Dimethylformamide → Ethyl 2-(3-tert-butoxycarbonylpropoxy)benzoate

HRID 412706Notes

Reaction equation

HRID 412706 reaction equation
[C:1]([O:10][CH2:11][CH3:12])(=[O:9])[C:2]1[C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[OH:4].C(=O)([O-])[O-].[Cs+].[Cs+].CN(C)C=O.Cl[CH2:25][CH2:26][CH2:27][C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29]>C(OCC)(=O)C>[C:31]([O:30][C:28]([CH2:27][CH2:26][CH2:25][O:4][C:3]1[CH:5]=[CH:6][CH:7]=[CH:8][C:2]=1[C:1]([O:10][CH2:11][CH3:12])=[O:9])=[O:29])([CH3:34])([CH3:33])[CH3:32]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 8365Ethyl SalicylateHCID 10796Cesium carbonateHCID 527695Butanoic acid, 4-chloro-, 1,1-dimethylethyl ester

Product 1

HCID 18537757Ethyl 2-(3-tert-butoxycarbonylpropoxy)benzoateYield 62%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A mixture comprising ethyl salicylate (3.14 g, 18.9 mmol) and cesium carbonate (6.2 g, 18.9 mmol), dimethylformamide (25 mL) and tert-butyl 4-chlorobutyrate (4.08 g, 22.8 mmol) was heated at 70° C. and stirred for 12 hours. The mixture was partitioned between ethyl ether (100 mL) and water and the organic layer was separated and washed with additional water (3×) and saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to afford a colorless oil. The residue was purified by silica gel flash chromatography using pure hexane to (10:1) hexane:ethyl acetate to provide ethyl 2-(3-tert-butoxycarbonylpropoxy)benzoate (3.6 g, 62% yield) as a colorless oil; 1H NMR (300 MHz, CDCl3): 7.80 (d, 1H), 7.49 (tr, 1H), 7.00 (m, 2H), 4.40 (q, 2H), 4.10 (tr, 2H), 2.50 (tr, 2H), 2.10 (m, 2H), 1.45 (s, 9H), 1.40 (tr, 3H).

Workup

  1. customThe mixture was partitioned between ethyl ether (100 mL) and water
  2. customthe organic layer was separated
  3. washwashed with additional water (3×) and saturated aqueous sodium chloride
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto afford a colorless oil
  8. customThe residue was purified by silica gel flash chromatography

Sources & evidence

ORD record
ord-d8acf5dfa19e4c43a2715c2f0fd46bf3
Source dataset
uspto-grants-2003_05
Patent number
US06562854B2

Reaction notes

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