Hydrochloric Acid → Palladium

HRID 1593927Notes

Reaction equation

HRID 1593927 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.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>C1COCC1>[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 11776TriphenylphosphineHCID 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 8028TetrahydrofuranSolvent

Procedure

The reaction of Example 1 (reaction scale: 71.5 kg, 177.29 mol of bromophenyl pyrazole) was conducted with 0.1 mole % of Pd2(dba)3. After the reaction was judged to be essentially complete, the reaction mixture was neutralized with 1N aq. HCl to a pH of 7.0 to 7.5. The crude solid was dissolved in THF (9 L/Kg of bromophenyl pyrazole starting material), and the mixture was stirred in the presence of PS-PPh3 resin (Fluka, 3.0 wt %) at ambient temperature. After stirring for 84.5 h, the resin was removed by filtration, and the filtrate was passed sequentially through a Darco zeta pad cartridge, then a 1.2 μm Cuno polish filter. The palladium levels after the Darco pad filtration and after polish filtration were less than 10 ppm and less than 13 ppm, respectively. The filtrate was concentrated and its solute recrystallized from THF/acetone/water to afford 2′-(5-ethyl-3,4-diphenyl-1H-pyrazol-1-yl)-[1,1′]-biphenyl-3-ol containing less than 10 ppm of palladium.

Workup

  1. customthe resin was removed by filtration
  2. filtrationa 1.2 μm Cuno polish filter
  3. filtrationThe palladium levels after the Darco pad filtration
  4. filtrationafter polish filtration
  5. concentrationThe filtrate was concentrated
  6. customits solute recrystallized from THF/acetone/water

Sources & evidence

ORD record
ord-262f80e0851b43bcb2a1e2809b17fed3
Source dataset
uspto-grants-2007_11
Patent number
US07300639B2

Reaction notes

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