Alkyl sulfates, preparation

The most widely used alkyl sulfate in shampoo preparation is lauryl sulfate. The alkyl component of this sulfate ranges from C-10 to C-18 with a predominance of the C-12 (lauryl) component. By distillation of the fatty alcohol, certain cuts can be obtained which offer the best effects in foaming, cleansing, and rinsing properties for the alkyl sulfate preparation. The range which appears to be most desirable is between C-12 and C-16. Lauryl sulfate detergents are available in various salt forms with the sodium, ammonium, and triethanolamine types being used most frequently in shampoos. 

Alkyl phosphates, preparation, 16, 9 Alkyl sulfates, preparation, 19, 27 Alkyl sulfides, preparation, 15, 72 Alkyl sulfites, preparation, 19, 29 Ai-AlkyW -toluidines, 18,42 Allanioin, 13,1 Allyl alcohol, 10, 107 16, 85 Allylamine, 18, 5 Allyl cyanide, 16, 85 Allyl isothiocyanate, 18, 5 Alumina, 17, 27... 

AlkylPtherSulfates. These surfactants are also found in shampoo appHcations. They are prepared similarly to alkyl sulfates except that the fatty alcohol is... 

A.lkyl Sulfosuccinate Half Asters. These detergents are prepared by reaction of maleic anhydride and a primary fatty alcohol, followed by sulfonation with sodium bisulfite. A typical member of this group is disodium lauryl sulfosucciaate [26838-05-1]. Although not known as effective foamers, these surfactants can boost foams and act as stabilizers when used ia combination with other anionic surfactants. In combination with alkyl sulfates, they are said to reduce the irritation effects of the latter (6). 

Mono- and dialkyl derivatives can also be prepared using alkyl sulfates. Aryl chlorides are usually inert, unless activated by an electron-withdrawing group. Conversion to alkoxides allows formation of ethers. 

Polyphosphoric acid, P2O5, POCl, and PCl are suitable phosphorylatiag agents. Reaction of an alkyl sulfate with sodium pyrophosphate has also been reported for preparation of alkyl pyrophosphates (77). In general, phosphorylation leads to a mixture of reaction products that are sold without further separation. Thus, when lauryltri(ethyleneoxy)ethanol reacts with 0.3 mol of P2O5 at 50°C and is neutralized with 50% aqueous NaOH, the reaction mixture contains the foUowiag products ... 

N-Alkylations, especially of oxo-di- and tetra-hydro derivatives, e.g. (28)->(29), have been carried out readily using a variety of reagents such as (usual) alkyl halide/alkali, alkyl sulfate/alkali, alkyl halide, tosylate or sulfate/NaH, trialkyloxonium fluoroborate and other Meerwein-type reagents, alcohols/DCCI, diazoalkanes, alkyl carbonates, oxalates or malon-ates, oxosulfonium ylides, DMF dimethyl acetal, and triethyl orthoformate/AcjO. Also used have been alkyl halide/lithium diisopropylamide and in one case benzyl chloride on the thallium derivative. In neutral conditions 8-alkylation is observed and preparation of some 8-nucleosides has also been reported (78JOC828, 77JOC997, 72JOC3975, 72JOC3980). 

Imidazolium PFg or BF4 salts were frequently used as solvent for the present lipase-catalyzed reaction. However, these salts are very expensive, and we should develop cheaper ILs. Imidazolium alkyl sulfates might be good candidates because various types of alkyl sulfates can be easily prepared. The imidazolium alkyl sulfate was prepared starting from the corresponding ammonium alkyl sulfate as follows ammonium alkyl sulfates ([NH4][RS04]) are easily prepared by the reaction of... 

We recently prepared various types of differently fiuorinated alkyl sulfate ILs and discovered that the hydrophobicity was dependent on the content ratio of the fluorine on the alkyl sulfate anion and 2,2,3,3,4,4,5,5-octafiuoropentyl sulfate salts showed hydrophobic properties. Melting point and viscosity were also dependent on the fluorine contents of the anionic part, while conductivity was determined by the cationic part and not influenced by the fluorine contents. Efficient lipase-catalyzed transesterificafion was demonstrated using hydrophobic 1-butyl-3-methylimidazolium 2,2,3,3,4,4,5,5-octafiuoropentyl sulfate ([bmim][C5E8]) as solvent (Eig. 6). ... 

Commercial AESs are produced via sulfation of AEs, which are also directly used as non-ionic surfactants (see below). AES preparations typically also contain some level of alkyl sulfates. The majority of technical AES blends are obtained from AE feed stocks that have alkyl chains in the range of 12-15 and an average degree of ethoxylation of three. 

Cosmetic Rinse off Preparations. In certain cosmetic products, tor example hair shampoos, it is not possible to use complexing agents because of the irritation of mucous membranes. Here a low sensitivity of surfactants to water hardness is a precondition for their application. Foam formation is generally considered to be a measure of shampoo quality (Table V). With increase in water hardness the foam volume of alkyl sulfates decreases very much, whereas with the corresponding alkyl ether sulfates this decrease is relatively small. For cosmetic applications, the good skin compatibility and low irritation to mucous membranes of alkyl ether sulfates is of high importance (37). 

Another class of detergents that merits attention is represented by the alkyl sulfates. These materials have been prepared by the direct sulfation of high boiling olefins resulting from the cracking of paraffin wax or the sulfation of alcohols derived from petroleum. 

