Alkyl sulfates with active hydrogen

Amino acid synthesis (8, 389). Alkylation of the aldimine (1) from glycine ethyl ester and /j-chlorobenzaldehyde under phase-transfer conditions offers a general route to amino acids. Either liquid-liquid phase-transfer or solid-liquid phase-transfer catalytic conditions are satisfactory with active halides, but alkylation with allylic halides and less active alkyl halides is best effected under ion-pair extraction conditions (6,41), with 1 equiv. of tetra-n-butylammonium hydrogen sulfate (76-95% yields).1... 

The chlorosulfonic acid-ether complex is a milder reagent than free chlorosulfonic acid for the sulfation of alcohols and is outstanding in respect of yield and purity of the alkyl hydrogen sulfates 45 produced. The use of chlorosulfonic acid in diethyl ether at low temperature (-50 °C) is a standard method for sulfation of higher (Cg-C28) primary and secondary alcohols. The latter have also been successfully sulfated using a mixture of chlorosulfonic acid in acetic acid the active entity here is probably acetyl sulfate. This method has been adapted for the synthesis of very pure sodium alkyl sulfates for use as detergents thus chlorosulfonic acid and 1-dodecanol were successively added to acetic acid at low temperature (—10 to -15 °C), the solid product was neutralized with sodium carbonate and unreacted alcohols extracted with solvents to give 98.6% pure dodecanyl sodium sulfate. ... 

Sinou and co-workers [73] studied the influence of different surfactants on the palladium-catalyzed asymmetric alkylation of l,3-diphenyl-2-propenyl acetate with dimethyl malonate in presence of potassium carbonate as base and non-water-soluble chiral ligands. Best results in activity and enatioselectivity (> 90% ee) were observed with 2,2 -bis(diphenylphosphino)-l,l -binaphthyl (BINAP) as ligand and cetyltrimethylammonium hydrogen sulfate as surfactant in aqueous medium. Water-stable Lewis acids as catalysts for aldol reactions were developed by Kobayashi and co-workers [74]. An acceleration of the reaction was indicated in presence of SDS as anionic surfactants. An additional promotion could be observed by combination of Lewis acid and surfactant (LASCs = Lewis acid-surfactant-combined catalysts) as shown in Eq. (3). Surfactant the anion of dodecanesulfonic acid. 

The palladium-catalyzed asymmetric alkylation of l,3-diphenyl-2-propenyl acetate with dimethyl malonate could be influenced in activity and enantioselectivity by the surfactant cetyltrimefhylammonium hydrogen sulfate [24],... 

Arata and coworkers studied extensively the alkylation of toluene with alkyl halides. They found that iron (II, or III) sulfate, when calcined at 973 K, became good catalysts for benzylation, benzoylation of toluene and also for polycondensation of benzyl chloride.Later, they found that the activity is significantly enhanced by treating the catalyst with hydrogen chloride. ... 

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