Acetic Acid → Phytyltrimethylhydroquinone

HRID 48197

Reaction equation

HRID 48197 reaction equation
[CH3:1][C:2]1[C:3]([OH:11])=[C:4]([CH3:10])[C:5]([CH3:9])=[C:6]([CH:8]=1)[OH:7].[CH3:12][CH:13]([CH2:15][CH2:16][CH2:17][CH:18]([CH2:20][CH2:21][CH2:22][CH:23]([CH2:25][CH2:26][CH2:27][C:28](O)([CH:30]=C)[CH3:29])[CH3:24])[CH3:19])[CH3:14].[C:33](O)(=O)C>CCOCC.CO.[Cl-].[Zn+2].[Cl-]>[CH2:1]([C:2]1[C:3]([OH:11])=[C:4]([CH3:10])[C:5]([CH3:9])=[C:6]([OH:7])[C:8]=1[CH3:33])/[CH:12]=[C:13](/[CH2:15][CH2:16][CH2:17][C@@H:18]([CH2:20][CH2:21][CH2:22][C@@H:23]([CH2:25][CH2:26][CH2:27][CH:28]([CH3:30])[CH3:29])[CH3:24])[CH3:19])\[CH3:14]

Participants

7

Reactant 3

HCID 176Acetic AcidHCID 10453IsophytolHCID 12785Trimethylhydroquinone

Product 1

HCID 87503419PhytyltrimethylhydroquinoneYield 47%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 887MethanolSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

The solution of trimethylhydroquinone (30, 7.5 g, 49.28 mmol), isophytol (12 g, 40.47 mmol), anhydrous zinc chloride (3 g, 22.01 mmol) and 0.4 mL of glacial acetic acid in 60 mL of absolute ether was refluxed for 1 h. The solvent was then removed in vacuo at 50° C. and the slurry obtained was dissolved in a mixture of 50 mL of petroleum ether and 20 mL of 70% aqueous methanol. The emulsion formed was destroyed by the addition of 20 mL of ether. The ether layer was dried (Na2SO4) and evaporated in vacuo to give a red solid paste that was triturated vigorously with 70 mL of petroleum ether. After cooling to −78° C., the suspension was centrifuged and the supernatant petroleum ether was decanted. Cold petroleum ether (10 mL) was added to the crystalline mass, and the operation was twice repeated to give 10 g (47%) of sticky white solid, which was used in the next step without further purification.

Workup

  1. customThe solvent was then removed in vacuo at 50° C.
  2. customthe slurry obtained
  3. customThe emulsion formed
  4. customwas destroyed by the addition of 20 mL of ether
  5. dry with materialThe ether layer was dried (Na2SO4)
  6. customevaporated in vacuo
  7. customto give a red solid paste that
  8. customwas triturated vigorously with 70 mL of petroleum ether
  9. customthe supernatant petroleum ether was decanted
  10. additionCold petroleum ether (10 mL) was added to the crystalline mass

Sources & evidence

ORD record
ord-dc07e42ebc2e4eedb1b3fa31aec964ab
Source dataset
uspto-grants-2004_03
Patent number
US06703384B2

Linked notes

Loading…