Water → tert-Butyl 4-[N-(tert-Butoxycarbonyl)-N-(methoxycarbonyl)aminomethyl]-3-nitrobenzoate

HRID 613374Notes

Reaction equation

HRID 613374 reaction equation
Br[CH2:2][C:3]1[CH:15]=[CH:14][C:6]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])=[CH:5][C:4]=1[N+:16]([O-:18])=[O:17].[NH:19]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C:20]([O:22][CH3:23])=[O:21].[K].O>CN(C)C=O>[C:27]([O:26][C:24]([N:19]([CH2:2][C:3]1[CH:15]=[CH:14][C:6]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])=[CH:5][C:4]=1[N+:16]([O-:18])=[O:17])[C:20]([O:22][CH3:23])=[O:21])=[O:25])([CH3:30])([CH3:29])[CH3:28]

Participants

5

Reactant 3

HCID 962WaterHCID 18462578t-Butyl 4-bromomethyl-3-nitrobenzoateHCID 86754983Potassium t-butyl methyl iminodicarboxylate

Product 1

HCID 19591949tert-Butyl 4-[N-(tert-Butoxycarbonyl)-N-(methoxycarbonyl)aminomethyl]-3-nitrobenzoateYield 73%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a solution of tert-butyl 4-bromomethyl-3-nitrobenzoate (2.27 g, 7.2 mmol) (Int. J. Peptide Res. 1990, 36, 31) in dimethylformamide (25 mL) was added a suspension of potassium tert-butyl methyl iminodicarboxylate (J.C.S. Perkin I 1977, 1088-90) (1.56 g, 7.3 mmol) in dimethylformamide (20 mL). The dark brown solution was stirred 1 h and poured into water (400 mL), extracted with ethyl acetate (3×100 mL) and the combined organic layers were washed with water (5×75 mL), dried (sodium sulfate) and concentrated to give a pale orange oil which was purified by flash chromatography on silica gel (20% ethyl acetate/hexane) to give the title compound (2.15 g, 73%): 1H NMR (400 MHz, CDCl3) δ 8.65 (s, 1H), 8.2 (d, 1H), 7.45 (d, 1H), 5.3 (s, 2H), 3.8 (s, 3H), 1.6 (s, 9H), 1.45 (s, 9H).

Workup

  1. extractionextracted with ethyl acetate (3×100 mL)
  2. washthe combined organic layers were washed with water (5×75 mL)
  3. dry with materialdried (sodium sulfate)
  4. concentrationconcentrated
  5. customto give a pale orange oil which
  6. customwas purified by flash chromatography on silica gel (20% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-5b8472431fa6446eb478c2e491917903
Source dataset
uspto-grants-1999_12
Patent number
US06008213

Reaction notes

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