Chloral → (4S,5R)-5-methoxycarbonyl-4-phenyl-2-trichloromethyl-1,3-oxazolidine

HRID 53914

反応式

HRID 53914 の反応式
C(O[C:6]([NH:8][C@@H:9]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C@@H:10]([OH:15])[C:11]([O:13][CH3:14])=[O:12])=O)(C)(C)C.O=C[C:24]([Cl:27])([Cl:26])[Cl:25].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1>C1(C)C=CC=CC=1>[CH3:14][O:13][C:11]([C@@H:10]1[O:15][CH:6]([C:24]([Cl:27])([Cl:26])[Cl:25])[NH:8][C@H:9]1[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:12]

参加物

5

反応物 3

HCID 6407ChloralHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 11140973Methyl (alphaR,betaS)-beta-(((1,1-dimethylethoxy)carbonyl)amino)-alpha-hydroxybenzenepropanoate

生成物 1

HCID 57158288(4S,5R)-5-methoxycarbonyl-4-phenyl-2-trichloromethyl-1,3-oxazolidine収率 91%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
20 °C

実験手順

A solution of 3.0 g of methyl (2R,3S)-3-(tert-butoxycarbonylamino)-2-hydroxy-3-phenylpropionate, of 5 cm3 of chloral and of 0.05 g of pyridinium p-toluenesulphonate in 40 cm3 of anhydrous toluene is heated at reflux with distillation of the solvent. 15 cm3 of solvent are distilled and then 5 cm3 of chloral and 0.05 g of pyridinium p-toluenesulphonate are added. 20 cm3 of solvent are distilled and then 5 cm3 of chloral as well as 30 cm3 of anhydrous toluene are added. 25 cm3 of solvent are distilled and 5 cm3 of chloral and 35 cm3 of anhydrous toluene are added. 25 cm3 of solvent are distilled and then the solution is cooled to a temperature in the region of 20° C. The organic solution is washed with water (2 times 50 cm3), dried over sodium sulphate and concentrated to dryness under reduced pressure at approximately 50° C. The residue obtained is purified by liquid chromatography on silica gel, the eluent being an ethyl acetate/cyclohexane (1/3 by volume) mixture. There are thus obtained, with a yield of 91%, 3.0 g of (4S,5R)-5-methoxycarbonyl-4-phenyl-2-trichloromethyl-1,3-oxazolidine whose characteristics are the following:

後処理

  1. temperatureat reflux with distillation of the solvent
  2. distillation15 cm3 of solvent are distilled
  3. addition5 cm3 of chloral and 0.05 g of pyridinium p-toluenesulphonate are added
  4. distillation20 cm3 of solvent are distilled
  5. addition5 cm3 of chloral as well as 30 cm3 of anhydrous toluene are added
  6. distillation25 cm3 of solvent are distilled
  7. addition5 cm3 of chloral and 35 cm3 of anhydrous toluene are added
  8. distillation25 cm3 of solvent are distilled
  9. washThe organic solution is washed with water (2 times 50 cm3)
  10. dry with materialdried over sodium sulphate
  11. concentrationconcentrated to dryness under reduced pressure at approximately 50° C
  12. customThe residue obtained
  13. customis purified by liquid chromatography on silica gel

出典と根拠

ORDレコード
ord-8427fd04fc21417bb545bda194cc10dd
出典データセット
uspto-grants-1997_04
特許番号
US05621121

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