Benzyl Bromide → 1-(Benzyloxy)-4-iodobenzene

HRID 1955477Notes

Reaction equation

HRID 1955477 reaction equation
[I:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[CH2:15](Br)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>CN(C)C=O>[CH2:15]([O:8][C:5]1[CH:6]=[CH:7][C:2]([I:1])=[CH:3][CH:4]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 108944-IodophenolHCID 11430Potassium Carbonate

Product 1

HCID 5196711-(Benzyloxy)-4-iodobenzene

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
65 °C

Procedure

To a 500 mL 3-necked flask equipped with reflux condenser, addition funnel, nitrogen inlet and magnetic stirring was added 50.0 g (0.277 mol, 1.0 eq.) 4-iodophenol (Aldrich), 37.69 g (0.2727 mol, 1.2 eq.) potassium carbonate (Fischer) and 250 mL dimethylformamide (DMF) and the mixture was heated to 65° C. for 20 minutes. To the addition funnel was added 48.61 g (0.284 mol., 1.25 eq) benzylbromide (Aldrich) and 50 mL DMF. The heat was turned off and the contents of the addition funnel were added dropwise over 15 minutes during which time an exotherm to 75° C. was produced with salt formation. Heating was resumed at 45° C. for an additional 20 hours after which liquid chromatography (LC) indicated complete conversion. The mixture was poured onto ice and extracted with Et2O, dried over sodium sulfate (Na2SO4), reduced in vacuo and recrystallized from ethanol giving 44.2 g of 1 as tan crystals (m.p.=55°-56° C.) in 63 percent isolated yield (99 percent by LC). It had the following spectral properties. 1H NMR (250 MHz, CDCl3): δ4.82 (s,2H), 6.54 (d), 7.12-7.2 (m), 7.34 (d). 13C NMR (63 MHz, CDCl3 : δ70.1, 117.3, 127.4, 128.1, 128.6, 136.5, 138.2, 158.7. HRMS m/z (EI) calcd (found) for C13H11 OI=309.9855 (309.9851).

Workup

  1. customTo a 500 mL 3-necked flask equipped
  2. temperaturewith reflux
  3. additioncondenser, addition funnel, nitrogen inlet
  4. additionthe contents of the addition funnel were added dropwise over 15 minutes during which time an exotherm to 75° C.
  5. customwas produced with salt formation
  6. temperatureHeating
  7. additionThe mixture was poured onto ice
  8. extractionextracted with Et2O
  9. dry with materialdried over sodium sulfate (Na2SO4)
  10. customrecrystallized from ethanol giving 44.2 g of 1 as tan crystals (m.p.=55°-56° C.) in 63 percent
  11. customisolated
  12. customyield (99 percent by LC)

Sources & evidence

ORD record
ord-89a5b92534e8428496dde19d95eb57e1
Source dataset
uspto-grants-1998_07
Patent number
US05776374

Reaction notes

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