Aniline → N-(2-Methylbut-3-yn-2-yl)aniline

Participants

Reaction Steps

In a 500 mL r.b., a solution of 2-methyl-3-butyn-2-ol (10.0 mL, 0.10 mol, 1.3 equiv) in CH2Cl2 (100 mL) was treated sequentially with Et3N (15.0 mL, 0.107 mol, 1.4 equiv), acetic anhydride (11.6 mL, 0.12 mol, 1.5 equiv), and DMAP (0.61 g, 5.0 mmol, 5.0 mol %). The reaction mixture was stirred at rt for 2 h and poured into sat'd NH4Cl (60 mL). The layers were separated. The aqueous layer was extracted with CH2Cl2 (2×100 mL). The organic layers were washed with 1 N HCl (2×100 mL), combined, dried (MgSO4), filtered through a pad of Celite, and the volatiles were removed by distillation (<45° C. distillate). The residue was dissolved in THF (100 mL) and aniline (7.00 mL, 77 mmol) was added slowly via syringe, followed by CuCl (0.76 g, 10 mol %). The reaction mixture was heated to reflux for 3 h. The resulting red solution was allowed to cool to rt, the bulk of the volatiles were removed in vacuo, and the residue was diluted with EtOAc (120 mL). The solution was washed with sat'd NH4Cl (2×100 mL) and brine (1×100 mL). The aqueous layers were extracted with EtOAc (2×100 mL). The combined organic layers were dried (MgSO4), filtered, and concentrated. Purfication by silica gel chromatography (hexane:EtOAc, 16:1) afforded 10.5 g (87%) of 2-methyl-3-butyn-2-yl(phenyl)amine as a pale yellow liquid. Data for 2-methyl-3-butyn-2-yl(phenyl)amine: 1H NMR (400 MHz, CDCl3) 7.20 (t, J=7.7, 2H), 6.95 (d, J=7.7, 2H), 6.80 (t, J=7.7, 1H), 3.65 (br s, 1H), 2.36 (s, 1H), 1.61 (s, 6H).

Provenance & Evidence