Methane → Palladium

HRID 1593926Notes

Reaction equation

HRID 1593926 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].C.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

8

Reactant 5

HCID 297MethaneHCID 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: 10 mmol of bromophenyl pyrazole) was conducted with 0.15 mole % of Pd2(dba)3. After the reaction was judged to be essentially complete, THF (10 mL/g of bromophenyl pyrazole starting material) was added to dissolve the precipitates, and the solution was passed through a Darco zeta pad twice. The filtrate was neutralized with 1N aq. HCl to a pH of 7.0 to 7.5. After filtration, the crude solid, whose palladium level was 111 ppm, was dissolved in THF (9 mL/g of bromophenyl pyrazole starting material), and the mixture was stirred in the presence of PS-PPh3 resin (Argonaut Technologies, 1.61 mmol PPh3/g, 5 wt %) at ambient temperature for 21 h, then filtered twice through a Darco zeta pad. The filtrate was concentrated and the product was 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 2 ppm of palladium.

Workup

  1. dissolutionto dissolve the precipitates
  2. filtrationAfter filtration
  3. dissolutionwas dissolved in THF (9 mL/g of bromophenyl pyrazole starting material)
  4. filtrationfiltered twice through a Darco zeta pad
  5. concentrationThe filtrate was concentrated
  6. customthe product was recrystallized from THF/acetone/water

Sources & evidence

ORD record
ord-79b9a0b8bf1346be8428627d02661132
Source dataset
uspto-grants-2007_11
Patent number
US07300639B2

Reaction notes

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