Toluene-p-sulphonamide, and

The sulphonylation method may be used for the S3mtheses of dichloramine-T and chloramine-T starting from toluene-p-sulphonamide and dichloramine-T respectively. 

Toluene-p-sulphonyl chloride either on heating with ammonium carbonate or liquid ammonia replaces the chloro group with an amino moiety to result the formation of toluene-p-sulphonamide and a mole of HCl gets eliminated. 

Add to the above solution quickly 5 g of finely powdered toluene-p-sulphonamide and cork the flask securedly. 

Dissolve log. of powdered toluene-p-sulphonamide in 6o ml. of 10% aqueous sodium hydroxide (2 5 mols.) diluted with 50 ml. of water to moderate the reaction. Then, using the same precautions as in the previous preparation, add 127 ml. (17 g., 2 3 mols.) of dimethyl sulphate and shake the mixture vigorously. The crystalline dimethylamide rapidly separates from the warm... 

Dichloramine-T. Dilute 80 ml, of freshly prepared 2N sodium hypochlorite soluticMi (preparation, p. 525) with 80 ml. of w ter, and then add with stirring 5 g. of finely powdered toluene-p-sulphonamide, a clear solution being rapidly obtained. Cool in ice-water, and then add about 50 ml. of a mixture of equal volumes of glacial acetic acid and water slowly with stirring until precipitation is complete the dichloro-amide separates at first as a fine emulsion, which rapidly forms brittle colourless crystals. Filter off the latter at the pump, wash well with... 

Choice of solvent for recrystallisation Obtain small samples (about 0.5 g) of the following compounds from the storeroom (i) salicylic acid (ii) acetanilide (iii) m-dinitrobenzene (iv) naphthalene and (v) toluene-p-sulphonamide. Use the following solvents distilled water, industrial spirit, rectified spirit, acetone, toluene, glacial acetic acid and hexane. 

When toluene-p-sulphonamide is dissolved in excess calcium hypochlorite solution and then acidified with acetic acid, the /V,/V-dichloro derivative [(6) dichloramine-T] separates rapidly. When this is heated with sodium hydroxide solution the sodium salt of the N-monochloro derivative [(7) chloramine-T)] is formed and crystallises out on cooling at a suitable concentration (Expt 6.43). 

Toluene-p-sulphonamide. Grind together 10 g (0.0525 mol) of toluene-p-sulphonyl chloride (Expt 6.41) and 20g of ammonium carbonate in a mortar until a fine uniform powder is obtained. Heat the mixture in an evaporating dish on a water bath for 1-2 hours and stir the mixture frequently with a glass rod. Allow to cool and extract with a little cold water to remove the excess of ammonium salts. Recrystallise the crude toluene-p-sulphonamide from boiling water (200-250ml), and dry the colourless crystals at 100 °C. The yield of pure product, m.p. 138 °C, is 7.9 g (88%). 

Dichloramine-T(jV,jV-dichlorotoluene-p-sulphonamide). Prepare about 200 ml of a saturated solution of calcium hypochlorite by grinding a fresh sample of bleaching powder with water and filtering with slight suction. Dissolve 5 g (0.029 mol) of toluene-p-sulphonamide in as small a volume of the calcium hypochlorite solution as possible (about 150 ml) and filter the solution if necessary. Cool in ice, and add about 50 ml of a mixture of equal volumes of glacial acetic acid and water slowly and with stirring until precipitation is complete. The dichloramine-T separates out first as a fine emulsion, which... 

Photo-substitution of benzene by the imidazolinone (294 R = Cl) yields the diphenyl compound (294 R = Ph). ATV -Diacetylimidazolin-2-one gives the Diels-Alder adduct (295) with cyclopentadiene, and the photoadduct (296) with ethylene.Treatment of 7V7V -dimethylimidazoline-2-thione with bromine and toluene-p-sulphonamide leads to the thione-5-imide (297). The thione-thiol tautomerism of the nitroxides (298)= 299) has been studied by e.s.r. spectroscopy... 

Tamaru et a 1. The products (125) are produced in good yields from the alkenyl toluene-p-sulphonamides (124) and under mild conditions. In a related procedure, Pd1 -catalysed cyclization of the allenic amine derivatives (126) in the presence of carbon monoxide and... 

Method-II. An alternate equally effective and feasible method for the preparation of toluene-p-sulphonamide is as stated below ... 

