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

HRID 1031622Notes

Reaction equation

HRID 1031622 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>C(O)(C)C.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

10

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 4

HCID 962WaterSolventHCID 3776IsopropanolSolventHCID 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-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 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 methanol and water (2:1)
  9. concentrationconcentrated
  10. customto give 99 g
  11. concentrationof the concentrate
  12. waitAfter 15 minutes
  13. customthe reaction liquid
  14. additionwas poured into 300 ml
  15. extractionextracted with 300 ml
  16. washThe extract was washed with three 100 ml
  17. dry with materialportions of water, dried over magnesium sulfate
  18. customevaporated
  19. customto remove the solvent
  20. dissolutionThe residue was dissolved in 200 ml
  21. customto crystallize it
  22. customThere was obtained 9.8 g

Sources & evidence

ORD record
ord-f46435c3187f49ca89cc0093f0b18ab2
Source dataset
uspto-grants-1990_09
Patent number
US04954525

Reaction notes

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