1,2-Dimethoxyethane → 2',4'-Dichloro-4-hydroxy[1,1'-biphenyl]-3-carbaldehyde

HRID 1193237ノート

反応式

HRID 1193237 の反応式
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1B(O)O.[C:12](=[O:15])([O-])[O-].[Na+].[Na+].CO[CH2:20][CH2:21][O:22]C>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:2]1[CH:3]=[CH:4][C:21]([OH:22])=[C:20]([CH:12]=[O:15])[CH:7]=1

参加物

5

反応物 3

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 2734659(2,4-Dichlorophenyl)boronic acid

生成物 1

HCID 532205482',4'-Dichloro-4-hydroxy[1,1'-biphenyl]-3-carbaldehyde収率 82%

試薬・触媒・溶媒 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒

実験手順

To a mixture of 5-bromosalicyaldehyde (30.0 g, 0.15 mol), 2,4-dichlorophenylboronic acid (32.0 g, 0.17 mol) and sodium carbonate (24.0 g, 0.23 mol) is added 1,2-dimethoxyethane (225 ml) and distilled water (75 ml), and the suspension is stirred under a nitrogen atmosphere. To this mixture is then added [1,1′-bis(diphenylphosphino)ferrocene]palladium(II)chloride (4.5 g, 7.5 mmol), followed by heating at reflux overnight. After cooling to room temperature and dilution with distilled water (500 ml) and dichloromethane (500 ml), the two phases are separated, and the aqueous phase extracted again with dichloromethane (2×500 ml). Organic fractions are combined, washed with brine (800 ml) then dried over magnesium sulphate. The suspension is filtered and the filtrate concentrated in vacuo. Then crude material is finally purified by flash column purification (10% ethyl acetate in isohexane eluant) to afford 2′,4′-dichloro-4-hydroxybiphenyl-3-carbaldehyde (32.73 g, 82%) as a pale yellow solid.

後処理

  1. distillationdistilled water (75 ml)
  2. temperatureby heating
  3. temperatureat reflux overnight
  4. customdilution with distilled water (500 ml) and dichloromethane (500 ml), the two phases are separated
  5. extractionthe aqueous phase extracted again with dichloromethane (2×500 ml)
  6. washwashed with brine (800 ml)
  7. dry with materialthen dried over magnesium sulphate
  8. filtrationThe suspension is filtered
  9. concentrationthe filtrate concentrated in vacuo
  10. customThen crude material is finally purified by flash column purification (10% ethyl acetate in isohexane eluant)

出典と根拠

ORDレコード
ord-26d2943926b34028a3b7a33543ed66e7
出典データセット
uspto-grants-2014_03
特許番号
US08680299B2

反応ノート

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