O-Xylene → alpha-Tocopherol

HRID 1734318Notes

Reaction equation

HRID 1734318 reaction equation
FC(F)(F)S([O-])(=O)=O.[Yb+3].FC(F)(F)S([O-])(=O)=O.F[C:19](F)(F)S([O-])(=O)=O.[CH3:26][CH:27]([CH2:29][CH2:30][CH2:31][CH:32]([CH2:34][CH2:35][CH2:36][CH:37]([CH2:39][CH2:40][CH2:41][C:42]([OH:46])([CH:44]=[CH2:45])[CH3:43])[CH3:38])[CH3:33])[CH3:28].C([O:50][CH2:51][CH3:52])(=O)C.[C:53]1(C)[C:54](C)=[CH:55][CH:56]=[CH:57][CH:58]=1>>[CH3:19][C:52]1[C:51]([OH:50])=[C:57]([CH3:56])[C:58]2[CH2:45][CH2:44][C@:42]([CH2:41][CH2:40][CH2:39][C@@H:37]([CH2:36][CH2:35][CH2:34][C@@H:32]([CH2:31][CH2:30][CH2:29][CH:27]([CH3:26])[CH3:28])[CH3:33])[CH3:38])([CH3:43])[O:46][C:53]=2[C:54]=1[CH3:55]

Participants

5

Reactant 4

HCID 7237O-Xylene2×HCID 8857Ethyl AcetateHCID 10453Isophytol2×HCID 2733225Ytterbium triflate

Product 1

HCID 14985alpha-TocopherolYield 59%

Procedure

Suspended in 100 ml of xylene were 20.0 g (131.6 mmol) of TMH and 16.3 g (26.3 mmol) of ytterbium trifluoromethanesulfonate, followed by heating under reflux for 5 minutes under an argon gas stream. After a solution of 43.0 g (145.0 mmol) of isophytol in 100 ml of xylene was added dropwise over 30 minutes under heating and reflux, TMH and isophytol were reacted for 3 hours. The reaction mixture was cooled, to which 1,000 ml of ethyl acetate were added. The resulting mixture was washed thrice with 2,000-ml portions of water and then with 2,000 ml of a saturated aqueous solution of sodium chloride. The organic layer was then dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by chromatography on a silica gel column (eluent: n-hexane-diethyl ether system), whereby 35.5 g of the title compound were obtained in the form of a brown oil. (Yield: 59%, GLC purity: 91%)

Workup

  1. temperatureby heating
  2. temperatureunder reflux for 5 minutes under an argon gas stream
  3. temperatureunder heating
  4. temperaturereflux
  5. additionwere added
  6. washThe resulting mixture was washed thrice with 2,000-ml portions of water
  7. dry with materialThe organic layer was then dried over magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by chromatography on a silica gel column (eluent: n-hexane-diethyl ether system)

Sources & evidence

ORD record
ord-ff300c4b3cdb433992f0847816b30cc5
Source dataset
uspto-grants-1996_07
Patent number
US05532387

Reaction notes

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