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

HRID 2417108Notes

Reaction equation

HRID 2417108 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) δ 7.41-7.28 (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-4450a794141c4c02adf3b4f39ade523b
Source dataset
uspto-grants-2004_11
Patent number
US06825222B2

Reaction notes

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