Pyrazole → HCID 66977306, compound

HRID 712364Notes

Reaction equation

HRID 712364 reaction equation
BrC1C=C(Cl)N2C=C(C([O-])=O)N=C2C=1.[Br:15][C:16]1[CH:21]=[C:20](Cl)[N:19]2[CH:23]=[C:24]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[N:25]=[C:18]2[CH:17]=1.[NH:31]1[CH:35]=[CH:34][CH:33]=[N:32]1.C(=O)([O-])[O-].[Cs+].[Cs+].[NH4+].[Cl-]>CN(C=O)C.O>[Br:15][C:16]1[CH:21]=[C:20]([N:31]2[CH:35]=[CH:34][CH:33]=[N:32]2)[N:19]2[CH:23]=[C:24]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[N:25]=[C:18]2[CH:17]=1

Participants

8

Reactant 5

HCID 1048PyrazoleHCID 10796Cesium carbonateHCID 25517Ammonium ChlorideHCID 86664060HCID 86664060, compoundHCID 86664062HCID 86664062, compound

Product 1

HCID 66977306HCID 66977306, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of 7-bromo-5-chloro-imidazo[1,2-a]pyridine-2-carboxylate (Intermediate 16) (0.867 g, 2.86 mmol) and pyrazole (0.194 g, 2.86 mmol) was dissolved in DMF (15 mL). Cesium carbonate (1.95 g, 2.1 eq.) was added and the mixture stirred at rt. After 16 hours TLC indicated clean but incomplete reaction and stirring was continued over the weekend. Saturated aqueous NH4Cl (50 mL) was added, resulting in effervescence and a gelatinous precipitate which was then broken up, water (30 mL) added and the solid filtered in vacuo. This material was washed with water and sucked dry to give a tan paste. The filtrate was extracted with EtOAc (100 mL), washed with water (30 mL), brine (30 mL), and set aside. The tan paste was dissolved in EtOAc (200 mL), combined with the filtrate, dried over MgSO4, filtered and evaporated to give a brown residue that crystallized upon standing. Trituration with EtOAc (15 mL) and heptane (50 mL) yielded a yellow powder, 0.363 g (38%). MS: 335, 337 [M+H]+.

Workup

  1. customincomplete reaction
  2. stirringstirring
  3. customresulting in effervescence
  4. filtrationthe solid filtered in vacuo
  5. washThis material was washed with water
  6. customsucked dry
  7. customto give a tan paste
  8. extractionThe filtrate was extracted with EtOAc (100 mL)
  9. washwashed with water (30 mL), brine (30 mL)
  10. dissolutionThe tan paste was dissolved in EtOAc (200 mL)
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. customevaporated
  14. customto give a brown residue that
  15. customcrystallized
  16. customTrituration with EtOAc (15 mL) and heptane (50 mL) yielded a yellow powder, 0.363 g (38%)

Sources & evidence

ORD record
ord-13b453f4f0614089a154e89636dd7c7f
Source dataset
uspto-grants-2015_11
Patent number
US09181234B2

Reaction notes

Loading…