N,N-Diethylethanamine trihydrofluoride → Ethyl-4,4-difluorocyclohexane carboxylate

HRID 1193009Notes

Reaction equation

HRID 1193009 reaction equation
[FH:1].[FH:2].F.C(N(CC)CC)C.[C:11]([CH:16]1[CH2:21][CH2:20][C:19](=O)[CH2:18][CH2:17]1)([O:13][CH2:14][CH3:15])=[O:12]>ClCCl>[C:11]([CH:16]1[CH2:21][CH2:20][C:19]([F:2])([F:1])[CH2:18][CH2:17]1)([O:13][CH2:14][CH3:15])=[O:12]

Participants

4

Reactant 2

HCID 175505N,N-Diethylethanamine trihydrofluorideHCID 317638Ethyl 4-oxocyclohexanecarboxylate

Product 1

HCID 2779138Ethyl-4,4-difluorocyclohexane carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Procedure for the fluorination of carbonyls (examples 85-96): To a suspension of disubstituted aminodifluorosulfinium salt (2.0 mmol) and triethylamine trihydrofluoride (163 μL, 1.0 mmol) in dichloromethane (2.0 mL), at room temperature and under nitrogen, is added 4-carboethoxy-cyclohexanone (159 μL, 1.0 mmol). The reaction mixture was stirred 20 h, then quenched with a 5% aqueous sodium bicarbonate solution, stirred for 15 min, and the resulting mixture was extracted using dichloromethane. The organic phases were combined, dried over magnesium sulfate and filtered through a pad of silica gel. Solvents were evaporated to provide 4-carbethoxy-1,1-difluorocyclohexane admixed with 4-carboethoxy-1-fluorocyclohex-1-ene as a clear oil (refer to the following table for yields and product distribution).

Workup

  1. customquenched with a 5% aqueous sodium bicarbonate solution
  2. stirringstirred for 15 min
  3. extractionthe resulting mixture was extracted
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered through a pad of silica gel
  6. customSolvents were evaporated

Sources & evidence

ORD record
ord-254480d634e94cb699ac2642b44edbe0
Source dataset
uspto-grants-2014_03
Patent number
US08680332B2

Reaction notes

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