Cesium carbonate → HCID 71699715, compound

HRID 1500177Notes

Reaction equation

HRID 1500177 reaction equation
C([O-])([O-])=O.[Cs+].[Cs+].[NH:7]1[CH:11]=[CH:10][C:9]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[N:8]1.Br[C:18]1[CH:23]=[CH:22][C:21]([O:24][CH2:25][CH3:26])=[CH:20][CH:19]=1>C(#N)C>[CH2:25]([O:24][C:21]1[CH:22]=[CH:23][C:18]([N:7]2[CH:11]=[CH:10][C:9]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[N:8]2)=[CH:19][CH:20]=1)[CH3:26]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 685234-BromophenetoleHCID 178469268HCID 178469268, compound

Product 1

HCID 71699715HCID 71699715, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
82 °C

Procedure

A 10 mL Schlenk tube was dried under vacuum, filled with nitrogen and consecutively charged with 19.4 mg (0.102 mmol, 0.2 eq) Cul, 332.3 mg (1.020 mmol, 2.0 eq) Cs2CO3, 100.0 mg (0.714 mmol, 1.4 eq) ethyl 1H-pyrazole-3-carboxylate (6), 102.4 mg (73.0 μL, 0.510 mmol, 1.0 eq) p-bromophenetol and 1 mL dry ACN. The light brown suspension was degassed by vaccum/N2 cycles and stirred first at 82° C. for 7 h and than after adding 0.5 mL dry DMF (solubility issue) at 120° C. for further 65 h. The GC-MS analysis showed full conversion. ACN and DMF were removed under high pressure and the brown residue was suspended in 10 mL EtOAc. After filtration of the brown suspension through a pad of silica and flushing with 150 mL EtOAc the colorless filtrate was concentrated under reduced pressure leading to 52.1 mg (39%) crude product as a green-brown oil. Final purification by column chromatography (CH/EtOAc 3:1, size: 15.5×2.0 cm, 20 g silica gel) yielded the pure title compound.

Workup

  1. customA 10 mL Schlenk tube was dried under vacuum
  2. additionfilled with nitrogen
  3. customThe light brown suspension was degassed by vaccum/N2 cycles
  4. additionthan after adding 0.5 mL dry DMF (solubility issue) at 120° C. for further 65 h
  5. customACN and DMF were removed under high pressure
  6. filtrationAfter filtration of the brown suspension through a pad of silica
  7. customflushing with 150 mL EtOAc the colorless filtrate
  8. concentrationwas concentrated under reduced pressure
  9. customFinal purification by column chromatography (CH/EtOAc 3:1, size: 15.5×2.0 cm, 20 g silica gel)

Sources & evidence

ORD record
ord-8d0e878007f04d3eb98e8ca92873d567
Source dataset
uspto-grants-2015_12
Patent number
US09206115B2

Reaction notes

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