Hydrochloric Acid → 3,7,11,15-Tetramethyl-2,4,6,8,10,14-hexadecahexaenoic acid

HRID 1762887Notes

Reaction equation

HRID 1762887 reaction equation
[O-]CC.[Na+].C([O:7][C:8]([CH:10]=[C:11]([CH3:21])[CH2:12]P(=O)(OCC)OCC)=[O:9])C.[CH3:22][C:23]([CH:27]=[CH:28][CH:29]=[C:30]([CH3:37])[CH2:31][CH2:32][CH:33]=[C:34]([CH3:36])[CH3:35])=[CH:24][CH2:25]O.Cl>CCCCCC.O.O1CCCC1>[CH3:21][C:11]([CH:12]=[CH:25][CH:24]=[C:23]([CH3:22])[CH:27]=[CH:28][CH:29]=[C:30]([CH3:37])[CH2:31][CH2:32][CH:33]=[C:34]([CH3:36])[CH3:35])=[CH:10][C:8]([OH:7])=[O:9]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 2723922Sodium ethoxideHCID 2773818Ethyl 4-(diethoxyphosphoryl)-3-methylcrotonateHCID 541499003,7,11-Trimethyl-2,4,6,10-dodecatetraene-1-ol

Product 1

HCID 542324823,7,11,15-Tetramethyl-2,4,6,8,10,14-hexadecahexaenoic acid

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-20 °C

Procedure

To a suspension of 30.3 g. of sodium ethoxide in 300 ml. of tetrahydrofuran was added 118 g. of diethyl 3-ethoxycarbonyl-2-methyl-2-propenylphosphonate. To the mixture was added 67 g. of 3,7,11-trimethyl-2,4,6,10-dodecatetraene-1-ol under stirring, chilling with ice and shielding from the light. After 1 hour, the reaction liquid was poured into 1 liter of water, and 1 liter of n-hexane was added for extraction. The n-hexane phase was separated, washed with two 100 ml. portions of a mixture of methanoland water (2:1), and concentrated to give 99 g. ofa concentrate. To a refluxing solution of 8.2 g. of potassium hydroxide and 80 ml. of isopropyl alcohol was added 21 g. of the concentrate under shielding from the light. After 15 minutes, the reaction liquid was poured into 300 ml. of ice-water, made acidic by addition of hydrochloric acid, and extracted with 300 ml. of diethyl ether. The extract was washed with three 100 ml. portions of water, dried over magnesium sulfate, and evaporated to remove the solvent. The residue was dissolved in 200 ml. of n-hexane and chilled to -20° C. to crystallize it. There was obtained 9.8 g. of the desired product as pale yellow crystals.

Workup

  1. additionTo a suspension of 30.3 g
  2. additionTo the mixture was added 67 g
  3. temperaturechilling with ice and shielding from the light
  4. customthe reaction liquid
  5. additionwas added for extraction
  6. customThe n-hexane phase was separated
  7. washwashed with two 100 ml
  8. additionportions of a mixture of methanoland water (2:1)
  9. concentrationconcentrated
  10. customto give 99 g
  11. concentrationofa concentrate
  12. additionof isopropyl alcohol was added 21 g
  13. concentrationof the concentrate
  14. waitAfter 15 minutes
  15. customthe reaction liquid
  16. additionwas poured into 300 ml
  17. extractionextracted with 300 ml
  18. washThe extract was washed with three 100 ml
  19. dry with materialportions of water, dried over magnesium sulfate
  20. customevaporated
  21. customto remove the solvent
  22. dissolutionThe residue was dissolved in 200 ml
  23. customto crystallize it
  24. customThere was obtained 9.8 g

Sources & evidence

ORD record
ord-9f47a118a0964241b7efab4d0d7e1087
Source dataset
uspto-grants-1989_05
Patent number
US04835183

Reaction notes

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