4-Iodophenol → Ethyl 2-(4-((4-hydroxyphenyl)ethynyl)phenoxy)acetate

HRID 2042992Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2042992
[C:1]([C:3]1[CH:15]=[CH:14][C:6]([O:7][CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:5][CH:4]=1)#[CH:2].I[C:17]1[CH:22]=[CH:21][C:20]([OH:23])=[CH:19][CH:18]=1.CCN(C(C)C)C(C)C.[NH4+].[Cl-]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I.O.CN(C=O)C>[OH:23][C:20]1[CH:21]=[CH:22][C:17]([C:2]#[C:1][C:3]2[CH:15]=[CH:14][C:6]([O:7][CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:5][CH:4]=2)=[CH:18][CH:19]=1

Komponenten

9

Edukt 4

HCID 108944-IodophenolHCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 22450859Ethyl 2-(4-ethynylphenoxy)acetate

Produkt 1

HCID 25150215Ethyl 2-(4-((4-hydroxyphenyl)ethynyl)phenoxy)acetate

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

To a dried Schlenk flask filled with nitrogen was added Pd(PPh3)4 (56.5 mg, 0.049 mmol), CuI (14.2 mg, 0.075 mmol), ethyl 2-(4-ethynylphenoxy)acetate (150.0 mg, 0.734 mmol), and 4-iodophenol (195.3 mg, 0.888 mmol) was added. The flask was evacuated, equipped with a septum, and filled with nitrogen. DMF (10 mL) and DIPEA (0.26 mL, 1.5 mmol) were added through the septum. The reaction was stirred for 3 days and was neutralized with saturated aqueous NH4Cl (5 mL). Water (5 mL) was added and the mixture was extracted with EtOAc (3×10 mL). The combined EtOAc phases was washed with brine, dried over MgSO4, and concentrated under reduced pressure. The product was purified with dry column vacuum chromatography (EtOAc:hexanes 1:90→90:1 v/v). The final product was white and solid (129.6 mg, 60%) Rf=0.48 (EtOAc:hexanes 1:1 v/v). 1H-NMR (DMSO-d6): □ 1.21 (t, 3H, J=7.2 Hz, CH2CH3); 4.17 (q, 2H, J=7.1 Hz, CH2CH3); 4.82 (s, 2H, OCH2); 6.78 (d, 2H, J=8.7 Hz, Ph); 6.95 (d, 2H, J=9.0 Hz, Ph); 7.34 (d, 2H, J=8.7 Hz, Ph); 7.43 (d, 2H, J=8.7 Hz, Ph); 9.67 (s, 1H, OH). 13C-NMR (DMSO-d6): □ 14.0 (CH2CH3); 60.7 (CH2CH3); 64.7 (OCH2); 87.1 (CC); 88.6 (CC); 112.8, 114.9, 115.6, 115.7, 132.6, 132.8, 157.5, 157.8 (Ph); 168.5 (COO). MALDI-MS: m/z calculated for C18H16O3 [M]+ 296.1043. found 296.1046.

Aufarbeitung

  1. additionTo a dried Schlenk flask filled with nitrogen
  2. additionwas added
  3. customThe flask was evacuated
  4. customequipped with a septum
  5. additionfilled with nitrogen
  6. extractionthe mixture was extracted with EtOAc (3×10 mL)
  7. washThe combined EtOAc phases was washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated under reduced pressure
  10. customThe product was purified
  11. dry with materialwith dry column vacuum chromatography (EtOAc:hexanes 1:90→90:1 v/v)

Quellen und Nachweise

ORD-Eintrag
ord-496668aa716d4ae6b98cf3b7282ea2c8
Quelldatensatz
uspto-grants-2013_11
Patentnummer
US08586607B2

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