Potassium Phosphate, Tribasic → 3-Propyl-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-one

HRID 2097497Notes

Reaction equation

HRID 2097497 reaction equation
Br[C:2]1[C:10]2[C:9](=[O:11])[N:8]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[N:7]=[CH:6][C:5]=2[N:4]([CH2:20][O:21][CH2:22][CH2:23][Si:24]([CH3:27])([CH3:26])[CH3:25])[CH:3]=1.[CH2:28](B(O)O)[CH2:29][CH3:30].P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(P(C12CC3CC(CC(C3)C1)C2)C12CC3CC(CC(C3)C1)C2)CCC>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C1(C)C=CC=CC=1>[CH2:28]([C:2]1[C:10]2[C:9](=[O:11])[N:8]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[N:7]=[CH:6][C:5]=2[N:4]([CH2:20][O:21][CH2:22][CH2:23][Si:24]([CH3:27])([CH3:26])[CH3:25])[CH:3]=1)[CH2:29][CH3:30]

Participants

8

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 3510651-Propylboronic acidHCID 11371790Bis(adamantan-1-yl)(butyl)phosphaneHCID 666025033-Bromo-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-one

Product 1

HCID 666027033-Propyl-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-oneYield 38.1%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To 2.37 g (5.00 mmol) of 3-bromo-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-one obtained in Reference example 20-(a) were added 1.76 g (20 mmol) of propylboronic acid, 4.25 g (20 mmol) of potassium phosphate, 15.8 ml of toluene, 0.95 ml of water, 56 mg of palladium acetate and 179 mg of butyl-di-1-adamantylphosphine, and the mixture was degassed under reduced pressure, replaced with argon and stirred at 100° C. for 5.5 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with toluene. The organic layer after separation was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was applied to silica gel column chromatography (Eluent; hexane:ethyl acetate=7:1→5:1 (V/V)), and the fractions containing the desired compound were concentrated under reduced pressure to obtain 834 mg of the title compound as a pale brownish solid. (Yield: 38%)

Workup

  1. customthe mixture was degassed under reduced pressure
  2. customAfter completion of the reaction, water
  3. additionwas added to the reaction mixture
  4. extractionthe mixture was extracted with toluene
  5. customThe organic layer after separation
  6. washwas washed with a saturated aqueous solution of sodium chloride
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. additionthe fractions containing the desired compound
  10. concentrationwere concentrated under reduced pressure

Sources & evidence

ORD record
ord-66c0732816c44b8f8a9145cfb6ae080b
Source dataset
uspto-grants-2013_05
Patent number
US08450319B2

Reaction notes

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