tert-Butyl methyl ether → (1S)-2-Methyl-1-methylthiocarbonyloxypropyl 2-methylpropanoate

HRID 558056Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 558056
COC(C)(C)C.[CH3:7][CH:8]([CH3:20])[C:9]([O:11][CH:12]([O:16][C:17]([CH3:19])=[S:18])[CH:13]([CH3:15])[CH3:14])=[O:10]>O>[CH3:7][CH:8]([CH3:20])[C:9]([O:11][C@@H:12]([O:16][C:17]([CH3:19])=[S:18])[CH:13]([CH3:14])[CH3:15])=[O:10]

Komponenten

4

Edukt 2

HCID 15413tert-Butyl methyl etherHCID 866102712-Methyl-1-methylthiocarbonyloxypropyl 2-methylpropanoate

Produkt 1

HCID 86633031(1S)-2-Methyl-1-methylthiocarbonyloxypropyl 2-methylpropanoateAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Versuchsvorschrift

A mixture of 990 mL methyl-tert-butylether (MTBE) and 10 mL water was stirred until a clear solution was obtained (ca. 5 hrs). To this solution was added 2-methyl-1-methylthiocarbonyloxypropyl 2-methylpropanoate (2b) (50 g) and PLE/MPEG (50 mg/1 g, 7.5 g). The resulting suspension was stirred at room temperature. The reaction was monitored by 1H-NMR using a chiral solvating agent. After 1H-NMR showed only one enantiomer remained in the reaction mixture (ca. 48 hrs), the reaction was quenched by filtration through a pad of CELITE® 545. The supernatant was washed with water, aqueous sodium bicarbonate (NaHCO3) and brine, and dried over anhydrous sodium sulfate (Na2SO4). After rotary evaporation, the title compound (12) was obtained with 70% yield. The enantiomeric excess of the S-enantiomer was 100% e.e. as determined by chiral HPLC. 1H-NMR (CDCl3): δ 0.96 (d, J=6.8 Hz, 6H), 1.16 (d, J=6.8 Hz, 3H), 1.17 (d, J=6.8 Hz, 3H), 1.98-2.07 (m, 1H), 2.32 (s, 3H), 2.56 (septet, J=7.2 Hz, 1H), 6.67 (d, J=5.6 Hz, 1H) ppm. 1H-NMR with chiral solvating agent (R)-(−)-2,2,2-trifluoro-1-(9-anthryl)ethanol: δ 0.98 (d, J=6.8 Hz, 3H), 0.99 (d, J=6.8 Hz, 3H), 1.19 (d, J=7.2 Hz, 1.5H), 1.19 (d, J=6.8 Hz, 1.5H), 1.20 (d, J=6.8 Hz, 1.5H), 1.20 (d, J=7.2 Hz, 1.5H), 2.01-2.09 (m, 1H), 2.34 1(s, 1.5H), 2.44 (s, 1.5H), 2.59 (septet, J=7.2 Hz, 0.5H), 2.59 (septet, J=6.8 Hz, 0.5H), 6.70 (d, J=5.6 Hz, 0.5H), 6.70 (d, J=5.2 Hz, 0.5H) ppm.

Aufarbeitung

  1. customwas obtained (ca. 5 hrs)
  2. stirringThe resulting suspension was stirred at room temperature
  3. customremained in the reaction mixture (ca. 48 hrs)
  4. customthe reaction was quenched by filtration through a pad of CELITE® 545
  5. washThe supernatant was washed with water, aqueous sodium bicarbonate (NaHCO3) and brine
  6. dry with materialdried over anhydrous sodium sulfate (Na2SO4)
  7. customAfter rotary evaporation

Quellen und Nachweise

ORD-Eintrag
ord-b19116388a4b447da217e8e5f7857c8c
Quelldatensatz
uspto-grants-2011_11
Patentnummer
US08062870B2

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