1,4-Dibromobenzene → 2-(4-Bromophenyl)-1,1,1,3,3,3-hexafluoropropan-2-ol

HRID 726750Notes

Reaction equation

HRID 726750 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=1.[F:14][C:15]([F:23])([F:22])[C:16]([C:18]([F:21])([F:20])[F:19])=[O:17].[NH4+].[Cl-]>CCOCC>[Br:13][C:10]1[CH:11]=[CH:12][C:7]([C:16]([OH:17])([C:18]([F:21])([F:20])[F:19])[C:15]([F:23])([F:22])[F:14])=[CH:8][CH:9]=1

Participants

6

Reactant 4

HCID 78041,4-DibromobenzeneHCID 12695HexafluoroacetoneHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 232335702-(4-Bromophenyl)-1,1,1,3,3,3-hexafluoropropan-2-olYield 78.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

n-Butyllithium (2.4M solution in hexane; 92.7 mL, 0.222 mol) was added dropwise (20 min) to a solution of p-dibromobenzene (50.0 g, 0.212 mol) in Et2O (1.2 L) at -60° C. After completion of the addition, the reaction was left at -50° C. for 30 min and hexafluoroacetone (42.2 g, 0.254 mol) was bubbled through the heterogeneous mixture, at the same temperature. The resulting solution was allowed to warm to -30° C. over 30 min before saturated aqueous NH4Cl was added. The aqueous layer was extracted with EtOAc (2×) and the combined organic extracts were successively washed with 25% aqueous NH4OAc buffer, water and brine, dried (MgSO4) and concentrated. The residue was distilled under reduced pressure (bp 85°-90° C./12 mmHg) to afford the title compound as colorless crystals (53.5 g, 78%).

Workup

  1. additionAfter completion of the addition
  2. additionwas added
  3. extractionThe aqueous layer was extracted with EtOAc (2×)
  4. washthe combined organic extracts were successively washed with 25% aqueous NH4OAc buffer, water and brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. distillationThe residue was distilled under reduced pressure (bp 85°-90° C./12 mmHg)

Sources & evidence

ORD record
ord-098788cb4a674a59bed4b0afc5ffcfab
Source dataset
uspto-grants-1998_01
Patent number
US05710170

Reaction notes

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