O-Xylene → alpha-Tocopherol

HRID 1734317Notes

Reaction equation

HRID 1734317 reaction equation
[C:1]1(C)[C:2](C)=[CH:3][CH:4]=[CH:5][CH:6]=1.FC(F)(F)S([O-])(=O)=O.[Eu+3].FC(F)(F)S([O-])(=O)=O.F[C:27](F)(F)S([O-])(=O)=O.[CH3:34][CH:35]([CH2:37][CH2:38][CH2:39][CH:40]([CH2:42][CH2:43][CH2:44][CH:45]([CH2:47][CH2:48][CH2:49][C:50]([OH:54])([CH:52]=[CH2:53])[CH3:51])[CH3:46])[CH3:41])[CH3:36].C([O:58][CH2:59][CH3:60])(=O)C>C(Cl)Cl>[CH3:27][C:60]1[C:59]([OH:58])=[C:5]([CH3:4])[C:6]2[CH2:53][CH2:52][C@:50]([CH2:49][CH2:48][CH2:47][C@@H:45]([CH2:44][CH2:43][CH2:42][C@@H:40]([CH2:39][CH2:38][CH2:37][CH:35]([CH3:34])[CH3:36])[CH3:41])[CH3:46])([CH3:51])[O:54][C:1]=2[C:2]=1[CH3:3]

Participants

6

Reactant 4

HCID 7237O-XyleneHCID 8857Ethyl AcetateHCID 10453Isophytol2×HCID 9960317europium trifluoromethanesulfonate

Product 1

HCID 14985alpha-TocopherolYield 84%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Suspended in 200 me of xylene were 20.0 g (131.6 mmol) of TMH and 15.8 g (26.3 mmol) of europium 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 200 ml of methylene chloride 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 47.7 g of the title compound were obtained in the form of a brown oil. (Yield: 84%, GLC purity: 80%)

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-cf2c3fe426194874b4ecfbf5feb947cd
Source dataset
uspto-grants-1996_07
Patent number
US05532387

Reaction notes

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