Allyl Alcohol → [4-Amino-2-(4-bromo-2-fluoro-benzylcarbamoyl)-phenoxy]-acetic acid allyl ester

HRID 457958Notes

Reaction equation

HRID 457958 reaction equation
[NH2:1][C:2]1[CH:12]=[CH:11][C:5]([O:6][CH2:7][C:8]([OH:10])=[O:9])=[C:4]([C:13](=[O:24])[NH:14][CH2:15][C:16]2[CH:21]=[CH:20][C:19]([Br:22])=[CH:18][C:17]=2[F:23])[CH:3]=1.[CH2:25](O)[CH:26]=[CH2:27]>OS(O)(=O)=O>[CH2:27]([O:9][C:8](=[O:10])[CH2:7][O:6][C:5]1[CH:11]=[CH:12][C:2]([NH2:1])=[CH:3][C:4]=1[C:13](=[O:24])[NH:14][CH2:15][C:16]1[CH:21]=[CH:20][C:19]([Br:22])=[CH:18][C:17]=1[F:23])[CH:26]=[CH2:25]

Participants

4

Reactant 2

HCID 7858Allyl AlcoholHCID 12968791HCID 12968791, compound

Product 1

HCID 22093473[4-Amino-2-(4-bromo-2-fluoro-benzylcarbamoyl)-phenoxy]-acetic acid allyl esterYield 20%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidCatalyst

Procedure

[4-Amino-2-(4-bromo-2-fluoro-benzylcarbamoyl)-phenoxy]acetic acid (0.62 g, 1.56 mmol) was dissolved in allyl alcohol (15 mL, 0.1 M). This solution was treated with 7 drops of concentrated H2SO4 and stirred at room temperature for 48 h. The reaction was concentrated, redissolved in ethyl acetate, washed with H2O, saturated aq NaCl (3×), dried over Na2SO4 and filtered. The filtrate was treated with decolorizing charcoal, boiled for 10 minutes, cooled to room temperature, filtered and concentrated. The crude solid was recrystallized from heptane and ethyl acetate to give [4-amino-2-(4-bromo-2-fluoro-benzylcarbamoyl)-phenoxy]-acetic acid allyl ester as a light orange solid (0.13 g, 20%). 1H NMR (DMSO-d6, 300 MHz) δ 8.92 (br t, J=5.4 Hz, 1 H), 7.49–7.80 (m, 4 H), 6.84 (d, J=8.7 Hz, 1 H), 6.63 (br dd, J1=8.7 Hz, J2=2.7 Hz, 1 H), 5.95–5.79 (m, 1 H), 5.29 (br d, J=17.1 Hz, 1 H), 5.19 (br d, J=10.5 Hz, 1 H), 4.91 (br s, 1 H), 4.83 (br s, 2 H), 4.61 (br d, J=5.4 Hz, 1 H).

Workup

  1. concentrationThe reaction was concentrated
  2. dissolutionredissolved in ethyl acetate
  3. washwashed with H2O, saturated aq NaCl (3×)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. additionThe filtrate was treated with decolorizing charcoal
  7. waitboiled for 10 minutes
  8. temperaturecooled to room temperature
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude solid was recrystallized from heptane and ethyl acetate

Sources & evidence

ORD record
ord-b0f88fd392154ef7bb241747e79355fe
Source dataset
uspto-grants-2007_03
Patent number
US07189749B2

Reaction notes

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