Hydrochloric Acid → Palladium

HRID 1593922Notes

Reaction equation

HRID 1593922 reaction equation
Br[C:2]1[C:3](C2C=CC=CC=2)=[N:4][NH:5][CH:6]=1.C1C=C[C:16](/[CH:19]=[CH:20]/[C:21](/[CH:23]=[CH:24]/[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=O)=[CH:17][CH:18]=1.C1C=C[C:34](/[CH:37]=[CH:38]/[C:39](/[CH:41]=[CH:42]/[C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)=[O:40])=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd:67].[Pd].Cl.C1COCC1>O>[CH2:2]([C:3]1[N:4]([C:48]2[CH:47]=[CH:46][CH:45]=[CH:44][C:43]=2[C:42]2[CH:34]=[CH:37][CH:38]=[C:39]([OH:40])[CH:41]=2)[N:5]=[C:24]([C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)[C:23]=1[C:21]1[CH:18]=[CH:17][CH:16]=[CH:19][CH:20]=1)[CH3:6].[Pd:67]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 9811564Bis(dibenzylideneacetone)palladiumHCID 1784194634-Bromo-3-phenyl-1H-pyrazole

Product 2

HCID 23938PalladiumHCID 272822142'-(5-Ethyl-3,4-diphenyl-1H-pyrazol-1-yl)-[1,1'-biphenyl]-3-ol

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
50 °C

Procedure

The reaction of Example 1 (reaction scale: 10 mmol of bromophenyl pyrazole) was conducted with 0.5 mole % of Pd2(dba)3. After the reaction was judged to be essentially complete, 5N aqueous HCl (1.25 mL/g of bromophenyl pyrazole starting material) was added followed by THF (12.5 mL/g) and water (2.5 mL/g). The mixture was heated to 50° C. to dissolve the precipitates, then cooled to 25° C. and filtered twice through a Darco zeta pad. To the filtrate was added TMT (5 mol %). The mixture was stirred at ambient temperature for 14 h and filtered again four times through the same Darco zeta pad employed in the previous filtration. The THF was removed by evaporation, and water (2.5 mL/g) and ethanol (2.5 mL/g) were added to precipitate the product, affording 2′-(5-ethyl-3,4-diphenyl-1H-pyrazol-1-yl)-[1,1′]-biphenyl-3-ol containing 146 ppm of palladium.

Workup

  1. dissolutionto dissolve the precipitates
  2. temperaturecooled to 25° C.
  3. filtrationfiltered twice through a Darco zeta pad
  4. additionTo the filtrate was added TMT (5 mol %)
  5. filtrationfiltered again four times through the same Darco zeta pad
  6. filtrationemployed in the previous filtration
  7. customThe THF was removed by evaporation, and water (2.5 mL/g) and ethanol (2.5 mL/g)
  8. additionwere added
  9. customto precipitate the product

Sources & evidence

ORD record
ord-1bc14417357d40998db9ebcb82d41929
Source dataset
uspto-grants-2007_11
Patent number
US07300639B2

Reaction notes

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