Ammonia → 2-allyl-6-(methylthio)-1-pyridin-2-yl-3H-pyrazolo[3,4-d]pyrimidin-3-one

HRID 526048Notes

Reaction equation

HRID 526048 reaction equation
CNCCNC.[CH2:7]([N:10]1[C:18](=[O:19])[C:17]2[C:12](=[N:13][C:14]([S:20][CH3:21])=[N:15][CH:16]=2)[NH:11]1)[CH:8]=[CH2:9].I[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][N:24]=1.C(=O)([O-])[O-].[K+].[K+].N>[Cu]I.O1CCOCC1>[CH2:7]([N:10]1[C:18](=[O:19])[C:17]2[C:12](=[N:13][C:14]([S:20][CH3:21])=[N:15][CH:16]=2)[N:11]1[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][N:24]=1)[CH:8]=[CH2:9]

Participants

8

Reactant 5

HCID 222AmmoniaHCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 2211262-IodopyridineHCID 671714702-Allyl-6-(methylthio)-1H-pyrazolo[3,4-d]pyrimidin-3(2H)-one

Product 1

HCID 671712462-allyl-6-(methylthio)-1-pyridin-2-yl-3H-pyrazolo[3,4-d]pyrimidin-3-oneYield 86.1%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

2.4 mL of N,N′-dimethylethylenediamine was added to 1,4-dioxane (50 mL) solution of 4.44 g of 2-allyl-6-(methylthio)-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-3-one, 3.80 g of copper(I) iodide, 5.33 g of 2-iodopyridine and 3.80 g of potassium carbonate, and stirred overnight at 95° C. The reaction liquid was cooled, aqueous ammonia was added thereto and extracted with ethyl acetate, washed with saturated saline water and dried with anhydrous magnesium sulfate. The solvent was evaporated away under reduced pressure, and crystallized with ethyl acetate to obtain 5.15 g of the entitled compound as a white solid. 1H-NMR (400 MHz, CDCl3) δ: 8.94 (1H, s), 8.52 (1H, d, J=5.1 Hz), 7.90 (2H, d, J=3.5 Hz), 7.29-7.25 (1H, m), 5.68 (1H, ddt, J=17.0, 10.2, 6.3 Hz), 5.05 (1H, d, J=10.2 Hz), 4.91 (1H, d, J=17.0 Hz), 4.85 (1H, d, J=6.3 Hz), 2.58 (3H, s).

Workup

  1. customThe reaction liquid
  2. temperaturewas cooled
  3. extractionextracted with ethyl acetate
  4. washwashed with saturated saline water
  5. dry with materialdried with anhydrous magnesium sulfate
  6. customThe solvent was evaporated away under reduced pressure
  7. customcrystallized with ethyl acetate

Sources & evidence

ORD record
ord-f9b71b7ce9194e798660180435fa2009
Source dataset
uspto-grants-2016_05
Patent number
US09345705B2

Reaction notes

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