Tributylphosphine oxide → (R)-[3-(3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl butyrate

HRID 583562

Reaktionsgleichung

Reaktionsgleichung von HRID 583562
[Br-].[Li+].C(P(=[O:16])(CCCC)CCCC)CCC.[C:17]([O:22][CH2:23][C@@H:24]1[O:26][CH2:25]1)(=[O:21])[CH2:18][CH2:19][CH3:20].[F:27][C:28]1[CH:29]=[C:30]([N:34]=[C:35]=O)[CH:31]=[CH:32][CH:33]=1>CC1C=CC=CC=1C>[C:17]([O:22][CH2:23][C@@H:24]1[O:26][C:25](=[O:16])[N:34]([C:30]2[CH:31]=[CH:32][CH:33]=[C:28]([F:27])[CH:29]=2)[CH2:35]1)(=[O:21])[CH2:18][CH2:19][CH3:20]

Komponenten

6

Edukt 4

HCID 13138Tributylphosphine oxideHCID 82050Lithium BromideHCID 1230643-Fluorophenyl isocyanateHCID 2724536(2R)-Oxiran-2-ylmethyl butanoate

Produkt 1

HCID 54327495(R)-[3-(3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl butyrate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 7237O-XyleneLösungsmittel2×

Versuchsvorschrift

A mixture of lithium bromide (0.181 g, 2.08 mmol), tri-n-butylphosphine oxide (0.454 g, 2.08 mmol), and dry o-xylene (10 ml) is azeotropically dried for 1 hr. After cooling below the reflux point, a mixture of (R)-glycidyl butyrate (5.000 g, 34.68 mmol) and 3-fluorophenyl isocyanate (4.755 g or 3.96 ml, 34.68 mmol) in dry o-xylene (10 ml) is added over 10 min to the hot mixture (some refluxing observed during the addition). When the addition is complete, the mixture is heated to reflux for 2 hr and then allowed to cool to 20-25°. The solvent is removed under reduced pressure and the residue chromatographed over silica gel, eluting with hexane/ethyl acetate (6:1, 4:1, and then 2:1), to give the title compound, [α]25D -46.7° (c 1.0, CHCl3); IR (mineral oil mull) 1758, 1615, 1591, 1498, 1229, 1197, 1169 cm-1 ; NMR (CDCl3, 300 MHz) δ 7.44, 7.34, 7.23, 6.86, 4.88, 4.39, 4.32, 4.13, 3.82, 2.33, 1.63, 0.92; MS (m/z) 281, 193, 180, 150, 148, 137, 123, 95, 43; HRMS (m/z) 281.1068 (calc'd for C14H16FNO4 =281.1063).

Aufarbeitung

  1. customis azeotropically dried for 1 hr
  2. temperatureAfter cooling below the reflux point
  3. additionis added over 10 min to the hot mixture (some refluxing
  4. additionobserved during the addition)
  5. additionWhen the addition
  6. temperaturethe mixture is heated
  7. temperatureto reflux for 2 hr
  8. temperatureto cool to 20-25°
  9. customThe solvent is removed under reduced pressure
  10. customthe residue chromatographed over silica gel
  11. washeluting with hexane/ethyl acetate (6:1, 4:1

Quellen und Nachweise

ORD-Eintrag
ord-7990187a80e24b86838d781b189fb5a9
Quelldatensatz
uspto-grants-1999_07
Patentnummer
US05929248

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