Methyl 3-Bromopyruvate → HCID 59233216, compound

HRID 1925140

Reaction equation

HRID 1925140 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[N:6]([C:8]([C:11]([F:20])([F:19])[C:12]3[N:17]=[N:16][C:15]([NH2:18])=[CH:14][CH:13]=3)=[N:9][N:10]=2)[CH:7]=1.Br[CH2:22][C:23](=O)[C:24]([O:26][CH3:27])=[O:25].C([O-])(O)=O.[Na+]>O1CCOCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[N:6]([C:8]([C:11]([F:20])([F:19])[C:12]3[CH:13]=[CH:14][C:15]4[N:16]([CH:22]=[C:23]([C:24]([O:26][CH3:27])=[O:25])[N:18]=4)[N:17]=3)=[N:9][N:10]=2)[CH:7]=1

Participants

5

Reactant 3

HCID 352524Methyl 3-BromopyruvateHCID 516892Sodium BicarbonateHCID 59233207HCID 59233207, compound

Product 1

HCID 59233216HCID 59233216, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A reaction mixture of 6-((6-bromo-[1,2,4]triazolo[4,3-a]pyridin-3-yl)difluoromethyl)pyridazin-3-amine (11.0 g, 32.2 mmol), methyl 3-bromo-2-oxopropanoate (11.67 g, 64.5 mmol), and NaHCO3 (10.84 g) in dioxane (150 mL) was heated at 80° C. for 4 hrs to provide a red reaction mixture. Solids were filtered off, rinsed with dioxane, and the combined filtrates were concentrated via rotary evaporation. The resulting residue was dissolved in EtOAc and washed with 0.1 N NaOH until the red color no longer persisted. The organic phase was then separated and concentrated to dryness. The resulting material was purified via MPLC (5:95, MeOH/EtOAc) to provide the title compound, 45I (4.0 g, 9.45 mmol, 30%). 1H NMR (400 MHz, DMSO-d6) δ ppm 3.88 (s, 3 H) 7.77 (dd, J=9.73, 1.64 Hz, 1 H) 7.85 (d, J=9.60 Hz, 1 H) 7.97-8.08 (m, 1 H) 8.53 (d, J=9.60 Hz, 1 H) 8.98 (d, J=1.01 Hz, 1 H) 9.02 (s, 1 H). ESI-MS:m/z 423.1 (M+H)+.

Workup

  1. customto provide a red reaction mixture
  2. filtrationSolids were filtered off
  3. washrinsed with dioxane
  4. concentrationthe combined filtrates were concentrated via rotary evaporation
  5. dissolutionThe resulting residue was dissolved in EtOAc
  6. washwashed with 0.1 N NaOH until the red color
  7. customThe organic phase was then separated
  8. concentrationconcentrated to dryness
  9. customThe resulting material was purified via MPLC (5:95, MeOH/EtOAc)

Sources & evidence

ORD record
ord-8969949d90cd41ceb02c5d5572e19037
Source dataset
uspto-grants-2012_05
Patent number
US08178534B2

Linked notes

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