Acetic Acid → Ethyl (2E,4E,6E,10E)-3,7,11,15-tetramethylhexadeca-2,4,6,10,14-pentaenoate

HRID 1611064Notes

Reaction equation

HRID 1611064 reaction equation
[O-:1][CH2:2][CH3:3].[Na+].[CH2:5]([C:7]([CH2:20]C)(P(O)(O)=O)/[C:8](/C)=C(\CC)/C([O-])=O)[CH3:6].[CH3:22][C:23]([CH3:37])=[CH:24][CH2:25][CH2:26]/[C:27](/[CH3:36])=[CH:28]/[CH2:29][CH2:30]/[C:31](/[CH3:35])=[CH:32]/[CH:33]=[O:34].C(O)(=O)C>CN(C)C=O>[CH2:2]([O:1][C:33](=[O:34])/[CH:32]=[C:31](\[CH3:35])/[CH:30]=[CH:29]/[CH:28]=[C:27](\[CH3:36])/[CH2:26][CH2:25]/[CH:24]=[C:23](\[CH3:37])/[CH2:22][CH2:6][CH:5]=[C:7]([CH3:20])[CH3:8])[CH3:3]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 2723922Sodium ethoxideHCID 5280598(2E,6E)-3,7,11-trimethyldodeca-2,6,10-trienalHCID 86584517Triethyl-3-methyl-4-phosphonocrotonate

Product 1

HCID 11984134Ethyl (2E,4E,6E,10E)-3,7,11,15-tetramethylhexadeca-2,4,6,10,14-pentaenoateYield 88%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Conditions

Temperature
-10 °C

Procedure

Under argon atmosphere, sodium ethoxide (2.16 g, 1.26 equivalents) was suspended in 20 ml of dimethylformamide, and the suspension was added dropwise with 5 ml dimethylformamide solution of triethyl-3-methyl-4-phosphonocrotonate (7.87 g, 1.2 equivalents, 23.28 mmol) at room temperature. The reaction mixture was then added dropwise with 5 ml dimethylformamide solution of farnesal (5.0 g, 22.7 ml) under stirring at −10° C., and further stirred at the same temperature for 30 minutes. The reaction mixture was added to ice-water. The solution was neutralized with acetic acid and extracted with n-heptane. The resulting organic layer was washed with saturated brine and dried over magnesium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 6.6 g of the title compound (yield 88%, 2E:2Z=86:14) as a yellow oil.

Workup

  1. stirringfurther stirred at the same temperature for 30 minutes
  2. extractionextracted with n-heptane
  3. washThe resulting organic layer was washed with saturated brine
  4. dry with materialdried over magnesium sulfate
  5. customThe solvent was evaporated under reduced pressure
  6. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-96cd9e35864f46eeb81d6aac8379ca43
Source dataset
uspto-grants-2006_01
Patent number
US06984742B2

Reaction notes

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