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Diethyl Oxalate → Ethyl 2-[4-benzyloxy-3-(2-benzyloxyethyl)phenyl]-2-hydroxyacetate

HRID 367342
ノート
印刷プレビュー

反応式

HRID 367342 の反応式
[CH2:1]([O:8][CH2:9][CH2:10][C:11]1[CH:16]=[C:15](Br)[CH:14]=[CH:13][C:12]=1[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])CCC.[C:31](OCC)(=[O:37])[C:32]([O:34][CH2:35][CH3:36])=[O:33].[BH4-].[Na+].C(=O)(O)[O-].[Na+]>O1CCCC1.CCCCCC.O.C(O)(=O)C.C(O)C>[CH2:19]([O:18][C:12]1[CH:13]=[CH:14][C:15]([CH:31]([OH:37])[C:32]([O:34][CH2:35][CH3:36])=[O:33])=[CH:16][C:11]=1[CH2:10][CH2:9][O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

11

反応物 5

HCID 7268Diethyl OxalateHCID 516892Sodium BicarbonateHCID 4311764Sodium borohydrideHCID 23287828Benzyl 2-(2-benzyloxyethyl)-4-bromophenyl etherHCID 178418339Butyllithium

生成物 1

HCID 23287822Ethyl 2-[4-benzyloxy-3-(2-benzyloxyethyl)phenyl]-2-hydroxyacetate収率 78.3%

試薬・触媒・溶媒 5

HCID 176Acetic Acid溶媒HCID 702Ethanol溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒

反応条件

温度
-95 °C

実験手順

Benzyl 2-(2-benzyloxyethyl)-4-bromophenyl ether (24.0 g) was dissolved in 200 ml of tetrahydrofuran, 47.0 ml of 1.57 M n-butyl lithium in hexane was added to the solution with stirring at -95° C., and the mixture was subjected to 15 minutes of reaction. The reaction solution was added to a solution of 10.8 g of diethyl oxalate in 300 ml of tetrahydrofuran with stirring at -95° C., and the resulting solution was subjected to 1 hour of reaction. Then, 200 ml of ethanol and 755 mg of sodium borohydride were added in that order. The reaction solution was stirred at -35° C. for 45 minutes, 4.70 ml of acetic acid was added, and the mixture was stirred for 15 minutes. Then, a solution of 6.9 g of sodium bicarbonate in 300 ml of water was added and then the mixture was concentrated under reduced pressure. The resulting concentrate was extracted with ethyl acetate, and the extract was washed with water and then dried over anhydrous magnesium sulfate. Thereafter, the solvent was evaporated under reduced pressure and the resulting residue was purified by silica gel medium pressure liquid column chromatography (eluent: hexane/ethyl acetate=3/1) to give 19.9 g of ethyl 2-[4-benzyloxy-3-(2benzyloxyethyl)phenyl]-2-hydroxyacetate in an oily form.

後処理

  1. customthe mixture was subjected to 15 minutes of reaction
  2. stirringwith stirring at -95° C.
  3. customthe resulting solution was subjected to 1 hour of reaction
  4. stirringThe reaction solution was stirred at -35° C. for 45 minutes
  5. stirringthe mixture was stirred for 15 minutes
  6. concentrationthe mixture was concentrated under reduced pressure
  7. concentrationThe resulting concentrate
  8. extractionwas extracted with ethyl acetate
  9. washthe extract was washed with water
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customThereafter, the solvent was evaporated under reduced pressure
  12. customthe resulting residue was purified by silica gel medium pressure liquid column chromatography (eluent: hexane/ethyl acetate=3/1)

出典と根拠

ORDレコード
ord-1df11644ae2b4033999203099a84f5c3
出典データセット
uspto-grants-2000_10
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06133266

反応ノート

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