Methyl iodide → HCID 131718281, compound

HRID 327308Notes

Reaction equation

HRID 327308 reaction equation
[CH2:1]([O:3][CH:4]([O:6][C@H:7]1[C@@H:12]2[C:13]([CH2:16][OH:17])=[CH:14][CH2:15][C@@H:11]2[C:10]([C:18]([O:20][CH3:21])=[O:19])=[CH:9][O:8]1)[CH3:5])[CH3:2].[H-].[Na+].[CH3:24]I>CN(C)C=O>[CH2:1]([O:3][CH:4]([O:6][C@H:7]1[C@@H:12]2[C:13]([CH2:16][O:17][CH3:24])=[CH:14][CH2:15][C@@H:11]2[C:10]([C:18]([O:20][CH3:21])=[O:19])=[CH:9][O:8]1)[CH3:5])[CH3:2]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 131718282HCID 131718282, compound

Product 1

HCID 131718281HCID 131718281, compoundYield 81.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Methyl (1S, 4aS, 7aS)-1-[1-(ethoxy)ethoxy]-7-(hydroxymethyl)-1, 4a, 5, 7a-tetrahydrocyclopenta[c]-pyran-4-carboxylate (2.0 g, 0.0067 mol) obtained in Example 16 was dissolved in 30 ml of dimethylformamide, and 540 mg (0.013 mol) of sodium hydride (in 60% oil) was added while the reaction mixture was being cooled by ice and stirred. After the reaction mixture was stirred at the same temperature for 30 minutes, 1.9 g (0.013 mol) of methyl iodide was added dropwise. After the temperature was raised up to the room temperature and the reaction mixture was stirred for 2 hours, the reaction mixture was extracted by adding 50 ml of 2N hydrochloric acid solution and 200 ml of ethyl acetate. The organic layer was washed with water (100 ml×2), saturated sodium bicarbonate solution (100 ml) and saturated sodium thiosulfate (100 ml), it was dried by adding magnesium sulfate and was then filtered, and thereafter concentrated under a reduced pressure. The residual matter was purified by chromatography using silica gel, and the solvent of the fraction obtained from hexane:ether=7:3 eluent was distilled off. A colorless oily substance was thus obtained, i.e., methyl (1S, 4aS, 7aS)-1-[1-(ethoxy)ethoxy]-7-(methoxymethyl)-1, 4a, 5, 7a-tetrahydrocyclopenta[c]pyran-4-carboxylate (1.71 g, yield=81.8%). This methyl (1S, 4aS, 7aS)-1-[1-(ethoxy)ethoxy]-7-(methoxymethyl)-1, 4a, 5, 7a-tetrahydrocyclopenta[c]pyran-4-carboxylate had the following physicochemical properties:

Workup

  1. temperaturewas being cooled by ice
  2. stirringAfter the reaction mixture was stirred at the same temperature for 30 minutes
  3. stirringthe reaction mixture was stirred for 2 hours
  4. extractionthe reaction mixture was extracted
  5. additionby adding 50 ml of 2N hydrochloric acid solution and 200 ml of ethyl acetate
  6. washThe organic layer was washed with water (100 ml×2), saturated sodium bicarbonate solution (100 ml) and saturated sodium thiosulfate (100 ml), it
  7. customwas dried
  8. additionby adding magnesium sulfate
  9. filtrationwas then filtered
  10. concentrationconcentrated under a reduced pressure
  11. customThe residual matter was purified by chromatography
  12. customthe solvent of the fraction obtained from hexane
  13. distillationether=7:3 eluent was distilled off
  14. customA colorless oily substance was thus obtained

Sources & evidence

ORD record
ord-4b985057b3b447fca87c2ebc428be834
Source dataset
uspto-grants-1993_12
Patent number
US05272172

Reaction notes

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