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

HRID 865367

反応式

HRID 865367 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 7237O-Xylene溶媒2 回

実験手順

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 20-25o. 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).

後処理

  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 20-25o
  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

出典と根拠

ORDレコード
ord-98c1814179f4457b9f2a892b4df52105
出典データセット
uspto-grants-1996_10
特許番号
US05565571

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