HCID 11106784, compound → HCID 10987736, compound

HRID 1767442Notes

Reaction equation

HRID 1767442 reaction equation
[CH3:1][CH:2]1[C:10]2[CH:9]=[C:8]3[O:11][CH2:12][C:13](=C)[CH2:14][O:15][C:7]3=[CH:6][C:5]=2[CH2:4][CH2:3]1.I([O-])(=O)(=O)=[O:18].[Na+]>C(#N)C.O.C(Cl)(Cl)(Cl)Cl.O.[Ru](Cl)(Cl)Cl>[CH3:1][CH:2]1[C:10]2[CH:9]=[C:8]3[O:11][CH2:12][C:13](=[O:18])[CH2:14][O:15][C:7]3=[CH:6][C:5]=2[CH2:4][CH2:3]1

Participants

7

Reactant 2

HCID 11106784HCID 11106784, compoundHCID 23667635Sodium periodate2×

Product 1

HCID 10987736HCID 10987736, compoundYield 50%

Reagents, catalysts & solvents 4

HCID 6093376Ruthenium trichloride hydrateCatalyst2×HCID 962WaterSolvent2×HCID 5943Carbon TetrachlorideSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
30 °C

Procedure

6.6 g (30.5 mmol) of 1-methyl-7-methylene-2,3,7,8-tetrahydro-1H,6H-5,9-dioxacyclohepta[f]indene were dissolved in a mixture of 140 ml of acetonitrile, 140 ml of water and 90 ml of carbon tetrachloride. 6.50 g (30.5 mmol) of sodium periodate were added at room temperature with stirring, with the temperature falling to 15° C. After stirring for 30 min, 0.3 g (1.5 mmol, 5 mol %) of ruthenium (III) chloride hydrate were then added, with the temperature increasing back to 30° C. The mixture was stirred for 48 h at room temperature, in the course of which, after 6 h, a further 6.50 g (30.5 mmol) of sodium periodate and 0.3 g (1.5 mmol, 5 mol %) of ruthenium (III) chloride hydrate were added. The reaction mixture was then poured into 500 ml of water and the product was extracted three times, each time with 200 ml of dichloromethane. The combined organic extracts were washed with 200 ml of 20% sodium hydrogen sulfite solution and 200 ml of water and dried over sodium sulfate. After removing the solvent on a rotary evaporator and flash chromatography (pentane/ether, 4:1, Rf=0.32) on silica gel, 3.3 g (50%) of 1-methyl-2,3-dihydro-1H-5,9-dioxacyclohepta[f]inden-7-one (2) were obtained as colorless crystals of m.p. 79-80° C.

Workup

  1. customfalling to 15° C
  2. stirringAfter stirring for 30 min
  3. stirringThe mixture was stirred for 48 h at room temperature, in the course of which, after 6 h
  4. extractionthe product was extracted three times
  5. washThe combined organic extracts were washed with 200 ml of 20% sodium hydrogen sulfite solution and 200 ml of water
  6. dry with materialdried over sodium sulfate
  7. customAfter removing the solvent
  8. customon a rotary evaporator and flash chromatography (pentane/ether, 4:1, Rf=0.32) on silica gel

Sources & evidence

ORD record
ord-778d8ca8f65f4c11b194e07c32e772d8
Source dataset
uspto-grants-2007_06
Patent number
US07235519B2

Reaction notes

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