p-Bromophenyl octyl ether → 2-[4-(Octyloxy)phenyl]thiophene

HRID 1269131Notes

Reaction equation

HRID 1269131 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])=[CH:4][CH:3]=1.C([Sn](CCCC)(CCCC)[C:22]1[S:23][CH:24]=[CH:25][CH:26]=1)CCC.[F-].[K+]>CN(C=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:9]([O:8][C:5]1[CH:6]=[CH:7][C:2]([C:22]2[S:23][CH:24]=[CH:25][CH:26]=2)=[CH:3][CH:4]=1)[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16]

Participants

6

Reactant 3

HCID 145298p-Bromophenyl octyl ether2×HCID 522689Potassium FluorideHCID 27793732-(Tri-n-butylstannyl)thiophene

Product 1

HCID 184481972-[4-(Octyloxy)phenyl]thiopheneYield 49.5%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 1-bromo-4-octyloxybenzene (compound 22) (10.0 g, 0.0351 mol), 2-(tributylstannyl)thiophene (14.4 g, 0.0386 mol) and tetrakis(triphenylphosphine)-palladium (0) (1.22 g, 1.05×10−3 mol) in DMF (200 cm3) was heated at 90° C. for 24 h. The mixture was allowed to cool to RT and the solution was treated with a saturated potassium fluoride solution (100 cm3) to destroy the tin side products. Hexane (2×200 cm3) was added and the combined organic layers were washed with brine (2×200 cm3), water (200 cm3), dried (MgSO4), filtered and concentrated under reduced pressure. Catalyst residues were removed by passing the crude product though a short column containing silica gel [DCM: hexane, 50%: 50%]. The product was recrystallised from ethanol, filtered and washed with cold ethanol (2×30 cm3) to yield a light blue crystalline solid (5.00 g, 49.5%). Melting point/° C.: 68–70.

Workup

  1. temperatureto cool to RT
  2. customto destroy the tin side products
  3. additionHexane (2×200 cm3) was added
  4. washthe combined organic layers were washed with brine (2×200 cm3), water (200 cm3)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customCatalyst residues were removed
  9. additioncontaining silica gel [DCM: hexane, 50%: 50%]
  10. customThe product was recrystallised from ethanol
  11. filtrationfiltered
  12. washwashed with cold ethanol (2×30 cm3)

Sources & evidence

ORD record
ord-28167fee74d24aed9d28e15603795c04
Source dataset
uspto-grants-2007_04
Patent number
US07199167B2

Reaction notes

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