Methanol → Methyl 5-oxo-5,6,7,8-tetrahydronaphthalene-1-carboxylate

HRID 1004445Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1004445
[CH3:1][OH:2].CC(C)(C)CCN[C:8]([C:10]1[C:19]2[CH2:18][CH2:17][CH:16](CCN3CCC(C4C=CC=CC=4)CC3)[C:15](=[O:34])[C:14]=2[CH:13]=[CH:12][CH:11]=1)=[O:9].C(N(CC)CC)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CN(C=O)C>[CH3:1][O:2][C:8]([C:10]1[C:19]2[CH2:18][CH2:17][CH2:16][C:15](=[O:34])[C:14]=2[CH:13]=[CH:12][CH:11]=1)=[O:9]

Komponenten

7

Edukt 3

HCID 887MethanolHCID 8471TriethylamineHCID 18794702N-(3,3-Dimethylbutyl)-5,6,7,8-tetrahydro-6-[2-(4-phenyl-1-piperidinyl)ethyl]-5-oxo-1-naphthalenecarboxamide

Produkt 1

HCID 12284900Methyl 5-oxo-5,6,7,8-tetrahydronaphthalene-1-carboxylateAusbeute 90 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 812191,3-Bis(diphenylphosphino)propaneKatalysatorHCID 167845palladium(II) acetateKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A 450-mL Parr bomb was charged with methanol (81 mL), DMF (160 mL), compound 2 (24.0 g, 81.6 mmol), palladium acetate (549 mg, 2.45 mmol), 1,3-bis(diphenylphosphino)-propane (1.01 g, 2.45 mmol), and triethylamine (23 mL, 163 mmol). The bomb was purged with carbon monoxide using 2 fill/vent cycles. The bomb was repressurized to 150 psi and was heated to 80° C. for 3 hours. During this time additional CO was admitted to maintain the pressure at 150 psi. The bomb was cooled to room temperature and vented. A second identical run was made. The combined reactions were diluted with methylene chloride (2 L), washed with water (4×800 mL), dried (MgSO4) and concentrated in vacuo to a black solid. Chromatography (flash, silica, 120 mm dia×20 cm, 2% ethyl acetate/methylene chloride) provided semi-pure product. Recrystallization of this material from hot hexanes in 2 crops followed by chromatography of the final mothor liquors (silica gel, methylene chloride (700 mL) then 2% ethyl acetate/methylene chloride) provided a total of 30.3 g (90%) of the title compound.

Aufarbeitung

  1. customThe bomb was purged with carbon monoxide using 2 fill/vent cycles
  2. temperatureto maintain the pressure at 150 psi
  3. temperatureThe bomb was cooled to room temperature
  4. additionThe combined reactions were diluted with methylene chloride (2 L)
  5. washwashed with water (4×800 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated in vacuo to a black solid
  8. customChromatography (flash, silica, 120 mm dia×20 cm, 2% ethyl acetate/methylene chloride) provided semi-pure product
  9. customRecrystallization of this material from hot hexanes in 2 crops

Quellen und Nachweise

ORD-Eintrag
ord-b5391f0ba54b4f22a602f601305abfca
Quelldatensatz
uspto-grants-2000_04
Patentnummer
US06048877

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