Methanol → HCID 57991940, compound

HRID 2075353Notes

Reaction equation

HRID 2075353 reaction equation
Br[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[N:5][N:6]=[CH:7]2.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:31]([O-:34])(=[O:33])C.[K+].[CH3:36]O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN(C=O)C>[CH:7]1[C:8]2[CH:9]=[CH:10][CH:11]=[C:2]([C:31]([O:34][CH3:36])=[O:33])[C:3]=2[CH:4]=[N:5][N:6]=1

Participants

7

Reactant 4

HCID 887MethanolHCID 11776TriphenylphosphineHCID 517044Potassium AcetateHCID 136493705-Bromophthalazine

Product 1

HCID 57991940HCID 57991940, compoundYield 32%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a 140 mL pressure flask was added 5-bromophthaiazine (3.5 g, 17 mmol), palladium (II) acetate (0.98 g, 4.4 mmol), triphenylphosphine (1.3 g, 5.0 mmol), potassium acetate (2.1 g, 21 mmol), MeOH (20 mL) and DMF (20 mL). The flask was sealed and purged with CO (3×). The flask was charged with CO to 40 PSI and stirred at 100° C. 15 hours. The suspension was filtered through Celite, the cake was washed with MeOH, and the filtrate was concentrated. The residue was taken up in DCM and washed with saturated sodium bicarbonate (2×), saturated sodium chloride (2×) and water (2×). The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo. The residue was adsorbed on to a plug of silica gel and purified by chromatography through a Redi-Sep pre-packed silica gel column, eluting with a gradient of EtOAc in hexane to provide methyl phthalazine-5-carboxylate (1.0 g, 32%). LCMS (M+H) 189.2 calc. for C10H9N2O2 189.1. 1H NMR (400 MHz, CDCl3): δ ppm 4.05 (s, 3H) 8.06 (d, J=8.41 Hz, 1H) 8.51-8.56 (m, 1H) 8.71 (d, 1H) 9.64 (s, 2H).

Workup

  1. customThe flask was sealed
  2. custompurged with CO (3×)
  3. additionThe flask was charged with CO to 40 PSI
  4. custom15 hours
  5. filtrationThe suspension was filtered through Celite
  6. washthe cake was washed with MeOH
  7. concentrationthe filtrate was concentrated
  8. washwashed with saturated sodium bicarbonate (2×), saturated sodium chloride (2×) and water (2×)
  9. dry with materialThe organic layer was dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. custompurified by chromatography through a Redi-Sep pre-packed silica gel column
  13. washeluting with a gradient of EtOAc in hexane

Sources & evidence

ORD record
ord-02c5ef89ed6e4e2b9d716bc2080fc751
Source dataset
uspto-grants-2011_04
Patent number
US07919504B2

Reaction notes

Loading…