Methyl 4-iodobenzoate → Methyl 4-(5-hydroxypentynyl)benzoate

HRID 2098368Notes

Reaction equation

HRID 2098368 reaction equation
I[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.[CH2:12]([OH:17])[CH2:13][CH2:14][C:15]#[CH:16]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[OH:17][CH2:12][CH2:13][CH2:14][C:15]#[C:16][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 69273Methyl 4-iodobenzoateHCID 793464-Pentyn-1-ol

Product 1

HCID 11974394Methyl 4-(5-hydroxypentynyl)benzoateYield 69%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
90 °C

Procedure

Methyl 4-iodobenzoate (13.1 g, 60 mmol), PdCl2(PPh3)2 (2.0 g, 3 mmol), and CuI (855 mg, 4.5 mmol) were added to TEA (60 mL). The mixture is degassed while stirring by bubbling N2 vigorously into the solution. Pent-4-yn-1-ol (5.5 g, 66 mmol) was added by syringe. The mixture was heated at 90° C. overnight. After cooling, the crude mixture was concentrated by rotary evaporation and pumped on the high vacuum for 1 h. The oil was dissolved in DCM and adsorbed onto Celite followed by purification by chromatography (gradient 10-100% EtOAc/Hexanes) to give the title compound as a light yellow powder (9 g, 69%). 1H NMR (400 MHz, CDCl3) δ 7.95 (dd, 2H, J=9.0, 1.5 Hz), 7.44 (dd, 2H, J=9.0, 1.5 Hz), 3.90 (s, 3H), 3.85 (m, 2H), 2.57 (t, 2H, J=5.5 Hz), 1.87 (m, 2H), 1.42 (t, 1H, J=5.5 Hz); ES/MS calcd. for C13H16O3+ 219.1, found m/z=219 (M+H)+.

Workup

  1. customThe mixture is degassed
  2. customby bubbling N2 vigorously into the solution
  3. temperatureAfter cooling
  4. concentrationthe crude mixture was concentrated by rotary evaporation
  5. dissolutionThe oil was dissolved in DCM
  6. customfollowed by purification by chromatography (gradient 10-100% EtOAc/Hexanes)

Sources & evidence

ORD record
ord-7d35fcf793cd43128768f8e2c2acb7c4
Source dataset
uspto-grants-2013_05
Patent number
US08450490B2

Reaction notes

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