Sulfuric acid esters alcohols

On evaporating the alcoholic solution under reduced pressure from a water bath held at 50-60° (Note 6) the residue weighs about 540 g. A mixture of 600 cc. of absolute alcohol and 10 cc. of concentrated sulfuric acid (Note 7) is then added. The mixture is then heated on the water bath under a reflux condenser for three hours. The excess of alcohol and some of the water formed are removed by distillation under reduced pressure and the residue again heated for two hours with 300 cc. of absolute alcohol and an additional 4 cc. of concentrated sulfuric acid. The alcohol is removed by distillation under reduced pressure, and when the ester has cooled to room temperature, the sulfuric acid is neutralized with a concentrated solution of sodium carbonate the ester (upper layer) is separated, and the aqueous solution extracted with ether, or preferably benzene about one-tenth of the yield is in the extract. The combined products are placed in a i-l. distilling flask and distilled under reduced pressure after the solvent and alcohol and water have been removed. The ester is collected at 94-990, chiefly at 97-98°/x6 mm. (Note 8). The yield of a product analyzing about 97-98 per cent ethyl cyanoacetate amounts to 474-492 g. (77-80 per cent of the theoretical amount) (Note 9). 

Acid-catalyzed reactions require the use of high alcohol-to-oil molar ratios in order to obtain good product yields in practical reaction times. However, ester yields do not proportionally increase with molar ratio. For instance, for soybean methanolysis using sulfuric acid, ester formation sharply improved from 77% using a methanol-to-oil ratio of 3.3 1 to 87.8% with a ratio of 6 1. Higher molar ratios showed only moderate improvement until reaching a maximum value at a 30 1 ratio (98.4%)." " " ... 

At a considerably later date. Frankland prepared ethyl methacrylate and methacrylic acid from ethyl a-hydroxyisobutyrate and phosphorus trichloride. Tollen prepared aciylate esters from 2,3-dibromopropionate esters and zinc. Otto Rohm, in 1901. described the structures of the liquid condensation products (including dimers and timers) obtained from the action of sodium alkoxides on methyl and ethyl acrylate. Shortly after World War 1, Rohm introduced a new acrylate synthesis, noting that an acrylate is formed in good yield from heating ethylene cyanohydrin and sulfuric acid and alcohol. A major incentive for the development of a clear, tough plastic acrylate was for use in the manufacture of safety glass. 

In addition to forming esters with carboxylic acids, alcohols form inorganic esters with inorganic acids such as nitric acid, sulfuric acid, and phosphoric acid. In each type of ester, the alkoxy (—OR) group of the alcohol replaces a hydroxyl group of the acid, with loss of water. We have already studied tosylate esters, composed of para-toluenesulfonic acid and alcohols (but made using tosyl chloride, Section 11-5). Tosylate esters are analogous to sulfate esters (Section 11-13A), which are composed of sulfuric acid and alcohols. 

Ethylenimine is conveniently prepared from ethanolamine by heating the inner salt of the sulfate ester with aqueous alkali (37%). The method has been applied to other /3-amino alcohols to form the C-alkyl homologs of ethylenimine in which one to three of the four hydrogens may be substituted. The general procedure is illustrated by the synthesis of 2,2-dim ethyl ethylenimine (51%). The N-alkyl analogs can be made by treating the N-alkylethanolamine hydrochlorides with chlorosulfonic acid followed by the action of base on the intermediate sulfuric acid esters, as in the preparation of N-ethylethylenimine (70%). ... 

The reagent is a mild sulfonating agent. It reacts with alcohols and phenols to form amine salts of the sulfuric acid ester. A mixture of 0.05 mole each of... 

