1: With diisobutylaluminium hydride in tetrahydrofuran; hexane T=-78°C; 2 h; 2: With methanol; water; ammonium chloride in tetrahydrofuran; hexane T=2°C; 1 h;

1: 2-bromo-4-methyl-phenylamine With hydrogenchloride; sodium acetate; copper(II) sulfate; sodium sulfite; sodium nitrite in water T=0°C; 2: formaldehyd With hydroxylamine hydrochloride; sodium acetate in water 3: With hydrogenchloride; water Reflux;

1: 3-Bromo-4-methylphenylamine With hydrogenchloride; sodium nitrite T=-10°C; Inert atmosphere; 2: formaldehyde oxime sodium salt With hydrogenchloride; sodium acetate; copper(II) sulfate; sodium sulfite RefluxInert atmosphere;

(i) (diazotization), (ii) /BRN= 1697325/, NaOAc, H2O, (iii) aq. HCl; Multistep reaction;

potassium carbonate; trifluoroacetic acid 1.) 120 deg C, 500 MPa, 9 h; Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts;

1: caesium carbonate; triphenylphosphine; palladium dichloride / tetrahydrofuran; water / 22 h / 85 °C / sealed tube; Inert atmosphere 2: bis(1,5-cyclooctadiene)-rhodium(I) tetrafluoroborate; 6-diphenylphosphinomethyl-3-methyl-2-aminopyridine / toluene / 1 h / 150 °C / Inert atmosphere View Scheme

1: 63 percent / conc. H2SO4, conc. HNO3 / 0.33 h / 15 °C 2: 1.) NaOEt / 1.) EtOH, 5 deg C, 20 min, 2.) EtOH, reflux, 3 h 3: 100 percent / aq. NaOH / ethanol / 3 h / Heating 4: 89 percent / Cu, quinoline / 3 h / 190 °C 5: 1.) pyrrolidine, 2.) aq. HCl / 1.) DMF, 150 deg C, 3 h, 2.) toluene, reflux, 30 min 6: 98 percent / NaBH4 / ethanol / 1 h / Ambient temperature View Scheme

1: 63 percent / conc. H2SO4, conc. HNO3 / 0.33 h / 15 °C 2: 1.) NaOEt / 1.) EtOH, 5 deg C, 20 min, 2.) EtOH, reflux, 3 h View Scheme

sulfuric acid; nitric acid T=5 - 15°C; 1 h;

copper(l) iodide; caesium carbonate; N-methyl-2-(methylamino)ethylamine in toluene T=110°C; 24 h; Inert atmosphereSealed tube;