Alkyl sulfates reaction

V-Alkylation can also be carried out with the appropriate alkyl haUde or alkyl sulfate. Reaction of aniline with ethylene, in the presence of metallic sodium supported on an inert carrier such as carbon or alumina, at high temperature and pressure yields V/-ethyl- or /V,/V-diethylaniline (11). At pressures below 10 MPa (100 atm), the monosubstituted product predominates. 

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). 

Pyrrohdinone can be alkylated by reaction with an alkyl haUde or sulfate and an alkaline acid acceptor (63,64). This reaction can be advantageously carried out with a phase-transfer catalyst (65). Alkylation can also be accompHshed with alcohols and either copper chromite or heterogenous acid catalysts... 

Sulfates. The chemistry of alkyl sulfates is dominated by two fundamental process types reaction with nucleophiles and reaction as acids. Reaction with nucleophiles results in alkylation. 

Carbanions ia the form of phenyllithium, sodium naphthalene complex, sodium acetyHde, or aromatic Grignard reagents react with alkyl sulfates to give a C-alkyl product (30—33). Grignard reagents require two moles of dimethyl sulfate for complete reaction. 

Reactions other than those of the nucleophilic reactivity of alkyl sulfates iavolve reactions with hydrocarbons, thermal degradation, sulfonation, halogenation of the alkyl groups, and reduction of the sulfate groups. Aromatic hydrocarbons, eg, benzene and naphthalene, react with alkyl sulfates when cataly2ed by aluminum chloride to give Fhedel-Crafts-type alkylation product mixtures (59). Isobutane is readily alkylated by a dipropyl sulfate mixture from the reaction of propylene ia propane with sulfuric acid (60). 

Sulfites. The Hterature concerning dialkyl sulfites is extensive, although less than for sulfates. Reactions involving alkylation are similar to those of sulfates. Sulfites also undergo elimination, transesterification, and isomerization. The last two parallel reactions of phosphites. 

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 ... 

C and 200°C. Catalysts such as aluminum hydrosilicate, phosphoric acid, sulfuric acid, BF3, tertiary amine, or sodium alkyl sulfate are used to increase the reaction rate see Eq. (64). 

The reaction of alkyl sulfates with alkoxide ions is quite similar to 10-12 in mechanism and scope. Other inorganic esters can also be used. One of the most common usages of the reaction is the formation of methyl ethers of alcohols and phenols by treatment of alkoxides or aroxides with methyl sulfate. The alcohol or phenol can be methylated directly, by treatment with dimethyl sulfate and alumina in cyclohexane. Carboxylic esters sometimes give ethers when treated with alkoxides (Bal2 mechanism, p. 473) in a very similar process (see also 10-24). 

Alkyl halides or alkyl sulfates, treated with the salts of sulfinic acids, give sulfones. A palladium catalyzed reaction with a chiral complexing agent led to sulfones with modest asymmetric induction. Alkyl sulfinates (R SO—OR) may be side products. Sulfonic acids themselves can be used, if DBU (p. 1337) is... 

Reaction between organometallic reagents and alkyl sulfates or... 

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... 

The alkylation reaction is initiated by the activation of the alkene. With liquid acids, the alkene forms the corresponding ester. This reaction follows Markovnikov s rule, so that the acid is added to the most highly substituted carbon atom. With H2S04, mono- and di-alkyl sulfates are produced, and with HF alkyl fluorides are produced. Triflic acid (CF3S020H) behaves in the same way and forms alkyl triflates (24). These esters are stable at low temperatures and low acid/hydrocarbon ratios. With a large excess of acid, the esters may also be stabilized in the form of free carbenium ions and anions (Reaction (1)). 

An interesting variation on sulfated metal oxide type catalysts was presented by Sun et al. (198), who impregnated a dealuminated zeolite BEA with titanium and iron salts and subsequently sulfated the material. The samples exhibited a better time-on-stream behavior in the isobutane/1-butene alkylation (the reaction temperature was not given) than H-BEA and a mixture of sulfated zirconia and H-BEA. The product distribution was also better for the sulfated metal oxide-impregnated BEA samples. These results were explained by the higher concentration of strong Brpnsted acid sites of the composite materials than in H-BEA. 

This enzyme [EC 2.S.2.2], also referred to as hydroxyste-roid sulfotransferase, catalyzes the reaction of 3 -phos-phoadenylylsulfate with an alcohol to produce adenosine 3, 5 -bisphosphate and an alkyl sulfate. The alcohols that can act as substrates include ahphatic alcohols, ascorbate, chloramphenicol, ephedrine, hydroxysteroids, and other primary and secondary alcohols. However, phenolic steroids will not serve as substrates (such alcohols can be acted upon by steroid sulfotransferases). 

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

Alkyl sulfates, tosylates, and other esters of sulfuric and sulfonic acids can be converted to alkyl halides with any of the four halide ions.979 Neopentyl tosylate reacts with Cl, Br, or I without rearrangement in HMPA.980 Similarly, allylic tosylates can be converted to chlorides without allylic rearrangement by reaction with LiCl in the same solvent.981 Inorganic esters are intermediates in the conversion of alcohols to alkyl halides with SOCl2, PC15, PC13, etc. (0-67), but are seldom isolated. 

Reduction of the C—N bond 0-86 Coupling of alkyl halides (Wurtz) 0-87 Coupling of alkyl halides with or-ganometallic reagents 0-89 Reaction between organometallic reagents and alkyl sulfates or sulfonates... 

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. 

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