Methanol → 2-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic Acid

HRID 272149Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 272149
C[O:2][C:3](=[O:34])[CH:4]([CH2:24][CH:25]=[CH:26][CH2:27][P:28]([O:32][CH3:33])([O:30][CH3:31])=[O:29])[CH2:5][C:6]([CH3:23])=[CH:7][CH2:8][C:9]1[C:10]([OH:22])=[C:11]2[C:15](=[C:16]([CH3:20])[C:17]=1[O:18][CH3:19])[CH2:14][O:13][C:12]2=[O:21].O.CO.O[Li].O>C1COCC1>[CH3:31][O:30][P:28]([CH2:27][CH:26]=[CH:25][CH2:24][CH:4]([CH2:5][C:6]([CH3:23])=[CH:7][CH2:8][C:9]1[C:10]([OH:22])=[C:11]2[C:15](=[C:16]([CH3:20])[C:17]=1[O:18][CH3:19])[CH2:14][O:13][C:12]2=[O:21])[C:3]([OH:34])=[O:2])([O:32][CH3:33])=[O:29]

Komponenten

6

Edukt 4

HCID 887MethanolHCID 962WaterHCID 168937Lithium hydroxide, monohydrate2×HCID 765461882-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic acid methyl ester

Produkt 1

HCID 765461892-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic Acid

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

2-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic acid methyl ester (460 mg, 0.927 mmol) in a solution of 1:1:2 of H2O, MeOH, THF (8 mL) was stirred with LiOH.H2O (78 mg, 1.86 mmol) at ambient temperature for 12 hours. A second batch of LiOH.H2O (40 mg, 0.952 mmol) was added. The reaction mixture was stirred at room temperature for another 16 hours, after which no further progress was observed. The reaction was quenched by addition of a saturated aqueous solution of NH4Cl. The organic layer was removed in vacuo and the product was extracted with EtOAc from the aqueous layer, which had been acidified by addition of 5 drops of 2 N HCl. The product was further purified by chromatography to provide the desired product. 1H NMR (300 MHz, CDCl3) δ 1.79 (s, 3H), 2.08-2.38 (m, 4H), 2.15 (s, 3H), 2.53 (d, 1H, J=22 Hz), 2.60 (d, 1H, J=22 Hz), 2.57-2.64 (m, 1H), 3.38 (d, 2H, J=7 Hz), 3.72 (d, 6H, J=11 Hz) 3.76 (s, 3H), 5.20 (s, 2H), 5.27 (t, 1H, J=6 Hz), 5.36-5.63 (m, 2H) ppm; 31P (121.4 MHz, CDCl3) δ 30.5 ppm; MS (m/z) 481.2 [M−H]−.

Aufarbeitung

  1. customThe reaction was quenched by addition of a saturated aqueous solution of NH4Cl
  2. customThe organic layer was removed in vacuo
  3. extractionthe product was extracted with EtOAc from the aqueous layer, which
  4. additionhad been acidified by addition of 5 drops of 2 N HCl
  5. customThe product was further purified by chromatography

Quellen und Nachweise

ORD-Eintrag
ord-db54db0cbca6411fbda3cea12f35ca19
Quelldatensatz
uspto-grants-2008_11
Patentnummer
US07452901B2

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