Hydrochloric Acid → 3-Bromo-N-methyl-5-nitrobenzamide

HRID 1766385Notes

Reaction equation

HRID 1766385 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)[C:5](O)=[O:6].C(Cl)(=O)C(Cl)=O.[CH3:20][NH2:21].Cl>ClCCl.CN(C)C=O.O1CCCC1.C(OCC)(=O)C.O>[CH3:20][NH:21][C:5](=[O:6])[C:4]1[CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=[C:2]([Br:1])[CH:3]=1

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 6329MethylamineHCID 65578Oxalyl chlorideHCID 2393363-Bromo-5-nitrobenzoic acid

Product 1

HCID 222526863-Bromo-N-methyl-5-nitrobenzamideYield 94%

Reagents, catalysts & solvents 5

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A suspension of 3-bromo-5-nitrobenzoic acid (7.10 g, 28.9 mmol) in dichloromethane (50 mL) was treated with oxalyl chloride (5.04 mL, 57.7 mmol) and a few drops of N,N-dimethylformamide, producing gas evolution. After 2 hours, the mixture was concentrated to give an oil, which was dissolved in tetrahydrofuran and added dropwise to a stirred solution of methylamine in tetrahydrofuran (2.0 M, 28.9 mL, 57.7 mmol) at 0° C. After stirring overnight, the mixture was treated with water, ethyl acetate and 0.2 N aqueous hydrochloric acid. The layers were separated after mixing, and the organic phase was washed with 0.2 N aqueous hydrochloric acid, then with saturated aqueous sodium chloride. The solution was dried over sodium sulfate and concentrated under vacuum to provide a yellow solid (7.0 g, 94%). 1H NMR (300 MHz, DMSO-d6) δ9.92 (m, 1H), 8.64 (s, 1H), 8.53 (s, 1H), 8.43 (s, 1H), 2.81 (d, J=7 Hz, 3H).

Workup

  1. customproducing gas evolution
  2. concentrationthe mixture was concentrated
  3. customto give an oil, which
  4. customThe layers were separated
  5. additionafter mixing
  6. washthe organic phase was washed with 0.2 N aqueous hydrochloric acid
  7. dry with materialThe solution was dried over sodium sulfate
  8. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-177ff5190ad74b9a8136a445da552380
Source dataset
uspto-grants-2007_06
Patent number
US07230022B2

Reaction notes

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