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

HRID 2211366Notes

Reaction equation

HRID 2211366 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-tridecatrienylphosphonate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

In Scheme I, step b, the alcohol (3) is oxidized to the ketone described by structure (5). For example, an equivalent of trifluoroacetic acid anhydride is added dropwise to 2 equivalents of dimethylsulfoxide in a suitable organic solvent, such as dichloromethane at approximately -60° C. After addition is complete, the reaction is stirred for approximately 2 minutes. An equivalent of an appropriately substituted alcohol (3), such as dimethyl 1,1-difluoro-2-hydroxy-4,8,12-trimethyl-3,7,11-tridecatrienylphosphonate dissolved in a suitable organic solvent, such as dichloromethane, is added to the reaction dropwise. After addition is complete, the reaction is stirred for approximately 45 minutes. The reaction is then cooled to -78° C. and an excess of triethylamine is added dropwise. The reaction is then allowed to warm to ambient temperature and stirred for approximately 45 minutes. The reaction mixture is then poured into water and extracted with a suitable organic solvent, such as diethyl ether. The organic phase is dried over a suitable drying agent, such as anhydrous magnesium sulfate, filtered and concentrated under vacuum. The residue is then purified by techniques well known in the art. For example, the residue can be purified by flash chromatography using a suitable organic eluent, such as 20% ethyl acetate/hexane, to provide dimethyl 1,1-difluoro-2-oxo-4,8,12-trimethyl-3,7,11-tridecatrienylphosphonate.

Workup

  1. additionAfter addition
  2. additionis added to the reaction dropwise
  3. additionAfter addition
  4. stirringthe reaction is stirred for approximately 45 minutes
  5. temperatureto warm to ambient temperature
  6. stirringstirred for approximately 45 minutes
  7. extractionextracted with a suitable organic solvent, such as diethyl ether
  8. dry with materialThe organic phase is dried over a suitable drying agent, such as anhydrous magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under vacuum
  11. customThe residue is then purified by techniques

Sources & evidence

ORD record
ord-a67ce9b4433543f7bb2e509a83488800
Source dataset
uspto-grants-1995_10
Patent number
US05463181

Reaction notes

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