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

HRID 638862노트

반응식

HRID 638862 반응식
[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>[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[CH:17]=[O:18]

참가 물질

8

반응물 4

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

생성물 1

HCID 222244824H,10H-pyrazolo[5,1-c][1,4]benzoxazepine-2-carbaldehyde

시약·촉매·용매 3

HCID 178419074HCID 178419074, 화합물촉매HCID 1140Toluene용매HCID 12679Hexamethylphosphoramide용매

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온도
95 °C

실험 절차

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%.

후처리

  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

출처 및 근거

ORD 기록
ord-bdcdb78a011f4af7a4d4374484d74c9e
출처 데이터셋
uspto-grants-2010_04
특허 번호
US07691842B2

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