Phosphorus oxychloride → Benzyl 4,4-difluorocyclohex-1-ene-1-carboxylate

HRID 1160622Notes

Reaction equation

HRID 1160622 reaction equation
[F:1][C:2]1([F:19])[CH2:7][CH2:6][C:5](O)([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[CH2:4][CH2:3]1.P(Cl)(Cl)(Cl)=O.[Cl-].[NH4+]>N1C=CC=CC=1>[F:1][C:2]1([F:19])[CH2:7][CH2:6][C:5]([C:8]([O:10][CH2:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[O:9])=[CH:4][CH2:3]1

Participants

5

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 25517Ammonium ChlorideHCID 68715338Benzyl 4,4-difluoro-1-hydroxycyclohexanecarboxylate

Product 1

HCID 68717850Benzyl 4,4-difluorocyclohex-1-ene-1-carboxylate

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a solution of benzyl 4,4-difluoro-1-hydroxycyclohexanecarboxylate (1.8 g, 6.66 mmol) in 13 ml of pyridine was added phosphorous oxychloride (1.12 g, 7.33 mmol). The resulting solution was stirred under nitrogen at room temperature for 18 hours, and then poured into 70 mL of saturated ammonium chloride solution and extracted with ethyl acetate. The combined ethyl acetate extracts were washed with 2 molar hydrochloric acid solution and brine and then dried over sodium sulfate. Filtration and concentration under vacuum afforded the crude product which was purified by chromatography on silica gel eluting 2% ethyl acetate in hexanes to give benzyl 4,4-difluorocyclohex-1-ene-1-carboxylate as an oil.

Workup

  1. extractionextracted with ethyl acetate
  2. washThe combined ethyl acetate extracts were washed with 2 molar hydrochloric acid solution and brine
  3. dry with materialdried over sodium sulfate
  4. filtrationFiltration and concentration under vacuum
  5. customafforded the crude product which
  6. customwas purified by chromatography on silica gel eluting 2% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-8b37ab2ea8a24490addb2ffc1bf42ae2
Source dataset
uspto-grants-2010_10
Patent number
US07816380B2

Reaction notes

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