Ethylene sulfate, reactions

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. 

These reactions iavolve mostly dimethyl and diethyl sulfate. CycHc sulfates are also reactive, and several have been compared by determining reaction rates with a substituted pyridine or with water (40). In both cases, 1,2-ethylene sulfate is more reactive than 1,3-propylene sulfate or dimethyl or diethyl sulfates. 

The sulfation reaction occurs in the liquid phase at approximately 35 °C. An 85 wt% alcohol yield could be realized. The reaction is similar to the sulfation of ethylene or propylene and results in a mixture of sec-butyl hydrogen sulfate and di-sec-butyl sulfate. The mixture is further hydrolyzed to sec-butanol and sulfuric acid ... 

Alkyl-substituted 1,3,2-dioxathiolane 2,2-dioxides can be prepared in a similar manner to the parent compound, ethylene sulfate (18) (66HC(2l-l)i) (cf. Scheme 10, Section 4.33.4.2.1). The method of choice is the permanganate oxidation of the corresponding cyclic sulfites (cf. Section 4.33.3.2.3) since the direct reaction of 1,2-diols with sulfuryl chloride often proceeds less smoothly than does the reaction with thionyl chloride. 4,5-Diaryl-l,3,2-dioxathiole 2,2-dioxides of type (186) are obtained by treatment of 9,10-... 

IZV118) and the formation of (31) is analogous to the reaction (197)->(98) via a four-membered 1,2-oxathietane 2,2-dioxide intermediate. Subsequent products derived from (31) by electrophilic addition reactions at the alkenic double bond have been described in Section 4.33.3.2.2 and the synthesis of 4,5-dichloro-l,3,2-dioxathiolane 2,2-dioxide (154) by chlorination of ethylene sulfate (18) is discussed in Section 4.33.3.5. Cyclic sulfites, on the other hand, cannot be halogenated without ring opening (cfSection 4.33.3.2.4). 

It is in this sense that cyclic sulfates are superior to epoxides. Further examples of double displacement reactions of cyclic sulfates are cited vide infra). In the absence of neighboring group participation, a -substituted ethylene sulfate may undergo an elimination reaction to furnish olefin. For example, when a cyclic sulfate was treated with sodium naphthalide in TFIF, only alkene 127 was obtained (90SL479) [Eq. (28)]. 

Reactions with ethylene sulfate Synthesis of sulfuric acid monoesters... 

Cetyl-stearyl stearate. See Cetearyl stearate Cetyl sulfate, sodium saH. See Sodium cetyl sulfote Cetyltrimethylammonium bromide. See Cetrimonium bromide Cetyl trimethyl ammonium chloride. See Cetrimonium chloride Cetyl trimethyl ammonium p-toluene sulfonate. See Cetrimonium tosylate Cevitamic acid. See L-Ascorbic acid Ceylon isinglass. See Agar C12 fotty alcohol ethoxylate. See Laureth (C16-18) fotty alcohol, ethylene oxide reaction prod.. See Ceteareth CFC113. See Trichlorotrifluoroethane Cl 8-20 glycol isostearate CAS 247169-05-7... 

Other acetyl chloride preparations include the reaction of acetic acid and chlorinated ethylenes in the presence of ferric chloride [7705-08-0] (29) a combination of ben2yl chloride [100-44-7] and acetic acid at 85% yield (30) conversion of ethyUdene dichloride, in 91% yield (31) and decomposition of ethyl acetate [141-78-6] by the action of phosgene [75-44-5] producing also ethyl chloride [75-00-3] (32). The expense of raw material and capital cost of plant probably make this last route prohibitive. Chlorination of acetic acid to monochloroacetic acid [79-11-8] also generates acetyl chloride as a by-product (33). Because acetyl chloride is cosdy to recover, it is usually recycled to be converted into monochloroacetic acid. A salvage method in which the mixture of HCl and acetyl chloride is scmbbed with H2SO4 to form acetyl sulfate has been patented (33). 

According to this mechanism, the reaction rate is proportional to the concentration of hydronium ion and is independent of the associated anion, ie, rate = / [CH3Hg][H3 0 ]. However, the acid anion may play a marked role in hydration rate, eg, phosphomolybdate and phosphotungstate anions exhibit hydration rates two or three times that of sulfate or phosphate (78). Association of the polyacid anion with the propyl carbonium ion is suggested. Protonation of propylene occurs more readily than that of ethylene as a result of the formation of a more stable secondary carbonium ion. Thus higher conversions are achieved in propylene hydration. 

Fats, Oils, or Fatty Acids. The primary products produced direcdy from fats, oils, or fatty acids without a nitrile iatermediate are the quatemized amidoamines, imidazolines, and ethoxylated derivatives (Fig. 3). Reaction of fatty acids or tallow with various polyamines produces the iatermediate dialkylarnidoarnine. By controlling reaction conditions, dehydration can be continued until the imidazoline is produced. Quaternaries are produced from both amidoamines and imidazolines by reaction with methyl chloride or dimethyl sulfate. The amidoamines can also react with ethylene oxide (qv) to produce ethoxylated amidoamines which are then quaternized. 

