Sulfuric acid, with alcohols

Sulfonimidothiazolines, 317, 318 Sulfonyl halides, with 2-aminothiazoles, 69 Sulfur (Sg), in synthesis of, A-4-thiazoline-2-thione, 373 Sulfur compounds, 69 Sulfuric acid, with alcohols, 38, 47, 80, 90 in bromination, 77 dealkylation by, 39 deuterated, 92 diazotization with, 66 in nitrations, 72 rearrangements in, 73, 113 Sulfuryl chloride, 432 Symbiotic behavior, see HSAB theory Symmetry. C2v and C2p, 120 Synthetic fibers, 154... 

Sulfinic acid amides are obtained in the reaction of sulfinic acids with amines in the presence of DCC." In the reaction of sulfuric acid with alcohols, thioalcohols and amines in the presence of DCC, the respective sulfates, thiosulfates and amides are obtained." The reaction of H3PO4 with DCC, followed by alcohol affords (R0)2P(0)H." ... 

Dhanuka showed that the mechanism of sulfuric acid-catalyzed esterification is the model of alkyl sulfuric intermediate. It s a two-step reaction. R -O-SO3H firstly is generated via sulfuric acid with alcohol, which is treated as a catalyst in the second step (Lide, 1994) ... 

The alkylation reaction of sulfuric acid with alcohol is irreversible (Aranda et al., 2008).Therefore the reaction rate can be expressed as ... 

All lnaphthalenesulfonic Acids. The aLkyLnaphthalenesulfonic acids can be made by sulfonation of aLkyLnaphthalenes, eg, with sulfuric acid at 160°C, or by alkylation of naphthalenesulfonic acids with alcohols or olefins. These products, as the acids or their sodium salts, are commercially important as textile auxiUaries, surfactants (qv), wetting agents, dispersants (qv), and emulsifying aids, eg, for dyes (qv), wettable powder pesticides, tars, clays (qv), and hydrotropes. 

Analytical Methods. The official NIOSH recommended method for determining sulfur dioxide in air consists of drawing a known prefiltered volume of air through a bubbler containing hydrogen peroxide, thus oxidising the sulfur dioxide to sulfuric acid. Isopropyl alcohol is then added to the contents in the bubbler and the pH of the sample is adjusted with dilute perchloric acid. The resultant solution is then titrated for sulfate with 0.005 M. barium perchlorate, and Thorin is used as the indicator. 

The sodium salt of CS [9005-22-5] is prepared by reaction of cellulose with sulfuric acid in alcohol followed by sodium hydroxide neutrali2ation (20). This water-soluble product yields relatively stable, clear, and highly viscous solutions. Introduced as a thickener for aqueous systems and an emulsion stabilizer, it is now of no economic significance. 

Tertiary butyl alcohol (900 ml., 702 g., 9.47 moles) is dissolved in a solution prepared by mixing 28 ml. (0.50 mole) of concentrated sulfuric acid with 1.5 1. of water in a 5-1. round-bottomed flask (Note 1) equipped with a thermometer, stirrer, gas inlet tube, and two addition burets. One buret is charged with 86 ml. (1 mole) of 11.6iH hydrogen peroxide (Note 2), and the other with a solution of 278 g. (1 mole) of ferrous sulfate pentahydrate and 55.5 ml. (1 mole) of concentrated sulfuric acid in 570 ml. of water (Note 3). The reaction flask is swept out with nitrogen and cooled to 10° by means of an ice bath. Stirring is commenced and the two solutions are added simultaneously and equivalently over a period of 20 minutes. The temperature is held below 20°. 

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). 

Alcohol sulfates were first obtained either by the reaction of olefins with sulfuric acid or by sulfation of alcohols produced by hydrogenolysis of oils and fats with sulfuric acid. With the advent of petrochemistry and the progress of chemistry and chemical engineering, alcohol sulfates and their derivatives have become one of the most important surfactants and are produced in large amounts using techniques different from those originally used. They are based on a wide range of alcohols and have found applications in almost all domestic and industrial sectors. 

A continuous process was described in 1939 [29] consisting of bringing together continuously flowing streams of sulfuric acid and alcohol without restraining the resulting rise of temperature, but with an immediate neutralization and cooling of the reaction flow. Inert solvents were used in instantaneous reactions. 

Table I. It is probable that all the indicated yields can be improved. However, using these data as a criterion, it appears that the chloral can be replaced by its hydrate or alcoholate and that a moderate excess of fluorobenzene favors the reaction. There is one report that aluminum chloride brings about this condensation (34), but here, as with DDT, the choice condensing agents are concentrated sulfuric acid (with or without the addition of oleum), and chlorostflfonic acid (84). A moderate temperature and prolonged stirring, which must also be vigorous, increase the yield.

