Ethyl Acetate → 3-(2-Bromobenzyl)-methoxy benzene

HRID 393256

反応式

HRID 393256 の反応式
[H-].[H-].[H-].[H-].[Li+].[Al+3].[Al+3].[Cl-].[Cl-].[Cl-].[Br:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[CH:18]([C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([O:26][CH3:27])[CH:21]=1)O.CCOC(C)=O>CCOCC>[Br:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[CH2:18][C:20]1[CH:21]=[C:22]([O:26][CH3:27])[CH:23]=[CH:24][CH:25]=1

参加物

6

反応物 4

HCID 8857Ethyl AcetateHCID 6451240Aluminum(III) ChlorideHCID 21226445Aluminium lithium hydride2 回HCID 22649669(2-Bromophenyl)(3-methoxyphenyl)methanol

生成物 1

HCID 121326383-(2-Bromobenzyl)-methoxy benzene収率 75.4%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
0 °C

実験手順

LiAlH4 (0.154 g, 4.06 mmol) was suspended in anhydrous Et2O (10 mL) under a N2 atmosphere and cooled (0° C.) with stirring. Anhydrous AlCl3 (1.08 g, 8.14 mmol)was dissolved in ice-cold anhydrous Et2O (20 mL) and added dropwise to the LiAlH4 suspension. After complete addition the suspension was stirred at the same temperature (20 min.). (2-Bromo-phenyl)-(3-methoxy-phenyl)-methanol [13] (0.68 g, 2.32 mmol) was dissolved in anhydrous Et2O (10 mL) and added dropwise via syringe to the suspension. After complete addition the reaction mixture was heated at reflux (4 h), cooled (0° C.) and EtOAc was added dropwise to destroy the excess of the reagent and the mixture was added to 20% aq. H2SO4 (50 mL). Et2O (50 mL) was added and extracted. The Et2O layer was separated, washed with water, brine, dried (MgSO4) and evaporated to give a reddish yellow oil. The oil was purified by mplc using pet. ether-CH2Cl2 (9:1) as eluent to give 0.485 g (75%) of the pure product as a colorless oil. 1H NMR (CDCl3)d: 3.81 (s, 3H, CH3), 4.14 (s, 2H, CH2), 6.79-7.62 (m, 8H, Ar—H). 13C NMR (CDCl3)d: 42.34, 55.69, 112.07, 122.02, 125.48, 128.07, 128.50, 130.02, 131.66, 133.43.

後処理

  1. additionAfter complete addition the suspension
  2. stirringwas stirred at the same temperature (20 min.)
  3. additionadded dropwise via syringe to the suspension
  4. additionAfter complete addition the reaction mixture
  5. temperaturewas heated
  6. temperatureat reflux (4 h)
  7. additionwas added dropwise
  8. customto destroy the excess of the reagent
  9. additionthe mixture was added to 20% aq. H2SO4 (50 mL)
  10. additionEt2O (50 mL) was added
  11. extractionextracted
  12. customThe Et2O layer was separated
  13. washwashed with water, brine
  14. dry with materialdried (MgSO4)
  15. customevaporated
  16. customto give a reddish yellow oil
  17. customThe oil was purified by mplc

出典と根拠

ORDレコード
ord-478ef5cf4b654d95b6e94522feec819e
出典データセット
uspto-grants-2004_10
特許番号
US06806283B2

関連ノート

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