Filter the crude product and reciystallize the toluene-p-sulphonamide from boiling water (add 0.5 g of decolourizing carbon, if required). The 3rield of pure product (mp 137.5-138°C) is nearly to that of theoretical 3ueld (4.89 g). 

Method-I. From Dichloramine-T, and Method-II. Direct from Toluene-p-Sulphonamide. 

The interaction between toluene-p-sulphonamide with freshly prepared sodium hypochlorite solution (2 M) in the presence of 10% NaOH solution results into the formation of chloramine-T, and a mole of H2O gets eliminated. 

Shake the contents of the flask vigorously by holding the cork-in-position for 5-8 minutes, whereupon the toluene-p-sulphonamide shall rmdergo complete dissolution and at the same time a white crystalline chloramine-T would appear almost distinctly. 

Synthesis.—A new route to alkyl-substituted crown compounds involves" the reaction of polyethylene glycols with alkenes in the presence of a positive halogen source (Scheme 51), followed by base-catalysed cyclization of the halohydrins produced. One approach to aza-crown molecules relies on alkylation of toluene-p-sulphonamide anions, and a study of some methods for N-detosylation of the cyclic products has been published. 

The ene addition of ethyl propiolate to P-pinene is catalysed by aluminium chloride as expected, the reaction is stereospecific and affords (545) in 82 % yield after 2 days at room temperature in benzene solution. Other 1,1-dialkylethylenes reacted similarly, but 1,2-dialkyl- and monosubstituted ethylenes, however, afforded products of stereospecific [2 +2] addition presumably short-lived dipolar intermediates are formed in the non-ene processes. Reaction of selenium tetrachloride with two equivalents of t-butylamine or toluene-p-sulphonamide in dichloromethane in the presence of four equivalents of an amine base produces solutions thought to contain iminoselenium compounds RN=Se=NR (R = Bu or Ts). Both compounds reacted with P-pinene to afford the allylic amination products (546). An even more... 

Improvements in the osmium-catalysed hydroxylation and oxyamination of olefins continue to appear." In the vicinal hydroxylation of olefins by t-butyl hydroperoxide earlier methods involved rather alkaline conditions, but this drawback has been overcome by using Et4NOAc instead of Et4NOH and changing the solvent from t-butyl alcohol to acetone."" Although the new method works well for base-sensitive compounds (e.g. esters), it fails with tetrasubstituted olefins. Yields are generally around 70%. Vicinal hydroxy-toluene-p-sulphonamides (8),... 

Selenium-A-tosylimides, e.g. (71), have been prepared by the reaction of selenides with Bu OCl and Af-sodio-toluene-/>-sulphonamides in MeCN. In the presence of HaO the imide is in equilibrium with the selenoxide (72) and toluene-p-sulphonamide, thus suggesting the successful preparation of (71) from (72) and the amide by azeotropic removal of water. ... 

Plasticisers are comparatively uncommon but plasticised grades are supplied by some manufacturers. Plasticisers lower the melting point and improve toughness and flexibility, particularly at low temperatures. An example of a plasticiser used commercially in Santicizer 8, a blend of o- and p-toluene ethyl sulphonamide (Figure 18.18). 

An ethereal solution of diazomethane is usually prepared immediately before it is required for reaction. A convenient precursor for the generation of diazomethane is IV-methyl-lV-nitrosotoluene-p-sulphonamide which is prepared by the action of nitrous acid on N-methyltoluene-p-sulphonamide. This latter is formed from toluene-p-sulphonyl chloride and methylamine in alkaline solution. The methylnitrosamide affords diazomethane on reaction with potassium hydroxide solution. 

These sulphonamides are highly crystalline, and in particular the derivatives from benzenesulphonyl chloride and toluene-p-sulphonyl chloride are used in the separation and identification of aromatic amines (Sections 9.6.21, p. 1273 and 9.7.1, p. 1287). 

Place 20g (0.105mol) of toluene-o-sulphonyl chloride (Expt 6.41) in a large evaporating dish mounted on a water bath. Add powdered ammonium carbonate cautiously with stirring until the mass is quite hard and solid and the unpleasant odour of the sulphonyl chloride has disappeared. Allow to cool, and extract with cold water to remove the excess of ammonium carbonate. Recrystallise the crude toluene-o-sulphonamide first from hot water (add a little decolourising carbon if it is dark in colour) and then from ethanol. The yield of pure product, m.p. 154°C, is 16 g (89%). 

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