Sulfation by sulfamic acid has been used ia the preparation of detergents from dodecyl, oleyl, and other higher alcohols. It is also used ia sulfating phenols and phenol—ethylene oxide condensation products. Secondary alcohols react ia the presence of an amide catalyst, eg, acetamide or urea (24). Pyridine has also been used. Tertiary alcohols do not react. Reactions with phenols yield phenyl ammonium sulfates. These reactions iaclude those of naphthols, cresol, anisole, anethole, pyrocatechol, and hydroquinone. Ammonium aryl sulfates are formed as iatermediates and sulfonates are formed by subsequent rearrangement (25,26). 

Passing a stream of nitrogen at 95—100°C through a reaction mixture of ethyl ether and 30 wt % oleum prepared at 15°C results in the entrainment of diethyl sulfate. Continuous operation provides a >50% yield (96). The most economical process for the manufacture of diethyl sulfate starts with ethylene and 96 wt % sulfuric acid heated at 60°C. The resulting mixture of 43 wt % diethyl sulfate, 45 wt % ethyl hydrogen sulfate, and 12 wt % sulfuric acid is heated with anhydrous sodium sulfate under vacuum, and diethyl sulfate is obtained in 86% yield the commercial product is >99% pure (97). 

Where X is Br or Q, the free acids may be obtained by acidification of the alkaline solution, but where X is I, the acids must be isolated as salts to avoid reduction of the arsonic acids by HI. Rather than using alkyl haUdes, alkyl or dialkyl sulfates or alkyl arenesulfonates can be used. Primary alkyl haUdes react rapidly and smoothly, secondary haUdes react only slowly, whereas tertiary haUdes do not give arsonic acids. AHyl haUdes undergo the Meyer reaction, but vinyl hahdes do not. Substituted alkyl haUdes can be used eg, ethylene chlorohydrin gives 2-hydroxyethylarsonic acid [65423-87-2], C2H2ASO4. Arsinic acids, R2AsO(OH), are also readily prepared by substituting an alkaU metal arsonite, RAs(OM)2, for sodium arsenite ... 

Other polyamine derivatives are used to break the oil/water emulsions produced at times by petroleum wells. Materials such as polyether polyols prepared by reaction of EDA with propylene and ethylene oxides (309) the products derived from various ethyleneamines reacting with isocyanate-capped polyols and quaternized with dimethyl sulfate (310) and mixtures of PEHA with oxyalkylated alkylphenol—formaldehyde resins (311) have been used. 

The reaction is cataly2ed by all but the weakest acids. In the dehydration of ethanol over heterogeneous catalysts, such as alumina (342—346), ether is the main product below 260°C at higher temperatures both ether and ethylene are produced. Other catalysts used include siUca—alumina (347,348), copper sulfate, tin chloride, manganous chloride, aluminum chloride, chrome alum, and chromium sulfate (349,350). 

Dinitroiodobenzene has been prepared by the nitration of 0- or /)-nitroiodobenzene, by treatment of 2,4-dinitrobenzenedi-azonium sulfate with potassium iodide, and by the reaction of sodium iodide with 2,4-dinitrochlorobenzene in refluxing ethylene glycol. The present procedure is a modification of the last-mentioned one. 

A stream of ethylene oxide is passed through a solution of 107 g of 2-(p-chlorophenoxy)-2-methylpropionic acid and 2 g of zinc chloride in 200 ml of toluene, previously heated to between 55°C and 60°C, until 24 g of the gas have been dissolved. The reaction is allowed to continue for five hours, with gentle stirring. After this time has elapsed, the solution is cooled and washed successively with water, dilute ammonia and water until its pH becomes neutral. It is dried over anhydrous sodium sulfate, the solvent Is separated off under vacuum, and the resulting liquid is the monoglycol ester of 2-(p-chlorophenoxv)-2-methylpropionlc acid. 

The reaction mixture was then shaken with 110 ml.of water and the organic and aqueous layers separated. The organic layer was dried over sodium sulfate and evaporated under diminished pressure giving a residue. The thus obtained residue was recrystallized from methanol giving 2.68 g of 11-keto-6j3-methylprogesterone 3,20-bis-(ethylene ketal) having a MP of 168° to 175°C. 

Older processes still use the sulfation route. The process is similar to that used for ethylene in the presence of H2SO4, hut the selectivity is a little lower than the modern vapor-phase processes. The reaction conditions are milder than those used for ethylene. This manifests the greater ease with which an isopropyl carhocation (a secondary carhonium ion) is formed than a primary ethyl carhonium ion ... 

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