Ethyl Acetate → tert-butyl N-(2-anilinophenyl)glycinate

HRID 1375353Notes

Reaction equation

HRID 1375353 reaction equation
[C:1]1([NH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[NH2:14])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([O-])([O-])=O.[K+].[K+].Br[CH2:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24].CCOC(C)=O>CN(C=O)C>[NH:7]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[NH:14][CH2:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 68297N-Phenyl-o-phenylenediamineHCID 79177tert-Butyl bromoacetate

Product 1

HCID 69425039tert-butyl N-(2-anilinophenyl)glycinateYield 92.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirring solution of N-phenyl-o-phenylene diamine (20 g, 180.55 n M) in 200 ml of DMF at RT was added K2CO3 (16.5 g, 120 mM) followed by tert-butyl bromoacetate (21.17 g 108.55 mM). The resulting mixture was stirred at RT until TLC (Hex:AcOEt 3:1) showed completion of reaction. The mixture was filtered to remove the K2CO3 and then diluted with 800 mL of EtOAc and 200 mL of Et2O. This solution was washed successively with H2O (2×400 mL), brine (1×400 mL), 1 N HCl (2×400 mL), and H2O (1×400 mL), and the organics dried (MgSO4) and concentrated to give a greenish-black oil. The resultant oil was purified by silica gel flash column chromatography using hexane/EtOAc 4/1 and the combined filtrates evaporated in vacuo to give 30 g of product.

Workup

  1. customcompletion of reaction
  2. filtrationThe mixture was filtered
  3. customto remove the K2CO3
  4. additiondiluted with 800 mL of EtOAc and 200 mL of Et2O
  5. washThis solution was washed successively with H2O (2×400 mL), brine (1×400 mL), 1 N HCl (2×400 mL), and H2O (1×400 mL)
  6. dry with materialthe organics dried (MgSO4)
  7. concentrationconcentrated
  8. customto give a greenish-black oil
  9. customThe resultant oil was purified by silica gel flash column chromatography
  10. customthe combined filtrates evaporated in vacuo

Sources & evidence

ORD record
ord-489248b5cc3c4e75b0fcaee6672fbcdf
Source dataset
uspto-grants-2007_01
Patent number
US07169773B2

Reaction notes

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