Sodium hydride → HCID 178446978, compound

HRID 1868960Notes

Reaction equation

HRID 1868960 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:14](=[CH:15][CH:16]=1)[C:8]1([CH2:13][CH2:12][O:11][CH2:10][CH2:9]1)[C:7]([OH:17])=[C:6]([C:18]([O:20]CC)=O)[C:5]2=[O:23].[H-].[Na+].[CH2:26]([Mg]Br)[CH2:27][CH:28]=[CH2:29]>C1COCC1>[Cl:1][C:2]1[CH:3]=[C:4]2[C:14](=[CH:15][CH:16]=1)[C:8]1([CH2:9][CH2:10][O:11][CH2:12][CH2:13]1)[C:7]([OH:17])=[C:6]([C:18](=[O:20])[CH2:29][CH2:28][CH:27]=[CH2:26])[C:5]2=[O:23]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 178418797HCID 178418797, compoundHCID 178470017HCID 178470017, compound

Product 1

HCID 178446978HCID 178446978, compoundYield 78.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of ethyl 6-chloro-2-hydroxy-4-oxo-2′,3′,5′,6′-tetrahydro-spiro[naphthalene-1,4′-pyran]-3-carboxylate (2.53 g, 8 mmol, Example 1 A-C) in 20 mL THF was stirred at room temperature and treated with sodium hydride (0.6 g, 15 mmol, 60% in oil). The resulting mixture was stirred for 10 minutes. The mixture was then treated with 3-butenylmagnesium bromide (15 mL, 8 mmol). After 5 minutes, the mixture was warmed to 60° C., and the reaction was stirred for another 0.5 hours. The mixture was cooled to 0° C., quenched with 20 mL saturated NH4Cl, and 100 mL EtOAc was added. The organic layer was separated, dried over anhydrous Na2SO4, and concentrated in vacuo. The crude product was purified by column chromatography eluting with 10-20% EtOAc/hexane to give 2.17 g white solid. MS m/e: 347 (M+H)+.

Workup

  1. stirringThe resulting mixture was stirred for 10 minutes
  2. temperaturethe mixture was warmed to 60° C.
  3. stirringthe reaction was stirred for another 0.5 hours
  4. temperatureThe mixture was cooled to 0° C.
  5. customquenched with 20 mL saturated NH4Cl, and 100 mL EtOAc
  6. additionwas added
  7. customThe organic layer was separated
  8. dry with materialdried over anhydrous Na2SO4
  9. concentrationconcentrated in vacuo
  10. customThe crude product was purified by column chromatography
  11. washeluting with 10-20% EtOAc/hexane

Sources & evidence

ORD record
ord-e5b18a211e01492389fa7c9d5f46cf19
Source dataset
uspto-grants-2009_12
Patent number
US07635715B2

Reaction notes

Loading…