3-Bromothiophene → 4-[(Pyridin-2-yl)sulfanyl]aniline

Temperature

130 °C

4-(3-Thienylthio)-1-nitrobenzene: To a solution of 4-nitrothiophenol (8%pure; 1.2 g, 6.1 mmol), 3-bromothiophene (1.0 g, 6.1 mmol) and copper(II) oxide (0.5 g, 3.7 mmol) in anhydrous DMF (20 mL) was added KOH (0.3 g, 6.1 mmol), and the resulting mixture was heated at 130° C. with stirring for 42 h and then allowed to cool to room temp. The reaction mixture was then poured into a mixture of ice and a 6N HCl solution (200 mL) and the resulting aqueous mixture was extracted with EtOAc (3×100 mL). The combined organic layers were sequentially washed with a 1M NaOH solution (2×100 mL) and a saturated NaCl solution (2×100 mL), dried (MgSO4), and concentrated in vacuo. The residual oil was purified by MPLC (silica gel; gradient from 10% EtOAc/90% hexane to 5% EtOAc/95% hexane) to afford of the desired product (0.5 g, 34%). GC-MS m/z 237 (M+).

1. temperatureto cool to room temp
2. additionThe reaction mixture was then poured into a mixture of ice
3. extractiona 6N HCl solution (200 mL) and the resulting aqueous mixture was extracted with EtOAc (3×100 mL)
4. washThe combined organic layers were sequentially washed with a 1M NaOH solution (2×100 mL)
5. dry with materiala saturated NaCl solution (2×100 mL), dried (MgSO4)
6. concentrationconcentrated in vacuo
7. customThe residual oil was purified by MPLC (silica gel; gradient from 10% EtOAc/90% hexane to 5% EtOAc/95% hexane)

ORD record

ord-62cd9fea3e854e1ca9cfbd230c61e099

Source dataset

uspto-grants-2009_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07517880B2