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

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).

1. customThe layers were separated
2. extractionThe aqueous layer was extracted with CH2Cl2 (2×100 mL)
3. washThe organic layers were washed with 1 N HCl (2×100 mL)
4. dry with materialdried (MgSO4)
5. filtrationfiltered through a pad of Celite
6. customthe volatiles were removed by distillation (<45° C. distillate)
7. dissolutionThe residue was dissolved in THF (100 mL)
8. temperatureThe reaction mixture was heated
9. temperatureto reflux for 3 h
10. temperatureto cool to rt
11. customthe bulk of the volatiles were removed in vacuo
12. additionthe residue was diluted with EtOAc (120 mL)
13. washThe solution was washed with sat'd NH4Cl (2×100 mL) and brine (1×100 mL)
14. extractionThe aqueous layers were extracted with EtOAc (2×100 mL)
15. dry with materialThe combined organic layers were dried (MgSO4)
16. filtrationfiltered
17. concentrationconcentrated

ORD record

ord-ca58a74e7a7549a99fdbaac46710622a

Source dataset

uspto-grants-2000_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06017924