2-Chloroaniline → 2-Chloro-3-(2-chlorophenyl)propanal

To a solution of 2-chloroaniline (12.7 g, 100. mmol) in hydrochloric acid (20% aqueous solution, 40 mL) was added dropwise a solution of sodium nitrite (7.5 g, 110 mmol) in water (20 mL) at 0 to 5° C. After stirring for 10 minutes, a cooled solution of acrolin (15 g, 270 mmol) in acetone (100 mL) containing calcium oxide (2.0 g, 36 mmol) was added gradually, and then followed by a solution of cuprous chloride (1 g, 10 mmol) in acetone (10 mL) containing hydrochloric acid (20% aqueous solution, 2 mL). The mixture was stirred at 0 to 30° C. for 3 hours and then extracted three times with dichloromethane (100 mL). The combined organic layers were washed with a saturated aqueous solution of sodium bicarbonate followed by a saturated aqueous solution of sodium chloride. The organic layer was separated, dried over sodium sulfate, and evaporated to dryness to give a black viscous oil. The crude product was passed through a short silica gel column to give 12 g of crude product, which was used directly in the next step.

1. additionwas added gradually
2. stirringThe mixture was stirred at 0 to 30° C. for 3 hours
3. extractionextracted three times with dichloromethane (100 mL)
4. washThe combined organic layers were washed with a saturated aqueous solution of sodium bicarbonate
5. customThe organic layer was separated
6. dry with materialdried over sodium sulfate
7. customevaporated to dryness
8. customto give a black viscous oil

ORD record

ord-03094f176fe24c05a43d916ad814b4ec

Source dataset

uspto-grants-2014_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08759335B2