4-(1-methylpiperidin-4-yloxy)-2-vinyl-9,10-dihydro-4H-3,10a-diaza-benzo[f]azulene oxalate → 2-ethyl-4-(1-methylpiperidin-4-yloxy)-9,10-dihydro-4H-3,10a-diaza-benzo[f]azulene

HRID 1773865Notes

Reaction equation

HRID 1773865 reaction equation
C(O)(=O)C(O)=O.[CH3:7][N:8]1[CH2:13][CH2:12][CH:11]([O:14][CH:15]2[C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=3[CH2:22][CH2:21][N:20]3[C:16]2=[N:17][C:18]([CH:29]=[CH2:30])=[CH:19]3)[CH2:10][CH2:9]1>CO.[Pd]>[CH2:29]([C:18]1[N:17]=[C:16]2[N:20]([CH2:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=3[CH:15]2[O:14][CH:11]2[CH2:12][CH2:13][N:8]([CH3:7])[CH2:9][CH2:10]2)[CH:19]=1)[CH3:30]

Participants

4

Reactant 1

HCID 867039514-(1-methylpiperidin-4-yloxy)-2-vinyl-9,10-dihydro-4H-3,10a-diaza-benzo[f]azulene oxalate

Product 1

HCID 867039522-ethyl-4-(1-methylpiperidin-4-yloxy)-9,10-dihydro-4H-3,10a-diaza-benzo[f]azulene

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

To a solution of 4-(1-methylpiperidin-4-yloxy)-2-vinyl-9,10-dihydro-4H-3,10a-diaza-benzo[f]azulene oxalate (example 9A) (110 mg, 0.34 mmole) in MeOH (1.7 mL) is added Pd/C 10% (11 mg). The flask is evacuated and filled with hydrogen (balloon). The reaction mixture is stirred at room temperature overnight, then filtered on celite and cake washed with MeOH. Solvent is removed under reduced pressure. The residue is pre-purified by silica gel chromatography using (CH2Cl2:MeOH:NH4OH) as eluent with a gradient from (98:2:0.2) to (95:5:0.5) and the residue is submitted to a preparative thin-layer chromatography eluting with (CH2Cl2:MeOH:NH4OH) (9:1:1) to afford 2-ethyl-4-(1-methylpiperidin-4-yloxy)-9,10-dihydro-4H-3,10a-diaza-benzo[f]azulene.

Workup

  1. customThe flask is evacuated
  2. additionfilled with hydrogen (balloon)
  3. filtrationfiltered on celite and cake
  4. washwashed with MeOH
  5. customSolvent is removed under reduced pressure
  6. customThe residue is pre-purified by silica gel chromatography
  7. washeluting with (CH2Cl2:MeOH:NH4OH) (9:1:1)

Sources & evidence

ORD record
ord-34f55ff65a26462087d93803ad702ea3
Source dataset
uspto-grants-2016_02
Patent number
US09255101B2

Reaction notes

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