Sulphonic acids Reactions

The sulphonic acids are usually prepared by the action of sulphuric acid upon a compound. The concentration of the acid and the temperature of reaction are varied according to the reactivity of the compound. Often oleum is used or even chiorosulphonic acid. Alternatively sulphur trioxide complexed to pyridine or dioxan can be used with reactive substrates. Aminosulphonic acids such as sulphanilic and naphthionic acids are most conveniently prepared by heating the sulphate of the amine at ISO C. 

The most important reaction of the sulphonic acids is their conversion into phenols by fusion with caustic alkalis. When they are fused with potassium cyanide, nitriles are obtained, e.g. benzonitriie from ben-zenesulphonic acid. 

Aromatic nitriles (or aryl cyanides) can be obtained by methods (1) and (3). but not by method (2). In addition, aromatic nitriles can be prepared by two other methods, (a) from the corresponding diazo compound by Sandmeyer s Reaction (p. 189), (b) by fusing the corresponding sulphonic acid (or its salts)... 

The Schotten-Baumann reaction may also be carried out, using, for example, benzene sulphonyl chloride, CeH,SO,Cl (. e., the acid chloride of benzene sulphonic acid, C H5SOjOH) in place of benzoyl chloride, and similar deri a-tives are obtained. Thus when phenol is dissolved in an excess of 10% sodium hydroxide solution, and then shaken with a small excess of benzene sulphonyl... 

Because of the great solubility of sulphonic acids in water and the consequent difficulty in crystallisation, the free sulphonic adds are not usually isolated but are converted directly into the sodium salts. The simplest procedure is partly to neutralise the reaction mixture (say, with solid sodium bicarbonate) and then to pour it into water and add excess of sodium chloride. An equilibrium is set up, for example ... 

Dissolve 1 0 g. of the compound in 5 ml. of dry chloroform in a dry test-tuhe, cool to 0°, and add dropwise 5g. (2-8 ml.) of redistilled chloro-sulphonic acid. When the evolution of hydrogen chloride subsides, allow the reaction mixture to stand at room temperature for 20 minutes. Pour the contents of the test-tube cautiously on to 25 g. of crushed ice contained in a small beaker. Separate the chloroform layer and wash it with a httle cold water. Add the chloroform layer, with stirring, to 10 ml. of concentrated ammonia solution. After 10 minutes, evaporate the chloroform on a water bath, cool the residue and treat it with 5 ml. of 10 per cent, sodium hydroxide solution the sulphonamide dissolves as the sodium derivative, RO.CgH4.SO,NHNa. Filter the solution to remove any insoluble matter (sulphone, etc.), acidify the filtrate with dilute hydrochloric acid, and cool in ice water. Collect the sulphonamide and recrystallise it from dilute alcohol. 

Aryl sulphonic acids, either free or in the form of tlieir sodium or potassium salts, are converted into the acid chlorides by reaction with phosphorus peutu-chloride or phosphorus oxychloride, for example ... 

The reaction product may then be examined for a sulphonic acid and an amine. 

Chapter IV. a-Chloromethylnaphthalene (IV,23) benzylamine (Gabriel synthesis) (IV,39) i r.N -dialkylanilines (from amines and trialkyl orthophosphates) (IV,42) a-naphthaldehyde (Sommelet reaction) (IV,120) a-phenyl-cinnamic acid (Perkin reaction using triethylamine) (IV,124) p-nitrostyrene (IV,129) p-bromonaphthalene and p naphthoic acid (from 2 naphthylamine-1 -sulphonic acid) (IV,62 and IV,164) diphenic acid (from phenanthrene) (IV,165). 

A number of basic materials such as hydroxides, hydrides and amides of alkaline and alkaline earth metals and metal oxides such as zinc oxide and antimony oxide are useful catalysts for the reaction. Acid ester-exchange catalysts such as boric acid, p-toluene sulphonic acid and zinc chloride are less... 

The sulphonic acids are also obtained by the o idation of thiophenols, a reaction which, at the same time, indicates then-constitution,... 

The salts of the sulphonic acids undergo the following reactions. —... 

Most of the inhibitors in use are organic nitrogen compounds and these have been classified by Bregman as (a) aliphatic fatty acid derivatives, b) imidazolines, (c) quaternaries, (d) rosin derivatives (complex amine mixtures based on abietic acid) all of these will tend to have long-chain hydrocarbons, e.g. CigH, as part of the structure, (e) petroleum sulphonic acid salts of long-chain diamines (preferred to the diamines), (/) other salts of diamines and (g) fatty amides of aliphatic diamines. Actual compounds in use in classes (a) to d) include oleic and naphthenic acid salts of n-tallowpropylenediamine diamines RNH(CH2) NH2 in which R is a carbon chain of 8-22 atoms and x = 2-10 and reaction products of diamines with acids from the partial oxidation of liquid hydrocarbons. Attention has also been drawn to polyethoxylated compounds in which the water solubility can be controlled by the amount of ethylene oxide added to the molecule. 

Conant and Peterson123 made the first kinetic study of the coupling of diazonium ions with aromatics, and measured the rates of reaction of diazotised aniline and its 2-MeO, 4-Me, 4-Br and 4-S03H derivatives with the sodium salts of 4-hydroxybenzenesulphonic acid, 2-naphthol-3,6-disulphonic acid, 1-naphthol-3,8-disulphonic acid, and l-naphthol-4-sulphonic acid. The reaction was second-order, viz. 

A further effect of steric hindrance in the transition state was shown by comparing the isotope effects obtained in the reactions of the sulphonic acids (II-V)... 

Eaborn and Taylor147 measured first-order rate coefficients for sulphonation of some aromatics in mixtures of trifluoroacctic acid-aqueous sulphuric acid, as sulphonation proved to be a troublesome side reaction accompanying hydrogen exchange in these media. They introduced a technique which has been found useful by later workers and makes use of the high solubility of sulphonic acids in... 

In a study of the sulphonation and desulphonation of naphthalene Lanz155 measured the proportion of naphthalene converted to sulphonic acids in its reaction with 51.4-94.4 wt. % acid at temperatures ranging from 60-180 °C, and from this data rough sulphonation rates may be deduced, but no conclusion concerning the mechanism was reached. 

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