Benzyl Bromide → 5-Benzyloxyadamantan-2-one

HRID 1015528

Reaktionsgleichung

Reaktionsgleichung von HRID 1015528
[H-].[Na+].O[CH:4]1[CH:11]2[CH2:12][CH:7]3[CH2:8][CH:9]([CH2:13][CH:5]1[C:6]3=[O:14])[CH2:10]2.C(Br)C1C=CC=CC=1.O[C:24]12[CH2:33][CH:28]3[CH2:29][CH:30](CC(C3)[C:25]1=[O:34])[CH2:31]2>C1COCC1.[N+](CCCC)(CCCC)(CCCC)CCCC.[I-]>[CH2:25]([O:34][C:11]12[CH2:12][CH:7]3[CH2:8][CH:9]([CH2:13][CH:5]([C:6]3=[O:14])[CH2:4]1)[CH2:10]2)[C:24]1[CH:33]=[CH:28][CH:29]=[CH:30][CH:31]=1

Komponenten

7

Edukt 4

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 5334354-Hydroxyadamantan-2-oneHCID 109648841-Hydroxyadamantan-2-one

Produkt 1

HCID 670177735-Benzyloxyadamantan-2-oneAusbeute 77 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 67553Tetrabutylammonium IodideKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To a suspension of NaH (60% dispersed in nujol, 1.92 g, 80 mmol) in THF (80 mL) cooled to ice bath temperature was added 4-hydroxyadamantanone (6.64 g, 40 mmol) dissolved in THF (80 mL) via a syringe over a period of 15 minutes. After stirring the reaction mixture for 30 min., nBu4NI (1.4 g, 4 mmol) was added followed by the addition of benzylbromide (5.26 mL). The reaction mixture was warmed to room temperature and stirred for 16 h until TLC revealed disappearance of hydroxyadamantanone. Excess NaH was quenched by adding sat. aq NH4Cl solution to the ice cooled reaction mixture. The two layers were separated and the aqueous layer was extracted with EtOAc. The combined organic layer was washed with brine, dried over anhydrous Na2SO4, and the solvent was evaporated under reduced pressure to obtain a crude reaction mass which was purified by column chromatography to obtain 5-(benzyloxy)adamantan-2-one as a gummy liquid (7.93 g) in 77% yield. m/z (M+1), 257; 1H NMR (CDCl3) 300 MHz δ 7.60-7.20 (m, 5H), 4.51 (s, 2H), 2.72-2.63 (m, 2H), 2.40-2.36 (m, 1H), 2.35-1.92 (m, 10H).

Aufarbeitung

  1. temperaturecooled to ice bath temperature
  2. stirringstirred for 16 h until TLC
  3. customExcess NaH was quenched
  4. additionby adding sat. aq NH4Cl solution to the ice
  5. temperaturecooled
  6. customreaction mixture
  7. customThe two layers were separated
  8. extractionthe aqueous layer was extracted with EtOAc
  9. washThe combined organic layer was washed with brine
  10. dry with materialdried over anhydrous Na2SO4
  11. customthe solvent was evaporated under reduced pressure
  12. customto obtain a crude
  13. customreaction mass which
  14. customwas purified by column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-b1003fa461c74cb08cc3702fc18003d0
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07985759B2

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