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

HRID 542149Notes

Reaction equation

HRID 542149 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][CH:25]=O.[OH-].[K+].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

9

Reactant 5

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 5497692,4,6,10-Dodecatetraenal, 3,7,11-trimethyl-HCID 2723922Sodium ethoxideHCID 2773818Ethyl 4-(diethoxyphosphoryl)-3-methylcrotonate

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 30.0 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-dodecatetraen-1-al 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 methanol and water (2:1), and concentrated to give 99 g. of a concentrate. To a refluxing solution of 8.2 g. of potassium hydroxide and 80 ml. of ispropyl 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. There was obtained 9.8 g. of the desired product as pale yellow crystals.

Workup

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

Sources & evidence

ORD record
ord-23c39f7ee5c14e4bbfd24689abc30a56
Source dataset
uspto-grants-1987_04
Patent number
US04655973

Reaction notes

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