Binap, (A+-)- → 1-(2,4-Dimethoxyphenyl)-4-(2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran-5-yl)piperazine

HRID 2063834ノート

反応式

HRID 2063834 の反応式
Br[C:2]1[C:3]([CH3:15])=[C:4]([CH3:14])[C:5]2[O:9][C:8]([CH3:11])([CH3:10])[CH2:7][C:6]=2[C:12]=1[CH3:13].[CH3:16][O:17][C:18]1[CH:23]=[C:22]([O:24][CH3:25])[CH:21]=[CH:20][C:19]=1[N:26]1[CH2:31][CH2:30][NH:29][CH2:28][CH2:27]1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC(C)([O-])C.[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C1(C)C=CC=CC=1>[CH3:16][O:17][C:18]1[CH:23]=[C:22]([O:24][CH3:25])[CH:21]=[CH:20][C:19]=1[N:26]1[CH2:27][CH2:28][N:29]([C:2]2[C:3]([CH3:15])=[C:4]([CH3:14])[C:5]3[O:9][C:8]([CH3:11])([CH3:10])[CH2:7][C:6]=3[C:12]=2[CH3:13])[CH2:30][CH2:31]1

参加物

8

反応物 4

HCID 634876Binap, (A+-)-HCID 27362041-(2,4-Dimethoxyphenyl)piperazineHCID 23676156Sodium t-butoxideHCID 667609285-Bromo-2,2,4,6,7-pentamethyl-2,3-dihydrobenzofuran

生成物 1

HCID 594851091-(2,4-Dimethoxyphenyl)-4-(2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran-5-yl)piperazine収率 56%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 1140Toluene溶媒

実験手順

To the toluene (10 mL) mixture solution of 5-bromo-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran (400 mg, 1.49 mmol) synthesized in Reference example 4, 1-(2,4-dimethoxyphenyl)piperazine (495 mg, 2.23 mmol), palladium acetate (17 mg, 0.0745 mmol) and BINAP (139 mg, 0.224 mmol), sodium t-butoxide (286 mg, 2.98 mmol) was added and stirred for 15 hours under reflux. After cooling to room temperature, water was added to the reaction solution, and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure. The residue was purified by silica gel chromatography (hexane-ethyl acetate 95:5-85:15) and crystallized from ethyl acetate-hexane to obtain the title compound 340 mg (yield 56%). Melting point was 154 to 156° C.

後処理

  1. additionwas added
  2. temperatureunder reflux
  3. extractionextracted with ethyl acetate
  4. washThe organic layer was washed with saturated brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customThe solvent was removed by distillation under reduced pressure
  7. customThe residue was purified by silica gel chromatography (hexane-ethyl acetate 95:5-85:15)
  8. customcrystallized from ethyl acetate-hexane

出典と根拠

ORDレコード
ord-f9d2933f4f6743aaa78cea114d2c14c7
出典データセット
uspto-grants-2012_10
特許番号
US08288390B2

反応ノート

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