Hexane → HCID 53902794, compound

HRID 1737424Notes

Reaction equation

HRID 1737424 reaction equation
[H-].[Na+].CCCCCC.[CH2:9]([O:12][C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=1[OH:20])[CH:10]=[CH2:11].S(C1C=CC(C)=CC=1)(O[CH2:25][C@@H:26]1[O:28][CH2:27]1)(=O)=O>CN(C=O)C>[CH2:9]([O:12][C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=1[O:20][CH2:25][C@H:26]1[CH2:27][O:28]1)[CH:10]=[CH2:11]

Participants

6

Reactant 4

HCID 8058HexaneHCID 24758Sodium hydrideHCID 154187Glycidyl tosylate, (R)-HCID 21842666HCID 21842666, compound

Product 1

HCID 53902794HCID 53902794, compoundYield 48.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To 4.0 g (79 mmole) of 60% sodium hydride/mineral oil dispersion in a one liter flask was added 300 ml of hexane. The mixture was swirled briefly, the solid allowed to settle and the supernatant liquid decanted. DMF (500 ml) was added, followed by a solution of 14.6 g (79 mmole) of 2-allyloxy-5-chlorophenol in 100 ml of DMF. The mixture was stirred at room temperature under nitrogen for 30 minutes, then 18.0 g (79 mmole) of (R)-glycidyl tosylate added. The mixture was heated under a nitrogen atmosphere at 80° C. for 24 hours. The solvent was evaporated in vacuum and replaced with 750 ml of methylene chloride. The solution was washed with 500 ml portions of 2 N HCl (aq), saturated aqueous sodium bicarbonate, saturated brine, dried over sodium sulfate, filtered and evaporated in vacuum to give 20 g of a crude gum. This was column chromatographed on silica gel using methylene chloride as eluant to give 9.2 g of the title compound as a colorless oil. 1H (CDCl3) singlet, 6.93 δ (1 H); doublet, 6.90 δ (1 H); doublet, 6.80 δ (1 H);.multiplet, 6.05 δ (1 H); doublet, 5.40 δ (1 H); doublet, 5.25 δ (1 H); doublet, 4.55 δ (2 H); doublet of doublets, 4.25 δ (1 H); doublet of doublets, 3.97 δ (1 H); multiplet, 3.35 δ (1 H); triplet, 2.95 δ (2H); triplet, 2.75 δ (1 H).

Workup

  1. customthe supernatant liquid decanted
  2. additionDMF (500 ml) was added
  3. temperatureThe mixture was heated under a nitrogen atmosphere at 80° C. for 24 hours
  4. customThe solvent was evaporated in vacuum
  5. washThe solution was washed with 500 ml portions of 2 N HCl (aq), saturated aqueous sodium bicarbonate, saturated brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated in vacuum
  9. customto give 20 g of a crude gum
  10. customThis was column chromatographed on silica gel

Sources & evidence

ORD record
ord-140d25fc179541e7b602e73805a0700e
Source dataset
uspto-grants-1999_10
Patent number
US05962465

Reaction notes

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