cin
I+!ECIunit processes Review
Sulfonation and Sulfation by EVERETT E. GILBERT and E. P A U L JONES General Chemical Division, Allied Chemical Corp., Morristown, N . J .
Petroleum sulfonates and polymeric sulfonates have attracted attention this past year, and varied types of heterocyclic sulfonates have been prepared. Interest continues high in improving continuous sulfonation processes and in sulfur trioxide as sulfonating agent
PETROLELM
sulfonates, industrially important for over a century, challenge researchers with two problems : they are complex mixtures of uncertain chemical structure, and they are obtained in low yield. An extensive structural study, based on desulfonation to the parent hydrocarbons followed by their analysis using modern physical and chemical methods, has helped alleviate the first problem. Two attacks have been made on the second problem. O n e has involved aromatization of the unsulfonated oil by dehydrogenation, followed by direct sulfonation in the usual manner. The other approach involves air peroxidation of the residual oil, followed by conversion to the sulfonate by treatment with bisulfite. A detailed description was published of a new commercial plant, operating batchwise, for preparing petroleum sulfonares with sulfur trioxide vapor. Continuous sulfonation of petroleum oils with sulfur trioxide was described in three patents. Two processes involved mixing of the oil and sulfur trioxide in a “flow-mixer.” The third process uses parallel perforated disks rotating in an externally cooled pipe. Polymeric sulfonates and sulfates attract increasing attention. A striking variety is noted in raw materials, sulfonating methods, reagents, and endproduct uses. R a w materials include aliphatic polymers such as poly(viny1 chloride), poly(viny1 alcohol), poly(viny1 thiocyanate), polyethylene, starch, and cellulose. Sulfochlorinarion of recently available polypropylene is being studied. ‘4romatic polymeric raw materials include polystyrene, polybenzyl, and phenol-formaldehyde resins. All four standard sulfonation procedures used for non-
polymeric materials are now being applied to polymers : direct sulfonation. oxidation, treatment with a compound of sulfur dioxide, and condensarion. The last method starts from sulfonated monomers, such as ethylene sulfonate, phenol sulfonate, styrene sulfonate, sulfoisophthalic acid and diamino-benzene sulfonate. Disulfonyl chlorides were prepared for making poly(su1fonate esters) and polysulfonamides. Water-soluble polvmeric sulfonates are used as drugs, lubricant additives, emulsifiers, synthetic gums, and anticoagulants. The water-soluble sulfonate polymers include fibers with improved dye receptivity, ion exchange resins, and membranes and films with improved cohesion to surface coatings. During the past year there was more activity than usual in the preparation of heterocyclic sulfonates. Many varied types were prepared, and all four standard s) nthetic procedures were employed. Direct sulfonation and oxidative methods were mainly used, however. These sulfonates are employed as dyes and pharmaceuticals. Methods for sulfonating with sulfur trioxide continue to appear in reports and patents. Fluorinated olefins gave p-sultones; other olefins formed ysultones. Sulfur trioxide was used, in vapor form, in four processes for sulfonating detergent alkylate; a fifth approach employed liquid sulfur dioxide solvent. This solvent was also used for butylated naphthalenes. Other naphthalene compounds were sulfonated with sulfur trioxide-dioxane. Three patents describe continuous sulfonation of petroleum lubricant raffinates with sulfur trioxide vapor; a report gives details of a commercial process, operated
batchwise. Sulfur trioxide in excess dimethylformamide was described as having unusually high solvency for reactants and products and high reactivity at low temperatures. Sulfur trioxide vapor was compared with chlorosulfonic acid in a laboratory study of the sulfation of ethenoxylated long-chain alcohols. Continuous processes for making sulfonates of major commercial interest are still being studied. Three patents and one article report sulfonation of detergent alkylate continuously with vaporized sulfur trioxide; one patent and one report cite the use of oleum. Two processes for continuously sulfating lauryl alcohol with chlorosulfonic acid were noted; one approach can alternatively use oleum to give a “low-active” product. For preparation of petroleum sulfonates, three patents mention continuous use of sulfur trioxide. Continuous disulfonation of benzene (for making resorcinol) was also described. Three of these continuous processes employ the “dominant bath” principle, the others operate “oncethrough.” I n spite of this increasing emphasis on continuous sulfonation, batch operation is still often preferable, as evidenced by one article describing commercial sulfation of lauryl alcohol with chlorosulfonic acid and another on the manufacture of petroleum sulfonates with sulfur trioxide.
Sulfonating Agents A British producer has discussed the manufacture, handling, and commercial use of stabilized liquid sulfur trioxide ( 2 A ) . An interesting R a m a n spectral study of the structure of very concenVOL. 52. NO. 7
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trated aqueous sulfuric acid (5.4) indicates the presence of a new ionic species:
4-
2H2S04
H2°
+
H5S05-
+
HS04-
The Same authors studied the Structure of oleums (4’4). Disulfuric acid (H&07) is an important species, but higher polyacids are absent, Other findings are summarized in Table I.
Table I. Mole Fraction SOP
Finding
0.00 0.33
Pure HnSOc H2S20,and HSzO,- about equal Molecular SO3 appears Molecular H z S O ~disappears; H&Oi HS.07at maxima SO3 trimer appears Pure SO1 (80% monomer20y0 trimer)
0.45 0.55 0.65 1.00
a
Structure of Oleums ( 4 A )
+
Stoichiometric mole fraction of 803 in
HzsO4.
.4 new method for analyzing chlorosulfonic acid (7‘4) depends on removal of free hydrogen chloride in vacuo at room temperature; it is compared with other analytical products. The sulfur trioxide-pyridine and sulfur trioxide-trimethylamine complexes are commercially available in experimental quantities. A patent ( 3 A ) describes new sulfur trioxide complexes with .V-alkylethylene carbamates; examples are given of their use in sulfating oleyl alcohol and castor oil. Aliphatic and Alicyclic Sulfonates
Direct Sulfonation. Chlorosulfonic acid a i 100 C. for 60 minutes was found best for converting poly(viny1 chloride) to an ion-exchange resin (59B); polyethylene. vinyl chloride copolymer, poly(vinyl alcohol), and poly(viny1 acetate) gave inferior results.
.4 series of fluorinated ethylenes was reacted with sulfur trioxide in t w o studies (70B, 738); p-sultones were isolated in most cases. Unfluorinated olefins usually yield these sultones only as transient intermediates which cannot be isolated, The P-sultone is a possible intermediate in converting 1,l-diphenylethene to the olefinic sulfonic acid using sulfur trioxidedioxane (4B). T h e same reagent - gave six new y-sultones from substituted butenes and pentenes (3B) and was used to evaluate olefin bond reactivity in halogenated styrenes (729. T h e quantity of sulfonate formed decreases with increasing distance of a fluorine atom from the olefinic bonds. Direct sulfonation of other aliphatic compounds is cited in Table 11. Oxidative Procedures. Peracetic acid converts 11-(acety1thio)undecanoic acid to the sulfonic acid (29B). Hydrogen peroxide gave the sulfonic acids from aminoethylthiopropionic acid lactam (28B), 2-aminoethanethiol (43B), and from polymers and copolymers derived from vinyl thiocyanate as well as from methoxymethyl vinyl sulfide (23B). Sulfonyl chlorides were made by aqueous chlorination of 2-thiocyanooctane (ZOB), bis( 2-chloroethyl) monosulfide ( 7 7B) and di-.t7-carbobenzoxycystine dibenzyl ester (45B).
