Aromatic hydrocarbons sulphonation

Chen, Y., Wu, Z., and Yu, K., Effect of Mechanism of Concrete Admixtures Based Aromatic Hydrocarbon Sulphonate, 9th Int. Congr. Chem. Cements, New Delhi, IV 550-556 (1992)... 

A further difference between aliphatic and aromatic hydrocarbons is that only the latter are capable of direct sulphonation. Thus benzene when heated with concentrated sulphuric acid gives benzenesulphonic acid, a reaction which proceeds more readily, however, if chlorosulphonic acid is used instead of sulphuric acid an excess of chlorosulphonic acid however may convert the sul phonic acid into the sulphonyl chloride (c/. p. 181). 

SULPHONATION OF AROMATIC HYDROCARBONS Aromatic hydrocarbons may be mono-sulphonated by heating with a slight excess of concentrated sulphuric acid for benzene, oleum (7-8 per cent. SOj) gives somewhat better results. The reaction is usually complete when all the hydrocarbon has dissolved. Examples are ... 

Concentrated sulphuric acid. The paraffin hydrocarbons, cych-paraffins, the less readily sulphonated aromatic hydrocarbons (benzene, toluene, xylenes, etc.) and their halogen derivatives, and the diaryl ethers are generally insoluble in cold concentrated sulphuric acid. Unsaturated hydrocarbons, certain polyalkylated aromatic hydrocarbons (such as mesitylene) and most oxygen-containing compounds are soluble in the cold acid. 

RCH=CHjj -H H3SO4 — RCHlCHjlOSOaOH Polyalkylated aromatic hydrocarbons and alkyl phenyl ethers are sulphonated ... 

Paraffin and Aromatic Hydi ocarbon may be separated by the action of fuming sulphuric acid, 4iich forms the sulphonic and with the aromatic hydrocarbon. The product is poured into water. The sulphonic acid dissolves readily in water, whereas the paiaffin is insoluble. 

Since N02 and S03H are substituents of the second order, a second substituent enters in the m-position. Oleum containing a high percentage of sulphur trioxide finally converts benzene into benzene tri-sulphonic acid. Chlorosulphonic acid condenses with aromatic hydrocarbons, giving aryl sulphochlorides. 

The range of organic compounds which have been subject to the Simons process is wide and includes aliphatic and aromatic hydrocarbons, halocarbons, ethers, aliphatic and aromatic amines, heterocyclics, thiols, alkyl sulphonic and carboxylic acids, and their derivatives, among others. 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

From its general behaviour it is clear that chlorosulphonic acid is closely related to sulphuric acid. Like the latter acid, but with more vigour, it attacks aromatic hydrocarbons with formation of organic sidphonic acids of the structure R.SOa.OH and sulphones of the structure Rx... 

Reaction CXLVI. Action of Concentrated Sulphuric Acid on Hydrocarbons or Substituted Hydrocarbons.—When cone, sulphuric acid acts on an aromatic hydrocarbon or substituted hydrocarbon, one or more of the H atoms in the nucleus is replaced by the sulphonic group (S02.0H). 

The compounds formed are termed sulphones they are also formed by the action of cone, and fuming sulphuric acid on hydrocarbons (see p. 313), and by heating aromatic sulphonic acids with an aromatic hydrocarbon in presence of a dehydrating agent, such as P205. 

The preparation of phenols by the hydrolysis of diazonium salts with hot aqueous acid, and by a recent milder procedure suitable for diazonium salts having additional acid-sensitive groups, is discussed in Section 6.7.1, p. 922, and illustrated in Expt 6.69. Although these methods enable an aromatic hydrocarbon system to be converted in good yield into a phenol via the corresponding nitro and amino derivatives, the shorter route involving the alkaline fusion of the sulphonic acid discussed above may often be preferred. 

For characterisation, aromatic hydrocarbons can be sulphonated, chloro-sulphonated, carboxybenzoylated and nitrated. Polynuclear aromatic hydrocarbons, and many of their derivatives, yield crystalline adducts with picric acid, styphnic acid, 1,3,5-trinitrobenzene and 2,4,7-trinitrofluorenone. 

A range of single and blended organic sulphonate standards in oil bases is available. These appear to offer excellent stability and may be diluted with paraffinic and aromatic hydrocarbons as well as ketones. These may be obtained from Conostan Division, Continental Oil Company, P.O. Box 1267, Ponca City, Oklahoma 74601, U.S.A. 

Di-(l-naphthylmethyl)sulphone forms an excimer but does not react to give an intramolecular cycloaddition product like the corresponding ether but rather fragments to give sulphur dioxide and (l-naphthyl)methyl radicals (Amiri and Mellor, 1978). I-Naphthylacetyl chloride has a very low quantum yield of fluorescence and this is possibly due to exciplex formation between the acyl group and the naphthalene nucleus (Tamaki, 1979). Irradiation leads to decarbonylation. It is known that acyl chlorides quench the fluorescence of aromatic hydrocarbons and that this process leads to acylation of the aromatic hydrocarbon (Tamaki, 1978a). The decarboxylation of anhydrides of phenylacetic acids [171] has been interpreted as shown in (53), involving... 

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