Hydrazine, dihydrochloride → HCID 178496140, compound

HRID 253317Notes

Reaction equation

HRID 253317 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([O:19][CH2:20][CH2:21][O:22][CH3:23])[C:5]([O:14][CH2:15][CH2:16][O:17][CH3:18])=[C:6]([CH:8]([C:11](=O)[CH3:12])[C:9]#[N:10])[CH:7]=1.Cl.Cl.[NH2:26][NH2:27].C(=O)(O)[O-].[Na+]>C(O)C>[F:1][C:2]1[CH:3]=[C:4]([O:19][CH2:20][CH2:21][O:22][CH3:23])[C:5]([O:14][CH2:15][CH2:16][O:17][CH3:18])=[C:6]([C:8]2[C:11]([CH3:12])=[N:26][NH:27][C:9]=2[NH2:10])[CH:7]=1

Participants

5

Reactant 3

HCID 17548Hydrazine, dihydrochlorideHCID 516892Sodium BicarbonateHCID 66891447HCID 66891447, compound

Product 1

HCID 178496140HCID 178496140, compoundYield 56.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 2-(5-fluoro-2,3-bis{[2-(methyloxy)ethyl]oxy}phenyl)-3-oxobutanenitrile (0.26 mg, 0.80 mmol) in ethanol (5 mL) was added hydrazine dihydrochloride (105 mg, 0.9 mmol). The resulting mixture was heated at reflux for 1 hour. It was cooled to room temperature then poured into a saturated sodium bicarbonate solution (10 mL) and the mixture was extracted with ethyl acetate (3×10 mL). The combined extract was washed with aqueous sodium bicarbonate solution, brine, dried over sodium sulfate, filtered and concentrated to give an oily residue which was purified by flash chromatography (silica gel, 5% methanol-dichloromethane) to provide 4-(5-fluoro-2,3-bis{[2-(methyloxy)ethyl]oxy}phenyl)-3-methyl-1H-pyrazol-5-amine (0.15 g, 0.45 mmol, 56%) yield 1H NMR (400 MHz, d6-DMSO): 7.06-7.02 (m, 1H), 6.72-6.69 (m, 1H), 4.18-4.16 (m, 2H), 3.83-3.81 (m, 2H), 3.71-3.69 (m. 2H), 3.36-3.64 (m, 2H), 3.32 (s, 3H), 3.10 (s, 3H), 2.16 (s, 3H); MS (EI) for C16H22FN3O4: 340 (MH+).

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux for 1 hour
  3. extractionthe mixture was extracted with ethyl acetate (3×10 mL)
  4. extractionThe combined extract
  5. washwas washed with aqueous sodium bicarbonate solution, brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give an oily residue which
  10. customwas purified by flash chromatography (silica gel, 5% methanol-dichloromethane)

Sources & evidence

ORD record
ord-7256c87a54444d36b474e9974e59a6e1
Source dataset
uspto-grants-2011_01
Patent number
US07872014B2

Reaction notes

Loading…