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

HRID 583562

반응식

HRID 583562 반응식
[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]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 7237O-Xylene용매2회

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-7990187a80e24b86838d781b189fb5a9
출처 데이터셋
uspto-grants-1999_07
특허 번호
US05929248

연결된 노트

불러오는 중…