Benzylamine → (+/-)-tert-Butyl 1-{[3-(benzylamino)-4-chlorophenyl](methoxy)methyl}cyclopropanecarboxylate

HRID 1475669ノート

反応式

HRID 1475669 の反応式
CC(C)([O-])C.[Na+].[CH2:7]([NH2:14])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:62]1[CH:63]=[C:64]([CH:69]([O:80][CH3:81])[C:70]2([C:73]([O:75][C:76]([CH3:79])([CH3:78])[CH3:77])=[O:74])[CH2:72][CH2:71]2)[CH:65]=[CH:66][C:67]=1[Cl:68].[Cl-].[NH4+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C.C1(C)C=CC=CC=1>[CH2:7]([NH:14][C:66]1[CH:65]=[C:64]([CH:69]([O:80][CH3:81])[C:70]2([C:73]([O:75][C:76]([CH3:77])([CH3:78])[CH3:79])=[O:74])[CH2:71][CH2:72]2)[CH:63]=[CH:62][C:67]=1[Cl:68])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

参加物

9

反応物 5

HCID 7504BenzylamineHCID 25517Ammonium ChlorideHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 68170327(+/-)-tert-Butyl 1-[(3-bromo-4-chlorophenyl)(methoxy)methyl]cyclopropanecarboxylate

生成物 1

HCID 68170328(+/-)-tert-Butyl 1-{[3-(benzylamino)-4-chlorophenyl](methoxy)methyl}cyclopropanecarboxylate

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
110 °C

実験手順

In a dry reaction flask which had been flushed with argon, 4.60 g (47.9 mmol) of sodium tert-butoxide were suspended in 100 ml of abs. toluene, and 5.2 ml (47.9 mmol) of benzylamine, 0.99 g (1.6 mmol) of rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, 1.83 g (2.0 mmol) of tris(dibenzylideneacetone)dipalladium and 15.0 g (39.9 mmol) of (+/−)-tert-butyl 1-[(3-bromo-4-chlorophenyl)(methoxy)methyl]cyclopropanecarboxylate were added. The reaction mixture was heated at 110° C. for 3 h. After cooling, ethyl acetate and saturated aqueous ammonium chloride solution were added and the mixture was filtered through Celite. The organic phase was washed with saturated ammonium chloride solution and saturated sodium chloride solution, dried over magnesium sulphate and concentrated under reduced pressure. The crude product was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 40:1→20:1). This gave 12.0 g of the target compound (74.8% of theory).

後処理

  1. customIn a dry reaction flask which
  2. temperatureAfter cooling
  3. filtrationthe mixture was filtered through Celite
  4. washThe organic phase was washed with saturated ammonium chloride solution and saturated sodium chloride solution
  5. dry with materialdried over magnesium sulphate
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 40:1→20:1)

出典と根拠

ORDレコード
ord-fb3a6adb6a9a4ce08935de33e37cd4ce
出典データセット
uspto-grants-2015_04
特許番号
US09018258B2

反応ノート

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