Bisulfite addition compounds (Le., hydroxysulfonates) were made from dialdehyde starch (35B)and from various aldoses (25B). T h e rate of addition of aqueous bisulfite to maleate esters is accelerated by ultraviolet light ( S B ) . Salts of olefinic di- and tricarboxylic acids add sodium bisulfite to form sulfonates useful as polymer stabilizers (78B). Sulfur dioxide, in the presence of peroxide, reacts with acrylate ester? to give relatively short polymer chains terminated at one or both ends with sulfonic groups (44B); the products have surface activity. Sulfuryl chlorofluoride adds to tetrafluoroethylene in the presence of peroxides to give telomers of perhaloethanesulfonyl fluoride (54B). STRECKER REACTION.Recent applications of this standard preparative method are given in Table 111. MISCELLANEOUS. Details have been published of the conversion of alkyl hydroperoxides (made by air blowing a purified petroleum gas oil fraction) to detergents by treatment with sodium bisulfite ( I B ) . T h e reaction is:
Sulfonation with Sulfur Dioxide Compounds. Sulfonates are formed by
ROOH
treatment of aliphatic or alicyclic compounds with sulfur dioxide, often in the presence of oxygen or chlorine, or its salts. SULFOCHLORINATION. Propane yields the 1.3-disulfonyl chloride Lvith sulfur dioxide and chlorine (75B). A Soviet laboratory process study of the sulfochlorination of a petroleum fraction to produce household detergents showed 30% conversion to the sulfonyl chloride to be optimum for minimal side reactions (57B). Sulfochlorination of low-pressure polyethylene can be effected in a fluidized bed (38B). A Soviet study of the sulfochlorination of polypropylene (60% isotactic) considered the effects of time and temperature on chlorine and sulfur content (55B). Products with
Table II. Direct Sulfonation of Aliphatic and Alicyclic Compounds Compounds Reagent and Conditions Remarks Polyethylene (low pressure) Polyethylene film Cyclic P-diketones Fenchone Cyclopentadienyl Mn tricarbonyl Long-chain olefins Olefin copolymer Acrylic acid, maleic anhydride
630
Conc. H 2 S 0 4 ; 5Oo-10O0 C. ClSOaH; 15 sec.; 25’ C. H2S04 with (CH3CO),0 HzS04 with ( C H 3 C 0 ) , 0 H2S04 with (CHBCO)~O
Heated 1 hr. Surface sulfonated Widely applicable 10-Sulfonate formed Yield excellent
SO3 in SO?; - l o o C. ClSOSH; 60 min.; 0’ C.
Product detergent Lubricant additive Products comonomers
ClS03H; 80°-1000 C.
INDUSTRIAL AND ENGINEERING CHEMISTRY
Ref. (46B) (37B) (1W
(34B) (6B)
(4W (COB) (21B )
over 2% sulfur are unstable. -4s the sulfur content increases from 0 to 67,, the consistency varies from crystalline to rubbery to brittle, the last resulting from complete cross linking.
ADDITIONTO
COhi-
UNSATURATED
POUNDS.
+ 2h’aHSO, R$QjNa
-L
+ NaHS04 + H:O
Ethylene sulfite can be converted to
2-hydroxyethanesulfonate (50B) as follows : CH,-0 ~
CH2-O/
\S=O
+ NaHCO?
+
+
HOCH2CHySOSNa CO,
Polymerization and Condensation Methods. Vinylsulfonic acid was polymerized with ultraviolet light (72B),and an extensive physicochemical study was made of the polysulfonate. The polymerization rate and conversion of sodium ethylenesulfonate depends upon the acidity of the solution (27B); copolymers with water-insoluble monomers were prepared in dimethyl sulfoxide solution. It copolymerizes easily with .+‘-vinylpyrrolidone (33B) over a n unexpectedly wide range. I n copolymerizing ethylenesulfonate esters with styrene, stronger ion-exchange resins result if one component is prepolymerized (56B). Ethylenesulfonyl chloride undergoes the DielsAlder reaction with hexachlorocyclopentadiene (67B). Sulfoalkylation. The reagents used in this mild sulfonation procedure may
a
Table 111. Reaction of Alkyl Halides with Sulfites-Strecker Halide Remarks
be regarded as "organic" sulfonating agents. T h e wide applicability of the method is well illustrated in a recent study (36B),in which ammonia and eight amines were sulfomethylated on nitrogen with hydroxymethane sulfonate, three of its alkyl derivatives, two of its aryl derivatives. and t\vo of its arylalkyl derivatives. Other examples are given in Table I\'.
M e c h a n i s m . Brand and co\torkeis. tontinuing their long-term studv of the mechanism of aromatic sulfonation Ivith acid and oleum (7C). conclude that stepwise attachment of monomeric sulfur trioxide and hydrogen ion to the substrate is followed bv loss of a proton from the benzene ring. This concept is in general agreement with current views. B e n z e n e , Toluene Series. I n the sulfonation of benzenr \vith sulfur trioxide. bv-product sulfone formation is a problem Recent patents inhibit sulfone formation bv adding minor amounts of bentonite (8C)or pyridine [gC). O n the other hand. \$hen sulfone is desired
Table IV. Compound -4lkylated
Ref.
as the major product, increased yields result by first converting the sulfur trioxide to dimethyl pyrosulfate (by reaction with dimethyl sulfate), then mixing the latter with the hydrocarbon (60C). This procedure was applied to toluene and chlorinated benzenes and can be used to make mixed aromatic sulfones. Sulfone formation is also a problem in the disulfonation of benzene, important for making resorcinol. 4 German patent (I7C) overcomes this by adding 1 part of sulfur trioxide to 80 parts of disulfonic acid reaction product a t 140' C.. follo\ved immediately by 0.5 part of benzene. T h e process operates in a cyclic system by the "dominant bath" principle with continuous addition of reagents and removal of product. Sulfone formation can be further reduced by adding sodium sulfate. D e t e r g e n t Alkylate. T h e Chemithon continuous process using oleum has been described (47C). X major feature is unusually rapid throughput, especiall?. a t the spent acid separation stage. T h e process can also be used for sulfating long-chain alcohols with oleum or chlorosulfonic acid, if desired in tandem with detergent alkylate. Integrated contin-
Aromatic Sulfonates
Sulfoalkylation
Reagent
Remarks
Ref.
Sulfomethylation Melamine Hydroxymethane sulfonate 3-Trifluoromethyl-4-chloro- Hydroxymethane sulfonate aniline Yacca gum Hydroxymethane sulfonate Alkali cellulose Chloromethane sulfonate
Benzoyl chloride, etc. Acryloyl chloride, etc. Lauric acid Cs- and &-aliphatic amines 2-Naphthoxyacetic acid 4-Iodophenol Potato starch
Sulfoethylation Isethionate Isethionate Isethionate Isethionate Isethionate Bromoethane sulfonate Chloroethane sulfonate
Cellulose bulking agent Converted to nitrile
(68B)
70" C. for 6 hr.
