Cesium carbonate → 2-(5-Benzyloxy-2-but-1-enylphenoxy)-2-methylpropionic Acid Ethyl Ester

HRID 2229055Notes

Reaction equation

HRID 2229055 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]([CH:16]=[CH:17][CH2:18][CH3:19])=[C:13]([OH:15])[CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[C:21]([CH3:28])([CH3:27])[C:22]([O:24][CH2:25][CH3:26])=[O:23].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[CH2:25]([O:24][C:22](=[O:23])[C:21]([O:15][C:13]1[CH:14]=[C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[CH:10]=[CH:11][C:12]=1[CH:16]=[CH:17][CH2:18][CH3:19])([CH3:28])[CH3:27])[CH3:26]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl esterHCID 693132605-Benzyloxy-2-but-1-enylphenol

Product 1

HCID 693103232-(5-Benzyloxy-2-but-1-enylphenoxy)-2-methylpropionic Acid Ethyl EsterYield 76%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
55 °C

Procedure

5-Benzyloxy-2-but-1-enylphenol (0.70 g, 2.75 mmol) (see Ex. 40, part A) was dissolved in anhydrous DMF (12 mL), followed by the addition of ethyl bromoisobutyrate (1.62 mL, 11.0 mmol), and cesium carbonate (3.58 g, 11.0 mmol). The mixture was then heated for 18 h (55° C.). The reaction mixture was then cooled and concentrated in vacuo. The crude residue was partitioned between ethyl acetate (70 mL) and water (40 mL). The organic layer was washed with brine, dried (Na2SO4), and removed in vacuo. The crude residue was purified using radial chromatography, eluting with 5% ethyl acetate/hexanes to give 0.77 g (76%) of a colorless oil. 1H NMR (400 MHz, CDCl3) δ7.41-7.28 (m, 6H), 6.65-6.59 (m, 2H), 6.40 (d, J 2.4 Hz, 1H), 6.14-6.07 (m, 1H), 4.99 (s, 2H), 4.22 (q, J=7.2 Hz, 2H), 2.22 (quintet, J=7.6 Hz, 2H), 1.56 (s, 6H), 1.26 (t, J=7.1 Hz, 3H), 1.08 (t, J=7.6 Hz, 3H), MS (ES) m/e 369 (M+1).

Workup

  1. temperatureThe reaction mixture was then cooled
  2. concentrationconcentrated in vacuo
  3. customThe crude residue was partitioned between ethyl acetate (70 mL) and water (40 mL)
  4. washThe organic layer was washed with brine
  5. dry with materialdried (Na2SO4)
  6. customremoved in vacuo
  7. customThe crude residue was purified
  8. washeluting with 5% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-6b1df55caeef4e39ae044c3003cd62f8
Source dataset
uspto-grants-2002_07
Patent number
US06417212B1

Reaction notes

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