Methyl Acrylate → Methyl (2E)-3-[4-(1-cyclohexyl-3-methyl-7-oxo-6,7-dihydro-1H-pyrazolo[4,3-d]pyrimidin-5-yl)-3-methoxyphenyl]-2-propenate

HRID 915979Notes

Reaction equation

HRID 915979 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[NH:9][C:10](=[O:24])[C:11]3[N:16]([CH:17]4[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]4)[N:15]=[C:14]([CH3:23])[C:12]=3[N:13]=2)=[C:4]([O:25][CH3:26])[CH:3]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C.[C:56]([O:60][CH3:61])(=[O:59])[CH:57]=[CH2:58]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.CN(C)C=O>[CH:17]1([N:16]2[C:11]3[C:10](=[O:24])[NH:9][C:8]([C:5]4[CH:6]=[CH:7][C:2](/[CH:58]=[CH:57]/[C:56]([O:60][CH3:61])=[O:59])=[CH:3][C:4]=4[O:25][CH3:26])=[N:13][C:12]=3[C:14]([CH3:23])=[N:15]2)[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1

Participants

8

Reactant 4

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 136005882HCID 136005882, compound

Product 1

HCID 136005762Methyl (2E)-3-[4-(1-cyclohexyl-3-methyl-7-oxo-6,7-dihydro-1H-pyrazolo[4,3-d]pyrimidin-5-yl)-3-methoxyphenyl]-2-propenateYield 85.5%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
115 °C

Procedure

To a 2 ml N,N-dimethylformamide solution of 150 mg (0.36 mmol) of the compound obtained in Example 15, 8 mg (0.036 mmol) of palladium acetate, 22 mg (0.072 mmol) of tri-o-tolylphosphine, 0.15 ml (1.08 mmol) of triethylamine, and 97 μl (1.08 mmol) of methyl acrylate were added, and the mixture was stirred at 115° C. in a sealed tube for 15 hours. Then, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and a saturated aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate, whereafter the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=2/1) to obtain 130 mg (85%) of the captioned compound.

Workup

  1. temperatureThen, the reaction mixture was cooled to room temperature
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with water
  4. dry with materiala saturated aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate, whereafter the solvent
  5. distillationwas distilled off under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=2/1)

Sources & evidence

ORD record
ord-1f8f83c38e66448c9e16404ac0efc6af
Source dataset
uspto-grants-2007_09
Patent number
US07268128B2

Reaction notes

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