Methyl iodide → HCID 131718281, compound

HRID 2210655Notes

Reaction equation

HRID 2210655 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 mι 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 mι of 2N hydrochloric acid solution and 200 mι of ethyl acetate. The organic layer was washed with water (100 mι×2), saturated sodium bicarbonate solution (100 mι) and saturated sodium thiosulfate (100 mι), 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. additionwas added while the reaction mixture
  2. temperaturewas being cooled by ice
  3. stirringAfter the reaction mixture was stirred at the same temperature for 30 minutes
  4. stirringthe reaction mixture was stirred for 2 hours
  5. extractionthe reaction mixture was extracted
  6. additionby adding 50 mι of 2N hydrochloric acid solution and 200 mι of ethyl acetate
  7. washThe organic layer was washed with water (100 mι×2), saturated sodium bicarbonate solution (100 mι) and saturated sodium thiosulfate (100 mι), it
  8. customwas dried
  9. additionby adding magnesium sulfate
  10. filtrationwas then filtered
  11. concentrationconcentrated under a reduced pressure
  12. customThe residual matter was purified by chromatography
  13. customthe solvent of the fraction obtained from hexane
  14. distillationether=7:3 eluent was distilled off
  15. customA colorless oily substance was thus obtained

Sources & evidence

ORD record
ord-d7d48d9ca3944eb3b261eb9f98b7164b
Source dataset
uspto-grants-1995_10
Patent number
US05459160

Reaction notes

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