Methyl formate → 5,5-(Ethylenedioxy)-3-Hydroxymethylene-4a-methyl-4,4a,5,6,7,8-hexahydro-3H-naphthalen-2-one

HRID 551298Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 551298
[CH2:1]1[CH2:16][O:15][C:3]2([CH2:12][CH2:11][CH2:10][C:9]3[C:4]2([CH3:14])[CH2:5][CH2:6][C:7](=[O:13])[CH:8]=3)[O:2]1.C[O-].[Na+].[CH:20](OC)=[O:21]>C1COCC1>[CH2:16]1[CH2:1][O:2][C:3]2([CH2:12][CH2:11][CH2:10][C:9]3[C:4]2([CH3:14])[CH2:5][C:6](=[CH:20][OH:21])[C:7](=[O:13])[CH:8]=3)[O:15]1

Komponenten

5

Edukt 3

HCID 7865Methyl formateHCID 109221015,5-(Ethylenedioxy)-4a-methyl-2,3,4,4a,5,6,7,8-octahydronaphtalen-2-oneHCID 10942334Sodium Methoxide

Produkt 1

HCID 671968285,5-(Ethylenedioxy)-3-Hydroxymethylene-4a-methyl-4,4a,5,6,7,8-hexahydro-3H-naphthalen-2-oneAusbeute 26.103 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

A solution of 201 (20 g, 0.090 mmol) in THF (200 mL) was cooled to −5° C. in an ice/methanol bath. NaOMe (19.45 g, 0.360 mol) was added and the mixture stirred for 30 minutes. After slow addition of a cooled solution of methyl formate (55.5 mL, 0.900 mol) in 60 mL THF, the mixture was stirred at room temperature for 24 hours. The mixture was poured into ice-water-HCl (˜50 mL conc. HCl in 500 mL H2O), stirred for 5 minutes and then transferred to a separatory funnel. The aqueous layer was extracted with ether (3×100 mL) and the pooled organic extracts were washed with brine, dried (MgSO4), and concentrated. The yellow residue was flash chromatographed (0-50% EtOAc-hexanes) to yield 203 (5.88 g, 26%) as a yellow oil. 1H NMR (CDCl3) δ 1.22 (s, 3H), 1.6-1.9 (m, 4H), 2.02 (d, J=14 Hz, 1H), 2.2-2.5 (2H), 2.91 (d, J=14 Hz, 1H), 3.9-4.1 (m, 4H), 5.86 (d, J=2.0 Hz, 1H), 7.37 (s, 1H); 13C NMR (CDCl3) 188.72, 166.86, 165.35, 165.12, 124.59, 124.25, 111.92, 106.39, 65.33, 65.17, 65.04, 64.89, 46.00, 29.87, 21.33, 20.74, 20.59.

Aufarbeitung

  1. stirringthe mixture was stirred at room temperature for 24 hours
  2. stirringstirred for 5 minutes
  3. customtransferred to a separatory funnel
  4. extractionThe aqueous layer was extracted with ether (3×100 mL)
  5. washthe pooled organic extracts were washed with brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customchromatographed (0-50% EtOAc-hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-feaadfe35e8245eb912186d0b1ccdce2
Quelldatensatz
uspto-grants-2011_05
Patentnummer
US07947726B2

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