2,4-Dihydroxybenzaldehyde → 4-(4-Chloro-benzyloxy)-2-hydroxybenzaldehyde

HRID 2426125ノート

反応式

HRID 2426125 の反応式
[OH:1][C:2]1[CH:9]=[C:8]([OH:10])[CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].[F-].[K+].[Cl:13][C:14]1[CH:21]=[CH:20][C:17]([CH2:18]Cl)=[CH:16][CH:15]=1>C(#N)C>[Cl:13][C:14]1[CH:21]=[CH:20][C:17]([CH2:18][O:10][C:8]2[CH:7]=[CH:6][C:3]([CH:4]=[O:5])=[C:2]([OH:1])[CH:9]=2)=[CH:16][CH:15]=1

参加物

5

反応物 3

HCID 72132,4-DihydroxybenzaldehydeHCID 77231-Chloro-4-(chloromethyl)benzeneHCID 522689Potassium Fluoride

生成物 1

HCID 861018764-(4-Chloro-benzyloxy)-2-hydroxybenzaldehyde

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

反応条件

温度
90 °C

実験手順

A mixture of 2,4-dihydroxybenzaldehyde (6.62 g, 48 mmol, Fluka), potassium fluoride (5.57 g, 96 mmol, Aldrich) and 4-chlorobenzyl chloride (13.50 g, 84 mmol, Aldrich) in acetonitrile (50 mL) was heated at 90° C. for 24 hours. After cooling, the mixture was partitioned between ether (2×100 mL) and water (2×100 mL). Organic layers were washed with brine (100 mL), combined, dried (MgSO4), filtered and concentrated. The residue was purified by flash chromatography (Biotage 75S, hexanes, then hexanes-dichloromethane 1:1 as solvent) to give partial separation. Pure fractions of product were combined and concentrated and the residue crystallized from hexanes with traces of dichloromethane to give 4-(4-chloro-benzyloxy)-2-hydroxy-benzaldehyde as white crystals. (Yield 4.74 g). Mother liquor and impure fractions were combined and further purified by flash chromatography (Biotage 40L, same solvent as before) and pure fractions were combined and concentrated. The residue was re-crystallized to give second crop of 4-(4-chloro-benzyloxy)-2-hydroxy-benzaldehyde. (Yield 3.03 g).

後処理

  1. temperatureAfter cooling
  2. customthe mixture was partitioned between ether (2×100 mL) and water (2×100 mL)
  3. washOrganic layers were washed with brine (100 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography (Biotage 75S, hexanes
  8. customhexanes-dichloromethane 1:1 as solvent) to give partial
  9. customseparation
  10. concentrationconcentrated
  11. customthe residue crystallized from hexanes with traces of dichloromethane

出典と根拠

ORDレコード
ord-53198408ebea4c9f907dae617b068106
出典データセット
uspto-grants-2011_06
特許番号
US07968554B2

反応ノート

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