Alkyl halides or alkyl sulfates, treated with the salts of sulfinic acids, give sulfones.795 Alkyl sulfinates R SO—OR may be side products.796 Sulfonic acids themselves can be used, if DBU (p. 1023) is present.797 Sulfones have also been prepared by treatment of alkyl halides with tosylhydrazide. ... 

The composition data obtained for the series of mixed fatty acid-potassium soap systems, prepared by both the ethanol and petroleum ether routes, lend strong support to the formation of 1 to 1 acid-soap complexes. It is of interest to inquire into the phase relationships in these two-component systems. A phase diagram presented by McBain and Field (15) for the lauric acid-potassium laurate system shows that compound formation takes place between the two components at the 1 to 1 molar ratio, but the compound undergoes melting with decomposition at 91.3 °C. [A similar type of phase behavior has been reported by us for the sodium alkyl sulfate-alkyl alcohol (9) and sodium alkyl sulfonate-alkyl alcohol (12) systems, but in these cases the stoichiometry is 2 to 1]. 

Methyl- or 2-ethyl-benzo[Z> ]thiophenes are conveniently prepared by treatment of 2-benzo[6]thienyllithium with the appropriate alkyl sulfate <70AHC(11)177). Clemmensen or Wolff-Kishner reductions of the 2-acylbenzo[Z>]thiophenes are useful, but since acylation produces a mixture of the 2- and 3-acyl isomers (Section 3.14.2.4), these must be separated. Cyclization of phenyl phenacyl sulfide with hydrofluoric acid leads exclusively to 2-phenyl-benzo[6]thiophene, and 3-phenylbenzo[6]thiophene can be rearranged to the 2-isomer in hydrofluoric acid (Section 3.15.2.3.2). Aromatization of 2-cycIohexenylbenzo[6]thiophene, obtained by condensation of the 2-lithio reagent with cyclohexanone, gives 2-phenyl-benzo[6]thiophene, and the reaction is adaptable to the 2-(l-naphthyl) derivative also. 

In fact, the reaction of alkoxides with alkyl halides or alkyl sulfates is an important general method for the preparation of ethers, and is known as the Williamson synthesis. Complications can occur because the increase of nucleo-philicity associated with the conversion of an alcohol to an alkoxide ion always is accompanied by an even greater increase in eliminating power by the E2 mechanism. The reaction of an alkyl halide with alkoxide then may be one of elimination rather than substitution, depending on the temperature, the structure of the halide, and the alkoxide (Section 8-8). For example, if we wish to prepare isopropyl methyl ether, better yields would be obtained if we were to... 

Polypyrrole can be prepared with n-alkyl sulfates and sulfonates as anions 490), forming layered structures with a bilayer of the detergent separating layers of polypyrrole. 

Alkyl Sulfates. The alkyl sulfates or alcohol sulfates are prepared very similarly to the ether sulfates shown above. 

The major derivatives of normal primary higher alcohols used in the detergent industry were discussed. These included alcohol ethoxylates, alcohol ether sulfates, and alkyl sulfates. The chemical reactions for preparation of each were also given. 

Laboratory Treatments. Colorfastness of the dyed wool samples was determined in aqueous and nonaqueous media. Colored samples were cut into 2- X 2-in. squares and sandwiched between multifiber fabrics (Test Fabrics) and undyed wool fabrics of the same dimensions. The fabrics were loosely sewn together by hand with white cotton thread. Two surfactants were chosen for the aqueous treatments Tergitol NPX, a nonionic ethoxylated nonylphenol (Union Carbide) and Orvus WA, an anionic sodium alkyl sulfate (Proctor Gamble). Solutions of 0.1% surfactant in distilled water were prepared. Tests were run in 250-mL Erlenmeyer flasks at a liquor-to-cloth ratio of 50 1. The flasks were placed in an Eberbach constant-temperature shaker bath adjusted to 30 °C and an agitation of 40 cycles/min. Treatment time was 1 h, after which the samples were opened and allowed to dry on blotter paper. This same procedure was used for the nonaqueous treatments. Commercial grade tetrachloroethylene (R. R. Street Co.) with and without 1% Aerosol OT, the anionic surfactant sodium sulfosuccinate (Aldrich Chemical) was selected. The treated samples were removed from the liquids, opened, and dried on blotter paper in a ventilated hood. 

Acetylenic Grignard reagents are less active than sodium alkydes but are readily alkylated by benzyl halides as well as by alkyl sulfates and sulfonates.. . The Grignard reagents are conveniently prepared from the acetylenes and ethylmagnesium bromide in ether solution. 

Alkylphthalimides, preparation, 676 reaction with hydrazine, 676 Alkyl sulfates, alkylation, of acetylenes by, 80 of alcohols by, 228 of amines by, 667-669 of 6-keto esters by, 347 of ketones by, 339 of malonic esters by, 489 of nitriles by, 600... 

Olefinic acyl halides, hydrolysis, 418 preparation, 547, 549 preparations listed in table 61, 551 Olefinic alcohols, alkylation by alkyl sulfates, 229 dehydration, 33, 42 isomerization, to aldehydes, 296 to ketones, 349... 

This reaction is analogous to similar methods for the preparation of ethers (methods 113 and 116), Both simple and mixed sulfides may be made from aliphatic mercaptans or thiophenols. The sodium mercaptides are formed from the mercaptans and aqueous or alcoholic solutions of sodium hydroxide or alcoholic sodium ethoxide. Alkylation is effected by halides, alkyl sulfates, or esters of sulfonic acids. The over-all yields of sulfides are usually above 70%. r-Butyl mercaptan is alkylated directly by /-butyl alcohol in strong sulfuric acid to give /-butyl sulfide in 87% yield. ... 

---