Dimethyl L-tartrate → HCID 86701304, Verbindung

HRID 1627038

Reaktionsgleichung

Reaktionsgleichung von HRID 1627038
[H-].[Na+].[C:3]([C@@H:7]([C@H:9]([C:11]([O:13][CH3:14])=[O:12])[OH:10])[OH:8])([O:5][CH3:6])=[O:4].Br[CH2:16][C:17]([CH3:19])=[CH2:18]>CN(C=O)C>[CH3:16][C:17](=[CH2:18])[CH2:19][O:10][C@H:9]([C@@H:7]([O:8][CH2:18][C:17]([CH3:19])=[CH2:16])[C:3]([O:5][CH3:6])=[O:4])[C:11]([O:13][CH3:14])=[O:12]

Komponenten

5

Edukt 3

HCID 11851Dimethyl L-tartrateHCID 24758Sodium hydrideHCID 3577853-Bromo-2-methyl-1-propene

Produkt 1

HCID 86701304HCID 86701304, VerbindungAusbeute 71 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel2×

Reaktionsbedingungen

Temperatur
-10 °C

Versuchsvorschrift

To a cooled (−10° C.) suspension of NaH (60% dispersion in mineral oil, 6.73 g, 168 mmol) in DMF (240 mL) was added dropwise a solution of (+)-dimethyl L-tartrate (15.0 g, 84.0 mmol) in DMF (40 mL) over a period of 30 min. After the addition was complete, the mixture was stirred for another 30 min at −10° C., and then 3-bromo-2-methylpropene (25.5 mL, 253 mmol) was added while maintaining the reaction temperature below 0° C. The mixture was stirred for 1.5 h at −10° C., quenched with H2O and saturated aqueous sodium chloride (NaCl, brine), and extracted with EtOAc. The phases were separated and the aqueous phase was further extracted with EtOAc. The combined organic phases were washed with brine, dried over magnesium sulfate (MgSO4), filtered, and concentrated to yield a yellow oil. Purification by flash chromatography (SiO2, hexanes/EtOAc gradient) yielded the title compound as a colorless oil (17.05 g, 71%): IR (neat) 2953, 1758, 1435, 1270, 1203, 1106 cm−1; 1H NMR (400 MHz, CDCl3) δ 4.92-4.86 (m, 4H), 4.37 (s, 2H), 4.19 (d, J=12.3 Hz, 2H), 3.82 (d, J=12.3 Hz, 2H), 3.77 (s, 6H), 1.68 (s, 6H); 13C NMR (101 MHz, CDCl3) δ 169.84, 141.04, 114.10, 78.60, 75.66, 52.22, 19.52; HRMS-ESI (m/z) [M]+ calcd for C14H22O6, 286.1416; found, 286.1417.

Aufarbeitung

  1. temperatureTo a cooled
  2. additionAfter the addition
  3. temperaturewhile maintaining the reaction temperature below 0° C
  4. stirringThe mixture was stirred for 1.5 h at −10° C.
  5. customquenched with H2O and saturated aqueous sodium chloride (NaCl, brine)
  6. extractionextracted with EtOAc
  7. customThe phases were separated
  8. extractionthe aqueous phase was further extracted with EtOAc
  9. washThe combined organic phases were washed with brine
  10. dry with materialdried over magnesium sulfate (MgSO4)
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customto yield a yellow oil
  14. customPurification by flash chromatography (SiO2, hexanes/EtOAc gradient)

Quellen und Nachweise

ORD-Eintrag
ord-4320b8f7a4eb40ffb985a0b9ae9b78d9
Quelldatensatz
uspto-grants-2014_07
Patentnummer
US08785479B2

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