Calcium Carbonate → N-(4-bromo-2-ethoxycarbonylaminophenyl)-N-ethoxycarbonyl-N',N'-dimethylethylenediamine

HRID 373055Notes

Reaction equation

HRID 373055 reaction equation
[CH2:1]([O:3][C:4]([NH:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[NH:13][CH2:14][CH2:15][N:16]([CH3:18])[CH3:17])=[O:5])[CH3:2].[C:19](=[O:22])([O-])[O-:20].[Ca+2].[Br-:24].[Br-].[Br-].C([N+](C)(C)C)[C:28]1[CH:33]=CC=CC=1.C([N+](C)(C)C)C1C=CC=CC=1.C([N+](C)(C)C)C1C=CC=CC=1>CO.ClCCl>[Br:24][C:11]1[CH:10]=[CH:9][C:8]([N:13]([C:19]([O:20][CH2:33][CH3:28])=[O:22])[CH2:14][CH2:15][N:16]([CH3:17])[CH3:18])=[C:7]([NH:6][C:4]([O:3][CH2:1][CH3:2])=[O:5])[CH:12]=1

Participants

6

Reactant 3

HCID 10112Calcium CarbonateHCID 19811338N-(2-ethoxycarbonylaminophenyl)-N',N'-dimethylethylenediamineHCID 53442637Benzyltrimethylammoniumtribromide

Product 1

HCID 19811310N-(4-bromo-2-ethoxycarbonylaminophenyl)-N-ethoxycarbonyl-N',N'-dimethylethylenediamineYield 111.7%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of N-(2-ethoxycarbonylaminophenyl)-N',N'-dimethylethylenediamine (0.94 g) in methanol (20 ml) and dichloromethane (30 ml) were added calcium carbonate (0.40 g) and benzyltrimethylammonium tribromide (1.46 g). The reaction mixture was stirred at room temperature for 1.5 hours. The insoluble matter was then filtered off and the solvent was distilled off under reduced pressure. The residue was diluted with 1N aqueous sodium hydroxide solution and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was dissolved in chloroform (30 ml). To the solution was added ethyl chloroformate (0.53 g) dropwise, and the reaction mixture was stirred at room temperature for 5 hours. The reaction mixture was successively washed with 1N aqueous sodium hydroxide solution and saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography (eluent:chloroform:methanol=50:1) to give 0.95 g of N-(4-bromo-2-ethoxycarbonylaminophenyl)-N-ethoxycarbonyl-N',N'-dimethylethylenediamine.

Workup

  1. filtrationThe insoluble matter was then filtered off
  2. distillationthe solvent was distilled off under reduced pressure
  3. additionThe residue was diluted with 1N aqueous sodium hydroxide solution
  4. extractionextracted with ethyl acetate
  5. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  6. distillationthe solvent was distilled off
  7. dissolutionthe residue was dissolved in chloroform (30 ml)
  8. additionTo the solution was added ethyl chloroformate (0.53 g) dropwise
  9. stirringthe reaction mixture was stirred at room temperature for 5 hours
  10. washThe reaction mixture was successively washed with 1N aqueous sodium hydroxide solution and saturated aqueous sodium chloride solution
  11. dry with materialdried over anhydrous sodium sulfate
  12. distillationThe solvent was distilled off under reduced pressure
  13. customthe residue was purified by silica gel chromatography (eluent:chloroform:methanol=50:1)

Sources & evidence

ORD record
ord-01eaa100a51549a48c12840fae79c06f
Source dataset
uspto-grants-1992_11
Patent number
US05162318

Reaction notes

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