Acetic Acid → ethyl (E,E)-2-cyano-3,7,11,15-tetramethyl-6,10,14-hexadecatrienoate

HRID 1263231Notes

Reaction equation

HRID 1263231 reaction equation
[CH2:1]([CH2:16][C:17](=O)[CH3:18])[CH:2]=[C:3]([CH2:5][CH2:6][CH:7]=[C:8]([CH2:10][CH2:11][CH:12]=[C:13]([CH3:15])[CH3:14])[CH3:9])[CH3:4].[C:20]([CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])#[N:21].C([O-])(=O)C.[NH4+].C(O)(=O)C>C1C=CC=CC=1>[C:20]([CH:22]([CH:17]([CH3:18])[CH2:16][CH2:1]/[CH:2]=[C:3](\[CH3:4])/[CH2:5][CH2:6]/[CH:7]=[C:8](\[CH3:9])/[CH2:10][CH2:11][CH:12]=[C:13]([CH3:15])[CH3:14])[C:23]([O:25][CH2:26][CH3:27])=[O:24])#[N:21]

Participants

6

Reactant 4

HCID 176Acetic Acid2×HCID 7764Ethyl cyanoacetateHCID 612065,9,13-Pentadecatrien-2-one, 6,10,14-trimethyl-HCID 517165Ammonium Acetate

Product 1

HCID 15589936ethyl (E,E)-2-cyano-3,7,11,15-tetramethyl-6,10,14-hexadecatrienoateYield 73.7%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

In 200 ml of benzene was dissolved 50 g of farnesylacetone, and 28 g of ethyl cyanoacetate, 5 g of ammonium acetate and 5 g of acetic acid were added to the solution. The mixture was refluxed for 8 hours while removing the water formed by the reaction. The liquid reaction mixture was washed with water and dried and a solution of 4.3 g of sodium borohydride in 50 ml of ethanol was added dropwise to the reaction mixture under agitation at 10° to 20° C. The resulting mixture was stirred for 1 hour. To the liquid reaction mixture was added 50 ml of 10% acetic acid, and the mixture was washed with water and dried. The solvent was removed by distillation and the residue was purified by column chromatography using silica gel to obtain 50.5 g of the intended compound in the form of an oil.

Workup

  1. additionwere added to the solution
  2. temperatureThe mixture was refluxed for 8 hours
  3. customwhile removing the water
  4. customformed by the reaction
  5. customThe liquid reaction mixture
  6. washwas washed with water
  7. customdried
  8. additiona solution of 4.3 g of sodium borohydride in 50 ml of ethanol was added dropwise to the reaction mixture under agitation at 10° to 20° C
  9. customTo the liquid reaction mixture
  10. washthe mixture was washed with water
  11. customdried
  12. customThe solvent was removed by distillation
  13. customthe residue was purified by column chromatography

Sources & evidence

ORD record
ord-68c2e82810754c5bbb66d2778282489c
Source dataset
uspto-grants-1984_06
Patent number
US04456603

Reaction notes

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