1-Bromo-4-methoxy-2-methyl-3-nitrobenzene → 3-Bromo-6-methoxy-2-methylaniline

To a stirring mixture of 1-bromo-4-methoxy-2-methyl-3-nitrobenzene (2.0 g, 8.13 mmol, see Tet. Lett., 2002, 43, 1063) in NH4OH (40 ml) was added a solution of (NH4)2Fe(SO4)2 (19.1 g, 48.8 mmol) in H2O (40 ml). The reaction mixture was stirred at reflux for 4 hours, cooled to room temperature, diluted with Et2O (120 ml), and filtered through celite. The filter cake was washed with Et2O. The aqueous layer was extracted with Et2O (50 ml). The combined organic layers were concentrated, and the residue was dissolved in Et2O and extracted with HCl (1M, 30 ml). The aqueous layer was basified until about pH 4 by addition of (NaOH 50%, 10 ml) and extracted with Et2O. The combined organic layers were dried over MgSO4, filtered, and concentrated affording 3-Bromo-6-methoxy-2-methyl-phenylamine CXCV as an off-white solid (0.98 g, 56% yield).

1. temperatureat reflux for 4 hours
2. filtrationfiltered through celite
3. washThe filter cake was washed with Et2O
4. extractionThe aqueous layer was extracted with Et2O (50 ml)
5. concentrationThe combined organic layers were concentrated
6. dissolutionthe residue was dissolved in Et2O
7. extractionextracted with HCl (1M, 30 ml)
8. additionThe aqueous layer was basified until about pH 4 by addition of (NaOH 50%, 10 ml)
9. extractionextracted with Et2O
10. dry with materialThe combined organic layers were dried over MgSO4
11. filtrationfiltered
12. concentrationconcentrated

ORD record

ord-57a2d10202704b81956b427d2327d8f5

Source dataset

uspto-grants-2008_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07446118B2