(41Bi (40Bi
Ratio varied widely
Product fungicide Product monomer Mixed salts used 205' C. for 1.5 hr. 250" C. for 2 hr. Reflux for 12 hr. Alcohol reaction medium
(Z3B)
(30B) (1QB) (S8B) (&B) (31B) (2B) (140)
High Sulfoalkylaticiii Sodium salicylate Various phenols, carbons
hydro-
Propane sultone Acetaldehyde disulfonate
F
q Unit Processes Review
uous sulfonation with oleum and neutralization are described in a recent patent
Reaction
1 hr. at 102O C. Refluxed Reflux 3 hr. Reflux 21 hr.; 43% yield pH controls yield Heat 1 hr.; 79% yield Product detergent Heat 3 hr.; 64% yield Strecker type Strecker type
Crotyl chloride 4-Phenyl-1-bromobutane [2-(4-Nitrophenyl)]-ethylbromide 2-Phenoxyethyl chloride 1 -Chloro-1 -nitrocyclohexane Benzal 2-bromopropane-1,3-dithiol Long chain chloroglyceryl ether A mannitol diiodide 2-Nitroethyl acetate Substituted benzyl alcohols
n
Dimethylformamide solvent ( 4 8 B ) Resins, surfactants formed ( 1 6 B )
(38C). Interest remains high in continuous sulfonation of detergent alkylate with sulfur trioxide vapor. LYhen using a \.otator? a constricted reaction zone is the single most important factor in obtaining a sulfonate of good quality ( I C ) . T h e "dominant bath" approach, which works well with oleum, was found unsuitable with s u l h r trioxide, although a British patent (48C)claims good results by this method using a packed tower reactor. .Another continuous process (4C) involves film sulfonation on a rotating, cooled, conical drum, along which the film is driven by centrifugal force. "Turboannular flow'' is involved in another continuous method ( 7 9 2 ) ; no moving parts are involved as reaction occurs in a tube. When using sulfur trioxide dissolved in liquid sulfur dioxide, stepwise reaction in a compartmented reactor gives best results (46C). T h e Soviet process for preparing isodecylbenzene sulfonate (Sulfonol XP-2) has been described (32C). T h e rate of spent acid separation after sulfonation can be increased if toluene is added before sulfonation (3IC). Residual sulfuric acid can be removed b>adding toluene after sulfonating detergent alkylate and reheating to promote sulfonation of the toluene (43C). Both of these products contain toluene sulfonate, which is often added in any case during formulation of the finished detergent. Spent acid can be separated by adding methylene chloride to the sulfonation mixture (49C), instead of diluting with water as usual. T h e acid is fortified for reuse, and the solvent is recovered. Bleaching of dodecylbenzenesulfonic acid with hydrogen peroxide is most effective if residual sulfuric acid is first converted to bisulfate ( 6 2 C ) . P o l y s t y r e n e and O t h e r Aromatic Resins. Preparation of M-ater-soluble poly(styrene sulfonate) Lvith 95% acid a t 100' C. has been studied in detail (25C). Reproducible preparation of a completely soluble product was ensured by using a finely ground polymer of molecular weight below 250,000, a high acid-to-organic ratio, and a reaction time not over 8 hours. Isolation and analysis are also discussed. Contrary to earlier reports, similar products were obtained from sulfonating polystyrene and b>polymerizing styrene sulfonate monomer. A British patent (39C) reports optimum yield of water-soluble product using chlorosulfonic acid with a chlorinated ether solvent. LVater-insoluble sulfonated polystyrenes can be prepared by treating the reaction mixture of the soluble resins with formaldehyde (57C, 58C). Resins prepared by copolymerization of s q r e n e VOL. 52, NO. 7
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chlorosulfonic acid. Adding sodium sulfate during reaction reduces the yield of benzenesulfonyl chloride with a small Compound Ref. excess of acid, increases product purity Hydroquinone 94% acid; 6 hr.; 100° C. Product oxygen carrier (65Cj with the same yield using a medium Isophthalic acid SO3; 205' C. 98% yield UOC) 4-Nitrochlorobenzene 62% oleum; llOo C. Better than 20% oleum (E) excess, a n d increases the yield from 78 to 1,2,4-Trichlorobenzene No details given Derivatives made ( 6 C 88% with a large excess (30C). Chlorosulfonation of 1-naphrhaleneacetic acid, 2-chloroacet-l-naphthalide,several Table VI. Sulfonation of 2-Naphthylamine (33C) bromo- and chloroethoxynaphthalenes, and related compounds was accomTemp., Monosulfonate Isomer c. Isomers Formed Ratio Reagent plished in 14 to 85% yields (63C). T h e reactions were run at 0' to 25' C. using Amine sulfate 130-2 10 6, 8, 1 4-2-1 Amine sulfate 220 6,8, 3 3-1-2 chloroform solvent in most cases. An 100% acid 210 6,7 (plus di-) extensive French study of the chloro100% acid Below 160 6, 8, 5 sulfonation of .+'-acetyldiphenylamine and related compounds gave yields of 10 to 65% (40C). T h e reactions were run for 3 hours at l j 0 to 60' C. using a 5 to 1 sulfonate monomer have higher exchange ture given (23C). Other phenols were mole ratio of acid to organic compound. capacity than those made by direct similarly monosulfonated. Data on the Other studies of the direct preparation sulfonation (ZOC)-in the former case the sulfonation of other nonhydrocarbon of aromatic sulfonyl chlorides are cited sulfonate groups are evenly distributed, benzene derivatives are given in Table V. in Table \'II. while in the latter they are more on the Isomer Separation, Sulfonation is Sulfonation with Sulfur Dioxide surface. often used to separate or purify aromatic Compounds. Anthrol bisulfite adducts T h e sulfonyl chloride of styrenecompounds. as both sulfonation and (identified as tetrahydroanthracenedivinylbenzene copolymer can be made desulfonation can be selective. This sulfonic acids) were prepared as starring by heating for 17 hours a t 65' C. with approach has recently been used to materials for a n extended series of chlorosulfonic acid (22C), the sulfonyl separate petroleum xylenes in a threeanthracene and anrhraquinone sulfochloride of styrene homopolymer by step process (26C), with careful adjustnates. including amino derivatives ment of temperature and acid strength treating the sulfonic acid with sulfuryl (6C). chloride (543. a t each step. Trialkylbenzenes, with a t Condensation Reactions (SulfoarylaA Russian group, continuing their least two of the groups methyl, can be tion). This method, comprising reaction separated similarly ( 7 2 2 ) . Purification study of the preparation of ion-exchange of aromatic sulfonates with other organic of 1,2-dichloro-4-nitrobenzene'is acresins from phenol-formaldehyde concompounds to form new sulfonates with complished by heating with oleum to densates, found (582)that chlorosulfonic modified properties, is analogous to sulfonate selectively the 1,2,3-isomer acid a t 190' C. gave resins of lower sulfoalkylation in rhe aliphatic series. (64C). strength but higher exchange capacity Phenol sulfonate was reacted with ethylNaphthalene Derivatives. Sulfur trithan those made with sulfuric acid. .4 ene oxide to a polyether alcohol derivaoxide-dioxane, in dichloroethane solvent, good emulsifier was made by sulfonating tive used as a polyester modifier ( T I C ) . gave good yields from tetralin (2a n ether solution of poly(nonylpheno1Steroids are made water-soluble by sulfonate) (21C); tert-butylnaphthalenes diethylene glycol vinyl ether) with sulfoarylation of the alcohol group by were p l f o n a t e d with chlorosulfonic acid chlorosulfonic acid (27C). 