Propargyl bromide → HCID 86616120, compound

HRID 545258Notes

Reaction equation

HRID 545258 reaction equation
C([O-])=O.[NH4+].[CH2:5]([N:8]1[C:16](=[O:17])[C:15]2[C:10](=[N:11][C:12]([S:18][CH3:19])=[N:13][CH:14]=2)[N:9]1[C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([C:26]([OH:29])([CH3:28])[CH3:27])[N:21]=1)[CH:6]=[CH2:7].[H-].[Na+].C(Br)C#C.C(=O)([O-])O.[Na+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].O.CN(C)C=O.O1CCCC1>[OH:29][C:26]([C:22]1[N:21]=[C:20]([N:9]2[C:10]3=[N:11][C:12]([S:18][CH3:19])=[N:13][CH:14]=[C:15]3[C:16](=[O:17])[N:8]2[CH2:5][C:6]#[CH:7])[CH:25]=[CH:24][CH:23]=1)([CH3:28])[CH3:27]

Participants

10

Reactant 5

HCID 7842Propargyl bromideHCID 24758Sodium hydrideHCID 516892Sodium BicarbonateHCID 2723923Ammonium formateHCID 671701891-[6-(2-Hydroxypropan-2-yl)pyridin-2-yl]-6-(methylsulfanyl)-2-(prop-2-en-1-yl)-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-3-one

Product 1

HCID 86616120HCID 86616120, compoundYield 51.1%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
90 °C

Procedure

440 mg of ammonium formate and 230 mg of [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride were added to tetrahydrofuran (13.6 mL) solution of 500 mg of 2-allyl-1-[6-(1-hydroxy-1-methylethyl)-2-pyridinyl]-6-(methylthio)-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-3-one produced in Example 53, and stirred at 90° C. for 3 hours. The reaction liquid was cooled to room temperature, distilled water was added thereof, and extracted with a mixed solution of chloroform/isopropanol (80/20). This was dried with anhydrous sodium sulfate, and the solvent was evaporated away under reduced pressure to obtain 770 mg of a black amorphous substance. 61.0 mg of sodium hydride was added to N,N-dimethylformamide (14.0 mL) solution of the resulting compound, and stirred for 30 minutes. 0.316 mL of propargyl bromide was added to the reaction solution, and stirred for 3.5 hours. Aqueous saturated sodium hydrogencarbonate solution and saturated saline water were added to the reaction liquid, and extracted with a mixed solution of chloroform/isopropanol (80/20). This was dried with anhydrous sodium sulfate, and the solvent was evaporated away under reduced pressure to obtain a black amorphous substance. The resulting amorphous substance was purified through silica gel column chromatography (hexane/ethyl acetate) to obtain 254 mg of the entitled compound as a white compound.

Workup

  1. customThe reaction liquid
  2. temperaturewas cooled to room temperature
  3. distillationdistilled water
  4. additionwas added
  5. extractionextracted with a mixed solution of chloroform/isopropanol (80/20)
  6. dry with materialThis was dried with anhydrous sodium sulfate
  7. customthe solvent was evaporated away under reduced pressure
  8. customto obtain 770 mg of a black amorphous substance
  9. stirringstirred for 30 minutes
  10. stirringstirred for 3.5 hours
  11. extractionextracted with a mixed solution of chloroform/isopropanol (80/20)
  12. dry with materialThis was dried with anhydrous sodium sulfate
  13. customthe solvent was evaporated away under reduced pressure
  14. customto obtain a black amorphous substance
  15. customThe resulting amorphous substance was purified through silica gel column chromatography (hexane/ethyl acetate)

Sources & evidence

ORD record
ord-81ff4026ac7947a5856b63e2dcb23fe7
Source dataset
uspto-grants-2011_05
Patent number
US07935708B2

Reaction notes

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