4-tert-Butylcyclohexanone → 4-tert-butyl-1,1-difluorocyclohexane

HRID 1193000Notes

Reaction equation

HRID 1193000 reaction equation
F[B-](F)(F)F.[C:6]([CH:10]1[CH2:15][CH2:14][C:13](=O)[CH2:12][CH2:11]1)([CH3:9])([CH3:8])[CH3:7].[FH:17].[FH:18].F.C(N(CC)CC)C.C(=O)(O)[O-].[Na+]>ClCCl>[C:6]([CH:10]1[CH2:15][CH2:14][C:13]([F:18])([F:17])[CH2:12][CH2:11]1)([CH3:9])([CH3:8])[CH3:7]

Participants

6

Reactant 4

HCID 73924-tert-ButylcyclohexanoneHCID 26255TetrafluoroborateHCID 175505N,N-Diethylethanamine trihydrofluorideHCID 516892Sodium Bicarbonate

Product 1

HCID 6404994-tert-butyl-1,1-difluorocyclohexaneYield 53%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of diethylaminosulfinium tetrafluoroborate (593 mg, 2.6 mmol) in dichloromethane (10 mL) at room temperature is added 4-tert-butylcyclohexanone (200 mg, 1.3 mmol) and triethylamine trihydrofluoride (266 μl, 1.3 mmol). The reaction mixture is stirred for 4 hours, then an aqueous solution of sodium bicarbonate (5%) is added and stirring is continued for 30 minutes. The organic phase is isolated and dried with magnesium sulphate. The solution is diluted with pentane (10 mL) and the solution is passed through a pad of silica gel with pentane elution. Solvent are evaporated in vacuo to provide 4-t-butyl-1,1-difluorocyclohexane (120 mg, 53%) as a clear liquid, admixed with 3% of the corresponding vinyl fluoride. Major compound: 1H NMR (CDCl3) 2.09-1.95 (m, 2H), 1.76-1.67 (m, 2H), 1.65-1.51 (m, 2H), 1.30-1.15 (m, 2H), 1.02-0.97 (s, 1H), 0.80 (s, 9H); 19F NMR (CDCl3)-91.9 (d, J=232.6 Hz, 1F), −103.5 (dm, J=232.6 Hz, 1F).

Workup

  1. stirringstirring
  2. waitis continued for 30 minutes
  3. customThe organic phase is isolated
  4. dry with materialdried with magnesium sulphate
  5. additionThe solution is diluted with pentane (10 mL)
  6. washthe solution is passed through a pad of silica gel with pentane elution
  7. customSolvent are evaporated in vacuo

Sources & evidence

ORD record
ord-63f0e535493442b88f2afd8bc1231879
Source dataset
uspto-grants-2014_03
Patent number
US08680332B2

Reaction notes

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