Hydrochloric Acid → 3-methyl-6-(methyloxy)-2-phenyl-3,4-dihydro-1(2H)-naphthalenone

HRID 1992811Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1992811
[CH3:1][CH:2]([CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([O:20][CH3:21])[CH:15]=1)[CH:3]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[C:4](O)=[O:5].C(Cl)(=O)C(Cl)=O.[Cl-].[Al+3].[Cl-].[Cl-].Cl>C(Cl)Cl>[CH3:1][CH:2]1[CH2:13][C:14]2[C:19](=[CH:18][CH:17]=[C:16]([O:20][CH3:21])[CH:15]=2)[C:4](=[O:5])[CH:3]1[C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1

Komponenten

6

Edukt 4

HCID 313Hydrochloric AcidHCID 65578Oxalyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 685372223-Methyl-4-[3-(methyloxy)phenyl]-2-phenylbutanoic acid

Produkt 1

HCID 685394423-methyl-6-(methyloxy)-2-phenyl-3,4-dihydro-1(2H)-naphthalenone

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
5 °C

Versuchsvorschrift

To a solution of 3-methyl-4-[3-(methyloxy)phenyl]-2-phenylbutanoic acid (4) (13 g, 45.7 mmol) in CH2Cl2 (300 mL) was added oxalyl chloride (12 mL, 137.1 mmol) at room temperature. The reaction mixture was stirred for 10 h and concentrated under reduced pressure to afford the crude acid chloride. The acid chloride was redissolved in CH2Cl2 (300 mL) and cooled to 5° C. Anhydrous aluminum chloride (9.2 g, 68.6 mmol) was added, portion-wise, over a period of 15 min. The resulting brown colored reaction mixture was stirred at 5° C. for 3 h under N2. The reaction mixture was poured onto 2 N HCl (400 mL), stirred for 15 min and the layers were separated. The aqueous phase was further extracted with CH2Cl2 (3×200 mL). The combined organic solution was washed with sat. NaHCO3 (1×150 mL), brine (1×100 mL), dried (Na2SO4) and then concentrated under reduced pressure to afford the crude product. The product was purified by SiO2 flash column chromatography using hexanes:EtOAc (9:1 to 4:1) as an eluent to afford 5.62 g (46% over 3 steps) of the title compound. 1H NMR (400 MHz, CDCl3): δ 8.03 (d, J1=8.00 Hz, 1H), 7.35-7.20 (m, 3H), 7.12 (d, J=8.00 Hz, 1H), 6.86 and 6.84 (dd, J1=12.0 Hz, J2=4.00 Hz, 1H), 6.73 (br.s, 1H), 3.87 (s, 3H), 3.34 (d, J=12.0 Hz, 1H), 3.03 and 3.0 (dd, J1=16.0 Hz, J2=4.0 Hz, 1H), 2.85 and 2.81 (dd, J1=16.0 Hz, J2=8.0 Hz, 1H), 2.53 (m, 1H), 0.95 (d, J=4.0 Hz, 3H). 6.84-6.78 (m, 3H), 4.32 (sextet, J=4.0 Hz, 1H), 3.82 (s, 3H), 3.25 and 3.21 (dd, J1=16.0 Hz, J2=8.0 Hz, 1H), 3.07 and 3.04 (dd, J1=16.0 Hz, J2=8.0 Hz, 1H), 1.71 (d, J=8.00 Hz, 1H).

Aufarbeitung

  1. concentrationconcentrated under reduced pressure
  2. customto afford the crude acid chloride
  3. waitportion-wise, over a period of 15 min
  4. stirringThe resulting brown colored reaction mixture was stirred at 5° C. for 3 h under N2
  5. stirringstirred for 15 min
  6. customthe layers were separated
  7. extractionThe aqueous phase was further extracted with CH2Cl2 (3×200 mL)
  8. washThe combined organic solution was washed with sat. NaHCO3 (1×150 mL), brine (1×100 mL)
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated under reduced pressure
  11. customto afford the crude product
  12. customThe product was purified by SiO2 flash column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-fbcb60df23424081a6505a967ce938b5
Quelldatensatz
uspto-grants-2010_01
Patentnummer
US07649093B2

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