Hydrochloric Acid → 1-vinyl-13-oxabicyclo[10.1.0]tridecane

HRID 1061085Notes

Reaction equation

HRID 1061085 reaction equation
[CH:1]([Mg])=[CH2:2].Cl[CH:5]1[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C:6]1=[O:17].Cl.[OH-].[Na+]>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.O1CCCC1>[CH:1]([C:7]12[O:17][CH:6]1[CH2:5][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]2)=[CH2:2]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 5665332-ChlorocyclododecanoneHCID 178461833HCID 178461833, compound

Product 1

HCID 50739381-vinyl-13-oxabicyclo[10.1.0]tridecaneYield 85%

Reagents, catalysts & solvents 3

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
95 °C

Procedure

A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (24 mmol), and to the solution, toluene (16 ml) was added. At 0° C., a toluene solution of 2-chlorocyclododecanone (2.94 g, 13.5 mol) was added dropwise for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (5 g) was added for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (6.8 g, 51.0 mmol) and tetrabutylammonium chloride (0.0417 g, 0.150 mmol), and the mixture was stirred for reaction at 95° C. for 2 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) and a saline solution (10 ml). The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (2.42 g, 11.5 mmol, chemical purity 99%, cis form:trans form=86:14). The yield was 85%.

Workup

  1. customA four-neck flask equipped with a thermometer, stirrer and condenser tube
  2. additionwas added for hydrolysis
  3. customthe solution was separated
  4. washThe organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml)
  5. additionTo the obtained toluene solution, added
  6. customAfter completion of reaction
  7. customthe solution was separated
  8. washthe organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml)
  9. distillationThe solvent was distilled away under reduced pressure
  10. distillationthe residue was distilled for purification under reduced pressure

Sources & evidence

ORD record
ord-e181076891934a84adbb7a9f84a79b8e
Source dataset
uspto-grants-2003_02
Patent number
US06525207B1

Reaction notes

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