Potassium Carbonate → 4-(1-(tris(4-methoxyphenyl)methyl)-1H-pyrazol-4-yl)benzaldehyde

HRID 512610Notes

Reaction equation

HRID 512610 reaction equation
Br[C:2]1[CH:3]=[N:4][N:5]([C:7]([C:24]2[CH:29]=[CH:28][C:27]([O:30][CH3:31])=[CH:26][CH:25]=2)([C:16]2[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=2)[C:8]2[CH:13]=[CH:12][C:11]([O:14][CH3:15])=[CH:10][CH:9]=2)[CH:6]=1.[CH:32]([C:34]1[CH:39]=[CH:38][C:37](B(O)O)=[CH:36][CH:35]=1)=[O:33].C([O-])([O-])=O.[K+].[K+]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:15][O:14][C:11]1[CH:12]=[CH:13][C:8]([C:7]([C:24]2[CH:29]=[CH:28][C:27]([O:30][CH3:31])=[CH:26][CH:25]=2)([C:16]2[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=2)[N:5]2[CH:6]=[C:2]([C:37]3[CH:38]=[CH:39][C:34]([CH:32]=[O:33])=[CH:35][CH:36]=3)[CH:3]=[N:4]2)=[CH:9][CH:10]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 5910734-Formylphenylboronic AcidHCID 584320664-bromo-1-(tris(4-methoxyphenyl)methyl)-1H-pyrazole

Product 1

HCID 584321174-(1-(tris(4-methoxyphenyl)methyl)-1H-pyrazol-4-yl)benzaldehydeYield 83.7%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 18180031Water 1,2-dimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-bromo-1-(tris(4-methoxyphenyl)methyl)-1H-pyrazole (1.47 g, 3.1 mmol), (4-formylphenyl)boronic acid (0.94 g, 6.3 mmol), and K2CO3 (0.65 g, 4.7 mmol) in DME-H2O (25 mL, 4:1) was degassed by alternately putting under house vacuum and argon three times for several minutes each. Tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol) was added then the mixture was degassed again. After heating for 16.5 hrs at 80° C. and cooling to room temperature, H2O was added. The mixture was extracted with EtOAc and the combined organics were washed with H2O, saturated aqueous NaHCO3 and brine then dried over Na2SO4 and concentrated in vacuo. Purification by chromatography (20-30% EtOAc-hexanes; EtOAc containing 1% Et3N) gave 4-(1-(tris(4-methoxyphenyl)methyl)-1H-pyrazol-4-yl)benzaldehyde (1.31 g combined from two reactions, 33%).

Workup

  1. customwas degassed
  2. waitby alternately putting under house vacuum and argon three times for several minutes
  3. customthe mixture was degassed again
  4. temperaturecooling to room temperature
  5. additionH2O was added
  6. extractionThe mixture was extracted with EtOAc
  7. washthe combined organics were washed with H2O, saturated aqueous NaHCO3 and brine
  8. dry with materialthen dried over Na2SO4
  9. concentrationconcentrated in vacuo
  10. customPurification by chromatography (20-30% EtOAc-hexanes; EtOAc containing 1% Et3N)

Sources & evidence

ORD record
ord-12cfa1a912b94835abb78142c307708d
Source dataset
uspto-grants-2015_08
Patent number
US09102643B2

Reaction notes

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