Water → t-butyl [N-(t-butoxycarbonyl)-N-(methoxycarbonyl)aminomethyl]-3-nitrobenzoate

HRID 2186052Notes

Reaction equation

HRID 2186052 reaction equation
BrC[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.[CH3:33]N(C=O)C>>[C:27]([O:26][C:24]([N:19]([CH2:33][C:5]1[C:4]([N+:16]([O-:18])=[O:17])=[CH:3][CH:15]=[CH:14][C:6]=1[C:7]([O:9][C:10]([CH3:11])([CH3:12])[CH3:13])=[O:8])[C:20]([O:22][CH3:23])=[O:21])=[O:25])([CH3:30])([CH3:29])[CH3:28]

Participants

5

Reactant 4

HCID 962WaterHCID 6228Dimethylformamide2×HCID 18462578t-Butyl 4-bromomethyl-3-nitrobenzoateHCID 86754983Potassium t-butyl methyl iminodicarboxylate

Product 1

HCID 86758139t-butyl [N-(t-butoxycarbonyl)-N-(methoxycarbonyl)aminomethyl]-3-nitrobenzoateYield 73%

Procedure

To a solution of t-butyl 4-bromomethyl-3-nitrobenzoate (2.27 g, 7.2 mmol) (Int. J. Peptide Res., 36, 31 (1990)) in DMF (25 mL) was added a suspension of potassium t-butyl methyl iminodicarboxylate (J.C.S. Perkin I, 1088, (1977)) (1.56 g, 7.3 mmol) in DMF (20 mL). The dark brown solution was stirred 1 h and poured into water and extracted with ethyl acetate. The combined organic layers were washed with water, dried (sodium sulfate) and concentrated to give a pale orange oil which was purified by flash chromatography (silica gel, 20% ethyl acetate/hexane) to give the title compound (2.15 g, 73%). 1H NMR (400 MHz, CDCl3) δ8.65 (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
  2. washThe combined organic layers were washed with water
  3. dry with materialdried (sodium sulfate)
  4. concentrationconcentrated
  5. customto give a pale orange oil which
  6. customwas purified by flash chromatography (silica gel, 20% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-c948812f004c4f168421cb9f6ffe02d7
Source dataset
uspto-grants-2002_06
Patent number
US06403578B1

Reaction notes

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