Potassium Carbonate → HCID 86685432, compound

HRID 1911037Notes

Reaction equation

HRID 1911037 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([F:11])[C:5]([OH:10])=[C:6]([CH:9]=1)[CH:7]=[O:8].Br[CH2:13][CH2:14][CH:15]=[CH2:16].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.CCOC(C)=O>[Br:1][C:2]1[CH:3]=[C:4]([F:11])[C:5]([O:10][CH2:16][CH2:15][CH:14]=[CH2:13])=[C:6]([CH:9]=1)[CH:7]=[O:8]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 21241Homoallyl bromideHCID 27792765-Bromo-3-fluoro-2-hydroxybenzaldehyde

Product 1

HCID 86685432HCID 86685432, compoundYield 95.4%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 5-bromo-3-fluoro-2-hydroxybenzaldehyde from step 4A (2.0 g, 9.13 mmol) in DMF (36.5 ml) was added 4-bromo-1-butene (3.71 ml, 36.5 mmol) and potassium carbonate (1.58 g, 11.4 mmol). The resulting mixture was stirred at rt overnight. The reaction mixture was diluted with EtOAc (100 mL), washed with water (3×30 mL) and brine (30 mL), dried over magnesium sulfate, and then filtered and concentrated in vacuo. Purification by silica gel column chromatography (0-20% EtOAc/hexanes) gave 5-bromo-2-(but-3-enyloxy)-3-fluorobenzaldehyde (2.38 g, 8.71 mmol, 95% yield). 1H NMR (500 MHz, DMSO-d6) δ 10.22 (d, J=0.9 Hz, 1H), 7.98 (dd, J=11.3, 2.4 Hz, 1H), 7.63 (dd, J=2.4, 1.2 Hz, 1H), 5.89 (ddt, J=17.1, 10.4, 6.7 Hz, 1H), 5.17 (dd, J=17.2, 1.7 Hz, 1H), 5.12-5.07 (m, 1H), 4.29 (t, J=6.4 Hz, 1H), 2.57-2.49 (m, 3H).

Workup

  1. washwashed with water (3×30 mL) and brine (30 mL)
  2. dry with materialdried over magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customPurification by silica gel column chromatography (0-20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-b172199d6af342ff90d02c3898166b51
Source dataset
uspto-grants-2013_12
Patent number
US08604024B2

Reaction notes

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