4-Bromophenol → 1-Bromo-4-(ethenyloxy)benzene

HRID 1427537Notes

Reaction equation

HRID 1427537 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.[C:9]([O-])(=O)[CH3:10].[Na+].C(OC=C)(=O)C>C1CC=CCCC=C1.C1CC=CCCC=C1.[Cl-].[Cl-].[Ir].[Ir].C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH:9]=[CH2:10])=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 78084-BromophenolHCID 7904Vinyl AcetateHCID 517045Sodium Acetate

Product 1

HCID 114013721-Bromo-4-(ethenyloxy)benzene

Reagents, catalysts & solvents 2

HCID 6436381Chloro(1,5-cyclooctadiene)iridium(I) dimerCatalystHCID 1140TolueneSolvent

Conditions

Temperature
102 °C

Procedure

Under nitrogen, a 250 milliliter round bottom flask was charged with 4-bromophenol (8.00 grams, 46.2 millimoles, 1.0 equivalent), sodium acetate (2.28 grams, 27.7 millimoles, 0.6 equivalent) and bis(1,5-cyclooctadiene)diiridium(I)dichloride (233 milligram, 347 micromoles, 0.0075 equivalent). Toluene (75 milliliter) was added to this and vinyl acetate (8.5 milliliter, 92 millimoles, 2.0 equivalents) was added via syringe. The reaction was heated to 102° C. for 3 hours and then allowed to cool to room temperature. The crude reaction was concentrated on a rotary evaporator and filtered through a plug of silica. The solvent was removed by rotary evaporation and the product dried under high vacuum. The final compound was obtained in form of a colorless to slightly yellow oil (6.97 gram, 35.0 millimoles, 76%). 1H NMR (500 MHz, CDCl3) δ 7.44-7.37 (m, 2H), 6.91-6.84 (m, 2H), 6.56 (dd, J=13.7, 6.1 Hz, 1H), 4.77 (dd, J=13.7, 1.8 Hz, 1H), 4.45 (dd, J=6.1, 1.8 Hz, 1H).

Workup

  1. additionwas added via syringe
  2. temperatureto cool to room temperature
  3. customThe crude reaction
  4. concentrationwas concentrated on a rotary evaporator
  5. filtrationfiltered through a plug of silica
  6. customThe solvent was removed by rotary evaporation
  7. customthe product dried under high vacuum

Sources & evidence

ORD record
ord-19209cb724db48eea1d63278e0425a01
Source dataset
uspto-grants-2015_01
Patent number
US08933239B1

Reaction notes

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