Potassium Phosphate, Dibasic → Ethyl 7,11-dimethyl-3-oxododeca-6,10-dienoate

HRID 1355631Notes

Reaction equation

HRID 1355631 reaction equation
[CH2:1](Br)/[CH:2]=[C:3](/[CH2:5][CH2:6][CH:7]=[C:8]([CH3:10])[CH3:9])\[CH3:4].P([O-])([O-])(O)=[O:13].[K+].[K+].CCCC[CH2:23][CH3:24].[C:25]([O:28][CH2:29][CH3:30])(=[O:27])[CH3:26]>>[CH3:4][C:3]([CH2:5][CH2:6][CH:7]=[C:8]([CH3:10])[CH3:9])=[CH:2][CH2:1][CH2:24][C:23](=[O:13])[CH2:26][C:25]([O:28][CH2:29][CH3:30])=[O:27]

Participants

4

Reactant 3

HCID 24450Potassium Phosphate, DibasicHCID 53658672,6-Octadiene, 1-bromo-3,7-dimethyl-, (2E)-2×HCID 21226206Ethyl acetate hexane

Product 1

HCID 54120364Ethyl 7,11-dimethyl-3-oxododeca-6,10-dienoateYield 77%

Procedure

The sodium salt of ethyl acetoacetate (Compound 11; 20.0 mmol, 3.04 g) was dissolved in 40 ml of tetra hydrofuran (THF) (distilled from sodium/benzophenone ketyl) and cooled to 0° C. n-Butyllithium (2.0 M in cyclohexane, 21.0 mmol, 10.6 ml) was added dropwise to the cooled solution to form a solution of the dianion Compound 12. After 20 minutes, geranyl bromide (Compound 13; 10.0 mmol, 1.98 ml, 2.16 g) was added to the solution of dianion and stirring was continued for an additional 30 minutes at 0° C. The reaction mixture was poured into a cold saturated solution of potassium hydrogen phosphate and extracted with ether (3×20 ml). The combined organic layers were washed with water (20 ml), dried over MgSO4, filtered, and concentrated. Flash chromatography (9:1 hexane/ethyl acetate) afforded 2.05 g (77% yield) of Compound 14 as an oil.

Workup

  1. waitwas continued for an additional 30 minutes at 0° C
  2. extractionextracted with ether (3×20 ml)
  3. washThe combined organic layers were washed with water (20 ml)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-54f4ddad81de4059a1ed6232e7792e4a
Source dataset
uspto-grants-2003_07
Patent number
US06586461B1

Reaction notes

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