2-sulfobenzoic acid (ZQC). Dyeability in nitrobenzene (44C) or boiling carbon Miscellaneous Benzene Derivatives. of polyesters is improved by adding sultetrachloride (45C). Results of a SUIAn orientation study of the sulfonation foisophthalic acid as comonomer (14C), fonation study of 2-naphthylamine are of chlorobenzene (57C) showed, with that of polyacrylonitrile by adding given in Table VI. 100% acid in 10 hours a t 220' C., 35% styrene-4-sulfonate (73C). Anthracene Derivatives. T h e 3-sulrn-sulfonate and 2.47, sulfone. At Water-soluble sulfonated polyureas fonate was produced from 4-amino238' C. the figures were 55 and 7.3%. are made by reacting aliphatic diamines alizarin with excess 20 to 40Yo oleum a t Phenol was converted to mono- (at with carbamates of disulfonated di135' C. for 45 to 75 minutes (78C). 50' C . ) ,di- (at 95' C.), and trisulfonates aminodibenzyls (76C). Sulfoarylation Direct Preparation of Aromatic Sul(at 150' C.) by adding stoichiometric by condensation with formaldehyde is fonyl Chloride (Chlorosulfonation). amounts of liquid sulfur trioxide a t important for making water-soluble This procedure involves treatment with 45' C. and then heating a t the temperaresins (tanning agents) and water-insoluble resins (ion-exchange resins). Those
Table V.
Miscellaneous Benzene Derivatives Conditions Comment
...
...
Table VII.
Preparation of Aromatic Sulfonyl Chlorides
Starting Material Dodecylbenzene Naphthalene Di-, trichlorobenzenes, trichlorobiphenyl Cinnamic acid and amide 3-Chloroaniline Phenylurea 6-Phenylhydrouracil
632
Remarks
Ref.
Methylene chloride solvent ; (iOC) 70% yield 1,5-Disulfonate ; pretreat (19C) with &So4 Disulfonates; 24 hr. re- ( S 4 C ) flux 0 . 5 hr.; 30'-55" C. (%!+C, 36C) Disulfonate ; 2 hr. ; 155' C. (5c) SOpClSOaH mixture used (37C) 2 hr.; 65O C. (28C
INDUSTRIAL AND ENGINEERINGCHEMISTRY
Table VIII, Sulfonic Acid from Phenol Phenol Phenol Phenol Phenol Acenaphthene Naphthalene
Aromatic Sulfonic Acid-Formaldehyde Condensates Remarks
Kef.
Reactant ratios varied Membrane prepared Chloroacetic acid added Very slow reaction Mineral oil reaction medium Exchange properties studied Aldehyde added under pressure
(420 (55C)
(50 (61C) (56C) (410 (560
a n w q Unit Processes Review noted during the past year (Table V I I I ) were largely of the second type.
Heterocyclic Compounds Sulfur trioxide sulfonates 2,6-di-tertbutylpyridine in the 3-position (70). This is surprising on steric grounds, as both groups are large. Other heterocyclic compounds sulfonated directly included dimethylpyrrole carboxylic esters (with 5% oleum for 10 minutes) (700), a diphenyldioxopyrazolidine (with 20% oleum a t 25' Cj. for 8 days) ( 5 0 ) , quinophthalone and quinonephthalone (with 25% oleum a t 70' C . for 1.5 hours] ( 7 7 0 ) , 2-aminopyrimidine (Lvith 25% oleum a t 180" C . for 5 hours) ( 2 0 ) . and 6-bromoquinoline ( 6 0 7 , oleum at 170' C . for 5 hours) ( 7 D ) . Heterocylcic sulfonates \rere also prepared by oxidative procedures. Conversion of mercapto heterocyclic compounds (thiazoles, imidazoles. pyridines, pyrimidines) to the sulfonyl chlorides by aqueous chlorination was facilitated by adding catalytic amounts of tin(I1) chloride or iron(II1) chloride ( 8 0 , SD). Aqueous chlorination was also used for an acetylthiothiadiazoline (30). However, use of this method with a mercaptobenzimidazole gave a poor yield ( 6 0 ) Bisulfite was used to sulfonate a coumarin carboxylic acid ( 4 0 ) . Decarboxylation occurred, giving the coumarin sulfonate.
Petroleum Oils, Asphalt, Coal An excellent detailed study (ZE) of the chemical structures of the various classes of oil- and water-soluble sulfonates obtained from a heavy naphthenic and a light paraffinic petroleum distillate was based on desulfonation to the parent hydrocarbons, followed by physical measurements before and after exhaustive hydrogenation. The water-soluble sulfonate fractions are generally of lower molecular weight, contain a larger percentage of rings, and are richer in disulfonates. I n the preparation of petroleum sulfonates by direct sulfonation of lubricating oil. a low yield is obtained, the residual "semiwhite" oil not being directly sulfonatable. This has prompted study of other methods for converting the residual oil to sulfonates. A recent study ( 3 E ) dehydrogenates the residual oil to aromatics which can then be sulfonated directly in the same manner as the original lubricant. Optimum conversion to aromatics is about 25% for subsequent direct sulfonation to best quality sulfonates. A second approach to using the residual oil involves air peroxidation, followed by conversion to sulfonate by treatment with bisulfite; this method
was cited in the section on aliphatic sulfonates. A commercial plant for lubricant raffiriate sulfonation, using gaseous sulfur trioxide, has been described in detail (6E). I n batchwise operation, this reagent gives higher sulfonate yield, lower chemical costs, and reduced sludge formation compared to oleum. A Soviet commercial plant for sulfonating kerosine, gas oil, or solar oil with sulfur trioxide a t 70" C. has been described ( 7 E ) . A patent (70E) describes equipment for continuously sulfonating lubricants with vaporized sulfur trioxide, comprising an externally cooled pipe, inside of i\.hich rotates a group of parallel perforated disks equipped with scraper blades. Another patent (9E) utilizes a "flow mixer." in which the oil entrains the sulfur trioxide gas. A similar process (7E) uses a n "ejector" to "atomize" the oil in the sulfur trioxide-inert gas mixture. I n working u p petroleum oil sulfonation reaction mixtures, it is advantageous to add Ivater to facilitate separation of the spent acid, either a small quantity (1557, of the Lveight of the oleum used) (8E;i. or a large quantity (500%) (TIE). I n the sulfonation of asphalts to ionexchange resins, products of improved capacity are obtained by adding a solid inorganic substance, such as fuller's earth, to enhance sulfonation ( 4 E ) . High-sulfur Indian coals were converted to ion-exchange resins by oxidation with nitrogen dioxide, oxygen, or nitric acid ivith permanganate (5E).
