Diisopropylamine → HCID 21951863, compound

HRID 2215865Notes

Reaction equation

HRID 2215865 reaction equation
CO[C:3](=[O:19])[C:4]1[CH:9]=[CH:8][C:7]([NH:10][C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[CH:6][C:5]=1[NH2:18].[N+:20]([C:23]1[CH:28]=[CH:27][C:26]([N:29]=[C:30]=[O:31])=[CH:25][CH:24]=1)([O-])=O.C(NC(C)C)(C)C>CN(C)C=O.CO.[Pd]>[NH2:20][C:23]1[CH:28]=[CH:27][C:26]([N:29]2[C:3](=[O:19])[C:4]3[C:5](=[CH:6][C:7]([NH:10][C:11](=[O:12])[O:13][C:14]([CH3:15])([CH3:16])[CH3:17])=[CH:8][CH:9]=3)[NH:18][C:30]2=[O:31])=[CH:25][CH:24]=1

Participants

7

Reactant 3

HCID 7912DiisopropylamineHCID 66012Benzene, 1-isocyanato-4-nitro-HCID 21056495Methyl 2-amino-4-[(tert-butoxycarbonyl)amino]benzoate

Product 1

HCID 21951863HCID 21951863, compoundYield 47.2%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 6228DimethylformamideSolvent2×

Procedure

A solution of 2-amino-4-(tert-butoxycarbonylamino)-benzoic acid methyl ester (6.3 g, 23.6 mmol) and 4-nitrophenyl isocyanate (7.8 g, 47.4 mmoles) in 100 mL dry dimethylformamide was stirred at room temperature for 20 hrs. To it was then added diisopropylamine (8.2 mL, 47.4 mmol), and the reaction mixture was heated in 80° C. bath for 2 hrs. It was cooled to room temperature and the solid precipitates were filtered off. The dimethylformamide filtrate was concentrated in vacuo to evaporate the solvent. To the residue was added 400 mL dichloromethane. After stirred and swirled, the solid was isolated by filtration. This solid was then dissolved in 100 mL dimethylformamide and 200 mL methanol. To it was added 1.0 g 10% Pd/C, and the mixture was subjected to standard hydrogenation using a balloon for 20 hrs. It was filtered through a celite bed. The filtrate was concentrated in vacuo and purified using flash column to afford the title compound (4.1 g, 44%). ES+ MS showed 397 m/z, the correct mass for the product.

Workup

  1. customthe solid precipitates
  2. filtrationwere filtered off
  3. concentrationThe dimethylformamide filtrate was concentrated in vacuo
  4. customto evaporate the solvent
  5. additionTo the residue was added 400 mL dichloromethane
  6. customthe solid was isolated by filtration
  7. customfor 20 hrs
  8. filtrationIt was filtered through a celite bed
  9. concentrationThe filtrate was concentrated in vacuo
  10. custompurified

Sources & evidence

ORD record
ord-7b59d108aac445f49dbbb089cdb00bd4
Source dataset
uspto-grants-2006_09
Patent number
US07109332B2

Reaction notes

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