Methanol → HCID 66670377, compound

HRID 1514654Notes

Reaction equation

HRID 1514654 reaction equation
[C:1]([C:5]1[N:9]([CH2:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[O:18]C)[C:8]([CH3:20])=[C:7]([C:21]([N:23]=[C:24]([NH2:26])[NH2:25])=[O:22])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[Cl:27]CCl.B(Br)(Br)Br.CO.C(OCC)(=O)C>ClCCl>[ClH:27].[C:1]([C:5]1[N:9]([CH2:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[OH:18])[C:8]([CH3:20])=[C:7]([C:21]([N:23]=[C:24]([NH2:25])[NH2:26])=[O:22])[CH:6]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 887MethanolHCID 8857Ethyl AcetateHCID 22277759Boron tribromide dichloromethaneHCID 66670266HCID 66670266, compound

Product 1

HCID 66670377HCID 66670377, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A 330 mg portion of 5-tert-butyl-N-(diaminomethylene)-1-[2-(2-methoxyphenyl)ethyl]-2-methyl-1H-pyrrole-3-carboxamide was dissolved in 10 ml of dichloromethane, and 2.78 ml of a 1 M boron tribromide dichloromethane solution was added dropwise thereto at −70° C. under an atmosphere of argon, followed by stirring at room temperature for 14 hours. Under ice-cooling, 5 ml of methanol was added to the reaction liquid, and the reaction liquid was concentrated under a reduced pressure. The residue was subjected to three times of azeotropy with methanol, and a saturated sodium bicarbonate aqueous solution and saturated brine were added to the residue, followed by extraction with 20% methanol/chloroform. After drying the organic layer with anhydrous sodium sulfate, the solvent was evaporated under a reduced pressure, and the residue was purified by silica gel column chromatography (Chromatorex (registered trademark), methanol:chloroform=10:90). The resulting product was dissolved in 3 ml of ethanol and, under ice-cooling, 0.263 ml of 4 M hydrogen chloride/ethyl acetate was added, followed by stirring at room temperature for 15 hours. Then, the solid formed by adding ethyl acetate was collected by filtration to obtain 206 mg of 5-tert-butyl-N-(diaminomethylene)-1-[2-(2-hydroxyphenyl)ethyl]-2-methyl-1H-pyrrole-3-carboxamide hydrochloride as a light brown solid.

Workup

  1. customat −70° C.
  2. temperatureUnder ice-cooling
  3. customthe reaction liquid
  4. concentrationwas concentrated under a reduced pressure
  5. additiona saturated sodium bicarbonate aqueous solution and saturated brine were added to the residue
  6. extractionfollowed by extraction with 20% methanol/chloroform
  7. dry with materialAfter drying the organic layer with anhydrous sodium sulfate
  8. customthe solvent was evaporated under a reduced pressure
  9. customthe residue was purified by silica gel column chromatography (Chromatorex (registered trademark), methanol:chloroform=10:90)
  10. dissolutionThe resulting product was dissolved in 3 ml of ethanol and, under ice-
  11. temperaturecooling
  12. addition0.263 ml of 4 M hydrogen chloride/ethyl acetate was added
  13. stirringby stirring at room temperature for 15 hours
  14. customThen, the solid formed
  15. filtrationwas collected by filtration

Sources & evidence

ORD record
ord-295c0edfafdb4063bcb0179ec42d821c
Source dataset
uspto-grants-2012_07
Patent number
US08222274B2

Reaction notes

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