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

HRID 1833476Notes

Reaction equation

HRID 1833476 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)C=O>[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 dimethylformamide (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 dimethyl-formamide (120 ml.). The resulting mixture is stirred at room temperature for 10 minutes, treated with bromoacetaldehyde diethylacetal (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. Dimethylformamide 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° C./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)δ1.17 (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. customDimethylformamide 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° C./0.05 mm

Sources & evidence

ORD record
ord-e3badc49ce9b45d9a155b6467324c32a
Source dataset
uspto-grants-1978_01
Patent number
US04066675

Reaction notes

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