Acetone → Justicidin A

HRID 1153819Notes

Reaction equation

HRID 1153819 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3[C:19]4[C:20](=[O:23])[O:21][CH2:22][C:18]=4[C:17]([OH:24])=[C:16]4[C:11]=3[CH:12]=[C:13]([O:27][CH3:28])[C:14]([O:25][CH3:26])=[CH:15]4)=[CH:9][C:4]=2[O:3][CH2:2]1.CI.[CH3:31]C(C)=O>>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3[C:19]4[C:20](=[O:23])[O:21][CH2:22][C:18]=4[C:17]([O:24][CH3:31])=[C:16]4[C:11]=3[CH:12]=[C:13]([O:27][CH3:28])[C:14]([O:25][CH3:26])=[CH:15]4)=[CH:9][C:4]=2[O:3][CH2:2]1

Participants

4

Reactant 3

HCID 180AcetoneHCID 6328Methyl iodideHCID 100492Diphyllin2×

Product 1

HCID 159982Justicidin A

Procedure

The product of step F, diphyllin, (10; 75 mg; 0.197 mmol), and 1 ml methyl iodide were dissolved in 5 ml acetone containing 82 mg potassium carbonate (0.6 mmol), and the resulting solution heated at about 60° for one hour. After removing acetone, a residue remained which was treated with methylene chloride and 10% aqueous hydrogen chloride. After separation of aqueous and organic layers, the organic layer was washed with saturated sodium chloride and dried over magnesium sulfate. Evaporation of solvent and purification on a preparative thin-layer chromatography plate provided ca. 67 mg of 9-(1,3-benzodioxol-5-yl)-4,6,7-trimethoxynaphtho[2,3-c]furan-1-(3H)-one, 11, mp 248°-250°. IR(CHCl3): 1770, 1620 cm-1 ; PMR (CDCl3): δ7.39 (s, 1H), 6.91 (s, 1H), 6.83-6.64 (m, 3H), 5.94 (2s, 2H), 5.42 (s, 2H), 4.05 (s, 3H), 3.98 (s, 3H), and 3.73 (s, 3H); MS: m/z 394.1006 (M+), calcd. for C22H18O7, 394.1049. A separate sample of product 11, prepared by substantially the foregoing procedure, was recrystallized from chloroform-ether, mp 256°-258°. This crystalline product was again recrystallized from chloroform-ether, mp 258°-260°.

Workup

  1. temperaturethe resulting solution heated at about 60° for one hour
  2. customAfter removing acetone
  3. additionwas treated with methylene chloride and 10% aqueous hydrogen chloride
  4. customAfter separation of aqueous and organic layers
  5. washthe organic layer was washed with saturated sodium chloride
  6. dry with materialdried over magnesium sulfate
  7. customEvaporation of solvent and purification on a preparative thin-layer chromatography plate

Sources & evidence

ORD record
ord-bc16623aa76e4aaea60db9c067651518
Source dataset
uspto-grants-1984_12
Patent number
US04486445

Reaction notes

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