Pyridine → HCID 118093858, compound

HRID 1056973Notes

Reaction equation

HRID 1056973 reaction equation
N1C=CC=CC=1.[Br:7][C:8]1[C:13](=O)[N:12]2[N:15]=[C:16]([CH3:18])[CH:17]=[C:11]2[NH:10][C:9]=1[CH3:19].P(Cl)(Cl)([Cl:22])=O.C(=O)(O)[O-].[Na+]>ClCCCl.ClCCl>[Br:7][C:8]1[C:9]([CH3:19])=[N:10][C:11]2[N:12]([N:15]=[C:16]([CH3:18])[CH:17]=2)[C:13]=1[Cl:22]

Participants

7

Reactant 4

HCID 1049PyridineHCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 178422354HCID 178422354, compound

Product 1

HCID 118093858HCID 118093858, compoundYield 89%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent2×

Procedure

Pyridine (0.179 mL, 2.22 mmol) was added dropwise to a solution of 6-bromo-2,5-dimethylpyrazolo[1,5-a]pyrimidin-7(4H)-one (0.179 g, 0.739 mmol) in phosphoryl chloride (1.85 mL, 19.8 mmol) and 1,2-dichloroethane (1.85 mL). The resultant reaction mixture was stirred at RT for 15 min, then warmed to 80° C. and stirred at that temperature for 15 h. The reaction mixture was concentrated in vacuo to yield a crude residue which was diluted with dichloromethane and the resultant solution was added dropwise to a saturated solution of sodium bicarbonate (40 mL) at 0° C. Additional dichloromethane (50 mL) was added, layers were separated and the organic layer was dried with sodium sulfate, filtered, and concentrated in vacuo to give a crude residue. Purification by flash column chromatography (100% hexanes to 30% EtOAc/hexanes) gave the desired product (171 mg, 89%) as a white solid. LCMS calculated for C8H8BrClN3 (M+H)+: m/z=260.0, 262.0. found: 259.9, 261.9.

Workup

  1. customThe resultant reaction mixture
  2. temperaturewarmed to 80° C.
  3. stirringstirred at that temperature for 15 h
  4. concentrationThe reaction mixture was concentrated in vacuo
  5. customto yield a crude residue which
  6. customlayers were separated
  7. dry with materialthe organic layer was dried with sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto give a crude residue
  11. customPurification by flash column chromatography (100% hexanes to 30% EtOAc/hexanes)

Sources & evidence

ORD record
ord-426881f1d0994eb28a11bebf4cfca4c9
Source dataset
uspto-grants-2016_07
Patent number
US09399640B2

Reaction notes

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