Potassium Carbonate → (12Z,14Z)-heptadeca-1,12,14-triene

HRID 3764

Reaction equation

HRID 3764 reaction equation
C(=O)([O-])[O-].C(=O)([O-])[O-].[K+].[K+].O1[CH2:16][CH2:15]OCC1.[CH:17](=O)[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26]/[CH:27]=[CH:28]\[CH:29]=[CH:30]/[CH2:31]C>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[CH2:31]=[CH:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]/[CH:20]=[CH:19]\[CH:18]=[CH:17]/[CH2:15][CH3:16]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 19660Carbonate IonHCID 312751,4-DioxaneHCID 6436739(Z,Z)-11,13-Hexadecadienal

Product 1

HCID 6443230(12Z,14Z)-heptadeca-1,12,14-triene

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 962WaterSolvent

Procedure

(Z,Z)-1,12,14-heptadecatriene (TRIENE) was synthesized conveniently from Wittig Salt and aldehyde in aqueous dioxidepotassium carbonate heterogeneous medium (Lechat 1982). A mixture of 3.57 g (0.01 mol) of methyl triphenylphosphonium bromide (Alfa Inorganics), 1.7 g (0.14 mol) of potassium carbonate, 10 ml of 1,4-dioxane, 0.15 ml of water and 2.36 g (0.01 mol) of (Z,Z)-11,13-hexadecadienal (AL. Albany International) was prepared in a 100 ml round bottomed flask equipped with a magnetic stirrer, thermometer and reflux condenser. The mixture was heated to reflux at 105°-110° with stirring while aliquots of 15 ul were withdrawn periodically and partitioned between 1 ml of H2O and 1 ml of hexane. Analysis by gas-liquid chromatography, showed 66, 70 and 99% triolefin and 30%, 26% and 1% starting aldehyde at 1.1 and 2.2 and 17 hr, respectively. More potassium carbonate (1.7 g) was added at 212 hr to drive the reaction to completion. The reaction mixture was cooled and extracted 3 times with 25 ml of hexane, then the organic layer was extracted with water, dried and the solvent removed to leave 1.8 g of yellow oil and a few crystals of triphenylphosphine oxide. The oil was taken up in hexane and passed through a 1×45 cm column of silica gel (60-200 mesh, Baker) with hexane, to yield 1.7 g (73% yield) of clear oil.

Workup

  1. customwas prepared in a 100 ml round bottomed flask
  2. customequipped with a magnetic stirrer
  3. temperaturethermometer and reflux condenser
  4. temperatureThe mixture was heated
  5. temperatureto reflux at 105°-110°
  6. customwere withdrawn periodically
  7. custompartitioned between 1 ml of H2O and 1 ml of hexane
  8. customat 1.1 and 2.2 and 17 hr
  9. additionMore potassium carbonate (1.7 g) was added at 212 hr
  10. customthe reaction to completion
  11. temperatureThe reaction mixture was cooled
  12. extractionextracted 3 times with 25 ml of hexane
  13. extractionthe organic layer was extracted with water
  14. customdried
  15. customthe solvent removed

Sources & evidence

ORD record
ord-d08bf726ee614cf79e621b0c1f4b7772
Source dataset
uspto-grants-1988_02
Patent number
US04722839

Linked notes

Loading…