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1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → 10-Chloro-1-(1,6-dimethyl-1H-benzimidazol-4-yl)-7-(1-ethylpropyl)-2,3,4,5-tetrahydro-1H-[1,3]diazepino[1,2-a]benzimidazole

HRID 1399143
ノート
印刷プレビュー

反応式

HRID 1399143 の反応式
[Cl:1][C:2]1[C:10]2[N:9]=[C:8]3[NH:11][CH2:12][CH2:13][CH2:14][CH2:15][N:7]3[C:6]=2[C:5]([CH:16]([CH2:19][CH3:20])[CH2:17][CH3:18])=[CH:4][CH:3]=1.Br[C:22]1[C:30]2[N:29]=[CH:28][N:27]([CH3:31])[C:26]=2[CH:25]=[C:24]([CH3:32])[CH:23]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.CC(C)([O-])C.[Na+]>C(OCC)(=O)C.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C1(C)C=CC=CC=1>[Cl:1][C:2]1[C:10]2[N:9]=[C:8]3[N:11]([C:22]4[C:30]5[N:29]=[CH:28][N:27]([CH3:31])[C:26]=5[CH:25]=[C:24]([CH3:32])[CH:23]=4)[CH2:12][CH2:13][CH2:14][CH2:15][N:7]3[C:6]=2[C:5]([CH:16]([CH2:19][CH3:20])[CH2:17][CH3:18])=[CH:4][CH:3]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 23676156Sodium t-butoxideHCID 687752484-bromo-1,6-dimethyl-1H-benzimidazoleHCID 13610182510-Chloro-7-(1-ethylpropyl)-2,3,4,5-tetrahydro-1H-[1,3]diazepino[1,2-a]benzimidazole

生成物 1

HCID 5778609210-Chloro-1-(1,6-dimethyl-1H-benzimidazol-4-yl)-7-(1-ethylpropyl)-2,3,4,5-tetrahydro-1H-[1,3]diazepino[1,2-a]benzimidazole

試薬・触媒・溶媒 3

HCID 9832798Tris(dibenzylideneacetone) dipalladium触媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
100 °C

実験手順

A mixture of 10-chloro-7-(1-ethylpropyl)-2,3,4,5-tetrahydro-1H-[1,3]diazepino[1,2-a]benzimidazole (100.0 mg, 0.343 mmol), 4-bromo-1,6-dimethyl-1H-benzimidazole (154.9 mg), xantphos (20.0 mg, 0.0343 mmol), sodium tert-butoxide (40.0 mg, 0.412 mmol), tris(dibenzylideneacetone) dipalladium (31.0 mg, 0.0343 mmol) and toluene (2.0 mL) was stirred at 100° C. for 3 days. After cooling, the mixture was diluted with ethyl acetate and the precipitate was removed by filtration and the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography eluting with a 0-80% ethyl acetate/n-hexane gradient mixture to give the mixture containing the title compound. The residue was purified by preparative HPLC to give the title compound as the trifluoroacetic acid salt. The salt was neutralized with aqueous sodium hydrogen carbonate and extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to give the title compound. The resulting solid was recrystallized from ethyl acetate/n-hexane to give the title compound as a colorless solid (51.0 mg, 0.117 mmol, 34%).

後処理

  1. temperatureAfter cooling
  2. customthe precipitate was removed by filtration
  3. concentrationthe filtrate was concentrated in vacuo
  4. customThe residue was purified by silica gel column chromatography
  5. washeluting with a 0-80% ethyl acetate/n-hexane gradient mixture
  6. customto give the mixture

出典と根拠

ORDレコード
ord-120fbefcd9b24d43b399daf4dce5186d
出典データセット
uspto-grants-2014_12
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08901141B2

反応ノート

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