Water → 2-Methyl-1-[2,4,6-trihydroxy-3-(3-methyl-2-buten-1-yl)phenyl]-1-propanone

HRID 567204Notes

Reaction equation

HRID 567204 reaction equation
[CH3:1][CH:2]([C:4]([C:6]1[C:11]([OH:12])=[CH:10][C:9]([OH:13])=[CH:8][C:7]=1[OH:14])=[O:5])[CH3:3].O.[B].[CH3:17][C:18]([CH3:22])=[CH:19][CH2:20]O>O1CCOCC1.CCOCC>[CH3:3][CH:2]([C:4]([C:6]1[C:7]([OH:14])=[CH:8][C:9]([OH:13])=[C:10]([CH2:20][CH:19]=[C:18]([CH3:22])[CH3:17])[C:11]=1[OH:12])=[O:5])[CH3:1].[CH3:17][C:18]([CH3:22])=[CH:19][CH2:20][C:10]1([CH2:6][CH:4]=[C:2]([CH3:3])[CH3:1])[C:9]([OH:13])=[CH:8][C:7]([OH:14])=[C:6]([C:4](=[O:5])[CH:2]([CH3:1])[CH3:3])[C:11]1=[O:12]

Participants

8

Reactant 4

HCID 962WaterHCID 111733-Methyl-2-buten-1-OLHCID 5326317PhlorisobutyrophenoneHCID 5462311Boron

Product 2

HCID 134117382-Methyl-1-[2,4,6-trihydroxy-3-(3-methyl-2-buten-1-yl)phenyl]-1-propanoneHCID 178442131HCID 178442131, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent2×

Procedure

Under an atmosphere of nitrogen, 981 mg (5.00 mmol) of (2,4,6-trihydroxyphenyl) (2-propyl) ketone (4) was dissolved in 10.0 ml of dioxane, cooled with cold water at about 10° C., and stirred. Into the stirred solution, 554 ml (639 mg, 4.50 mmol, 0.900 equivalent) of boron trifluorideether complex was added by the use of a microsyringe. The resultant mixture was further stirred for 15 minutes and then a dioxane (9 ml) solution of 861 mg of 3-methyl-2-butenol was slowly added dropwise. After four hours, the reaction solution was poured into 100 ml of ether. The ether layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and saturated brine and dried over sodium sulfate. The produced solution was distilled under a reduced pressure to remove the solvent and obtain 1.76 g of a crude product in the form of a red viscous oily substance. The crude product was treated by silica gel column chromatography (50 g of Wako Gel C-300, and eluted sequentially with 200 ml each of petroleum ether:ether at varying ratios=9:1, 7:3, and 5:5) to isolate 417 mg of {3-(3-methyl-2-butenyl)-2,4,6-trihydroxyphenyl} (2-propyl) ketone (23) and 338 mg of 2,2-bis(3-methyl-2-butenyl)-3,5-dihydroxy-6-(2-methyl-1-oxopropyl) cyclohexa-3,5-dienone (13).

Workup

  1. washThe ether layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and saturated brine
  2. dry with materialdried over sodium sulfate
  3. distillationThe produced solution was distilled under a reduced pressure
  4. customto remove the solvent
  5. customobtain 1.76 g of a crude product in the form of a red viscous oily substance
  6. washeluted sequentially with 200 ml each of petroleum ether

Sources & evidence

ORD record
ord-bf97e293525e42b79006e1a556995e8d
Source dataset
uspto-grants-2001_01
Patent number
US06177474B1

Reaction notes

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