Toluene: acylation sulphonation

Mixed anhydrides with methanesulphonic or toluene-4-sulphonic acid are also reported to be good acylating agents. They are made as indicated in the following equations ... 

The fact that the one-pot synthesis of caUxarenes works best with p-f-butylphenoP was beneficial for the whole area, since the f-butyl groups are easUy removed by trans-butylation with AICI3 in toluene (as solvent and acceptor), converting calixarenes 2a-e into the p-unsubstituted calixarenes 2na-e. Thus, the p-positions at the wide rim are available for virtually all kinds of electrophilic substitution reactions which are possible with phenols . Sulphonation, nitration, bromination (or iodination), bromomethyla-tion, aminomethylation, formylation, acylation and coupling with diazonium salts are examples. 

Poly(2-alkyl oxazoline)s having methacrylate or acrylate end groups were prepared by two methods [182]. a) Living polyoxazoline chains, prepared using methyl p-toluene sulphonate as initiator, were end-capped by reaction with metal salts or tetraalkylammonium salts of acrylic or methacrylic acid or a trialky-lammonium salt or trimethylsilyl ester of methacrylic acid (functional termination). b) The living polymers were terminated with water in the presence of Na2C03 to provide hydroxyl-terminated chains. Subsequent acylation with acry-loyl or methacryloyl chloride in the presence of triethylamine led to the formation of the macromonomers. The procedures are outlined in the following Scheme 51. 

Virtually all of the methods for determining acyl groups developed up to now are based on re-esterification of the initial compound with sulphuric acid, a mixture of methanol with hydrochloric or p-toluenesulphonic acid, or with a mixture of p-toluene-sulphonic acid and its methyl ester [165—170]. The esters formed in the reaction were determined by analysing an aliquot of the reaction solution or by blowing-off the reactor with a carrier gas. Alkaline hydrolysis with subsequent determination of acetic acid has also been used for identifying acyl groups [167]. 

Mayr [35] has shown very recently that, for very reactive systems, reaction will proceed without a catalyst. Bromination of phenol is claimed to occur with high / -selectivity [31], but this is unexceptional. A solution of sulphur trioxide in sulphur dioxide is claimed to be an especially mild sul-phonating agent. Sulphonation of toluene gives mainly /7-isomer, with no sulphones. Acylation of hindered alcohols with acid chlorides occurs unusually rapidly at ambient temperature [33] (equation 12.17). 

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