Pyridine → N-(4-bromo-2-nitrophenyl)acetamide

HRID 1936428Notes

Reaction equation

HRID 1936428 reaction equation
[N+:1]([C:4]1[CH:10]=[C:9]([Br:11])[CH:8]=[CH:7][C:5]=1[NH2:6])([O-:3])=[O:2].[C:12](OC(=O)C)(=[O:14])[CH3:13].C(Cl)(=O)C.N1C=CC=CC=1>O1CCCC1.C(OCC)C.O>[Br:11][C:9]1[CH:8]=[CH:7][C:5]([NH:6][C:12](=[O:14])[CH3:13])=[C:4]([N+:1]([O-:3])=[O:2])[CH:10]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 6367Acetyl chlorideHCID 7918Acetic AnhydrideHCID 701324-Bromo-2-nitroaniline

Product 1

HCID 136690N-(4-bromo-2-nitrophenyl)acetamideYield 81%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2-nitro-4-bromoaniline (7.07 g, 32.6 mmol) in dry tetrahydrofuran (33 mL) was cooled to 0° C. and then treated with acetic anhydride (6.66 g, 65.2 mmol). The reaction mixture was stirred at 0° C. for 110 min and then allowed to warm to 25° C. The reaction mixture was stirred at 25° C. for 15 h, at which time, thin layer chromatography analysis of the reaction mixture indicated the presence of only starting material. The reaction mixture was then slowly treated with acetyl chloride (5 mL) and pyridine (5 mL) at 25° C. The resulting orange suspension was stirred at 25° C. for 2 h and then treated with water (50 mL). The organic compound was extracted into ethyl acetate (2×70 mL). The combined extracts were washed with a 3N aqueous hydrochloric acid solution (1×100 mL) and a saturated aqueous sodium chloride solution (1×100 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to afford a yellow solid. The yellow solid was treated with diethyl ether (50 mL) and hexanes (50 mL). The solid was collected by filtration and washed with hexanes to afford N-(4-bromo-2-nitro-phenyl)-acetamide (6.82 g, 81%) as a yellow solid: mp 100-102° C.; EI-HRMS m/e cared for C8H7BrN2O3 (M+) 257.9640, found 257.9641.

Workup

  1. temperatureto warm to 25° C
  2. stirringThe reaction mixture was stirred at 25° C. for 15 h, at which time, thin layer chromatography analysis of the reaction mixture
  3. stirringThe resulting orange suspension was stirred at 25° C. for 2 h
  4. extractionThe organic compound was extracted into ethyl acetate (2×70 mL)
  5. washThe combined extracts were washed with a 3N aqueous hydrochloric acid solution (1×100 mL)
  6. dry with materiala saturated aqueous sodium chloride solution (1×100 mL), dried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto afford a yellow solid
  10. filtrationThe solid was collected by filtration
  11. washwashed with hexanes

Sources & evidence

ORD record
ord-6ef7d3d5646d482c9130f6562377de69
Source dataset
uspto-grants-2002_05
Patent number
US06388088B1

Reaction notes

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