Fatty Acids Pure erucic acid was found ( 2 F ) to sulfonate a t the same rate and extent as oleic acid. An American patent cites large scale (123 pounds) sulfonation of oleic acid with sulfur trioxide in liquid sulfur dioxide solvent ( I F ) .
Sulfation Alkenes. Ethylene and isobutylene ivere sulfated u i t h deuterium sulfate, and the sulfates were hydrolyzed to the Product analysis showed alcohol (7"). that hydrogen did not transfer from the olefin to sulfuric acid, thus confirming formation of a pi complex rather than reversible formation of a carbonium ion. Monohydric Alcohols. Long-chain alcohols (C-12, -14,-16, -18) weresulfated ufith chlorosulfonic acid a t 30" C. (73G). Properties (surface activity, stability in storage and to hydrolysis) were determined for the acid sulfates and for the salts of amines and amino acids. A Romanian study of the sulfonation of synthetic long-chain fatty alcohols (71G)
showed sulfur trioxide and chlorosulfonic acid to be the most convenient reagents, advantageously used with ethyl ether or petroleum ether as solvents to ensure light-colored products. Organic solvents, such as acetic acid, are used y h e n sulfating ,V-3-hydroxypropyl stearaniide with chlorosulfonic acid-urea at 40' C. ( 2 G ) . Completely deuterated dimethyl sulfate \vas made in 90% yield by reacting methan-da-ol with chlorosulfonic acid followed by distillation (75G). An .4merican plant (9G) sulfates lauryl alcohol batchwise in a glass-lined kettle by adding 700 pounds of chlorosulfonic acid over 3 hours to the alcohol with anchor agitation and jacket cooling at about 30' C. A German patent (70G) describes continuous sulfation of longchain fatty alcohols Lvith the same reagent, which is precooled. mixed Lvith the alcohol in a nozzle. and fed into a cylinder cooled both externally and internally. T h e cooling surfaces are not more than 1 cm. apart and residence time is less than 30 seconds. Continuous sulfation of long-chain alcohols can be run in Chemithon equipment, using either oleum or chlorosulfonic acid (47C). Glycol Esters a n d Ethers. Lauric acid esters react with sulfuric acid reversibly by a cyclic carbonium ion mechanism (3G). T h e glycol esters give the monolaurate monosulfates as transient intermediates. Lauroxyethyl sulfate was prepared by treating ethylene glycol monolaurate with chlorosulfonic acid a t 10' C. using ethylene dichloride solvent. Sulfur trioxide vapor and chlorosulfonic acid were compared respecting cost, processing factors, and product quality in a laboratory study employing ethylene oxide condensates made from lauryl, tridecyl (OXO)?and tallow alcohols (7G). During sulfation of ethylene oxide condensates with chlorosulfonic acid, foaming caused by hydrogen chloride evolution is often excessive. This can be alleviated by adding a silicone antifoaming agent which surprisingly does not inhibit desirable foaming of the finished detergent ( 7 S G ) . A patent (5G) describes sulfation of ethylene glycol ethers of long-chain thiols with chlorosulfonic acid a t 10' C. using ethyl ether as solvent. T h e ether is recovered by direct distillation from the reaction mixture. Although glycerol can be disulfated smoothly with vaporized sulfur trioxide, attempted trisulfation resulted in excessive decomposition (8G) and was best performed with oleum. Polystyrene alkylated with hydroxyundecyl groups was 80% sulfated with chlorosulfonic acid a t room temperature in butanone solvent ( 7 4 G ) . Carbohydrates. T h e sulfation of these and similar polymeric polyhydroxy and polyamino compounds is of interest VOL. 52, NO. 7
JULY 1960
633
m4-I
Unit Processes Review Table IX.
Material Sulfated Hexoses (glucose, mannitol, etc.) Polymerized glucoses Cellulose Cellulose Dextramic acid Alginic acid
Sulfation of Carbohydrates
Sulfating Agent
Comments
Ref. (18G)
SO*-pyridine
Mono- and disulfates separated 6 hr.; 70’ C. Acid sulfodextrin formed Acetate sulfate formed In excess pyridine at SOo-
SOs-pyridine
1000 3 hr. at 9 5 O C.
SOa-pyridine SOa-pyridine ClSOaR
HI SO^-acetic anhydride
for preparing synthetic blood anticoagulants a n d water-soluble gums. Recent examples are summarized in Table IX. T h e preparation of sulfur trioxide-dimethylformamide for the sulfation of chitosan has been described (ZOG). This reagent, which is reactive a t a low temperature, may find general use with excess dimethylformamide functioning as a n unusually excellent solvent for the sulfating agent as well as for many polymeric materials being sulfated. Cyclic Sulfates. Estrone was sulfared with sulfamic acid a t 105’ C. using pyridine as solvent (76G).
literature Cited Sulfonating Agents (1.4) Korinth. R., dngen.. Chem. 72, 108-9
(1960). ( 2 k ) Royle, A . T.; Chem. Ind. (London) 1959, 1140-4. (3.4) Smith, J. I., Harrington, R. C., Jr. (to Eastman Kodak Co.), U. S. Patent 2,891,962 (June 23, 1959). (4.4) Walrafen, G. E., Young, T. F.. Division of Inorganic Chemistry, 136th Meeting, ACS, Atlantic City, N. J., September 1959. (5.4) Young, T. F.. Walrafen, G. E., Ibid. Aliphatic a n d Alicyclic Sulfonates.
(1B) Baniel, A.: Vroman, B. H., Proc. 5th World Petrol. Congr., Sect. IV, 1959. (2Bj Beringer, F. M., Falk, R . .4.,J . Am. Chem. SOC. 81, 2997-3000 (1959). (3B) Bordwell, F. G.: Chapman, R. D., Osborne, C. H.: Ihid., 81, 2002-7 (1959). (4B) Bordwell, F. G., Peterson, M. L., Ibid., 81, 2000-2 (1959). (5B) Broderick, E. (to Rohm 8: Haas Go.), U. S. Patent 2,900,393 (Aug. 18, 1959). (6B) Cais, M., Kosikowski, J., Division of Organic Chemistry, 136th Meeting, ACS, .4tlantic City, N. J., September 1959. (7B! Carpenter, S., Ph.D. Dissertation, Lniversity of Missouri, 1958. (8B) De La Mater, G. B. (to Mallinckrodt Chemical Works), C . S. Patent 2,913,451 (Nov. 17, 1959). (9B) Divine, R. D. (to American Cyanamid C0.i: U. S. Patent 2,879,214 (March 24, 1959:. (10B) Dmitriev, M. .4.,Sokol’skii, G. A , , Knunyants, I. L., Khim. Nauka i Prom. 3, 826-8 (1958); Doklady Akad. Nauk S.S.S.R. 124, 581-2 (1959). (11B) Du Pant d e Nemours, E. I., & Co., Brit. Patent 814,494 (June 3, 1959).
