Acetic Acid → Dodeca-8,10-dien-1-yl acetate

HRID 1416988Notes

Reaction equation

HRID 1416988 reaction equation
[CH:1](Cl)=[CH:2][CH:3]=[CH:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].C(Cl)CCCCCCC=CC=CC.[C:27]([O-:30])(=[O:29])[CH3:28].[K+].C(O)(=O)C>C(OCC)(=O)C.O>[C:27]([O:30][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH:8]=[CH:9][CH:10]=[CH:11][CH3:12])(=[O:29])[CH3:28]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 517044Potassium AcetateHCID 53734465Dodecadienyl chlorideHCID 544146658,10-Dodecadien-1-yl chloride

Product 1

HCID 93292Dodeca-8,10-dien-1-yl acetate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

The particulars of the conversion of the dodecadienyl chloride to the alcohol that is CM pheromone are set forth below. To a 100 mL glass round-bottomed flask equipped with a reflux condenser, a stir bar and a nitrogen atmosphere were added 1.0 g (5 mmol) of 8,10-dodecadien-1-yl chloride, 8.1 g (8.3 mmol) potassium acetate and 40 ml of glacial acetic acid. This mixture was placed in a 150° C. oil bath for 76 hours, after which time GC analysis indicated that the reaction was >98% complete. The reaction mixture was poured into 100 ml of water and ice and stirred for one hour. Ethyl acetate (100 ml) was added and the organic phase was separated from the aqueous phase. The organic phase was washed with 4×50 mL of sodium bicarbonate-saturated water until the pH of the water was neutral, dried with sodium sulfate, filtered and the organic solvent was removed under reduced pressure to yield 8,10-dodecadienyl acetate as a yellow liquid. This acetate was dissolved into 30 ml of methanol and 1 ml of 6 M sodium hydroxide and stirred at room temperature for two hours. Methanol was removed under reduced pressure, 10 mL of heptane and 1 mL of 1 M HCl were added and the aqueous phase removed. The organic phase was placed in a -20° C. freezer for 18 hours. White crystals were removed by filtration to yield 200 mg of E,E-8,10-dedecadienol. Gas chromatography, 1H NMR and 13C NMR analysis of the product were identical to a standard sample of E,E-8,10-dodecadienol.

Workup

  1. customTo a 100 mL glass round-bottomed flask equipped with a reflux condenser, a stir bar
  2. customwas placed in a 150° C.
  3. customfor 76 hours
  4. customthe organic phase was separated from the aqueous phase
  5. washThe organic phase was washed with 4×50 mL of sodium bicarbonate-saturated water until the pH of the water
  6. dry with materialdried with sodium sulfate
  7. filtrationfiltered
  8. customthe organic solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-d282c6250ac044209ea0c4868bef34af
Source dataset
uspto-grants-1999_06
Patent number
US05916983

Reaction notes

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