Acetonitrile → 10H-pyrazolo[5,1-c][1,4]benzoxazepine-2-carbaldehyde

HRID 1744944ノート

反応式

HRID 1744944 の反応式
[H-].[Na+].[N:3]1[N:12]2[C:6]([CH2:7][O:8][C:9]3[CH:16]=[CH:15][CH:14]=[CH:13][C:10]=3[CH2:11]2)=[CH:5][C:4]=1[CH2:17][OH:18].C[N+]1([O-])CCOCC1.C(#N)C>CN(P(N(C)C)(N(C)C)=O)C.C1(C)C=CC=CC=1.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[NH:3]1[N:12]2[C:6](=[CH:7][O:8][C:9]3[CH:16]=[CH:15][CH:14]=[CH:13][C:10]=3[CH2:11]2)[CH:5]=[C:4]1[CH:17]=[O:18]

参加物

8

反応物 4

HCID 6342AcetonitrileHCID 24758Sodium hydrideHCID 82029Methyl morpholine oxideHCID 222244534H,10H-pyrazolo[5,1-c][1,4]benzoxazepin-2-ylmethanol

生成物 1

HCID 2222448910H-pyrazolo[5,1-c][1,4]benzoxazepine-2-carbaldehyde

試薬・触媒・溶媒 3

HCID 178419074HCID 178419074、化合物触媒HCID 1140Toluene溶媒HCID 12679Hexamethylphosphoramide溶媒

反応条件

温度
95 °C

実験手順

The diol compound (3.83 g, 16.21 mmol) in HMPA (24 ml) was added to a suspension of NaH (60%, 1.34 g, 33.5 mmol) in toluene (330 ml) under N2. Rapidly heated to 95° C. for three hours and cooled to room temperature. Quenched with water and extracted with EtOAc. Washed organics with water and brine. Dried organics over sodium sulfate and filtered and concentrated. Purified with silica gel column and 2% MeOH in CH2Cl2. Obtained 4H,10H-pyrazolo[5,1-c][1,4]benzoxazepin-2-ylmethanol (white solid). Yield: 0.71 g 20%. 4H,10H-pyrazolo[5,1-c][1,4]benzoxazepin-2-ylmethanol (0.71 g, 3.28 mmol), 4-methylmorpholine N-oxide (1/198 g, 10.23 mmol), molecular sieves (powder, 4 angstroms) (3.32 g), and acetonitrile (0.07M) were placed together under N2. Tetrapropylammoniumperruthenate (0.113 g, 0.322 mmol) was added and after three hours the reaction solution was filtered through celite and concentrated. Purified with silica gel column and 1:1 EtOAc/Hexane. Obtained 4H, 10H-pyrazolo[5,1-c][1,4]benzoxazepine-2-carbaldehyde (white solid). Yield: 0.31 g 44%.

後処理

  1. temperaturecooled to room temperature
  2. customQuenched with water
  3. extractionextracted with EtOAc
  4. filtrationDried organics over sodium sulfate and filtered
  5. concentrationconcentrated
  6. customPurified with silica gel column and 2% MeOH in CH2Cl2
  7. filtrationwas filtered through celite
  8. concentrationconcentrated
  9. customPurified with silica gel column and 1:1 EtOAc/Hexane

出典と根拠

ORDレコード
ord-8c035fedc6d9495bb0e0460b15a09b68
出典データセット
uspto-grants-2006_03
特許番号
US07018997B2

反応ノート

読み込み中…