Dialkyl sulfate

Dialkyl sulfates are esters of sulfuric acid tnalkyl phosphites are esters of phos phorous acid (H3PO3) and tnalkyl phosphates are esters of phosphoric acid (H3PO4)... 

Formation of esters of inorganic acids (Section 15 9) Alkyl nitrates dialkyl sulfates trialkyl phos phites and trialkyl phosphates are examples of alkyl esters of inor game acids In some cases these compounds are prepared by the direct reaction of an alcohol and the inorganic acid... 

All lation. Alkylating agents such as diaLkyl sulfates and alkyl hahdes react with ahphatic amine oxides to form trialkylalkoxyammonium quaternaries. For example (33), methyl iodide reacts with trimethyl amine oxide to form trimethylmethoxyammonium iodide... 

Alkenes. The sulfation of low molecular weight alkenes using concentrated sulfuric acid is amenable to continuous operation. Good agitation is required and the reaction is performed at 70—80°C. Dialkyl sulfates ate also formed. Longer (C 2 i8) carbon chain alkenes yield detergent products. Order... 

Stabihty depends mosdy on purity, with purer materials having longer shelf Hves (1). For the higher alkyl groups, the anhydrous compounds are soluble and the monohydrates are insoluble in ether. Solutions in water are strongly ionized and acidic. The lower dialkyl sulfates are Hquids with faint but pleasant odors n-nonyX and higher normal aHphatic and cycHc sulfates are soHds. 

All lation. In alkylation, the dialkyl sulfates react much faster than do the alkyl haHdes, because the monoalkyl sulfate anion (ROSO ) is more effective as a leaving group than a haHde ion. The high rate is most apparent with small primary alkyl groups, eg, methyl and ethyl. Some leaving groups, such as the fluorinated sulfonate anion, eg, the triflate anion, CF SO, react even faster in ester form (4). Against phenoxide anion, the reaction rate is methyl triflate [333-27-7] dimethyl sulfate methyl toluenesulfonate [23373-38-8] (5). Dialkyl sulfates, as compared to alkyl chlorides, lack chloride ions in their products chloride corrodes and requires the use of a gas instead of a Hquid. The lower sulfates are much less expensive than lower bromides or iodides, and they also alkylate quickly. 

CycHc esters show accelerated hydrolysis rates. Ethylene sulfate compared to dimethyl sulfate is twice as fast ia weak acid (first order) and 20 times as fast ia weak alkaH (second order) (50). Catechol sulfate [4074-55-9] is 2 x 10 times faster than diphenyl sulfate ia alkaline solution (52). Alcoholysis rates of several dialkyl sulfates at 35—85°C are also known (53). 

Studies of reaction mechanisms ia O-enriched water show the foUowiag cleavage of dialkyl sulfates is primarily at the C—O bond under alkaline and acid conditions, and monoalkyl sulfates cleave at the C—O bond under alkaline conditions and at the S—O bond under acid conditions (45,54). An optically active half ester (j -butyl sulfate [3004-76-0]) hydroly2es at 100°C with iaversion under alkaline conditions and with retention plus some racemization under acid conditions (55). Effects of solvent and substituted stmcture have been studied, with moist dioxane giving marked rate enhancement (44,56,57). Hydrolysis of monophenyl sulfate [4074-56-0] has been similarly examined (58). 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Detergents have been manufactured from long-chain alkenes and sulfuhc acid, especially those obtained from shale oil or cracking of petroleum wax. These are sulfated with 90—98 wt % acid at 10—15°C for a 5-min contact time and at an acid—alkene molar ratio of 2 1 (82). Dialkyl sulfate initially forms when 96 wt % acid is added to 1-dodecene at 0°C, but it is subsequently converted to the hydrogen sulfate in 80% yield upon the further addition of sulfuhc acid. The yield can be increased to 90% by using 98 wt % sulfuhc acid and pentane as the solvent at -15°C (83). 

Diorgano Sulfates. Dialkyl sulfates up to octadecyl can be made from the alcohols by a general method involving the following reactions (90) ... 

The only commercially important dialkyl sulfates are dimethyl sulfate and diethyl sulfate. Estimated worldwide production in 1996 for dimethyl sulfate was 90,000 metric tons per year. Dimethyl sulfate was initially made by vacuum pyrolysis of methyl hydrogen sulfate ... 

Lower dialkyl sulfates were made from the alcohols in earlier work the reaction mass at ca 100°C was stripped by a recirculated inert-gas stream, and the product was recovered by passage through a partial condenser. Yields of 90% for diethyl sulfate and 85% for dimethyl sulfate were reported (98). 

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 ... 

Formation of Ethers. Very high ether yields can be obtained from alcohols and phenols with dialkyl sulfates in CH2CI2 and concentrated NaOH—tetrabutylammonium chloride at room temperature or slightly elevated temperature within 1—5 h (18). Using excess aqueous caustic—N(C4H2)4HS04, unsymmetrical aUphatic ethers can be prepared with alkyl chlorides at 25—70°C in 3—4 h (19) (see Ethers). 

