Hydrochloric Acid → Palladium

HRID 1593923Notes

Reaction equation

HRID 1593923 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.[Pd]>CC(C)=O.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

8

Reactant 4

HCID 313Hydrochloric AcidHCID 23938Palladium2×HCID 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 2

HCID 180AcetoneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

The reaction of Example 1 (reaction scale: 10 mmol 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 aqueous HCl to a pH of 7.0 to 7.5. The crude product, whose palladium level was 270 ppm, was dissolved in acetone (16 mL/g of bromophenyl pyrazole starting material) and THF (2.65 mL/g) at 50° C. TMT (0.23 equiv.) was added, and the mixture was stirred at 50° C. for 15 min, cooled to room temperature, and filtered three times through a Darco zeta pad. A sample of filtrate was evaporated to dryness, affording a solid containing 92 ppm of palladium. The remaining filtrate was concentrated and recrystallized by adding water, affording 2′-(5-ethyl-3,4-diphenyl-1H-pyrazol-1-yl)-[1,1′]-biphenyl-3-ol containing 51 ppm of palladium.

Workup

  1. customat 50° C
  2. additionTMT (0.23 equiv.) was added
  3. temperaturecooled to room temperature
  4. filtrationfiltered three times through a Darco zeta pad
  5. customA sample of filtrate was evaporated to dryness
  6. customaffording a solid
  7. concentrationThe remaining filtrate was concentrated
  8. customrecrystallized
  9. additionby adding water

Sources & evidence

ORD record
ord-6d7f17ebd98c447d9d79f0afade30516
Source dataset
uspto-grants-2007_11
Patent number
US07300639B2

Reaction notes

Loading…