Water → Tocol

HRID 1165093Notes

Reaction equation

HRID 1165093 reaction equation
[CH3:1][C:2]([CH2:6][CH2:7][CH2:8][CH:9]([CH3:21])[CH2:10][CH2:11][CH2:12][CH:13]([CH3:20])[CH2:14][CH2:15][CH2:16][CH:17]([CH3:19])[CH3:18])=[CH:3][CH2:4]O.[OH2:22].[CH3:23][CH2:24][CH2:25][CH2:26]CC.C([O:32][CH2:33][CH3:34])(=O)C>C(OCCCC)(=O)C.[Cl-].[Zn+2].[Cl-]>[CH3:1][C:2]1([CH2:6][CH2:7][CH2:8][CH:9]([CH3:21])[CH2:10][CH2:11][CH2:12][CH:13]([CH3:20])[CH2:14][CH2:15][CH2:16][CH:17]([CH3:19])[CH3:18])[CH2:3][CH2:4][C:26]2[C:25](=[CH:24][CH:23]=[C:33]([OH:32])[CH:34]=2)[O:22]1

Participants

6

Reactant 3

HCID 962WaterHCID 1453863,7,11,15-Tetramethylhexadec-2-en-1-olHCID 21226206Ethyl acetate hexane

Product 1

HCID 9865117TocolYield 40%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 31272Butyl AcetateSolvent2×

Procedure

To 1.10 g (10.0 mmole) of 1,4-hydroquinone and 409 mg (3.00 mmole) of zinc chloride in 5 ml of butyl acetate there was dropwise added, under nitrogen atmosphere, 1.48 g (5.00 mmole) of 3,7,11,15-tetramethyl-2-hexadecen-1-ol in 5 ml of butyl acetate over one hour while refluxing under heating. After the completion of the dropwise addition, the reaction solution was refluxed under heating for additional 30 minutes, followed by allowing the reaction solution to cool, pouring it into water (100 ml) and extracting it twice with ether (100 ml×1; 50 ml×1). The combined extract was successively washed with 150 ml of 5% (w/v) aqueous sodium hydroxide solution (one time), 150 ml of water (one time) and 150 ml of saturated aqueous solution of sodium chloride (one time), followed by drying over anhydrous magnesium sulfate, distilling off the solvent and subjecting the residue to silica gel column chromatography. Thus, 770 mg (2.0 mmole) of the title compound (2) was recovered from the eluted fractions (eluent:hexane-ethyl acetate (10:1). Yield:40%.

Workup

  1. temperatureunder heating
  2. additionAfter the completion of the dropwise addition
  3. temperaturethe reaction solution was refluxed
  4. temperatureunder heating for additional 30 minutes
  5. temperatureto cool
  6. extractionextracting it twice with ether (100 ml×1; 50 ml×1)
  7. extractionThe combined extract
  8. washwas successively washed with 150 ml of 5% (w/v) aqueous sodium hydroxide solution (one time), 150 ml of water (one time) and 150 ml of saturated aqueous solution of sodium chloride (one time)
  9. dry with materialby drying over anhydrous magnesium sulfate
  10. distillationdistilling off the solvent

Sources & evidence

ORD record
ord-9ce534e93fb649359a9ff39b4498272b
Source dataset
uspto-grants-1990_03
Patent number
US04906669

Reaction notes

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