反应详情

42.9 ml (0.50 mol, 3 eq) of oxalyl chloride were added dropwise to a suspension of 30 g (0.16 mol, 1 eq) of 3-nitrosalicylic acid in 1200 ml of dichloromethane. 30 drops of N,N-dimethylformamide were added (large amount of gas given off, adaptation of a system for trapping toxic carbon monoxide vapors). The reaction medium was stirred at ambient temperature for 24 hours. The reaction medium was cooled to 0-5° C. and then 246 ml (0.49 mol, 3 eq) of a 2 N solution of dimethylamine in tetrahydrofuran were added. The reaction medium was stirred at ambient temperature for 2 days. The reaction medium was concentrated to dryness and the residue was dissolved in 300 ml 1 N sodium hydroxide. The aqueous solution (red) was extracted 3 times with 300 ml of dichloromethane. The aqueous phase was cooled in a water-ice bath, and the pH was adjusted to 2 with approximately 50 ml of 6 N hydrochloric acid. The mixture (which had become yellow) was extracted 3 times with 300 ml of dichloromethane. The organic phases were combined, washed twice with 250 ml of water and then once with 250 ml of a saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. 33.5 g of 2-hydroxy-N,N-dimethyl-3-nitrobenzamide were obtained in the form of a yellow cotton solid. Yield=97%.

1. temperatureThe reaction medium was cooled to 0-5° C.
2. stirringThe reaction medium was stirred at ambient temperature for 2 days
3. concentrationThe reaction medium was concentrated to dryness
4. dissolutionthe residue was dissolved in 300 ml 1 N sodium hydroxide
5. extractionThe aqueous solution (red) was extracted 3 times with 300 ml of dichloromethane
6. temperatureThe aqueous phase was cooled in a water-ice bath
7. extractionThe mixture (which had become yellow) was extracted 3 times with 300 ml of dichloromethane
8. washwashed twice with 250 ml of water
9. dry with materialonce with 250 ml of a saturated sodium chloride solution, dried over anhydrous magnesium sulfate
10. customevaporated