Hexane → 1-(2,2-Diethoxyethoxy)-4-fluorobenzene

HRID 1730119Notes

Reaction equation

HRID 1730119 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.CCCCCC.[H-].[Na+].[CH2:17]([O:19][CH:20]([O:23][CH2:24][CH3:25])[CH2:21]Br)[CH3:18]>CN(C=O)C>[CH2:17]([O:19][CH:20]([O:23][CH2:24][CH3:25])[CH2:21][O:8][C:5]1[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=1)[CH3:18]

Participants

6

Reactant 4

HCID 8058HexaneHCID 97324-FluorophenolHCID 24758Sodium hydrideHCID 74852Ethane, 2-bromo-1,1-diethoxy-

Product 1

HCID 114475181-(2,2-Diethoxyethoxy)-4-fluorobenzeneYield 82%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of p-fluorophenol (28.1 g., 0.25 mole) in DMF (30 ml.) is added dropwise to a suspension of hexane (2 × 30 ml.)-prewashed sodium hydride (50% oil dispersion, 12.5 g., 0.26 mole) in DMF (120 ml.). The resulting mixture is stirred at room temperature for 10 minutes, treated with bromoacetaldehyde diethyl acetal (49.3 g., 0.25 mole), and finally heated on a steam bath for 4 hours. The reaction mixture is allowed to come to room temperature and the precipitated sodium bromide is filtered off. DMF is then removed on a rotary evaporator, the oil residue is diluted with acetone (100 ml.) and another quantity of sodium bromide is precipitated which again is removed by filtration. The filtrate is then concentrated on a rotary evaporator leaving an oil residue which is vacuum distilled at 87°/0.05 mm to yield the desired product as colorless oil (46.7 g., 0.205 mole, 82%). ir (neat) 3.4~3.5, 6.21, 6.64, 8.00, 8.25, 8.83, 9.32, 12.08, 13.20μ; pmr (CCl4) δ 1.17 (6H, t, J=7.5Hz), 3.57 (2H, q, J=7.5Hz), 3.61 (2H, q, J=7.5Hz), 3.85 (2H, d, J=5Hz), 4.68 (1H, t, J=5Hz), 6.6- 7.1 (4H, m).

Workup

  1. temperaturefinally heated on a steam bath for 4 hours
  2. customto come to room temperature
  3. filtrationthe precipitated sodium bromide is filtered off
  4. customDMF is then removed on a rotary evaporator
  5. additionthe oil residue is diluted with acetone (100 ml.)
  6. customanother quantity of sodium bromide is precipitated which
  7. customagain is removed by filtration
  8. concentrationThe filtrate is then concentrated on a rotary evaporator
  9. customleaving an oil residue which
  10. distillationdistilled at 87°/0.05 mm

Sources & evidence

ORD record
ord-c41f776d68a44b13a1acfda0c8c7975b
Source dataset
uspto-grants-1976_11
Patent number
US03991106

Reaction notes

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