Hydrochloric Acid → 2-Mercaptobenzonitrile
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[Cl-].[Al+3].[Cl-].[Cl-].C([S:12][C:13]1[CH:20]=[CH:19][CH:18]=[CH:17][C:14]=1[C:15]#[N:16])C1C=CC=CC=1.[OH-].[Na+].Cl>C1C=CC=CC=1>[SH:12][C:13]1[CH:20]=[CH:19][CH:18]=[CH:17][C:14]=1[C:15]#[N:16][Cl-].[Al+3].[Cl-].[Cl-].C([S:12][C:13]1[CH:20]=[CH:19][CH:18]=[CH:17][C:14]=1[C:15]#[N:16])C1C=CC=CC=1.[OH-].[Na+].Cl>C1C=CC=CC=1>[SH:12][C:13]1[CH:20]=[CH:19][CH:18]=[CH:17][C:14]=1[C:15]#[N:16]In a 3-neck round bottom flask that contained an addition funnel was added benzene (40 mL). The flask was placed under N2 atmosphere and cooled in an ice water bath (0° C.). Aluminum chloride (4.88 g, 36.61 mmol) was added to the benzene solution. A solution of 2-(benzylthio)benzonitrile (5.0 g, 22.19 mmol) from Step 1(A) in benzene (40 mL) was added to the addition funnel. The solution was added dropwise over forty minutes and the reaction mixture was stirred at 0° C. for one hour and then stirred at room temperature for 48 hours. The reaction was worked up by pouring the crude mixture into ice water (200 mL) and stirring for 30 minutes. 10% NaOH (100 mL) solution was added and the mixture was stirred for 10 minutes. The solution was acidified (pH=2) by addition of 6N hydrochloric acid (HCl). The solution was placed in a separatory funnel and extracted with dichloromethane (3×100 mL). The combined organics were dried over Na2SO4 and then concentrated under reduced pressure to afford a brown oil. The product was purified by flash silica column chromatography. Elution through an 80-g Silicycle® flash silica cartridge with 5% ethyl acetate in heptanes afforded the title compound as a brown oil (2.55 g, 85%); Rf of 0.56″ with 70:30 v/v heptanes: ethyl acetate; 1H-NMR (400 MHz; CDCl3) δ 7.52 (d, 1H), 7.39-7.32 (m, 2H), 7.19-7.14 (m, 1H), 4.01 (s, 1H); MS (ESI−) m/z 134.05 (Mz−1).
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