Sodium chlorodifluoroacetate → HCID 86690099, compound

HRID 520385Notes

Reaction equation

HRID 520385 reaction equation
[CH2:1]=[C:2]1[CH2:7][CH2:6][CH:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4][CH2:3]1.Cl[C:14]([F:19])([F:18])C([O-])=O.[Na+]>COCCOCCOC.C(Cl)Cl>[F:18][C:14]1([F:19])[C:2]2([CH2:3][CH2:4][CH:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:6][CH2:7]2)[CH2:1]1

Participants

5

Reactant 2

HCID 2734985Sodium chlorodifluoroacetateHCID 15151435Ethyl 4-methylidenecyclohexane-1-carboxylate

Product 1

HCID 86690099HCID 86690099, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8150DiglymeSolvent2×

Procedure

To a solution of ethyl 4-methylenecyclohexanecarboxylate (0.15 g, 0.892 mmol) in diglyme (3 mL) was added a solution of sodium 2-chloro-2,2-difluoroacetate (0.544 g, 3.57 mmol) in 5 ml of diglyme via syringe pump at 0.5 ml/h at 150° C. The reaction was cooled to rt, then diluted with DCM and washed with water, brine, dried over Na2SO4, filtered and concentrated. The residue was charged to a 40 g silica gel cartridge which was eluted with a 20 min gradient of 0-20% EtOAc in hexane to yield ethyl 1,1-difluorospiro[2.5]octane-6-carboxylate. 1H NMR (400 MHz, CDCl3) ppm 4.09-4.19 (2H, m), 2.29-2.45 (1H, m), 1.89-2.03 (2H, m), 1.55-1.72 (5H, m), 1.45-1.54 (1H, m), 1.31-1.39 (1H, m), 1.21-1.30 (3H, m), 0.84-0.94 (1H, m).

Workup

  1. washwashed with water, brine
  2. dry with materialdried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. additionThe residue was charged to a 40 g silica gel cartridge which
  6. washwas eluted with a 20 min gradient of 0-20% EtOAc in hexane

Sources & evidence

ORD record
ord-121daf425f5a4da8883ee2ab6c291dd1
Source dataset
uspto-grants-2016_05
Patent number
US09326973B2

Reaction notes

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