Sulfuric acid reaction with aromatic compounds

Keim and co-workers have carried out various alkylation reactions of aromatic compounds in ionic liquids substantially free of Lewis acidity [84]. An example is the reaction between benzene and decene in [BMIM][HS04], which was used together with sulfuric acid as the catalyst (Scheme 5.1-54). These authors have also claimed that these acid-ionic liquids systems can be used for esterification reactions. 

Shipment and. Storage, Sulfur monochloride is minimally corrosive to carbon steel and iron when dry. If it is necessary to avoid discoloration caused by iron sulfide formation or chloride stress cracking, 310 stainless steel should be used. Sulfur monochloride is shipped in tank cars, tank trucks, and steel drums. When wet, it behaves like hydrochloric acid and attacks steel, cast iron, aluminum, stainless steels, copper and copper alloys, and many nickel-based materials. Alloys of 62 Ni—28 Mo and 54 Ni—15 Cr—16 Mo are useful under these conditions. Under DOT HM-181 sulfur monochloride is classified as a Poison Inhalation Hazard (PIH) Zone B, as well as a Corrosive Material (DOT Hazard Class B). Shipment information is available (140). Uses, The reaction of S-CL with aromatic compounds can yield disulfides or mixtures of mono-, di-, and polysulfides. 

For some time Tanasescu held the view that a group of compounds obtained by reaction of o-nitrobenzaldehydes with aromatic compounds in concentrated sulfuric acid, containing one oxygen atom more than the arylanthranils formed concurrently, were anthranil-A-oxides (e.g., 172).2QQ 201,206 Lehmstedt opposed this, and put forward the A-hydroxyacridone structure (173),213 312 which Tanasescu himself later adopted, although he preferred the tautomeric hydroxy-acridine- A-oxide structure (174).195 198 199 313... 

Aluminum and Sulfuric Acid. Treatment of aromatic nitro compounds, containing a free para position, with aluminum in 15-50 per cent mineral acid, particularly sulfuric acid, results in the formation of p-aminophenols along with amines. The reactions taking place may be represented as follows ... 

The sulfonation of aromatic compounds occurs readily in ionic liquids, with the simplest case being the direct sulfonation of aromatic compounds with sulfur trioxide to give the aryl sulfonic acid [113]. Ionic liquids such as triflate or triflimide ionic liquids were found to enhance the reaction rate. In the reaction of chloro-sulfuric acid with aromatic compounds, the reaction in the ionic liquid gave a... 

Sulfonation with Sulfuric Acid and Sulfur Triozide. Various mechanisms for the reaction of aromatic hydrocarbons or aryl halides with sulfuric acid or with sulfur trioxide have been proposed. Since.the reaction is heterogeneous, it is not favorable for experimental study. Solvents that dissolve sulfuric acid or sulfur trioxide form addition compounds with the reagent hence any conclusion drawn from a homogene ous sulfonation might not be applicable to the ordinary sulfonation. One possibility is that an electrophilic reagent such as sulfur trioxide with its relatively positive sulfur atom or an ion such as HOaS" " in the case of sulfuric acid attacks the negative center of the polarized form of the hydrocarbon, as illustrated for benzene. 

Make acid yields coumaUc acid when treated with fuming sulfuric acid (19). Similar treatment of malic acid in the presence of phenol and substituted phenols is a facile method of synthesi2ing coumarins that are substituted in the aromatic nucleus (20,21) (see Coumarin). Similar reactions take place with thiophenol and substituted thiophenols, yielding, among other compounds, a red dye (22) (see Dyes and dye intermediates). Oxidation of an aqueous solution of malic acid with hydrogen peroxide (qv) cataly2ed by ferrous ions yields oxalacetic acid (23). If this oxidation is performed in the presence of chromium, ferric, or titanium ions, or mixtures of these, the product is tartaric acid (24). Chlorals react with malic acid in the presence of sulfuric acid or other acidic catalysts to produce 4-ketodioxolones (25,26). 

The aHphatic iodine derivatives are usually prepared by reaction of an alcohol with hydroiodic acid or phosphoms trHodide by reaction of iodine, an alcohol, and red phosphoms addition of iodine monochloride, monobromide, or iodine to an olefin replacement reaction by heating the chlorine or bromine compound with an alkaH iodide ia a suitable solvent and the reaction of triphenyl phosphite with methyl iodide and an alcohol. The aromatic iodine derivatives are prepared by reacting iodine and the aromatic system with oxidising agents such as nitric acid, filming sulfuric acid, or mercuric oxide. 

Organic Reactions. Nitric acid is used extensively ia iadustry to nitrate aHphatic and aromatic compounds (21). In many iastances nitration requires the use of sulfuric acid as a dehydrating agent or catalyst the extent of nitration achieved depends on the concentration of nitric and sulfuric acids used. This is of iadustrial importance ia the manufacture of nitrobenzene and dinitrotoluene, which are iatermediates ia the manufacture of polyurethanes. Trinitrotoluene (TNT) is an explosive. Various isomers of mononitrotoluene are used to make optical brighteners, herbicides (qv), and iasecticides. Such nitrations are generally attributed to the presence of the nitronium ion, NO2, the concentration of which iacreases with acid strength (see Nitration). 

Electrolytic reductions generally caimot compete economically with chemical reductions of nitro compounds to amines, but they have been appHed in some specific reactions, such as the preparation of aminophenols (qv) from aromatic nitro compounds. For example, in the presence of sulfuric acid, cathodic reduction of aromatic nitro compounds with a free para-position leads to -aminophenol [123-30-8] hy rearrangement of the intermediate N-phenyl-hydroxylamine [100-65-2] (61). 

Nitrobenzotrichloride is also obtained in high yield with no significant hydrolysis when nitration with a mixture of nitric and sulfuric acids is carried out below 30°C (31). 2,4-Dihydroxybenzophenone [131 -56-6] is formed in 90% yield by the uncatalyzed reaction of benzotrichloride with resorcinol in hydroxyHc solvents (32) or in benzene containing methanol or ethanol (33). Benzophenone derivatives are formed from a variety of aromatic compounds by reaction with benzotrichloride in aqueous or alcohoHc hydrofluoric acid (34). 

Participation of fluorocarbocations, derived from carboxylic acids and from halo acetones, in reactions of carbonyl compounds with sulfur tetrafluoride has been directly evidenced by trapping them with aromatic hydrocarbons [207, 20S],... 

Tnfluoroacetic anhydnde in a mixture with sulfuric acid is an efficient reagent for the sulfonylation of aromatic compounds [44] The reaction of benzene with this system in nitromethane at room temperature gives diphenyl sulfone in 61% yield Alkyl and alkoxy benzenes under similar conditions form the corresponding diaryl sulfones in almost quantitative yield, whereas yields of sulfones from deactivated arenes such as chlorobenzene are substantially lower [44] The same reagent (tnfluoroacetic anhydride-sulfunc acid) reacts with adamantane and its derivatives with formation of isomeric adamantanols, adamantanones, and cyclic sultones [45]... 

The C-nitrosation of aromatic compounds is characterized by similar reaction conditions and mechanisms to those discussed earlier in this section. The reaction is normally carried out in a strongly acidic solution, and in most cases it is the nitrosyl ion which attacks the aromatic ring in the manner of an electrophilic aromatic substitution, i. e., via a a-complex as steady-state intermediate (see review by Williams, 1988, p. 58). We mention C-nitrosation here because it may interfere with diazotization of strongly basic aromatic amines if the reaction is carried out in concentrated sulfuric acid. Little information on such unwanted C-nitrosations of aromatic amines has been published (Blangey, 1938 see Sec. 2.2). 

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