L. C. Cat. No. k c . 59-6317; Dissertation Abstr. 20, 3082 (1960). (60C) Shestov, A. P., Osipova, N. A., J . Gen. Chem. U.S.S.R. 29, 591 (1959). (61C) Short, J. H., Biermacher, U., J . Am. Chem. Soc. 82, 1135 (1960). (62C) Spence, J. A. (to California Research Gorp.): U. S. Patent 2,943,121 (June 28, 1960). (63C) Starobinets, G. L.: Sevost’yanova, L. I., Bulatskaya, G. N.: Zhur. Priklad. Khim. 33, 690 (1960). (64C) Stavric, B., Cerkovnikov, E., Croat. Chem. Acta 31, 107 (1959). (65C) Stroanova-Ivanova, B., Compt. rend. acad. bulgaresci. 12, 321 (1959). (66C) Tedeschi, R. J. (to American Cyanamid Go.): U. S. Patent 2,955,134 (Oct. 4, 1960). (67C) Veldhuis, B., Anal Chem. 32, 1681 (1960). (68C) Vorozhtsov, N. N., Jr., Koptyug, W. A , , Komagorov, A. M., Zhur. Vsesoyuz Khim. Obschchestva im D. I. Mendelseoa 5, 232 (1960). \
’
,
a (69C) Wessely, F., Swoboda, J., Schmidt, G., Monatsh. 91, 57 (1960). (70C) Yale, H. L., Losee, K., Bernstein, J., J . Am. Chem. Soc. 82, 2042 (1960). (71C) Yale, H . L., Sowinski, F., J . Or,
