Butyl vinyl ether → 3-(1-Butoxyvinyl)-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-one

HRID 2097544Notes

Reaction equation

HRID 2097544 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.[CH:28]([O:30][CH2:31][CH2:32][CH2:33][CH3:34])=[CH2:29].C([O-])(=O)C.[Tl+].C(N(CC)C(C)C)(C)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN(C)C=O>[CH2:31]([O:30][C: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])[CH2:32][CH2:33][CH3:34]

Participants

8

Reactant 5

HCID 8108Butyl vinyl etherHCID 11247thallium(I) acetateHCID 812191,3-Bis(diphenylphosphino)propaneHCID 81531DiisopropylethylamineHCID 666025033-Bromo-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-one

Product 1

HCID 666030473-(1-Butoxyvinyl)-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-oneYield 84.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To 215 ml of N,N-dimethylformamide solution containing 10.1 g (21.2 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 13.9 ml (108 mmol) of butyl vinyl ether, 5.59 g (21.2 mmol) of thallium acetate, 6.24 ml (36.7 mmol) of N,N-diisopropylethylamine, 482 mg (2.15 mmol) of palladium acetate and 1.86 g (4.51 mmol) of 1,3-bis(diphenylphosphino)propane in this order, and after degassing under reduced pressure, the atmosphere was replaced by a nitrogen gas, and the mixture was stirred at 100° C. for 2 hours. After completion of the reaction, water was added to the reaction mixture, and extracted with toluene. The organic layer was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate, and then, concentrated under reduced pressure. The obtained residue was applied to silica gel column chromatography (Eluent; hexane:ethyl acetate=1:1 (V/V)), and the fractions containing the desired compound were concentrated under reduced pressure to obtain 8.80 g of the title compound as a pale brownish oil. (Yield: 84%)

Workup

  1. customafter degassing under reduced pressure
  2. customAfter completion of the reaction, water
  3. additionwas added to the reaction mixture
  4. extractionextracted with toluene
  5. washThe organic layer was washed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. additionthe fractions containing the desired compound
  9. concentrationwere concentrated under reduced pressure

Sources & evidence

ORD record
ord-16ceaeacd6c94b7a88c7347feae8c733
Source dataset
uspto-grants-2013_05
Patent number
US08450319B2

Reaction notes

Loading…