Sodium → HCID 14647994, compound

HRID 1606674Notes

Reaction equation

HRID 1606674 reaction equation
[Na].C([C:4]([CH2:11][CH3:12])([C:8]([O-:10])=[O:9])C([O-])=O)C.Cl[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19]/[CH:20]=[CH:21]\[CH2:22]/[CH:23]=[CH:24]\[CH2:25]/[CH:26]=[CH:27]\[CH2:28][CH2:29][CH2:30]CC>C(O)CCC>[C:8]([OH:10])(=[O:9])[CH2:4][CH2:11][CH2:12][CH2:30][CH2:29][CH2:28][CH2:27]/[CH:26]=[CH:25]\[CH2:24]/[CH:23]=[CH:22]\[CH2:21]/[CH:20]=[CH:19]\[CH2:18][CH2:17][CH2:16][CH2:15][CH3:14]

Participants

5

Reactant 3

HCID 5360545Sodium2×HCID 69515632,2-DiethylpropanedioateHCID 86733357HCID 86733357, compound

Product 1

HCID 14647994HCID 14647994, compound

Reagents, catalysts & solvents 1

HCID 2631-ButanolSolvent2×

Conditions

Temperature
140 °C

Procedure

To 15 ml. of n-butanol under nitrogen was added 211 mg. of sodium in pieces. The mixture was heated gently until all the sodium had dissolved, then 1.2 ml. of diethylmalonate was added and the mixture was refluxed one hour, then cooled, and a solution of 2.0 g. of 1-chloro-cis,cis,cis-7,10,13-nonadecatriene in 7.5 ml. of n-butanol was added. The resulting reaction mixture was refluxed for 3 hrs. under nitrogen, then allowed to stand for about 20 hrs., and concentrated under reduced pressure. The thus obtained residue was dissolved in a solution of 1.9 g. of potassium hydroxide in 38 ml. of 95% ethanol and heated under reflux for 3.5 hrs., then was concentrated to about 1/3 volume, diluted with water, and extracted with ether. The ether solution was extracted with 1N aqueous sodium hydroxide. The sodium hydroxide solution was made acid with 3N hydrochloric acid and extracted twice with ether. The ether extracts were washed with water, then with saturated aqueous sodium chloride, dried over sodium sulfate, and evaporated to give 1.72 g. of a pale yellow oil. The thus obtained oil was heated in a short path distillation tube at 140°C. under reduced pressure until decarboxylation was complete, then was distilled at a bath temperature of 180°-200°/0.006 mm., thus obtaining a distillate comprising cis,cis,cis-9,12,15-heneicosatrienoic acid.

Workup

  1. dissolutionhad dissolved
  2. temperaturethe mixture was refluxed one hour
  3. temperaturecooled
  4. customThe resulting reaction mixture
  5. temperaturewas refluxed for 3 hrs
  6. concentration, and concentrated under reduced pressure
  7. dissolutionThe thus obtained residue was dissolved in a solution of 1.9 g
  8. temperatureof 95% ethanol and heated
  9. temperatureunder reflux for 3.5 hrs
  10. concentration, then was concentrated to about 1/3 volume
  11. additiondiluted with water
  12. extractionextracted with ether
  13. extractionThe ether solution was extracted with 1N aqueous sodium hydroxide
  14. extractionextracted twice with ether
  15. washThe ether extracts were washed with water
  16. dry with materialwith saturated aqueous sodium chloride, dried over sodium sulfate
  17. customevaporated
  18. customto give 1.72 g
  19. distillationwas distilled at a bath temperature of 180°-200°/0.006 mm

Sources & evidence

ORD record
ord-be938ed1f4f34247a0d6e9789ae838f7
Source dataset
uspto-grants-1976_04
Patent number
US03953499

Reaction notes

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