3-肼基苯酚

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2,2-Dimethyl-3-oxo-pentanedinitrile (WO 2008/034008, which is incorporated herein by reference in its entirety, 353 mg, 2.80 mmol) and Intermediate 20a (387 mg, 2.80 mmol) were suspended in EtOH (10 mL) and concentrated HCl was added (711 μL, 8.53 mmol) and the reaction was refluxed for 90 min. The reaction was cooled, concentrated in vacuo and partitioned between H2O and EtOAc. The organic layer was separated, dried over MgSO4 and concentrated in vacuo and the resulting oil was triturated with pentane/Et2O (9:1) to afford the title compound as a brown solid (363 mg, 53%). LCMS (Method 3): Rt 2.77 min, m/z 243.3 [MH+]. the reaction was refluxed for 90 min The reaction was cooled concentrated in vacuo partitioned between H2O and EtOAc The organic layer was separated dried over MgSO4 concentrated in vacuo the resulting oil was triturated with pentane/Et2O (9:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a stirred, ice cooled solution of 3-aminophenol (2.00 g, 18.3 mmol) in concentrated HCl (20 mL) was added dropwise a solution of sodium nitrite (1.33 g, 19.24 mmol) in H2O (10 mL), ensuring the internal temperature did not exceed 10° C. After 10 min, a solution of tin (II) chloride (7.645 g, 40.3 mmol) in concentrated HCl (10 mL) was added dropwise, and the ice bath removed. After stirring at RT for 45 min, the reaction was basified to pH 10 with careful addition of 10 M NaOH solution (50 mL), and then extracted with EtOAc (3×). The organic extracts were dried over MgSO4, concentrated in vacuo and triturated with Et2O to afford the title compound as a brown solid (353 mg, 16%). 1H NMR (300 MHz, d6-DMSO): 3.83 (2H, br s), 5.96-6.02 (1H, m), 6.15-6.21 (1H, m), 6.22 (1H, t, J=2.2 Hz), 6.52 (1H, br s), 6.84 (1H, t, J=8.0 Hz), 8.91 (1H, br s). did not exceed 10° C the ice bath removed the reaction was basified to pH 10 with careful addition of 10 M NaOH solution (50 mL) extracted with EtOAc (3×) The organic extracts were dried over MgSO4 concentrated in vacuo triturated with Et2O