Thioanisole → 3-Nitrobenzaldehyde

3-nitrobenzoylchloride (5.0 g, 26.94 mmol) was added to a solution of thioanisole (3.16 mL, 26.94 mmol) and 1,2-dichlorethane (95 mL). The resulting reaction mixture was cooled to 0° C. (ice/H2O bath) and 0.5 equivalents of aluminum trichloride (1.8 g, 13.47 mmol) was added. The reaction was allowed to stir for 15 min at this temperature and the cold bath was removed followed by addition of the remaining equivalents of AlCl3 (2.51 g, 18.87). The reaction solution turned a dark greenish/yellow and was allowed to stir at room temp. for 18 h, after which time the reaction was quenched slowly with H2O (50 mL). The mixture was diluted with CH2Cl2 (50 mL) and washed with H2O (3×50 mL), and the combined organic phases were washed with satd NaHCO3 (50 mL), dried (MgSO4) and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (EtOAc/hexane, 1/4) to afford 3.3 g (44%) of 4-(methylsulfanyl)phenyl](3-nitrophenyl)methanone as a solid. EI-LRMS m/z 274 (M+); TLC Rf0.68 (EtOAc/Hex, 2/3). Step 2. Preparation of (3-aminophenyl)[4-(methylsulfanyl)phenyl]methanone

1. customThe resulting reaction mixture
2. additionwas added
3. customthe cold bath was removed
4. additionfollowed by addition of the remaining equivalents of AlCl3 (2.51 g, 18.87)
5. stirringto stir at room temp. for 18 h
6. customafter which time the reaction was quenched slowly with H2O (50 mL)
7. additionThe mixture was diluted with CH2Cl2 (50 mL)
8. washwashed with H2O (3×50 mL)
9. washthe combined organic phases were washed with satd NaHCO3 (50 mL)
10. dry with materialdried (MgSO4)
11. concentrationconcentrated under reduced pressure
12. customThe crude material was purified by silica gel column chromatography (EtOAc/hexane, 1/4)

ORD record

ord-4797bc472a2247dfb23d8b8a5c37dbb4

Source dataset

uspto-grants-2005_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06924290B2