634
(21 G ) (fZG)
(6G) (;G)
c.
(1 G)
(12B) Eisenberg, H., Mohan. G. R.. J. Phys. Chem. 63, 671-80 (1959). 3B) England, D. C., Dietrich. M. A. Lindsey, R. V., Jr.. Delaware Science Symposium, 1960. 4B) Fuller, M. F. (to E. I. du Pant de Nemours 8: Co.). E. S. Patent 2,883,375 (April 21, 1959). 5B) Geiseler, G., Kuschmiers. R.. Chem. Ber. 91, 1512-15 (1958). 6B’l Gilbert, E. E., McGough, C. J., Otto, J. A , IHD.ENG.CHEW51, 925-8 (1959). 7B) Gladshtein, B M.. Kuliulin, I. P.. Soborovskii, L. Z., Zhur. Obshchei Khtm. 28, 2417-19 (1958); J . Gen. Chem. (U.S.S.R.) 28. 2454-6 11958) ( E n”d . transl.). (18Bj Grace. M’. R.. 8: Co.. Austral. Patent -4ppl. 44,180/58. (19B) Gudriniece, E., Levins, A , Vanags. G., Nauch. Doklady Vysshei Shkoly Khim. i Khim. Tekhnol. 1958, pp. 746-50. (20B) Hebrandson, H. F., Kelly, M’. S., Versnel, J., J . Am. Chem. SOC.80, 3301-3 (1958). (21B) Hendry, C. M. (to B. F. Goodrich Co.), U. S. Patent 2,895,987 (July 21> 1959). (22B) Higuchi, T., Schroeter, L. C., J . Am. Pharm. Assoc., Sei. Ed. 48, 535-40 (1959). (23B) Hwa? J. C. H., J . Am. Chem. Soc. 81, 3604-7 (1939). (24B) Imperial Chemical Industries, Ltd.! Brit. Patent 815,167 (June 17, 1959). (25B) Ingles, D. C.; Australian J . Chem. 12. 97-101 119591. (26Bj Ingles, D. L.: Chem. 0” Ind. (London) 1959,pp. 1217-18. (27B) Kern, rV., Kale, V. V.; Schering, B., Makromol. Chem. 32, 37-44 (1959). (28B) Knunyants, I. L., Domitriev, M. .A,, Sokol’skii, G. .4., Russ. Patent 116,577 (Jan. 19, 1959). (29B) Koenig,N. H., Swern, D. (t0U.S.A.: Secretary of .lariculture). U. S. Patent 2,892,852 (Junk30, 1959). (30B) Kosmin, M. (to Monsanto Chemical Co.), Ibid., 2,875,122 (Feb. 24, 19591. (31B) Ibid., 2,913,324 (Nov. 17: 1959). (32B) Krumrei, W. C. (to Procter 8( Gamble Co.), Ihid., 2,877,186 (March 10, 1959). (33B) Kutner, A., Breslow, D. S., J . Polymer Sci.38, 274-5 (1959). (34B) Kuusinen, T.: Lampinen, M., Suomen Kemistilehti 31B, 381-2 (1958). (35B) Mehltretter, C. L., Van Cleve, J. W., Watson, P. R . (to U.S.A., Secretary of .4ericulture) U. S. Patent 2.880.236 (March 31, 1959). (36B) Neelakantan, I . , Hartung, W. H., J . Ore. Chem. 24. 1943-8 11959). (37B) Gelson, J. i., Jr., Vollmer, W. K. (to Union Carbide Corp.), U. S. Patent 2,879,177 (March 24, 1959). (38B) Noeske, H., Roelen, C. (to Ruhrchemie A. G.), Ibid., 2,889,259 (June 2, 1959).
INDUSTRIAL AND ENGINEERINGCHEMISTRY
I
>
(39B) Petrun’kin, V. E., Lysenko, N. M., Zhur. Ohschchel Khim. 29, 309-13 (1959). (40Bj Porath, J. 0. (to Moaoch Dams j o Aktiobolag), U. S. Patent 2.891.057 (June 16,7959). (41Bj Putnam, R. C., Hayes, S. I., Jr. (to United Shoe Machinerv Coru.). Ihid., 2,872,278 (Feb. 3, 1959).‘ (42B) Puzitskii, K . V.? Eidus, Ya. T., Rabinovich, .4. Yu., Zhur. Priklad. Khim. 32. 1819-24 11959). (43Bj Rachinskii, F. Y u . , Slavachevskaia, N. M., Ioffe, D. V., Zhur. Obshcher Khzm. 28, 2998-3003 (1958); J . Gen. Chem. (U.S.S.R.) 28, 3027-32 (1958) (Engl. transl.) (44B) Rees, R. W. (to Shawinigan Chemicals, Ltd.), U. S. Patent 2,883,369 (April 21, 1959). (45B) Ross, D. L., Skinner, C. G.. Shive, W., J . Org. Chem. 24, 1372-4 (1959). (46B) Ruhrchemie .4. G., Belg. Patent 572,811 (May 1959). (47B) Rumpf, P., Sadet, J . , Bull. sot. chim. France 1958, No. 4, 447-50. (48B) Schenck, R . T . ( t o Keystone Chemurgic Corp.), U. S. Patent 2,900,410 (Aug. 18, 1959). (49B) Sheetz, D. P. (to Dow Chemical Co.), Ihid., 2,914,499 (Nov. 24, 19591. (50B) Smith, R. M . (to Dow Chemical Co. 1, Ihid., 2,899,461 (Aug. 11, 1959). (51B) Soborovskii, L. Z., Gladshtein, B. M.. others. Zhur. Obshchei Khim. 28,188670 (1958). 152B) Takahashi. M.. Jauan. Patent 636 ’ (’59) (February 12). (53B) Takeda, A , , Contribs. Boyce Thompson Inst. 20, 191-6 (1959). (54B) Tiers, G. V. D., Koshar, R . J. ( t o Minnesota Miring and Manufacturire; Co.), U. S.Patent 2,877,267 (March 10, 1959). (55B) Topchiev, A. F., Krentsel, B. A , Ilyna, D. E., Angew. Chem. 72, 116 (1960). (56B) Tsunoda, Y., Seko, M., others (to Asahi Kasei Kogyo), U. S. Patent 2,898,311 (Aug. 4, 1959). (57B) Tyutunikov, B. N., Volkov, Yu. M., Khim. i Tekhnol. Topliv i Masel 3, No. 12, 49-52 (1958). (58B) Unilever N. V., Belg. Patent 578,179 (Aug. 16, 1959). (59B) Vasil’ev, A. A , , Vansheidt, .A. -4., Zhur. Priklad. Khim. 32, 150-7 (1959). (6OB) Wasley, W. L., Wilson, C. E. (to Union Oil Co. of California), U. S. Patent 2,883,340 (April 21, 19591. (61B) LVygant, J. C. (to Monsanto Chemical Co.), U. S. Patent 2,875,123 (Feb. 24, 1959). ,
I
.
