Ethyl 2-bromobenzoate → Ethyl 2-(3-(3-(((2-tetrahydropyranyl)oxy)methyl)phenyl)-3-oxopropyl)benzoate

HRID 2259491Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2259491
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]1[CH:10]=[C:11]([CH:15]([OH:18])[CH:16]=[CH2:17])[CH:12]=[CH:13][CH:14]=1.Br[C:20]1[CH:30]=[CH:29][CH:28]=[CH:27][C:21]=1[C:22]([O:24][CH2:25][CH3:26])=[O:23].[Li+].[Cl-].[Li]OC(C)=O.O.O>CN(C=O)C>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]1[CH:10]=[C:11]([C:15](=[O:18])[CH2:16][CH2:17][C:27]2[CH:28]=[CH:29][CH:30]=[CH:20][C:21]=2[C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH:12]=[CH:13][CH:14]=1

Komponenten

6

Edukt 4

HCID 80186Ethyl 2-bromobenzoateHCID 433294Lithium ChlorideHCID 190029401-(3-(((2-Tetrahydropyranyl)oxy)methyl)phenyl)-2-propen-1-olHCID 178526966lithium;acetate;dihydrate

Produkt 1

HCID 22417658Ethyl 2-(3-(3-(((2-tetrahydropyranyl)oxy)methyl)phenyl)-3-oxopropyl)benzoateAusbeute 86 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

The allylic alcohol of Step 11 (24.8 g, 100 mmol) and ethyl 2-bromobenzoate (25.2 g, 110 mmol) were dissolved in DMF (200 mL). LiCl (4.2 g, 100 mmol), LiOAc.2H2O(25.5 g, 250 mmol) and n-BU4N+Cl-(55 g, 200 mmol) were added and the resulting mixture was degassed three times. Pd(OAc)2 (1 g) was then added and the mixture was degassed three more times before heating it at 100° C. with stirring for 1 hr. After cooling to r.t., the reaction mixture was poured onto H2O(600 mL), 10% aq. NaHCO3 (200 mL) and Et2O. The crude product was extracted with Et2O(2×), washed with H2O and brine, and dried over Na2SO4 before concentrating in vacuo. Purification on a short silica gel column (20% EtOAc in hexanes) gave 34 g (86%) of the title compound.

Aufarbeitung

  1. customthe resulting mixture was degassed three times
  2. additionPd(OAc)2 (1 g) was then added
  3. customthe mixture was degassed three more times
  4. temperatureAfter cooling to r.t.
  5. additionthe reaction mixture was poured onto H2O(600 mL), 10% aq. NaHCO3 (200 mL) and Et2O
  6. extractionThe crude product was extracted with Et2O(2×)
  7. washwashed with H2O and brine
  8. dry with materialdried over Na2SO4
  9. concentrationbefore concentrating in vacuo
  10. customPurification on a short silica gel column (20% EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-dc8fedb2ac00464e955fead24603d1d2
Quelldatensatz
uspto-grants-1995_12
Patentnummer
US05472964

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