Benzene, 1-chloro-4-fluoro- → HCID 18445904, compound

HRID 460324Notes

Reaction equation

HRID 460324 reaction equation
C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1)(C)(C)C.[C:22]1(=[O:28])[CH2:26][CH2:25][C:24](=[O:27])[CH2:23]1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].Cl[C:38]1[CH:43]=[CH:42][C:41]([F:44])=[CH:40][CH:39]=1>CC([O-])=O.CC([O-])=O.[Pd+2].O1CCOCC1>[F:44][C:41]1[CH:42]=[CH:43][C:38]([CH:23]2[C:24](=[O:27])[CH2:25][CH2:26][C:22]2=[O:28])=[CH:39][CH:40]=1

Participants

7

Reactant 4

HCID 9604Benzene, 1-chloro-4-fluoro-HCID 62657Potassium Phosphate, TribasicHCID 774661,3-CyclopentanedioneHCID 27342152-(Di-tert-butylphosphino)biphenyl

Product 1

HCID 18445904HCID 18445904, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Procedure

The title compound was also prepared as follows. To a 100 L flask was charged sequentially 113.3 g (0.50 mol) of Pd(OAc)2, 331.4 g (1.11 mol) of 2-(di-t-butylphosphino)biphenyl, 2.476 kg (25.24 mol) of 1,3-cyclopentanedione, and 10.72 kg (50.5 mol) of powdered K3PO4. The resulting mixture was degassed (3×) by vacuum/N2 back fills. The vessel was then charged with 26 L of 1,4-dioxane and 4.28 kg (32.78 mol) of 1-chloro-4-fluorbenzene and the vessel degassed (3×) with vacuum/N2 back fills. The resulting slurry was heated to reflux for 12 h, cooled to rt, and water (23 L) was added. The vessel was rinsed with an additional 6 L of water and the reaction mixture further diluted with an additional 46 L of water. To the homogeneous solution was added 9 L of conc. HCl to adjust the pH to 1 and the solution aged for 2.5 h. The slurry was then filtered and the cake washed with 17 L of water and 17 L of toluene. The solid was then dried at 60° C. for 48 h, providing 2-(4-fluoro -phenyl)-1,3-cyclopentanedione as a light tan solid.

Workup

  1. customThe resulting mixture was degassed (3×) by vacuum/N2
  2. customthe vessel degassed (3×) with vacuum/N2
  3. temperatureThe resulting slurry was heated
  4. temperatureto reflux for 12 h
  5. additionwater (23 L) was added
  6. washThe vessel was rinsed with an additional 6 L of water
  7. additionthe reaction mixture further diluted with an additional 46 L of water
  8. additionTo the homogeneous solution was added 9 L of conc. HCl
  9. filtrationThe slurry was then filtered
  10. washthe cake washed with 17 L of water and 17 L of toluene
  11. customThe solid was then dried at 60° C. for 48 h

Sources & evidence

ORD record
ord-2123463b53f8425daeaf0c06e51d56b2
Source dataset
uspto-grants-2007_03
Patent number
US07196113B2

Reaction notes

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