I ,
A
Aromatic Sulfonates
(1C) .4brams, A , , Carlson. E. J.. others, J.Am. Or1 Chemists’ SOC.37, 63-8 (1960). (2C) .411an, 2 . J., Chem. listy 52, 2014-15 (1958). (3C) Ashida, K., Yokoyama, Y., Nishimura, M.: Japan. Patent 3241 (’58) (April 26). 14C) Berol Aktiebolae.. Bele. Patent 577.‘ 738 (April 15, 19597.’ (5C) Biniecki, S.,Gora, D., .4ch Polon. Pharm. 15, 385-6 (1958). (6C) Bogdanov, S. V., Gorelik, N. V., Zhur. ObshcheE Khrm. 29, 136-9 (1959). (7C) Brand, J. C. D., Jarvil. A . W. P., Horning, W. C., J. Chem. Soc. 1959, pp. 3844-53. (8C) Brooks, R. F. (to Monsanto Chemical Co.), U. S. Patent 2,889,360 (June 2, 1959). (9C) Ibzd., 2,889,361.
-
a OC) Burns, H . PV. (to E. I . du Pont de Nemours & Co.i, Ibzd.. 2,895,986 (July 21, 1959). 1C) Chemstrand Corp., Belg. Patent 573.418 (Nov. 28. 1958). > 2C) Corson, B. B., Schwartman, L. H. (to Koppers Co., Inc.). U. S . Patent 2,873,300 (Feb. IO, 1959). 3C) Davis, C. W., Ehlers, F. A . Taylor, T. G. (to Dow Chemical Co.), Ibid., 2.913.438 (Nov. 17, 1959). 4C) i u Pont de Nemours, E. I.. & Co., Brit. Patent 826,248 (Dec. 31, 1959). 5C) Falk, K.. Taplin, W. R . (to E. I. du Pont de Nemours & Co.). U. S . Patent 2,923,728 (Feb. 2, 1960). 6C) Farbenfabriken Bayer, A. G.. Ger. Patent 1,042,892 (April 23, 1959). 7C) Farbwwke Hoechst .4. G., Ger. Patent 1,063,151 (Aug. 13, 1959). 8C) Frankel. M., Moses, P.. Chem. 3 Ind. ilondon) 1959. DD. 401-2. (19C) ‘General Tire”& Rubber Co.. Brit. Patent 802.654 (Oct. 8. 19581. (20C) Graydon, W. F., U. S. Patent 2,877,191 (March 10, 1959). 121C) Gudriniece, E., Lielbriedis. I., LatuQas Valsts LTnic. Kim. Fak., Zinatniski Raksti 22, 115-17 (1958). (22C) Hagge, M‘., Quaedvlieg, M., Seifert, H. (to Farbenfabriken Bayer A. G.), U. S. Patent 2,906,715 (Sept. 29, 1959). (23C) Hardman & Holden, Ltd.: Brit. Patent 820,659 (Sept. 23, 1959). (24C) Hardy, E. M., Hosler, J. F., Lamb, G. (to American Cyanamid Co.). U. S. Patent 2,879,198 (March 24, 1959). (25C) Hart. R . , Timmerman. D., Ind. chim. beige 24, Spec. No. 11,364-8 (1959). (26C) Jezl: J . L., Hague, L. D. (to Sun Oil Co.), U.S.Patent 2,880,253 (March 31, 1959). (27C) Kawada, M., Sugiyama, T . (to Daiichi Pharmaceutical Co.), Japan. Patent 9793 (’58‘1(November 12). (28C) Kurtev, B. I.: Golovinski, E., Compt. rend. acad. bulgaresci. 11, 383-6 (1958). (29C) Laboratoires Francais de Chimiotherapie, Belg. Patent 571,750 (April 15, 1959). i30C) Levina, I,. I., Patrakova, S. N., Patrushev, D. A , , Zhur. Obshchei Khim. 28, 2427-8 (1958). (31C) Lewis: A. H. (to California Research Gorp.), LT.S. Patent 2,897,156 (July 28. 1959). (32C) Lyuter, ,4. C.. Popolovskii: L. .A,, Khim. i Tekhnol. Toplirm i Masel 4, No. 9 . 37-42 (1959). (33C) Manabe, 0.. Sugawara, M., Hiyama, H.: Kagaku to Kdgyd (Osaka) 33, 22-9 (1959). (34C) Murphey. W..4.(to E. I. du Pont de Nemours & Co., Inc.), U. S. Patent 2,875,183 (Feb. 24, 1959). (35C) Oda, K., Matsuda, S., Saito, T. (to Noguchi Research Institute, Inc.), Japan. Patents 9489 (’58)-9491 (’58) (October 25). (36C) Overberger. C. G., Biletch, H., Orttung, F. W., J . Org. Chem. 24, 289-91 (1959). (37C) Pal’m, V. A . , Russ. Patent 116,532 (Jan. 19: 1959). (38C) Palmqvist, F. T . D. (to Aktiebolaget Separator), U. S. Patent 2,906,760 (Sept. 29, 1959‘1. (39C) Permutit Co., Ltd., Brit. Patent 825,422 (Dec. 16>1959). (40C) Perrot, R.: Bourgau, Y . . Chim. ind. (Paris) 81, 690-4 (1959). (41C) Pirs, M., Dolar. D.. Mohorcic. G.. “1. Stefan” Inst. Repts. (Ljubijana) 5, 53-9 (1958). (42C) Polak, F., Bartel, B.. Przemsvl Chem. 37, 651-7 (1958). %
I
\
(43C) Rachlin, A. I . (to ..\Hied Chemical Corp.), U. S. Patent 2,898,370 (Aug. 4, 1959). (44C) Ravensburg G.m.b.H., Ger. Patent 1,057,105 (May 14, 1959). (45C) Ibzd., 1,058,983 (June 11, 1959). (46C) Smith, J. H . (to Continental Oil Co.), U. S. Patent 2,863,912 (Dec. 9, 1058). (47C) Soap Chem. Speczalties 35, No. 4, 131, 133, 135 (April 1959). (48C) Socittt anon. d’Innovations Chimiaues Dite: “Sinnova” ou “Sadic.” ‘ Brit. Patent 799,199 (Aug. 6, 1958). (49C) Spengler, Gunter. Ger. Patent 1,050,329 (Feb. 12, 1959). (50C) Spivack. J. D., Peterson. J. B., Kroll, H . (to Geigy Chemical Corp.), U. S.Patent 2,908,648 (Oct. 13. 1959). ( 5 l C ) Spryskov, -4.A , , Kachurin. 0. I., Zhur. ObshchefKhim.28,2213-17 (1958). (52C) Stota, Z . , Chem. zmsti 13, 32-7 (1959). (53C) Szombathv. K . V. (to Andre von ‘ Szombathy), k. S. Paient 2,911,438 (Nov. 3, 1959). (54C) Teot, A. S., U. S . Patent 2,867,611 (Jan. 6. 1959). (55C:) Titov. V. S., Bykhovskii. S. B., others, Russ. Patent 116.075 iNov. 22. 