N,N'-Dimethylethylenediamine → Methyl 6-(2,2-dimethylpropionylamino)-2-nitro-3-(2-oxopyrrolidin-1-yl)-benzoate

HRID 715988Notes

Reaction equation

HRID 715988 reaction equation
CNCCNC.Br[C:8]1[C:9]([N+:25]([O-:27])=[O:26])=[C:10]([C:15]([NH:18][C:19](=[O:24])[C:20]([CH3:23])([CH3:22])[CH3:21])=[CH:16][CH:17]=1)[C:11]([O:13][CH3:14])=[O:12].[NH:28]1[CH2:32][CH2:31][CH2:30][C:29]1=[O:33].C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.O.C(OCC)(=O)C.[Cu]I>[CH3:21][C:20]([CH3:23])([CH3:22])[C:19]([NH:18][C:15]1[C:10]([C:11]([O:13][CH3:14])=[O:12])=[C:9]([N+:25]([O-:27])=[O:26])[C:8]([N:28]2[CH2:32][CH2:31][CH2:30][C:29]2=[O:33])=[CH:17][CH:16]=1)=[O:24]

Participants

9

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 120252-PyrrolidoneHCID 70982880Methyl 3-bromo-6-(2,2-dimethylpropionyl-amino)-2-nitrobenzoate2×

Product 1

HCID 70982623Methyl 6-(2,2-dimethylpropionylamino)-2-nitro-3-(2-oxopyrrolidin-1-yl)-benzoateYield 17.8%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

A solution of N,N′-dimethylethylenediamine (1.72 g) in toluene (15 mL) was added to a mixture of methyl 3-bromo-6-(2,2-dimethylpropionylamino)-2-nitro-benzoate (Intermediate 58, 1.72 g), pyrrolidin-2-one (0.489 g), copper(I) iodide (0.091 g) and potassium carbonate (1.32 g) and the mixture was stirred and heated under nitrogen at 110° C. for 5 hours. After cooling, the mixture was diluted with water and ethyl acetate and the organic phase was dried (Na2SO4) and filtered. The filtrate was concentrated in vacuo and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 10-80% to give methyl 6-(2,2-dimethylpropionylamino)-2-nitro-3-(2-oxopyrrolidin-1-yl)-benzoate (0.310 g) as an off-white solid.

Workup

  1. temperatureAfter cooling
  2. dry with materialthe organic phase was dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated in vacuo
  5. customthe residue was purified by chromatography on silica
  6. washeluting with a mixture of ethyl acetate and cyclohexane with a gradient of 10-80%

Sources & evidence

ORD record
ord-48bcd428ce9c4c60affb03714d8d0fb0
Source dataset
uspto-grants-2015_11
Patent number
US09187494B2

Reaction notes

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