Phenol → 2-(2-Allyloxy4-nitrophenoxymethyl)-oxirane

HRID 392635Notes

Reaction equation

HRID 392635 reaction equation
[H-].[Na+].[CH2:3]([O:6][C:7]1[CH:12]=[C:11]([N+:13]([O-:15])=[O:14])[CH:10]=[CH:9][C:8]=1[OH:16])[CH:4]=[CH2:5].[C:17]1([OH:23])C=CC=[CH:19][CH:18]=1.S(C1C=CC(C)=CC=1)(OC[C@@H]1OC1)(=O)=O>>[CH2:3]([O:6][C:7]1[CH:12]=[C:11]([N+:13]([O-:15])=[O:14])[CH:10]=[CH:9][C:8]=1[O:16][CH2:19][CH:18]1[CH2:17][O:23]1)[CH:4]=[CH2:5]

Participants

5

Reactant 4

HCID 996PhenolHCID 24758Sodium hydrideHCID 154187Glycidyl tosylate, (R)-HCID 120822032-Allyloxy-4-nitrophenol

Product 1

HCID 218920512-(2-Allyloxy4-nitrophenoxymethyl)-oxirane

Procedure

20 g (0.50 mole) of 60% NaH/mineral oil was placed in a two liter flask and washed with 500 mL of hexane. 1 L of DMF was added, followed by 77 g (0.40 mole) of the 2-allyloxy-4-nitrophenol prepared in the previous step. Addition of the phenol was performed in portions under argon. After stirring the mixture for 30 minutes at room temperature under argon, 108 g (0.48 moles) of (R)-glycidyl tosylate was added and the mixture heated at 70-75° C. under nitrogen overnight. Upon cooling, the DMF was removed in vacuum and replaced with one liter of methylene chloride. This was washed with 500 mL portions of 2 N HCl, saturated sodium bicarbonate and saturated brine and dried over sodium sulfate. The mixture was filtered, concentrated to an oil in vacuum and column chromatographed on silica gel using 1:1 hexane/methylene chloride as eluant. This gave 43 g of product contaminated with traces of the two starting materials, followed by 21 g of pure product as a pale yellow solid. The impure material was recrystallized from 1.2 L of 10% ethyl acetate/hexane to give 34 g of pure (homogeneous on silica gel tic with 1:1 hexane/methylene chloride) (R)-2-(2-allyloxy-4-nitrophenoxymethyl)-oxirane (m.p. 64° C.).

Workup

  1. washwashed with 500 mL of hexane
  2. addition1 L of DMF was added
  3. customprepared in the previous step
  4. temperaturethe mixture heated at 70-75° C. under nitrogen overnight
  5. temperatureUpon cooling
  6. customthe DMF was removed in vacuum
  7. washThis was washed with 500 mL portions of 2 N HCl, saturated sodium bicarbonate and saturated brine
  8. dry with materialdried over sodium sulfate
  9. filtrationThe mixture was filtered
  10. concentrationconcentrated to an oil in vacuum and column
  11. customchromatographed on silica gel using 1:1 hexane/methylene chloride as eluant
  12. customThe impure material was recrystallized from 1.2 L of 10% ethyl acetate/hexane
  13. customto give 34 g of pure (homogeneous on silica gel tic with 1:1 hexane/methylene chloride) (R)-2-(2-allyloxy-4-nitrophenoxymethyl)-oxirane (m.p. 64° C.)

Sources & evidence

ORD record
ord-d1d1689233e74cbf8011ebcd1ab0771f
Source dataset
uspto-grants-2004_10
Patent number
US06800648B2

Reaction notes

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