Potassium Iodide → Methyl 2-[2-(tert-butoxycarbonylamino)ethoxy]-4-methoxybenzoate

HRID 1445447Notes

Reaction equation

HRID 1445447 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([OH:13])[C:6](=[CH:11][CH:12]=1)[C:7]([O:9][CH3:10])=[O:8].[C:14](=O)([O-])[O-].[K+].[K+].BrC([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])CN.[I-].[K+].C[N:34]([CH3:37])C=O>O>[C:27]([O:26][C:24]([NH:34][CH2:37][CH2:14][O:13][C:5]1[CH:4]=[C:3]([O:2][CH3:1])[CH:12]=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8])=[O:25])([CH3:28])([CH3:29])[CH3:30]

Participants

7

Reactant 5

HCID 4875Potassium IodideHCID 6228Dimethylformamide2×HCID 11430Potassium CarbonateHCID 79523Methyl 4-methoxysalicylateHCID 866284082-bromo-N-tert-butyloxycarbonylethylamine

Product 1

HCID 68530686Methyl 2-[2-(tert-butoxycarbonylamino)ethoxy]-4-methoxybenzoateYield 81%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Methyl 4-methoxysalicylate (7.05 g, 38.7 mmol) and anhydrous potassium carbonate (16.03 g, 116 mmol) were stirred together in 30 ml dimethylformamide (DMF) for a few minutes at room temperature. To the stirring mixture was added 2-bromo-N-(tert-butoxycarbonyl)ethylamine (26.0 g, 116 mmol) in 30 ml DMF and 500 mg of freshly ground potassium iodide, then the mixture was placed under nitrogen and stirred at room temperature for several days. The reaction mixture was diluted with water (250 ml) and extracted with two 250 ml portions of dichloromethane. The organic extracts were pooled, washed (twice each with 1 N NaOH, water, and brine), then dried over Na2SO4 and concentrated in vacuo to afford a colorless oil. The oil was purified on a 1200 ml silica column packed and eluted with 95:5 CH2Cl2:EtOAc to yield methyl 2-[2-(tert-butoxycarbonylamino)ethoxy]-4-methoxybenzoate (10.29 g, 81%) as a viscous colorless oil.

Workup

  1. extractionextracted with two 250 ml portions of dichloromethane
  2. washwashed (twice each with 1 N NaOH, water, and brine),
  3. dry with materialthen dried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. customto afford a colorless oil
  6. customThe oil was purified on a 1200 ml silica column
  7. washeluted with 95:5 CH2Cl2

Sources & evidence

ORD record
ord-8f404c63596a47ba8bcce37c0346edda
Source dataset
uspto-grants-2010_02
Patent number
US07666866B2

Reaction notes

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