Ethyl Acetate → (E)-3-(4-bromophenyl)-3-(4-chlorophenyl)-prop-2-en-1-ol

HRID 1810704Notes

Reaction equation

HRID 1810704 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C[O-].[Na+].[Br:10][C:11]1[CH:16]=[CH:15][C:14]([C:17]#[C:18][CH2:19][OH:20])=[CH:13][CH:12]=1.C(OCC)(=O)C.[Cl:27][C:28]1[CH:33]=[CH:32][C:31](I)=[CH:30][CH:29]=1.O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1>O1CCCC1.[Cl-].[Zn+2].[Cl-]>[Br:10][C:11]1[CH:12]=[CH:13][C:14](/[C:17](/[C:31]2[CH:32]=[CH:33][C:28]([Cl:27])=[CH:29][CH:30]=2)=[CH:18]/[CH2:19][OH:20])=[CH:15][CH:16]=1

Participants

9

Reactant 6

HCID 8857Ethyl AcetateHCID 125101-Chloro-4-iodobenzeneHCID 521585Tris(furan-2-yl)phosphaneHCID 40481813-(4-bromophenyl)prop-2-yn-1-olHCID 10942334Sodium MethoxideHCID 21226445Aluminium lithium hydride

Product 1

HCID 67145730(E)-3-(4-bromophenyl)-3-(4-chlorophenyl)-prop-2-en-1-ol

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

1 M Solution of lithium aluminum hydride in tetrahydrofuran (7.9 mL, 7.9 mmol) was added to sodium methoxide (21 mg, 0.396 mmol) under nitrogen. The mixture was cooled to 0° C. and a solution of 3-(4-bromophenyl)-prop-2-yn-1-ol (1.67 g, 7.91 mmol) in dry tetrahydrofuran (12 mL) was added dropwise. The reaction mixture was stirred at 0° C. for 3.5 h; dry ethyl acetate (2.4 mL, 15.8 mmol) was added and the whole mixture was stirred at ambient temperature for 30 min. A degassed solution of 1-chloro-4-iodobenzene (1.89 g, 7.91 mmol) in anhydrous tetrahydrofuran (12 mL), anhydrous zinc chloride (0.65 g, 4.77 mmol), tris(dibenzylidene-acetone)dipalladium chloroform complex (0.165 g, 0.16 mmol) and tri-(2-furyl)phosphine (0.184 g, 0.791 mmol) were added; the mixture was degassed and stirred at 65° C. for 22 h under atmosphere of nitrogen. The suspension was cooled down; methanol (3.5 mL) was added and the mixture was stirred for additional 1 h. The mixture was diluted with ether (40 mL) and saturated aqueous solution of ammonium chloride (2 mL), was filtered through a pad of silica gel and the pad was thoroughly washed with ether (80 mL). the filtrate was evaporated in vacuo and the residue was purified by flash column chromatography (silica gel Fluka 60, dichloromethane/ethyl acetate 20:1) affording (E)-3-(4-bromophenyl)-3-(4-chlorophenyl)-prop-2-en-1-ol as yellow oil, which solidified in fridge.

Workup

  1. stirringthe whole mixture was stirred at ambient temperature for 30 min
  2. customthe mixture was degassed
  3. stirringstirred at 65° C. for 22 h under atmosphere of nitrogen
  4. temperatureThe suspension was cooled down
  5. additionmethanol (3.5 mL) was added
  6. stirringthe mixture was stirred for additional 1 h
  7. additionThe mixture was diluted with ether (40 mL) and saturated aqueous solution of ammonium chloride (2 mL)
  8. filtrationwas filtered through a pad of silica gel
  9. washthe pad was thoroughly washed with ether (80 mL)
  10. customthe filtrate was evaporated in vacuo
  11. customthe residue was purified by flash column chromatography (silica gel Fluka 60, dichloromethane/ethyl acetate 20:1)

Sources & evidence

ORD record
ord-f36996d9116f4d648eccb59dc1716ee8
Source dataset
uspto-grants-2013_01
Patent number
US08362016B2

Reaction notes

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