Chloride → HCID 178468112, compound

HRID 903677Notes

Reaction equation

HRID 903677 reaction equation
[CH3:1][O:2][C:3](=[O:8])[CH2:4][C:5]([CH3:7])=[O:6].[O-]CC.[Na+:12].[Cl-]>C(O)C>[Na:12][CH2:1][O:2][C:3](=[O:8])[CH2:4][C:5]([CH3:7])=[O:6]

Participants

5

Reactant 3

HCID 312ChlorideHCID 7757Methyl acetoacetateHCID 2723922Sodium ethoxide

Product 1

HCID 178468112HCID 178468112, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Sodiomethylacetoacetate was prepared by adding an excess of methylacetoacetate (74.3 g, 0.64 mole) to a solution of sodium ethoxide (31.3 g, 0.46 mole) in 150 mls. absolute ethanol at 25°. The reaction mixture was cooled to 0° and then the crude chloride prepared above was added dropwise over a 25-minute period and stirring was continued at 0° for an additional 3 hours. After this period, the temperature was allowed to rise to ambient over a 40-minute period. A portion of the ethanol (78.0 g) was distilled at this point by stirring the reaction mixture at 60°-65° for 2 hours under a slight vacuum. After cooling to 30°, 550 mls. of 10% aqueous NaOH was added over a 15-minute period and the reaction mixture was stirred at 70° for 4 hours. After settling, the layers were separated and the aqueous layer was saturated with NaCl and extracted with three 200-ml. portions of pentane. The combined oils were washed once with 1 liter H2O and once with 1 liter saturated NaCl to yield, after solvent removal, 139.2 g of crude 6,10,14-trimethylpentadecan-5,9-dien-2-one. Gas chromotographic analysis indicated 53.2% purity which represents an estimated theory yield from 10,11-dihydrofarnesene of 78.8%.

Workup

  1. customat 25°
  2. temperatureThe reaction mixture was cooled to 0°
  3. additionabove was added dropwise over a 25-minute period
  4. waitAfter this period
  5. waitto ambient over a 40-minute period
  6. distillationA portion of the ethanol (78.0 g) was distilled at this point
  7. stirringby stirring the reaction mixture at 60°-65° for 2 hours under a slight vacuum
  8. temperatureAfter cooling to 30°
  9. additionof 10% aqueous NaOH was added over a 15-minute period
  10. stirringthe reaction mixture was stirred at 70° for 4 hours
  11. customthe layers were separated
  12. extractionextracted with three 200-ml
  13. washThe combined oils were washed once with 1 liter H2O and once with 1 liter saturated NaCl
  14. customto yield
  15. customafter solvent removal, 139.2 g of crude 6,10,14-trimethylpentadecan-5,9-dien-2-one
  16. customyield from 10,11-dihydrofarnesene of 78.8%

Sources & evidence

ORD record
ord-936caa7b88304dcbab2e828ecebd7623
Source dataset
uspto-grants-1980_10
Patent number
US04228313

Reaction notes

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