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

HRID 367342
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HRID 367342 반응식
[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
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참가 물질

11

반응물 5

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

생성물 1

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

시약·촉매·용매 5

HCID 176Acetic Acid용매HCID 702Ethanol용매HCID 962Water용매HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매

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온도
-95 °C

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-1df11644ae2b4033999203099a84f5c3
출처 데이터셋
uspto-grants-2000_10
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06133266

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