19 58) .’ (56C:) Ibid., 116,084 (Nov. 22, 1958). (57C:) Vansheidt, A. .4., Kuznetsova, N. N., Russ. Patent 114,231 (July 30, 1958). (58‘2) Vasil’ev, A. 4.,Vansheidt, A. A , Zhur. Priklad. Khim. 31, 1436-7 (1958). (59C:) Ibid.? pp. 1692-7. (60‘2) Velluz, I., Joly, R., Bucourt, R., Compt. rend. 248, 114-15 (1959). (61C) Vozunesenskii, S.A., Romachenko, N. T.. others, Russ. Patent 114,913 (Oct. 6, 1958). (62C) Weaver, L. J.. Eccles, E. J.? Jr. (to Monsanto Chemical Co.), U. S. Patent 2,880,235 (March 31, 1959). (63‘2) Weinstein, .4. H . , Pierson, R . M., others, J . Org. Chem. 23, 363-72 (1958). (64C) Welch, E. (to General Aniline & Film Corp.), U. S. Patent 2,883,435 (.4pril 21, 1959). I
,
Heterocyclic Compounds ( I D ) Bankovskii, Yu. A , Lovanova, E. F., Zhur. Obshchel Khim. 28, 2857-9 (1958): J . Gen. Chem. U.S.S.R. 28, 2884-6 (1958) (Engl. transl.). (2D) Caldwell, W.T.. Jaffe, G. E.?J . Am. Chem. Soc. 81, 5166-7 (1959). (3D) Chinoin Gyogyszer es Vegyeszeti Termekek Gyara R . T., Brit. Patent 789,583 (Jan. 22. 1958). (4D) Daniewski, W., Rocrniki Chem. 32, 66-1-70 (1958). (5D) Khaletskii, A . M., Pesin, V. G., Jun-Hsiang, T.. Zhur. Obshchel Khim. 28,3027-9 (1958); J . Gen. Chem. U.S.S.R 28, 3057-9 (1958) (Engl. transl.). (6D) Knobloch, W., Rintelen, K., Arch. Pharm. 291, 180-4 (1958). (7D) Muller, N., Wallace, W. J.: J . Org. Chem. 24, 1151-2 (1959). (8D) Pala, G., Farmaco (Pavia), Ed. sci. 13, 461-9 (1958). (9D) Ibid., pp. 650-4. (10D:l Treibs, A., Bader, H., Chem. Ber. 91, 2615-19 (1958). j l l D : Yamazaki, Y . Ishii, T., Shiro, K., YGki GBsei Kagaku KyBkai Shi 17, 229-31 (1959). Petroleum Oils, Asphalt, Coal (1E) Ashinov. M. .4., Akhmedov, M. iV,, Doklady Akad. A’auk Azerbaidzhan. S.S.R. 15, 493-5 (1959).
n
r
w Unit Processes Review
(2E) Brown, A. B.. Knobloch, J. O., “Symposium on Composition of Petroleum Oils, Determination and Evaluation,” pp. 213-29, Am. SOC. Testing Materials, Philadelphia, 1958. (3E) Brown, T. F.. Mathews, P., Proc. 5th World Petrol. Congr., Sect. 3, 1959. (4E) Goren, M. B., Pickell, M. M., Grawin, I. (to Kerr-McGee Oil Industries), U. S. Patent 2,911,373 (Nov. 3, 1959). (5E) India Council of Sci. & Ind. Research, Indian Patent 61,771 (July 1959). (6E) Kaye, H., Forsyth, E., Mills, .4.I., Proc. 5th World Petrol. Congr., Sect. 3, 1959. (?E) Shell Research. Ltd., Brit. Patent 791,995 (March 19, 1958). (8E) Ibid., 795,642 (May 28. 1958). (9E) Shell Research. Ltd.. South African Patrnt .ADDL 4023/58. (10E) SonidbornSons, Inc., Belg. Patent 572,820 (Feb. 28. 1959). (11E) M’hitney, W. B. (to Phillips Petroleum Co.), U. S. Patent 2,909,563 (Oct. 20, 1959). Fatty Acids ( I F ) Little, W. S., Wylie, L. M . (to Tennessee Gorp.), U. S. Patent 2,878,271 (March 17, 1959). (2F) Mehta, T . N., Rao, B. Y.. India12 J . Appl. Chem. 21, 1-8 (1958). Sulfation ( I G ) Alpine Chemische .A. G.. Austrian Patent 198,429 (July 10, 1958). (2G) Badische .\nilin- & Soda-Fabrik, Ger. Patent 1,072,251 (Dec. 31, 1959). (3G) Bauman. R . B.: Krems. I. J., J . Am. Chem. Soc. 81, 1620-7 (1959). (4G) Commonwealth Engineering Co. of Ohio, Belg. Patent 577,947 (Aug. 16, 1959). (5G) Doerr. E. L. (to Monsanto Chemical Co.)! U. S. Patent 2,909,554 (Oct. 20, 1959). (6G) Gavaert Photo-Production N. V., Belg. Patent 581,794 (Dec. 15. 1959). (7G) Gilbert, E. E.: Veldhuis, B., J . Am. Oil Chemists’ Soc. 36, 208-10 (1959). (8G) Gray, F. W. (to Colgate-Palmolive Co.). U. S. Patent 2,868,812 (Jan. 13, 1959). (9G) Gushee, D. E.. Scherr. 0. L., IKD. ENG.CHEM.51, 798-805 (1959). (10G) Henkel & Cie G.m.b.H., Ger. Patent 1,058,984 ( J u n e 11. 1959). (11G) Klang, M.. Stoica, R.. Rev. chim. (Bucharest) 9 , 23-8 (1958). (12G) Lyandzberg, G. Ya., Zhur. Priklad. Khim. 31,1900-2 (1958). 113G) Maurer. E. W..Stirton. A . J.. Weil, J. K., J . Am. Oil ChemzstJ’ Soc: 37, 34-6 (1960). 4G) Medalia, A. I.. Freedman. H. H., Sinha. S., J . Polqmer Sci. 40,15-33(1959). 5G) Morse, .4. T., Massiah, T. F., Leitch. L. C.. Can. J . Chem. 37, 1-3 (1959). 6G) Price, \I‘ H. (to Parke, Davis & Co.), U. S. Patent 2,917,522 (Dec. 15, 19593. 7G) Shilov. .A, E.. Sabirova, R. D., Gorshkov, V. I.. Doklady -4kad. .Vauk S.S.S.R. 119, 533-6 (1958). (18G) Turvey, .J. R.. Clancy, M. J., dVature 183, 537-8 (1959). (19G) Unilever. Ltd.. Australian Patent Appl. 45044/59; Belg. Patent 574,842 (May 16, 1959). (20G) Wolfrom. M. L.. Han. T . hl. S., J . Am. Chem. Soc. S i , 1764-6 (1959). (21G) Wood, J. W.. Mora, P. T., Ibzd., 80, 3700-2 (1958). VOL. 52, NO. 7
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