Methylamine → Methyl 4-(methylamino)carbonyl-3-nitrobenzoate

HRID 1451113Notes

Reaction equation

HRID 1451113 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:13]=[CH:12][C:8]([C:9](O)=[O:10])=[C:7]([N+:14]([O-:16])=[O:15])[CH:6]=1)=[O:4].[CH3:17][NH2:18]>S(Cl)(Cl)=O.CN(C)C=O.O>[CH3:17][NH:18][C:9]([C:8]1[CH:12]=[CH:13][C:5]([C:3]([O:2][CH3:1])=[O:4])=[CH:6][C:7]=1[N+:14]([O-:16])=[O:15])=[O:10]

Participants

6

Reactant 2

HCID 6329MethylamineHCID 219064744-(Methoxycarbonyl)-2-nitrobenzoic acid

Product 1

HCID 10752388Methyl 4-(methylamino)carbonyl-3-nitrobenzoateYield 55.1%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 24386Thionyl ChlorideSolvent

Procedure

A mixture of 4-methoxycarbonyl-2-nitrobenzoic acid (3.6 g, 0.016 mol) in thionyl chloride (32 mL) was heated to reflux in the presence of two drops of dimethylformamide for 3 h. Thionyl chloride was distilled and the concentrate was left under vacuum for 0.5 h. The residue was dissolved in dichloromethane (10 mL) and added to a solution of aqueous methylamine (40%, 2.0 g, 0.026 mol) in water (5 mL) over a period of 5 min. The mixture was further stirred for 10 min and the white precipitate was collected by filtration. The cake was washed with water, dried, and recrystallized from ethyl acetate-hexane to give 2.1 g (55%) of methyl 4-(methylamino)carbonyl-3-nitrobenzoate as white needles, mp 155° C.

Workup

  1. temperaturewas heated
  2. distillationThionyl chloride was distilled
  3. dissolutionThe residue was dissolved in dichloromethane (10 mL)
  4. filtrationthe white precipitate was collected by filtration
  5. washThe cake was washed with water
  6. customdried
  7. customrecrystallized from ethyl acetate-hexane

Sources & evidence

ORD record
ord-ba8c75a6aa7a4fcc83029df6a4887317
Source dataset
uspto-grants-1997_02
Patent number
US05602277

Reaction notes

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