Sulfuric Acid → 3-Chloro-4-(methylthio)phenol
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[Cl:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[S:9][CH3:10])N.[OH:11]S(O)(=O)=O.N([O-])=O.[Na+]>C1COCC1.O>[Cl:1][C:2]1[CH:3]=[C:4]([OH:11])[CH:6]=[CH:7][C:8]=1[S:9][CH3:10][Cl:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[S:9][CH3:10])N.[OH:11]S(O)(=O)=O.N([O-])=O.[Na+]>C1COCC1.O>[Cl:1][C:2]1[CH:3]=[C:4]([OH:11])[CH:6]=[CH:7][C:8]=1[S:9][CH3:10]The product from stage (ii) (11.5 g, 66.2 mmol) was dissolved in the minimum THF (˜15 mL) and water (500 mL) was added with vigorous stirring, followed by conc H2SO4 (25 mL). The mixture was cooled in an ice-water bath and a solution of NaNO2 (5.0 g, 72.5 mmol) in iced water (10 mL), was added via pipette under the surface of the reaction mixture. The reaction was stirred at 0° C. for 1.5 h and the resulting yellow/brown solution was decanted from the remaining solid into a dropping funnel containing ice (˜200 g). This solution was added at a steady rate over 7 min to a vigorously stirred mixture of Cu(NO3)2 (230 g, 0.99 mol) and Cu2O (8.52 g, 67.4 mmol) in water (1 L) at room temperature. After the addition was complete the mixture was stirred for a further 15 min before being extracted with ether (500 mL). The residual red/brown solid in the reaction flask was taken up in MeOH (100 mL) and diluted with ether (300 mL) before being poured into the aqueous layer from above. The ether layer was separated and the combined organic layers were extracted with 1M NaOH (3×100 mL). The aqueous extracts were acidified with conc. HCl and then extracted with ether (2×150 mL). The ether layers were then washed with brine, dried (MgSO4) and the solvent was removed in vacuo to give the phenol (5.465 g, 47%) as a brown crystalline solid; δH (400 MHz, CDCl3) 2.44 (3H, s), 5.08 (1H, br), 6.77 (1H, d), 6.93 (1H, d), 7.18 (1H, d); MS m/z (ES−) 173 (M−H+).
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