Diiodomethane → HCID 86586194, compound

HRID 2186284Notes

Reaction equation

HRID 2186284 reaction equation
[CH2:1]([Zn][CH2:4][CH3:5])[CH3:2].ICI.[C:9]([C:13]1[C:27]([OH:28])=[CH:26][C:16]2[CH2:17][C:18]3([O:25][C:15]=2[CH:14]=1)[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]3)([CH3:12])([CH3:11])[CH3:10].C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1>[C:9]([C:13]1[C:27]([OH:28])=[C:4]([CH3:5])[C:16]2[CH2:17][C:18]3([O:25][C:15]=2[CH:14]=1)[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24]3)([CH3:12])([CH3:10])[CH3:11].[C:9]([C:13]1[C:27]([OH:28])=[C:26]([CH2:1][CH3:2])[C:16]2[CH2:17][C:18]3([O:25][C:15]=2[CH:14]=1)[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]3)([CH3:12])([CH3:10])[CH3:11]

Participants

7

Reactant 4

HCID 6346DiiodomethaneHCID 516892Sodium BicarbonateHCID 12094374HCID 12094374, compoundHCID 178418750HCID 178418750, compound

Product 2

HCID 86586193HCID 86586193, compoundYield 13%HCID 86586194HCID 86586194, compoundYield 15%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

Under a nitrogen stream, 1.64 ml of diethylzinc (1M in n-hexane) was added dropwise into a solution of 0.18 ml of diiodomethane in 4 ml of anhydrous toluene at 0° C. Further to this solution was added dropwise 0.30 g of 6-t-butyl-5-hydroxy-2,3-dihydrobenzofuran-2-spiro-1′-cycloheptane synthesized in Example 7 and dissolved in 4 ml of anhydrous toluene. After stirring for 5 minutes, the solution was refluxed for 1.5 hours. The reaction solution was allowed to cool down, and then combined with a saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate, and the organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate and then concentrated. The concentrate was purified by silica gel column chromatography (in n-hexane containing 1%-2% ethyl acetate) to give 0.04 g of 6-t-butyl-5-hydroxy-4-methyl-2,3-dihydrobenzofuran-2-spiro-1′-cycloheptane (yield 13%) and 0.05 g of 6-t-butyl-4-ethyl-5-hydroxy-2,3-dihydrobenzofuran-2-spiro-1′-cycloheptane (yield 15%) both as white solids.

Workup

  1. temperaturethe solution was refluxed for 1.5 hours
  2. temperatureto cool down
  3. extractionextracted with ethyl acetate
  4. washthe organic layers were washed with saturated brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated
  7. customThe concentrate was purified by silica gel column chromatography (in n-hexane containing 1%-2% ethyl acetate)

Sources & evidence

ORD record
ord-cf219df7f17f43579d6786d607a85591
Source dataset
uspto-grants-2002_06
Patent number
US06403639B1

Reaction notes

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