Dimethylformamide → 5-Fluoro-2-(2-propen-1-yloxy)benzaldehyde

HRID 1771270Notes

Reaction equation

HRID 1771270 reaction equation
[F:1][C:2]1[CH:9]=[C:6]([CH:7]=[O:8])[C:5]([OH:10])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].CN(C=O)C.[CH2:22](Br)[CH:23]=[CH2:24]>O>[CH2:24]([O:10][C:5]1[CH:4]=[CH:3][C:2]([F:1])=[CH:9][C:6]=1[CH:7]=[O:8])[CH:23]=[CH2:22]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 27373285-Fluorosalicylaldehyde

Product 1

HCID 152741635-Fluoro-2-(2-propen-1-yloxy)benzaldehydeYield 90.4%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a round bottom flask were added 5-fluorosalicylaldehyde (47c, 4.0 g, 28.5 mmol, 1.0 equiv.), potassium carbonate (4.92 g, 35.6 mmol, 1.25 equiv.), and DMF (20 mL). Allyl bromide (3.7 mL, 42.8 mmol, 1.5 equiv.) was added slowly to the mixture. The reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with water (50 mL) and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with water (2×25 mL), 0.1M KOH (2×25 mL), water (2×25 mL), and brine (2×25 mL), dried over MgSO4, filtered, and concentrated to yield 53b (4.64 g, 90.2%) as a pale yellow liquid. 1H-NMR (500 MHz, CDCl3) δ 10.47 (d, 1H, J=3.0 Hz), 7.50 (dd, 1H, J=3.0, 8.0 Hz), 7.23 (ddd, 1H, J=3.0, 7.5, 11.0 Hz), 6.95 (dd, 1H, J=4.0, 9.0 Hz), 6.06 (tdd, 1H, J=5.0, 10.5, 17.5 Hz), 5.44 (qd, 1H, J=1.5, 17.0 Hz), 5.34 (ddd, 1H, J=1.5, 2.5, 10.5 Hz), 4.64 (td, 2H, J=1.5, 5.0 Hz). 13C-NMR (125 MHz, CDCl3) δ 188.8, 157.4 (d, JC-F=1.9 Hz), 157.2 (d, JC-F=240.5 Hz), 132.4, 126.1 (d, JC-F=5.9 Hz), 122.6 (d, JC-F=23.8 Hz), 118.5, 114.8 (d, JC-F=7.1 Hz), 114.2 (d, JC-F=23.1 Hz), 70.1. 19F-NMR (470 MHz, CDCl3) δ −125.5. HRMS (EI): 180.05789 (M+); calcd. for C10H9FO2: 180.05866.

Workup

  1. extractionextracted with ethyl acetate (3×50 mL)
  2. washThe combined organic layers were washed with water (2×25 mL), 0.1M KOH (2×25 mL), water (2×25 mL), and brine (2×25 mL)
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-e6a6eaf12b8649839819ccb016f12d01
Source dataset
uspto-grants-2016_02
Patent number
US09249116B2

Reaction notes

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