2-(Dimethylamino)ethanol → (2R)-1-acetoxy-2-((4S)-2-(3-acetoxy-2-methylphenyl)-4,5-dihydrooxazol-4-yl)-2-methanesulfonyloxyethane

HRID 1016694Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1016694
[CH3:1][S:2]([O:5][C@@H:6]1[C@@H:12]([NH:13][C:14](=[O:26])[C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([O:21][C:22](=[O:24])[CH3:23])[C:16]=2[CH3:25])[CH2:11][O:10][C:9]([CH3:28])(C)[O:8][CH2:7]1)(=[O:4])=[O:3].B(F)(F)F.CCOCC.C(OC(=O)C)(=O)C.CN(C)CCO>ClCCl.O.C1(C)C=CC=CC=1>[C:9]([O:8][CH2:7][C@@H:6]([C@@H:12]1[CH2:11][O:26][C:14]([C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([O:21][C:22](=[O:24])[CH3:23])[C:16]=2[CH3:25])=[N:13]1)[O:5][S:2]([CH3:1])(=[O:4])=[O:3])(=[O:10])[CH3:28]

Komponenten

8

Edukt 4

HCID 79022-(Dimethylamino)ethanolHCID 7918Acetic AnhydrideHCID 8000Boron trifluoride etherateHCID 10787996(5R,6S)-N-(5-methanesulfonyloxy-2,2-dimethyl-1,3-dioxepan-6-yl)-3-acetoxy-2-methylbenzamide2×

Produkt 1

HCID 10524958(2R)-1-acetoxy-2-((4S)-2-(3-acetoxy-2-methylphenyl)-4,5-dihydrooxazol-4-yl)-2-methanesulfonyloxyethane

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

(5R, 6S)-N-(5-Methanesulfonyloxy-2,2-dimethyl-1,3-dioxepan-6-yl)-3-acetoxy-2-methylbenzamide (compound [9], 786 g, 1.89 mol) was dissolved in dichloromethane (6.29 L), and boron trifluoride diethyl ether (698 ml, 5.68 mol) was added, which was followed by stirring at room temperature for 23 hours. The reaction mixture was cooled to 11° C. and acetic anhydride (268 ml, 2.84 mol) was added, which was followed by stirring at said temperature for 2 hours. The reaction mixture was concentrated to 2.0 kg under reduced pressure and toluene (3.8 L) was added to the obtained residue to give a suspension. N,N-Dimethylethanolamine (571 ml, 5.68 mol) was added to the suspension over 40 minutes at not more than 20° C. Toluene (1.5 L) and water (4.8 L) were added and the mixture was stirred for one hour at room temperature. The organic layer was separated, washed successively with a 10% aqueous citric acid solution (5.00 L) and a 2% aqueous potassium carbonate solution (5.00 L) and dried over magnesium sulfate. The desiccant was filtered off and the filtrate was concentrated under reduced pressure to give (2R)-1-acetoxy-2-((4S)-2-(3-acetoxy-2-methylphenyl)-4,5-dihydrooxazol-4-yl)-2-methanesulfonyloxyethane (compound [10′], 1.04 kg) as a dark red oil. 1H-NMR (CDCl3, 300 MHz) δ: 7.68 (d,1H,J=7.7 Hz), 7.26 (t,1H,J=7.9 Hz), 7.14 (d,1H,J=8.0 Hz), 5.02 (dt,1H,J=7.7,3.7 Hz), 4.66 (ddd,1H, J=3.6,8.1,9.5 Hz), 4.53 (dd,1H,J=3.3,12.4 Hz), 4.47-4.38 (m,3H), 3.11 (s,3H), 2.40 (s,3H), 2.34 (s,3H), 2.10 (2,3H)

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to 11° C.
  2. stirringby stirring
  3. customfor 2 hours
  4. concentrationThe reaction mixture was concentrated to 2.0 kg under reduced pressure and toluene (3.8 L)
  5. additionwas added to the obtained residue
  6. customto give a suspension
  7. stirringthe mixture was stirred for one hour at room temperature
  8. customThe organic layer was separated
  9. washwashed successively with a 10% aqueous citric acid solution (5.00 L)
  10. dry with materiala 2% aqueous potassium carbonate solution (5.00 L) and dried over magnesium sulfate
  11. filtrationThe desiccant was filtered off
  12. concentrationthe filtrate was concentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-6cd43a407fc847f8990cc766e151d3a7
Quelldatensatz
uspto-grants-2002_11
Patentnummer
US06476232B2

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