The hydration of olefins to alcohols has been carried out on a large scale by hydrolyzing the sulfuric acid esters formed by the absorption of the olefins in sulfuric acid. In the case of the higher olefins these reactions occur with comparative ease. Thus, isobutylene may be hydrated to tertiary butanol in cold, moderately concentrated sulfuric acid.81 Some of the pentenes and heptenes may be hydrated in dilute (5 to 10 per cent) solutions of formic, acetic, or oxalic acids as well as in weak solutions of the mineral acids.83 With 60 per cent concentrations of hydroiodic acid, isobutylene yields the iodide almost exclusively, but at lower concentrations increasing amounts of the alcohol are fonned84 Similar phenomena attend the absorption of the higher olefins in hydrobromic acid. Hydrochloric acid, on the other hand, does not show such marked activity toward the higher olefins ind is practically devoid of activity toward ethylene. 

Synonyms Lauryl alcohol, polymer with oxirane, sulfuric acid ester, 2-hydroxy-1-aminopropane salt Monoisopropanolamine lauryl ether sulfate Poly(oxy-1,2-ethanediyl), o-sulfo-cu-(dodecyloxy)-, compd. with 1-amino-2-propanol... 

Definition Sulfuric acid ester of the triisopropanolamine salt of ethoxylated lauryl alcohol... 

To use sodium alkyl sulfate as a standard material, one has to ensure that the substance does not contain any impurities. One of the ways to create such a pure substance is to use the reaction of n-dodecanol with an adduct of chlorosulfuric acid and diethyl ether. The fatty alcohol is added to the ether solution while being cooled with ice. A stoichiometric surplus of 5-10% of chlorosulfuric acid is used to avoid forming the dialkyl sulfuric acid ester. The major part of the hydrogen chloride gas formed will evaporate. 

The alcohol dodecanol already encountered can be sulfated by a relatively simple process to produce the dodecane sulfuric acid ester, having a carbon-oxygen-sulfur linkage... 

Alkylsulfates. The salts of sulfuric acid ester form the alkyl sulfate surfactant family. They are produced by sulfation with sulfur trioxide of linear alcohols ... 

Sulfuric acid esters with alcoholic or phenolic hydroxy groups, the mixed anhydrides adenosine-5 -sulfatophosphate and its 3 -phosphorylated derivative, as well as secondary products derived from L-cysteine occur in microorganisms, plants and animals. Sulfuric acid amides, e.g., the glucosinolates (D 9.4), are formed in certain plants. 

Alkyl sulfates, also called alcohol sulfates, are formed by making the sulfuric acid esters of linear alcohols. Alkyl chain lengths range from Cp) to Cig. The properties of the alkyl sulfates vary with the alkyl chain length distribution. The alcohol source can be either natural (linear) or synthetic oxo (some branching) alcohols. About 15% of the detergent range alcohols in the United States come from saponification of natural oil and fat. Products are called, for example, tallow alcohol sulfate or coconut alcohol sulfate. They tend to... 

The amide group is readily hydrolyzed to acrylic acid, and this reaction is kinetically faster in base than in acid solutions (5,32,33). However, hydrolysis of N-alkyl derivatives proceeds at slower rates. The presence of an electron-with-drawing group on nitrogen not only facilitates hydrolysis but also affects the polymerization behavior of these derivatives (34,35). With concentrated sulfuric acid, acrylamide forms acrylamide sulfate salt, the intermediate of the former sulfuric acid process for producing acrylamide commercially. Further reaction of the salt with alcohols produces acrylate esters (5). In strongly alkaline anhydrous solutions a potassium salt can be formed by reaction with potassium / /-butoxide in tert-huty alcohol at room temperature (36). 

Esters. Most acryhc acid is used in the form of its methyl, ethyl, and butyl esters. Specialty monomeric esters with a hydroxyl, amino, or other functional group are used to provide adhesion, latent cross-linking capabihty, or different solubihty characteristics. The principal routes to esters are direct esterification with alcohols in the presence of a strong acid catalyst such as sulfuric acid, a soluble sulfonic acid, or sulfonic acid resins addition to alkylene oxides to give hydroxyalkyl acryhc esters and addition to the double bond of olefins in the presence of strong acid catalyst (19,20) to give ethyl or secondary alkyl acrylates. 

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