Synthesis of Organic Compounds 55 The structure is confirmed by the "HNMR spectrum (CDCls + DMSO-de, TMS) which shows signals at 6 5.35 (broad s, 1H, OH) and 9.14 (8, 2H, aromatic proton), ° Wega od At Mo “ © ae ase Ne oo ania A 10 2 oe 3 ett pay ata 2 ° Figure 1.42. H-NMR spectrum of picric acid 1.34, SULPHONATION 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 (H»SO.) gives benzenesulphonie acid, a reaction which proceeds more readily, however, if chlorosulphonic acid is used instead of sulphuric acid: an excess of chlorosulphonie acid however may convert the sulphonic acid into the sulphonyl chloride, CH + HOSO;H ————_CH5S0}H + H,0 CcHsH + CISO;H —————__—CeHsSOH + HCL ‘Aromatic sulphonic acids are frequently difficult to obtain pure, since they almost invariably decompose on attempted distillation, and many are very soluble in water: such aqueous solutions on being concentrated often give syrupy solutions from which the sulphonic acid crystallizes with difficulty. : ‘Toluene however sulphonates readily, and the following preparation illustrates the rapid formation of toluene-p-sulphonic acid mixed with a small proportion of the Geliquescent o-sulphonic acid, and the isolation of the pure crystalline para-isomer. The mechanism of aromatic sulphonation is complex and may vary, e.g. with the coneentration of water or oleum in the acid, the temperature, and the hydrocarbon, One active agent is SOs, and one simplified route may be: + $0 O LF ; SCF 4 by tie ‘This direct sulphondtion should be Compared with the indirect methods for the preparation of aliphatic sulphonic acids, e.g., oxidation of a thiol (RSH-+RSOsH), and Prteraction of an alkyl halide with sodium sulphite to give the sodium sulphonate (RBr + Na:SOx — RSO:Na + NaBr).: sac 56 Advanced Experimental Organic Chemistry iH. 1.34, 'TOLUENE-p-SULPHONIC ACID. (CHs-CsHs-SOs! 4 \ em \ \ H3S0, He : ‘TOLUENE-p-SULPHONIC ACID 1.34.1. Synthesis Sen : Required: Pure toluene, 30 mL (26 g); concentrated sulphuric acid, 6 mL. (11 6) S00 ine : ntrated sulphuric acid (Hs Place 30 mL of pure toluene and 6mL of conce: de ctmoay ee 100 ml conieal flask fitted with a refx water condenser. Boil the mixture gently over a gauze for 5 minutes, with frequent and thorough shaking to mix the two laye Bote the mixture (whilst still in the flask) in ice-water, when the lower layer of the cue sulphonic acid will solidify. Decant off and discard the upper layer of toluene. Now a mL of concentrated hydrochloric’acid, attach the condenser, and heat the mixture gently ‘until a clear solution is just obtained, and then cool as before. (If the boiling is prolonged, dnd the concentration of the HCl thus reduced, the sulphonic acid will subsequently remain dissolved.) ‘The toluene:p-sulphonic acid separates as white crystals, which are contaminated with the deliquescent o-sulphonic acid. Therefore, filter off the crystals using a small Buchner funnel, drain quickly, and return the crystals to the flask. Now add 15 mL of cone. HCl and repeat the recrystallization as before. The crystalline toluene-p-sutlphonic acid can now be drained more thoroughly at the pump, and should then be dried in a vacuum desiccator. Yield, 6.3 g. M.p. 103-105°C. A further crystallization from 15 mL of HCI gives the sulphonic acid, 5.5 g., m.p. 105°C, almost devoid of deliquescent properties, On a larger scale, the acid may be purified by dissolving it in a minimum of cold water, and then saturating the solution with hydrogen chloride, when the acid will crystallize. 1.34.2. Spectroscopic analysis The structure is confirmed by the ‘HNMR spectrum (D:0, TMS) which shows signals at 6 2.34 (s, 1H, OH), 5.14 (6, 3H, CHs), 7.40 (dd, 2H, aromatic Protons), and 7.74 (dd, 2H, aromatie protons). 0:0 Q€-300 28g aot) @ oo . 7 y . i] 3 2 1 ° Figure 1.43. 1H FY-NMR spectrum of Toluene-p-sulphonie Acid, DOp