Methyl iodide → HCID 15037566, compound

HRID 613185Notes

Reaction equation

HRID 613185 reaction equation
[Mg].CI.Br[C:5]1[CH:10]=[CH:9][C:8]([C:11]2([CH3:16])[O:15]CCO2)=[C:7]([O:17][Si](C)(C)C)[CH:6]=1.[CH3:22][Si:23](Cl)([CH3:25])[CH3:24].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.C(=O)(O)[O-].[Na+]>O1CCCC1.CC(C)=O.O>[OH:17][C:7]1[CH:6]=[C:5]([Si:23]([CH3:25])([CH3:24])[CH3:22])[CH:10]=[CH:9][C:8]=1[C:11](=[O:15])[CH3:16]

Participants

10

Reactant 6

HCID 6328Methyl iodideHCID 6397ChlorotrimethylsilaneHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 516892Sodium BicarbonateHCID 5462224MagnesiumHCID 15037565HCID 15037565, compound

Product 1

HCID 15037566HCID 15037566, compoundYield 43%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent3×

Procedure

A mixture of 321 mg (13.2 mmol) of magnesium and 0.07 ml of methyl iodide in 1.32 ml of dry tetrahydrofuran was refluxed. After cooling, the mixture was diluted with 3.96 ml of dry tetrahydrofuran. To the mixture was added a solution of 4.0 g of crude 2-(4-bromo-2-trimethylsilyloxyphenyl)-2-methyl-1,3-dioxolane obtained above in 9.6 ml of dry tetrahydrofuran dropwise under refluxing and the mixture was refluxed for additional 2 hours. After cooling, 1.68 ml (13.2 mmol) of trimethylsilyl chloride was added to the reaction mixture and the mixture was refluxed for 2 hours. After cooling, water was added to the reaction mixture. The mixture was extracted with ether. The organic layer was washed with H2O and brine, dried over anhydrous Na2SO4, and evaporated. To the residue were added 72 ml of acetone, 10.8 ml (600 mmol) of water and 0.46 g (1.8 mmol) of pyridinium p-toluenesulfonate (PPTS). The mixture was refluxed for 4 hours, neutralized with aqueous sodium bicarbonate solution, and evaporated. The residue was dissolved in ether. The solution was washed with water, sodium bicarbonate and brine, dried over anhydrous Na2SO4, and evaporated. The residue was purified by column chromatography on silica gel [eluent: n-hexane-AcOEt (15:1)] to give 1.08 g of pale yellow liquid (yield 43%). MS spectrum m/z: 208 (M+), 198 (M+ -15).

Workup

  1. temperaturewas refluxed
  2. temperatureAfter cooling
  3. temperatureunder refluxing
  4. temperaturethe mixture was refluxed for additional 2 hours
  5. temperatureAfter cooling
  6. temperaturethe mixture was refluxed for 2 hours
  7. temperatureAfter cooling
  8. extractionThe mixture was extracted with ether
  9. washThe organic layer was washed with H2O and brine
  10. dry with materialdried over anhydrous Na2SO4
  11. customevaporated
  12. temperatureThe mixture was refluxed for 4 hours
  13. customevaporated
  14. dissolutionThe residue was dissolved in ether
  15. washThe solution was washed with water, sodium bicarbonate and brine
  16. dry with materialdried over anhydrous Na2SO4
  17. customevaporated
  18. customThe residue was purified by column chromatography on silica gel [eluent: n-hexane-AcOEt (15:1)]

Sources & evidence

ORD record
ord-4af9c3a559c04c0292ca67c32e181608
Source dataset
uspto-grants-1999_12
Patent number
USRE036477

Reaction notes

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