Dialkyl sulfates can replace the halogen derivatives, and this modification is especially useful for the preparation of phenoHc ethers ... 

IV-Methylated pyridazinones can be obtained from 3,6-dialkoxypyridazines by treatment with alkyl halides or dialkyl sulfates. Methyl iodide and dimethyl sulfate are most frequently used. According to the proposed mechanism, an intermediate quaternary pyridazinium salt is formed, followed by elimination of a group R from the alkoxy group. At higher temperature, l,2-dimethylpyridazine-3,6(l//,2//)-dione is formed with dimethyl sulfate. 

Sulfonates react with a variety of nucleophiles. Synthesis of M A -bis(trifluoro-methyl)aminotnfluoromethanesulfonate and its reactions with nucleophiles were investigated [33] (equation 31) (Table 13). Nucleophilic attack occurs at either nitrogen or sulfur amines give complex mixtures [33]. Polyfluoroalkyl fluorosul-fates react with amines, alcohols, or alkoxides to yield polyfluoroalkyl sulfamates and dialkyl sulfates, respectively [34] (equation 32) (Table 13). In these reactions. 

The alkylation of 6-azauracil will be treated later. The first, but not exactly identified dimethyl derivative was prepared by Grundmann." The course of alkylation was studied in greater detail by Gut et al. These authors found that in aqueous alkaline solution and on using alkyl halides or dialkyl sulfates, the main alkylation product is the 1,3-dialkyl derivative (64). Since, however, the alkylation is to some... 

As alkylating agents may for example be used alkyl halides, dialkyl sulfates, alkyl sulfonates and epoxides. Aryl halides and vinylic halides do not react. 

As alkylating agent an alkyl halide, alkyl tosylate or dialkyl sulfate is used in most cases the latter type of reagent is often used in the preparation of methyl and ethyl ethers by employing dimethyl sulfate and diethyl sulfate respectively. Dimethyl sulfate is an excellent methylating agent, but is acutely toxic as well as carcinogenic." ... 

The advance of sulfur trioxide as sulfating agent largely depended on advances in sulfonation/sulfation reactor development and changes in raw material quality. Undiluted sulfur trioxide cannot be used as a sulfating agent except in special cases where suitable equipment is used because of its violent nature. Sulfur trioxide diluted in an inert gas, usually air, when used in batch processes can cause excessive dehydration and dark-colored products. However, batch processes were used years ago and inert liquid solvents were often suggested or used to moderate the reaction. Inadequate reaction conditions lead to a finished product that can contain dialkyl sulfate, dialkyl ether, isomeric alcohols, and olefins whereas inadequate neutralization conditions can increase the content of the parent alcohol due to hydrolysis of the unstable acid sulfate accompanied by an increase of mineral sulfate. 

An important feature of sulfation chemistry is the thermal instability of the acid sulfate, which breaks down to a mixture of products including the parent alcohol, the dialkyl sulfate (R0S020R), the dialkyl ether (ROR), isomeric alcohols, olefins (R CH=CH2), and esters (R0S03R). Because of the thermal instability of the acid sulfate it is necessary to avoid high sulfation temperatures and to neutralize the acid sulfation product soon after its formation. An aging time of about 1 min at 30-50°C is adequate for the second reaction whereby the desired alkyl hydrogen sulfate is formed. In practice the minimum sulfation feasible temperature is determined by the need for the feedstock and reaction mixture to be mobile liquids (Table 3). 

The alkoxide ion reacts with the substrate in an SN2 reaction, with the resulting formation of the ether. The substrate must bear a good leaving group. Typical substrates are alkyl halides, alkyl sulfonates, and dialkyl sulfates, i.e. 

In the present procedure, the method of Decker and Becker 3 has been modified by substitution of a dialkyl sulfate for the corresponding alkyl halide. 

The method gives better yields, utilizes more readily available starting materials, and is much less laborious than the hydrolysis of N-methyl-N-alkylarenesulfonamides and -nitroso-N, N-di-alkylanilines, or the lithium aluminum hydride reduction of alkyl isocyanates. Compared to the closely related procedure of Lucier, Harris, and Korosec,12 in which the N-benzylidenealkyl-amine is treated with dialkyl sulfate at atmospheric pressure, the present procedure tends to give higher yields and purer products, but it is less convenient because of the need for a pressure vessel. 

Af-(2,3-Dihydroimidazo[2,l-6]benzothiazol-6-, 7- and 8-yl)aminomethy-lenemalonates (1474, R2 = H) were alkylated with dialkyl sulfate or alkyl halide in hexamethylphosphortriamide in the presence of sodium hydride to give N-alkyl-N-(2,3-dihydroimidazo[2, l-fe]benzothiazolyl)aminomethy-lenemalonates (1474, R2 = H). The hydrolysis of1474 by heating in boiling dilute hydrochloric acid for 15 min gave alkylamino derivatives (1475) (81EUP21806). 

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