Dimethyl Sulfoxide → Dimethyl 1,1-difluoro-2-oxo-4,8,12-trimethyl-3,7,11-tridecatrienylphosphonate

HRID 2211368Notes

Reaction equation

HRID 2211368 reaction equation
FC(F)(F)C(OC(=O)C(F)(F)F)=O.CS(C)=O.[F:18][C:19]([P:37](=[O:42])([O:40][CH3:41])[O:38][CH3:39])([F:36])[CH:20]([OH:35])[CH:21]=[C:22]([CH3:34])[CH2:23][CH2:24][CH:25]=[C:26]([CH3:33])[CH2:27][CH2:28][CH:29]=[C:30]([CH3:32])[CH3:31].C(N(CC)CC)C>ClCCl.O>[F:36][C:19]([P:37](=[O:42])([O:40][CH3:41])[O:38][CH3:39])([F:18])[C:20](=[O:35])[CH:21]=[C:22]([CH3:34])[CH2:23][CH2:24][CH:25]=[C:26]([CH3:33])[CH2:27][CH2:28][CH:29]=[C:30]([CH3:32])[CH3:31]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 9845Trifluoroacetic anhydrideHCID 54561178Dimethyl 1,1-difluoro-2-hydroxy-4,8,12-trimethyl-3,7,11-tridecatrienylphosphonate

Product 1

HCID 53731468Dimethyl 1,1-difluoro-2-oxo-4,8,12-trimethyl-3,7,11-tridecatrienylphosphonateYield 69.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Procedure

Combine trifluoroacetic acid anhydride (1.30 mL, 0.0096 mol) with dichloromethane (20 mL) and cool to -60° C. Add dropwise a solution of dimethylsulfoxide (1.30 mL, 0.0183 mol) in dichloromethane (2 mL) while maintaining the temperature below -55° C. After addition is complete, stir for stir for 2 minutes. Add a solution of the dimethyl 1,1-difluoro-2-hydroxy-4,8,12-trimethyl-3,7,11-tridecatrienylphosphonate (1.60 g, 0.0042 mol) prepared in example 1 in dichloromethane (4 mL) and stir for 45 minutes. Cool the reaction to -78° C. and add triethylamine (3.0 mL, 0.021 mol) dropwise. Allow the reaction to warm to ambient temperature and stir for 45 minutes. Pour the reaction into water (100 mL). Extract this mixture with diethyl ether (400 mL). Dry the organic phase over anhydrous magnesium sulfate, filter and concentrate under vacuum. Purify the residue by flash chromatography (20% ethyl acetate/hexane, Rf = 0.18) to provide the title compound (1.1 g, 69%) as an oil.

Workup

  1. temperaturewhile maintaining the temperature below -55° C
  2. additionAfter addition
  3. stirringfor stir for 2 minutes
  4. stirringstir for 45 minutes
  5. temperatureCool
  6. customthe reaction to -78° C.
  7. customthe reaction
  8. stirringstir for 45 minutes
  9. additionPour
  10. extractionExtract this mixture with diethyl ether (400 mL)
  11. dry with materialDry the organic phase over anhydrous magnesium sulfate
  12. filtrationfilter
  13. concentrationconcentrate under vacuum
  14. customPurify the residue by flash chromatography (20% ethyl acetate/hexane, Rf = 0.18)

Sources & evidence

ORD record
ord-42a8d50d435849b5aff05c5743671a69
Source dataset
uspto-grants-1995_10
Patent number
US05463181

Reaction notes

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