The weak nucleophilic nature of polynitroaliphatic alcohols means that reactions often need to be catalyzed by Brpnsted acids or Lewis acids. The following methods are commonly used for the esterification of polynitroaliphatic alcohols (1) heating a solution of the alcohol and acid in the presence of sulfuric acid with Dean-Stark removal of water ° (2) using the acid chloride or anhydride in the presence of aluminium chloride " (3) reacting the acid and alcohol... 

Currently, the esterification of fatty acids with alcohols is achieved commercially using liquid catalysts, such as sulfuric acid, hydrochloric acid and p-toluenesulfonic acid (Figure 10.4). 

The result of the reaction of sulfur tetrafluoride with alcohols strongly depends on the structure of the alcohol. Simple aliphatic alcohols, such as methanol, ethanol and propan-2-ol, give alkyl ethers as the main product with only small amounts of fluoroalkanes.41 42 Yields of fluorinated products increase with increasing acidity of the hydroxy group and, in general, the reaction is only synthetically useful with alcohols equally or more acidic than tropolone (p K, = 6.42). 

Halide formation proceeds at a useful rate only in the presence of strong acid, which can be furnished by excess hydrogen bromide or, usually and more economically, by sulfuric acid. The alcohol accepts a proton from the acid to give an alkyloxonium ion, which is more reactive in subsequent displacement with bromide ion than the alcohol (by either SN2 or SN1 mechanisms) because H20 is a better leaving group than eOH ... 

In the reaction of an alcohol with hot concentrated sulfuric acid, the alcohol is dehydrated to an alkene ... 

Reactions of 2-[l-(thietan-3-yl)-benzimidazolyl-2-thio]acetic acid 43a and 2-[T(l,l-dioxothietan-3-yl)-benzimida-zolyl-2-thio]acetic acid 43b with bases (amino alcohols or sodium hydroxide) led to the corresponding salts 44a-h. By treatment of the ethyl esters 45a and 45b, obtained by the reaction of acids 43a and 43b with ethanol in the presence of sulfuric acid, with hydrazines, (benzimidazolyl-2-thio)acetic acid hydrazides 46a and 46b were synthesized and subsequently converted into the corresponding dihydrochlorides 47a and 47b (Scheme 16). Salts 44a-h and 47a and 47b were tested as immunotropic compounds <2001PCJ11>. 

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. 

Direct esterification of methacrylic acid with alcohols using sulfuric acid or other catalysts can be used to prepare methyl methacrylate (MMA) and other esters. Commercial routes for the direct preparation of MMA and some lower alkyl esters also exist. In the 1990s, researchers at Shell developed a direct route to MMA from propyne (methylacetylene), carbon monoxide, and methanol using a Pd(II) catalyst. The limited availability of propyne may slow the expansion of this highly efficient route to high purity MMA. Transesterification of MMA is often the preferred route for the preparation of other esters. 

Test Solution Transfer an accurately weighed amount of sample, equivalent to about 200 mg of a-tocopherol, into a 150-mL round-bottom, glass-stoppered flask, and dissolve it in 25 mL of absolute alcohol. Add 20 mL of a 1 7 mixture of 2 N sulfuric acid in alcohol, and reflux in an all-glass apparatus for 3 h, protected from sunlight. Cool, transfer into a 200-mL volumetric flask, dilute to volume with a 1 72 mixture of 2 N sulfuric acid in alcohol, and mix. Retain 10 mL of this solution for Identification Test A (above). 

Acetic acid or acetates, when warmed with sulfuric acid and alcohol, form ethyl acetate, recognizable by its characteristic odor. With neutral solutions of acetates, ferric chloride TS produces a deep red color that is destroyed by the addition of a mineral acid. 

Sulfuric Acid, Alcoholic, 0.5 N Add cautiously, with stirring, 13.9 mL of sulfuric acid to a sufficient quantity of absolute alcohol to make 1000.0 mL. Alternatively, prepare this solution by diluting 100.0 mL of 5 N Sulfuric Acid with absolute alcohol to make 1000.0 mL. 

Dimethyl sulfate is produced by acting on fuming. sulfuric acid with methyl alcohol and distilling in vacuo. Before Uie war it was used in industry as a methylating agent for amines and phenols and as a reagent for detecting coal-tar oils. 

Atropine Sulfate, (JSP. Atropine sulfate (Auupisoli is prepared by neutralizing atropine in acetone or elher solulioo with an alcoholic solution of sulfuric acid, with care uwi lo prevent hydrolysis. The sail occurs as colorless ctystak... 

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