Sodium hydride → Methyl 2-(4-(4-bromophenyl)-2-oxabicyclo[2.2.2]octan-1-yl)acetate

HRID 881717Notes

Reaction equation

HRID 881717 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([CH2:19][OH:20])[CH2:13][CH2:12][C:11](=[CH:14][C:15]([O:17][CH3:18])=[O:16])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.[H-].[Na+]>O1CCOCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]23[CH2:9][CH2:10][C:11]([CH2:14][C:15]([O:17][CH3:18])=[O:16])([CH2:12][CH2:13]2)[O:20][CH2:19]3)=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 24758Sodium hydrideHCID 86700824Methyl 2-(4-(4-bromophenyl)-4-(hydroxymethyl)cyclohexylidene)acetate

Product 1

HCID 86700823Methyl 2-(4-(4-bromophenyl)-2-oxabicyclo[2.2.2]octan-1-yl)acetateYield 78%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a round bottom flask containing methyl 2-(4-(4-bromophenyl)-4-(hydroxymethyl)cyclohexylidene)acetate (4.36 g, 12.85 mmol) was added 1,4-dioxane (161 ml). The clear solution was cooled in an ice-bath and sodium hydride (0.67 g, 16.75 mmol) was then added portion-wise. After the addition, the mixture was warmed to room temperature and stirred for 10 minutes. After 10 minutes of stirring, the content was heated to 100° C. in an oil bath (with a reflux condenser) for 30 minutes. The reaction mixture was cooled to room temperature and quenched with a saturated solution of ammonium chloride and subsequently concentrated to remove excess dioxane. The residue was taken in saturated ammonium chloride solution and extracted twice with EtOAc. The combined organic portion was dried over sodium sulfate and concentrated to afford a crude product. Column purification afforded the title compound as white solid (3.4 g, 78% yield). LC/MS, ESI-MS: 341.2 (M+H+), RT: 1.40 (Condition E).

Workup

  1. temperatureThe clear solution was cooled in an ice-bath
  2. additionAfter the addition
  3. stirringAfter 10 minutes of stirring
  4. temperaturethe content was heated to 100° C. in an oil bath (with a reflux condenser) for 30 minutes
  5. temperatureThe reaction mixture was cooled to room temperature
  6. customquenched with a saturated solution of ammonium chloride
  7. concentrationsubsequently concentrated
  8. customto remove excess dioxane
  9. extractionextracted twice with EtOAc
  10. dry with materialThe combined organic portion was dried over sodium sulfate
  11. concentrationconcentrated
  12. customto afford a crude product
  13. customColumn purification

Sources & evidence

ORD record
ord-2826d89c971d4fb585060a78b90c0961
Source dataset
uspto-grants-2015_03
Patent number
US08993619B2

Reaction notes

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