Hydrochloric Acid → 1-Tetralone

HRID 1992863Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1992863
[CH3:1][CH:2]([CH:4]1[CH2:13][C:12]2[C:7](=[CH:8][CH:9]=[C:10]([O:14][CH3:15])[CH:11]=2)[C:6](=[O:16])[CH2:5]1)[CH3:3].[Br:17]Br.C1CCN2C(=NCCC2)CC1.Cl>C(Cl)Cl.CC#N.[Cl-].[Na+].O>[C:6]1(=[O:16])[C:7]2[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH2:13][CH2:4][CH2:5]1.[Br:17][C:5]1[C:4]([CH:2]([CH3:1])[CH3:3])=[CH:13][C:12]2[C:7](=[CH:8][CH:9]=[C:10]([O:14][CH3:15])[CH:11]=2)[C:6]=1[OH:16]

Komponenten

9

Edukt 4

HCID 313Hydrochloric AcidHCID 24408BromineHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 68536766HCID 68536766, Verbindung

Produkt 2

HCID 107241-TetraloneHCID 68536740HCID 68536740, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6342AcetonitrileLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Versuchsvorschrift

To a solution of 3-(1-methylethyl)-6-(methyloxy)-3,4-dihydro-1(2H)-naphthalenone (68) (0.40 g, 1.83 mmol) in CH2CO2 (15 mL) was added a solution of bromine (0.59 g, 3.68 mmol) in CH2Cl2 (5 mL). The mixture was stirred at room temperature overnight. Volatiles were removed under vacuum at room temperature. The residue was dissolved in CH3CN (15 mL), cooled in an acetone-ice bath, DBU (0.44 g, 2.75 mmol) in CH3CN (2 mL) was added dropwise. The resulting mixture was allowed to warm up to room temperature and stirred for 1 h. 5 N HCl (1 mL) was added followed by brine (50 mL), and the mixture was extracted with CH2Cl2. The extracts were combined and washed with brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as a brown oil. The crude product was purified by flash chromatography over SiO2 with hexanes:EtOAc (25:1) to give 0.43 g (79% from tetralone) of the title compound (69) as a colorless viscous oil. 1H NMR (400 MHz, CDCl3): δ 1.32 (d, J=6.8 Hz, 6H), 3.35 (sept, J=6.8 Hz, 1H), 3.91 (s, 3H), 6.11 (s, 1H), 7.04 (d, J=2.4 Hz, 1H), 7.08 (dd, J1=9.1 Hz, J2=2.5 Hz, 1H), 7.21 (s, 1H), 8.08 (d, J=9.1 Hz, 1H).

Aufarbeitung

  1. customVolatiles were removed under vacuum at room temperature
  2. dissolutionThe residue was dissolved in CH3CN (15 mL)
  3. temperaturecooled in an acetone-ice bath
  4. temperatureto warm up to room temperature
  5. stirringstirred for 1 h
  6. extractionthe mixture was extracted with CH2Cl2
  7. washwashed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationthe filtrate was concentrated
  11. customto give the crude product as a brown oil
  12. customThe crude product was purified by flash chromatography over SiO2 with hexanes:EtOAc (25:1)

Quellen und Nachweise

ORD-Eintrag
ord-1e4ce0ab09b84880a6a537e25f7be6f5
Quelldatensatz
uspto-grants-2010_01
Patentnummer
US07649093B2

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