Chlorodifluoromethane → ((Difluoromethyl)thio)benzene

HRID 359206Notes

Reaction equation

HRID 359206 reaction equation
[OH-].[Na+].[C:3]1([SH:9])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Cl[CH:11]([F:13])[F:12]>CCCCC.C(OCC)C.O.O1CCOCC1>[C:3]1([S:9][CH:11]([F:13])[F:12])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

8

Reactant 3

HCID 6372Chlorodifluoromethane2×HCID 7969ThiophenolHCID 14798Sodium Hydroxide

Product 1

HCID 73752((Difluoromethyl)thio)benzeneYield 69%

Reagents, catalysts & solvents 4

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolventHCID 8003PentaneSolventHCID 312751,4-DioxaneSolvent

Procedure

A 6 ounce Fisher-Porter bottle was charged with 10.0 g (250 mmol) of sodium hydroxide, 13 mL of water, 15 mL of paradioxane, and 5.5 mL (54 mmol) of thiophenol. The bottle and overhead system were closed, the rapidly stirred mixture was heated to 60°-70° C. by means of an oil bath, and the system was charged to 50 psig with chlorodifluoromethane. Heating was continued for 1 hour, during which time the pressure gradually decreased and the system was occasionally recharged to 50 psig with chlorodifluoromethane. After cooling to room temperature, the system was opened and the reaction mixture was treated with 50 mL of water and 25 mL of diethyl ether. Filtration through glass wool paper followed by removal of the ether layer afforded an aqueous solution that was extracted with three 15 mL portions of diethyl ether. The ether layers were combined and concentrated in vacuo to give a residue which was dissolved in 50 mL of pentane. The pentane solution was washed with five 10 mL portions of water, dried (MgSO4), and concentrated in vacuo. Short path distillation of the residue gave 5.88 g (69% yield) of difluoromethyl phenyl sulfide: bp 24°-26° C. (1 torr): 1H NMR (CDCl3) 6.80 (t, IH, JHF =57Hz), 7.30-7.68 (m, 5H).

Workup

  1. customThe bottle and overhead system were closed
  2. temperaturethe rapidly stirred mixture was heated to 60°-70° C. by means of an oil bath
  3. temperatureHeating
  4. filtrationFiltration through glass wool paper
  5. customfollowed by removal of the ether layer
  6. customafforded an aqueous solution that
  7. extractionwas extracted with three 15 mL portions of diethyl ether
  8. concentrationconcentrated in vacuo
  9. customto give a residue which
  10. washThe pentane solution was washed with five 10 mL portions of water
  11. dry with materialdried (MgSO4)
  12. concentrationconcentrated in vacuo
  13. distillationShort path distillation of the residue

Sources & evidence

ORD record
ord-56bb434c80884f2282ed1f206ebcfca2
Source dataset
uspto-grants-1991_03
Patent number
US04999429

Reaction notes

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