4-Pentyn-1-ol → HCID 69286085, compound

HRID 2220586Notes

Reaction equation

HRID 2220586 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1I.[CH2:13]([OH:18])[CH2:14][CH2:15][C:16]#[CH:17]>N1C=CC=CC=1.CCOC(C)=O.[Pd].[Cu-]=O>[OH:18][CH2:13][CH2:14][CH2:15][C:16]1[O:1][C:2]2[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=2[CH:17]=1

Participants

7

Reactant 2

HCID 793464-Pentyn-1-olHCID 11346465Methyl 4-hydroxy-3-iodobenzoate

Product 1

HCID 69286085HCID 69286085, compoundYield 49%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 178419072HCID 178419072, compoundCatalystHCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

See Fancelli D.; Fagnola, M. C.; Bedeschi, A. Solid phase Synthesis of 2-Substituted Benzofurans via the Palladium-catalyzed Heteroannulation of acetylenes. Tetrahedron Letters 1997, 38, 2311-2314. A mixture of methyl 4-hydroxy-3-iodobenzoate (93) (35 g, 125.9 mmol), 4-pentyn-1-ol (11.00 g, 130.7 mmol) and copper (I) oxide (12.62 g, 88.2 mmol) in dyr pyridine (150 mL) was stirred at 100-120° C. overnight. The mixture was allowed to cool to room temperature, diluted with EtOAc (200 mL), filtered through a Celite pad (5 cm) and concentrated. The residue was dissolved in EtOAc (300 mL), washed with 2 M HCl (50 mL), brine (100 mL), dried over Na2SO4, filtered and concentrated. Column chromatography (SiO2, EtOAc/hexanes, 1/1) followed by recrystallization (hexanes/diethyl ether, 2/1) afforded 95 as light yellow crystals (14.39 g, 49%). 1H NMR (DMSO-d6) δ8.20 (s, 1H), 7.86 (d, J=8.2 Hz, 1H), 7.13 (d, J=8.2 Hz, 1H), 6.74 (s, 1H), 4.59 (b, 1H), 3.49 (b, 2H), 3.86 (s, 3H), 2.84 (t, J=7.1 Hz, 2H), 1.85 (m, 2H). HPLC (method B) tR 4.20 min (100.00 area %).

Workup

  1. temperatureto cool to room temperature
  2. filtrationfiltered through a Celite pad (5 cm)
  3. concentrationconcentrated
  4. dissolutionThe residue was dissolved in EtOAc (300 mL)
  5. washwashed with 2 M HCl (50 mL), brine (100 mL)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customColumn chromatography (SiO2, EtOAc/hexanes, 1/1) followed by recrystallization (hexanes/diethyl ether, 2/1)

Sources & evidence

ORD record
ord-75c5fd94a8904b98b0fc6b9ea6cec00a
Source dataset
uspto-grants-2008_08
Patent number
US07417158B2

Reaction notes

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